United States
            Environmental Protection
            Agency
             Municipal Environmental Research
             Laboratory
             Cincinnati OH 45268
EPA-600 2 80 122
August 1980
            Research and Development
6EPA
Pyrolytic Oils

Characterization  and
Data Development for
Continuous Processing


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                RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency,  have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology.  Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:

      1.   Environmental  Health Effects Research
      2.   Environmental  Protection Technology
      3.   Ecological Research
      4.   Environmental  Monitoring
      5.   Socioeconomic Environmental Studies
      6.   Scientific and Technical Assessment Reports (STAR)
      7.   Interagency Energy-Environment Research and Development
      8.   "Special" Reports
      9.   Miscellaneous Reports

This report has been assigned to the  ENVIRONMENTAL PROTECTION TECH-
NOLOGY  series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for  the control and treatment
of pollution-sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                                      EPA-600/2-80-122
                                      August 1980
 PYROLYTIC OILS - CHARACTERIZATION AND DATA
   DEVELOPMENT FOR CONTINUOUS PROCESSING
                     by

          J. A. Knight, L. W. Elston,
         D. R. Hurst, and R. J. Kovac
        Engineering Experiment Station
        Georgia Institute of Technology
            Atlanta, Georgia 30332
     Grant Nos. R-804416 and R-806403
              Project Officer

             Charles J. Rogers
Solid and Hazardous Waste Research Division
Municipal Environmental Research Laboratory
           Cincinnati, Ohio 45268
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
     OFFICE OF RESEARCH AND DEVELOPMENT
   U. S. ENVIRONMENTAL PROTECTION AGENCY
          CINCINNATI, OHIO  45268

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                                 DISCLAIMER
       This report has been reviewed by the Municipal Environmental Research
Laboratory, U. S. Environmental Protection Agency, arid approved for publica-
tion.  Approval does not signify that the contents necessarily reflect the
views and policies of the U. S. Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement or recom-
mendation for use.
                                      ii

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                                  FOREWORD
       The U. S. Environmental Protection Agency was created because of
increasing public and government concern about the dangers of pollution to
the health and welfare of the American people.  Noxious air, foul water, and
spoiled land are tragic testimonies to the deterioration of our natural
environment.  The complexity of that environment and the interplay of its
components require a concentrated and integrated attack on the problem.

       Research and development is that necessary first step in problem solu-
tion; it involves defining the problem, measuring its impact, and searching
for solutions.  The Municipal Environmental Research Laboratory develops new
and improved technology and systems to prevent, treat, and manage wastewater
and solid and hazardous waste pollutant discharges from municipal and comm-
unity sources, to preserve and treat public drinking water supplies, and to
minimize the adverse economic, social, health, and aesthetic effects of pollu-
tion.  This publication is one of the products of that research and provides
a most vital communications link between the researcher and the user community.

       This is a report on the characterization of oils obtained by the
pyrblysis of lignocellulosic wastes and the development of processing tech-
niques that would yield fractions suitable for industrial applications.
                                     iii

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                                   ABSTRACT
        Pyrolytic oils  produced by the pyrolysis of forestry residues in a ver-
 tical bed,  countercurrent  flow reactor  (Georgia Tech pyrolysis process) have
 been thoroughly characterized.  The pyrolytic oils were produced in a 500 Ib
 per hour pilot plant and in a 50 ton per day field development facility.  The
 overall chemical and physical properties have been determined by standard ana-
 lytical techniques.  The oils are dark brown to black with a burnt, pungent
 odor and have  a boiling range of about 100°C to approximately 200°C at which
 point thermal  degradation  begins to occur.  The heating values of the oils,
 which burn  cleanly, are approximately two-thirds of petroleum fuel oil heating
 values.   The oils, which are acidic, exhibit some corrosive characteristics.
 The oils are composed  of a large number of oxygenated compounds which exhibit
 a wide spectrum of chemical functionality.  Based on the results of this study,
 the pyrolytic  oils contained phenolics, polyhydroxy neutral compounds, neutral
 compounds of a high degree of aromaticity and volatile acidic compounds.

        A number of approaches to separating the oils into fractions, each of
 which would  contain a  predominant chemical species, were investigated on a
 batch basis.   These approaches employed extraction techniques with water,
 organic solvents, aqueous  alkaline solutions, and aqueous salt solutions.
 Based on the experimental  results on a batch basis, two approaches were selec-
 ted for continuous extraction experiments at the bench level with both raw oil
 and vacuum  stripped oil.   The results of these continuous extraction experi-
 ments show  that these  approaches are very promising as processing methods for
 producing oil  fractions which would be useful for industrial chemical applica-
 tions.   Based  on the results of the continuous extraction experiments, a ver-
 satile pilot plant was designed for further investigation of pyrolytic oils
 which would  yield data for scale up of the process for a commercial plant and
 produce  oil  fractions  for  studies for industrial applications.  Preliminary
 economic assessments, based on two approaches, indicate that the processing of
 pyrolytic oils  could be economically viable.  The results indicate that, for a
 50  percent net  return on investment, the selling price for the oil fractions
would  have to be in the range of 8.4 to 10.6 cents per pound which is in the
 same  range as 9  cents per  pound for coal tar creosote and well below 54 cents
per pound for cresylic acid, which were quoted market prices in December, 1979.
The preliminary  economic assessments are encouraging for processing pyrolytic
oils  into fractions suitable for industrial chemical applications.

       This report was submitted in fulfillment of Grant Nos. R-804416 and
R-806403 by Georgia Institute of Technology under the sponsorship of the U. S.
Environmental Protection Agency.  This report covers the period June 21, 1976
to March 31, 1980, and work was completed as of March 31, 1980.
                                      iv

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                                   CONTENTS

                                         /                               Page

Foreword	   ill
Abstract . 	 ..........    iv
Figures	    vi
Tables	-.	    ix
Acknowledgment	   xii

    1.  Introduction	     1
    2.  Summary  <	     3
    3.  Recommendations	     6
    4.  Background Information 	 .  	     7
    5.  Experimental	    11
        Phase I	'	    11
        Phase II	    38
        Phase III	    52
    6.  Pilot Plant Design	    77
    7.  Design and Economics of Commercial Size Plant  	    88
    8.  Discussion	   116

References	   126
Appendices
    A.  Material Balance Calculations  	  ...   128
    B.  Pilot Plant Calculations 	 .   137
    C.  Commercial Plant Calculations  	   159
    D.  Physical Properties	   181

Glossary	   184

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                                  FIGURES

Number                                                                   Page

  1   Viscosity of condenser oil	     16

  2   Viscosity of draft fan oil	     16

  3   Vacuum stripped condenser oil  	     17

  4   Vacuum stripped draft fan oil	     18

  5   Effect of heating condenser oil at 110°C for
        different time periods on viscosity  	     19

  6   Viscosity curves for condenser oil (initial)  and
        No. 2 and No. 6 fuel oils	     20

  7   Liquid chromatogram of wood oil.   Partisil  PAC  column with
        0-100% solvent gradient of 2-propanol in iso-octane   	     22

  8   Liquid chromatogram of wood oil.   Partisil  ODS  column with
        10-100% solvent gradient of acetonitrile  in water   	     22

  9   Liquid chromatogram of wood oil.   Partisil  ODS  column
        with 10-100% solvent gradient of acetonitrile in
        water with 20 minute hold at 40% acetonitrile  .	     23

 10   Liquid chromatogram of wood oil at 210 nm	     25

 11   Liquid chromatogram of wood oil at 254 nm	     25

 12   Liquid chromatogram of wood oil at 280 nm	     26
                                                   »

 13   Liquid chromatogram of wood oil at 300 nm	     26

 14   Liquid chromatogram of wood oil at 360 nm	     27

 15   Survey liquid chromatogram of raw condenser oil	     28

 16    Survey liquid chromatogram of draft fan oil	     28

 17    Survey liquid chromatogram of combined fractions
        from vacuum distillation 	     32
                                     vi

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                              FIGURES (Continued)

Number                                                                   Page

  18   Survey liquid chromatogram of spinning band fraction 1  ....    32

  19   Survey liquid chromatogram of spinning band fraction 5  ....    33

  20 v.  Survey liquid chromatogram of spinning band fraction 9  ....    33

  21   Survey liquid chromatogram of condenser oil vacuum
         stripped without heat	    34

  22   Survey liquid chromatogram of 100° - 105°C organic
         layer from steam distillation	    34

  23   Survey liquid chromatogram of 100° - 105°C aqueous phase
         from steam distillation	    35

  24   Removal of volatiles from pyrolytic oil 	 ........    39

  25   Extraction of oil sequentially with water at 25°C,
         50°C, and 95°C	    40

  26   Liquid chromatogram of 25°C water extract of
         pyrolytic oil ...'....	    41

  27   Liquid chromatogram of pyrolytic oil after successive
         extraction with water at 25°C, 50°C, and 95°C  ........    41

  28   Extraction of .pyrolytic oil with sodium sulfate solution  ...    42

  29   Combined diisopropyl and water extraction of pyrolytic oil  .  .    44

  30   Combined anisole and water extraction of pyrolytic oil  ....    45

  31   Extraction of pyrolytic oil with 2% sodium hydroxide
         solution	    46

  32   Extraction of methylene chloride solution of pyrolytic
         oil with water followed by diisopropyl  ether extraction
         of aqueous fraction 	    49

  33   Extraction of methylene chloride solution of pyrolytic
         oil with water followed by methylisobutyl ketone
         extraction of aqueous fraction  	    50

  34   Extraction of n-butanol solution of pyrolytic oil
         with water	    51

  35   Aqueous batch extraction, Process No. 1 	    54
                                      vii

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                             FIGURES (Continued)

Number                                                                   Page

  36   Three phase extraction, Process No. 2 	    57

  37   Sequential organic water extraction, Process No. 3  	    59

  38   Countercurrent extractor  	    62

  39   Separation process No. 1A—raw oil—2 stage extraction  ....    78

  40   Separation process IB—vacuum stripped—2 stage extraction  .   .    80

  41   Separation process 2A—raw oil—simultaneous extraction ....    82

  42   Separation process 2B—vacuum stripped—
         simultaneous extraction 	    84

  43   Pyrolysis oil pilot plant schematic—continuous process ....    87
                                    viii

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                                   TABLES

Number                                                                   Page

  1    Properties of Pine Bark-Sawdust Feed Material .  .  . ..... ..... .  12

  2    Properties of Wood Oils from Tech-Air 50 Dry ,
         Ton/day Facility	  13

  3    Variation of Oil Properties over Eight Months Period  ......  14

  4    Typical Properties of Wood Oils and Fuel Oils ..........  15

  5    Preliminary Average Molecular Weight Determinations . . . ,,. . . .;  29

  6    Hydrogenations at Moderate Pressure 	  36

  7    Hydrogenations at Intermediate Pressure 	  37

  8    Yields of Fractions from Water Extraction of Oil  . . *	42

  9    Yields from Methylene Chloride Extractions of Alkaline
         Solutions of Pyrolytic Oil	- . .  50

 10    Yields in Final Fractions from Separation Techniques
         in Figures 32 and 33	51

 11    Properties of Pyrolytic Oil Sample	,  53

 12    Composition of Yields from Batch Water Extractions,
       Process No. 1	4	56

 13    Composition of Yields from Batch Three Phase
       Extractions, Process No. 2	t  59

 14    Composition of Yields, Process No. 3	* . .  61

 15    Inputs and Yields, Process 1A	64

 16    Inputs and Yields, Process IB	65

 17    Inputs and Yields, Process 2A   	66

 18    Inputs and Yields, Process 2B	  67

 19    Composition of Continuous Extraction Yields .... * 	  68

                                     ix

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                              TABLES (Continued)

Number                                                                   JL^&

  20   Vacuum Stripping Experiments 	 •   69

  21   Organics Eluted from Aqueous Carbon Column	.=.•..   70

  22   Elution of Unstripped Oil from Activated Carbon Column .....   71

  23   Distillation Data for Water-Insoluble Oil  	...--..   72

  24   Analytical Results from Batch Experiment Process, 1A  ......   74

  25   TLC Solvents and Detection Reagents	•„» ....   75

  26   Infrared Bands	.......   76

  27   Liquid Chromatography Conditions 	 •   76

  28   Input Rates to Extractor	   85

  29   Required Extractor Volume   	  . 	 ...'..   86

  30   Pilot Plant - Cost Summary	   86

  31   Process 1A—2 Stage Continuous Extraction—Raw Oil—
       Installed Equipment Cost Summary 	   90

  32   Process IB—2 Stage Continuous Extraction—
       Vacuum Stripped Oil—Installed Equipment Cost Summary  	   90

  33   Process 2A—Continuous, Simultaneous Extraction—
       Raw Oil—Installed Equipment Cost Summary  	   91

  34   Process 2B—Continuous, Simultaneous Extraction—
       Vacuum Stripped Oil—Installed Equipment Cost Summary  	   91

  35   Depreciation—Process LA	100

  36   Depreciation—Process IB	100

  37   Depreciation—Process 2A	101

  38   Depreciation—Process 2B	

  39   Price Survey of Various Chemicals	

  40   Return on Investment—Summary	

  41   Cash Flow—Process 1-A—Case I—$0.30/lb	1Q7

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                              TABLES  (Continued)




Number                                                                    Page




  42.  Cash Flow—Process 1-A—Case II—$0.50/lb	    108




  43.  Cash Flow—Process 1-B—Case I—$0.30/lb	    1°9




  44.  Cash Flow—Process 1-B—Case II—$0.50/lb	    110




  45   Cash Flow-Process 2-A—Case I—$0.30/lb	    1H




  46   Cash Flow—Process 2-A—Case II—$0.50/lb	    112




  47   Cash Flow—Process 2-B—Case I— $0.30/lb	    113




  48   Cash Flow—Process 2-B—Case II—$0.50/lb	    114




  49   Minimum Selling Price per Pound to Justify Investment  	    115




  50   Average Selling Price for Pyrolytic Oil Products   	    124




  51   Return on Investment—Percent	    125

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                               ACKNOWLEDGMENTS
       This investigation was supported by the Municipal Environmental Research
Laboratory (MERL), U. S. Environmental Protection Agency, under Grant Numbers
R 804 416 010 and R 806 403 010.  We express our appreciation to Mr. Charles J.
Rogers of the Municipal Environmental Research Laboratory for his contributions,
suggestions, and encouragement during the course of this investigation.

       We express our thanks to the Tech Air Corporation for supplying us with
oil samples from their 50 dry ton/day pyrolysis facility.
                                      xii

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                                 SECTION 1

                                INTRODUCTION
        Large quantities of agricultural, .forestry  and  municipal  wastes  are
 produced each year in the United States.   The  proper utilization of  these
 materials is of extreme importance to the  country  so that  they can be con-
 sidered a resource rather than wastes.  At the same time,  the disposal  and
 environmental problems these wastes create would be solved.   One approach
 for the utilization of these materials  that has received a great deal of
 attention in the past several years is  pyrolysis.  Pyrolysis  of  lignocellu-
 losic or cellulosic material produces char, pyrolytic  oil,  water containing
 water-soluble organic substances,  and non-condensible  gases.   The char  is
 primarily carbon and can be used as a fuel or  converted to activated carbon,
 to producer gas for use as a clean burning gaseous fuel or to synthesis gas
 for organic synthesis.  The major components of  the non-condensible gases
 are hydrogen  carbon monoxide,  carbon dioxide  and  methane  along  with minor
 amounts of the other hydrocarbon gases.  The gas can be utilized on  site  as
, a clean burning low BTU gaseous fuel.   The pyrolytic oils  are clean  burning
 with heating values approximately two-thirds the heating values  of fuel oils.
 There is, however,  a great potential for utilizing pyrolytic  oils as a
 source of chemical materials for industrial applications and/or  as a chemi-
 cal feedstock.   By upgrading the oils for  uses  of  greater  value  than as a
 fuel the total  economic benefit from waste materials would be of greater
 significance to the country.   Also,  the utilization of oils produced from
 current waste materials as a source of  chemical materials  would  reduce  the
 demand on petroleum materials for chemical feedstock.  In  order  to realize
 the potential of pyrolytic oils as a source of  materials for  chemical appli-
 cations,  it is  necessary to develop the processing technology to produce
 refined fractions for industrial use.

        Pyrolytic oils are complex mixtures of  organic  compounds  ranging from
 very volatile to high boiling materials.   Many  of  the  components are oxygen-
 ated,  and the oils  therefore are quite  different in their  chemical and
 physical  properties from petroleum and  its products.   Experimental data indi-
 cate that the *soil may contain as many as 200 or more compounds.   The charac-
 terization of the pyrolytic oils as produced and fractions obtained  from
 them by determination of physical and chemical  properties  provides data
 needed for the  development of the technology to process the oils into more
 useful chemical materials.

        The overall  approach to  developing  technology for processing  the oils
 to  yield  more useful fractions  has been mainly with distillation techniques
 and separation  (extraction)  techniques.  Distillation  experiments include

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atmospheric and vacuum distillation, fractional distillation, steam distil-
lation and vacuum stripping of water and volatile components.  Separation
techniques include extraction with water at different temperatures and an
aqueous salt solution, simultaneous extraction with water and an organic
solvent, extraction with alkaline solutions, and extraction of organic
solvent solutions of pyrolytic oils with water.  The extraction techniques
show promise of having the greatest potential for processing the oil into
fractions containing fairly specific chemical classes of compounds.  These
fractions should find ready utilization in industrial applications.  Distil-
lation offers more promise as a method for processing a specific fraction
of oil into more highly refined and purified products.  There are several
potential approaches utilizing extraction techniques which could produce
three or four oil fractions that would have potential for industrial appli-
cations.  Experimental work was conducted at the bench level on both a bath
basis and a continuous basis.  Based on the results from the continuous
extraction experiments, a pilot plant has been designed for investigating
the continuous processing of pyrolytic oils.  Also, the preliminary economics
of processing the pyrolytic oils on a commercial scale have been evaluated.

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                                 SECTION 2

                                  SUMMARY
       Oils produced by the Georgia Tech pyrolysls process from the Tech-Air
50 dry ton/day pyrolysis facility have been thoroughly characterized.  The
overall chemical and physical properties have been determined by standard
analytical techniques.  The oils are dark brown to black and have a burnt,
pungent odor.  The viscosity of the oils depends upon a number of factors,
such as the pyrolysis mode, the operating conditions and the amount of water
emulsified in the oil.  Oils which contain 10 to^ 15% water are relatively
free flowing.  The oils have heating values which are approximately two-thirds
the heating values of petroleum fuel oils and burn cleanly.  The oils are
acidic and exhibit some corrosive characteristics.

       The oils are complex chemical materials with a wide spectrum of oxy-
genated compounds which exhibit a variety of functional groups and wide
boiling range.  The chemical composition of the oils is of importance in
devising processing methods for producing useful chemical fractions from the
raw oils.  The analytical techniques of choice for determining the chemical
composition of the oils and fractions produced from them are liquid chro-
matography, thin layer chromatography, gas chromatography and gas chromato-
graphy/mass spectroscopy.  The major classes of organic chemical species
found in the pyrolytic oils investigated in this program from forestry
materials were phenolics, polyhydroxy neutral compounds, neutral compounds of
high aromaticity, and volatile acidic compounds.

       The development of processing methods to produce fractions of the oils
for potential chemical applications was focused on producing fractions which
would contain predominantly a specific class of compounds.  Distillation is
a highly developed chemical operation and offers a possible method for
processing and refining pyrolytic oils.  Therefore, various distillation
techniques were tested.  Due to the heat sensitivity of the oils, the pyro-
lytic oil in the flask, after distilling about 50% to 65% of the charge,
would begin to decompose.  In addition, fractional distillation at low
pressure did not produce any narrow cut fractions  over  the whole boiling
range with a predominantly chemical species.  Although distillation should
not be considered as the initial processing step for pyrolytic oils, it
should be considered as means of refining fractions of the oil produced by
other processes.   Some preliminary catalytic hydrogenations were carried out
at about four and 20 atmospheres pressure.  Based on the results of these
experiments,  hydrogenation should not be considered as the first processing
step,  but should be considered as a potential refining method for some of
oil fractions produced by other processing methods.

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        Separation processes based on extraction techniques employing the
 solubility of the oil in water and various organic solvents .offer a poten-
 tial approach for separation of the oil into three or four major fractions,
 each of which would contain a predominant chemical species.  Five major
 approaches involving extraction techniques were tested at the bench level on
 a batch basis.  These approaches were extraction:  (1) with water at differ-
 ent temperatures; (2) with sodium sulfate solution (salting-out effect);
 (3) with water and a water-insoluble organic solvent "(three phase system);
 (4) of sodium hydroxide solutions at different pH ranges with methylene
 chloride; and (5) of organic solvent solutions of oil with water.  The
 results of these extraction techniques and experiments showed promise and
 the approaches selected for additional work at the batch level were aqueous
 extraction, simultaneous extraction with waiter and an organic solvent and
 aqueous extraction of an organic solution of the oil!.  Both vacuum stripped
 and unstripped oil samples were examined by all three processes and the
 effects of both polar and nonpolar solvents were studied.

        Based on the results of these experiments, aqueous extraction (Process
 No. 1) and simultaneous extraction with water' and an organic"solvent (Process
 No. 2) were selected for continuous extraction experiments at the bench
 level.  Continuous extraction experiments were conducted with both vacuum
 stripped and unstripped oil samples.  The data from the continuous experi-
 ments indicated the complexity of processing pyrolytic oils.  The oils have
 a large number of compounds which exhibit a wide boiling point range and a
 high degree of chemical functionality and chemical nature, such as solubility,
 polarity, etc.  The results from the continuous experiments show that both
 aqueous extraction, Process 1, and simultaneous extraction, Process  2 , have
 promise  as  the  initial  steps  in processing  pyrolytic oils.  The  insoluble
 oil phases from Process 1 and the MIBK phases from Process  2  did not contain
 any polyhydroxy neutral compounds, based on the analysis.  The aqueous phases
 from both Processes 1 and  2  contained phenolic, polyhydroxy neutral com-
 pounds, and neutrals of high aromaticity.  MIBK extraction of these aqueous
 phases removed the major portion of the neutrals of high aromaticity.  Pre-
 liminary extraction experiments with alkali solution of the MIBK fractions
 showed that the phenolic fraction could be removed, which would provide two
 fractions, one predominantly phenolics and the other predominantly neutrals
 of high aromaticity.  In order to obtain fractions of the oils which contain
 predominantly a group of compounds that are chemically similar, it would be
 necessary to further process the phases obtained by extraction techniques.
 Additional processing could include extraction steps and distillation.

        In order to produce fractions of oil for chemical applications from
 raw pyrolytic oil from biomass, there are two major areas that need further
 investigation.   Additional experimental work must be conducted at the small
 scale  pilot  plant level to yield  suitable fractions  of  the oils  for inves-
tigations for industrial applications and to produce  data for  the design of
a commercial plant.  In addition,  the studies  at  the  pilot plant  level should
include additional processing,  such as distillation,  of  the fractions obtained
by the extraction techniques.   The application studies for the oil studies are
necessary as each fraction would consist of  a  mixture of compounds.   A versa-
tile pilot plant was designed for  testing at the  rate of four  gallons per
minute, the extraction processes developed in  this  program.  Additional

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processing of the fractions, such as distillation, could also be investigated
with the pilot plant.  The processing of pyrolytic oils with the pilot plant
could be optimized to produce fractions most suitable for industrial uses as
indicated by application studies and to provide the data for design of a com-
mercial plant.

       Preliminary economic assessments of the processing of pyrolytic oils
were made, based on two approaches.  These preliminary assessments are prom-
ising,  lii one approach, the average selling price per pound for the processed
oil products was determined that would be necessary to provide a 15, 30 and 50
percent net return on investment.  For a 50 percent return, the price range of
8.4 to 10.6 cents per pound is in the same range as 9 cents per pound for coal
tar creosote and well below 54 cents per pound for coal tar cresylic acid,
which were quoted market prices in December, 1979.  In the other approach,
two schedules of selling prices were assumed for each product in Processes 1
and 2, based on quoted market values of chemical materials which were consi-
dered to be similar.  The returns on investment were very promising for both
price schedules.  The significance of this economic assessment is that at a
relative low selling price, processing of pyrolytic oils should be economi-
cally viable and that if suitable industrial applications for the processed
oil fractions can be found, processing pyrolytic oils should be very profi-
table.

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                                  SECTION 3

                               RECOMMENDATIONS


       The results of this study have indicated that the processing of pyrolytic
oils from wood into products suitable for commercial applications is technically
feasible and the preliminary economic assessment is very promising.  However,
additional research and development work is needed so that this industrial
potential for pyrolytic oils can be realized.  The two major areas in which
additional work is required are processing studies with pyrolytic oils at the
pilot plant level and studies on utilization of the products in industrial'
applications.

       It is recommended that investigations with pyrolytic oils be conducted
at the pilot plant level with both aqueous extraction (Process 1) and simultan-
eous extraction with water and an organic solvent (Process 2).  With both pro-
cesses, additional processing of the initial phases should be investigated, and
both raw oil and vacuum stripped oil should be tested.  The objectives of this
program would be to develop optimum operating conditions for producing suitable
oil fractions for industrial applications, to obtain engineering data for scale
up for a commercial plant, to produce sufficient quantities of oil fractions to
use in a study for industrial utilization, and to obtain adequate data to -make
an economic analysis of the process and of the potential market for the products.
A significant part of these recommendations is the investigation for potential
chemical applications for the oil fractions, such as utilization in the produc-
tion of resins.  The objective of this phase of the program would be to estab-
lish specific applications for the oil fractions and to determine the potential
markets.  The results of this recommended program should provide the necessary
information and data for the utilization of pyrolytic oils in chemical appli-
cations on an industrial scale.

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                                SECTION 4

                          BACKGROUND INFORMATION


PYROLYSIS AND DESTRUCTIVE DISTILLATION OF WOOD

       Pyrolysis  is an old process and has been used industrially in the past
on'a batch basis  to produce charcoal, pyroligneous liquor (mostly water with
dissolved organic compounds), insoluble tars, and non-condensible gases.
It was utilized during and after World War I in this country and was known
as wood distillation.  With the utilization of petroleum as a chemical feed-
stock, the pyrolysis process became uneconomical and is no longer practiced
in this country.   Various aspects of destructive wood distillation and the
products have been discussed in representative literature references [1, 2,
3, 4 and 5].
 f~
       The destructive distillation of wood was generally carried out as a
batch process in  a retort with external heat and produced the products men-
tioned above.  The significant and important difference between the Engi-
neering Experiment Station pyrolysis process and the old wood distillation
process is that the Engineering Experiment Station pyrolysis process is a
self-sustained continuous process.  This is of significance because the
pyrolytic oil produced in this manner from a given feed material under
specific operating conditions is a reproducible product with definite
physical and chemical properties.  Therefore, it has potential as a feed-
stock for processing into other products on a commercial scale.  Its poten-
tial for uses other than as a fuel warrants extensive investigation.

GEORGIA TECH PYROLYSIS PROCESS

       The Georgia Tech pyrolysis process  is a continuous, self-sustained
pyrolysis system  which was developed over the past several years by staff
members of the Engineering Experiment Station.  Particular attention is
devoted to this process since all the pyrolytic oil used in this investiga-
tion was produced in either one of the pilot plants on the Georgia Tech
campus or at the  field development facility owned by the Tech-Air Corporation.
A wide variety of  agricultural, forestry and municipal wastes have been pro-
cessed under a variety of operational conditions with the Engineering
Experiment Station pilot plant pyrolysis systems.
jg
 Licensed to the Tech-Air Corporation, a wholly owned subsidiary of  the
American Can Company.

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 Background Experience and Pilot  Plants  -  Georgia Tech Pyrolysis Process

        Workers at the Engineering  Experiment  Station, Georgia Tech, have
 found that pyrolysis is readily  adaptable for the conversion of cellulosic
 and lignocellulosic wastes into  useful  fuels  and other products.  Involve-
 ment at Georgia Tech in the area of  conversion of solid wastes by pyrolysis
 began with work in 1968 to develop a means  to dispose of peanut hulls with-
 out producing the pollution problems of incineration.

        The steady-flow, low temperature pyrolysis process developed at the
 EES involves processing of the wastes in  a  porous, vertical bed.  Among the
 advantages of the process are its  simplicity  and its low temperature opera-
 tion.  These features,  together, lead to  a  highly economical design.  In
 addition,  the system is self-sustaining and requires a minimum of processing
 of the wood wastes prior to pyrolysis [6,7].

        The first pilot  plant system, approximately five feet tall, was
 designed to reduce peanut hulls  to a char and a combustible gas.  The system
 built in 1968 was operated on a  batch basis at first and then on a continu-
 ous basis  with a manual input feed.  Hundreds of pounds of peanut hulls were
 converted  to char and off-gases  during  several months of testing with this
 equipment.  Enough data were obtained to  demonstrate the feasibility of
 developing an automated prototype  converter with the vertical, porous bed
 design.

        The large prototype,  constructed in  1971, was built to operate contin-
 uously at  an input feed rate of  4,000 pounds  per hour.  The unit was approxi-
 mately 11  feet in height,  and the  reaction  chamber was mounted on top of a
 water-cooled collection chamber.   The feed-out was accomplished by a hori-
 zontal screw at the base of the  chamber.  The off-gases were treated as <„*.
 potentially explosive in these tests, and consequently, a system was con-
 structed to burn the gases in an unconfined,  diffusion controlled flame.
 Experience with these gases showed that they  could be burned safely and
 easily by  premixing and igniting in  a conventional fashion.  This system was
 operated over a period  of many months,  while  processing thousands of pounds
 of feed.   The reaction  chamber of  this  converter was designed to have a mini-
 mum weight and only enough operating life to  demonstrate the automatic
 operation  of the process.   This  was  done  to reduce the overall cost of this
 experimental prototype.   Consequently,  the  test program started with low
 temperature operation and on succeeding tests the temperature was raised.
 The internal structure  of the reaction  chamber eventually failed after
 approximately six months of  testing  as  a  result of the elevated temperature.

        Based on the data and results from the first pilot plant unit and the
 experimental prototype,  a  third  pilot plant was designed and built.  This
 system  was  used to  process  a wide  variety of  feed materials to determine
 operating  characteristics  and investigate operating parameters.  This system
was completely  rebuilt  in  the fall of 1975.   Presently, the system includes
a waste receiving bin,  a belt conveyor  to the converter, the converter and
char handling system, an off-gas cyclone, a condenser by-pass, demister,
draft fan,  and  vortex after-burner.  The  present system will process 500 to
800 Ibs. waste/hour  depending on the density  of the feed material.  Types of

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waste processed through the converter include peanut hulls, wood chips, pine
bark and sawdust, automobile wastes, municipal wastes, macadamia nut shells,
and cotton gin wastes.  The pyrolytic oil used in the third phase of the
experimental program was produced in this unit in 1978.

       The fourth Engineering Experiment Station pyrolysis pilot plant, which
is larger and more versatile, was designed, assembled and put into operation
by the staff of the Engineering Experiment Station in September, 1974.   This
unit has a design capacity of 1,500 pounds of dry material/hour and has been
used extensively to test municipal wastes, peanut hulls, and wood wastes.

 Commercialization  of  EES  Pyrolysis  Process

        The  pyrolysis  process  developed by workers of  the Engineering Experi-
 ment  Station,  Georgia Tech, was  licensed  to  the Tech-Air Corporation in  1971
 for commercialization.  Tech-Air field tested pyrolysis converters at  a
 peanut  shelling plant and a  lumber  yard.  The most  extensive field testing
 and development,program was  conducted at  a lumber yard  in  Cordele, Georgia,
 over  a  five year period.   The Tech-Air field demonstration facility processed
 approximately  40 dry  tons/day of a  mixture of pine  bark and sawdust and  pro-
 duced char,  oil and noncondensed gases.   The char was used for making  char-
 coal  briquettes, the  oil  was  sold as a fuel, and the  gases were being  used
 on-site as  a fuel  for drying  input  feedstock.  The  char and oil can be
 stored  and  transported, and  the  noncondensed gases  must be burned on-site.
 In the  Tech-Air demonstration facility part  of the  combustion gases are  used
 in a  drier  of  Tech-Air  design to reduce the  moisture  content of the feed
 material to less than 10%.  The  input feed material varies in moisture con-
 tent  from 30%  to 55%  on a wet basis, depending on weather  conditions,  season
 of year,  and amount of  sawdust in the feed.  A number of improvements  were
 made  in the system, and the system  was operated for a period of several
 months  on a 24 hour basis  with a reliability of operation  at design through-
 put of "better  than 90%.   An analysis of the  combustion  stack gases was made
 and comparison of  these data  with the EPA exhaust standards revealed that
 the system  easily  met all federal standards.  The Georgia  Tech pyrolysis
 system  can  be  operated  in a highly  reliable  manner  with a  wide range of
 feed  materials and offers  a high degree of flexibility  for the conversion
 of agricultural and forestry  residues and municipal wastes to char, oil  and
 gas.  The pyrolytic oil for the  first and second phases of the experimental
 program was  produced  in this  facility.

 PYROLYTIC OIL  FROM WASTE  MATERIALS

        Pyrolytic oil  from different waste materials represents a potential
 source  of feedstock for the chemical industry and/or  as a  source of chemicals.
 It has  been  reported  that  about  six percent  of United States consumption for
 oil goes  for feedstock  for the chemical industry  [8].   On  an annual basis
 this would  amount  to  approximately  50,000,000 tons  of petroleum.  The  yield
 of pyrolytic oil from lignocellulosic material processed by the Engineering
Experiment  Station pyrolysis  process varies  from 15 to  25  percent depending
upon feed material and  operation conditions.  Consequently, it would require

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200 to 330 million tons of dry lignocellulosic material to supply a tonnage
of pyrolytic oil in the same tonnage range of petroleum used by the chemical
industry.  It should be pointed out that this does not imply that pyrolytic
oil would be processed in the same manner as petroleum feedstock or that one
ton of pyrolytic oil is equivalent on a feedstock basis to one ton of
petroleum.

       Accurate estimates of wastes from different sources are difficult to
obtain.  Based on our inquiries, particularly with the U. S. Forest Service,
the amount of forestry wastes in the U. S. is estimated at 100 million dry
tons annually (Heywood T. Taylor, U.S.F.S., Private Communication).  This
quantity of material has the potential of supplying 33 to 50 percent of the
tonnage of petroleum now used by the chemical industry.  The significance of
these data is that from the standpoint of quantity the potential exists for
pyrolytic oil from forestry wastes alone to make a significant contribution
as a source of chemical feedstock.  Anderson in 1972 estimated in his study
net oil potential of 1.1 billion barrels of oil per year from the total
organic wastes generated annually in the U. S. [9].  Tillman has recently
reported that there is a potential source of approximately one billion dry
tons of cull or rough trees and salvable dead trees in the U. S. [10].  The
important fact that these data provide is that there are large quantities of
waste material which have the potential for being converted to resources,
and therefore, making a real impact on the material and energy needs of the
U. S.
                                    10

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                                 SECTION 5

                           EXPERIMENTAL—PHASE I


ANALYSIS AND CHARACTERIZATION OF PYROLYTIC OILS

       The oils obtained from the pyrolysis of lignocellulosic materials are
complex mixtures of organic compounds and usually contain some water.  Con-
sequently, the characterization of the physical and chemical properties of
pyrolytic oils requires that one use a variety of analytical and testing
techniques.  Properties that are of interest in characterizing pyrolytic oils
include but are not necessarily limited to density, water content, heating
value, acidity, flash point, pour point, corrosiveness, filterable solids,
ash, solubility in various solvents, distillation range, viscosity and ele-
mental content, particularly carbon, hydrogen, nitrogen, sulfur and oxygen.

       The identification of the chemical species and compounds and the rela-
tive quantities are data that are needed for developing methods for utiliza-
tion of the oils for applications other than as a fuel oil.  Among the most
useful techniques for obtaining this information and data are gas, thin-layer
and liquid chromatography, gas chromatography/mass spectroscopy, and infrared
and ultraviolet spectroscopy.

Sources of Oil

       Samples of pyrolytic oils for Phase I were obtained from two major
sources:  (1) the 50 dry tons/day field demonstration pyrolysis facility of
the Tech-Air Corporation at Cordele, Georgia, and (2) the 500 to 800 Ibs/hr
pyrolysis pilot plant (Blue IV) of the Engineering Experiment Station,
Georgia Tech, which is operated on campus.  Some samples of oil were produced
in a six inch tube furnace fitted with a condensation train and gas collec-
tion system.  A complete description of this apparatus and the pyrolysis pro-
cedure has been reported
       The physical and chemical characteristics of pyrolytic oils depend
upon the feed material, the pyrolysis process and the conditions under which
pyrolysis occurs.  In the old wood distillation industry, the retort batch
process produced organic materials which varied from the low boiling com-
pounds such as methyl alcohol to the insoluble tars.  Continuous pyrolysis
processes of today, such as the Georgia Tech process [6, 7], can  be oper-
ated at steady state conditions with a given feed material to produce oils
of fairly constant compositions and properties.  These oils have greater
potential than those from the old wood distillation industry as a source of
chemical materials for industrial applications and are much more suitable
feedstock for continuous processing to produce fractions of oil suitable for

                                     11

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 specific  applications.   For  these reasons, the oils used in this investiga-
 tion were mainly  those  produced  in  the continuous pyrolysis facility of the
 Tech-Air  Corporation  or in the pyrolysis pilot plant of the EES, Georgia
 Tech.

        Samples  of oil were obtained from the Tech-Air facility in July, 1976,
 and May,  1977.  In each case, oil samples were obtained from the air-cooled
 condenser and the draft fan.  The feed material for this facility was pine
 bark-sawdust, and a representative  sample had the properties listed in TABLE
 1.
 	TABLE 1.   PROPERTIES OP PINE BARK-SAWDUST FEED MATERIAL	

    Property                     Results                      Method


 Pinebark                          70                    Microseparation by
 Pine sawdust                      30                      visual means

 Bulk density                   213 kg/m   „
                                (13.3 Ibs/ft )

 Moisture                         10.3%                   ASTM D-1762-64' ••. '

 Ash (weight %)                     1.3%                   ASTM D-1762-64

 Acid Insoluble                    <0.1%                         -       £.. , (.
   Ash (weight %)

 Heating  Value                   21.2 MJ/kg                ASTM D-240-74
   (dry basis)                  (9109 Btu/lb)
       Oil samples, produced in the Georgia Tech pilot plant on July 22 and
 27,  1977, from pine chips and on September 16, 1977, from hardwood chips,
 were also used in these studies.

       During the course of this investigation, samples of oil have been sup-
 plied to Dr. M. B. Polk of Atlanta University for use on E.P.A. Grant No.
 R 804 440 010.  The oil samples provided were those obtained from Tech-Air in
 July, 1976, and May, 1977, and those produced in the Georgia Tech pilot
 plant in July, 1977, from pine chips and in September, 1977, from hardwood
 chips.  In addition, oil samples produced in the six inch tube furnace
 pyrolysis facility (batch process) from a pine bark-sawdust mixture and
 hardwood chips were supplied.

Analytical and Test Data—
       The condenser and draft fan oils obtained from the Tech Air facility in
 July, 1976, were characterized extensively, and the results are illustrative
 of the physical and chemical properties of pyrolytic oils and of the many
analytical techniques and methods that can be used   [12] .  The data for  the
 condenser and draft fan oils from the Tech-Air ton/day facility are given  in
TABLE 2.

                                     12

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TABLE 2.  PROPERTIES OF WOOD OILS FROM TECH-AIR 50 DRY TON/DAY FACILITY
Property
Density
Water content
(weight %)
Heating Value
(wet basis)
PH
Acid Number
Flash Point
Filterable Solids
(weight %)
Copper Strip
Corrosion
Sulfur (weight %)
Pour Point
Ash (weight %)
Distillation
First Drop
10% Point
48% Endpoint
53% Endpoint
Solubility
(weight %)
Acetone
Methylene
Chloride
Toluene
Hexane
Elemental Analysis
(weight %)
Carbon
Hydrogen
Nitrogen
Condenser Oil
1,141 kg/m3
(9.525 Ibs/gal)
14.0%
21.2 MJ/kg
(9,100 Btu/lb)
2.9
75 mg KOH/g
111°F
(233°F)
0.3%
1
0.01%
26.7°C
(80°F)
0.08%
98°C
103°C
NA
282°C
99.6%
93.5%
Slightly
Slightly
51.2
7.6
0.8
Draft Fan Oil
1,107 kg/m3
(9.242 Ibs/gal)
10.4%
24.6 MJ/kg
(10,590 Btu/lb)
3.3
31 mg KOH/g
121°C
(240°F)
0.4%
1
0.01%
26.7°C
(80°F)
0.03%
101°C
105°C
265°C
NA
99.6%
97.8%
Slightly
Slightly
65.6
7.8
0-9
Method
-
ASTM D 95-70
ASTM D 240-64
5% Oil dispersed
in water
ASTM D-664-58
ASTM D-93-73
Acetone Insoluble
Classification-
ASTM D-130-7
ASTM D-129-64
ASTM D-97-66
-
ASTM D-86
Group 3
-
-
                                  13

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        Samples of the condenser and  draft  fan  oils were stored at ambient
 temperature and 0°C for approximately  eight months and then certain proper-
 ties were determined.  These data, presented in TABLE 3, show that the oils
 can be stored for periods  of five  to six months without any deleterious
 effects if the oils are to be used as  fuels only.  If the oils are to be
 used as a source of chemical materials, then it would be necessary to con-
 sider the effect of storage on the processing  characteristics of the oils.
        TABLE 3.   VARIATION OF OIL  PROPERTIES OVER EIGHT MONTHS PERIOD
 Property
                                               Stored Eight Months
Initial Value
   0°C
Ambient Temperature
                                Condenser  Oil
 Water Content
   (weight %)
 Heating Value
   (wet basis)
 Acid Number

 Viscosity*

 pH
 Water Content
   (weight %)
 Heating Value
   (wet basis)
    14.0%
 21.2 MJ/kg
(9,100 Btu/lb)

 75 mg KOH/g

 0.275 Pa
    2.6
  20.5%


 22.8 MJ/kg
(9,800 Btu/lb)

 87 mg KOH/g

 0.350 Pa

   3.4
                               Draft  Fan  Oil
    10.4%
 24.6 MJ/kg
(10,590 Btu/lb)
  15.5%


 24.8 MJ/kg
(10,660 Btu/lb)
      24.1%


   21.4 MJ/kg
  (9,190 Btu/lb)

   89 mg KOH/g

   0.175 Pa

       2.9
      12.7%


   24.9 MJ/kg
  (10,690 Btu/lb)
Acid Number
Viscosity*
PH
31 mg KOH/g
0.233 Pa
3.3
71 mg KOH/g
0.079 Pa
3.1
60 mg KOH/g
0.475 Pa
3.0
* Determined with Brookfield Viscosimeter, Model LV with  Thermosel  system at
  25°C at 60 r/min.
       Some typical properties of  the  condenser  and  draft  fan oils  and fuel
oils are compared in TABLE 4.

       Viscosity—The viscosity of liquids  and its change  with temperature
is a significant property in the material handling and processing of liquids.
A Brookfield viscosimeter, Model LV, with Thermosel  system was used to deter-
mine viscosity values.  The viscosity  versus  temperature was  determined for
both the condenser and draft fan oils  initially  and  on samples which had
                                      14

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            TABLE 4.  TYPICAL PROPERTIES OF WOOD OILS AND FUEL OILS
                                 Wood Oils*
Fuel Oils
Property
Water Content, %
Heating Value, MJ/kg
(Btu/lb)
(Btu/gal)
3
Density, kg/m
(lb/gal)
Pour Point, °C
Flash Point, °C
Viscosity, Pa's*
Elemental Analysis
Carbon %
Hydrogen %
Nitrogen %
Sulfur %
Condenser
14
21.2
(9,100)
(86,700)
1,141
9.525
26.7
111
0.225
51.2
7.6
0.8
<0.01
Draft Fan
10.4
24.6
(10,590)
(97,850)
1,107
9.242
26.7
121
0.233
65.6
7.8
0.9
<0.01
#2
Trace
45.7
(19,630)
(139,400)
851
7.10
-18 max
38 min
0.020
86.1
13.2
0.6-0.8
#6
2
43.2
(18,590)
(148,900)
960
8.01
18-29
65
2.262
87.0
11.7
0.9-2.3
 * Values obtained on oils with moisture content as  reported.

 '  Values for fuel oils are considered typical.   Sulfur will vary  depending
   on origin of oil.   Ref., North American Combustion Handbook,  1st  ed.,
   North American Mfg.  Co., Cleveland, Ohio,  1952.

 |  Determined with Brookfield Viscosimeter,' Model LV with Thermosel  system at
   25°Ciat 60 r/min.
 been stored at 0°C and ambient temperature for approximately  eight  months.
 These viscosity curves are given in Figures 1 and 2.   The  viscosity versus
 temperature curves of samples  of both oils which had  been  vacuum stripped for
 removal of  water and volatiles are given in Figures 3 and  4.   In order  to
 determine the effect of prolonged heat upon the viscosity  of  condenser  oil,
 samples of  sealed oil were heated at 110°C for different time periods,  and
 the  viscosity was then determined for each sample.  These  data are  presented
 in Figure 5.   For comparison,  the viscosities of the  condenser oil  and  #2
 and  #6 fuel oils are presented in Figure 6.

        Liquid chromatography—The wood oils are heat  sensitive,  reactive and
 contain a relatively large number of organic compounds.  An analytical  tech-
 nique was needed which could be used in analyzing the fractions  of  oil
 obtained by the different processing methods that would not change  the  chem-
-ical character of the fractions.   Liquid chromatography  (LC)  appears  to be
 the  method  of choice because LC is carried out at ambient  temperature,  is
                                     15

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Cd
w
M
O
PM
1-1
H


O
                         A - Initial viscosity curve

                         B - Sample stored at 0° C for eight months
                         C - Sample stored at ambient temperature
                             for eight months
                                     _L
                                          _L
         20   30   **Q  50    60   70   80   90  100


                           TEMPERATURE,  °C

         Figure 1.  Viscosity of condenser oil.
    600


    500


w
en   400
H
O


1   30°
CJ
    200


    100
                           - Initial viscosity  curve

                           - Sample stored  at 0°  C for eight months

                           - Sample stored  at ambient temperature
                             for eight months
                            _L
                                      _L
        20    30    'tO   50   60    70   80   90   100


                           TEMPERATURE,  °C

        Figure 2.  Viscosity of  draft  fan oil.
                              16

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Pd
CO
M
O
                           A -  Initial viscosity curve

                           B -  Vacuum stripped viscosity curve
                                        l
          20   30   kO   50  60   70   80    90   100

                            TEMPERATURE, °C


             Figure 3.  Condenser oil.
                             17

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rn
UJ
u
1900



1800



1700



1600



1500



1400



1300



1200



1100



1000



 900



 800



 700



 600



 500



 400



 300




 200




 100
                           A - Initial viscosity curve

                           B - Vacuum stripped viscosity curve
         20    30   40   50    60    70    80   90   100


                             TEMPERATURE,  °C


               Figure 4.  Draft  fan oil.
                              18

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M
O
W
CJ
1800


1700


1600


1500


11+00


1300


1200


1100


1000


 900


 800


 700


 600


 500


 400


 300


 200


 100
         20  30   40   50  60   70   80   90  100

                             TEMPERATURE, °C

    Figure 5.   Effect of heating condenser oil at 110°C
               for different time periods on viscosity.
                              19

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 1900

 1800

 1700

 1600

 1500

 11*00

 1300

 1200

 1100

 1000

  900

  800

  700

  600

  500

,  400

  300

  200

  100

    0
                         - Condenser oil
                         - No.  2 Fuel oil
                         - No.  6 Fuel oil
      20
30   kO   50   60   70   80    90   100
 Figure 6.   Viscosity curves for condenser oil  (initial)
            and No. 2 and No. 6 fuel oils.
                            20

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capable  of high  resolution of  complex mixtures,  and  component detection  is
nondestructive.   In addition,  the wood oils  are  soluble  in  organic-aqueous
solvent  systems  which  are  very useful in  LC.   The main initial objective of
utilizing LC  in  the work with  the wood oils  is to provide a method to obtain
"fingerprints" of the  raw  oil  and fractions  produced from it for comparison
and  correlation.

Testing  of LC Variables—
       The variables that  were studied to find satisfactory LC conditions
were LC  columns,  uv wave length,  solvent  gradient and solvent flow rate.  The
condenser oil (July, 1976) was used for testing  all  of these variables.

       LC columns—In  order to select the most suitable  LC  column, several
columns  were  tested with the raw  condenser wood  oil  (July,  1976) using one
ml/min flow rate and uv  detector  at 254 nm.   The chromatographic columns and
conditions tested and  the  results are given  below in the order in which  the
testing  was carried out.

       A.  Vydac adsorption silica gel 30y column.   Solvent, 0-100%
           2-propanol  in isooctane,  20 min gradient  20 concave.*
           Results:  No  resolution obtained;  only one large peak.
       B.  Partisil adsorption silica gel 5p  column.  Solvent, 5-30%
           2-propanol  in isooctane,  20 min gradient,  linear.  Results:
           Resolution  of only  eight peaks.
       C.  Partisil PAC  5\i column.   Solvent,  0-100%  2-propanol in iso-
           octane,  30  min  gradient 35 concave.   Results:  Resolution
           of 12 to 20 peaks.   See Figure 7.
       D.  Partisil ODS  5y column.   Solvent,  10-100%  acetonitrile in
           water,  30 min gradient 35 concave.  Results:  Resolution
           of 30-40 peaks.  See Figure 8.
       E.  Partisil ODS  5y column.   Solvent,  10-100%  acetonitrile in
           water,  10 to  40% with  20 minute hold, then 40% to 100% 35
           concave gradient.   Results:  Resolution of 46-50 peaks.
           Total run time  60 minutes.   See Figure 9.
       F.  Partisil ODS  5y column.   Solvent,  10-100%  acetonitrile in
           water,  30 min linear gradient.  Results:   Better overall
           presentation  of chromatogram and  better resolution of later
           peaks  without excessive runtime.

From the above results,  the resolution obtained  with the conditions given in
D above  are very suitable  for  our survey  chromatograms  and the conditions
in E  and F for obtaining of greater resolution.

       Wavelength—The wavelengths 200, 220,  254, 280, 300, 320, 360 nm
were  selected and  LC runs  were made using constant conditions (E above)
other  than wavelength.   The results were:  (a) It was noted that many compo-
nent  responses appeared  or disappeared with  the  change in wavelength;
(b) no one wavelength  was  entirely satisfactory  because  at  the shorter wave-
lengths  of 200-220  nm  peak resolution;  (c) the longer wavelength of 300-360
nm produced sharply  resolved peaks,  but only  a small  total  number of peaks

*Term used as a dial setting for  logarithmic  slope control  on Micrometritics
 LC models only.

                                     21

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  Figure 7.   Liquid  chromatogram of wood oil.  Partisil PAC column with 0-100%
             solvent gradient of 2-propanol in iso-octane.
Figure 8^  Liquid chromatogram of wood oil.  Partisil ODS column with 10-100%
           solvent gradient of acetonitrile in water.
                                       22

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     NJ

     U)
  cu TJ
  in ft>
0
N3«

CTJ C
rT1 —:
/=k -""

--• r?  &>

li-g
       :q^
                 Figure 9.   Liquid chromatogram of wood oil.  Partisil ODS column with 10-100% solvent

                             gradient of acetonitrile in water with 20 minute hold at  40% acetonitrile.
         cr

         53

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 actually appeared; (d)  and the most satisfactory  results  for our purposes
 were obtained at 280 nm with 254 nm being the  alternative choice.  See
 Figures 10 through 14 for representative  liquid chromatograms  of this study
 with condenser wood oil using conditions  in E  above.

        Solvent gradient—The water-acetonitrile solvent system was found to
 be satisfactory for these wood oils.   Water-methanol was  tested but was
 unsatisfactory.

        A.  10-100% acetonitrile solvent gradient  with  35  concave
            instrument setting, 30 min long run with no solvent holds
            produced a short, fairly well  resolved chromatogram with
            crowding of peaks during the last 25%  of the run.   See
            Figure 8.
        B.  A 10-40% acetonitrile solvent  gradient with 35 concave
            instrument setting, and solvent hold for 20 min, then to
            100% for 10 min produced a very well resolved  chromatogram
            in 60 min.  This run produces  typically 50  discernible peaks
            from the raw condenser oil test sample.  See Figure 9.
        C.  A gradient with 5 min solvent  holds at 20%, 30%, 40%, then
            10 min at 100% did not produce a better resolved chromatogram
            than condition B.  Condition B was  selected as a standard
            gradient with condition A being used for survey scans.

        Flow rate—Liquid chromatograms were made  using flow rates of 1 ml/min,
 2 ml/min and 0.5 ml/min.   A flow rate of  1 ml/min was  selected because it
 produced the best resolution consistent with a practical  time  limitation of
 1 hour per LC run.

 Liquid Chromatograms of Wood Oils—
        Two sets of liquid chromatographic conditions were selected for obtain-
 ing liquid chromatograms of the oil samples.   Survey liquid chromatograms
 are obtained with the conditions given in D and greater resolution liquid
 chromatograms are obtained with the conditions given in E in the above dis-
 cussion on liquid chromatography.   Survey liquid  chromatograms are presented
 in Figures 15 and 16 for the condenser and draft  fan wood oils obtained
 July,  1976,  from the Tech-Air Corporation.   An examination of  these chroma-
 tograms shows that all  of the samples have a large number of components and
 that each chromatogram  has distinctive features.

 Molecular Weight Determinations of Oils by LC—
        The results from the processing of wood oils from  pyrolysis of wood,
 particularly when subjected to heat,  indicate  that reactions occur which
 produce higher molecular  weight components.  It is also desirable to have
 information  on the molecular weight distribution  of the raw wood oils.   In
 an  attempt to obtain some information which would be indicative of the
 molecular weight range  of the oils and fractions  of oil,  the newly available
 size exclusion liquid chromatographic columns  of  silica gel with narrow
 pore size  distribution  were utilized.  The column selected was a 25  cm  col-
 umn of  DuPont SE-60  controlled size deactivated silica which has a molecular
weight  range  of  linear  operation of approximately 100  to  800 Mw.  Polystyrene
 standards  of  800,  2200  and  9000 were  obtained  from Pressure Chemical Company,


                                      24

-------
Ln
                                 Figure 10.   Liquid chromatogram of wood oil at 210 nm.
                                Figure  11.  Liquid chromatogram of wood  oil  at  254  nm.

-------
Figure  12.  Liquid chromatogram of wood oil at 280 nm.
Figure 13.  Liquid chromatogram of wood oil at 300 nm.

-------
l-o
                             Figure 14.  Liquid chromatogram of wood oil at 360 run.

-------
                              20
                          Minutes
                       25
                          30
                     35
Figure 15.  Survey liquid chromatogram of raw condenser oil.
        10
15
    20
Minutes
25
30
35
 Figure 16.  Survey  liquid  chromatogram of draft fan oil.
                              28

-------
Pittsburgh, Pennsylvania.  Benzene, molecular weight 78, was also used.  In
these LC runs, the solvent was tetrahydrofuran and the UV detector was set
at 280 nm.  The average molecular weights of raw wood oils and some oil frac-
tions were obtained.  In addition, the still bottoms from a commercial
distillation of a wood oil was tested.  The preliminary results from this
initial work are given in TABLE 5.
       TABLE 5.  PRELIMINARY AVERAGE MOLECULAR WEIGHT DETERMINATIONS	

Sample Description                        Mw                 Comment

Raw Condenser Oil                        160
Raw Draft Fan Oil                        150

Still Bottoms from Atmospheric           150
   Distilled Oil

Vacuum Spinning Distillation
   Fractions 1-4  (combined)              100

   Fraction 8                          80 and 120       Two Main Components
   Fraction 12s                          150

Still Bottoms Steam Distilled Oil        150
         ^3to»
Still Bottoms "from Commercially
   Distilled Oil*                      112 - 9000      Broad Mw Distribution
           .^ -rip


* Obtained from Tech-Air Corporation

Gas Chromatography

       Gas chromatography  (GC) offers an excellent technique for analyzing
complex mixtures of organic compounds.  The apparent disadvantage in
analyzing wood oils (produced by pyrolysis) by GC is the heat sensitivity of
some components in wood oils and the possible effect of the heat on these
components during GC analysis.  Recognizing this possible constraint, GC
should be useful for analysis for fractions containing more volatile compo-
nents, for water soluble components and for fractions obtained in experiments
designed to separate pyrolytic oils into fractions containing a major chemi-
cal class of compounds.

       In addition, it was considered appropriate to do some preliminary
analysis of the raw wood oils because of the powerful analytical capability
of GC.  The instruments used were a Perkin Elmer Model 900 with a flame
ionization detector with dual column and temperature programmed capability,
and a Perkin Elmer Model 990 with thermal conductivity detector, dual column,
and isothermal oven.
                                      29

-------
        The objectives of this gas chromatographic work are  to  be  able to
 resolve the low molecular weight components in the  aqueous  phases of  various
 distilled fractions, to resolve the more volatile components of the oils and
 fractions of oil, and to analyze the higher molecular  weight components  of
 the relatively water-free wood oils and fractions obtained  from the oils.
 To date, two columns were selected from several GC  trial runs  with the raw
 condenser oil and a distilled aqueous fraction.  The list of columns  and con-
 ditions that have been tried are given below.

        Initial Conditions:  P.E. 900 FID detector.  Carrier gas,  N? at 20
                   ml/min temperature program as shown.
                   P.E. 990 T.C..  detector.   Helium carrier gas  at  20 ml/min;
                   isothermal oven.
                   Samples tested were raw condenser oil and aqueous distilla-
                   tion fraction.
        Column 1.  Porapak Q, 9'  x 1/8",  with 1'  x 1/8" Porapak Q  precolumn
                   to retain and prevent the heavy organics  from entering the
                   main column.  Oven 120°C,  injector 200°C, thermal conduc-
                   tivity 225 ma, Helium carrier at  20  ml/min.  Results:   The
                   determination of water,  lower alcohols, formaldehyde and
                   acetone was accomplished.
        Column 2.  3% Poly-m-phenoxylene on 80/100 Chrom P DMCS, 6'  x  1/8".
                   Injector 250°C, manifold 250°C, oven 130° - 200°C @  8°/min.
                   FID, N- at 20 ml/min.   Results:   moderate resolution of
                   sample, 18 peaks, from raw oil.
        Column 3.  10% Dow Corning High Vacuum  Grease on 80/100 AWFB-DMCS
                   10' x 1/8".  Injector 340°C,  oven 150° - 350°C @ 10°/min
                   FID, N2 20 ml/min.   Results:   48  peaks minimum  resolution
                   from raw oil.
        Column 4.  1% Polyphenylether (6 rings)  on 80/100 AWFB-DMCS 3' x  1/8".
                   Injector 250°C, manifold 250°C, oven 130°C @ 10°/min FID,
                   N£ 20 ml/min.   Results:   moderate resolution of sample,
                   23 peaks from raw oil.
        Column 5.  10% SP-2100 on 80/100 Suppelcoport 6'  x 1/8".   Injector
                   250°C,  manifold 250°C,  oven  60° - 250°C @ 5%nin.  FID,
                   N2 20 ml/min.   Results:   Better resolution of components;
                   58 - 52 peaks from raw oil with better baseline  separations.
        Column 6.   10% Carbowax 20 M on 80/100  Supelcoport 6' x 1/8".
                   Injector 250°C, manifold 250°C, oven 60°- 250°C @  5%nin,
                   FID,  N£ 20 ml/min.   Results:   Good" resolution of low boil-
                   ing compounds.

DISTILLATION  OF  PYROLYTIC OILS

       Distillation  offers a possible method for processing and refining
pyrolytic oils obtained from lignocellulosic materials to yield more  desir-
able and useful  products  of greater value, and thereby, increasing the
economic value of  these oils.   The  oils  contain a wide spectrum of organic
compounds including  a large number  of aromatic compounds.  Because of the
wide variety  of  organic compounds in the oils,  they offer the  potential  as
a source of chemical  materials which should find many  industrial  applica-
tions .
                                     30

-------
       A number of distillation experiments were conducted with oils obtained
from the Tech-Air Corporation.  These include distillation at atmospheric
pressure and at 0.2-0.4 mm mercury, fractional distillation at reduced
pressure, steam distillation and vacuum stripping.  The data from these
experiments have been  reported  [12].  Representative liquid chromatograms
are presented  in Figures 17, 18, 19, 20,  21, 22, and 23.

HYDROGENATION

       Oil samples from different sources were hydrogenated catalytically to
determine how much hydrogenation would occur and the effect of hydrogenation
on the stability of  the oil and to prepare samples for use in various separa-
tion schemes.  Hydrogenation was carried out in a Parr Model 3911 hydrogena-
tion apparatus which provides for agitation by shaking and can be used at
pressures up to approximately 4 atmospheres.  One hydrogenation was conducted
at atmospheric pressure utilizing a recycling of the hydrogen in a stirred
flask containing the sample and catalyst.  Anhydrous ethanol was used as a
solvent, and five percent palladium on activated carbon or five percent plat-
inum on activated carbon was used as a catalyst.  The results from the hydro-
genations with the low pressure Parr apparatus and at atmospheric pressure
are given in TABLE 6.

       The data from hydrogenations 5,6 and 7 show that the Pd catalyst per-
forms better as the  hydrogen absorbed is approximately fifty percent greater
in one-third of the  time used for the hydrogenations with Pt.  The data from
hydrogenation  4 show that hydrogenation at atmospheric pressure is too slow.
Examination of the data from hydrogenations 5, 8 and 9 shows that the Blue
IV fan oil from both hardwood and pine chips absorbed approximately the same
amount of hydrogen under similar conditions, whereas the Blue IV composite
hardwood oil adsorbed  2.2 times as much hydrogen as the Blue IV composite
pine oil.  It  is of  interest that the vacuum stripped hardwood oil, hydro-
genation 11, absorbed  1.56 as much hydrogen as the vacuum stripped pine oil,
hydrogenation  10.

       Hydrogenations  are frequently carried out at a much higher pressure
than those discussed above.  In order to test a higher initial hydrogen
pressure, a Parr Model 1108 calorimeter bomb was connected to a high pressure
hydrogen reservoir (lecture bottle size) utilizing a Parr oxygen bomb filter
hose assembly and stainless steel tubing.  Agitation was provided by means
of a magnetic stirrer.  Three hydrogenations were carried out with this
apparatus with vacuum  stripped Blue IV fan pine oil.  In each hydrogenation,
two grams of five percent palladium on activated carbon and 100 ml of abso-
lute ethanol were used.  The hydrogenated oil was recovered by removal of
the catalyst by filtration and then vacuum stripping of the ethanol at 2 mm
pressure.  The results of these three hydrogenations are given in TABLE 7.
An examination of the  data shows that the hydrogen absorption is the same
for each experiment  and that the samples absorbed approximately seventeen
percent more hydrogen  than the same sample at approximately 4 atmospheres
(hydrogenation 10 TABLE 6).
                                     31

-------
                                  20
                              Minutes
                                      35
     Figure 17.  Survey liquid chromatogram of combined fractions
                 from vacuum distillation.
               10
15
                              Minutes
25
                                                      30
                                       35
Figure 18.  Survey liquid chromatogram of spinning band  fraction one.
                                  32

-------
0        5         10        15         20         25        30        35
                                 Minutes

  Figure 19.  Survey liquid chromatogram of  spinning band fraction five.
0        5        10        15         20         25        30       35
                                  Minutes       "

  Figure 20.  Survey liquid chromatogram  of  spinning  band fraction nine.
                                     33

-------
                      15        20
                            Minutes
                  25
       30
       35
   Figure 21.   Survey liquid chromatogram of condenser oil vacuum
               stripped without heat.
               10
15        20
      Minutes
25
30
                                                               35
Figure 22.  Survey liquid chromatogram of 100°-105°C  organic layer
            from steam distillation.
                                34

-------
Figure 23.  Survey liquid chromatogram of 100 -105 C aqueous phase
            from steam distillation.
                                35

-------
                TABLE 6.   HYDROGENATIONS AT MODERATE PRESSURE*
No. Sample Source
1 Coredle Condenser
Oil
2 Blue IV Hardwood
Composite Oil
3 Blue IV Pine
Composite Oil
4 Blue IV Fan
Hardwood Oil?
5 Blue IV; Fan
Hardwood Oil
6 Blue IV Fan
Hardwood Oil
7 Blue IVi-Fan
Hardwood Oil
8 Blue IV Fan
Pine Oil
9 Blue IV, Fan "-
Pine Oil
10 Blue IV Fan
Pine Oil, Vacuum
Stripped
11 Blue IV Fan
Hardwood Oil,
Vacuum Stripped
Weight
8

32.2

20.8

24.1

65.1

54.0

52.1

68.8

45.9

56.9


34.4


59.0
Water
%

19.5

' 12.8

17.8

12.4

12.4
,«-s
12.4

12.4

17.9

17.9


0


0
Weight
"dry"
oil?

26.0

18.1

19.8

57.0

47.3

45.6

60.3

37.7

46.7


34.4


59.0
Initial
pressure,
psig

55.2

55.5

56.0
Ambient
pressure

55.1
. f
55.3

56.2

57.2

57.1


58.1


59.0
Time
hrs

18

20

26

60

22

72

72

24

24


26


60
H2 Absorbed
mg/g on
"dry" basis

1.4

4.9

2.2

1.1

2.7

1.9

1.4

2.4

2.4


1.8


2.8
* 5% Pd on activated carbon was used in all experiments except 6 and 7, in
  which 5% Pt on activated carbon was used.  Two grams of catalyst were used
  in each experiment.  Approximately 200 ml of absolute ethanol was used for
  each hydrogenation.

t Calculated dry weight of oil based on percent water.

^ This experiment was conducted in the recycle apparatus at ambient pressure.
                                    36

-------
             TABLE 7.  HYDROGENATIONS AT INTERMEDIATE PRESSURE
                                      Initial Pressure          H£ Absorbed
No.           Sample Source             Atmospheres                mg/g


12         Blue IV Fan Pine Oil            18.0                    2.1

13         Blue IV Fan Pine Oil            19.5                    2.1

14         Blue IV Fan Pine Oil            20.0                    2.1
                                      37

-------
                             EXPERIMENTAL—PHASE  II

 SEPARATION EXPERIMENTS

        The objective of this phase  on separation work with pyrolytic oils was
 to obtain preliminary data on some  approaches that could possibly be used for
 development of a process that would produce more refined fractions of oil
 that contain predominantly one chemical  class of compounds.  The broad classes
 of chemical substances  in raw pyrolysis  oil are  phenolics, aromatic neutral
 compounds (neutrals of  high aromaticity, NHA) , acidic compounds, and a group
 of substances with "sugar-type" characteristics  which are termed polyhydroxy
 neutral compounds (PNC).  The emphasis in the separation experiments has been,
 therefore, to focus on  obtaining fractions of the oil that contain essentially
 one of the general classes of substances in the  oils.  This is a report of
 the laboratory work of  this phase at the bench level on a batch basis.

        The five major approaches involving extraction techniques that were
 tested are:

        A - Extraction of oil sequentially with water at 25°C, 50°C, and 95°C.

        B - Extraction of oil with sodium sulfate solution (salting-out effect).

        C - Extraction of oil simultaneously with an organic solvent and water
            (three phase system).

        D - Extraction of sodium hydroxide soluble fractions of pyrolysis oil.

        E - Extraction of organic solvent solutions of pyrolysis oil with
           water.

Vacuum Stripping of Raw Oil

        Based  on  a number of extraction and separation experiments on a batch
basis  with raw and vacuum stripped  pyrolysis oils, vaouum stripped oil gave
better results than the raw oils.   The vacuum stripping provides for the
removal of the volatile organics  and most of the water in the oil with poten-
tial subsequent  recovery of these organic compounds.  Our analysis show that
the major  organic component in the  volatile fraction is acetic acid.  For
these  reasons, our preliminary separation techniques are based on using vacuum
stripped oil.  Figure 24  shows schematically the vacuum stripping of the  oil
with yields.
                                     38

-------
                        Crude  Pyrolysis Oil,  100 g

                                   1
                          Vacuum stripped  at
                            2 mm and  ambient
                             temperature
       Vacuum  Stripped  Oil,  82.1  g            Volatile Fraction
                                                Water 10.8 g
                                                Acids  7.1 g

             Figure  24.   Removal  of volatiles from pyrolytic oil.


Extraction  of  Oil  Sequentially with Water at 25°C, 50°C, and 95°C

       A  sample  of vacuum stripped oil was extracted sequentially with water
at 25°C,  50°C  and  95°C  in an effort to separate the more water soluble sub-
stances.  Figure 25  shows schematically this separation process and the
recovery  of the  different fractions are given in  TABLE 8.  The overall
recovery  was good.   The liquid chromatogram, Figure 26, shows that the water
extract is  essentially  free  of the components of  the oil which emerge in the
latter two-thirds  of the liquid chromatogram of the raw oil,  Figure 15.  The
liquid chromatogram,  Figure  27, shows that most of the components that appear
in the initial part  of  the liquid chromatogram of the raw oil has been
extracted sequentially  with  water at 25°C, 50°C,  and 95°C.  The liquid chro-
matograms of the water  extract fractions at 50°C  and 95°C were very similar
to Figure 26 of  the  25°C water extract.

       The  significance of these  results is that  the oil can be separated
into water  soluble and  water insoluble fractions  which offer the opportunity
for recovery of  useful  fractions  of aromatic compounds.  The water insoluble
fractions,  based on  our analysis, are composed of  phenolics and neutral aro-
matics.   The separation of this fraction into a highly concentrated phenolic
fraction  and highly  concentrated  fraction of aromatic neutral compounds could
probably  be accomplished by  either fractional distillation or extraction
with alkaline  solution.   The aqueous phases could be combined and subjected
to a separation  of the  components with an aqueous salt solution as described
below to  yield a fraction with mainly phenolics and another fraction with
mainly polyhydroxy neutral substances.

Extraction  of  Oil  with  Sodium Sulfate Solution

       An extraction experiment with a sodium sulfate solution (90% saturated)
was conducted  to determine if extraction with aqueous salt solutions would
offer a useful separation of the  oil.  The schematic for this extraction is
shown in  Figure  28,  and  the  overall recovery was  good.
                                     39

-------
                    Vacuum Stripped Pyrolysis  Oil,  82.1  g*

                               	L
                                  KM-u-n
              Water at 25°C	
       Insoluble Organic
        Fraction- 73.1%
             Water at 50°C-
       Insoluble Organic
        Fraction- 63.8%
            Water  at  95°C-
Mixer and
Separation
                    Aqueous Fraction
                    Phenolics - 8.2%
              Polyhydroxy neutrals-18.8%
Mixer and
Separation
                    Aqueous Fraction
                    Phenolics - 2.1%
              Polyhydroxy neutrals-7.2%
Mixer and
Separation
      Insoluble Organic
       Fraction - 49.2g
       Phenolics-12.2%
       Aromatic neutrals-47.7%
                    Aqueous Fraction
                    Phenolics - 0.7%
              Polyhydroxy neutrals-3.2%
 82.Ig of vacuum stripped oil was obtained  from  lOOg  of  this  raw oil.
Figure 25.  Extraction of oil sequentially with water  at  25°C,  50°C,  and 95°C.
                                     40

-------
   Figure 26.  Liquid chromatogram of 25 C water extract of pyrolytic oil.
Figure 27.  Liquid chromatogram of pyrolytic oil after successive extraction
            with water at 25°C, 50°C, and 95°C.
                                     41

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          TABLE 8.   YIELDS  OF  FRACTIONS FROM WATER EXTRACTION OF OIL

Phenolics
Water Insoluble
Fraction
10 g

25°
6.7 g
Water Soluble
50°
1-7 g
Fractions
95°
0.6 g

Total
9.0 g
Aromatic
neutrals 39.2 g
Polyhydroxy
neutrals
Totals 49.2 g
—

15.4 g
22.1 g
—

5.9 g
7.6 g
—

2.6 g
3.2 g
—

23.9 g
32.9 g
                    Vacuum  Stripped Pyrolysis Oil, 82.1 g

                                     I
              f
      Insoluble Fraction
      Phenolics- 12.7%
         Aromatic and
 polyhydroxy neutrals-71.5%
Saturated
SO. Solution "
4
Mixer and
Separation



            1
     Aqueous Fraction
     Phenolics- 11.1%
Polyhydroxy neutrals-4.8%
        Figure  28.  Extraction of pyrolytic oil with sodium sulfate solution.
       The  importance of these results is that with the sodium sulfate solu-
 tion approximately 82% of  the polyhydroxy neutrals  are in the insoluble
 fraction with about 18% in the aqueous fraction.  The phenolics are approxi-
 mately 70%  of the organics in this aqueous fraction.  There are two approaches
 that can be used involving the sodium sulfate extraction.  One approach would
 be to use the sodium sulfate extraction as the first step as shown in Figure
 28 to produce an aqueous fraction of mainly phenolics.  The insoluble
 organic fraction would then be treated with water extraction as depicted in
 Figure 25 to remove the polyhydroxy  neutrals.   The other approach would
 be to treat the oil as outlined in Figure 25, and then the three aqueous
 fractions would be combined followed by the addition of sodium sulfate.  This
 approach could possibly provide a good separation between the phenolics and
 the  polyhydroxy  neutrals.   The addition of a water insoluble organic sol-
vent may be necessary in such a step to serve as a solvent for the poly-
 hydroxy neutrals.
                                    42

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 Extraction of Oil Simultaneously with Organic Solvents and Water:  Three
 Phase System

        Organic solvents offer a good potential for effecting separation of
 pyrolysis oils into fractions which contain very similar organic compounds.
 Some extractions with diisopropyl ether and anisole (methylphenyl ether) were
 tried with vacuum stripped oil.  It was found difficult to have good contact
 of the organic solvent with only the oil because of the increase in the
 viscosity of the oil.  Addition of an equal volume of water to the mixture
 produced a nonviscous three-phase-system containing an ether phase, an
 aqueous phase and a heavy oil phase with an overall recovery of approximately
 96%.  The schematic for diisopropyl ether and water separation along with
 yields is shown in Figure 29 and the schematic for anisole and water, Figure
 30.  Based on our analysis, the phenolics in the water fraction are mainly
 dihydroxy phenols; in the diisopropyl ether phase, alkylphenols; and in oil
 phase, ether phenols.  The aqueous phases from both of the diisopropyl
 ether-water separations could be combined and possibly separated into a
 highly concentrated phenolic fraction by salting out the polyhydroxy neutrals
 with addition of sodium sulfate or some other salt.

        In the anisole experiment, the phenolics were evenly divided between
 the anisole fraction and the aqueous fraction with a small amount in an oil
 insoluble fraction.  About 88% of the aromatic neutrals were extracted into
 the anisole fraction, which contained about 62% of the original charge.  A
 good potential step for processing this fraction would be fractional distil-
 lation.  The oil insoluble fraction, which contained about 8.4% of the origi-
 nal charge, was approximately 85% aromatic neutrals and could be further
 processed by fractional distillation.  The aqueous phase could be treated by
 the salting out technique with sodium sulfate as shown in Figure 27 to yield
 a highly concentrated phenolic fraction.

 Extraction of Sodium Hydroxide Soluble Fractions of Pyrolysis Oil

        A sample of vacuum stripped pyrolysis oil (154 g) was treated with 300
 mi of 2% sodium hydroxide solution and approximately 52.6% dissolved.  A
 series of methylene chloride extractions then were made at three different pH
 ranges.  The "insoluble oil phase" upon treatment with additional 2% sodium
 hydroxide solution, dissolved in 400 ml of the alkaline solution.  This solu-
 tion was subjected to a series of methylene chloride extractions at the same
 pH ranges.  The schematic for these extractions were presented in Figure 31.
! The overall recoveries were good, and the yield data are presented in TABLE
 9.   An examination of the data shows that phenolics are obtained with methyl-
 ene chloride at each pH range and approximately 52% of the phenolics remain
 in the aqueous phase at pH range 1 to 3.  The significance of this experiment
 is  that the pyrolysis oil will dissolve in sufficient sodium hydroxide solu-
 tion which offers the opportunity for a series of extractions at different pH
 ranges and also with a variety of organic solvents.
                                     43

-------
                   Vacuum Stripped Pyrolysis Oil, 100 g
           100 ml Water-
           100 ml Diiso-
            propyl  ether
    Mixer and
    Separation
  Oil Fraction
  Phenolic - 6%
  Aromatic
   neutrals-24.9%
Ether Fraction
Phenolic - 5%
Aromatic
 neutrals-16.7%
         I
Aqueous Fraction
Phenolic - 11.2%
Polyhydroxy neutrals-34.3%
              Diisopropyl
                ether
    Mixer and
    Separation
 Oil Fraction
                        Ether Fraction
                        Phenolic- 1.5%
                    Water
    Mixer and
    Separation
        I -
 Oil Fraction
 Phenol!cs-4.4%
 Aromatic
  neutrals-16.2%
                       Aqueous Fraction
                       Phenolic - 1.5%
                       Neutrals* - 5.2%
Chemical nature unknown.

   Figure 29.  Combined diisopropyl and water extraction  of pyrolytic oil.
                                    44

-------
                   Vacuum  Stripped Pyrolysis Oil, 110 g
              100 ml Water —
              100 ml Anisole
              Three  Phases
Mixer and
Separation
                            Anisole Fraction*
                            Phenolic - 12.5 g
                            Aromatic neutrals - 56 g
                            Aqueous Fraction
                            Phenolic - 12.5 g
                            Polyhydroxy neutrals-32.1 g

                            Oil  Insoluble Fraction
                            Phenolic - 1.4 g
                            Aromatic neutrals - 7.8 g
 The removal of all anisole from this fraction was difficult so that total
recovery is greater than 100%.
    Figure 30.  Combined anisole and water extraction of pyrolytic oil.
Extraction of Organic Solvent Solutions of Oil

       The vacuum stripped pyrolysis oil dissolves in methylene chloride and
in n-butanol to give complete solutions.  Solutions of vacuum stripped oil in
methylene chloride were extracted with water and the combined water extracts
were then extracted in one experiment with diisopropyl ether and in a second
experiment with methyl isobutyl ketone (MIBK).  The schematics for these two
experiments are shown in Figures 32 and 33.  The data are summarized in
TABLE 10.  The significance of the data in these experiments is that a
fraction of phenolics is obtained with MIBK which contains less than 10%
other organics.  An examination of the data will also indicate one of the
difficulties encountered in working with pyrolysis oils.  One would expect
the quantity of phenolics in the final methylene chloride fractions to be in
closer agreement.  The lack of agreement can be attributed to differences in
experimental techniques and to the need of improvement in analytical tech-
niques .
                                     45

-------
                   Vacuum Stripped Pyrolysis  Oil,  154  g
            300 ml 2% NaOH-
              Solution
                                    1
Mixer and
Separation
         Aqueous Solution
            pH 8 to 10
         Organics- 81 g (52.6%)
                     Insoluble Oil Phase
                     Organics- 74 g (49.1%)
                       (see next page)
                   CH2C12-
         Aqueous Solution
         Adjust pH 5 to 7
                   CH2C12-
         Aqueous  Solution
         Adjust pH  1  to  3
Mixer and
Separation
Mixer and
Separation
                                Mixer  and
                                Separation
        Aqueous Solution
        Phenolics - 9.9%
    Polyhydroxy neutrals-70.1%
                     CH2C1_ Extract

                     Phenolic- 1.8%*
                  Aromatic neutrals - 7.!
                     CH2C1  Extract

                     Phenolic- 1.1%
                  Aromatic neutrals -2.0%
                     CH-C1  Extract

                     Phenolic -5.3%
                  Aromatic neutrals - 0.7%
Percent yield is based on weight of material  extracted  from 81 g of organics.


Figure 31.  Extraction of pyrolytic oil with  2%  sodium  hydroxide solution.
                                    46

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                Vacuum Stripped  Pyrolysis Oil, 154 g  (cont'd)
                          Insoluble  Oil Phase,  74 g
             400 ml  2%  NaOH.
               Solution
       Aqueous  Solution
       Adjust pH  5  to  7
       Aqueous  Solution
Mixer and
Separation
       Aqueous Solution
       Phenolic - 12.5%
   Polyhydroxy neutrals-9.2%
                                       i
                              Aqueous  Solution
                                  pH  8  to 10
                              Organics - 74 g
                                 Mixer and
                                 Separation
                                  Mixer and
                                  Separation
                                  Mixer and
                                  Separation
                      CH Cl  Extract

                      Phenolic- 2.5%*
                  Aromatic  neutrals - 28.3%
                      CH Cl  Extract

                      Phenolic -  5.1%
                  Aromatic neutrals -8.9%
                      CH Cl  Extract

                      Phenolic -5.3%
                 Aromatic neutrals -2.4%
 Percent yield is based on weight of material extracted from 74 g organics.


Figure 31 (cont'd).  Extraction of pyrolytic oil with 2% sodium hydroxide
                     solution.
                                     47

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   TABLE 9.   YIELDS FROM METHYLENE CHLORIDE EXTRACTIONS OF ALKALINE SOLUTIONS
  	OF PYROLYTIC OIL	

                             First Series   Second Series
     Fraction
Extractions
 Weighting
Extractions
 Weighting
Total
Yield
  %
Yield
 pH 8 to 10

   Phenolics
   Aromatic neutrals

 pH 5 to 7

   Phenolics
   Aromatic neutrals

 pH 1 to 3

   Phenolics
   Aromatic neutrals

 Aqueous Phase

   Phenolics
   Polyhydroxy neutrals
   Tar neutrals
    1.46
    6.4
    0.89
    1.62
    4.29
    0.57
    8.02
   56.8
   1.85
  20.9
   3.77
   6.56
   3-92
   1.78
   9.25
   6.81
  17.5
 3.31
23.3
 4.67
 8.21
 8.21
 2.35
17.3
63.6
17.5
 2.17
17.9
 3.06
 5.38
 5.38
 1.54
11.3
41.7
11.8
Totals
Phenolics
Aromatic neutrals
Polyhydroxy neutrals
Tar neutrals

33.5
37.9
63.9
17.5

21.9
24.8
41.7
11.8
       The vacuum stripped pyrolysis oil is soluble in n-butanol, and an
aqueous extraction experiment with a n-butanol solution of pyrolysis oil was
carried out to determine the distribution of the phenolic and other organics
between the aqueous and n-butanol fractions.  The schematic for this experi-
ment with yields for each fraction is given in Figure 34.  The important
result of this experiment is the reduced amount of polyhydroxy  neutrals
in the aqueous phase as compared with the other extractions with the excep-
tion of the sodium sulfate extraction.  There is the potential that extraction
of a n-butanol solution of pyrolysis oil with sodium sulfate solution could
yield an aqueous solution with a high concentration of phenolics relative  to
other organics.  In this experiment, material recovery is not too good  because
in the removal of the n-butanol at low vacuum, some of the more volatile aro-
matic compounds were lost.
                                     48

-------
               Vacuum Stripped Pyrolysis Oil, 101 g
       Methylene
       Chloride
    Dissolve in
Methylene Chloride
               Water-
     Mixer and
     Separation
         I
Aqueous Fraction
Phenolics -11.5%
Polyhydroxy neutrals-33.3%
                   Methylene Chloride Fraction
                       Phenolics - 13.4%
                    Aromatic neutrals - 41.3%
          Diisopropyl
            ether
     Mixer and
     Separation
  Ether Fraction
  Phenolics- 2.2%
                         Aqueous Fraction
                         Phenolics - 12.3%
                    Polyhydroxy neutrals-28.1%
 Figure 32.  Extraction of methylene chloride solution of pyrolytic
             oil with water followed by diisopropyl ether extraction of
             aqueous frac t ion.
                                  49

-------
                  Vacuum Stripped  Pyrolysis  Oil,  100  g
          Methylene_
          Chloride
   Dissolve in
Methylene Chloride
                  Water•
     Mixer and
     Separation
             f
      Aqueous Fraction
      Phenolic- 16.3%
  Polyhydroxy neutrals-32.4%
                  Methylene Chloride Fraction
                       Phenolics - 8.8%  /
                   Aromatic neutrals - 42.9%
          Methyl  isobutyl
             ketone
     Mixer and
     Separation
     Ketone Fraction
     Phenolics-8.8%
 Aromatic neutrals - 0.8%
                        Aqueous Fraction
                        Phenolics - 7.5%
                   Polyhydroxy neutrals-30.1%
Figure 33.  Extraction of methylene chloride solution of  pyrolytic  oil
            with water followed by methylisobutyl ketone  extraction
            of aqueous fraction.
                                  50

-------
  TABLE 10.  YIELDS IN FINAL FRACTIONS FROM SEPARATION TECHNIQUES
                        IN FIGURES 32 AND 33
Final Fraction
Methylene chloride
Phenolics
Aromatic neutrals
Aqueous
Phenolics
Polyhydroxy neutrals
Organic solvent
Phenolics
Aromatic neutrals
Diisopropyl Ether
Experiment
13.5 g
41.7 g
12.4 g
28.4 g
2.2 g
0
Methylisobutyl
Ketone Experiment
8.8 g
42.9 g
7.5 g
30.1 g
8.8 g
0.8 g
                Vacuum Stripped Pyrolysis Oil, 100 g
            n-Butanol•
                Water
Dissolve in
 n-butanol
 Mixer and
 Separation
    Aqueous Fraction
    Phenolics- 10.7 g
Polyhydroxy neutrals-13.6 g
                  n-Butanol Fraction
                  Phenolics - 11.2 g
                  Aromatic neutrals and
              Polyhydroxy neutrals-49 g
Figure 34.  Extraction of n-butanol solution of pyrolytic oil with
            water.
                                  51

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                          EXPERIMENTAL—PHASE III

 PYROLYTIC  OIL

        The pyrolytic  oil  for this experimental phase was taken from the oil
 produced in a run in  the  Georgia Tech pyrolysis pilot plant (capacity, 225
 kg/hr)  on  October 12,  1978.  The converter feedstock was pine chips dried to
 contain approximately six percent moisture, and the air-to-feed input ratio
 was continually adjusted  within a narrow range to maintain a temperature of
 125° to 130°C in the  off-gases passing from the headspace of the reactor to
 the condensers.   The  condenser temperatures were held near 75°C.  These
 closely controlled low temperatures resulted in less thermal cracking than
 had been observed in  earlier converter runs with higher temperatures.    "

        The selected containers of pyrolytic oil were stirred thoroughly and
 the moisture content  of the oil in each container was determined.  Two four-
 liter reference samples were taken from each container and stored in tightly
 capped  plastic containers for future reference.  The remaining oil was com-
 bined and  thoroughly  mixed.  Eight four-liter samples were stored in tightly
 closed  plastic containers for laboratory work.  The remaining oil was stored
 in tightly closed plastic lined containers as a reserve supply.

 Characterization of Pyrolytic Oil Sample

        The percent moisture in the sample was determined by azeotropic dis-
 tillation  with toluene (Dean and Stark Method).  The percent solid material,
 mainly  fine fiber and char fines, was determined by dissolving a weighed por-
 tion of the oil  in a  large excess of acetone and passing the solution through
 a  tared glass  filter  paper.  The filter paper and residue were thoroughly
 washed  with acetone,  dried, and weighed.  The percent ash was determined by
 charring weighed oil  samples in tared crucibles by means of an infra-red
 lamp, igniting the char in a muffle furnace, and determining the weight of
 the  ash.   Sulfur was  determined by igniting two-gram oil samples at  30  "
 atmospheres  in an oxygen  bomb calorimeter.  No turbidity was observed when
 barium  chloride  was added to filtered washings from the oxygen bomb, and no
 increase was observed  in  the weight of tared Gooch crucibles used to filter
 the  solution of  barium chloride in the washings.  The density of the mixed
 oil  sample was calculated from the weight of 200 ml at 25°C.  The percent of
 carbon,  hydrogen and nitrogen was determined using a Perkin Elmer Model 240
 Elemental Analyzer.  Results of these characterizations are shown in TABLE 11.

 SEPARATION EXPERIMENTS

       The results of  the experimental work in Phase II with different  extrac-
tion techniques with pyrolytic oil were carefully evaluated for  further
investigation  for  the  development of a pilot plant concept for processing

                                     52

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               TABLE 11.  PROPERTIES OF PYROLYTIC OIL SAMPLE
Determined
Percent Moisture
Percent Solids
Percent Ash
Percent Sulfur
Percent Carbon
Percent Hydrogen
Percent Nitrogen
Density (g/m£)
— — '•""• 	 • - . ... — - — -
Sample 1
14.7
0.38
0.055
<0.001
57.27
6.72
0.06
1.234
Sample 2
14.9
0.43
0.054
<0.001
57.34
6.76
0.06
1.234
-- - • • — 	
Average
14.8
0.41
0.055
<0.001
57.30
6.74
0.06
1.234
pyrolytic oils.  The  selected processes were aqueous extraction (Process No.
1) , simultaneous extraction with water and an organic solvent (Process No. 2),
and dissolution of the pyrolytic oil in an organic solvent followed by aque-
ous extraction of the solution  (Process No. 3).  The first efforts were with
batch experiments of  all  three  processes in which both vacuum stripped and
unstripped oil samples were examined and the effects of both polar and non-
polar solvents were studied.  Based on the results of the batch experiments,
Process No. 1 and Process No. 2 using a polar organic solvent were chosen
for:continuous countercurrent extractions of both vacuum stripped and
unstripped pyrolytic  oil.  The  batch experiments will be described first
followed by the description of  the continuous extraction experiments.

Initial Batch Separation Procedures

       The batch separations were performed by stirring approximately 100,
200, or 500 g of oil, weighed to the nearest 0.1 g, with the extracting sol-
vent system for 30 minutes in a tall form 1,000 ml beaker at approximately
900 revolutions per minute using a 4 cm PTFE coated bar with a magnetic
stirrer.  At the end  of the contact period the beaker was chilled to immobil-
ize the insoluble tar phase so  that the extracting solvent phase or phases
could be removed by decantation.  Conventional separately funnels were used
to separate the aqueous and immiscible organic solvent phases.

Process No. 1.  Water Extraction Procedures—
       Six samples of pyrolytic oil were extracted with water, and the water
phases were separated from the  insoluble organic phases by decantation.  Two
additional aqueous extractions  were made, each using the insoluble organic
phase from the preceding extraction.  A schematic flow diagram of this pro-
cedure is shown in Figure 35, x^hich shows the treatment of unstripped pyro-
lytic oil by vacuum stripping and subsequent water extraction as solid lines
at the top of the figure and by water extraction without vacuum stripping as
a broken line at the  top of the figure.  The broken lines at the bottom of
the figure indicate generalized further treatments of the separated phases.

       Six samples of oil were  extracted with water as listed below.  The
aqueous phase and insoluble organic phase from Extraction I  (1) were used to

                                    53

-------
          UNSTRIPPED PYROLYTIC OIL'
                            •Vacuum Strip1
                    L
                                 STRIPPED
                                   OIL
                         VOLATILES
                           PHASE
                                   Water
                                 extraction
       INSOLUBLE PHASE 1
                           AQUEOU
             S  PHASE  1 —i
        Water extraction
       INSOLUBLE PHASE 2
        Water extraction
                           AQUEOUS PHASE 2-
       INSOLUBLE PHASE 3
                           AQUEOUS PHASE 3-
TO ANALYSIS
Extractions,
distillations,
etc.
                            Combine
                                    r
  Extract weighed
	portion with^	
  3  portions  of
  organic solvent
              FRACTIONS
      COMBINED
      ORGANIC
      FRACTION
                                         i
   COMBINED
	 AQUEOUS
    PHASE
                                         ANALYTICAL
                                           SAMPLE
                                       COMBINED
                                       AQUEOUS
                                       FRACTION
  Samples and yields shown in UPPER CASE LETTERS
 'Operations  shown in lower case letters


             Figure 35.   Aqueous batch extraction,   Process No. 1.
develop  analytical  techniques  at Georgia Tech and at Atlanta University.  The
fractions  from Extraction I (2-6)  were used to experiment with techniques to
obtain additional fractions.   The separation techniques are described in a
later section  of this  report.

-------
       0 Extraction I  (1)—A 102.9 g sample of vacuum stripped oil was
         extracted with three 100 ml portions of deionized water.

       o Extraction I  (2)—This experiment was a duplicate of I  (1) to pro-
         vide a water  solution for subsequent extraction with a polar organic
        • solvent.

       o Extraction I  (3)—This experiment was run as I (1) and I (2) to pro-
         vide an aqueous solution for extraction with a nonpolar organic
         solvent.
       0 Extraction I  (4)—This extraction was performed as I (1) except that
         a  203.4 g portion of unstripped  oil was extracted with two 200 ml
         portions of water.  The water  extract was reserved for contact exper-
         iments with activated carbon.

       0 Extraction I  (5)—This experiment was similar to I (4) .
       o Extraction I  (6)—A 400 g unstripped oil sample was extracted with
         400 ml water  followed by two successive extractions with 200 ml
       ^  portions of water.
 The "water solution fraction and water insoluble fraction were used for further
 analysis and testing of additional separation techniques.

       No attempt was  made to  isolate individual compounds from  the large
 number present  in each separated phase  or fraction.  Quantitative analysis
 was  directed only toward separating  and identifying  classes of compounds
 having similar  solubilities or measurable chemical properties, which might
 be related  to  their potential  commercial  use.  Based on analytical methods,
 which will  be  described  in a later section of this report, the vacuum strip-
 ping and extraction yields were  determined as volatile organics, nonvolatile
 organics  (NVO),  phenolics, polyhydroxy  neutral compounds  (PNC) and neutrals
 of high aromaticity  (NBA).  The  polyhydroxy neutral  compounds were estimated
 by subtracting  the phenolics in  the  water phases or  fractions from the
 corresponding  total nonvolatile  organics.  Neutrals  of high aromaticity were
 estimated by  subtracting  the phenolics  from the  total organics in an organic
 solvent phase  or fraction.  The  results of the batch extraction, expressed
 as percent  of  the moisture-free  unstripped oil sample, are shown in TABLE 12.
 Since the moisture  free  oil  contained  seven percent  volatile  compounds the
 total nonvolatile organics  should  approach 93 percent.

       The  percent nonvolatile organics (NVO) was  determined  by  removing the
 solvent from a  weighed sample  of the separated phase on  a rotary vacuum
 evaporator  with caution  to  avoid heating.  It  is believed that  incomplete
 solvent removal from  the  organic phase  led to  the  apparently  high  total NVO
 values in Extractions  I  (2)  and  I  (6).   The aqueous  phase from Extraction
 I (2) was extracted with three successive portions of methylisobutyl ketone
 (MIBK).  The MIBK extracts  were  combined to form the MIBK fraction.  The
 distributions  of the  classes  of  organic compounds  in the MIBK fraction and
 the extracted  water  fraction are shown in parentheses.   The  distributions
'resulting  from a similar extraction of the water phase in Experiment I (3)
 with-chloroform are  represented in a similar manner.  The percent NVO was
 determined  separately for- each of  the four successive water phases in
 Extraction  I  (6)  to  show the quantity of organic material removed by each
 extraction  step.   Since most of  the water soluble material was found in the

                                      55

-------
 TABLE 12.   COMPOSITION OF YIELDS FROM BATCH WATER EXTRACTIONS, PROCESS NO. 1
Extraction Experiment
Extraction I (1)
Aqueous Phase
Insoluble Organic Phase
Extraction I (2)
Aqueous Phase
Aqueous Fraction
MIBK Fraction
Insoluble Organic Phase
Extraction I (3)
Aqueous Phase
Aqueous Fraction
Chloroform Fraction
Insoluble Organic Phase
Extraction I (4)
Aqueous Phase
Insoluble Organic Phase
Extraction I (5)
Aqueous Phase
Insoluble Organic Phase
Extraction I (6)
First Aqueous Phase, 1(6) Al
Second Aqueous Phase, I (6) A2
Third Aqueous Phase, I (6) A3 -
Fourth Aqueous Phase, I (6) 4
Insoluble Organic Phase, I (6)0
Percent
NVO*

53.8
39-8

50.4
(38.5)
(11.9)
55.5

52.8
(41.7)
(11.1)
39.9

40.1
51.4

52.3
41.4

44.6
6.0
2.5
0.1
55.8
Percent
Phenolic

28.7
13.7

34.0
(24.0)
(10.0)
5.5

41.4
(33.2)
(8.2)
23.3

Percent
PNCt

25.1
-

14.5
(14.5)
-

12.2
(12.2)
-

Not Determined [Stock
Not Determined [Stock


Not Determined [Stock
Not Determined [Stock

13.6

31.0
Percent
NHAT

-
26.1

1.9
(1.9)
50.0

2.9
(2.9)
15.6

K4)A]
1(4)0]

K5)A]
1(5)0]

-
Not Determined
Not Determined
Not Determined
11.9
-
43.9
* Non Volatile Organics
t Polyhydroxy Neutral Compounds
$ Neutrals of High Aromatic!ty
                                     56

-------
first water phase, 1(6) Al, only this phase was analyzed and reserved for
further experiments.

Process No. 2.  Three Phase Extraction Procedure—
       In the three phase extraction technique the oil sample was extracted
with a vigorously stirred mixture of water and an immiscible solvent.  The
liquid phases were decanted from the insoluble tar phase and separated into
aqueous and organic phases.  A schematic diagram of this process is shown
in Figure 36.


       UNSTRIPPED PYROLYTIC OIL*	»~ Vacuum Strip1-
                                                       f               t
                 |	STRIPPED      VOLATILES
                                                      OIL          PHASE
                               Extract with
                             mixture of water
                           and organic solvent

J I

I J
WATER ORGANIC INSOLUBLE
PHASE PHASE TAR
  Samples and yields shown in UPPER CASE LETTERS
t Operations shown in lower case letters


              Figure 36.  Three phase extraction, Process No. 2.


       Four batch extractions were performed using mixtures of water with
MIBK as a polar organic solvent or water with chloroform as a nonpolar sol-
vent as follows.

       0 Extraction II (1)—A 103.1 g sample of vacuum stripped oil was
         stirred with a mixture of 1QO mT water and 100 ml MIBK.  The
         mixture was allowed to stand, and the water and organic phases
         were separated.
       0 Extraction II (2)—Extraction II (2) was performed as II (1) using
         105.6 g unstripped oil, 200 ml chloroform, and 100 ml water.
       o Extraction II (3)—This extraction was similar to II  (1) except
         that the sample was 97.9 g unstripped oil.
       o Extraction II (4)—This experiment was run in the same manner as
         II (1).
                                     57

-------
        The  distributions of the main classes of compounds were determined
 following the  scheme described above for Process No. 1.  These distributions
 are  shown in TABLE 13.  The letter codes, e.g., II(1)A, shown after each
 phase  are included to facilitate their identification as starting materials
 for  additional experiments to be described in later sections of this report.

 Process No. 3.  Dissolution in an Organic Solvent Followed by Water
 Extraction—
        In these experiments listed below, the oil sample was dissolved in an
 organic solvent,  and the resulting solution  was extracted with water.  A
 schematic diagram of this process is shown in Figure 37.

        o Extraction III (1)—A 102.6 g sample of vacuum stripped oil was
         stirred  with 200 ml chloroform.  The chloroform solution was
         extracted with three 100 ml portions of water.
        ° Extraction III (2)—This experiment was similar to III (1) except
         that  200 ml MIBK was used to dissolve the oil, and the three water
         extractions were carried out with a weighed fraction of the MIBK
         solution with proportionally smaller quantities of water.
        ° Extraction III (3)—This experiment was similar to III (2) except
         that  the sample was unstripped oil.

        The  distributions of the identifiable classes of compounds were deter-
 mined.   These  distributions are shown in TABLE 14.  The chloroform insoluble
 material in Extraction III (1) was readily soluble in acetone or five percent
 •aqueous alkali, which indicates that the neutral material in the insoluble
 tar  phase contained a large number of hydroxyl groups.  This interpretation
 was  supported  by  infra-red examination.  The MIBK insoluble tars in Extrac-
 tions  III (2)  and III (3) were readily soluble in acetone but only partially
 dissolved in five percent aqueous alkali.  With the support of infra-red
 evidence it was concluded that these MIBK insoluble tars were a mixture of
 polyhydroxy compounds and neutrals of high aromaticity.

 Cbntinuous Countercurrent Extraction Procedures

        Results of the batch extraction experiments indicated that continuous
 countercurrent extraction work should be concentrated on Process No. 1 with
 subsequent extraction of the resulting solution phase with MIBK and on
 Process  No.  2 using water and MIBK.  Four experimental runs were made using
 Process  No.  1 with vacuum stripped oil, Process No. 1 with unstripped oil,
 Process  No.  2 with vacuum stripped oil and Process No. 2 with unstripped oil.

       Modular construction was chosen for the countercurrent extractor to
permit relocation of the inlet and outlet points and to permit variations in
the length of the unstirred phase separation zones.  A schematic diagram of
the counter  current extractor is shown in Figure 38.

       The apparatus consisted of a vertical tube with a heavy tar outlet at
the bottom and side inlets for solvent admission and a recycling line out-
let in the  lower sections of the tube.  The diameter of the mixing chamber
ras larger  than that of the settling zones to prolong the residence time of

                                     58

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   _TABLE 13.   COMPOSITION OF YIELDS FROM BATCH THREE PHASE EXTRACTIONS,
                               PROCESS NO. 2
Extraction Experiment
Extraction II (1)
Aqueous Phase 11(1) A
MIBK Phase II(1)M
Insoluble Tar Phase
Extraction 11(2)
Aqueous Phase II (2) A
.Chloroform Phase II(2)C
Insoluble Tar Phase
Extraction 11(3)
Aqueous Phase II (3) A
MIBK Phase II(3)M
Insoluble Tar Phase
Extraction 11(4)
Aqueous Phase II (4) A
MIBK Phase II(4)M
Insoluble Tar Phase
Percent
NVO*

39.2
53.0
0.1

41.0
51.7
2.2

38.7
50.7
2.1

41.6
54.1
0.5
Percent Percent
Phenolic PNCt

16.9 22.3
22.1
ND*

17.9 23.1
21.3
ND

ND
ND


7.9 33.7
27.6
ND
Percent
NBA**

-
30.9


-
30.4






-
26.5

 Non volatile hydrocarbons
"fpolyhydroxy neutral compounds
**Neutrals of high aromaticity
     determined
                                     59

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          UNSTRIPPED PYROLYTIC OIL
•*• Vacuum Strip
                  I	
      STRIPPED
         OIL
VOLATILES
 PHASE
                              Dissolve in
                            organic solvent
           ORGANIC SOLUTION
               PHASE
INSOLUBLE TAR
              Extract
            three times
            with water
             EXTRACTED
         ORGANIC FRACTION
   COMBINED
WATER FRACTION
Samples and yields shown in UPPER CASE LETTERS.
Operations shown in lower case letters.


     Figure 37.  Sequential organic water extraction, Process No.  3,
                                   60

-------
Extraction Experiments
Extraction III(l)
Chloroform Phase III(1)C
First Aqueous Fraction III(1)A1
Second Aqueous Fraction III(1)A2
Third Aqueous Fraction III (1) A3
Extracted Chloroform Fraction III(1)CE
Insoluble Tar Phase III(1)MR
Extraction 111(2)
MIBK Phase III(2)M
First Aqueous Fraction III(2)A1
Second Aqueous Fraction III(2)A2
Third Aqueous Fraction III(2)A3
Extracted MIBK Fraction III(2)ME
Insoluble Tar Phase III(2)MR
Extraction 111(3)
First Aqueous Fraction III(3)A1
Second Aqueous Fraction III(3)A2
Third Aqueous Fraction III (3) A3
Extracted MIBK Fraction III(3)ME
Insoluble Tar Phase III(3)MR
' — «
Percent
NVO*

85.7
(27.5)
(3.5)
(1.4)
(36.6)
7.8

77.1
(23.1)
(4.9)
(4.9)
(44.2)
15.3
AS 1
D D • J_
(17.9)
(3.9)
(1.6)
(41.1)
37.9
Percent
Phenolics

20.3
(12.8)
(2.5)
(0.8)
(6.4)
4.5

23.4
(12.0)
(4.9)
(0.5)
(6.5)
' 3.7

(9.7)
(3.9)
(1.4)
(7.6)
8.0
Percent
PNC+

(14.7)
(1.0)
(0.6)
3.3

(11.1)
(0)
(0)
	

(8.2)
(0)
(0.2)
	
Percent
NHA**

65.4 	
(30.2)
-

53.7 	
(37.7)
11.6 	

(33.5)
29.9 	
* Non volatile organic
t Polyhydroxy neutral compounds
**Neutrals of high aromaticity

-------
            T
           20 cm
           22 cm
  Recycle
           63 cm
Circulating
   Pump
                           10 cm od
                                        ^
                                     oo
                                    V>
4.5 cm od
                                Solution Out
                                Stagnant Zone
                                                           Oil  In
                                                           Stirring Zone
Settling Zone
                                                           Water In

                                                           MIBK In
                                                   Insoluble Oil Out
                     Figure 38.   Countercurrent extractor.
                                   62

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the oil and solvent in the vigorously stirred zone.  A recycling line was
provided to withdraw a portion of the stream containing undissolved oil
droplets and return it to the top of the mixing chamber.  The solvent supply
rate and the recycle flow rate were controlled by means of "Masterflex"*
variable speed tubing pumps.

       The oil sample was led through the top of the stirring chamber to a
point level with the blades of a high speed propeller type stirrer.  The
undissolved oil droplets settled downward through the tube countercurrent to
the incoming solvent stream.  A portion of the rising solution phase and
descending undissolved oil droplets was withdrawn through the recycle loop
at a flow rate fifty times greater than the solvent intake rate and returned
to the top of the stirring zone.  The heavy extracted oil phase was collected
and discharged at the bottom of the apparatus.  The oil solution passed
through a constriction at the top of the mixing chamber into the stagnant
zone, and the dissolved oil stream flowed from an outlet near the top of the
tube.

Process 1A.  Continuous Countercurrent Water Extraction of Unstripped Oil —
       The experimental procedure was as follows .  The apparatus was filled
with deionized water, and the stirrer and pumps were turned on.  Unstripped
pyrolytic oil was admitted to the apparatus.  The undissolved oil was with-
drawn from the bottom of the extractor and portions of the solution phase
which eluted from the top of the extractor were analyzed for dissolved non-
volatile organics (NVO) .  The system was considered to be equilibrated when
no change was observed in the NVO concentration of the successive portions
of the diluted aqueous phase.
                                               .1

       Pyrolytic oil and water were fed into the equilibrated reactor at
carefully controlled rates from calibrated reservoirs.  The undissolved oil
phase and the diluted water solution were collected in tared receiving
vessels and weighed, and the percent NVO in the oil and aqueous phases was
determined.  The inputs and yields from this three hour experiment are shown
in TABLE 15.

       The apparent loss of nonvolatile organic material was believed to be
distributed between the adherent tar and the solution remaining in the
extractor.  The loss in water and volatile organics was attributed to evapo-
ration and leakage.

Process IB.  Continuous Countercurrent Water Extraction of Vacuum Stripped
       This experiment was conducted by the same method as Process LA using
vacuum stripped oil.  The duration of the experiment was two hours and ten
minutes.  The inputs and yields for this experiment are summarized in TABLE
16.
 Cole Farmer Instrument Company, Chicago, Illinois.
                                     63

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                   TABLE 15.  INPUTS AND YIELDS. PROCESS 1A
 Operation
Total g
g/minute
(average)
 Inputs

   Oil Sample  In
     Total  Sample
     Non Volatile Organic
     Volatile  Organic
     Sample Moisture

   Extraction  Solvent In
     Water

 Outputs

   Aqueous  Phase
     Non Volatile Organics
     Water  and Volatile Organics

   Insoluble Oil Phase
     Non Volatile Organics
     Water  and Volatile Organics
 1,998
 1,698
   140
   160

 4,120
 4,806
   808
 3,998
 1,121
   818
   303
  10.8
   9.2
   0.8
   0.9

   22.3
  25.8
   4.4
  44.4
   6.1
   4.4
   1.6
Apparent Losses
Total
Non Volatile Organics
Water and Volatile Organics

191.0
72.0
119.0

1.0
0.4
0.6
       The loss of nonvolatile organics may be attributed to trapped tars in
 the extractor and to dissolution in the remaining liquid phase.  Evaporation
 is believed to be the major cause of water and volatile losses.

 Process  2 A.  Continuous Countercurrent Three Phase Extraction of Unstripped
 Oil—
       The apparatus was filled by pumping in approximately equal parts by
 volume of MIBK and water.  The stirrer and recirculating pump were then
 turned on, and the two solvent phases were thoroughly mixed for thirty min-
 utes.  The extractor was then equilibrated by passing in constant rate
 streams of unstripped oil, MIBK, and water until 800 ml of oil had passed
 into the extractor and the NVO concentration in the effluent stream was con-
 stant.  At this point the levels of oil, MIBK and water in the calibrated
 feed reservoirs were recorded and the effluent stream was diverted into a
 tared receiver.  The levels of oil and solvents in the reservoirs and the
weight of the receiver were recorded at approximately five minute intervals
 to insure constant input and output rates.  At the end of 90 minutes the
 final oil and solvent levels and the weight of the collected effluent were
                                    64

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                  TABLE 16.  INPUTS AND YIELDS, PROCESS IB
Operation
Total g
g/minute
(average)
Inputs

  Oil Sample
    Total Sample
    Non Volatile Organic
    Volatile Organic
    Sample Moisture

  Extraction Solvent In
    Water

Outputs

  Aqueous Phase
    Non Volatile Organics
    Water and Volatile Organics

  Insoluble Oil Phase
    Non Volatile Organics
    Water and Volatile Organics

Apparent Losses

  Total
  Non Volatile Organics
  Water and Non Volatile Organics
 1648
 1621
   27
    0


 2830
 3294
  667
 2527
 1129
  903
  226
   57.0
  ,104
 12,
 12.
  0.
  0
 21.8
 20.5
  5.1
 15.4

  8.7
  6.9
  1.7
  0.4
  0.8
recorded.  The effluent was a well mixed dispersion, which required overnight
standing to separate into two distinct phases.  No insoluble oil phase
occurred.  The input and yield data for this experiment are shown in TABLE
17.

Process  2B.  Continuous Countercurrent Three Phase Extraction of Vacuum
Stripped Oil—
       This experiment was conducted with'vacuum stripped oil by the same
method used in Process  2A.   The inputs and yields for this experiment are
shown in TABLE 18.

       The loss of nonvolatile organics is attributed to retention in the
solution remaining in the extractor at the end of the experiment.  Evapora-
tion from the vigorously stirred system and minor leakage resulted in some
loss of solvents and volatiles.
                                    65

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                    TABLE  17,   INPUTS AND YIELDS. PROCESS  2A
 Operation
Total g
g/minute
(average)
 Inputs

   Oil Sample In
     Total Sample
     Nonvolatile Organic
     Volatile Organic
     Sample Moisture

   Extraction Solvent In
     Water
     MIBK
 555
 472
  38
  44


 780
 562
  6.2
  5.2
  0.4
  0.5

  8.7
  6.2
 Outputs

   Aqueous Phase
     Nonvolatile  Organics
     Solvents  and Volatile Organics

   MIBK Phase
     Nonvolatile  Organics
     Solvents  and Volatile Organics

   Insoluble Oil  Phase

 Apparent  Losses

   Nonvolatile Organics
   Solvents and Volatile Organics
1153
 358
  795

 741
 114
 627

None
   0
   3.0
 12.8
  4.0
  8.8

  8.2
  1.3
  7.0
  0
 ~0
Extraction of Continuous Countercurrent Aqueous Phases

       The water solution from Process 1A, Process IB, and Process  2B were
exhaustively extracted with successive small portions of MIBK.  The aqueous
phase from Process  2A was not extracted with MIBK.  The results of these
extractions and the results of the subsequent analyses of the phases and
fractions are summarized in TABLE 19.
                                j ..'.

       The percent yields are expressed in terms of water-free oil including
volatile organics.  The total nonvolatile organics recovered should approach
93 percent for unstripped oil and 97 percent for vacuum stripped oil.  The
nonvolatile organics were approximately evenly distributed between the water
phase and the insoluble oil phase in Process 1A.  The solubility of the
vacuum stripped oil was somewhat less than that of the unstripped oil.

       In Process  2A the nonvolatile organics from the unstripped oil
appeared to concentrate in the aqueous phase, and the two phases separated
very slowly.   These phases were stored for future applications research.  In
                                    66

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                  TABLE  18.   INPUTS AND YIELDS. PROCESS 2B
                                                                  g/tnlnute
 Operation                                       Total g           (average)

 Inputs

   Oil Sample  In
     Total  Sample                                 1,678             13.4
     Nonvolatile Organics                         1,629             13.0
     Volatile  Organics                               49              0.4
   Extraction  Solvents  In
     Water                                        1,900             15.2
     MIBK                                        1.198              9.6
Outputs
Aqueous Phase
Nonvolatile Organics
Solvents and Volatile Organics
MIBK Phase
Nonvolatile Organics
Solvents and Volatile Organics
Insoluble Oil Phase
Apparent Losses
Nonvolatile Organics
Solvents and Volatile Organics

2,746
735
'2,011
1,812
798
1,014
None

96
122

22.0
5.9
16.1
14.5
6.4
8.1


0.8
1.0
Process  2B , the nonvolatile organics were distributed almost equally between
the aqueous and MIBK phases.  Whether in water extraction (Process 1) or
three phase extraction  (Process  2) the presence of volatile organics enhanced
the water  solubility of  the nonvolatile organics.

       The apparent yields and distributions of phenolic compounds also were
strongly dependent on the extraction method.  In the water extraction experi-
ments (Process l) the total percent phenolic was apparently half of that
detected in the three phase extraction (Process  2) products.  In the three
phase extraction of unstripped oil more than 80 percent of the phenolics were
concentrated in the aqueous phase.  With stripped oil the phenolics were
distributed almost evenly between  the aqueous and MIBK phases.  The concen-
trations of polyhydroxy  neutral compounds found in the water phases of
Process 1A, Process IB,  and Process  2B  are similar.  The high apparent con-
centration of PNC in the Process  2 A water phase was believed to include some
neutrals of high aromaticity (NHA).  The solubility of NHA compounds in water
was believed to be enhanced by the presence of volatile compounds from the
unstripped oil.  This supposition was supported by the similarity of the sums
of PNC plus NHA in Process  2 A and Process 2B.   Both sums are near 56 per-
cent.

                                     67

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	TABLE 19.  COMPOSITION OF CONTINUOUS EXTRACTION YIELDS
                                    Percent    Percent    Percent    Percent
Process                              NVO*     Phenolic     PrtCf       NHA**
Process 1A (Unstripped oil)
Aqueous Phase
Extracted Aqueous Fraction
MIBK Extract Fraction
Insoluble Oil Phase
Process IB (Vacuum stripped oil)
Aqueous Phase
Extracted Aqueous Fraction
MIBK Extract Fraction
Insoluble Oil Phase
Process 2 A (Unstripped oil)
Aqueous Phase
MIBK Phase
Process 2 B (Vacuum stripped oil)
Aqueous Phase
Extracted Aqueous Fraction
MIBK Extract Fraction
MIBK Phase

44.0
(33.4)
(10.6)
44.5

40.5
(33.1)
(7.4)
54.8

70.2
22.3

43.8
(35.7)
(8.1)
47.6

9.1 26.9
(6.5) (26.9)
(2.6) (-)
8.4

6.5 28.1
(5.0) (28.1)
(1.5)
7.9

31.4 38.7
5.9

16.1 24.4
(11.4) (24.4)
(4.7) (-)
17.6

8.0
(8.0)
36.1

5.9
(5.9)
46.9

16.4

3.4
(3.4)
30.0
* Non volatile organics
^ Polyhydroxy neutral compounds
**Neutrals of high aromaticity
                                    68

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Vacuum Stripping of Oil

       Moisture analyses of the oil samples by azeotropic distillation with
toluene indicated that about 14.7 percent of the sample was water and low
boiling water soluble compounds.  Gas chromatography showed 8.2 percent
water and 6.5 percent volatile organics.  These volatile materials could
represent a possible sample cut for separate processing and could also inter-
fere in the extraction of  groups of higher molecular weight compounds in the
oil.  Samples of the oil were vacuum stripped in a rotary evaporator at
three temperatures for varying lengths of time to determine the rate and
extent of volatiles removal.  Results of these experiments are shown in
TABLE 20.
                 TABLE  20.  VACUUM STRIPPING EXPERIMENTS
Temperature
(°c)
23.0
23.0
53.0
53.0
53.0
73.0
73.0
73.0
73.0
Time
(Hours )
40
60
0.5
1.0
4.0
0.4
0.7
1.0
2.5
P(min)
Torr
2
2
24
14
2
15
2
2
2
Percent Volatiles
Removed
13.7
13.8
8.2
11.2
16.4
9.8
13.8
15.0
18.7
       The time required for vacuum stripping at 23°C was prohibitively long
for a continuous process.  Heating the oil during vacuum stripping apparently
caused some chemical reactions, as the viscosity of the stripped oils
increased with both increasing time and temperature.

       The percent of volatiles removed in these experiments is based on the
whole oil including volatiles but not water.  The percent of volatiles
removed was calculated from the weight of the condensate in dry ice traps
between the evaporator and the vacuum pump.  The thirty minute stripping
operation at 53°C was chosen as the basis for a semicontinuous stripping
operation to prepare oil samples for the continuous countercurrent extrac-
tions.  The 8.2 percent volatiles removed included 5.1 percent water and 3.1
percent volatile organics by gas chromatography, and only minimal thickening
was observed in the stripped oil.
                                     69

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        Semicontinuous vacuum stripping experiments were carried out in
 Buchler Model FE-2C* continuous rotary evaporators.  The unstripped oil from
 a calibrated  reservoir wasqadmitted to the rotating evaporator bulb immersed
 in a 53°C water  bath and held under vacuum for 25 minutes before being
 aspirated to  a "stripped oil" reservoir.  The distilled volatiles were col-
 lected continuously in dry  ice traps, and subsequently weighed and analyzed
 by gas chromatography.  The process was repeated using 200 ml portions of
 unstripped  oil until six liters of vacuum stripped oil had been collected.
 The collected volatiles totalled 8.9 percent of the dry sample weight—5.9
 percent water and  3.0 percent volatile organics.

 Activated Carbon Adsorption Experiments

        Three  experiments were run contacting water extracts of pyrolytic oil
 with activated carbon (Nuchar WV-G, Westvaco Carbon Co., Charleston, S.C.).

 Slurry Contact with Stepwise Carbon Addition—
        A  50 ml aqueous extract containing 15.9 g nonvolatile dissolved
 organic material was stirred vigorously and treated with successive portions
 of carbon until  there was no further clarification of the color.  After fil-
 tering and  washing the carbon with water, the combined filtrate and washings
 were diluted  with  water to  100 ml.  Evaporation of an aliquot portion of the
 residing  solution  indicated that 8.9 g organics remained in solution and 7.0
 g had been  adsorbed on the  carbon.

 Elution of  Aqueous Extract  Through Activated Carbon—
        A  10 ml portion of aqueous extract containing 2.9 g dissolved organics
 was  eluted  through a 2.5 cm ID x 20 cm activated carbon column with water,
 1:9  of methanol:water, 1:1  of methanol:water, methanol, and finally with
 carbon disulfide.  The eluted fractions were collected and evaporated to
 dryness on  a  rotary vacuum  evaporator.  The results of this experiment are
 summarized  in TABLE 21.
           TABLE 21.  ORGANICS ELUTED FROM AQUEOUS CARBON COLUMN
Fraction
D-l
D-2
D-3
D-4
D-5
Eluting Solvent
Deionized Water
1:9 Methanol :Water
1:1 Methanol :Water
Methanol
Carbon Disulfide
ml
470
210
370
650
280
Organics
Eluted (g)
9
0.4405
0.2892
0.9968
0.5563
0.5557*
Total Organic
Eluted (g)
0.4405
0.7297
1.7265
2.2828
2.8385
* Eluted as small amount of very dark methanol phase  and  about 265 ml of
  very pale carbon disulfide phase.
 Buchler Instruments, Inc., Fort Lee, N. J.

                                     70

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       Inspection of TABLE 21 indicates that 15 percent of the organic
material eluted with water and nearly 63 percent eluted with methanol and
mixtures of methanol and water.  The roughly 19 percent washed from the col-
umn with carbon disulfide was concentrated in a methanol layer on top of the
heavier carbon disulfide.  Thus although carbon disulfide displaces the
adsorbed organic material left by methanol from the activated carbon, the
organic material is much more soluble in methanol than in carbon disulfide.
The fractions D-l through D-5 isolated in this experiment were analyzed by
TLC, LC and IR  techniques, and the results were interpreted as follows.  The
D-l fraction was shown to be quite polar from the TLG and LC reversed phase
column results.  The IR spectra resembled the spectra of maltitol, an
alcohol carbohydrate.  The results of the D-2 fraction were similar to those
of D-l.  The data from TLC and LC with the D-3 fraction indicated the mater-
ial was polar, acidic and nonaromatic.  The IR spectra resembled glyoxylic
acid.  The TLC and LC results with D-4 indicated at least three polar compo-
nents were present, and the IR spectra of one of the components resembled
3-hydroxy-4-methoxyphenylethylene glycol.

Separation of Unstripped Oil on Activated Carbon—
       A 50 g sample of unstripped oil was dissolved in methanol, and a 50
ml portion of the resulting solution containing 25.1 g of nonvolatile
organics was passed through a 2.5 cm ID x 50 cm carbon adsorption column,
previously prepared with a methanol-carbon slurry.  The eluent in 30 ml por-
tions was returned to the top of the column until no further clarification
of the solution color was observed.  The column was eluted with methanol (670
ml) until the eluted liquid was nearly colorless followed by elution with
210 ml carbon disulfide.  The column was eluted then by 260 ml methanol which
was followed by a final elution with 100 ml of water.  The results of these
elutions are summarized in TABLE 22, which show that 20 percent of the
organics were not eluted.
     TABLE 22.  ELUTION OF UNSTRIPPED OIL FROM ACTIVATED CARBON COLUMN

Elution Step
1-Methanol
2-Carbon Disulfide*
3-Methanol
4-Water

Solvent (ml)
560
210
260
100
Organic
Eluted (g)
13.12
4.99
1.60
0.40
Total Organic
Eluted (g)
13.12
18.11
19.71
20.11
* The eluent consisted of immiscible layers of methanol and carbon disulfide
and the organic material was concentrated in immiscible methanol layer.


Slurry Contact of Aqueous Extract of Pyrolytic Oil with Activated Carbon—
       A 100 ml aliquot portion of a water extract from unstripped oil con-
taining 31.2 g dissolved nonvolatile organics was contacted with activated
carbon for 3 hours.  Small quantities of the liquid were removed from the


                                     71

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 mixture at intervals,  filtered  and  evaporated at 35°C on a vacuum evaporator.
 These small samples  indicated that  the adsorption was nearly completed  during
 the first 10 minutes.   After 3  hours  the carbon was filtered from the solu-
 tion, washed with water,  and dried.   The combined filtrate and washings were
 evaporated to dryness  in  vacuo.  The  solutions contained 15.7 g organics
 (50.3 percent of the organics in the  sample).  The dried carbon was  exhaus-
 tively extracted with  N,N-dimethyl  formamide  (DMF), and the DMF extract con-
 tained 11.1 organics (35.6  percent  of the sample).  The results show that
 14.1% of the organics  remained  on the carbon.

 Acid-Base Extraction of MIBK Phase  with Ether

        A portion of  the MIBK solution from Extraction 11(4) which contained
 phenolics,  nonvolatile hydrocarbons,  and neutrals of high aromaticity was
 extracted with aqueous sodium hydroxide solution.  The aqueous alkali
 extract was extracted  with  diethyl  ether and then acidified with dilute
 sulfuric acid.  The  acidified solution was extracted with diethyl ether.
 The phenolics in the final  diethyl  ether were determined by the NAT  tech-
 niques, and these results indicated that more than 90 percent of the phenolics
 in the original MIBK phase  had  been extracted.

 Fractional Distillation and Analysis  of Fractions
                          • 'j
        A 50 g sample of water-insoluble stripped oil, prepared by water
 extraction of vacuum stripped oil,  was vacuum distilled at approximately 6mm
 in a short path simple column  apparatus.   The head  temperatures  and yields
 are given in TABLE 23 below.
            TABLE  23.  DISTILLATION DATA FOR WATER-INSOLUBLE OIL
Fraction
No.
F-l
F-2
F-3
F-4
F-5
Residue
r,
Head Temperature
(°C)
50-100
100-110
110-120
120-175
175-193

Yields
(wt%)
10.5
6.3
4.6
7.9
17.3
53.4
       The fractions F-l through F-5 were examined by  several analytical
techniques to determine qualitatively the classes of the  compounds and rela-
tive amounts.  Thin layer chrotnatography indicated that F-l  through F-4 con-
tained mainly two classes of  compounds, phenolic aromatics and phenolic
ethers.  TLC indicated that F-5 contained phenolic ethers, aromatic neutrals
and a trace of polyhydroxy neutral compounds.   The analysis  by liquid
chromatography confirmed TLC  findings but yielded greater resolving power
among the phenolic compounds  indicating F-l and F-2 had as many as 13

                                     72

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compounds that were ultraviolet  light  absorbing.   Infrared  data  indicate
predominantly phenolics and phenolic ethers  in F-l through  F-4 and  aromatic
neutrals mixed with phenolic  ethers in F-5.

Analytical Techniques

       The identification  of  the different classes of  organic functionality
has been accomplished by a variety of  chemical analytical techniques.  Our
immediate objective in this phase has  been to  rapidly  determine  the progress
of a separation process and identify the  polyhydroxy compounds, dihydroxy
phenolics, phenolics, phenolic ethers  and neutral  aromatic  classes  in the
various phases or  fractions.  In most  cases  only a qualitative indication
was needed to complete the experiment  since  the phenolic components were
being determined by a NAT  method.  The fraction of neutrals of the  sample was
determined by difference.  To determine whether the neutral fraction was
primarily polyhydroxy aliphatic  or aromatic  or both, a TLC  plate was run with
carbohydrate, phenolic and phenolic ether standards.   To confirm these find-
ings an LC analysis at two wavelengths was made.   An example of the results
obtained from all  of the techniques applied  to the three different  phases
from a single process extraction is given in TABLE 24.

Nonaqueous Titration (NAT)—
       A literature search was performed  to  determine  suitable titration
methods for total  phenolic material in the presence of carboxylic acids and
traces of water.   Most of  the conventional procedures  utilized methods which
allowed only anhydrous conditions for  determination.   Based on the  literature
search and experimental work, potassium hydroxide  in methanol was chosen on
the basis of availability, ease  of preparation and stability in storage.  The
titration solvent  chosen was  dimethyl  formamide because it  has the  required
basicity and compatibility with  the water, neutral compounds and phenols
present in pyrolytic oils.  DMF  is relatively  safe as  compared to more vola-
tile amines and apparently yields adequate endpoint potentiometric  millivolt
shifts.

       Electrode systems were selected based on apparent end-point  shifts in
millivolts on real pyrolytic  oil samples.  Both a  glass calomel and platinum
versus platinum polarized  electrode systems  functioned adequately with known
standards which included acetic  acid,  benzoic  acid, phenol  and guaiacol.
However, the platinum polarized  electrode system was the system that operated
best with real pyrolytic oil  samples.   Standardization was  accomplished with
benzoic acid and guaiacol  solutions, each 0.01N in DMF.  The equipment used
to titrate samples was a semi-automatic recording  titrimeter consisting of
the following components:  (1)   Pump - Cole  Farmer Single channel,  Variable
speed peristalic pump at 2.1  ml  per minute;  (2)  Electrode  - Platinum couple
Fisher Scientific  K-F Titrimeter electrode;  (3)  Polarizer  - Fisher Scientific
K-F Titrimeter Model 391;  and (4)  Recorder  -  Perkins  Elmer Model 56.

       The procedure for a determination  was to standardize the semi-automatic
titration equipment with 3 ml samples  of  standard  0.01N benzoic acid and
0.01N guaiacol solutions in DMF.  Oil  samples  for  analysis  were weighed in
the titrating vessel by difference.  Each sample was titrated with  the
methanolic potassium hydroxide solution until  no further endpoints  were noted.


                                      73

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        TABLE 24.  ANALYTICAL RESULTS FROM BATCH EXPERIMENT PROCESS, l.A
Analytical
Technique

Aqueous Phase
extracted with MIBK
Phases
MIBK Extract of
Aqueous Phase

Insoluble Oil Phase
    LC       Predominately polar
             polyhydroxy cpds; 3
             dihydroxy phenolics
             in moderate amts.
    TLC      Main components
             polyhydroxy neutral
             cpds with 3
             dihydroxy phenolics
    NAT      6.5% phenolic
             27% polyhydroxy
             neutrals
Predominately
phenols, dihydroxy
phenolics; trace
of polyhydroxy cpds
Three phenolic
cpds; only trace
amts. of poly-
hydroxy neutrals
2.9% phenolic
6.2% neutrals
Predominately
aromatic neutrals;
moderate amt. of
phenolics and trace
of polyhydroxy cpds

Strongly aromatic
neutral components;
moderate phenolic
content; no trace
of polyhydroxy cpds

8.4% phenolic
36% neutrals
             Strong hydroxy func-
             tionality; strong
             ether functionality;
             weak phenolic   (,
             indications
Indicated strong
phenolics and
ethers
Aromatic ketones;
subt'd aromatics;
phenolic
    GC       Only small amount of
             sample eluted,
             approx.  80% of  sample
             coked in the
             inj ector

    GC       Silylation of sample
             produced three  irregu-
             lar  peaks of high
             boiling  character
             similar  to sugar  cpds
Many phenolic and
creslyic cpds
Some phenols; ether
phenols
In calculating  the results,  it was  assumed  that  the average molecular weight
of the phenolics was  125 and of  the carboxylic acids,  100.

Thin Layer Chromatography—
       Thin layer chromatography (TLC) offered an analytical technique which
could supplement the  other techniques used  in this study, particularly HPLC.
A separation by TLC of the general  classes  include the polyhydroxy
                                      74

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carbohydrates, dihydroxy phenolics, phenolics, ether phenolics and aromatic
neutrals.  The TLC separations were carried out with EM Silica Gel 60F-254
plates, 20 x 20 cm, and the solvent systems and detection (visualization)
reagents are given in TABLE 25.
               TABLE 25.  TLC SOLVENTS AND DETECTION REAGENTS
   S-l"
       Solvent Systems
            S-2
                                 S-3
Ethyl acetate
Acetonitrile
Water
65
25
10
N-butanol
Acetone
Water
40
50
10
Methanol
Benzene
Water
14
79
7
   D-l
D-2
Detection Reagents

                D-3
D-4
Bial's Orcinol
reagents used at
110 °C for 5 min.
Sulfuric acid
and potassium
dichromate
charring at 160°
for 10 min.
Ultraviolet
light at
254 and
365 nm
Diazotized
R Salt.
Scarlet
* The numbers after each solvent represents the percent by volume of each
solvent in the three component system.
       The general procedure for a TLC analysis was as follows.  The TLC
plates were normally activated for 15 min in a HO°C oven.  Three microliter
samples 10 mg/ml in acetonitrile were applied.  Each spot was dried and the
plate was developed in a presaturated tank of a chosen solvent system.  After
a 10 to 14 cm rise of solvent the plate was dried in a low heat oven 80°C for
10 minutes and visualized with the detection agent of choice.  Inspection by
U V light was usually done before any chemical reagent was applied.  Rf values
were calculated by conventional means using the solvent front as R£ 100 and
the spotting point as Rj 0.  Interpretation of the chromatograms was made
using standard compounds when possible and color reactions of the various
visualization reagents.

Gas Chromatography—
       Gas chromatography as an analytical method was used almost exclusively
in Phase III of this project to analyze the volatiles fraction, obtained from
the vacuum stripping separation process.  The conditions used for these
analyses were:
                                      75

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Column 1.  Pora Pak Q, 270 cm x 0.31 cm S.S.; oven, 180°C; injector, 200°C;
           thermal conductivity detection, 175 ma; Helium carrier at 20
           ml/min
           Used for the determination of water, methanol, formic acid,
           acetic acid, and propionic acid.

Column 2.  SP-2100, 10% on HMDCS treated 100-120 mesh Supelcoport;
           300 cm x 0.31 cm S.S.; FID; N_ carrier at 20 ml/min; oven
           60°C; injector 100°C;
           Used for the determination of furfural.

Infrared Spectroscopy—
           Infrared spectra were made of the various fractions obtained in
the experiments with the continuous extraction processes.  The spectra were
found to contain only fragmentary information due to the multiplicity of
compounds in each fraction.  The overlapping of peaks precluded interpreta-
tion in only but the most general terms.  Main bands of interest used in
this program are given in TABLE 26.
	TABLE 26.  INFRARED BANDS	

Micron Wavelength              Description


       3.0                     Broad hydrogen bonded OH function
       3.8                     Shoulder of carboxylic acid OH stretching
   5.85 - 5.95                 Carbonyl absorption
   6.25 - 7.35                 Carboxylate anion absorptions
   10, 11, 7.1                 Vinyl group absorptions
   6.24, 12-14                 Aromatic absorption bands
Liquid Chromatography—
       Conditions used for LC analysis of fractions of the oils in this
phase of the project are given in TABLE 27.
      	TABLE 27.  LIQUID CHROMATOGRAPHY CONDITIONS	

       Item                       Condition


       Column:                    Spherosol ODS CTO  25 cm

       Solvent Gradient:          0 - 100% linear.  Total time 60 min,

       S.olvent:                   0 - 100% Acetonitrile in water

       Detection:                  254 nm,  190 nm

       Sensitivity:                0.2 absolute
       Chart speed:                8 inches per hour
                                      76

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                                  SECTION 6

                              PILOT PLANT DESIGN
 PROCESS DESCRIPTION

       Pyrolysis  oils  contain four  classes  of  organic  compounds in addition
 to water which  is condensed  along with  the  organics.   The classes are:
 phenolics, neutrals of  high aromaticity  (NHA),  polyhydroxy aromatics, acids,
 and water.   Separation work  at the  bench  level led  to  the development of four
 individual processing  schemes:

       Process  1-A    2  Stage continuous  extraction—raw oil
       Process  1-B    2  Stage continuous  extraction—vacuum stripped oil
       Process  2-A    Continuous, simultaneous extraction—raw oil
       Process  2-B    Continuous, simultaneous extraction—vacuum stripped oil

 Flow sheets  for the four separation process and for the combined pilot plant
 system are presented in  Figures  39 through  A3.  A component-by-component
 description  of  the processes follows.

 Process 1-A  2  Stage Continuous  Extraction—Raw Oil

       Starting at the left  in Figure  39 ,  raw pyrolytic oil, received in
 barrels, is  pumped into  the  raw  oil storage tank (1).  In preparation for a
 processing run  the raw oil is pumped into the  raw oil  feed tank (2).  The raw
 oil feed tank is  equipped with a stirrer  or mixer,  to  provide a homogeneous
 feedstock.   As  the ambient temperature  decreases  the pyrolytic oil becomes
 more viscous.   A  recycle loop with  a heating device is included to raise the
 temperature  of  the pyrolytic oil into the 100-130°F range, as necessary, to
 provide the  proper flow  of oil.

       Raw pyrolytic Oil is  pumped  into the extractor  (3) above the mixers
 (near the top of  the extractor).  Water from the  water storage tank (4) is
 pumped into  the extractor at approximately the same height as the pyrolytic
 oil (and above  the mixers).   Two or more  mixers provide violent agitation and
 intimate mixing of the pyrolytic oil and  water.   A  recycle stream draws a
 portion of the  oil-water mixture from approximately the height of the mixers
 and returns  the mixture  to the extractor  near  the bottom, above the level of
 the spent, insoluble oil.  The recycle  line is equipped with a heating
 device to raise the  temperature  of  the mixture from ambient to about 150°F,
 as is necessary.   Spent  oil  droplets descend through the extractor and
 accumulate in the  bottom of  the  extractor.  Excess  spent, insoluble oil is
pumped to the spent  oil  storage  tank (6), while always maintaining a level
of spent oil in the  extractor.

                                      77

-------
oo
        Fan Oil
      Storage Tank
       Preheater
                            n
                         Raw Oil
                        Feed Tank
             (7)
                                      Water Soluble
          /
         lup
                                                                              Extractor
               Water
             Storage Tank
ank (
Ho]
\
{
(9)
„
>-
MTBK Soluble
~1
Ldup Tank JF
f^\




(10)
~-~
Extractor
^\
(8)
tfl


Water
Soluble
^ \ .
-v, U3) y ^


To
Recycle
                                                                    Holdup  Tank
                                                                                        (14)
                  M1BK
                                              MIBK Soluble
                          Column or
                          Evaporator
              M1BK
              Storage Tank


              Spent Oil
              Storage Tank
                   Water
                   lnsolubl<
                    Water
                    Soluble
                 (15)
  N	x         Product
 Vacuum       Storage  Tank
Evaporator
                                       •Storage Tank

                        Figure 39.   Separation process no.  lA--raw oil-—2 stage  extraction

-------
       The stream of water and soluble orgaiiics exits near the top of the
extractor and is pumped into a holdup tank  (7).  The material in the holdup
tank is pumped into the 2nd stage extractor  (8) at a level above the mixers.
Methyl isobutyl ketone (MIBK) is pumped into the extractor from the MIBK stor-
age tank (5), at approximately the same level  as the water soluble organic
inlet stream.  Two or more mixers or stirrers  provide violent agitation and
intimate mixing of the water soluble organics  and the MIBK.  A recycle stream
draws a portion of the water soluble organic—solvent mixture from the level
of the mixers and returns the mixture to the extractor near the bottom.  A
phase separation occurs in the extractor, with the heavier aqueous solution
settling to  the bottom of the extractor, and the lighter organic solution
moving toward the top of the extractor.  The aqueous solution is removed from
the extractor near the bottom and is pumped into the water soluble holdup
tank (13), and then into the vacuum evaporator (14) where the water soluble
organics are separated from the water.  The water is vaporized and returned
to,the water storage tank (4).  The organics are pumped into the water soluble
organics—product storage tank (15).

       The organic phase from the second stage extractor exits near the top
of the extractor and is pumped into the MIBK soluble holdup tank (9).  The
organic phase is then fed into an evaporator (or column) (1Q) where the MIBK
is vaporized and collected in the MIBK-holdup  tank (11).  The recovered MIBK
is then returned to the MIBK storage tank (5).  The MIBK soluble organics are
concentrated in the evaporator and pumped to the MIBK soluble organics—pro-
duct storage tank (12).

Process 1-B  2 Stage Continuous Extractor—Vacuum Stripped Oil

       Starting at the left in Figure  40, raw pyrolytic oil, received in
barrels, is  pumped into the raw oil storage tank (1).  In preparation for a
processing run the raw oil is pumped into the  raw oil feed tank (2) .  The
raw oil feed tank is equipped with a stirrer or mixer, to provide a homogene-
ous feed stock.  A recycle loop with a heating device is included to raise
the temperature of the pyrolytic oil into the  100-130°F range, as necessary,
to provide the proper flow of oil.

       The raw pyrolytic oil is pumped into a  vacuum evaporator (or vacuum
stripping  column) (3), to remove the volatiles.  The volatiles are components
that are vaporized at atmospheric pressure at  100°F (212°F).  They consist
of water (60-70%), acetic acid ( ~ 20%) and small amounts of other low boiling
organic compounds.  The volatiles are condensed and pumped to the volatiles
storage tank (4).  The vacuum stripped oil is  pumped from the stripper to the
1st stage extractor (5), and enters the extractor above the mixers (near the
top of the extractor).  Water from the water storage tank (6) is pumped into
the extractor at approximately the same height as the vacuum stripped oil
(and above the mixers).  Two or more mixers provide violent agitation and
intimate mixing of the vacuum stripped oil and water.  A recycle stream draws
a portion of the oil-water mixture from approximately the height of the
mixers and returns the mixture to the extractor near the bottom, above the
level of the spent insoluble oil.  The recycle line is equipped with a heating
device to raise the temperature of the mixture from ambient to about 150°F,
                                      79

-------
oo
O
          Raw Oil
       Storage Tank
        Preheater
                          n
                                            Condenser
                                          Volatiles
            (9)
        Raw Oil
        Feed Tank
                     Vacuum Stripper or
                     Vacuum Evaporator
                                      (3)
              !3_1
                                                    Storage
                                                     Tank
                                   Reheateri
                                        Water  Soluble
I





1


1










1
c






ly
->-
A

n
Q-


(5)



— L
r—
— L




1
1.


c*>


T
« * 1


                                                                 Recycle
                                                                         Extractor
      To
      Recycle
f MIBK Soluble
Tank C

Hoi
i
(11)
>-
~l
dup Tank Jf




/•-ION
Extractor


fK
(10)
^


Water
. . . .-^
Soluble
^/ /I C\ \ _


(16)
                                                                Holdup Tank
  MIBK
Holdup Tank
                       Column or
                       Evaporator
~»i   MIBK Soluble
   -W
                                                                              Water
                                                                             Storage Tank
                                                         MIBK
                                                       Storage Tank


                                                        Spent Oil
                                                       Storage Tank
                                                                                                 Water
                                                                                                Insoluble
                                               (14)
                                                                                  Water
                                                                                 Soluble
                                                         (17)
              /
                                                                              Product
                                                                 Vacuum     Storage Tank
                                                               Evaporator
                           Storage Tank

          Figure 40.  Separation process  IB—vacuum stripped—2  stage extraction

-------
as is necessary.   Spent  oil  droplets  descend through the  extractor  and  accum-
ulate in the bottom of the extractor.   Excess,  spent insoluble  oil  is pumped
to the spent oil storage tank  (8), while  always maintaining  a level of  spent
oil in the extractor.

       The stream  of water and  soluble  organics exits near the  top  of the
extractor and  is pumped  into a  holdup tank  (9).   The material in  the holdup
tank is pumped into the  2nd  stage  extractor (10)  at  a level  above the mixers.
Methyl isobutyl ketone (MIBK) is pumped into the extractor from the MIBK stor-
age tank (7),  at approximately  the same level as the water soluble  organic
inlet stream.  Two or more mixers  or  stirrers provide violent agitation and
intimate mixing of the water soluble  organics and the MIBK.  A  recycle  stream
draws a portion of the water soluble  organic—solvent mixture from  the  level
of the mixers  and  returns the mixture to  the extractor near  the bottom.  A
phase separation occurs  in the  extractor, with  the heavier aqueous  solution
settling to the bottom of the extractor,  and the lighter  organic  solution
moving toward  the  top of the extractor.  The aqueous solution is  removed from
the extractor  near the bottom and  is  pumped into the water soluble  holdup tank
(15), and then into the  vacuum  evaporator (16)  where the  water  soluble  organics
are separated  from the water.   The water  is vaporized and returned  to the
water storage  tank (6).   The organics are pumped into the water soluble organ-
ics—product storage tank (17).

       The organic phase from the  second  stage  extractor  exits  near the top
of the extractor and is  pumped  into the MIBK soluble-holdup  tank  (11).  The
organic phase  is then fed into  an  evaporator (or column)  (12) where the MIBK
is vaporized and then collected in the  MIBK-Holdup tank (13).   The  recovered
MIBK is then returned to the MIBK  storage tank  (7) .   The  MIBK soluble organics
are concentrated in the  evaporator and  pumped to the MIBK soluble organics—
product storage tank (14).

Process 2-A Continuous,  Simultaneous  Extraction—Raw Oil

       Starting at the left  in  Figure 41, raw pyrolytic oil, received in
barrels,-is pumped into  the  raw oil storage tank (1).  In preparation for a
processing run the raw oil is pumped  into the raw oil feed tank (2).  The raw
oil feed tank  is equipped with  a stirrer  or mixer, to provide a homogeneous
feedstock.  As the ambient temperature  decreases  the pyrolytic  oil  becomes
more viscous.  A recycle loop with a  heating device  is included to  raise the
temperature of the pyrolytic oil into the 100-130°F  range, as necessary, to
provide the proper flow  of oil.

       Raw pyrolytic oil is  pumped into the extractor (3) above the mixers
(near the top  of the extractor).   Water from the water storage  tank (4) is
pumped into the extractor at approximately  the  same  height as the pyrolytic
oil (and above the mixers).  MIBK  is  pumped into the extractor  from the MIBK
storage tank (5) at a level  below  the mixers.   Two or more mixers provide
violent agitation  and intimate  mixing of  the pyrolytic oil,  water,  and  MIBK.
A recycle stream draws a portion of the oil-water-MIBK mixture  from
approximately  the  height of  the mixers  and  returns the mixture  to the extractor
near the bottom.   The recycle line is equipped  with  a heating device to raise
the temperature of the mixture  from ambient to  about 150°F,  as  is necessary.


                                      81

-------
oo
    Raw Oil
  Storage Tank

    Reheater
                      -.    r.
                        Raw Oil
                       Feed Tank
             (6)
                            MIBK  Soluble
        Separator
                       (7)
                  Holdup Tank

                    ft	2.
       ©•	(   <»>   )
To
Recycle
                  MIBK
               Holdup Tank
                                (8)
                                 Extractor
                       Column or
                       Evaporator
                                     (_UO)  )
                                                                      Q+°
                                                                     (3)
                                                                Recycle
                                                                       Extractor
                                                            Water
                                                           Soluble
                                                                  (11)
                                                              Holdup
                                                               Tank
                                                                           (12)
  Vacuum
Evaporator
                                          Storage  Tank

                       Figure 41.   Separation process 2A—raw oil—simultaneous  extraction.
                                                                                            Water
                                                                                          Storage Tank
                                                                                             (5)
                                                                                             MIBK
                                                                                           Storage Tank
                  Water
                 Soluble
                (13)
  Product
Storage Tank

-------
       The oll-water-MIBK mixture exits near the top of the extractor and is
pumped into a separator (6).  A phase separation occurs, with the heavier
aqueous solution settling to the bottom, and the lighter organic solution
moving toward the top of the separator.  The aqueous solution is pumped from
the separator to the water soluble holdup tank (11), and then into the vacuum
evaporator (12) where the water soluble organics are separated from the water.
The water is vaporized and returned to the water storage tank (4).  The
organics are pumped into the water soluble organics—product storage tank (13).

       The organic phase from the separator exits from the top of the separa-
tor and is pumped into the MIBK soluble-holdup tank (7).  The organic phase
is then fed into an evaporator (or column) (8) where the MIBK is vaporized
and collected in the MIBK holdup tank (9).  The recovered MIBK is then
returned to the MIBK storage tank (5).  The MIBK soluble organics are concen-
trated in the evaporator and pumped to the MIBK soluble organics—product
storage tank (10).

Process 2-B  Continuous, Simultaneous Extraction—Vacuum Stripped Oil

       Starting at the left in Figure  42 , raw pyrolytic oil, received in
barrels, is pumped into the raw oil storage tank (1).  In preparation for a
processing run the raw oil is pumped into the raw oil feed tank (2).  The raw
oil feed tank is equipped with a stirrer or mixer, to provide a homogeneous
feedstock.  A recycle loop with a heating device is included to raise the
temperature of the pyrolytic oil into the 100-130°F range, as necessary, to
provide the proper flow of oil.

       The raw pyrolytic oil is pumped into a vacuum evaporator (or vacuum
stripping column) (3), to remove the volatiles.  The volatiles are components
that are vaporized at atmospheric pressure at 100°F (212°F).  They consist of
water (60-70%), acetic acid ( S20%) and small amounts of other low boiling
organic compounds.  The volatiles are condensed and pumped to the volatiles
storage tank (4).  The vacuum stripped oil is pumped from the stripper to the
extractor (5), above the mixers (near the top of the extractor).  Water from
the water storage tank (6) is pumped into the extractor at approximately the
same height as the vacuum stripped oil (and above the mixers).  MIBK is pumped
into the extractor from the MIBK storage tank (7) at a level below the mixers.
Two or more mixers provide violent agitation and intimate mixing of the vacuum
stripped oil, water and MIBK.  A recycle stream draws a portion of the oil-
water-MIBK from approximately the height of the mixers and returns the mixture
to the extractor near the bottom.  The recycle line is equipped with a heating
device to raise the temperature of the mixture from ambient to about 150°F,
as is necessary.

       The vacuum stripped oil-water-MIBK mixture exits near the top of the
extractor and is pumped into a separator (8).  A phase separation occurs, with
the heavier aqueous solution settling to the bottom, and the lighter organic
solution moving toward the top of the separator.  The aqueous solution  is
pumped from the separator to the water soluble holdup tank (13), and then into
the vacuum evaporator (14) where the water soluble organics are separated from
the water.  The water is vaporized and returned to the water storage tank  (6).
                                      83

-------
00
       OED
                                              Condenser
                                                           Volatiles
   Raw Oil
Storage Tank
        Preheater
        «-
            (8)
±
                 Raw Oil
                Feed Tank  ^r
             Vacuum Stripper or
             Vacuum Evaporator
                                                                Recycle  ,   Extractor
      To           MIBK
      Recycle   Holdup
                Column or
                Evaporator
                                                                                               Water
                                                                                              Storage Tank
                                                                                               MIBK
                                                                                              Storage Tank
                                           Storage Tank                         Evaporator


                      Figure 42.  Separation process 2B—vacuum stripped—simultaneous extraction.
                                                                                                   Water
                                                                                                   Soluble
                                                                                             ,  Product
                                                                                             Storage  Tank

-------
The organics are pumped  into  the water  soluble  organics - product storage tank
(15).

       The organic phase from the  separator  exits  from the  top of the separator
and is pumped into the MIBK soluble-holdup tank (9) .  The organic phase is
then fed into an evaporator (or column)  (10), where the MIBK is vaporized and
collected in the MIBK holdup  tank  (11).   The recovered MIBK is then returned
to the MIBK storage  tank (7).  The MIBK soluble organics are concentrated in
the evaporator and pumped to  the MIBK soluble organics-product storage tank
(12).
DESIGN OF THE PILOT PLANT

       The pilot plant  processing scheme,  in  each of the four cases is based
on  the results  of  the batch  and  continuous extraction data produced during
the laboratory  experiments.   Pilot equipment  must be large enough to provide
the data necessary to accurately scale  up  to  design a commercial pyrolytic oil
processing plant.  But  a major constraint  on  the size of the pilot plant is
the availability of the pyrolytic oil.  The basis for the sizing of the pilot
plant is given  below.   (See  Appendices  A and  B  for calculations.)

Size of Pilot Plant

       The proportions  of the input and output  streams for the four cases of
the pilot plane design  are determined by the  rate data provided by the lab
scale continuous extraction  data.   To arrive  at a flowrate for pilot plant
use, the actual residence time for each extraction method is inspected.  TABLE
28   shows the input rates in grams per  minute and ml  per minute for each
component, the  total volume  flowrate in ml per minute, the extractor volume
in  ml , and the residence time in minutes.
                    TABLE  28
INPUT RATES TO EXTRACTOR
Total
Input Rate
grains /min
Process Oil Water
1-A
1-B
2-A
2-B
10.
13.
6.
13.
60
10
19
28
22.34
23.30
9.39
15.54
Input Rate
ml /min
MIBK Oil Water
8
— 10
6.18 5
9.75 10
.72
.58
.02
.73
4
22.34
23.30
9.39
15.54
Input
Rate
MIBK ml /min
31
33
7.72 22
12.17 38
.06
.88
.13
.44
Extractor
Volume
ml
1950
1950
1950
1950
Residence
Time
Min.
62.
57.
88.
50.
77
56
13
73
Choosing a minimum residence time of 65 minutes, TABLE 29  shows the required
extractor volume for various oil input rates and total input rates.
                                      85

-------
                     TABLE  29. REQUIRED EXTRACTOR VOLUME
Input
Rate
GPM
3
4
5
6
Total Input
Rate
GPM
9
12
15
18
Extractor
Volume
Gal.
588
780
975
1170
Minimum
Oil Input Rate
Gal.
195
260
325
390
 As calculated  from TABLE  29  the  oil  input rate  (in ml per minute) is approxi-
 mately 1/3  of  the total input rate  (ml per min).  The oil input rate for  the
 pilot plant design was selected  to be 4 GPM.

 COST SUMMARY

        The  costs  for  the  major equipment necessary to conduct  tests using any
 of the 4 processing schemes  is shown in TABLE 30.  The total installed  equip-
 ment cost is $365,900.  The  pilot plant equipment cost including  instrumenta-
 tion and controls,  electrical, and piping is $508,000.   (See Appendix B).


                      TABLE   30.  PILOT PLANT -  COST  SUMMARY
Raw Oil Storage Tank
Raw Oil Feed Tank
Vacuum Evaporator (Stripper)
Extractor (1st Stage)
Separator (or Holdup Tank
Extractor (2nd Stage)
MIBK Soluble - Holdup Tank
Evaporator
MIBK Holdup Tank
MIBK Soluble - Product Storage Tank
Water Soluble - Holdup Tank
Vacuum Evaporator
Water Soluble - Product Storage Tank
MIBK Storage Tank
Volatiles - Product Storage Tank
Spent Oil - Product Storage Tank
Water Storage Tank
Total Installed Equipment Cost
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)

$9,382
9,382
39,090
48,790
23,454
48,790
9,382
46,908
3,440
4,691
9,382
87,561
7,193
3,440
4,691
4,691
5,629
365,900
Instrumentation and Controls  (9.35% of installed
                              equipment cost)                 34,200
Piping - (22.3% of installed  equipment cost)                  81,600
Electrical - (7.2% of installed equipment  cost)               26,300
Total Pilot Plant Equipment Cost                            $508,000
                                      86

-------
00
        d       IK
   Raw Oil
Storage Tank
        Preheater
        •«-
  ±
                   Raw Oil
                  Feed Tank
                   Vacuum Stripper
                        or
                   Vacuum Evaporator
           S
                                         (L_D
                                                  d
Condenser
                                                                                                   Water
                                                                                                 Storage Tank
        ,.  /
        Separator or  Holdup
        Holdup Tank   Tank
 o
      To            MIBK
      Recycle   Holdup Tank
Column or
Evaporator
                                              Storage Tank
                                                                            Vacuum
                                                                          Evaporator
                                                                                            MIBK
                                                                                           Storage Tank
                                                                                                  Spent Oil
                                                                                                 Storage Tank
                                                                                                       Water
                                                                                                      Soluble
                                                                                                   Product
                                                                                                 Storage Tank
                         Figure 43.   Pyrolysis oil pilot plant schematic—continuous process.

-------
                                  SECTION 7

                 DESIGN AND  ECONOMICS OF COMMERCIAL SIZE PLANT
 PROCESS DESCRIPTION

        The four  processing schemes examined at the pilot plant scale are fur-
 ther investigated  at  the size of a commercial facility.  A component by com-
 ponent description of the four processes  is  given in Section 6.  Flow sheets
 for the four  separation processes are shown in Figures 39 through 42.  At this
 preliminary stage  of  the process design, the commercial size plant and the
 pilot plant differ only in the size of the major process equipment.  The pro-
 cess descriptions  remain the same.

 DESIGN BASIS

        The full  scale, commercial pyrolytic oil processing plant is based on
 the availability of pyrolytic oil.  The oil will be provided by one or more
 wood pyrolysis plants.  It is possible that future pyrolytic oil processing
 plants will use  oil produced from sources other than wood - other agricultural
 or  cellulosic materials, or municipal refuse - but for the purposes of this
 design only wood pyrolysis will be considered.

        Georgia Tech has had considerable experience with the Georgia Tech -
 Tech-Air Corporation  pyrolysis system, which produces char and pyrolytic oil
 by  the pyrolysis of wood.  Although other processes are available to produce
 pyrolytic  oil, no  other process has performed reliably on a continuous basis
 over an extended period of time.  The Tech-Air Corporation has operated a
 pyrolysis  plant, using the Georgia Tech - Tech-Air process over a period of
 several years in South Georgia.  That plant had a nominal processing rate of
 1-1/2  to 2  tons  per hour of dried wood material.  In addition the Stanford
 Research Institute (SRI) stated that the Georgia Tech - Tech-Air technology
 was  the closest  to commercialization of all the processes investigated  [24].
 Therefore,  the Georgia Tech Pyrolysis Process [6] will be used as a basis for
 the  supply  of pyrolytic oil.

        Preliminary design calculations have been made to scale the Georgia
 Tech pyrolysis process up to anywhere from 3.5 tons per hour to several hun-
 dred tons per hour, based on a dried wood feed material.  SRI uses a plant
 size of 1,000 ton per  day , dry wood feed rate, or approximately 42  tons per
hour.  The  SRI study  used four  10 ton per hour  (dry  feed rate) pyrolyzers
 operating  in parallel.

       Since the size of the largest operating pyrolysis plant to date  is only
1-1/2 to 2  tons  of dried feed per hour, it is not likely that the next


                                      88

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generation of pyrolyzers will be scaled up to 10 tons per hour.  An interme-
diate size in the range of 3.5 to 7 tons per hour will probably be built and
tested for a period of time.  It is estimated that the data currently avail-
able will permit the construction of a nominal 5 ton per hour pyrolyzer with
limited risk regarding performance.  It has been projected that 5 ton per hour
pyrolyzer is large enough to adequately provide a return on the capital
investment, while minimizing the unknowns associated with scale up.

       Therefore it is projected that five  5 ton per hour (dry feed rate)
pyrolysis plants will provide oil to the pyrolytic oil processing plant.  The
pyrolysis plants are estimated to operate with an 18% oil yield based on the
dry feed rate to the pyrolyzers, with an operating year of 345 days.  Thus the
oil processing plant must be located in proximity to 25 tons per hour of
pyrolysis processing capacity.  This requirement is conservative when compared
to the SRI scenario of individual pyrolysis plants of 42 tons per hour.  Based
on the conditions above, one 5 ton per hour pyrolysis plant will produce
14,904,000 pounds of oil per operating year or 1,419,400 gallons per year.
The combined output of the 5 pyrolysis plants is 74,520,000 pounds per year or
7,097,000 gallons per year.

ECONOMICS AND FEASIBILITY

       The economic feasibility of each process discussed in Section 6 has
been considered for a commercial size plant.  This analysis included total
capital investment with equipment costs, manufacturing and product costs,
depreciation and estimated income.

       Itemized equipment posts and equipment sizing calculations are included
in Appendix C.  Each of the processes (1A, IB, 2A, 2B) were treated as a sep-
arate case.  Cost summaries for the major equipment for each of the processes
are~given in Appendix C and in TABLES 31-34.  The total installed equipment
costs for each of the processes are:  1A, $1,127,000; IB, $1,172,000; 2A,
$1,025,000; and 2B, $1,036,000.  The equipment costs are included in the
direct costs of the total capital investment.

       The total capital investment, which included direct and indirect costs
and working capital, were calculated for each process and are summarized on
pages^93-96.  The manufacturing and total product costs which include raw
materials, labor, utilities, maintenance, operating supplies, laboratory costs
and direct production costs are summarized on pages 97-100.  Depreciation is
discussed on pages 101-102.

       In order to arrive at estimated current selling prices for potential
chemical fractions from pyrolytic oil, prices for similar organic substances
were selected and used from the Chemical Marketing Reporter of December, 1979.
Income,-,was calculated for a minimum, average and maximum selling price, and
thes^ results are summarized on pages 102-107.  The rate of return analysis
is presented on pages 107-116.
                                      89

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TABLE 31.  PROCESS 1A  - 2 STAGE CONTINUOUS EXTRACTION -
       RAW OIL - INSTALLED EQUIPMENT COST SUMMARY
Raw Oil Storage Tank
Raw Oil Feed Tank
Extractor - 1st Stage
Water Storage Tank
MIBK Storage Tank
Spent Oil Storage Tank
Holdup Tank
Extractor - 2nd Stage
MIBK Soluble - Holdup Tank
Evaporator
MIBK Holdup Tank
MIBK Soluble - Product Storage Tank
Water Soluble - Holdup Tank
Vacuum Evaporator
Water Soluble - Product Storage Tank
Total Installed Equipment Cost
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(ID
(12)
(13)
(14)
(15)

$187,600
9,400
91,500
31,300
8,100
136,100
39,100
99,100'
31,300
71,300
31,J300
50,000
41,900
187,600
111,000
$1,126,600

 TABLE 32.   PROCESS IB - 2 STAGE CONTINUOUS EXTRACTION -
  VACUUM STRIPPED OIL-INSTALLED EQUIPMENT COST SUMMARY

Raw- Oil Storage Tank
Raw 'Oil Feed Tank
Vacuum Evaporator - Raw Oil
Volatiles Storage Tank
Extractor - 1st Stage
Water Storage Tank
MIBK Storage Tank
Spent Oil Storage Tank
Holdup Tank
Extractor - 2nd Stage
MIBK Soluble - Holdup Tank
Evaporator
MIBK Holdup Tank
MIBK Soluble - Product Storage Tank
Water Soluble - Holdup Tank
Vacuum Evaporator
Water Soluble - Product Storage Tank
Total Installed Equipment Cost
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)

$187,600
9;400
78,200
73,500
77,800
46,900
7,500
139,500
36,000
80,800
29,100
51,600
28,100
39 , 100
36; 900
150,100
100,000
$1,172,100
                           90

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TABLE 33.  PROCESS 2A - CONTINUOUS, SIMULTANEOUS EXTRACTION -
         RAW OIL - INSTALLED EQUIPMENT COST SUMMARY
Raw Oil Storage Tank
Raw Oil, Feed Tank
Extractor
j >
Water,,; Storage Tank
MIBK Storage Tank
Separator
MIBK Soluble - Holdup Tank
Evaporator
MIBK Holdup Tank
MIBK-.Soluble - Product Storage Tank
Water. Soluble - Holdup Tank
Vacuum* Evaporator
Water Soluble - Product Storage Tank
,. Total Installed Equipment Cost
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)

$187,600
9,400
120,400
46,900
8,100
55,400
36,600
100,100
31,300
79,400
40,700
156,400
153,200
$1,025,500

TABLE 34.  PROCESS 2B - CONTINUOUS, SIMULTANEOUS EXTRACTION -
   VACUUM STRIPPED OIL - INSTALLED EQUIPMENT COST SUMMARY

Raw Oil Storage Tank
Raw Oil Feed Tank
Vacuum Evaporator
Volat,iles Storage Tank
Extractor
Water, Storage Tank
MIBK "Storage Tank
Separator
MIBK Soluble - Holdup Tank
Evaporator
MIBK Holdup Tank
MIBK "Soluble - Product Storage Tank
Water Soluble - HOldup Tank
Vacuum Evaporator
Water Soluble - Product Storage Tank
Total Installed Equipment Cost
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(ID
(12)
(13)
(14)
(15)

$187,600
9,400
78,200
73,500
83,900
37,500
6,900
41,900
28,100
65,700
23,400
111,000
36,000
134,500
118,800
$1,036,400
                              91

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 Total Capital Investment

 Direct Costs—Process  1-A  2 Stage Continuous Extraction—Raw Oil

        Purchased  Equipment—Installed  (End  '79)                $1,126,600
        Instrumentation and Controls—Installed                    105,300
           - 9.35% of Installed Equipment Costs
        Piping—Installed                                         251,200
           - 22.3% of Installed Equipment Costs
        Electrical—Installed                                       81,100
           - 7.2%  of Installed Equipment Costs
        Buildings—Including Services                              234,300
           - 20.8% of Installed Equipment Costs
        Yard Improvements                                           81,100
           - 7.2%  of Installed Equipment Costs
        Service Facilities—Installed                              446,100
           - 39.6% of Installed Equipment Costs

        Total  Direct Plant  Cost                                 $2,325,700


 Indirect Costs—

        Engineering and Supervision                             $   283,900
           - 25.2%  of Installed Equipment Costs
        Construction Expense                                       235,500
           - 20.9%  of Installed Equipment Costs

        Total Direct and  Indirect Costs                         $2,845,100

        Contractor's Fee                                           142,300
           - 5% of  Direct and Indirect Costs
        Contingency                                               284,500
           - 10% of Direct  and Indirect Costs

Fixed Capital  Investment                                       3,271,900

       Working Capital                                            363,500
          - 10% of Total Capital Investment

Total Capital Investment                                       $3,635,400
                                     92

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Direct Costs—Process IB—2 Stage Continuous Extraction—Vacuum Stripped Oil

       Purchased Equipment—Installed (End '79)               $1,172,100
       Instrumentation and Controls—Installed                   109,600
          - 9.35% of Installed Equipment Costs
       Piping—Installed                                         261,400
          - 22.3% of Installed Equipment Costs
       Electrical—Installed                                      84,400
          - 7.2% of Installed Equipment Costs
       Buildings—Including Services     ;                        243,800
          - 20.8% of Installed Equipment Costs
       Yard Improvements                                          84,400
          - 7.2% of Installed Equipment Costs
       Service Facilities—Installed                             464,100
          - 39.6% of Installed Equipment Costs
       Total Direct Plant Cost—                               2,419,800

 Indirect Costs—

       Engineering and Supervision                               295,400
          - 25.2% of Installed Equipment Costs
       Construction Expense                                      244,900
          - 20.9% of Installed Equipment Costs
       Total Direct and Indirect Costs                         2,960,100
       Contractor's Fee                                          148,000
          - 5% of Direct and Indirect Costs
       Contingency                                               296,000
          - 10% of Direct and Indirect Costs
 Fixed Capital Investment                                       3,404,100
       Working Capital                                           378,200
          - 10% of Total Capital Investment
 Total Capital Investment                                  '    $3,782,300
                                     93

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Direct Costs—Process 2A—Continuous, Simultaneous Extraction—Raw Oil

       Purchased Equipment—Installed (End  '79)               $1,025,500
       Instrumentation and Controls—Installed                    95,900
          - 9.35% of Installed Equipment Costs
       Piping—Installed                                         228,700
          - 22.3% of Installed Equipment Costs
       Electrical—Installed                                      73,800
          - 7.2% of Installed Equipment Costs
       Buildings—Including Services                             213,300
          - 20.8% of Installed Equipment Costs
       Yard Improvements                                          73,800
          - 7.2% of Installed Equipment Costs
       Services Facilities—Installed                            406,100
          - 39.6% of Installed Equipment Costs

       Total Direct Plant Cost—                              $2,117,100

Indirect Costs

       Engineering and Supervision                               258,400
          - 25.2% of Installed Equipment Costs
       Construction Expense                                      214,300
          - 20.9% of Installed Equipment Costs

       Total Direct and Indirect Costs                         2,589,800

       Contractor's Fee                                          129,500
          - 5% of Direct and Indirect Costs
       Contingency                            .                   259,000
          - 10% of Direct and Indirect Costs

Fixed Capital Investment                                       2,978,300

       Working Capital                                           330,900
          - 10% of Total Capital Incestment

Total Capital Investment                                      $3,309,200
                                     94

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Direct Costs—Process 2B—Continuous, Simultaneous Extraction—Vacuum
Stripped Oil

       Purchased Equipment—Installed (End '79)               $1,036,400
       Instrumentation and Controls—Installed                    96,900
          - 9.35% of Installed Equipment Costs
       Piping—Installed                                         231,100
          - 22.3% of Installed Equipment Costs
       Electrical—Installed                                      74,600
          - 7.2% of Installed Equipment Costs
       Buildings—Including Services                             215,600
          - 20.8% of Installed Equipment Costs
       Yard Improvements                                          74,600
          - 7.2% of Installed Equipment Costs
       Services Facilities—Installed                            410,400
          - 39.6% of Installed Equipment Costs

       Total Direct Plant Cost—                               2,139,600

Indirect Costs

       Engineering and Supervision       ,                        261,200
          - 25.2% of Installed Equipment Costs
       Construction Expense              ,                        216,600
          - 20.9% of Installed Equipment Costs

       Total Direct and Indirect Costs                         2,617,400

       Contractor's Fee                     ,                     130,900
          - 5% of Direct and Indirect Costs
       Contingency                                               261,700
          - 10% of Direct and Indirect Costs

Fixed Capital Investment                                       3,010,000
       Working Capital                                           334,500
          - 10% of Total Capital Investment

Total Capital Investment                                      $3,344,500
                                      95

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Manufacturing and Product Costs

Labor Requirements [16]—

       Process 1-A—
       Extractor—1st Stage
       Extractor—2nd Stage
       Evaporator
       Vacuum Evaporator
                                 Operating Labor
                              Men Required Per Shift

                                       1
                                       1
                                       1
                                       1
       4 men
              3 shifts i 8 hr  , $7.00
                day

       Process 1-B—
      shift
       Vacuum Evaporator
       Extractor—1st Stage
       Extractor—2nd Stage
       Evaporator
       Vacuum Evaporator
     hr
                       345 day
    operating year
                                        $231,840
                                       1
                                       1
                                       1
                                       1
                                       1
       _     i 3 shifts  i 8 hr
       j men  —5	  , . _
             1   day    ' shift
       Process  2-A—

       Extractor
       Separator
       Evaporator
       Vacuum Evaporator
             $7.00 i    345^day
               hr  ' operating year
       3  1/2  men
                  3  shifts i  8 hr
                    day
       Process  2-B—

       Vacuum Evaporator
       Extractor
       Separator
       Evaporator
       Vacuum Evaporator
      4 1/2 men
3 shifts
  day
          shift
 8 hr
shift
       $7.00
         hr
                           345 day
                           = $289,800
                                       1
                                      1/2
                                       1
                                       1
       operating year
                    3 1/2

                      | = $202,860
                                       1
                                       1
                                      1/2
                                       1
                                       1
                                                       4 1/2
$7.00 i    345 day
 hr   ' operating year
= $260,820
                                    96

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Raw Materials Cost [16] —




                                   Base          Gal/Year          $l/Year



     Process 1-A—
Pyrolytic Oil
MIBK
Process 1-B —
Pyrolytic Oil
MIBK
Process 2- A —
Pyrolytic Oil
MIBK
Process 2-B —
Pyrolytic Oil
MIBK
Utility Summary —
Basis: 100% Capacity;
Steam —

Demand (#/hr)
Cost $/#(1000)
Cost Per Year ($)
Cooling Water —
Gal/Hr
Gal /da
Cost: $/1000 gal
Cost/yr ($)
Electricity — Estimate
#/day product
kwhr/da
Cost $/kwhr
Cost/yr
.24/gal
.34/#
($2.272/gal)
.24/gal
.34/#
($2,272/gal)
. .24/gal
.34/#
($2.272/gal)
.24/gal
.34/#
($2.272/gal)

345 days /year
7,100,000
111,700
7,100,000
77,400
7,100,000
112,900
7,100,000
67,900


1-A 1-B 2-A
21,540 16
2.30 2
410,200 313
7,640 16
183,460 391
0.07 0
4,430 9
0.10 kwhr/# Product
228,700 215
22,870 21
.042
331,386 311
,440 17,510
.30 2.30
,100 333,500
,320 7,720
,760 185,370
.07 0.07
,460 4,480
[16]
,200 198,700
,520 19,870
042 .042
,825 287,916
1,704,000
253,800
1,957,800
1,704,000
175,800
1,879,800
1,704,000
256,500
1,960,500
1,704,000
154,300
1,858,300


2-B
13,360
2.30
254,400
15,670
376,140
0.07
9,080

190,700
19,070
.042
276,324
                                     97

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Process 1-A—

     Manufacturing Cost—

     Raw Materials                                          1,957,800
     Operating Labor                                          231,800
     Operating Supervision + Clerical
       - 15% of Operating Labor                                34,800
     Utilities
       Steam                                                  410,200
       Cooling Water                                            4,400
       Electricity                                            331,400
     Maintenance and Repairs
       - 7% of Fixed Capital Investment/yr                    229,000
     Operating Supplies
       - 15% of Total Cost of M + R                            34,300
     Laboratory Charges
       - 15% of Operating Labor                                34,800

     Direct Production Costs                                3,268,500

     Fixed Charges - (Depreciation, Taxes, Insurance,
       Rent) - 10% of Total Product Cost                      390,700
     Plant Overhead Costs
       - 50% of (Operating Labor+Supervision+Maintenance)    247,800

     Total Product Cost                                     3,907,000

Process 1-B—

     Manufacturing Cost—

     Raw Materials                                          1,879,800
     Operating Labor                                          289,800
     Operating Supervision + Clerical
       - 15% of Operating Labor                                43,500
     Utilities
       Steam                                                  313,100
       Cooling Water                                            9,500
       Electricity                                            311,800
     Maintenance and Repairs
       - 7% of Fixed Capital Investment/yr                    238,300
     Operating Supplies
     .  - 15% of Total Cost of M + R                            35,700
     Laboratory Charges
     ••;- 15% of Operating Labor                                43,500

     Direct Production Costs                                3,165,000

     Fixed  Charges - (Depreciation, Taxes, Insurance,
       Rent)  - 10% of Total Product Cost                      383,400
     Plant  Overhead Costs
       - 50% of (Operating Labor+Supervision+Maintenance)    285,800

     Total  Product Cost                                     3,834,200

                                    98

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Process 2-A—

     Manufacturing Cost—

     Raw Materials                                          1,960,500
     Operating Labor                                          202,900
     Operating Supervision + Clerical
       - 15% of Operating Labor                                30,400
     Utilities
       Steam                                                  333,500
       Cooling Water                                            4,500
       Electricity                                            287,900
     Maintenance and Repairs
       - 7% of Fixed Capital Investment/yr                    208,500
     Operating Supplies
       - 15% of Total Cost of M + R                            31,300
     Laboratory Charges
       - 15% of Operating Labor                 '               30.400
     Direct Production Costs                                3,089,900

     Fixed Charges - (Depreciation, Taxes, Insurance,
       Rent) - 10% of Total Product Cost                      367,800
     Plant Overhead Costs
       - 50% of (Operating Labor + Supervision+Maintenance)   220,900
     Total Product Cost                                     3,678,600

Process 2-B—

     Manufacturing Cost—

     Raw Materials                                          1,858,300
     Operating Labor                                          260,800
     Operating Supervision + Clerical
       - 15% of Operating Labor                                39,100
     Utilities
       Steam                                                  254,400
       Cooling Water                                            9,100
       Electricity                                            276,300
    *Maintenance and Repairs
       - 7% of Fixed Capital Investment/yr                    210,700
     Operating Supplies
       - 15% of Total Cost of M + R                            31,600
     Laboratory Charges
       - 15% of Operating Labor                                39.100

     Direct Production Costs                                2,979,400

     Fixed Charges - (Depreciation, Taxes, Insurance,
       Rent) - 10% of Total Product Cost                      359,400
     Plant Overhead Costs
       - 50% of (Operating Labor+Supervision+Maintenance    255,300

     Total Product Cost                                     3,594,100

                                     99

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Depreciation

       The depreciation over the 10 year life of the plant is shown for each
of the four processes in TABLES 35 to 38.  The tables give the annual and
cumulative depreciation based on the double-declining balance method for the
first five years with a switch to straight line depreciation for the remaining
five years.  The total depreciable amount includes (installed):  equipment,
instrumentation and controls, piping, electrical,  buildings and services, yard
improvements, service facilities and land.  The total direct plant costs for
each process are shown below:

               Process 1A              $2,325,768
               Process IB               2,419,277
               Process 2A               2,117,055
               Process 2B               2,139,646
                      TABLE .35.   DEPRECIATION - PROCESS 1A

End of Year
1
2
3
4
5
6
7
8
9
10
Annual
465,154
372,123
297,698
238,159
190,527
152,422
152,422
152,421
152,421
152,421
Cumulative
465,154
837,277
1,134,975
1,373,134
1,563,661
1,716,083
1,868,505
2,020,926
2,173,347
2,325,768

                    TABLE 36.   DEPRECIATION - PROCESS IB

End of Year
1
2
3
4
5
6
7
8
9
10
Annual
483,855
387,084
309,668
247,734
198, 187^
158,550
158,550
158,550
158,550
158,549
Cumulative
483,855
870,939
1,180,607
1,428,341
1,626,528
1,785,078
1,943,628
2,102,178
2,260,728
2,419,277
                                     100

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                       TABLE 37.  DEPRECIATION - PROCESS 2A
End of Year
1
2
3
4
5
6
7
8
9
10
Annual
423,411
338,729
270,983
216,786
173,429
138,744
138,744
138,743
138,743
138,743
Cumulative
423,411
762,140
1,033,123
1,249,909
1,423,338
1,562,082
1,700,826
1,839,569
1,978,312
2,117,055
                        TABLE 38.  DEPRECIATION - PROCESS 2B
               End of Year          Annual          Cumulative
1
2
3
4
5
6
7
8
9
10
427,929
342,343
273,875
219,100
175,280
140,224
140,224
140,224
140,224
140,223
427,929
770,272
1,044,147
1,263,247
1,438,527
1,578,751
1,718,975
1,859,199
1,999,423
2,139,646

Products

       The products generated by each of the four pyrolytic oil extraction
processes are:  Process 1A—insoluble oil, MIBK soluble organics and water
soluble organics; Process IB—volatiles,  insoluble oil, MIBK soluble organics
and water soluble organics; Process 2A, water soluble organics and MIBK solu-
ble organics; and Process 2B, volatiles, water soluble organics and MIBK
soluble organics.  A survey of the prices of various chemicals was taken with
the results listed in TABLE 39.

       The volatiles contain about 68% water with about 20% acetic acid, by
weight.  The current market price of acetic acid is $0.23/lb.  The selling
price of the volatiles was estimated to be $0.23/lb of acetic acid contained
in the fraction.
                                     101

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                TABLE 39.  PRICE SURVEY OF VARIOUS CHEMICALS [18]
        Compound
Alcohol  (Synthetic)-(C-12  to  C-15)

Acetic Acid
Acetic Anhydride
Acetyldehyde
Acetone
MEK
Ethyl Atnyl Ketone
MIBK
Mineral Spirits
Naptha (VM + P)               ,-•
  (Varnish + Paint Makers)

Tallow (Fatty Acids-Tech)
Tall Oil (Crude)
Napthol (Tech)
Lacquer Diluent-Pet. Base
                                                          Price
                                                $/lb
                        $/gal
Benzene
Cyclo Hexane
Toluene
Toluene (Coal Tar)
Xylenes
Ortho-Xylene
Para-Xylene
Meta-Xylene
Cumene
Napthalene
Styrene
Para-Tert-Amylphenol
Di-Tert-Amylphenol (85%)
Di-Tert-Amylphenol (95%)
Di-Tert-Amylphenol (97%)
Bis-Phenol-Polycarbonate Grade
Bis-Phenol-Epoxy Grade
Phenol (Synthetic)
Phenyl Acetate
Acetophenone
Benzaldehyde
Benzophenone
Benzyl Alcohol
Bisphenol-A Epoxy Grade
Diphenyl (99.9%)
0-Phenyl Phenol
P-Phenyl Phenol
.225
.279
.17
.19
.185
.22
.28
.31
.15
.25
.35
.74
.61
.78
.79
.61
.57
.38
1.04
.40
1.05-1.15
2.80-2.85
1.00-1.09
.47- .52
.495
1.35-2.00
1.10-1.25
1.65
1.75
1.25
1.35
1.35






















  .45

  .23
  .34
  .265,
  .26
  .31
  .38
  • 34
  .43
.32- .49
       ($150-160/ton)
 1.03
.38- .40
                         .38
                                 (continued)
                                      102

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                            TABLE 3g (continued)
            Compound
           Price
                                              $/lb
                      $/gal
Epoxy Resin
Sucrose (#2)
Asphalt
Coal Tar Pitch
Creosote-Coal Tar
Creosote (80/20 Solution)
M-Cresol (95-98%)
M,P-Cresol (90%)
M,P-Cresol (94%)
M,P-Cresol (97%)
0-Cresol (98%)
0-Cresol (99%)
P-Cresol (98%)
Cresylic Acid-Coal Tar Der.
  (Resin Grade)
Molasses
 .93
 .25

 .085
 .083
 .081
 .98
 .54
 .55
 .70
 .55
 .555
1.08

 .54
($170/ton)
.55-.65

  .83
  .81
      ($26/100#)
       The insoluble oil product is a heavy oil, somewhat similar to Bunker C.
It was estimated to be comparable to coal tar pitch ($170 per ton or $0.085
per pound) or creosote - coal tar ($0.83 per gallon or $0.08 per pound).  The
insoluble oil fraction was given a selling price of $0.08 per pound in the
minimum selling price case and a selling price of $0.09 per pound in the aver-r
age and maximum selling price cases.

       The uses of the water soluble organics and the MIBK soluble organics,
the major products, have been discussed in detail.  Some of the possible uses
are, to review:  a rubber oil additive, an epoxy intermediate, a resin feed-
stock, and an antioxidant additive for rubber.  Prices of similar types of
chemicals are:  Styrene - $0.35/lb, Napthalene - $0.25/lb, Acetophenone -
$0.40/lb, Bisphenol A Epoxy Grade - $0.47 to $0.52/lb, Cresylic Acid - $0.54/
Ib, 0-Cresol - $0.55/lb, M-Cresol - $0.98/lb, P-Cresol - $1.08/lb, and Mixed
Cresols - $0.54 to $0.70/lb.

       The estimated range of the selling price of the organics was $0.30 to
$0.60/lb.  These figures are based on the pounds of organics contained in a
given quantity of product solution.  Thus the water soluble organics and the
MIBK soluble organics were given a selling price of $0.30/lb for the minimum
selling price case, $0.50/lb for the average selling price case, and'1 $0.60/lb
for the maximum selling price case.

Sales Income

       As shown in the products section, the main products, the MIBK soluble
organics and the water soluble organics are estimated to have a selling price
in the range of $0.30 per pound to $0.60 per pound.  The average selling
                                     103

-------
 price,  estimated by comparing the current market price of similar chemicals,
 is  $0.50 per pound.

        The sales income, in dollars per year, is shown below for 3 cases:
 minimum selling price  ($0.30/lb), average selling price ($0.50/lb), and maxi-
 mum selling price  ($0.60/lb).  The sales figures are based on a 24 hour per
 day operation, 345 day operating year at 100% capacity.

  SALES  INCOME—MINIMUM SELLING PRICE
      Process 1-A—
       Insoluble Oil
       MIBK Soluble Organics
       Water Soluble Organics
 Basis

0.08/lb
0.30/lb
0.30/lb
  Quantity
  Produced

5049.6 Ib/hr
 877.3 Ib/hr
3603.4 Ib/hr
                                                                  $/Yr
   3,344,860
   2,179,210
   8.950,850

 $14,474,920
      Process 1-B—

      Volatiles
      Insoluble Oil
      MIBK Soluble Organics
      Water Soluble Organics
0.23/lb
0.08/lb
0.30/lb
0.30/lb
 269.1 Ib/hr
5259.3 Ib/hr
 565 Ib/hr
2873.8 Ib/hr
     512,470
   3,483,760
   1,403,460
   7,138,530

 $12,538,220
      Process 2-A—
      Water Soluble Organics
      MIBK Soluble Organics
      Process 2-B—

      Volatiles
      Water Soluble Organics
      MIBK Soluble Organics

SALES INCOME—AVERAGE SELLING PRICE
 Basis

0.30/lb
0.30/lb
0.23/lb
0.30/lb
0.30/lb
  Quantity
  Produced

6186.4 Ib/hr
2094 Ib/hr
 269.1 Ib/hr
3954.2 Ib/hr
2722.8 Ib/hr
    $/Yr

  15,367,020
   5.201,500

 $20,568,520
     512,470
   9,822,230
   6.763.440
 $16,585,670
      Process 1-A—
      Insoluble Oil
      MIBK Soluble Organics
      Water Soluble Organics
 Basis
0.09/lb
0.50/lb
0.50/lb
                                     104
  Quantity
  Produced
5049.6 Ib/hr
 877.3 Ib/hr
3603.4 Ib/hr
                                                                  $/Yr
  3,762,960
  3,632,020
 14,918.080

$22,313,060

-------
    Process 1-B—

    Volatiles
    Insoluble Oil
    MIBK Soluble Organics
    Water Soluble Organics
0.23/lb
0.09/lb
0.50/lb
0.50/lb
 269.1 Ib/hr
5259.3 Ib/hr
 565 Ib/hr
2873.8 Ib/hr
    512,470
  3,919,230
  2,339,100
 11,897,530

$18,668,330
     Process 2-A—
     Water Soluble Organics
     MIBK Soluble Organics
 Basis

0.50/lb
0.50/lb
  Quantity
  Produced

6186.4 Ib/hr
2094 Ib/hr
                                                                 $/Yr
  25,611,700
   8,669,160
 $34,280,860
     Process 2-B—

     Volatiles
     Water Soluble Organics
     MIBK Soluble Organics
0.23/lb
0.50/lb
0.50/lb
 269-1 Ib/hr
3954.2 Ib/hr
2722.8 Ib/hr
     512,470
  16,370,390
  11,272,390
  28,155,250
SALES INCOME—MAXIMUM SELLING PRICE
     Process 1-A—
     Insoluble Oil
     MIBK Soluble Organics
     Water Soluble Organics
     Process 1-B—

     Volatiles
     Insoluble Oil
     MIBK Soluble Organics
     Water Soluble Organics
     Process 2-A—
     Water Soluble Organics
     MIBK Soluble Organics
 Basis
0.09/lb
0.60/lb
0.60/lb
0.23/lb
0.09/lb
0.60/lb
0.60/lb
 Basis
 0.60/lb
 0.60/lb
                                                                 $/Yr
  Quantity
  Produced
5049.6 Ib/hr   3,762,960
 877.3 Ib/hr   4,358,430
3603.4 Ib/hr  17,901,690

             $26,023,080
 269-1 Ib/hr
5259.3 Ib/hr
 565 Ib/hr
2873.8 Ib/hr
    512,470
  3,919,230
  2,806,920
 14,277.040

$21,515,660
  Quantity
  Produced

 6186.4  Ib/hr
 2094  Ib/hr
     $/Yr

   30,734,040
   10.403,000

  $41,137,040
                                    105

-------
       Process 2-B—

       Volatiles                   0.23/lb       269-1 Ib/hr       512,470
       Water Soluble Organics      0.60/lb      3954.2 Ib/hr    19,644,470
       MIBK Soluble Organics       0.60/lb      2722.8 Ib/hr    13.526.870
                                                               $33,683,810

RATE OF RETURN ANALYSIS

       To obtain a rate of return discounted cash flow for the life of the
plant, the following method was adopted:  the plant life was assumed to be ten
years beginning at year zero with the total initial investment spread over one
year and ending at year zero.

       Although an operating plant would be brought to full capacity gradually
(i.e., 50% capacity 1st year, 75% capacity 2nd year, 100% capacity 3rd year
on), for simplicity of calculation it was assumed that the plant would operate
at  100% capacity over the 10-year period.

       It was assumed that the initial investment was the sum of the fixed
capital investment plus working capital.  At the end of year 10, salvage was
assumed to be zero, but the working capital would be recovered.

       The depreciation schedules were calculated using the double-declining
balance method for the first five years, switching to straight line deprecia-
tion for years 6-10.

       Cash flows were calculated for each of the four processes before and
after taxes, and are presented in TABLES 40 through 48.  Taxes are 46% of
gross profit.   The average annual profit and return on investment (ROI) were
calculated on an after tax basis.

       For each process two cases were examined, in which annual sales income
was varied.   The change in annual sales income is based on the minimum selling
price of $0.30 per pound and the average selling price of $0.50 per pound of
the soluble organic products.  The ROI for each of the cases is shown in
TABLE 40 and expressed as a percent.
      	TABLE 40.  RETURN ON INVESTMENT—SUMMARY	

       Process                           	Product Selling Price
                                         $0.30/lb                 $0.50/lb
1A
IB
2A
2B
156.31%
123.60%
274.95%
209.10%
272.74%
211.12%
498.72%
395.90%
                                     106

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TABLE  41.   CASH  FLOW—PROCESS 1-A— Case  I—$0.30/lb


Year
0
1
2
3
4
5
6
7
8
9
10


Deprec.

465,154
372,123
397,698
238,159
190,527
152,422
152,422
152,421
152,421
152,421
Cumulative
Cash Position
Before Taxes
(3,635,416)
7,397,598
18,337,581
29,203,139
40,009,158
50,767,545
61,487,827
72,208,109
82,928,390
93,648,671
104,368,952
Gross
Profit -
Dep.

10,102,706
10,195,737
10,270,162
10,329,701
10,377,333
10,415,438
10,415,438
10,415,439
10,415,439
10,415,439


Taxes

4,647,245
4,690,039
4,724,275
4,751,662
4,773,573
4,791,101
4,791,101
4,791,102
4,791,102
4,791,102
Gross
Profit -
Taxes

5,920,615
5,877,821
5,843,585
5,816,198
5,794,287
5,776,759
5,776,759
5,776,758
5,776,758
5,776,758
Net Profit
+
Deprec.

6,385,769
6,249,944
6,141,283
6,054,357
5,984,814
5,929,181
5,929,181
5,929,179
5,929,179
5,929,179

Cash Position
After Taxes
(3,635,416)
2,750,353
9,000,297
15,141,580
21,195,937
27,180,751
33,109,932
39,039,113
44,968,292
50,897,471
56,826,650
 Fixed  Capital Investment  $3,271,874
 Total  Capital Investment  $3,635,416

 Sales  (for each year)  = $14,474,920
 Manufacturing cost (for each year)  = $3,907,060
 Gross  Profit (for each year) = $10,567,860

"Average Annual Profit  = $56,826,650/10  years  = $5,682,665
 ROI  =  $5,682,665/3,635,416 * 100% = 156.31%

-------
                            TABLE 42.   CASH FLOW—PROCESS 1-A—CASE II—$0.50/lb
o
00


Year
0
1
2
3
4
5
'6
7
8
9
10


Deprec .

465,154
372,123
297,698
238,159
190,527
152,422
152/422
152,421
152,421
152,421
Cumulative
Cash Position
Before Taxes
(3,635,416)
15,235,738
34,013,861
52,717,559
71,361,718
89,958,245
108,516,667
127,075,089
145,633,510
164,191,931
182,750,352
Gross
Profit-
Dep.

17,940,846
18,033,877
18,108,302
18,167,841
18,215,473
18,253,578
18,253,578
18,253,579
18,253,579
18,253,579


Taxes

8,252,789
8,295,583
8,329,819
8,357,207
8,379,118
8,396,646
8,396,646
8,396,646
8,396,646
8,396,646
Gross
Prof it -
Taxes

10,153,211
10,110,417
10,076,181
10,048,793
10,026,882
10,009,354
10,009,354
10,009,354
10,009,354
10,009,354
Net Profit
+
Deprec.

10,618,365
10,482,540
10,373,879
10,286,952
10,217,409
10,161,776
10,161,776
10,161,775
10,161,775
10,161,775

Cash Position
After Taxes
(3,635,416)
6,982,949
17,465,488
27,839,368
38,126,320
48,343,729
58,505,505
68,667,281
78,829,056
88,990,831
99,152,605
                               Fixed Capital Investment $3,271,874
                               Total Capital Investment $3,635,416

                               Sales (for each year) =$22,313,060
                               Manufacturing cost (for each year) = $3,907,060
                               Gross Profit (for each year) = $18,406,000

                               Average Annual Profit = $99,152,605/10 years - $9,915,261
                               ROI = $9,915,261/3,635,416  *  100% - 272.74%

-------
                              TABLE  43. CASH FLOW—PROCESS  1-B—CASE  I->$0.30/lb
o
vo
Year
0
1
2
3
4
5
6
7
8
9
10


Deprec .

483,855
387,084
309,668
247,734
198,187
158,550
158,550
158,550
158,550
158,549


Cumulative Gross '-
Cash Position Prof it -
Before Taxes Dep.
(3,782,363)
5,405,512
14,496,616
23,510,304
32,462,058
41,364,265
50,226,835
59,089,405
67,951,975
76-, 814, 545
85,677,114
Fixed
Total

8,220,165
8,316,936
8,394,352
8,456,286
8,505,833
8,545,470
8,545,470
8,545,470
8,545,470
8,545,471
Capital Investment
Capital Investment
Taxes

3,781,276
3,8*25,791
3,861,402
3,889,892
3,912,683
3,930,916
3,930,916
3,930,916
3,930,916
3,930,916
= $3,404,127
- $3,782,363
Gross
Profit -
Taxes
'' .
4,922,744
4,878,229
4,842,618
4,814,128
4,791,337
4,773,104
4,773,104
4,773,104
4,773,104
4,773,104


Net Profit
+
Deprec.

5,406,599
5,265,313
5,152,286
5,061,862
4,989,524
4,931,654
4,931,654
4,931,654
4,931,654
4,931,653


Cash Position
After Taxes
(3,782,363)
1,624,236
6,889,550
12,041,836
17,103,698
22,093,222
27,024,876
31,956,529
36,888,183
41,819,837
46,751,490


                              Sales  (for each year) = $12,538,220
                              Manufacturing cost  (for each year) = $3,834,200
                              Gross Profit (for each year) = $8,704,020
                              Average Annual Profit = $46,751,490/10 years =  $4,675,149
                              ROI = $4,675,149/$3,782,363  *  100% = 123.

-------
TABLE  44.  CASH FLOW—PROCESS 1-B—CASE II--$0.50/lb


Year
0
1
2
3
4
5
6
7
8
9
10


Deprec.

483,855
387,084
309,668
247,734
198,187
158,550
158,550
158,550
158,550
158,549
	 - 	
Cumulative
Cash Position
Before Taxes
(3,782,363)
11,535,622
26,756,836
41,900,634
56,982,498
72,014,815
87,007,495
102,000,175
116,992,855
131,985,535
146,978,214
Gross
Profit -
Dep.

14,350,275
14,447,046
14,524,462
14,586,396
14,635,943
14,675,580
14,675,580
14,675,580
14,675,580
14,675*581
-- • 	 •• 	 •• -

Taxes

6,601,127
6,645,641
6,681,253
6,709,742
6,732,534
6,750,767
6,750,767
6,750,767
6,750,767
6,750,767
Gross
Profit -
Taxes

8,233,004
8,188,489
8,152,877
8,124,388
8,101,596
8,083,363
8,083,363
8,083,363
8,083,363
8,083,363
Net Profit
+
Deprec .

8,716,859
8,575,573
8,462,545
8,372,122
8,299,783
8,241,913
8,241,913
8,241,913
8,241,913
8,241,912

Cash Position
After Taxes
(3,782,363)
4,934,496
13,510,068
21,972,614
30,344,736
38,644,519
46,886,432
55,128,345
63,370,258
71,612,172
79,854,085
Fixed Capital Investment = $3,404,127
Total Capital Investment = $3,782,363

Sales (for each year) = $18,668,330
Manufacturing cost  (for each year) =$3,834,200
Gross Profit (for each year) = $14,834,130

Average Annual Profit = $79,854,085/10 years = $7,985,409
ROI = $7,985,409/$3,782,363  *  100% = 211.12%

-------
TABLE  45. CASH FLOW-PROCESS 2-A—CASE I—$0.30/lb


Year
0
1
2
3
4
5
6
7
8
9
10


Deprec.

423,411
338,729
270,983
216,786
173,429
138,744
138,744
138,743
138,743
138,743
Cumulative
Cash Position
Before Taxes
(3,309,177)
14,004,134
31,232,763
48,393,646
65,500,332
82,563,661
99,592,305
116,620,949
133,649,592
150,678,235
167,706,878
Gross
Profit -
Dep.

16,466,489
16,551,171
16,618,917
16,673,114
16,716,471
16,751,156
16,751,156
16,751,157
16,751,157
16,751,157


Taxes

7,574,585
7,613,539
7,644,702
7,669,632
7,689,577
7,705,532
7,705,532
7,705,532
7,705,532
7,705,532
Gross
Profit -
Taxes

9,315,315
9,276,361
9,245,198
9,220,268
9,200,323
9,184,368
9,184,368
9,184,368
9,184,368
9,184,368
Net Profit
+
Deprec.

9,738,726
9,615,090
9,516,181
9,437,054
9,373,752
9,323,112
9,323,112
9,323,111
9,323,111
9,323,111

Cash Position
After Taxes
(3,309,177)
6,429,549
16,044,639
25,560,821
34,997,874
44,371,626
53,694,739
63,017,851
72,340,962
81,664,073
90,987,185
   Fixed Capital Investment = $2,978,259
   Total Capital Investment = $3,309,177

   Sales (for each year) = $20,568,520
   Manufacturing cost  (for each year) = $3,678,620
   Gross Profit (for each year) = $16,889,900

   Average Annual Profit = $90,987,185/10 years = $9,098,719
   ROI = $9,098,719/$3,309,177  *  100% = 274.95%

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TABLE 46.  CASH FLOW—PROCESS 2-A—CASE II—$0.50/lb
Year
0
1
2
3
4
5
6
7
8
9
10
'

Deprec.

423,411
338,729
270,983
216,786
173,429
138,744
138,744
138,743
138,743
138,743


Cumulative Gross
Cash Position Profit -
Before Taxes Dep.
(3,309,177)
27,716,474
58,657,443
89,530,666
120,349,692
151,125,361
181,866,345
212,607,329
243,348,312
274,089,295
304,830,278
Fixed
Total

30,178,829
30,263,511
30,331,257
30,385,454
30,428,811
30,463,496
30,463,496
30,463,497
30,463,497
30,463,497
Capital Investment
Capital Investment
Gross
Profit -
Taxes Taxes

13,882,261 16,719,979
13,921,215 16,681,025
13,952,378 16,649,862
13,977,309 16,624,931
13,997,253 16,604,987
14,013,208 16,589,032
14,013,208 16,589,032
14,013,208 16,589,032
14,013,208 16,589,032
14,013,208 16,589,032
= $2,978,259
•- $3,309,177
Net Profit
+
Deprec.

17,143,390
17,019,754
16,920,845
16,841,717
16,778,416
16,727,776
16,727,776
16,727,775
16,727,775
16,727,775


Cash Position
After Taxes
(3,309,177)
13,834,213
30,853,967
47,774,811
64,616,529
81,394,944
98,122,720
114,850,496
131,578,271
148,306,046
165,033,821


  Sales (for each year) = $34,280,860
  Manufacturing cost (for each year) = $3,678,620
  Gross Profit (for each year) =  $30,602,240

  Average Annual Profit = $165,033,821/10 years = $16,503,382
  ROI = $16,503,382/$3,309,177  *  100% = $498,72%

-------
                              TABLE  47.  CASH FLOW—PROCESS 2-B--CASE I—$0.30/lb
u>


Year
0
1
2
3
4
5
6
7
8
9
10


Deprec.

427,929
342,343
273,875
219,100
175,280
140,224
140,224
140,224
140,224
140,223
Cumulative
Cash Position
Before Taxes
(3,344,489)
10,074,940
23,408,783
36,674,158
49,884,758
63,051,538
76,183,262
89,314,986
102,446,710
115,578,434
128,710,157
Gross
. Profit -
Dep.

12,563,571
12,649,157
12,717,625
12,772,400
12,816,220
12,851,276
12,851,276
12,851,276
12,851,276
12,851,277


Taxes

5,779,243
5,818,612
5,850,108
5,875,304
5,895,461
5,911,587
5,911,587
5,911,587
5,911,587
5,911,587
Gross
Profit -
Taxes

7,212,257
7,172,888
7,141,393
7,116,196
7,096,039
7,079,913
7,079,913
7.079,913
7.079,913
7.079,913
Net Profit
+
Deprec.

7,640,186
7,515,231
7,415,268
7,335,296
7,271,319
7,220,137
7,220,137
7,220,137
7,220,137
7,220,136

Cash Position
After Taxes
(3,344,489)
4,295,697
11,810,928
19,226,196
26,561,492
33,832,810
41,052,947
48,273,085
55,493,222
62,713,359
69,933,495
                               Fixed Capital Investment = $3,010,040
                               Total Capital Investment <= $3,344,489

                               Sales (for each year) = $16,585,670
                               Manufacturing cost (for each year) = $3,594,170
                               Gross Profit (for each year) = $12,991,500

                               Average Annual Profit = $69,933,495/10 years = $6,993,350
                               ROI = $6,993,350/$3,344,489  *  100% = 209.10%

-------
TABLE 48.  CASH FLOW—PROCESS 2-B—CASE II—$0.50/lb


Year
0
1
2
3
4
5
6
7
8
9
10


Deprec.

427,929
342,343
273,875
219,100
175,280
140,224
140,224
140,224
140,224
140,223
Cumulative
Cash Position
Before Taxes
(3,344,489)
21,644,520
46,547,943
71,382,898
96,163,078
120,899,438
145,600,742
170,302,046
195,003,350
219,704,654
244,405,958
Gross
Profit -
Dep.

24,133,151
24,218,737
24,287,205
24,341,980
24,385,800
24,420,856
24,420,856
24,420,856
24,420,856
24,420,857


Taxes

11,101,249
11,140,619
11,172,114
11,197,311
11,217,468
11,233,594
11,233,594
11,233,594
11,233,594
11,233,594
Gross
Profit -
Taxes

13,459,831
13,420,461
13,388,966
13,363,769
13,343,612
13,327,486
13,327,486
13,327,486
13,327,486
13,327,486
Net Profit
+
Deprec.

13,887,760
13,762,804
13,662,841
13,582,869
13,518,892
13,467,710
13,467,710
13,467,710
13,467,710
13,467,709

Cash Position
After Taxes
(3,344,489)
10,543,271
24,306,075
37,968,916
51,551,785
65,070,677
78,538,387
92,006,097
105,473,807
118,941,518
132,409,927
  Fixed Capital Investment = $3,010,040
  Total Capital Investment = $3,344,489

  Sales (for each year) = $28,155,250
  Manufacturing cost (for each year) = $3,594,170
  Gross Profit (for each year) = $24,561,080

  Average Annual Profit = $132,409,927/10 years = $13,240,993
  ROI = $13,240,993/$3,344,489  *  100% = 395.90%

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       Since the ROI for each case presented in TABLE 40 is extremely high, and
not normally encountered in practice, a second method was adopted to determine
the profitability of the pyrolytic oil separation processes.  Using all the
assumptions previously stated, three rates of return were selected - 15%, 30%,
and 50%, and the selling price of the products necessary to produce this ROI
was calculated.  For this analysis the product streams were totaled and all
products were assumed to have the same selling price per pound.  The results
are presented in TABLE 49.  The rates of return are on an after tax basis.  The
required average selling price per pound of product varies from $0.0543 per
pound to $0.1063 per pound.  This corresponds to a raw pyrolytic oil cost
(feedstock) of $0.24 per gallon, based on $2.30 per MM BTU, or $0.023 per
pound.
	TABLE  49. MINIMUM SELLING PRICE PER POUND TO JUSTIFY INVESTMENT	

Process   Average Annual     Price Per Pound of Product to    Total Product
          Profit Required       Generate the Given ROI          106 Ib/yr
                               15%        30%        50%

  1A        $  545,300       0.0543                               78.91
             1,090,600                  0.0671
             1,817,700                             0.0842

  IB           567,400       0.0569                               74.23
             1,134,700                  0.0711
             1,891,200                             0.0899

  2A           496,400       0.0587                               68.56
               992,800                  0.0721
             1,654,600                             0.0899

  2B           501,700       0.0686                               57.51
             1,003,300                  0.0847
             1,672,200                             0.1063
                                     115

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                                 SECTION 8

                                 DISCUSSION


 PYROLYSIS  OF LIGNOCELLULOSIC MATERIALS AND PROPERTIES OF THE OILS

        The pyrolysis of lignocellulosic and similar materials produces char,
 organic substances, water and gases.  Condensation of the off-gas stream from
 the pyrolysis will yield an organic phase and an aqueous phase.  Pyrolysis of
 pine sawdust on  a batch basis and the products has been described in detail
 [11].   The oils  produced from pyrolytic processes were the focus of this
 investigation with the emphasis on characterization and maximum resource-
 recovery by processing to produce more useful fractions for chemical appli-
 cations.

        Pyrolytic oils contain a wide spectrum of organic compounds, both
 aromatic and aliphatic.  Most of these compounds are oxygenated, and cpnse-
 quently, the oils contain many functional groups.  The oils must be consid-
 ered therefore as a chemical feedstock and as a source of chemical materials
 for industrial applications.  In order to develop the potential of pyrolytic
 oils as a  chemical feedstock, characterization of chemical and physical
 properties of the pyrolytic oils is absolutely necessary.  The data from the
 characterization of the oils can then be used in the development of processes
 for the oils to  yield fractions that have chemical applications or that can
 be  further refined or processed to yield useful chemical products.

        The production of pyrolytic oils is an important and significant fac-
 tor in  the overall utilization of these oils.  Some of the factors that
 affect  the quality and characteristics of the oils are feed materials,
 pyrolysis  mode (vertical bed reactor, flash pyrolysis, fluidized bed reactor,
 etc.),  pyrolysis conditions (temperature, presence or absence of air, feed
 material size, etc.) and recovery mode from the off-gas stream.  For this
 investigation, the oils were obtained from the Tech-Air Corporation's 50 dry
 ton/day pyrolysis facility and the pyrolysis pilot plants on the Georgia Tech
 campus which  utilize the Georgia Tech process [6, 7].  Oils obtained from
 pilot plants  and field demonstration units which operate on a continuous
 basis at steady  state conditions are representative of the oils that would
be produced  on a commercial scale.  Therefore, the results and data obtained
 from a study with these oils will be more applicable in the processing and
recovery of useful products from commercially produced pyrolytic oils.

       Pyrolytic oils from the Tech-Air 50 dry ton/day facility have been
thoroughly characterized as to overall general properties such as heating
value, elemental content, acidity, etc., and these results have been reported
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[12].  In general, the oils are dark brown  to black and have a pungent, burnt
odor.  The viscosity of the oils will depend upon  the amount of water present
in the oils.  The water is well emulsified  and does not separate on standing.
With a water content of 25% or greater  the  oils are relatively thin and free
flowing.  Oils which are essentially free of water are viscous, and some have
a grease-like consistency at ambient temperature.  The viscosity decreases
with temperature for short periods of heating.  The oils are heat sensitive
and prolonged heating will result in increasing viscosity with eventual for-
mation of solids.  The oils are combustible and can be burned very satisfac-
torily with the proper burner.  Burning tests of the oils admixed with fuel
oil and with char have been very satisfactory.  The oils are acidic and exhi-
bit corrosive properties.  This characteristic must be taken into account in
the storage and processing of the oils.
  f\  ">
ANALYSIS-1AND CHARACTERIZATION OF PYROLYTIC  OILS

       The pyrolytic oils are a complex mixture of organic compounds with a
wider range in boiling point from highly volatile substances to very high
boiling substances.  The oils contain oxygen in the range of 20 to 40 percent,
and therefore, there is a large number  of oxygen containing compounds present
which have a variety of organic functional  groups  such as carbonyl, hydroxyl,
ether, etc.  The oils are heat sensitive and begin to decompose at 175° to
200°C.  The chemical and physical analysis  of pyrolytic oils therefore is not
a simple task.  It is very difficult to analyze the oils, or fractions obtained
frotethe oils, for chemical content as  to classes  of organic compounds and as
to functionality.  This aspect of this  project has been very difficult, and
there is a need for additional work in  the  chemical analysis of pyrolytic oils.
      !.                             • ''
=fe '   r For overall properties of pyrolytic  oils, many of the ASTM methods are
applicable to pyrolytic oils.  The tests used in characterizing and analyzing
pyrolytic oils from the Tech-Air Cordele development unit are given in TABLE 2.
The distillation test, ASTMD-86, is not too useful as most of the oils start
to decompose at the point when approximately 50 to 60 percent of the oil has
distilled.  The development of more meaningful tests will be necessary as pyro-
lytic oils find greater utility as fuels.

..-(.:>:; .•*...• The chemical composition of the  pyrolytic oils are of importance and
significance in developing processing methods for  the oils.  A knowledge of
thercomponents in the oils will serve as guidelines for devising processing
methods for separation of the oils into fractions  containing a major chemical
class of substances, i.e., phenolics.   The  oils are chemically complex and
contain a wide variety of aliphatic, aromatic and  heterocyclic compounds.  The
analytical techniques that are very useful  and valuable in determining the
composition of the oils are liquid chromatography  (LC), gas chromatography
(GC), thin layer chromatography (TLC),  gas  chromatography/mass spectroscopy
(GC/MS), and infrared spectroscopy. .

       Considerable effort was placed on both liquid and gas chromatography in
this investigation and both were used extensively  in this work with the oils.
LC is an excellent analytical technique for these  oils as it is carried out at
ambient temperature,'is capable of high resolution of complex organic mixtures
and component detection is nondestructive.  The oils are heat sensitive,  and

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 hence, LC is particularly useful with these oils.  In addition, the pyrolytic
 oils are soluble in organic-water solvent systems which are very useful in LC.
 A variety of LC columns and conditions were tested in determining suitable
 conditions for analyzing pyrolytic oils.  Particular interest was in using LC
 as a "finger-printing" method for the oils and fractions obtained from them
 by various processing techniques.  A Partisil ODS 5p column with a water-
 acetonitrile solvent system and a flow rate of one ml per minute was found to
 produce very satisfactory chromatograms.  In Phase III of the experimental
 work, the column used for LC was a 25 cm Spherosal ODS CIQ column.  The most
 useful ultraviolet detector settings are 280 nm and 254 nm for our purposes.
 LC was used throughout this investigation for the "finger-printing" of the
 oils and fractions of the oils obtaining by different processing methods.

        Gas chromatography (GC) offers an excellent technique for analyzing
 complex mixture of organic compounds.  The disadvantage with GC with pyrolytic
 oils is the heat sensitivity of the oils since GC analysis involves tempera-
 tures up to 250°C for these oils.  Recognizing this as a possible constraint:,
 GC should be useful for analysis of fractions containing more volatile compo-
 nents, of water soluble components and of fractions obtained in experiments
 designed to separate the raw oils into fractions containing a major chemical
 class of compounds.  A variety of column packings and conditions were tested.
 A column containing 10% methylsilicone fluid has been found to be very useful
 with the raw oils and fractions with higher boiling components, and a column
 containing 10% Carbowax 20M has been found satisfactory for low boiling com-
 ponents.  In Phase III of the experimental work, a Pora Pak Q column was used
 for water and water soluble organics.

        Thin layer chromatography was utilized in Phase III of the experimental
 program as it offered a very rapid and useful technique for analyzing the dif-
 ferent phases and fractions obtained in the extraction experiments.  Details
 are given in Phase III of the experimental section.

        A nonaqueous titration method was devised and used to determine the
 presence of phenolics in the oils and fractions obtained from the oils by the
 various extraction techniques.  The technique has utility with thesefoils rso
 long as the limitations are recognized.  More details are given in the exper-
 imental section,  Phase III.

        In our'attempts to analyze the pyrolytic oils, and particularly the
 fractions obtained from the oils by the various processing techniques, the
 data from LC,  TLC,  IR, GC and nonaqueous titration were used and evaluated.
 The most promising avenues for improving the chemical analytical data with
 the fractions  obtained from the oils are to correlate the components obtained
 in GC,  LC and  TLC with GC/MS and IR data.  For pilot work with pyrolytic oils,
 there is a need for rapid analytical techniques to follow the process during
 actual  operation.   TLC may offer a potential method for this need.

 DISTILLATION

        The distillation of complex liquids is a widely used process  that has
 reached  a high  degree of sophistication in the chemical industry.  Therefore,
'distillation offers a possible method for processing and refining pyrolytic
 oils.  It is  particularly useful for obtaining  fractions with  fairly close

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boiling range.  A number  of  distillation  experiments were  conducted with  the
raw oils.  These included distillation  at atmospheric pressure, and at
0.2 - 0.4 mm mercury,  fractional  distillation at  reduced pressure, steam  dis-
tillation and vacuum stripping.

       The distillation of the raw  oils at both atmospheric and low pressures
would yield from 55 to 65 percent distillate.  The  charge  in the flask would
become more viscous as the distillation proceeded,  and when 55 to 65 percent
had distilled,  the remaining oil  in the flask would begin  to decompose and
smoke.  In some cases, the charge would decompose quickly  with an evolution
of gases.  From these  experiments,  it was concluded that distillation of  the
raw oils was not a suitable  first step  for processing the  oils.

       The distillate  from a simple vacuum distillation of raw pyrolytic  oil
was^fractionated at approximately 2 mm pressure.  The distillation did not
yield any fractions with  a close  boiling  range.   The liquid chromatograms of
the fractions indicated,  however, that  the more polar and  water soluble com-
ponents were concentrated in the  low boiling fractions whereas the less polar
components were concentrated in the higher boiling  fractions.  A sample of
water-insoluble oil, which had been prepared by the water  extraction of vacuum
stripped oil, was distilled  at approximately 6 mm pressure.  Approximately,
47 percent of the sample  distilled  from 50°C up to  193°C,  and no close-boiling
fractions were  obtained.   Analysis  of the five fractions by TLC, LC, and  IR
indicated that  the first  four fractions,  approximately 29  percent of the,
charge, contained mainly  phenolic aromatics and phenolic ethers.  The chemical
analyses indicated that fraction  5,  boiling point range 175° - 193°C and
approximately 17 percent  of  the charge, contained mainly phenolic ethers  and
aromatic neutrals with a  trace of polyhydroxy neutral compounds.  The results
with the distillation  of  fractions  obtained from  raw pyrolytic oil samples  ,
show that distillation of oil fractions produced  from raw  oil by other separa-
tion techniques can be used  to yield more highly  refined chemical materials.

   F  j .Steam distillation of pyrolytic oil samples  showed  that a relatively
small amount of the oils  were steam distilled.  The steam  distillate contained
more polar and  water soluble components of the oil.  The liquid chromatogram
of, the steam distillate was  very  similar  to the liquid chromatograms of the
water extracts  at 25°C, 50°C and  95°C of  the oil, indicating that steam dis-
tillation and water extraction of the oils produced very similar fractions of
the oils.  These results  indicate that steam distillation  is not a suitable
processing step for the raw  oils.   Vacuum stripping of the oils .,at ambient
temperature was found  to  be  an effective  way to remove the water and some of
the volatile organics, which included the acids.

HYDROGENATION

       Hydrogenation was  considered as a  possible means of improving the  pro-
cessing characteristics of the oils.  A series of hydrogenation experiments
with raw pyrolytic oil samples were  carried out at  4 atmospheres and 20 atmos-
pheres.   The Pd catalyst  performed  better than the  Pt catalyst.  The amount of
hydrogen absorbed was  in  the range  of 2 mg/g of oil from pine wood and 3  to 5
mg/g of oil from hardwood.   If one  assumes an average molecular weight of 150
for the oil, then approximately 0.15 mole of hydrogen is absorbed.per mole of
oil. for 2 mg of hydrogen  absorbed/g  of oil.  These  preliminary experiments at

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 relative low pressure Indicated that  hydrogenation  should not be  considered
 as an initial step in processing pyrolytic  oils.  Additional hydrogenation
 experiments should be conducted with  fractions  of oil  obtained by various
 separation techniques including some  at  higher  pressures than used  in  this
 work.

 EXTRACTION EXPERIMENTS

        Some factors that are  important and  must be  considered in  developing
 processing technology to produce fractions  of pyrolytic oil that  are suitable
 for chemical applications are the wide spectrum of  organic compounds present
 in the oils, the quantity of  each compound  is relatively low, the oils are
 heat sensitive and chemically reactive,  the solubility characteristics of  the
 oils, and the volatiles  (boiling point 100°C or less)  including water  in the
 raw oils.  Two chemical  operations  that  seemed  most appropriate to  investigate
 as processing steps were distillation and extraction.  Distillation has been
 discussed above, and based on our results fractional distillation at reduced
 pressure on oil fractions obtained  by an extraction process should  be  seriously
 considered as an operation to yield highly  refined  products.  The focus of
 the processing study and the  major  effort was with  extraction methods.  The
 study initially was based on  bench  scale experiments with five different
 approaches.   Based on the results of  these  experiments, three processes were
 selected for further investigation  with  batch processing.  For the  continuous
 extraction experiments,  two processes were  selected from the batch  processing
 studies  for  investigation with both raw  pyrolytic oil  and vacuum  stripped  oil.

 Bench Scale  Extraction Experiments

       Five  major approaches  involving extraction techniques were tested at
 the bench level.   These  approaches, which are discussed in the experimental
 section  with results,  were as follows:

       A - Extraction of oil  sequentially with  water at 25°C, 50°C  and 95°C.
       B - Extraction of oil  with sodium sulfate solution (salting  out effect).
       C - Extraction of oil  simultaneously with an organic solvent and water
            (three phase  system).
       D - Extraction of sodium hydroxide solution  at  different pH  ranges  with
           methylene chloride.
       E - Extraction of organic solvent solutions  of  pyrolytic oil with water.

       Each  of  these approaches, or  combinations, offer  possibilities that can
be  utilized  in  a  final process  that will result in  the production of fractions
of  oil for chemical  applications.   Based on some initial results  with  both raw
and vacuum stripped  oil,  it was  decided  to  use  vacuum  stripped oil  in  these
batch experiments  at the bench  level.  Treatment of the raw oil at  reduced
pressure  and  ambient temperature removes volatiles  (largely acidic) and most
of  the water.   The significant  results for  each approach are presented.

       From process  A, approximately  50% of the original raw oil  was isolated
as a water insoluble  organic  fraction, which contained about 20%  phenolics and
80% aromatic neutrals.   The separation of this  fraction into the  two major com-
pound classes is very  desirable.  Subsequent processing techniques  that  are


                                     120

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potentially useful  are  fractional distillation and other  extraction  steps.
The *3w?ee  aqueous fractions,  if combined,  would contain approximately  34% of
the original  oil with 27% phenolics  and 73% polyhydroxy neutral  substances.
A potential means for separation of  these  two chemical classes is  the  use of
the salting-out technique which is the basis of process B.   The  advantage of
process A  is  that water is a  cheap solvent and nonhazardous,  and the process
should be  relatively simple.

       Process B, which involves essentially a salting out effect  with sodium
'sulfate, offers a possibility for separation of the polyhydroxy  neutral sub-
stances.   The first step would be as depicted in Figure 28.   The aqueous
fraction contained  organics with approximately 70% phenolics.  This  separation
could possibly be improved by determining  optimum conditions.  The insoluble
fraction could be extracted with water to  remove the polyhydroxy neutral sub-
stances leaving an  insoluble  oil fraction.  The salting out  technique  has the
disadvantages of the organics having to be recovered from the concentrated
salt solution and of the recovery and recycling the salt  solution.

       :Process C, the three phase system,  offers some interesting  separation
possibilities.  It  should be  noted that the phenolics in  the oil are separated
about 50-50 in processes A and B and in process C,  Figure 29, the  aqueous
phase"contains about 50% of the phenolics  and the remaining  50%  is about
evenly-divided between  the ether phase and the insoluble  oil phase.  Fractional
distillation  of the separate  oil and ether fractions should  yield  fractions
with>high  concentration of phenolics and the aromatic neutrals.  The three
phase approach with anisole produced results as shown in  Figure  30.  The
quantities of the components  in the  aqueous fraction are  about the same as
when diisopropyl ether  was used.  The anisole,  however, dissolves  a  much
greater portion of  the  oil than diisopropyl ether.

       In  process D, two percent sodium hydroxide solution was used  as a sol-
vent for the  oil followed by  extraction with methylene chloride  at three dif-
ferent pH  ranges, 8 to  10, 5  to 7, and 1 to 3.   Approximately, 53% of  the
oil"charge dissolved in 300 ml of 2% NaOH.  The extraction with  CH2C12 at
p"Hc8 to'J10 gave predominantly aromatic neutrals whereas at the low pH  range,
the extract contained predominantly  phenolics.   Approximately 55%  of the
phenolics  were in the aqueous phase  with the remainder distributed in  the
three CHoCl2  extracts.   The remainder of the charge dissolved in 400 ml of
2% NdOH, and  the solution was extracted in the same manner as above.   It
should be  noted that in the first CH^C^ extract,  approximately  92%  of the
organics was  aromatic neutral compounds.  Also, in the aqueous phase,  approx-
imately 58% of the  organics was phenolics.  Additional bench scale work is
needed with this process to determine its  usefulness as a method of  processing
pyrolysis  oil.  This-approach has the disadvantages that  it  involves a number
of'processing steps and no one extraction  produced a clear fraction  of a given
class of compounds  present in the pyrolytic oil.

       In  process E, the organic solvents  tested were methylene  chloride and
n-bufcanol.  Two solutions of  pyrolysis oil in methylene chloride were  extracted
with water followed by  extraction of the aqueous solution in one experiment
with diisopropyl ether  and in the second experiment with  methyl  isobutyl
ketone (MIBK).  The results-are shown schematically for the  two  experiments


                                     121

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 in Figures 32 and 33,  respectively.   A significant  result  of  these  two  experi-
 ments is that the polyhydroxy neutral substances  are  concentrated in  the
 aqueous phase along with 50  to 60% of the  phenolics in  the oil.  The  methylene
 chloride fraction contains phenolics  and aromatic neutral  compounds which
 could be fractional distilled to  provide more  desirable and useful  fractions
 of the oil.   Another approach to  the  treatment of the aqueous fraction  is
 extraction with MIBK.   The extraction of the aqueous  fraction with MIBK gave
 a solution with approximately 92% phenolics, which  represents approximately 35%
 of the phenolics in the aqueous fraction.

        A solution of pyrolysis oil in n-butanol was extracted with water to
 determine the separation that would be obtained and the results  are shown
 schematically in Figure 34.   The  polyhydroxy neutral  substances  are distri-
 buted between the aqueous fraction and the n-butanol  fraction which is  not a
 desirable result.  Consequently,  this approach was  not  pursued.

  :      An examination of the  data from the process  approaches discussed above
 shows that for each approach  approximately 50% of the phenolic content  of the
 oil is in the aqueous  fraction with the remainder in  the insoluble oil  phase
 or in the organic solvent phase.  This could be of  significance  in that each
 of these phenolic fractions could have greater utility  for specific uses than
 a single combined fraction of the phenolics.   The aqueous  fractions from all
 of the approaches contain relatively  large amounts  of polyhydroxy neutral
 substances with the exception of  the  salting out  techniques.

        The aqueous  insoluble  fractions contain approximately  50% of the phe-
 nolic content of the oil along with most of the aromatic neutral compounds
 with ratios  of phenolics to aromatic  neutral compounds  in  the range of  1 to 3
 and 1 to 4.   The separation of this fraction into the two  major  classes of
 compounds could possibly be accomplished by fractional  distillation or
 extraction with an  alkaline solution.

        Careful examination of the data from the bench scale experiments with
 the five processes  and  consideration  of each overall  process  as  a continuous
 chemical process indicated that processes  A and C are the  most promising with
 process  E offering  some  potential.

 Continuous Extraction Experiments

       The extraction experiments and related  work  for  this phase of  the
 program  is described in  the Experimental Section*, Phase III.   The pyrolytic
 oil used  in  these experiments  was produced in  the Georgia  Tech pyrolysis pilot
 plant under  carefully controlled  conditions in October,  1978, from  pine cljips.

       Based  on  the  results from  the  bench scale  extraction experiments
described above,  the decision was made to  investigate further the three
extraction methods,  listed below, with both raw and vacuum stripped pyrolytic
oil.
       •Process No.  1 - Water  Extraction
       •Process No.  2 -  Simultaneous  Extraction with  Water and an Organic
                         Solvent
       •Process No.  3 - Dissolution in an  Organic Solvent  Followed  by
                        Water  Extraction

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        Additional batch experiments were conducted with 100, 200 or 500 g oil
 samples using the three approaches.  The results with Process No. 1 in this
 phase were comparable to the results in Experimental Phase II with aqueous
 extraction.  The results indicate that MIBK is a better solvent than chloro-
 form for extraction of the aqueous phase.  Based on the results and observa-
 tions of the experiments with Process No. 2, MIBK was selected as the solvent
 for the continuous extraction experiments.  Also, in these batch experiments
 with the three phase system, the insoluble tar phase was very small, 2 percent
 or less, whereas in the initial experiments with the three phase process using
 diisopropyl ether, the insoluble phase was 25 percent.  With Process No. 3, an
 insoluble tar phase was present in each experiment.  It was decided to dis-
 continue experimentation with this approach as it did not appear to offer any
 advantage over the simultaneous use of water and an organic solvent, Process
 N6.:; 2.

        The continuous countercurrent experiments were conducted with Process
 No. 1 and Process No. 2 with both raw and vacuum stripped pyrolytic oil.  Some
 Important observations from the results of the continuous extraction experi-
 ments are that the polyhydroxy neutrals are essentially concentrated in the
 aqueous phases f6r all four experiments, that the aromatic neutrals in the
 aqueous phase are extracted essentially completely into the MIBK fraction
 along with some phenolics, and that the insoluble oil phases of Process No. 1
 and the MIBK phases of Process No. 2 contain phenolics and aromatic neutrals.
 The MIBK phases and fractions and the insoluble oil phases which contain
 mainly phenolics and aromatic neutrals could be further processed by frac-
 tional distillation.  Concentration of the extracted aqueous fractions, which
 contain phenolics (approximately 15 to 30 percent) and polyhydroxy neutrals,
 from both processes could yield a solution from which additional phenolics
 could be extracted.  The results of these experiments are very promising that
 pyrolytic oils can be processed by extraction techniques to yield fractions
 that have potential for chemical applications or that can be refined through
 additional chemical processing operations.
  iiJlV XJj, '                       '
 PILOT''MANT                                        : '

        Based on the data obtained from the continuous countercurrent extrac-
 tion experiments at the bench level, a versatile pilot plant was designed which
 can be used to test the water extraction Process No. 1 arid the simultaneous
 extraction Process No. 2 with water and an organic solvent.  The processes can
 be tested with both raw oil and vacuum stripped oil at a rate of four gallons
 pef^minute.  In addition to the various extraction operations, oil fractions
• could be further processed by distillation.  The data from the continuous
 extraction experiments indicate that the1 extraction approach'is a very promis-
 ing one by which fractions of the oil can be obtained which can be processed
 by additional operations, particularly fractional distillation, to yield
 products of greater utility.  With a pilot plant, the concept can be demon-
 strated and sufficient quantities of oil fractions can be obtained for testing
 and development for industrial applications.  More details on the pilot plant
 and schematics are given in Section 6.
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ECONOMICS

       In order to make some preliminary economic assessments for processing
pyrolytic oils into materials for chemical applications, it was necessary to
base the analysis on the data from the bench scale countercurrent continuous
extraction experiments with the two processing modes with raw and vacuum
stripped oils.  The major assumptions were that pyrolytic oils, either raw or
vacuum stripped, could be processed on a continuous basis by the two proces-
sing modes and that the processing modes would yield oil fractions which would
be suitable for commercial applications.  The major objective of this analysis
was to determine if the processing of  pyrolytic  oils  appeared to be  economically
feasible.

       It was assumed the pyrolytic oil plant would process oil produced by
five wood pyrolysis plants, each processing five dry tons per hour for 345
days per year.  The yield of oil was assumed to be 18 percent on a dry weight
basis, which amounts to approximately 7,100,000 gallons per year.   The oil
was assumed to have a heating value of 10,000 Btu/lb and a density of 10 Ib
per gallon.  The cost of the oil to the plant was based on a value of $2.30
per million Btu.

       The analysis was approached in two ways.  In one method, the average
selling price per pound for the total output from each process mode was deter-
mined to provide a net return on investment (ROI) for 15, 30, and 50 percent.
The average selling price per pound for each process for this approach is
given in TABLE 50.  The significance of this analysis is that it shows that
the selling price — 8.4 to 10.6 cents per pound — for the oil fractions for
a 50 percent return on investment is in the range of quoted market prices in
December, 1979, for similar materials, such as coal tar creosote at 9 cents
per pound and well below the quoted prices for coal tar cresylic acid at 54
cents per pound.  In the other method, the analysis was made on the basis that
for case one, the oil product selling prices would be 8 cents per pound for
the insoluble oil, 23 cents per pound for the organic volatiles from the oil
stripping and 30 cents per pound for both the MIBK soluble and water soluble
organics.  In case two, the insoluble oil was 9 cents per pound, the organic
volatile fraction, 23 cents per pound and both the MIBK soluble and water
soluble organics, 50 cents per pound.  The return on investment for each case
is presented in TABLE 51.  Each specific process for each case provides an
         TABLE  50.  AVERAGE SELLING PRICE FOR PYROLYTIC OIL PRODUCTS
                                    Net Return on Investment
Process
15%
30%
50%
1A
IB
2A
2B
5.4c/lb
5.7
-------
                  TABLE 51.  RETURN ON INVESTMENT - PERCENT
          Process                  Case 1                  Case 2
1A
IB
2A
2B
156
124
275
209
273
211
499
396
excellent return on investment.  The significance of these results is that the
economic feasibility appears to be very promising for processing the oil into
products for commercialization.  In order to realize the potential for proces-
sing pyrolytic oil into chemical materials on a commercial scale,  it would be
necessary to study and obtain more data by processing pyrolytic oils with a
small scale pilot plant (see Section 6) and to investigate commercial appli-
cations for oil fractions produced with the pilot plant.  In this  way, reli-
able operating costs could be established and commercial value of  the products
could be determined.
                                     125

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                                 REFERENCES
  1,  E. Hagglund.  Chemistry of Wood. Academic Press, Inc., New York, 1952.

  2.  A. J. Hamm and E. E. Harris.  Chemical Processing of Wood.  Chemical
     Publishing Co., Inc., New York, 1953.

  3.  L. F. Hawley and L. E. Wise.  The Chemistry of Wood.  Chemical Catalog
     Co., New York, 1926.

  4.  R. H. Farmer.  Chemistry in the Utilization of Wood.  Pergamon Press,
     Oxford, 1967.

  5.  L. A. Hawley.  Wood Distillation.  The Chemical Catalog Co., Inc., New
     York, 1923.

  6.  M. D. Bowen, E. D. Smyly, J. A. Knight, and K. R. Purdy.  A Vertical Bed
     Pyrolysis System in Solid Wastes and Residues:  Conversion by Advanced
     Thermal Processes.  J."L. Jones and S. B. Radding, eds., pp. 94-125-
     ACS Symposium Series 76, American Chemical Society, 1978.

  7.  J. A. Knight.  Pyrolysis of Wood Residues with a Vertical Bed Reactor in
     Progress in Biomass Conversion, Volume 1.  K." V. Sarkanen. and D. A.
     Tillman, eds., pp. 87-115.  Academic Press, Inc., 1979.

  8.  F. L. Rissinger.  Changing Feedstocks-Chemicals or Calories? - Chemical
     Engineering Progress, 71: 30-33 (1975).

  9.  L. L. Anderson.  Energy Potential from Organic Wastes.  U.S. Department
     of the Interior.  Circular 8549 (1972).

10.  D. A. Tillman.  Wood as an Energy Source.  Academic Press, Inc., New
     York, 1978.

11.  J. A. Knight.  Pyrolysis of Pine Sawdust in Thermal Uses and Properties
     of Carbohydrates and Lignins.  F. Shafizadeh, K. V. Sarkanen and D. A.
     Tillman, eds., pp. 159-173.  Academic Press, Inc., 1976.

12.  J. A. Knight, D. R. Hurst, and L. W. Elston.  Wood Oil  from Pyrolysis of
     Pine Bark-Sawdust Mixture in Fuels and Energy from Renewable Resources.
     D. A. Tillman, K. V. Sarkanen and Larry L. Anderson,  eds., pp.  169-195.
     Academic Press, Inc., 1977.
                                     126

-------
13.  M. B. Polk.  Development of Methods for the Stabilization of Pyrolytic
     Oils.  Annual Report.  June, 1977.  Grant No. R 804 440 010.  U. S.
     Environmental Protection Agency, Cincinnati, Ohio 45268.

14.  Peters, M. S., and K. D. Timmerhouse.  Plant Design and Economics for
     Chemical Engineers, 2nd ed., McGraw-Hill Book Co., New York, N. Y., 1968.

15.  Perry, R. H., and C. H. Chilton.  Chemical Engineers Handbook, 5th ed.,
     McGraw-Hill Book Co., New York, N. Y., 1973, Sections 13, 15, 21, 23,  '
     25.

16.  Aries, R. S., and R. D. Newton.  Chemical Engineering Cost Estimation.
     McGraw-Hill Book Co., New York, N. Y., 1955, pp. 118-182.

17.  Guthrie, K. M.  Capital Cost Estimating.  In: Modern Cost-Engineering
     Techniques, H. Popper, ed., McGraw-Hill Book Co., New York, N. Y.,
     1970, pp. 80-108.

18.  Current Prices of Chemicals and Related Materials.  Chemical Marketing
     Reporter, V216 (#24): 38-48, Dec. 10, 1979.
                                                 '..'
19.  The Chemical Rubber Co. Handbook of Chemistry and Physics, 47th ed.,
     R. C. Weast, ed.  Chemical Rubber Publishing Co., Cleveland, Ohio, 1966,
     Sections C, D.

20.  Dean, J. A. Lange's Handbook of Chemistry Method.  McGraw-Hill Book Co.,
     New York, N. Y., 1974, pp. 9-85—9-96.

21.  Drew, J. W.  Design for Solvent-,Recovery.  Chemical Engineering Progress
     V71 (No. 2): 92-99, Feb. 1975.

22.  McCabe, W. L., and J. C. Smith.  Unit Operations of Chemical Engineering,
     2nd ed.  McGraw-Hill Book Co., New York, N. Y., 1967, pp. 299-321.

23.  Combustion Engineering, Inc.  Steam Tables—Properties of Saturated and
     Superheated Steam, 2nd printing, Windsor, Connecticut, 1967, 35 pp.

24.  Mission Analysis for the Federal Fuels From Biomass Program.  Volume IV:
     Thermochemical Conversion of Biomass to Fuels and Chemicals.  Report:
     Jan. 1979.  SRI International; Menco Park, CA, pp. 105-121.
                                     127

-------
                                APPENDIX A

                      MATERIAL BALANCE CALCULATIONS


LABORATORY SCALE—CONTINUOUS EXTRACTION

Process 1-A—Raw Oil-Two Stage Extraction—Total Reactant and Product Balance

Extractor—1st Stage
Raw Oil - 1998g
Nonvolatile Organics - 1698g
Volatile Organics - 140g
Water - 160g
                           ;

Water - 4120g
Aqueous Phase - 4806g
Nonvolatile Organics - 808g
Volatile Organics - 108.7g
Water - 3889.3g


Insoluble Oil Phase - 1121g
Nonvolatile Organics-818g
Volatile Organics - 25.3g
Water - 211.1%
                            Apparent Losses - 191g
                            Nonvolatile Organics - 72g
                            Volatile Organics - 6.0g
                            Water - 113g
                                     128

-------
                      TABLE A-l.  FLOWRATES—RUN NO. 1-A
HP-29C — Linear Curve Fit*
The data is fitted to a straight line (linear regression) .  The form of the
equation is shown below, with x = time, (min.)» y = accumulated stream input
or output (grams) .
                                 y = a + bx
Raw Oil Input Rate
      n = 21

Water Input Rate
      n = 13

Aqueous Phase Output Rate
      n = 21

Insoluble Oil Output Rate
      n = 9
                                           a  = 10.949
                                           b  = 10.5964 grams/min
                                           r2 = 0.99732
                                           a  = 8.0936
                                           b  = 22.3411 grams/min
                                           r2 - 0.9985
                                           a  = -4.785531
                                           b  = 26.3342 grams/min
                                           r2 - 0.9983
                                           a  = -105.51
                                           b  = 5.831 grams/min
                                           r2 - 0.9604
 Hewlett-Packard HP-19C-29C Applications Book, p. 102-106.
                                     129

-------
        TABLE A-2.   SEPARATION PROCESS 1-A—RAW OIL--2 STAGE EXTRACTION--
                    CUMULATIVE REACTANT AND PRODUCT WEIGHTS
Time
Min.
0
5
10
20
30
50
60
65
70
80
90
100
110
120
130
140
150
160
170
180
185
Input
Raw Oil*
g
0
61
126
237
361
534
607
667
760
906
1001
1092
1165
1231
1328
1446
1643
1741
1789
1935
1998

Water
g
0
120
250
470
570
1000
1190
1360
1570
1830
2000
2250
2460
2630
2880
3150
3420
3620
3820
4000
4120
Output
Aqueous Phase
g
0
115
292
594
813
1209
1439
1605
1861
2158
2449
2679
2960
3127
3336
3732
3982
4170
4482
4785
4805

Oil
g
0
-
-
-
89
-
200
226
-
-
369
-
-
512
-
-
738
-
-
927
1121
 Raw Oil Density = 1.215 g/ml
Process 1-B—Vacuum Stripped Oil—Two Stage Extraction—Total Reactant and
Product Balance
	•	— '• i "•'•	•	•	  	— — i ..             \

Vacuum Evaporator-(Stripper)—
Raw Oil - 1932g
Water - 226.3g
Organics - 1705.7g

Steam
	 Volatiles - 284g
       Water - 226.3g
       Organics - 57.7g

167°F  Vacuum Stripped Oil - 1648g
       Nonvolatile Organics-1621g
       Volatile Organics - 27g
                                           75°C
                                     130

-------
       The raw pyrolytic oil had a water  content of 11.712% and an organics
content of 88.288%.  The purpose of  the stripping operation was to remove the
water from the pyrolytic oil.  However, small scale tests to strip the oil
showed that the raw pyrolytic oil had  a volatiles content of 14.7% (composed
of 79.57% water and 20.43% organics).  Thus, some organics had been volatilized
in the process of stripping the water  from  the pyrolytic oil.

Extractor-lst Stage—
Vacuum Stripped Oil-1648g
Nonvolatile Organics-1621g
Volatile Organics - 27g
Water - 2830g
       Aqueous Phase - 3194g
       Nonvolatile Organics - 667g
       Volatile Organics - 19.3g
       Water - 2507.7g

       Insoluble Oil Phase-1129g
       Nonvolatile Organics-903g
       Volatile Organics - 6.8g
       Water - 219.2g
                          Apparent Losses - 155g
                          Nonvolatile Organics - 51g
                          Volatile Organics - 0.9g
                          Water - 103.Ig
                       TABLE A-3.  FLOWRATES—RUN NO. IB
HP-29C—Linear Curve Fit*             ,,
The data is fitted to a straight line  (linear regression).  The form of the
equation is

                                 y = a + bx

where x = time (min); y = accumulated stream input or output (grams)
Vacuum Stripped Oil Rate

         n = 7

Water Input Rate

         n = 10

Aqueous Phase Output Rate
         n = 10

Insoluble Oil Output Rate

         n = 4
a  - -19.259
b  = 13.098 grams/min
r2 = 0.9741

a  = -34.406
b  = 23.297 grams/min
r2 = 0.9711

a  = -58.849
b  = 25.617 grams/min
r2 = 0.9925

a  = -34.49
b  = 8.777 grams/min
r2 = 0-9837
 Hewlett-Packard HP-19C/HP-29C Applications Book, p. 102-106.
                                     131

-------
       TABLE A-4.   SEPARATION PROCESS  1-B—VACUUM STRIPPED OIL—2 STAGE
                   EXTRACTION—CUMULATIVE REACTANT AND PRODUCT WEIGHTS
                           Input
          Output
Time
Mln.
0
10
20
50
60
70
75
90
115
130
Vacuum
Stripped Oil*
g
0
42
105
336
672
787
1113
1217
1501
1648
Water
g
0
200
490
1000
1150
1400
2000
2280
2750
2830
Aqueous
Phase
g
0
190
502
1054
1476
1606
1949
2310
3013
3194
Oil
g
0
-
-
-
402
—
657
-
-
1129
  Vacuum stripped oil density = 1.238 g/ml
 Process 2-A—Raw Oil—Simultaneous MIBK and Water Extraction—Total Reactant
 and Product Balance

 Extractor—
Raw Oil - 555.3g
Nonvolatile Organics-472g
Volatile Organics - 38.9g
Water - 44.4g
MIBK - 562g
Water - 780g
Aqueous Phase - 1153g
Nonvolatile Organics-358g
Volatile Organics - 23.6g
Water - 748.3g
MIBK - 23.1 g

MIBK Phase - 741g
Nonvolatile Organics-114g
Volatile Organics-15.2g
Water - 74.2g
MIBK - 537.6g
                           Apparent Losses - 3.3g
                           Nonvolatile Organics - Og
                           Volatile Organics - O.lg
                           Water - 1.9g
                           MIBK - 1.3g
                                    132

-------
                     TABLE A-5.   FLOWRATES—RUN No.  2-A
                     HHBH^VIBBIIBHBIIBBBHIBBVBB
HP-29C—Linear Curve Fit*
The data is fitted to a  straight  line (linear regression).   The form of the
equation is
                                  y = a + bx
where x = time (min); y  = accumulated stream input or output (grams)

Raw Oil Input Rate                          a  = 19.5851
      n - 7                                 b  = 6.19224
                                            r2 = 0.98756
Water Input Rate                            a  = -31.19097
      n = 7                                 b  = 9.38692
                                            r2 = 0.98394
MIBK Input Rate                             a  = -28.9572
      n = 7                                 b  = 6.17643
                                            r2 = 0.98622
Total Output Rate                           a  =  -74.80375
                                                 21.8058]
                                                 0.99509
n = 7                                 b   = 21.80581
                                      2
 Hewlett-Packard HP-19C/HP-29C Applications  Book,  p.  102-106.
  TABLE A-6.  SEPARATION PROCESS  2-A—RAW OIL—SIMULTANEOUS  EXTRACTION WITH
              MIBK AND WATER—CUMULATIVE  REACTANT AND PRODUCT WEIGHTS

Time
Min.
0
10
22
30
53
75
90

Raw Oil*
g
0
49.4
129.6
197.4
377.6
499.7
555.3
Input
Water
g
0
70
150
190
500
720
780

MIBK
g
0
24.1
96.5
160.8
265.3
418.0
562.0
Output
Total
g
0
140
380
534
1009
1601
1918
 Raw Oil Density = 1.234 g/ml
                                     133

-------
 Process 2-B—Vacuum Stripped Oil—Simultaneous  MIBK and Water  Extraction-
 Total Reactant and Product Balance

 Vacuum Evaporator-(Strlpper)—
 Raw Oil - 1967.2g
 Water - 230.4g
 Organics - 1736.8g

 Steam
Volatiles - 289.2g
Water - 230.4g
Organics - 58.8g

Vacuum Stripped Oil-1678g
Nonvolatile Organics-1629g
Volatile Organics - 49g
 Extractor—
 Vacuum Stripped Oil-1678g  _
 Nonvolatile Organics - 1629g
 Volatile Organics - 49g
 Water -  1900g

 MIBK  -  1198g
Aqueous Phase - 2746g
Nonvolatile Organics-735g
Volatile Organics - 31.4g
Water - 1790.Ig
MIBK - 189.5g

MIBK Phase - 1812g
Nonvolatile Organics-798g
Volatile Organics-15.7g
Water - 36.2g
MIBK  -  962:lg
                           Apparent Losses -  218g
                           Nonvolatile Organics-96g
                           Volatile Organics -1.9g
                           Water - 73.7g
                           MIBK - 46.4g
       All inputs were measured quantities, as were  the quantities  in  the
Aqueous Phase and the MIBK Phase.  The total amount  of Apparent Losses was
found by difference.  Nonvolatile Organic content of the Aqueous Phase and
the MIBK Phase was measured.  Nonvolatile Organic content  in Apparent  Losses
was determined by difference.

       The remaining constituents of Apparent Losses  (solvents and volatile
organics) were calculated as explained below.  Losses occurred by two  methods,
spillage and evaporation.  It was assumed that the losses  due to spillage
were much greater than the losses due to evaporation.  Thus, the losses  of
                                     134

-------
solvents and volatile organics of "apparent losses" will occur in the same
proportion as their proportion in the well-mixed extractor fluid.

       The percentage of volatile organics in each of the output streams was
estimated to be the same as the percent volatile organics in the solvents
and volatile organics portion of the input stream.

       The four remaining components were the amounts of water and MIBK in
both the aqueous and the MIBK phases.  As stated previously the extractor
effluent was a well mixed dispersion.  The effluent was allowed to stand
overnight to separate into 2 phases.  But even after overnight settling,
some MIBK remained dissolved and/or mixed in the Aqueous Phase and some
water remained dissolved and/or unseparated in the MIBK phase.  For design
purposes it was estimated that the water content of the MIBK phase was 2%.
The remainder of the mass balance was calculated.  The resulting MIBK content
of the aqueous phase was 6.9%.
                      TABLE A-7.  FLOWRATES—RUN NO. 2-B
HP-29C  Linear Curve Fit*
The data is fitted to a straight line  (linear regression).  The form of the
equation is

                                y = a + bx

where x = time (min) ; y = accumulated stream input or outp.ut, (grams).


Vacuum Stripped Oil Rate                   a  = -45.7056
           0                               b  = 13.2809
       n = o                                «
                                           r  = 0.99105

Water Input Rate                           a  = 1.55937
                                           b  = 15.540
       n = 12                               7
                                           r  = 0.9944

MIBK Input Rate                            a  = 48.94185
                                           b  = 9.74807
       n = 11                               9
                                           r  = 0.97695

Total Output Rate                          a  = -197.6378
                                        !   b  =''38.4628

       n = 9                               r2 = 0.961935


*Hewlett-Packard HP-19C/HP-29C Applications Book, p. 102-106.
                                    135

-------
     TABLE A-8.  SEPARATION PROCESS 2-B--VACUUM STRIPPED OIL—SIMULTANEOUS
                 EXTRACTION WITH MIBK AND WATER—CUMULATIVE REACTANT
                 AND PRODUCT WEIGHTS

Time
Min.
0
10
30
45
60
70
80
90
100
115
120
125
Input
Vacuum Stripped Oil
g
0
30
70
347
595
864
983
1092
1231
1469
1614
1678

Water
g
0
160
480
670
920
1000
1320
1460
1620
1800
1820
1900

MIBK
g
0
24
281
458
723
804
892
973
1045
1138
1164
1198
Output
Total
g
0
213
Ilk
1113
1858
2159
2551
3650
4116
4255
4306
4558
*
 Vacuum Stripped Oil Density = 1.238g/ml
                                     136

-------
                                 APPENDIX B

                          PILOT PLANT CALCULATIONS


MAJOR EQUIPMENT—MATERIAL BALANCES

Process 1-A—Raw Oil—Two Stage Extraction

Extractor—1st Stage
Raw Oil - 2432.6 Ib/hr
Nonvolatile Organics -
       2067.3 Ib/hr
Volatile Organics
        170.5 Ib/hr
Water - 194.8 Ib/hr


Water - 5016.2 Ib/hr




Aqueous Phase-6083.9
Nonvolatile Organics
1071.4 Ib/hr
Volatile Organics -
139.7 Ib/hr
Water - 4872.8 Ib/hr
Insoluble Oil Phase
1364.8 Ib/hr
Nonvolatile Organics
995.9 Ib/hr
Volatile Organics-30
Water - 338.1 Ib/hr
Ib/hr
.8 Ib/hr
       Raw Oil = 4 gal/min
                               ft'
                                      62.4 Ib
                                        ft'
                                               1.215
60 min
  hr
= 2432.6 Ib/hr
                            7.48 gal

Nonvolatile Organics = 2432.6 Ib/hr  |1698/1998| = 2067.3 Ib/hr

Volatile Organics = 2432.6 Ib/hr |140/1998] =  170.5 Ib/hr

Water - 2432.6 Ib/hr |160/1998|  - 194.8 Ib/hr

       Water = 2432.6 Ib/hr |4120/1998| - 5016.2 Ib/hr - 602 gal/hr

       Aqueous Phase = 2432.6 Ib/hr  |(4806+191)/1998| = 6083.9 Ib/hr
                                    137

-------
Nonvolatile Organics = 6083.9 Ib/hr  |(808+72)/499?| = 1071.4 Ib/hr

Volatile Organics = 6083.9 Ib/hr  |(108.7 + 6.0)/4997| = 139.7 Ib/hr

Water = 6083.9 Ib/hr  |(3889.3 + 113)/4997| = 4872.8 Ib/hr

       Insoluble Oil Phase = 2432.6 Ib/hr  |1121/1998) = 1364.8 Ib/hr

Nonvolatile Organics - 1364.8 Ib/hr  |818/1121| = 995.9 Ib/hr

Volatile Organics - 1364.8 Ib/hr  (25.3/1121| =30.8 Ib/hr

Water - 1364.8 Ib/hr  |277.7/112l| = 338.1 Ib/hr

Extractor-2nd Stage
Aqueous Phase-6083.9 Ib/hr
Nonvolatile Organics -
              1071.4 Ib/hr
Volatile Organics -
               139.7 Ib/hr
Water - 4872.8 Ib/hr

MIBK  -  2436.6 Ib/hr
r


1200
2400



ml MIBK
g AQ PHASE
MIBK Soluble Phase -
2673.7 Ib/hr
MIBK - 2436.6 Ib/hr
Organics - 237.1 Ib/hr
Water Soluble Phase -
5846.8 Ib/hr
Water - 4872.8 Ib/hr
r\-v cr an •{ r^ey Q 7 "^ Q"7 1 "K /Tit*
urganics jijtji j-o/nr
O.SOlg „,., , 1K/K-.-
, Z'tju.O J.D/111.
ml
       MIBK = 6083.9 Ib/hr
From laboratory analysis 19.58% of the organics in the Aqueous Phase  input
stream were present in the MIBK soluble phase, and 80.42% of the organics in
the Aqueous Phase input stream were present in the Water Soluble Phase.

       MIBK Soluble Phase

Organics = 1211.1 Ib/hr |.1958| = 237.13 Ib/hr

       Water Soluble Phase

Organics - 1211.1 Ib/hr |.8042J - 973.97 Ib/hr
                                     138

-------
Evaporator—
MIBK Soluble Phase -         70°F
           2673.7 Ib/hr
MIBK - 2436.6 Ib/hr
Organics-237.1 Ib/hr
Steam -                  358.43°F
150 psia saturated
                                             249°F  MIBK - 2436.6 Ib/hr
                                             244°F  Organics-237.1 Ib/hr
                                             244°F  Condensate-432 Ib/hr
       MIBK = 2436.6 Ib/hr
                                        (244 - 70)°F| +
              2436.6 Ib/hr  |82.5 BTU/lb| + 2436.6 Ib/hr  | °5^ ™ \
                     (249 - 244°F)| = 401,213 BTU/hr

                                            BTU
       Organics'-  (Estimate cp to be 0.55
                                          Ib
                                                  ) =
                 237.1 Ib/hr
                              0.55 BTU
                              Ib • °F
(244 - 70)°F  =  22,690  BTU/hr
       Total = 423,903 BTU/hr

       Steam Use = x Ib/hr  |(1194.1 BTU/lb - 1162.0 BTU/lb)|  +

                   x Ib/hr  |949.5 BTU/lb| = 423,903 BTU/hr

                   x = 432 Ib/hr, 150 psia sat steam
                                                 s
Vacuum Evaporator—
Water Soluble Phase -
             5846.8 Ib/hr
Water - 4872.8 Ib/hr
Organics - 973.97 Ib/hr
                            70°F
Steam - 5390 Ib/hr
150 psia saturated
                        358.43°F
     170°F Water  -  4872.8  Ib/hr
     220°F   Organics-973.97  Ib/hr
                                     139

-------
        Water = 4872.8 Ib/hr  |(1134.2  BTU/lb  -  137.97  BTU/lb|

               + 4872.8 Ib/hr  |TT~?= |  (170  -  70°F| - 5,341,710  BTU/hr
Organics = 973.97 Ib/hr \

Total = 5,422,062 BTU/hr
                                           (220  -  70)°F|  =  80,353  BTU/hr
        Steam Use =  x Ib/hr  | (1194.1  BTU/lb  -  1153.4 BTU/lb) |

                  + x Ib/hr  | 965. 2 BTU/lb |  =  5,422,062 BTU/hr

                    x = 5390  Ib/hr steam, 150  psia saturated

 Process 1-B — Vacuum Stripped Oil — Two  Stage Extraction

 Vacuum Evaporator- (Stripper) —
 Raw Oil -  2432.6  Ib/hr
 Water - 284.9  Ib/hr
 Organics - 2147.7 Ib/hr

 Steam - 499 Ib/hr
70°F
358.43°F



170°F Volatiles - 357.6 Ib/hr
Water - 284.9 Ib/hr
Organics - 72.7 Ib/hr
220°F Vacuum Stripped Oil -
2075.0 Ib/hr
Nonvolatile Organics -
L 2041.0 Ib/hr
Volatile Organics-34.0 ib/hr
       Raw Oil = 4 gal/min
                                ft"
                               62.4 Ib
                             7.48 gal '   ft3
                                         !.215
Water = 2432.6 Ib/hr  |.117l| = 284.9 Ib/hr

Organics = 2432.6 Ib/hr  |.8829| =  2147.7  Ib/hr

       Volatiles - 2432.6 Ib/hr  |.147| =  357.6  Ib/hr

Organics = 357.6 Ib/hr  |.2032J = 72.7 Ib/hr

Water = 357.6 Ib/hr |.7968| = 284.9 Ib/hr

       Vacuum Stripped Oil = 2432.6 Ib/hr |.853| -  2075.0 Ib/hr

Nonvolatile Organic  = 2075.0 Ib/hr  |.9836| = 2041.0  Ib/hr

Volatile Organic -  2075.0 Ib/hr |.0164|  = 34.0 Ib/hr
                                     140

-------
       Volatiles

Water - 284.9 Ib/hr  |j^°.B°f 1(170 -  70)°F| + 284.9 Ib/hr  J996.2 BTU/lb|

              = 312,307 BTU/hr

Organics = 72.7 Ib/hr  I^i5] LBTU I  (170 - 70)°F | + 72.7 Ib/hr  |l95.5 BTU/lb|
       = 17,969 BTU/hr

Vacuum Stripped Oil - 2075.0 Ib/hr \^5.

       = 171,188 BTU/hr

Total » 501,464 BTU/hr
                                                      (220 - 70)°F|
       Steam Use - x Ib/hr  | (1194.1 BTU/lb - 1153.4 BTU/lb) | + x Ib/hr

                  •|965.2 BTU/lb| - 501,464 BTU/hr

                   x = 499  Ib/hr steam, 150 psia saturated

Extractor-lst Stage' —
Vacuum Stripped Oil -
         2075.0 Ib/hr
Nonvolatile Organics -
         2041.0 Ib/hr
Volatile Organics -
         34.0 Ib/hr

Water - 3563.3 Ib/hr
                                            Aqueous Phase-4216.7 Ib/hr
                                            Nonvolatile Organics -
                                                    904.0 Ib/hr
                                            Volatile Organics -
                                                    25.4 Ib/hr
                                            Water - 3287.3 Ib/hr

                                            Insoluble Oil Phase -
                                                              1421.6 Ib/hr
                                                   Nonvolatile Organics -
                                                              1137.0 Ib/hr
                                                   Volatile Organics-8.6 Ib/hr
                                                   Water - 276.0 Ib/hr

       Water = 2075.0 Ib/hr  |2830/1648] = 3563.3 Ib/hr

       Aqueous Phase - 2075.0 Ib/hr  |(3194 + 155)/1648| = 4216.7 Ib/hr

Nonvolatile Organics = 4216.7 Ib/hr  |(667 + 51)/3349| = 904.0 Ib/hr

Volatile Organics - 4216.7 Ib/hr  |(19.3 + 0.9)/3349| = 25.4 Ib/hr

Water • 4216.7 Ib/hr |(2507.7 + 103.1)/3349| = 3287.3 Ib/hr
                                     141

-------
        Insoluble Oil  Phase =  2075.0  Ib/hr  |1129/1648[ = 1421.6 Ib/hr

 Nonvolatile Organics  =  1421.6 Ib/hr  |903/1129| = 1137.0 Ib/hr

 Volatile Organics = 1421.6 Ib/hr  |6.8/1129) =8.6 Ib/hr

 Water = 1421.6  Ib/hr  |219.2/1129|  =  276.0  Ib/hr

 Extractor-2nd Stage
 Aqueous Phase - 4216.7  Ib/hr
 Nonvolatile Organics -
                 904.0  Ib/hr
 Volatile Organics  -
                 25.4 Ib/hr
 Water  - 3287.3  Ib/hr


 MIBK -  1688.8  Ib/hr
       MIBK = 4216.7  Ib/hr
     MIBK Soluble Phase  -
                   1841.5-Ib/hr
     MIBK -  1688.8 Ib/hr
     Organics  -  152.7  Ib/hr
     Water  Soluble Phase -
                                                              4064.0 Ib/hr
                                                 Water - 3287.3 Ib/hr
                                                 Organics - 776.7 Ib/hr
                             1200 ml MIBK
                             2400g Aq Phase
0.801E
  ml
= 1688.8 Ib/hr
 From laboratory analysis 16.43% of the organics in  the Aqueous Phase  input
 stream were present in the MIBK soluble phase, and  83.57% of  the  organics
 in' the aqueous phase input stream were present in the water soluble phase.

       MIBK Soluble Phase

 Organics = 929.4 Ib/hr  .1643  = 152.7 Ib/hr

       Water Soluble Phase

 Organics = 929.4 Ib/hr  .8357  = 776.7 Ib/hr

 Evaporator—
MIBK Soluble Phase -        70°F
           1841.5 Ib/hr
MIBK - 1688.8 Ib/hr
Organics - 152.7 Ib/hr

Steam                   358.43°F
 249°F  MIBK  -  1688.8 Ib/hr
 244°F   Organics  - 152.7 Ib/hr
 244°F   Condensate - 298 Ib/hr
                                     142

-------
MIBK = 1688.8 Ib/hr
                                      [(244 - 70)°F| +
               1688.8 Ib/hr  J82.5 BTU/lb| + 1688.8 Ib/hr
                                                   I 0.459 BTUi
                                                   1 Ib  • °F  '
          (249-244)°F| = 278,080 BTU/hr

                                  '    BTU
Organics -  (Estimate cp to  be
                                                  ) = 152.7 Ib/hr
                                                                  |0>55 BTU
               •| (244 - 70)°F | = 14,613 BTU/hr

       Total = 292,693 BTU/hr

      'Steam Use = x Ib/hr  ((1194.1 BTU/lb - 1162.0 BTU/lb)|

                   + x Ib/hr [949-5 BTU/lb  = 292,693 BTU/hr

                   x = 298  Ib/hr Steam, 150 psia sat

Vacuum Evaporator
Water Soluble Phase -
            4064.0 Ib/hr
Water - 3287.3 Ib/hr
Organics - 776.7 Ib/hr
                     70°F
Steam - 3646 Ib/hr
150 psi saturated
                 348.43°F
170°F  Water - 3287.3 Ib/hr
220°F  Organics - 776.7 Ib/hr
       Water - 3287.3 Ib/hr  |(1134.2 BTU/lb - 137.97 BTU/lb)|

                             i1.0 BTU,
                3287.3 Ib/hr
Organics = 776.7 Ib/hr
                                (170 - 70)°F  = 3,603,637 BTU/hr
                                        |(220 - 70)°F| = 64,078 BTU/hr
       Total = 3,667,715 BTU/hr

       Steam Use = x Ib/hr | (1194.1 BTU/lb - 1153.4 BTU/lb) | +

                   x Ib/hr | 965. 2 BTU/lb |  = 3,667,715 BTU/hr

                   x = 3,646 Ib/hr steam,  150 psia saturated
                                     143

-------
 Process 2-A—Raw Oil—Simultaneous MIBK and Water Extraction

 Extractor
 Raw Oil - 2470.6 Ib/hr
 Nonvolatile Organics -
               2100.0 Ib/hr
 Volatile Organics -
                173.1 Ib/hr
 Water - 197.5 Ib/hr
 MIBK  -  2500.4 Ib/hr
 Water -  3470.3 Ib/hr
Raw Oil
                    8al/min









ft










3 62.4
Overhead Effluent -
8441.3 Ib/hr
Nonvolatile Organics -
2100.0 Ib/hr
Volatile Organics -
173.1 Ib/hr
Water - 3667.8 Ib/hr
MIBK - 2500.4 Ib/hr
Insoluble Oil Phase - 0 Ib/hr
.4 . i 9Q/. 1 f.n m-Sn /V>»- — O/,7n £ 1U/V,v
                             7.48 gal
                                         ft"
 Nonvolatile Organics = 2470.6 Ib/hr J472/555.3J  = 2100.0 Ib/hr

 Volatile Organics = 2470.6 Ib/hr 138.9/555.31  =  173.1 Ib/hr

 Water = 2470.6 Ib/hr j44.4/555.3|  = 197.5 Ib/hr

        MIBK = 2470.6 Ib/hr )562/555.3|  = 2500.4  Ib/hr

        Water = 2470.6 Ib/hr |780/555.3|  = 3470.3 Ib/hr

 Separator
 Overhead  Effluent  -
              8441.3  Ib/hr
 Nonvolatile  Organics -
              2100.0  Ib/hr
 Volatile  Organics  -
           '   173.1  Ib/hr
Water - 3667.8 Ib/hr
MIBK - 2500.4 Ib/hr
                                          Aqueous Phase - 5144.5 Ib/hr
                                          Nonvolatile Organics -
                                                        1592.8 Ib/hr
                                          Volatile Organics -
                                                         105.4 Ib/hr
                                          Water - 3337.7 Ib/hr
                                          MIBK - 10.8.6 Ib/hr

                                          MIBK Phase - 3296.8 Ib/hr
                                          Nonvolatile Organics -
                                                        507.2 Ib/hr
                                          Volatile Organics-67.7 Ib/hr
                                          Water - 330.1 Ib/hr
                                          MIBK - 2391.8 Ib/hr
                                     144

-------
       Aqueous Phase = 8441.3 Ib/hr  |(1153 + 3.3)/1897.3| = 5144.5 Ib/hr

Nonvolatile Organics = 5144.5 Ib/hr  |358/(1153 + 3.3)| = 1592.8 Ib/hr

Volatile Organics = 5144.5 Ib/hr  |(23.6 + O.I)/(1153 + 3.3)| = 105.4 Ib/hr

Water = 5144.5 Ib/hr |(748.3 + 1.9)7(1153 + 3.3)| = 3337.7 Ib/hr

MIBK = 5144.5 Ib/hr |(23.1 + 1.3)/(1153 + 3.3)| = 108.6 Ib/hr

       MIBK Phase = 8441.3 Ib/hr  |741/1897.3| = 3296.8 Ib/hr

Nonvolatile Organics = 3296.8 Ib/hr  |114/741| = 507.2 Ib/hr

Volatile Organics = 3296.8 Ib/hr  |15.2/741| =67.7 Ib/hr

Water = 3296.8 Ib/hr J74.2/74l| =  330.1 Ib/hr

MIBK = 3296.8 Ib/hr |537.6/741| =  2391.8 Ib/hr

Evaporator (or Column)—
MIBK Soluble Phase -
             3296.8 Ib/hr
Nonvolatile Organics -
              507.2 Ib/hr
Volatile Organics -
               67.7 Ib/hr
Water - 330.1 Ib/hr
MIBK - 2391.8 Ib/hr

Steam
150 psia saturated
       MIBK = 2391.8 Ib/hr
70°F
r
r
r
358.43°F




249°F MIBK - 2391.8 Ib/hr
244°F Organics - 574.9 Ib/hr
244°F Condensate - 831 Ib/hr

                            0.459 BTU
                             Ib • °F

              • |82.5 BTU/lb| + 2391.8 Ib/hr

              = 393,836 BTU/hr
                                    (244 - 70)°F| + 2391.8 Ib/hr

                                                     (249 -
                                             BTU
..,, Organics - (Estimate cp to be 0.55 | ^— OF

                 •  1(244 - 70)°F| = 55,018 BTU/hr
                                                    )  =574.9 Ib/hr  |
0.55BTUi
Ib •  °F '
                                    145

-------
 Water = 330.1 Ib/hr
                                     (212 - 70)°FJ + | 330.1 lb/hr|970.3 BTU/lb
                    = 367,170 BTU/hr

       Total = 816,024 BTU/hr

       Steam Use = x Ib/hr | (1194.1 BTU/lb - 1162.0 BTU/lb) |  + x Ib/hr

                    •| 949. 5 BTU/lb |  = 816,024 BTU/hr

                   x = 831 Ib/hr steam, 150 psia saturated

Vacuum Evaporator (Double Effect) —
Water Soluble Phase -
             5144.5 Ib/hr
Nonvolatile Organics -
             1592.8 Ib/hr
Volatile Organics -
              105.4 Ib/hr
Water - 3337.1 Ib/hr
MIBK - 108.6 Ib/hr

Steam
150 psia saturated
Water = 3337.7 Ib/hr
70°F
r
r
r
358.43°F





249°F MIBK - 108.6 Ib/hr
244°F Organics - 1698.2 Ib/hr
244°F Condensate - 3963 Ib/hr

                                      (212 - 70)°F|  +
                                                                  82.5 BTU
                                                                  lb
         3337.7 Ib/hr  1970.3 BTU/lb] = 3,712,523 BTU/hr

MIBK - 108.6 Ib/hr  [°^4590pTU|  (244 - 70)°F  +  108.6  Ib/hr


        + 108.6 Ib/hr  ^90pTU  | (249-244) 9F | -  17,882  BTU/hr

Organics - (estimate cp to be 0.55 ——=Wr)  =
                                   lb •  F

            1698.2 Ib/hr  1°^  o™  |(244 - 70)°F|  = 162,518 BTU/hr

Total = 3,892,923 BTU/hr

Steam Use = x Ib/hr ((1194.1 BTU/lb - 1162.0 BTU/lb)|

            + x Ib/hr  (949.5 BTU/lb| = 3,892,923 BTU/hr

            x = 3966 Ib/hr steam, 150 psia saturated
                                    146

-------
Process 2-B—Vacuum Stripped Oil—Simultaneous MIBK and Water Extraction

Vacuum Evaporator-(Stripper)—
Raw Oil - 2478.6 Ib/hr
Organics - 2188.4 Ib/hr
Water - 290.2 Ib/hr
                             70°F
Steam
                         358.43°F
Volatiles 364.4 Ib/hr
Organics - 74.2 Ib/hr
Water - 290.2 Ib/hr

Vacuum Stripped Oil -
       Raw Oil = 4 gal/min  [ ?  ^   ^  \

                                                                2114.2 Ib/hr
                                                  Nonvolatile Organics -
                                                                2052.5 Ib/hr
                                                  Volatile Organics-61.7 Ib/hr


                                               1.238 | 60 min/hr| =2478.6 Ib/hr
Water = 2478.6 Ib/hr  |.117l| =  290.2  Ib/hr

Organics = 2478.6 Ib/hr  |.8829| =  2188.4  Ib/hr

   t  ,^ Volatiles = 2478.6 Ib/hr |.147| =  364.4  Ib/hr

Organics = 364.4 Ib/hr  |.2032|  =74.2 Ib/hr

Water = 364.4 Ib/hr  |.7968J = 290.3 Ib/hr

       Vacuum Stripped Oil = 2478.6 Ib/hr |.853| = 2114.2 Ib/hr

Nonvolatile Organics = 2114.2 Ib/hr |1629/1678] = 2052.5 Ib/hr

Volatile Organics = 2114.2 Ib/hr  |49/1678) =61.7 Ib/hr

       Volatiles

                     1.0 BTU i(17Q _  70)oF| +   290>2 lb/hr  |996-2 BTU/lb|
Water = 290.2 Ib/hr
                     Ib  • °F

        = 318,217 BTU/hr
Organics = 74.2 Ib/hr
        = 18,340 BTU/hr

Vacuum Stripped Oil = 2114.2 Ib/hr
     Total = 510,979 BTU/hr
                                    (170 - 70)°F|+ 74.2 Ib/hr  |l95.5 BTU/lb|
                                             \  (220 - 70)°F| = 174,422 BTU/hr
       Steam Use = x Ib/hr  | (1194.1 BTU/lb - 1153.4 BTU/lb) |

                  + x Ib/hr | 965. 2 BTU/lb | = 510,979 BTU/hr

                  x = 508 Ib/hr steam, 150 psia saturated

                                     147

-------
 Extractor—
 Vacuum Stripped Oil -
               2114.2 Ib/hr
 Nonvolatile Organics -
               2052.5 Ib/hr
 Volatile Organics-61.7 Ib/ht


 Water - 2393.9 Ib/hr


 MIBK - 1509.4  Ib/hr
     Overhead Effluent -
                6017.5 Ib/hr
     Nonvolatile Organics -
                2052.5 Ib/hr
     Volatile Organics-61.7 Ib/hr
     Water - 2393.9 Ib/hr
     MIBK - 1509.4 Ib/hr
     Insoluble Oil Phase- 0 Ib/hr
        MIBK =  2114.2  Ib/hr  |1198/1678| - 1509.4  Ib/hr

        Water = 2114.2 Ib/hr  |l900/1678| = 2393.9 Ib/hr

 Separator—
 Overhead  Effluent -
                6017.5 Ib/hr "
 Nonvolatile Organics -
                2052.5 Ib/hr
 Volatile  Organics-61.7 Ib/hr
 Water - 2393.9  Ib/hr
 MIBK - 1509.4 Ib/hr
       Aqueous Phase = 6017.5 Ib/hr  |(2746 +

Nonvolatile Organics = 3734.5 Ib/hr  |(735 +

Volatile Organics = 3734.5 Ib/hr  |(31.4 + 1.

Water = 3734.5 Ib/hr |(1790.1 + 73.7)/2964|

MIBK = 3734.5 Ib/hr |(189.5 + 46.4)/2964| =
	 Aqueous Phase-3734.5 Ib/hr
     Nonvolatile Organics -
                    1047.0 Ib/hr
     Volatile Organics-42.0 Ib/hr
     Water - 2348.3 Ib/hr
     MIBK - 297.2 Ib/hr

	 MIBK Phase - 2283 Ib/hr
     Nonvolatile Organics -
                    1005.5 Ib/hr
     Volatile Organics-19-7 Ib/hr
     Water - 45.6 Ib/hr
     MIBK - 1212.2 Ib/hr

218)/4776| = 3734.5 Ib/hr

96)/2964| = 1047.0 Ib/hr

9)/2964| = 42.0 Ib/hr

= 2348.3 Ib/hr

297.2 Ib/hr
                                     148

-------
       MIBK Phase = 6017.5 Ib/hr  |l812/4776| = 2283.0 Ib/hr

Nonvolatile Organics = 2283.0 Ib/hr  |798/1812] = 1005.5 Ib/hr

Volatile Organic = 2283.0 Ib/hr  |15.7/1812| =19.7 Ib/hr

Water ='2283.0 Ib/hr |36.2/1812]  =45.6 Ib/hr
    ', •
MIBK =2283.0 Ib/hr 1962.1/18121  = 1212.2 Ib/hr

Evaporator (or Column)
MIBK Soluble Phase -
            2283.0 Ib/hr
Nonvolatile Organics -
            1005.5 Ib/hr
Volatile Organics -
             19.7 Ib/hr
Water - 45.6 Ib/hr
MIBK - 1212.2
Steam
ISO.psia saturated


       MIBK = 1212.2 Ib/hr
70°F
358.43°F
hr °'459


BTU
111 Ib • °F




(244
249°F MIBK - 1212.2 Ib/hr
244°F Organics - 1025.2 Ib/hr
244°F Condensate - 355 Ib/hr
- 70) OF
              + 1212.2 Ib/hr  |82.5 BTU/lb| + 1212.2 Ib/hr |
                                                    0.459 BTU
                                                     Ib • °F
         (249 - 244) °F | = 199,602 BTU/hr
                              0.55 BTU
           t               v
Organics - (estimate cp to be
                                              x    ino, 0 ....
                                              )  = 1025.2 Ib/hr
                                                                0.55 BTU
                                     -,  _ OF

                •| (244 - 70)°F| = 98,112 BTU/hr

       Water = 45.6 Ib/hr [ ]^° .™ I (212 - 70)°F| +45.6 Ib/hr J970.3 BTU/lb |

                = 50,721 BTU/hr

       Total = 348,435 BTU/hr

       Steam Use - x Ib/hr | (1194.1 BTU/lb - 1162.0 BTU/lb) |

                  + x Ib/hr | 949. 5 BTU/lb |  - 348,435 BTU/hr

                  x = 355 Ib/hr steam, 150 psia saturated
                                    149

-------
 Vacuum  Evaporator  (Double Effect)—
Water  Soluble Phase -
             3734.5 Ib/hr
Nonvolatile  Organics -
             1047.0 Ib/hr
Volatile Organics -
              42.0 Ib/hr
Water  - 2348.3 Ib/hr
MIBK - 297.2 Ib/hr
Steam

150 psia saturated


       Water = 2348.3 Ib/hr
70°F
358.43°F






249°F MIBK - 297.2 Ib/hr
244°F Organics - 1089 Ib/hr
244 °F Condensate - 2817 Ib/hr


                                      (212 - 70)°F| -I-
                             J.D •  r

               2348.3 Ib/hr  |970.3 BTU/lb| = 2,612,014 BTU/hr
       MIBK = 297.2 Ib/hr
               + 297.2  Ib/hr
                               Ib
                                      (244 - 70)°F|+ 297.2 Ib/hr  |82.5 BTlJ/lb1
                                         (249 - 244)°F= 48,937 BTU/hr
       Organics -  (estimate cp to be °'55 *™ ) = 1089 Ib/hr  |0'55 BTU
                                     Ib • °F

                   •|(244 - 70)°F| = 104,217 BTU/hr

       Total = 2,765,169 BTU/hr

       Steam Use = x Ib/hr |(1194.1 BTU/lb - 1162.0 BTU/lb)|

                   + x Ib/hr|949.5 BTU/lb| = 2,765,169 BTU/hr
                                                   »
                   x = 2,817 Ib/hr steam, 150 psia saturated
                                                              Ib
MAJOR EQUIPMENT COST ESTIMATE

       Four individual processing schemes have been  investigated on the
laboratory scale.  Two use raw pyrolytic oil as  a  feed  stock for extraction
while two require that the raw pyrolytic oil undergo a  stripping operation
prior to extraction.  Two processes employ  two stage extraction while two
processes perform a simultaneous extraction in a single stage.
                                     150

-------
       The pilot  plant  was  designed so that each of the four processes  could
be  tested using the  single  pilot  plant installation.   For each piece  of equip-
ment,  the four processes were examined to determine the largest capacity or
size necessary for that particular piece of equipment.   For example:  process
1-B requires  a 1st stage extractor with a volume of 90.96 ft3,  while  process
2-A requires  a volume of 149.2 ft3.  Process 2-A was  used as the basis  for the
design calculations.  The pilot plant design basis  is a 4 GPM feed  rate of raw
pyrolytic oil into the  pilot  plant system.   All pilot equipment is  scaled up
directly from experimental  results.

       Equipment  cost estimates are taken from Peters and Timmerhouse [14],
except for estimates of the extractors which are taken from an article  by
J.  W.  Drew  [21].  All costs are updated to the period Nov.-Dec.  1979  using the
Chemical Engineering Plant  Cost Index.  Installations costs are estimated to
be  39% of purchased  equipment costs [14].  The evaporators  and strippers  were
not designed  in detail. The  heat requirements necessary to perform the par-
ticular ,unit  operation  were estimated.  The results were used directly  to
estimate the  cost of a  piece  of equipment that would  satisfy the heat require-
ments.  The extractor cost  estimates are based on Fig.  10,  which uses an  arbi-
trary  column  height  of  20 feet as a reference point.   Although the  pilot  plant
extractor dimensions would  not be expected to be the  same as those  in the design
calculations, the reference height of 20 feet was used to calculate the equip-
ment cost estimate.

EQUIPMENT COSTS
Pilot Plant—Cost Summary

Raw Oil Storage Tank                      (1)                  $ 9,382
Raw Oil Feed  Tank                         (2)                   9,382
Vacuum Evaporator (Stripper)              (3)                  39,090
Extractor (1st Stage)                     (4)                  48,790
Separator (or Holdup Tank)                (5)                  23,454
Extractor (2nd Stage)                     (6)                  48,790
MIBK Soluble  - Holdup Tank                (7)                   9,382
Evaporator                                (8)                  46,908
MIBK Holdup Tank                          (9)                    3>440
MIBK Soluble  - Product  Storage  Tank     (10)                   4,691
Water Soluble - Holdup  Tank             (11)                   9,382
Vacuum Evaporator                        (12)                  87,561
Water Soluble - Product Storage Tank    (13)                    7,193
MIBK Storage  Tank                        (14)                    3,440
Volatiles - Product Storage Tank         (15)                    4,691
Spent Oil - Product Storage Tank         (16)                    4,691
Water Storage Tank                       (17)                    5,629

Total Installed Equipment Cost                                365,896

Instrumentation and controls  -  (9.35%  of
  installed equipment cost)                                    o  01,
Piping - (22.3% of installed  equipment cost)                   81,211
Electrical -  (7.2% of installed equipment cost)                26,345

Total Pilot Plant Equipment Cost                             $508,047

                                      151

-------
 Pilot Plant Cost Estimates—Combined Scheme for all Four Continuous
 Extraction Processes

 Raw Oil Storage Tank—(1)
 Use a Tank volume of 500 gal (304ss)
 From Figure 13-56 f 14 1 Cost of mixing, storage, and pressure tanks:

 Purchased cost = $3000 if^f^f I = $6749

 Installed cost = $6749|l.39| = $9382

 Raw Oil Feed Tank—(2)
 Use a tank volume of 500 gal (304ss)
 From Figure 13-56 [ 14] Cost of mixing, storage, and pressure tanks:
 Purchased cost = $3000 l^gyl = $6749

 Installed cost = $6749 |l.39| = $9,382

 Vacuum Evaporator—(Stripper)— (3)

 Heat Requirements—From Process 1-B  q = 501,464 BTU/hr

                    From Process 2-B  q = 510,979 BTU/hr

 Use Process 2-B for design calculations

        A^ = (358.43 - 70) °F   At, = (220 - 170) °F

        A*   =  Atl ~ At2    = 288.43 - 50
         Clm   ln(At1/At2)     ln(288.43/50) =

        q = UAAt,  ;   estimate U =  200 	^JJL
                  _ 510,979   _         2
                  ~ 200(136)  - 18'78 ft

From Figure  14-28 [ 14 ]  agitated  falling-film evaporators (304ss)

Purchased cost =  $12,500  if^f^l = $28,122

Installed cost =  $28,122  |l.39| =  $39,090

Extractor-lst Stage—(4)

Process 1-A

Ra» Oil . 2432.6  Ib/hr  ll   IL |-        65 »in |  - 34.76 ft3
                                     152

-------
Water = 5016.2  Ib/hr  \-^ I ^ I 65 min| . 87.09 ft3

Total volume =  121.85  ft3

Process 1-B

Vacu™ Stripped Oil -  2075.0  Ib/hr |      - \-     _t_ | 65 Mn| . 29.10 ft3
Water -  3563.3  Ib/hr  \^^ |^_ | 65 ^ , 61.86 ft3

Total Volume =  90.96  ft3

Process  2-A

Raw Oil  -  2470.6  Ib/hr  \^^ \^ |^- | 65 min| - 34.76 ft3
                            3
Water =  3470.3  Ib/hr  |-      |        | 65 min| - 60.25 ft3
MIBK = 2500.4 Ib/hr  |     ^ |^ |^ | 65 min| = 54.19 ft3

Total Volume =  149.2 ft3

Process 2-B
                                        3
Vacuum Stripped Oil  = 2114.2 Ib/hr |   *J 1U | -~^ I ,.hr,  | 65 min| = 29.65 ft3
                                    O/.4 J.D  l.ZJo  oO min
Water = 2393.9 Ib/hr |         I         65 min  = 41'56
MIBK = 1509.4 Ib/hr | -      OoT ' 60      65 m±nl = 32'72

Total Volume = 121.85  ft3

Use Process 2-A for design calculations
Use an extractor volume of 150 ft^ (304ss)

From Ref . [21]:     V  = 7-  d h

.where h is assumed to  be 20 feet

      150 ft3 = ^ d2(20)

      d = 3.09 ft or 37.08 inches

From Figure 10 [21] - Cost of Columns:

Purchased cost - $32, 000. | 0.8 | |^|y| | - $35,100

The factor given for converting from a 316ss column to a 304ss column is 0.8.
Installed cost - $35,100 |l.39| - $48,790
                                     153

-------
  Separator  (or Holdup Tank) — (5)



  Use Process  2-A for design calculations
                             rt


  Raw Oil =  2470.6  Ib/hr | ^\ ^  T~234' = 32'085





  MIBK - 2500.4 Ib/hr | ^hb ' 0^01 ' = 5°'°26


                         ft3  ,            3
  Water = 3470.3 Ib/hr  ,.  . ..   = 55.61 ft /hr
                       oz . 4 Ib



  Total Volume = 137.72 ft3/hr [ 7.48 gal j = 103Q gal/hr


                                 ft

  Choose a 3 hour Holdup  =  3090 gal

  Use a separator volume of  3000 gal (304ss)

  From Figure  13-56  [ 14  ]  Cost of mixing, storage, and pressure  tanks:
 Purchased cost = $7500  ~fj  = $16,873



 Installed cost = $16,873  |l.39J = $23,454



 Extractor-2nd Stage-- (6)



 Process 1-A

                                   3

 Aqueous Phase = 6083.9 Ib/hr | ,.fj .. I . *   I ,.hr.  I 65 min| =  85.52  ft3
                               b£. 4 Ib  I.ZJD  oO mm

                          3

 MIBK = 2436.6 Ib/hr |   ** ..  |n „., | ,.-hr.  | 65 min| = 52.81  ft3
                     1 62.4 Ib ' 0.801  60 mm '        '


 Total volume = 138.34 ft



 Process 2-A

                                   3

 Aqueous Phase - 4216.7 Ib/hr |   lL_ |       |      _ | 65 min| =59.28  ft3
                          3

 MIBK = 1688.8 Ib/hr  ,.fj    \   ^   I .-hr.  I 65 mini = 36.60  ft3
                      62.4 Ib ' 0.801 ' 60 mm '        '


 Total Volume = 95.88 ft3


                                  3
' Use an extractor volume of 150 ft  (304ss)



 From Ref .  [  21 J:    V = y d2h
                          4


 where  h is  assumed to be 20 feet



        150 ft3 = 2- d2(20)



        d = 307 ft2 or 37.08 inches
                                      154

-------
From Figure 10  [ 21  ] - Cost of  columns:



Purchased cost  = $32,000  | 0.8  1 14|^||  =  $35,100
                               -LU.7 * /


The factor given for converting  from  a 316ss  column to a 304ss column is 0.8.



Installed cost  = $35,100  | 1.39J  =  $48,790



MIBK Soluble—Holdup Tank — ( 7 )

Use a tank volume of 500  gal  (304ss)

From Figure 13-56  [ 14  J  Cost  of mixing, storage, and pressure tanks:



Purchased cost  = $3000 |~   1 " $6749
Installed cost =  $6749 |l.39| -  $9382



Evaporator  (MIBK  Phase)-- (8)



Heat Requirements — From  Process  1-A   q = 423,903 BTU/hr



                   From  Process  1-B   q = 292,693 BTU/hr



                   From  Process  2-A   q = 816,024 BTU/hr



                   From  Process  2-B   q = 348,435 BTU/hr



Use Process  2-A for  design  calculations



       At  = (244 -  70) °F    At  =  (358.43 - 249) °F

              Atl  "  At2     174 -  109.43
          lm    ln(At/At  )  ~  ln(174/109.43)
                                         TirnTT

       q  = UAAt,  ;    Estimate U =  200 - = -
                1m                    ,  ,.2  OT,
                                      hr-ft  • F


       A  -   q    _ 816,024       9Q  ,n  .2

          ~ UAt,    200(139.23)
               -im


From Figures 14-28 [14] agitated falling-film evaporators  (304ss)



Purchased cost  =  $15,000  if^fl = $33,747



Installed cost  =  $33,747  |l.39| =  $46,908



MIBK Holdup Tank~( 9 )



Use Process 1-A for design  calculations

                          o


MIBK - 2436.6 Ib/hr |         I       l =  48'75
Capacity - 47.75 ft3/hr  J7.48 gal/ft3 | =  364.6  gal/hr




                                     155

-------
 Choose a 3  hour Holdup  =  1094  gal
 Use a tank  volume  of  1100 gal  (C-S)
 From Figure  13-56 [  14 ]  Cost of mixing, storage, and pressure  tanks:
 Purchased  cost  =  $1100  |    ' 7 1 =  $2475
 Installed  cost  =  $2475  |l.39| =  $3440

 MIBK Soluble -  Product  Storage Tank — (10)
 Use Process 2-B for design calculations

 MIBK Soluble Organics = 1025.2 Ib/hr | ^ * lfa  Ij-f^jl " 13-3
 Capacity  =13.3  ft3/hr  |7.48 gal/ft  | =99.5 gal/hr

 Use a tank volume of  150 gal (304ss)
 From Figure  13-56  [ 14 ] Cost of mixing, storage, and pressure  tanks:
 Purchased  cost =  $1500  ~     = $3375
                        xuy • /
 Installed  cost =  $3375  |l.39| = $4691

 Water  soluble-Holdup Tank — (11)
 Use a  tank volume of 500 gal (304ss)
 From Figures 13-56  [ 14 ] Cost of mixing, storage, and pressure  tanks:
Purchased cost = $3000    o'? | - $6749
                        xuy • /

Installed cost = $6749  |l.39| = $9382

Vacuum Evaporator (Water Soluble Phase) — (12)

Heat Requirements — From Process 1-A   q = 5,422,062 BTU/hr

                        Process 1-B   q = 3,667,715 BTU/hr

                        Process 2-A   q « 3,892,923 BTU/hr

                        Process 2-B   q = 2,765,169 BTU/hr

Use Process 1-A for design calculations

       At^ = (220 - 70) °F   At2 =  (358.43 - 220) °F

       ..       Atl " At2    150 -  138.43
         lm " ln(At1/At2) ~ In (150/138. 43)
                                            BTTT
       q = UA t, ;  Estimate U = 500 BTU - =~
               lm                        hr.ft2
             q   = 5.422.062 _        2
                   500(144)    °-J rt
                                     156

-------
From Figure  14-28  [ 14  ] Agitated falling-film evaporators (304ss)

Purchased cost = $28,000  if^fl = $62,994

Installed cost = $62,994  |l.39J = $87,561

Water Soluble - Product Storage Tank — (13)
Use Process 2-A for design calculations

Water Soluble Organics =  1698.2 Ib/hr | ^ *    |   *| = 22.04 ft3/hr
Capacity = 22.04 ft3/hr  J7.48 gal/ft3 | = 164.8 gal/hr

Use a tank volume of 300 gal (304ss)
From Figures 13-56  [ 14  ] Cost of mixing, storage, and pressure tanks:
Purchased cost = $2300      '   = $5174
                        _Luy • /

Installed cost = $5174  |l.39| = $7193

MIBK Storage Tank— (14)
Use a tank volume of 1100 gal (C-S)
From Figure  13-56  [ 14 ] Cost of mixing, storage, and pressure tanks:
Purchased cost - $1100 | ^°'°| = $2475

Installed cost = $2475 |l.39| - $3440

Volatiles-Product Storage Tank—(15)
Use Process 2-B for design calculations

       Volatiles—

                      ,   ft3   ,   1   ,           3
Organics = 74.1 Ib/hr [,  , ., \   n,.\ = 1.134 ft /hr
                       f 3              3
Water = 290.3 Ib/hr  |fi2" lb| = 4.652 ft /hr


Total Volume - 5.786 ft3/hr  |7-48 gal[ =43.28 gal/hr
                               ft

Choose a 3 hour Holdup  = 129.8 gal
Use a tank volume of 150 gal (304ss)
From Figure  13-56 [ 14  ] Cost of mixing, storage, and pressure tanks:
Purchased cost = $1500      y  = $3375

Installed cost = $3375  |l.39| = $4691
                                     157

-------
 Spent Oil  Storage Tank— (16)
 Use Process  1-A  for design calculations

        Insoluble Oil Phase —

 Organics = 1026.7 Ib/hr  I ^ 4 Ib I 1 234 I " 13>334  ft3/hr

                       fi-3 '        '   3
 Water = 338.1 Ib/hr  A0  . ..  | = 5.42 ft /hr
                     O/.4 ±b .

 Total Volume = 18.76 ft3/hr [ 7'48 gal [ = 140 gal/hr
                               ft
 Use a tank volume of 150 gal (304ss)
 From Figure  13-56 [ 14  ] Cost of mixing, storage, and pressure  tanks:

 Purchased  cost = $1500 | ?Qg'y| = $3375

 Installed  cost = $3375 |l.39| = $4691

 Water Storage Tank — (17)
 Use Process  1-A for design calculations

 Water =5016.2 Ib/hr | ,0f* .. I  = 80.39 ft3/hr
                      DZ . 4 Ib

 Capacity = 80.39 ft3/hr |7.48 gal/ft3 |  = 601.3 gal/hr

 Choose a 3 hour Holdup =  1804 gal
Use a tank volume of 200. gal (C-S)
From Figure  13-56 [ 14 1 Cost of mixing, storage, and pressure  tanks:
Purchased cost = $1800         - $4050

Installed cost = $4050 1 1.39 1  = $5629
                                     158

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                                  APPENDIX  C

                       COMMERCIAL  PLANT  CALCULATIONS


MAJOR EQUIPMENT—MATERIAL  BALANCES

Process  1-A—Raw Oil—Two  Stage Extraction

Extractor-lst  Stage—
Raw Oil - 9000  Ib/hr
Nonvolatile Organics  -
              7648.7  Ib/hr
Volatile Organics  -
                630.6  Ib/hr
Water - 720-7 Ib/hr


Water - 18,558.6 Ib/hr
Aqueous Phase-22,509 Ib/hr
Nonvolatile Organics -
               3964.0 Ib/hr
Volatile Organics -
                516.7 Ib/hr
Water - 18,028.3 Ib/hr


Insoluble Oil Phase -
                                                                5049.6 Ib/hr
                                                 Nonvolatile Organics -
                                                                3684.7 Ib/hr
                                                 Volatile Organics -
                                                                 114.0 Ib/hr
                                                 Water - 1250.9 Ib/hr
       Raw Oil
Nonvolatile Organics =  9000  Ib/hr  |1698/1998| =  7648.7 Ib/hr

Volatile Organics = 9000  Ib/hr  |140/1998] = 630.6 Ib/hr

Water = 9000 Ib/hr  |160/1998| =  720.7  Ib/hr

       Water = 9000 Ib/hr |4120/1998|  = 18,558.6 Ib/hr

       Aqueous Phase =  9000  Ib/hr  |(4806+191)/1998| = 22,509 Ib/hr

Nonvolatile Organics =  22,509 Ib/hr |(808+72)/4997| = 3964.0 Ib/hr

Volatile Organics = 22,509 Ib/hr |(108.7+6.0/4997| = 516.7 Ib/hr

Water = 22,509 Ib/hr  | (3889.3 +113)/49971 = 18,028.3 Ib/hr
                                     159

-------
        Insoluble Oil Phase = 9000 Ib/hr  11121/19981  =  5049.6  Ib/hr

 Nonvolatile Organics = 5049.6 Ib/hr  |818/1121|  =  3684.7  Ib/hr

 Volatile Organics = 5049.6 Ib/hr  j25.3/1121| =  114.0 Ib/hr

 Water = 5049.6 Ib/hr |277.7/1121|  =  1250.9 Ib/hr

 Extractor—2nd Stage
 Aqueous Phase-22,509  Ib/hr
 Nonvolatile Organics  -
              3,964.0  Ib/hr
 Volatile Organics  -
                516.7  Ib/hr
 Water - 18,028.3 Ib/hr


 MIBK - 9014.9 Ib/hr






MIBK Soluble Phase -
9,892.2 Ib/hr
MIBK- 9,014.9 Ib/hr
Organics - 877.3 Ib/hr
Water Soluble Phase -
21,631.7 Ib/hr
Water - 18,028.3 Ib/hr
Organics - 3603.4 Ib/hr
MIBK = 22,509 Ib/hr
                             1200 ml MIBK  i  .801g
                            '2400g Aq Phase   ml
                                                   = 9014.9 Ib/hr
 From laboratory analysis 19.58% of the organics in the Aqueous Phase  input
 stream were present in the MIBK Soluble Phase, and 80.42% of  the Organics
 in  the Aqueous Phase input stream were present in the Water Soluble Phase.

       MIBK Soluble Phase

 Organics = 4480.7 Ib/hr  |.1958| = 877.3 Ib/hr

       Water Soluble Phase

 Organics - 4480.7 Ib/hr  |.8042| = 3603.4 Ib/hr

 Evaporator—
MIBK Soluble Phase -
            9892.2 Ib/hr
MIBK - 9014.9 Ib/hr
Organics - 877.3 Ib/hr
                     70°F
Steam
 150 psia saturated
                 358.43°F
249°F  MIBK - 9014.9 Ib/hr
                                     244°F  Organics - 877.3 Ib/hr
244°F  Condensate - 1598 Ib/hr
                                     160

-------
MIBK = 9014.9 Ib/hr
                                        (244.70)°F | +  9014.9 lb/hr|82.5 BTU/lb[
       + 9014.9 Ib/hr
                                          (249-244)°F| =  1,484,402 BTU/hr
Organlcs - (estimate cp to  be
                                  55
                                      -LD
                                                 =877.3 Ib/hr
                                                               °'55
                                                               Xb
                   •|(244 - 70)°F| = 83.958 BTU/hr
       Total = 1,568,360 BTU/hr

       Steam Use = x Ib/hr | (1194.1 BTU/lb - 1162.0 BTD/lb) | + x Ib/hr

                   •|949.5 BTU/lb | = 1,568,360 BTU/hr

                   x = 1,598 Ib/hr steam  150 psia saturated

Vacuum Evaporator —
Water Soluble Phase -
          21,631.7 Ib/hr
Water - 18,028.3 Ib/hr
Organics - 3603.4 Ib/hr
                     70°F
Steam - 19,943 Ib/hr
150 psia saturated
                 3-58.43°F
170°F  Water - 18,028.3 Ib/hr
220°F  Organics - 3603.4 Ib/hr
Water = 18,028.3 Ib/hr  | (1134. 2 BTU/lb - 137.97 BTU/lb) |

        + 18,028.3 Ib/hr
                          J.D
Organics = 3603.4 Ib/hr
                                           (170 - 70)°F| = 19,763,163 BTU/hr

                                           (220 - 70)°F| = 297,281 BTU/hr
       Total = 20,060,444 BTU/hr

       Steam Use = x Ib/hr | (1194.1 BTU/lb - 1153.4 BTU/lb) | + x Ib/hr

                   • |965.2  BTU/lb | = 20,060,444 BTU/hr

                   x = 19,943 Ib/hr steam  150 psia saturated
                                     161

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 Process 1-B—Vacuum Stripped Oil—Two  Stage  Extraction

 Vacuum Evaporator (Stripper)—
 Raw Oil - 9000 Ib/hr
 Water - 1053.9 Ib/hr
 Organics - 7946.1  Ib/hr

 Steam - 1844  Ib/hr
                                                 Volatiles  -  1323.0  Ib/hr
                                                 Water - 1053.9  Ib/hr
                                                 Organics -  269.1  Ib/hr

                                                 Vacuum Stripped Oil -
                                                                 7677.0  Ib/hr
                                                 Nonvolatile Organics -
                                                                 7551.2  Ib/hr
                                                 Volatile Organics -
                                                                 125.8 Ib/hr
        Raw Oil
 Organics  =  9000  Ib/hr  |.8829| = 7946.1 Ib/hr

 Water  = 9000  Ib/hr  |.117l| = 1053,9 Ib/hr

       Volatiles =  9000 Ib/hr  |.14?| = 1323.0 Ib/hr

 Organics  =  1323.0 Ib/hr |.2034| = 269.1 Ib/hr

 Water  = 1323.0 Ib/hr  |.7966| = 1053.9 Ib/hr

       Vacuum Stripped Oil = 9000 Ib/hr |.853| = 7677.0 Ib/hr

 Nonvolatile Organics = 7677 Ib/hr |1621/1648| = 7551.2 Ib/hr

 Volatile Organics = 7677 Ib/hr |27/1648|  = 125.8 Ib/hr

       Volatiles

                      11.0 BTU
Water - 1053.9 Ib/hr
                      Ib • °F
           = 1,155,285 BTU/hr
Organics = 269.1 Ib/hr
                               |(170 - 70)°F|+ 1053.9 Ib/hr|996.2 BTU/hr|
                                    (170 - 70)°F|+ 269.1 Ib/hr  J195.5  BTU/lb|
           = 66,513 BTU/hr
       Vacuum Stripped Oil = 7677.0 Ib/hr
                                             55
                                           Ib  • °F
                                  633.353 BTU/hr
                                                      (220 -  70)°FJ
       Total = 1,855,151 BTU/hr
                                    162

-------
       Steam Use =x  Ib/hr  | (1194.1  BTU/lb  -  1153.4 BTU/lb) | + x Ib/hr

               •|965.2  BTU/lb|  =  1,855,151  BTU/tir

                x =  1844 Ib/br steam 150 psia  saturated

Extractor-lst  Stage—
Vacuum Stripped Oil
              7677.0  Ib/hr
Nonvolatile Organics -
              7551.2  Ib/hr
Volatile Organics  -
               125.8  Ib/hr

Water - 13,183.2 Ib/hr
Aqueous Phase-15,600.9 Ib/hr
Nonvolatile Organics -
               3344.7  Ib/hr
Volatile Organics-94.1 Ib/hr
Water - 12,162.1 Ib/hr
Insoluble Oil Phase -
                                                                5259.3 Ib/hr
                                                 Nonvolatile Organics -
                                                                4206.5 Ib/hr
                                                 Volatile Organics - 31.7 Ib/hr
                                                 Water - 1021.1 Ib/hr

       Water =  7677.0  Ib/hr  |2830/1648| = 13,183.2 Ib/hr

       Aqueous  Phase = 7677.0  Ib/hr  |(3194 + 155)/1648| = 15,600.9  Ib/hr

Nonvolatile Organics = 15,600.9  Ib/hr  |(667 + 51)/3349| = 3344.7 Ib/hr

Volatile Organics = 15,600.9 Ib/hr  |(19-3 + 0.9)/3349| =94.1 Ib/hr

Water = 15,600.9 Ib/hr ](2507.7  + 103.1)/3349| = 12,162.1 Ib/hr

       Insoluble Oil Phase = 7677.0  Ib/hr  |1129/1648| = 5259.3 Ib/hr

Nonvolatile Organics = 5259.3  Ib/hr  |903/1129| = 4206.5 Ib/hr

Volatile Organics = 5259.3 Ib/hr j6.8/1129) =31.7 Ib/hr

Water = 5259.3  Ib/hr 1219.2/11291 =  1021.1 Ib/hr
                                     163

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Extractor-2nd Stage—
Aqueous Phase-15,600.9 Ib/hr
Nonvolatile Organics -
                3344.7 Ib/hr
Volatile Organics-94.1 Ib/hr
Water - 12,162.1 Ib/hr


MIBK - 6248.2 Ib/hr





MIBK Soluble Phase -
6813.2 Ib/hr
MIBK - 6248.2 Ib/hr
Organics - 565.0 Ib/hr
Water Soluble Phase -
15,035.9 Ib/hr
Water - 12,162.1 Ib/hr
n-i-oaiTi^Q 9«7T ft 1K/V.1-
       MIBK = 15,600.9 Ib/hr
                         1200 ml MIBK   . .801g
                        2400g Aq Phase  '  ml
                                                       6248.2 Ib/hr
From laboratory analysis 16.43% of the organics in the Aqueous Phase input
stream were present in the MIBK Soluble Phase, and 83.57% of the organics in
the Aqueous Phase input stream were present in the Water Soluble Phase.

       MIBK Soluble Phase

Organics = 3438.8 Ib/hr |.1643| = 565.0 Ib/hr

       Water Soluble Phase

Organics = 3438.8 Ib/hr |.835?| - 2873.8 Ib/hr

Evaporator—
MIBK Soluble Phase -
            6813.2 Ib/hr
MIBK - 6248.2 Ib/hr
Organics-565.0 Ib/hr

Steam
                            70°F
                        358.43°F
                            0.459
MIBK = 6248.2 Ib/hr  \^~^
                        BTU

       Organics  -  (estimate cp to be
                                     249 °F  MIBK - 6248.2  Ib/hr
                                            244°F  Organics - 565.0 Ib/hr
                                     244°F  Condensate  -  1103  Ib/hr
                                                  F|+ 6248.2 Ib/hr

                                           = 1,028,836 BTU/hr

                                                565.0 Ib/hr  I0'55
Total
                         •|(244 - 70)°F|  = 54,071 BTU/hr
               1,082,907  BTU/hr
                                    164

-------
 Steam Use = x Ib/hr |(1194.1 BTU/lb - 1162.0 BTU/lb)|  + x Ib/hr

                      •|949.5 BTU/lb|  = 1,082,907 BTU/hr

             x = 1103 Ib/hr steam 150 psia saturated

 Vacuum Evaporator—
 Water Soluble Phase -
            15,035.9 Ib/hr
 Water - 12,162.1 Ib/hr
 Organics - 2873.8 Ib/hr
    70°F
 Steam - 13,490 Ib/hr
 150 psia saturated
358.43°F
170°F  Water - 12,162.1 Ib/hr
220°F  Organics - 2873.8 Ib/hr
        Water = 12,162.1 Ib/hr |(1134.2 BTU/lb - ,137.97 BTU/lb)|

                + 12,162.1 Ib/hr |^°.BIp | (170-70)°F|  = 13,332,459  BTU/lb

        Organics = 2873.8 Ib/hr l-^f-tp | (220 - 70)°F|  = 237,089  BTU/hr

        Total = 13,569,548 BTU/hr

        Steam Use = x Ib/hr |(1194.1 BTU/lb  - 1153.4  BTU/lb)|  +
                                     -.   ' :~J
                    x Ib/hr |965.2 BTU/lb| = 13,569,548 BTU/hr

                    x = 13,490 Ib/hr steam,  150 psia  saturated

Process 2-A—Raw Oil—Simultaneous MIBK and Water Extraction

Extractor—
Raw Oil -  9000  Ib/hr
Nonvolatile Organics -
           7649.9  Ib/hr
Volatile Organics -
           630.5  Ib/hr
Water - 719.6 Ib/hr

MIBK - 9108.6 Ib/hr
Water - 12,641.8 Ib/hr
                         Overhead Effluent  -
                                      30,750.4  Ib/hr
                         Nonvolatile Organics -
                                        7649.9  Ib/hr
                         Volatile Organics-630.5  Ib/hr
                         Water - 13,361.4 Ib/hr
                         MIBK - 9108.6 Ib/hr
                         Insoluble Oil Phase - 0 Ib/hr
                                     165

-------
       Raw Oil

Nonvolatile Organics = 9000 Ib/hr (472/555.3|  = 7649.9 Ib/hr

Volatile Organics = 9000 Ib/hr |38.9/555.3| = 630.5 Ib/hr

Water = 9000 Ib/hr  |44.4/555.3|  = 719.6 Ib/hr

       Water = 9000 Ib/hr [780/555.31  = 12,641.8 Ib/hr

       MIBK = 9000 Ib/hr J562/55.3|  =  9108.6 Ib/hr
       Separator—
Overhead Effluent -
            30,750.4 Ib/hr
Nonvolatile Organics -
              7649.9 Ib/hr
Volatile Organics -
               630.5 Ib/hr

Water - 13,361.4 Ib/hr
MIBK - 9,108.6 Ib/hr
                                                   Aqueous Phase-18,740.7 Ib/hr
                                                   Nonvolatile Organics -
                                                                   5802.3 Ib/hr
                                                   Volatile Organics-384.1 Ib/hr
                                                   Water - 12,158.8 Ib/hr
                                                   MIBK - 395.5

                                                   MIBKFhase-12,009.7 Ib/hr
                                                   Nonvolatile Organics -
                                                                1847.6 Ib/hr
                                                   Volatile Organics -
                                                                 246.4 Ib/hr
                                                   Water - 1202.6 Ib/hr
                                                   MIBK - 8713.1 Ib/hr

        Aqueous  Phase = 30,750.4 Ib/hr  [(1153 + 3.3)/1897.3|  = 18,740.7 Ib/hr

 Nonvolatile Organics = 18,740.7 Ib/hr  (358/1156.31 = 5802.3 Ib/hr

 Volatile  Organics  =  18,740.7  Ib/hr [(23.6 + OJ)/1156.3 |  = 384.1 Ib/hr

 Water = 18,740.7 Ib/hr | (748.3 + 0.9)/1156.31  = 12,158.8 Ib/hr

 MIBK =  18,740.7 Ib/hr |(23.1 +0.3)/1156.31  =  395.5  Ib/hr

        MIBK Phase  =  30,750.4  Ib/hr  [741/1897.3|  =  12,009.7 Ib/hr

 Nonvolatile Organics  = 12,009.7 Ib/hr  |114/741|  =  1847.6 Ib/hr

 Volatile  Organics  =  12,009.7  Ib/hr  j15.2/741|  = 246.4 Ib/hr

Water = 12,009.7 Ib/hr |74.2/741| = 1,202-6  Ib/hr

MIBK =  12,009.7 Ib/hr |537.6/74l| = 8,713.1  Ib/hr
                                    166

-------
Evaporator (or Column)—
70°F
hr
hr
hr
358.43°F
/^- 0.45


9 BTU


f)/,
249 °F MIBK - 8713.1 Ib/hr
244°F Organics - 2094.0 Ib/hr
244°F Condensate - 3028 Ib/hr
/, 7rA°W 4. S71 ^ 1 IK /tit- .
MIBK Soluble Phase -
           12,009.7 Ib/hr
Nonvolatile Organics -
             1847.6 Ib/hr
Volatile Organics -
              246.4 Ib/hr
Water - 1202.6 Ib/hr
MIBK - 8713.1 Ib/hr
Steam
150 psia saturated
       MIBK = 8713.1 Ib/hr
                            J.D    r

                182.5 BTU/lb | + 8713.1 Ib/hr  ifj^T^T^ 1  (2^9 - 244) °FJ =

                       1,434,708 BTU/hr

       Organics =  (estimate cp to be °^ ^ }  = 2094'° lb/hr l^5?  opU| '


                       |(244 - 70)°F| = 200,396 BTU/hr

       Water = 1202.6 lb/hr  |^°.BIp| (212 - 70)°F| + 1202.6 lb/hr | •

                        [970.3 BTU/lb  = 1,337,652 BTU/hr

       Total = 2,972,756 BTU/hr

       Steam Use = x lb/hr  [(1194.1 BTU/lb - 1162.0 BTU/lb)|+

                   x lb/hr  [949.5 BTU/lb| =  2,972,756 BTU/hr

                   x = 3,028 lb/hr steam, 150 psia saturated
                                     167

-------
 Vacuum Evaporator (Double Effect)—
 Water Soluble Phase -
           18,740.7 Ib/hr
 Nonvolatile Organics -
             5802.3 Ib/hr
 Volatile Organics  -
              384.1 Ib/hr
 Water - 12,158.8 Ib/hr
 MIBK - 395.5 Ib/hr
 Steam
  150 psia saturated
Water = 12,158.8 Ib/hr
70°F
358.43°F





249°F MIBK - 395.5 Ib/hr
244°F Organics - 6186.4 Ib/hr
244°F Condensate

                                         (212  -  70)°F|+ 12,158.8  Ib/hr
                • | 970. 3  BTU/lb |  =  13,524,233  BTU/hr

       MIBK =  395.5  Ib/hr  [°90TU|  (244 - 70)°F|+ 395.5  Ib/hr

                                                          (249 - 244) °F | =
         I 82.5 BTU/lb|   + 395.5 Ib/hr

                 65,124 BTU/hr
        Organics  =  (estimate  cp  to be
                                      10.55  BTUi
                                            6186.4 Ib/hr
iQ.55 BTUi
'Ib  • °F I
                                      lib  .  °F  i>

                 •|(244 -  70)°F|  =  592,038  BTU/hr

       Total = 14,181,395  BTU/hr

       Steam Use = x  Ib/hr |(1194.1 BTU/lb - 1162.0 BTU/lb)|  +

                   x  Ib/hr 1949.5  BTU/lb |  = 14,181,,395 BTU/hr

                   x  = 14,447  Ib/hr steam,  150  psia saturated

Process 2-B—Vacuum Stripped Oil—Simultaneous  MIBK and Water Extraction —

Vacuum Evaporator (Stripper)—
                                     168

-------
Raw Oil - 9000 Ib/hr
Organics -7946.1 Ib/hr
Water - 1053.9 Ib/hr
Steam - 1844 Ib/hr
                                                 Volatiles - 1323.0 Ib/hr
                                                 Organics - 269.1 Ib/hr
                                                 Water - 1053.9 Ib/hr
                                                 Vacuum Stripped Oil -
                                                               7677.0 Ib/hr
                                                 Nonvolatile Organics -
                                                               7452.8 Ib/hr
                                                 Volatile Organics
                                                                224.2 Ib/hr
       Raw Oil
Organics = 9000 Ib/hr  |.8829| =  7946.1 Ib/hr

Water = 9000 Ib/hr  |.117l| = 1053.9 Ib/hr

       Volatiles =  9000 Ib/hr  |.147| = 1323.0 Ib/hr

Organics = 1323.0 Ib/hr  |.2034|  = 269.1 Ib/hr

Water = 1323.0 Ib/hr  |.7966J = 1053.9 Ib/hr

       Vacuum Stripped Oil = 9000 Ib/hr |.853| = 7677.0 Ib/hr

Nonvolatile Organics = 7677.0 Ib/hr |1629/1678| = 7452.8 Ib/hr

Volatile Organics = 7677.0 Ib/hr |49/1678| = 224.2 Ib/hr

       Volatiles

Water = 1053.9 Ib/hr  I*'0 BI^ 1(170 - 70)°F[ + 1053.9 Ib/hr  |996.2 BTU/lb|
Organics = 269.1 Ib/hr

                   = 66,513 BTU/hr

Vacuum Stripped Oil = 7677.0 Ib/hr

       Total = 1,855,151 BTU/hr
                     1,155,285 BTU/hr

                        °;5j-6I17BTU |(170 - 70)°F| + |269.1 lb/hr| 195.5 BTU/lb|

                                             1(220 - 70)°F| = 633,353 BTU/hr
       Steam Use = x Ib/hr  | (1194.1 BTU/lb - 1153.4 BTU/lb) |

                    + x Ib/hr  | 965. 2 BTU/lb | = 1,855,151 BTU/hr

                   x = 1844  Ib/hr steam, 150 psia saturated
                                     169

-------
 Extractor—
 Vacuum Stripped Oil -
               7677.0 Ib/hr
 Nonvolatile Organics -
               7452.8 Ib/hr
 Volatile Organics -
                224.2 Ib/hr
 Water - 8692.7 Ib/hr
 MIBK - 5481.0 Ib/hr
                                                 Overhead Effluent -
                                                              21,850.7 Ib/hr
                                                 Nonvolatile Organics -
                                                                7452.8 Ib/hr
                                                 Volatile Organics -
                                                                 224.2 Ib/hr
                                                 Water - 8692.7 Ib/hr
                                                 MIBK - 5481.0 Ib/hr
                                                 Insoluble Oil Phase - 0 Ib/hr
        MIBK = 7677.0 Ib/hr |1198/1678]  =  5481.0  Ib/hr

        Water = 7677.0 Ib/hr |l900/1678| = 8692.7 Ib/hr

        Separator—

                                                  Aqueous Phase-13,560.6 Ib/hr
Overhead Effluent -
            21,850.7 Ib/hr
Nonvolatile Organics -
              7452.8 Ib/hr
Volatile Organics -
               224.2 Ib/hr
Water - 8692.7 Ib/hr
MIBK - 5481.0 Ib/hr
                                                 Nonvolatile Organics  -
                                                                  3801.8  Ib/hr
                                                 Volatile Organics -
                                                                  152.4  Ib/hr
                                                 Water - 8527.1 Ib/hr
                                                 MIBK - 1079.3  Ib/hr


                                                 MIBK Phase - 8290.1 Ib/hr
                                                 Nonvolatile Organics -
                                                               3651.0 Ib/hr
                                                 Volatile Organics-71.8  Ib/hr
                                                 Water - 165.6 Ib/hr
                                                 MIBK - 4401.7 Ib/hr

       Aqueous Phaee---23^850,7-lb/hr  |(2746 + 218)/4776| = 13,560.6 Ib/hr

Nonvolatile Organics = 13,560.6 Ib/hr  |(735 + 96)/2964| = 3801.8  Ib/hr

Volatile Organics = 13,560.6 Ib/hr  |(31.4 + 1.9)/2964| = 152.4 Ib/hr

Water = 13,560.6 Ib/hr |(1790.1 + 73.7)/2964| = 8527.1 Ib/hr

MIBK = 13,560.6 Ib/hr | (189.5 + 46.4)/2964| = 1079-.3 Ib/hr
                                     170

-------
       MIBK Phase =  21,850.7  Ib/hr  |1812/4776| = 8290.1 Ib/hr

Nonvolatile Organics =  8290.1 Ib/hr  |798/1812] = 3651.0 Ib/hr

Volatile Organics =  8290.1  Ib/hr  |15.7/1812| =71.8 Ib/hr

Water = 8290.1  Ib/hr |36.2/1812)  = 165.6 Ib/hr

MIBK = 8290.1 Ib/hr  |962.1/1812|  = 4401.7 Ib/hr

Evaporator  (or  Column)—
MIBK  Soluble  Phase -
              8290.1 Ib/hr
Nonvolatile Organics  -
              3651.0 Ib/hr
Volatile  Organics  -
                71.8 Ib/hr
Water - 165.6 Ib/hr
MIBK  - 4401.7 Ib/hr


Steam
'150 psia  saturated
       MIBK =  4401.7  Ib/hr
70°F
r
r
r
358.43°F
0.459


BTU


OLI,
249°F MIBK - 4401.7 Ib/hr
244°F Organics - 3722.8 Ib/hr
244°F Condensate - 1289 Ib/hr
_ 7fA°T7 4- AAD1 7 Th/'hr- •
             lib  •  °F    'v

|82.5  BTU/lb|  + 4401.7  Ib/hr

          = 724,788 BTU/hr
                                                       (249 - 244)°F|
       Organics  =  (estimate  cp  to  be  ^  .  »F  ) =  3722.8 Ib/hr  1]^  . °F  I


                    |(244  - 70)°F|  = 356,272 BTU/hr

       Water = 165.6  Ib/hr  |J-;°.B^|  (212  - 70)°F| +  165.6 Ib/hr | •
                    |(970.3  BTU/lb|  = 184,197  BTU/hr

       Total =  1,265,257  BTU/hr

       Steam Use  = x Ib/hr  |(1194.1 BTU/lb  -  1162.0  BTU/lb)|

                   + x Ib/hr |949.5 BTU/lb| = 1,265,257  BTU/hr

                   x = 1289 Ib/hr  steam,  150  psia  saturated
                                      171

-------
 Vacuum Evaporator (Double  Effect)—
 Water Soluble Phase -
            13,560.6 Ib/hr
 Nonvolatile Organics -
              3801.8 Ib/hr
 Volatile Organics  -
               152.4 Ib/hr
 Water - 8527.1 Ib/hr
 MIBK - 1079.3 Ib/hr
 Steam
 150 psia saturated
        Water  = 8527.1  Ib/hr
70°F
r
r
r
358.43°F





249°F MIBK - 1079.3 Ib/hr
244°F Organics - 3954.2 Ib/hr
244 °F Condensate - 10,229 Ib/hr

                             11.0 BTU
                              Ib  •  °F

                   970.3  BTU/lb|  =  9,484,693 BTU/hr
                                (212 - 70)°F| + 8527.1 lb/hr| •
MIBK = 1079.3 Ib/hr
                                        (244 -  70)°F| +  1079.3  Ib/hr |
                                                                Ib
           |82.5 BTU/lb| + 1079.3 Ib/hr  |^'4^90^TU  |(249 - 244)°F|

                   = 177,718 BTU/hr

r,     •     f  ...  ^     ,.  ^  0.55 BTU^   ,__. 0 ., ,,   10.55 BTU
Organics = (estimate cp to be —	5^—) =  3954.2 Ib/hr
—~~^   :                        Ib •  F

                  |(244 - 70)°F| = 378,417 BTU/hr

Total = 10,040,828 BTU/hr

Steam Use = x Ib/hr  |(1194.1 BTU/lb - 1162.0 BTU/lb)|

            + x Ib/hr  |949.5 BTU/lb| =  10,0401828  BTU/hr

            x = 10,229 Ib/hr steam, 150 psia saturated
MAJOR EQUIPMENT COST ESTIMATE

       Total installed equipment  cost  estimates were developed for each of
the four extraction processes.  The  equipment  cost  summary for each of the
processes is shown below.  Detailed  equipment  cost  estimate calculations
are included for Process 1-B only, as  an  example.
                                     172

-------
       The plant design basis is a 9000 Ib/hr or 14.3 GPM feed rate of raw
pyrolytic oil into the plant.  All equipment is scaled up directly from exper-
imental results.

       Equipment cost estimates are taken from Peters and Timmerhouse [14]
except for estimates of the extractors which are taken from an article by
J. W. Drew [21].  All costs are updated to the period Nov. - Dec. 1979 using
the Chemical Engineering Plant Cost Index.  Installation costs are estimated
to be 39% of purchased equipment costs [14],

       The evaporators and strippers were not designed in detail.  The heat
requirements necessary to perform the particular unit operation were esti-
mated.  The results were used to directly, to estimate the cost of a piece of
equipment that would satisfy the heat requirements.  The extractor cost esti-
mates are based on Drew [21], which uses an arbitrary column height of 20 feet
as a reference point.  Although the plant extractor dimensions would not be
expected to be the same as those in the design calculations, the reference
height of 20 feet was used to calculate the equipment cost estimate.


EQUIPMENT COSTS


Process IB—(2 Stage Continuous Extraction—Vacuum Stripped Oil)—Cost Summary

Raw Oil Storage Tank                          1             $187,631
Raw Oil Feed Tank                             2                9,382
Vacuum Evaporator - Raw Oil                   3               78,180
Volatiles Storage Tank                ,        4               73,489
Extractor - 1st Stage                         5               77,758
Water Storage Tank                            6               46,908
MIBK Storage Tank                             7              139,472
Spent Oil Storage Tank                        8                7,505
Holdup Tank                                   9               35,963
Extractor - 2nd Stage                        10               80,808
MIBK Soluble - Holdup Tank                   11               28,145
Evaporator                                   12               51,599
MIBK Holdup Tank                             13               28,145
MIBK Soluble - Product Storage               14               39,090
Water Soluble - Holdup Tank                  15               36,901
Vacuum Evaporator                            16              150,105
Water Soluble - Product Storage Tank         17              101,008

Total Installed Equipment Cost                            $1,172,089
                                      173

-------
 Raw Oil Storage Tank — 1

 Raw Oil = 9000 Ib/hr I   *J ..  I T~T|  = 118.7 ft3/hr
                      1 62.4 ID ' 1. 215 '

 Capacity = 118.7 ft3/hr ]7.48 gal/ft3]  =887.9 gal/hr

 Assume a two week supply = 887.9 gal/hr | 24 hr/da | 14 da|  = 298,348 gal

 Use a tank volume of 300, OOQ gal (304ss)
 From Figures 13-59  [14]   Storage Tanks:

 Purchased cost = $16,000 |3.75 | 246.8/109. 7 1  = $134,986

 The factor for converting from C-steel  to 304ss is 3.75.

 Installed cost = $134,986 I.1.39J  = $187,631

 Raw Oil Feed Tank —  2

 Raw Oil = 9000 Ib/hr [         \      |  = 118.7 ft3/hr
 Capacity = 118.7  ft3/hr | 7.48  gal/ft3 1' =  887.8 gal/hr

 Choose a 4 hour Holdup   = 474.8  gal
 Use a tank volume of  500 gal  (304ss)
 From Figures 13-56 [14]  Cost of  Mixing,  storage,  and pressure tanks:

 Purchased cost  -  $3000  | 246.8/109.7 | = $6749

 Installed cost  =  $6749  |l.39|  =  $9382

 Vacuum Evaporator (Stripper) — 3

 Heat  requirements —  q  = 1,855,151 BTU/hr

        At1  = (358.43  -  70) °F   At2 = (220  - 170)°F

                Atl "  At2      288.43-50
          1m   ln(At1/At2)   ln(288.43/50)

       q  = UAAt.  ;  Estimate U =  200 	^12	
               lm                   hr.ft2.°F,s ,.

       A	g_  = 1.855,151 =         2
       A   U t.    200(136)    oo.z.rt
              lm

From;Figure  14-28  [14] agitated  falling-film evaporators (304ss)

Purchas-ed cost =  $25,000 | 246.8/109.1\ = $56,244

Installed cost =  $56,244  1.39| = $78,180
                                     174

-------
Volatiles - Product  Storage  Tank—   4


       Volatiles—



Organics = 269.1  Ib/hr |  ft3/62.4  Ib  | 1/1.047| - 4.12 ft3/hr


Water = 1053.9 Ib/hr |ft3/62.4  Ib | = 16.89 ft3/hr


Total Volume = 21.01 ft3/hr  J7.48 gal/ft3 | = 157 gal/hr



Assume a 1 week capacity = 157  gal/hr  | 24 hr/da | 7 da| = 26,400 gal


Use a tank volume of 26,000  gal (304ss)

From Figures 13-56  [ 14]  Cost  of mixing, storage, and pressure tanks:


Purchased cost =  $23,500 | 246.8/109.7| = $52,870


Installed cost =  $52,870 |l.39| - $73,489


Extractor - 1st Stage—  5



Vacuum Stripped Oil  = 7677 Ib/hr  |ft3/62.4 Ib | 1/1.238 | hr/60 min | 65 min |


                       = 107.66 ft3


Water'= 13,183.2  Ib/hr |ft3/62.4  Ib  | hr/60 min | 65 min| = 228.88 ft3


Use a residence time of  65 min.

                         3
Total volume = 336.53 ft

                                  3
Use an extractor  volume  of 350  ft  (304ss)

                             IT  2
From Reference  [  21] :   V = 7-  d h


where  h is assumed  to be 20 feet


       350 ft3 =  (Tr/4)d2(20)


       d = 4.72 ft or 56.64 inches



From Figure 10  [ 21]  - Cost of  columns:


Purchased cost =  $51,000 | 0.8 |  246.8/1801 = $55,941


The factor given  for converting from a 316ss column to a 304ss column is 0.8.



Installed cost =  $55,941 |l.39| = $77,758
                                    175

-------
 Water Storage Tank—   6

 Water = 13,183.2 Ib/hr |ft3/62.4  Ib| =  211.27 ft3/hr

 Capacity = 211.27 ft3/hr | 7.48  gal/ft3| =1580 gal/hr

 Assume a 3 day supply =  1580  gal/hr  | 24 hr/da | 3 da| = 113,781 gal

 Use a tank volume of  110,000  gal  (C-S)

 From Figures 13-56 [14]  Cost  of mixing, storage, and pressure tanks:

 Purchased cost = $15,000 |246.8/109.7|  = $33,747

 Installed cost = $33,747 |l.39| = $46,908

 MIBK Storage tank—   7

 MIBK = 6248.2 Ib/hr |  ft3/62.4 Ib  |1/0.8011 = 125.01 ft3/hr

 Capacity = 125.01 ft3/hr |7.48  gal/ft3| = 935 gal/hr

 Assume a 1% loss of MIBK in system through pumps, leakage, etc., which
 requires makeup.

 Assume a two week supply = 935  gal/hr | 24 hr/da | 14 da |  .Ol| = 3142 gal

 Use a tank volume of  3500 gal (C-S)
 From Figures 13-56 [  14 ]  Cost  of mixing, storagej and pressure tanks:

 Purchased cost = $2400 | 246.8/109.71 =  $5400

 Installed cost = $5400 |l.39| = $7505

 Spent  Oil Storage Tank—  8

 Insoluble Oil Phase

 Organics  =  4238.2 Ib/hr  |ft3/62.4 Ib |1/1.235| = 55 ft3/hr

 Water  =  1021.1  Ib/hr  |ft3/62.4  Ib| = 16.36 ft3/hr

 Total  Capacity  =  71.36 ft3/hr J7.48  gal/ft3|= 533.77 gal/hr

Assume a  one week capacity =  533.77  gal/hr  24 hr/da | 7/da  = 89,673  gal

Use a  tank volume of  90,000 gal (304ss)
From Figures  13-56  [  14  ]  Cost of mixing, storage, and pressure tanks:

Purchased cost  =  $44,600  |246.8/109.7|  = $100,340

Installed cost  =  $100,340  |l.39| = 139,472

                                     176

-------
Holdup Tank—  9


Aqueous Phase = 15,600.9 Ib/hr | ft3/62.4 Ib |1/1.235] - 202.44 ft3/hr


Capacity = 202.44 ft3/hr |7.48 gal/ft3| = 1514.3 gal/hr


Choose a 4 hour Holdup  = 6057 gal


Use a tank volume of  600 gal  (308ss)


From Figures 13-56  [ 14 ] (Cost of mixing, storage, and pressure tanks:


Purchased cost = $11,500 | 246.8/109.7| = $25,872


Installed cost = $25,872 |l.39| = $35,963


Extractor - 2nd Stage—  10


Aqueous Phase = 15,600.9 Ib/hr |ft3/62.4 Ib |1/1.235 |hr/60 min | 65 minj


                        = 219.31 ft


MIBK = 6248.2 Ib/hr |ft3/62.4 Ib |1/0.801 | hr/60 min | 65 min| = 135.43 ft3


Use a residence time  of 65 min

                        3
Total volume = 354.74 ft

                                 3
Use an extractor volume of 375 ft  (304ss)

                                   2
From Reference [ 21 J  :   V =  (ir/4)d h


where  h is assumed to be 20  feet


       375 ft3 = (TT/4)d2(20)


       d = 4.89 ft or 58.63 inches


From Figure 10  [ 21J - Cost  of columns:


Purchased cost = $53,000 | 0.8 | 246.8/1801 = $58,135


The factor given for  converting from a 316ss column to a 304ss column is 0.8.


Installed cost - $58,135 |l.39| = $80,808


MIBK Soluble - Holdup Tank—  11
                                                      A

MIBK = 6248.2 Ib/hr |ft3/62.4 Ib | l/0.80l| = 125.01 ft /hr


Organics = 565 Ib/hr  | ft3/62.4 Ib | 1/1.235] =7.33 ft3/hr
                                     177

-------
 Capacity = 132.34 ft3/hr | 7.48 gal/ft3 |  = 990 gal/hr


 Choose a 4 hour Holdup = 3960 gal


 Use a tank volume of 4000 gal (304ss)


 From Figure  13- 56  [14] Cost of mixing, storage,  and pressure  tanks:


 Purchased cost = $9,000 | 246. 8/109. 7 |  =  $20,248


 Installed cost = $20,248 |l.39|  = $28,145


 Evaporator (MIBK Phase) —   12


 Heat Requirements—  q = 1,082,907 BTU/hr


        A^ = (244 - 70) °F   At2  = (358.43 -  249) °F


                At. - At_        1 74 -
        AI-
        fl
          lm   ln(At1/At2)     ln(174/109.43)
        q = UAAt,  ;   Estimate U =  200 -   -
                lm                   hr  • ft2 • °F

        A -   a   -  1*082.907 _          2
        A   UAt.   "   200(139)   Ja-y:)  "
               lm

 From Figures  14-28  [14]  agitated  falling film evaporators:


 Purchased cost = $16,500 1 246. 8/109. 7 | = $37,121


 Installed cost = $37,121 |l.39| = $51,599

 MIBK Holdup Tank—    13


 MIBK =  6248.2 Ib/hr |ft3/62.4 Ib  | 1/0. 801 1  =  125.01  ft3/hr


 Capacity = 125.01 ft3/hr |7.48  gal/ft3)  = 935.1  gal/hr


 Choose  a 4 hour  Holdup = 3740 gal

 Use  a tank volume of 4000 gal (304ss)


 From Figure  13-56   [14]  Cost  of mixing,  storage, and  pressure tanks:

 Purchased  cost =  $9,000  | 246.8/109.7 1  =  $20,248

 Installed  cost =  $20,248 |l.39| = $28,145


MIBK Soluble  - Product Storage  Tank —    14


MIBK Soluble  Organics =  565  Ib/hr ft3/62.4 Ib | 1/1.235]  =  7.33 ft3/hr


Capacity =7.33 ft3/hr |  7.48 gal/f t3 |  =54.8  gal/hr



                                      178

-------
Assume 1 week capacity = 54.8 gal/hr  (24 hr/da | 7 da/wk|  = 9211 gal

Use a tank volume of 9,000 gal (304ss)

From Figure  13-56  [14]  Cost of mixing, storage, and pressure tanks:

Purchased cost = $12,500 | 246.8/109.7] = $28,122

Installed cost = $28,122 | 1.39| = $39,090

Water Soluble - Holdup Tank—  15

Water = 12,162.1 Ib/hr |ft3/62.4 lb| = 194.9 ft3/hr

Organics = 2873.8 Ib/hr | ft3/62.4 lb| 1/1.235) = 37.29 ft3/hr

Capacity = 232.2 ft3/hr | 7.48 gal/ft3] = 1736.8 gal/hr

Choose a 4 hour Holdup  = 6947 gal

Use a tank volume of 7,000 gal (304ss)

From   Figure  13-56  [ 14]  Cost of mixing, storage, and pressure tanks:

Purchased cost = $11,800 | 246.8/109.7 | = $26,547

Installed cost = $26,547 |l.39| = $36,901

Vacuum Evaporator —  16

Heat Requirements — q = 13,569,548 BTU/hr

       At-L = (220 - 70)°F    At2 =  (358.43 - 220)°F

               Atl"At2        150- 138.43  _  ,.„
       Atlm   ln(At1/At2)  " ln(150/138.43)
       q = UAAtn  ;   Estimate U = 500 - = -
               lm                    hr-ft  -°F

       A = q/UATlm = 13,569,548/500(144) = 188.46 ft2

From Figure   14-28  [14] agitated falling-film evaporators

Purchased cost =  $48,000 |  246.8/109.7 | = $107,989

Installed cost =  $107,989  |l.39| = $150,105

Water Soluble - Product Storage Tank —  17
                                         q                             O
Water Soluble Organics = 2873.8 Ib/hr | ft /62.4 Ib | 1/1.235] = 37.29 ft ,/hr
                                     179

-------
Capacity = 37.29 ft3/hr |7.48 gal/ft3|  = 279 gal/hr




Assumg a 1 week capacity = 279 gal/hr | 24 hr/da | 7 da/wk|  = 46,860 gal




Use a tank volume of 50,000 gal (304ss)




From  Figure  13-56   [14]  Cost of mixing, storage, and pressure tanks:




Purchased cost • $32,300 | 246.8/109.7]  = $72,668




Installed cost = $72,668 I 1.39| - $101,008
                                    180

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                                  APPENDIX D


                             PHYSICAL PROPERTIES




                  TABLE D-l.  TYPICAL VOLATILES ANALYSIS*
Component

Water
Acetic Acid
Methanol
Furfural
Formic Acid
Propionic Acid
Unknown
Weight
Per cent
68.24
20.48
1.70
2.00
2.42
0.60
4.56
*
 Experimental Results
                TABLE D-2.  HEAT CAPACITY ESTIMATION* - VOLATILES


Component

Water
Acetic Acid
Methanol
Furfural
Formic Acid
Propionic Acid
Unknown
cp
(A)
Weight
Per cent

68.24
20.48
1.70
2.00
2.42
0.60
4.56
- Weighted Average -
(B)
cp
BTU
Ib • °F
1.00
0.522
0.590
0.416
0.524
0.560
0.50 (Est.)


(A) * (B)


0.6824
0.1069
0.0100
0.0083
0.0127
0.0034
0.0228
0.8465
  [ 15  ]  Table 3-176 Specific Heats of Organic Liquids
                                      181

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       TABLE D-3.   HEAT CAPACITY ESTIMATION—-VOLATILES  LESS WATER


Component
Methanol
Formic Acid
Acetic Acid
Propionic Acid
Furfural
Unknown
Total


grams
1.4
2.0
16.9
0.5
1.65
3.75
26.2
(C)
cp
BTU
Ib • °F
0.590
0.524
0.522
0.560
0.416
0.50 (Est.)

(D)
Weight
Fraction
0.0534
0.0763
0.6450
0.0191
0.0630
0.1431



(C) * (D)
0.0315
0.0400
0.3367
0.0107
0.0262
0.0716

             cp - weighted average = 0.5167
Experimental Results
           TABLE D-4.   DENSITY ESTIMATION—VOLATILES  LESS WATER

Component

Acetic -Acid
Methanol
Furfural
Formic Acid
Propionic Acid
Unknown
(A)
Weight
Fraction
0.6450
0.0534
0.0630
0.0763
0.0191
0.1431
(B)
Density
g/ml
1.0491
0.7914
1.1598
1.220
0.992
1.00 (Est.)
•-.v'-:."
(A) * (B)-"';-1*'
-/i...-
0.6767
0.0423
0.0731
0.0931
0.0189
0.1431
             Density (p)  - Weighted Average = 1.0472
     TABLE D-5.   HEAT OF VAPORIZATION*  ESTIMATION—VOLATILES LESS WATER
Component
Acetic Acid
Methanol
Furfural
Formic Acid
Propionic Acid
Unknown
Boiling
Point- 0;C
118.3
64.7
60.5
101
139.5
—
Heat of Vaporization
cal/g BTU/lb
96.8
262.8
107.5
120
98.8
100 (Est)
174.24
473.04
193.5
216.0
177.84
180 (Est)
Weight
Per cent
0.6450
0.0534
0.0630
0.0763
0.0191
0.1431

112.3848
25.2603
12.1905
16.4808
3.3967
25.7580
                   Heat  of Vaporization - Weighted Average = 195.5 BTU/lb



[20]  , pp. 9-85 — 9.95
                                    182

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          TABLE D-6.  SPECIFIC HEATS OF VARIOUS ORGANIC COMPOUNDS*

Compound
Methyl Ethyl Ketone
Methyl Isobutyl Ketone
Methyl Isopropyl Ketone
Methyl Hexyl Ketone
Water
Specific Heat
BTU CAL
Ib • °F "1 g • °F
0.549
0.459
0.525
0.55
1.0
Temperature
Range (°C)
20 - 78°C
20
20 - 91
22 - 168
15
  [ 20 ],pp. 9-133
        TABLE D-7.  HEAT OF VAPORIZATION OF VARIOUS ORGANIC COMPOUNDS
Compound
Methyl Ethyl Ketone
Methyl Isopropyl Ketone
Methyl n-Butyl Ketone
Methyl n-Amyl Ketone
Methyl Hexyl Ketone
Water
Heat of Vaporization
cal/gram
106.0
89.8
82.4
82.7
74.1
539.55
Temperature
°C
78.2
92
127
149.2
173
100
  [ 20 ], pp. 9-91
                       TABLE D-8.  PROPERTIES OF MIBK*
Molecular Weight
Density g/ml
Melting Point
Boiling Range
Solubility in Water
      100.16
   0.801 @20°/408
      -84.7 °C
   117 - 119 °C
2g/100g Water at 20°C
  [20], pp. 7-54
                                      183

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                                 GLOSSARY

 dissolved  organics:  The nonvolatile material remaining after evaporation of
        solvent  of  a  fraction  or phase.

 fraction:  A  solution or solid derived from extracting a phase  (as defined
        below) with an immiscible solvent.

 neutrals of high aromaticity  (NHA):  Compounds in the pyrolytic oils which
        are nonpolar  and nonacidic  and exhibit UV fluorescing and absorbing
        (254 nm) characteristics.

 nonvolatile organics (NVO):   The fraction of organic material remaining after
        vacuum stripping at approximately 2 mm Hg and ambient temperature
        which  contains phenolics, polyhydroxy neutral compounds, and neu-
        tral compounds of high aromaticity.                               «&*.

 organic volatiles:   The organic volatiles is equal to the difference between
        the total volatiles and amount of water in the total volatiles. !'!
                                                                        •"•j
 phase:  A  solution or solid derived from the original pyrolytic oil sample
        by  evaporation or extraction, e.g. volatile phase, aqueous phase,
        organic  phase, insoluble tar.
                                                                      - - i
 phenolics:  The class of acidic compounds which are titratable with meth- '
        anolic potassium hydroxide  in N,N-dimethyl formamide solvent, and
        identifications are confirmed by GC, LC, TLC and IR evidence.

 polyhydroxy compounds:  The class  of nonacidic compounds which are very
       water soluble, produce a blue color with Orcinol reagent, which  is
       a characteristic of sugars, and have RF values similar to those  of
       known sugar on a TLC plate.

 total volatiles:   The total volatile material, including both water and
       organics, removed by vacuum stripping at approximately 2 mm Hg and
       ambient  temperature.

organic volatiles:  The organic volatiles is equal to the difference between
       the total volatiles and amount of water in the total volatiles.
                                     184

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                                    TECHNICAL REPORT DATA
                             {Please read Instructions on the reverse before completing)
 1. REPORT NO.
  EPA-600/2-80-122
             3. RECIPIENT'S ACCESSION NO.
 4. TITLE AND SUBTITLE
                                                            5. REPORT DATE
 Pyrolytic Oils - Characterization and  Data Development
 for  Continuous Processing
                August  1980 (Issuing Date)
             6. PERFORMING ORGANIZATION CODE
 . AUTHOR(S)
 ]. A.  Knight, L. W.  Elston, D. R. Hurst,  and
 R. J.  Kovac
             8. PERFORMING ORGANIZATION REPORT NO.
 9. PERFORMING ORGANIZATION NAME AND ADDRESS

  Engineering Experiment Station
  Georgia Institute of Technology
  Atlanta, Georgia  30332
             10. PROGRAM ELEMENT NO.

                IDr.Ria	
             11. CONTRACT/GRANT NO.


              R804416  and  R806403
 12. SPONSORING AGENCY NAME AND ADDRESS
  Municipal  Environmental  Research Laboratory— Cin., OH
  Office of Research  and Development
  U.S.  Environmental  Research Agency
  Cincinnati, Ohio 45268
                                                            13. TYPE OF REPORT AND PERIOD COVERED
             14.'SPONSORING AGENCY CODE


              EPA/600/14
 15. SUPPLEMENTARY NOTES
  Project Officer:   Charles J. Rogers   (513)  684-4335
 16. ABSTRACT
  Pyrolytic oils produced by the pyrolysis  of forestry residues  in  a  vertical bed,
  countercurrent flow  reactor have been  thoroughly characterized.   The pyrolytic oils
  were  produced in a 500-1b. per hour pilot plant and in a 50-ton per day field
  development facility.   The overall chemical  and physical properties have been de-
  termined by standard analytical techniques.   The oils are dark brown to black with
  a  burnt, pungent odor and have a boiling  range of about 100°C  to  approximately 200°C
  at which point thermal  degradation begins to occur.  Pyrolytic oils contained
  phenolics, polyhydroxy neutral compounds  and volatile acidic compounds.
 7.
                                 KEY WORDS AND DOCUMENT ANALYSIS
                   DESCRIPTORS
                                               b.IDENTIFIERS/OPEN ENDED TERMS
                             COSATI Field/Group
 Pyrolytic  oils
 Pyrolysis
 Polyhydroxy neutral compounds
 Degradation
 Extraction
 Phenols
  thermal degradation
  volatilization and
    compounds
13B
 8. DISTRIBUTION STATEMENT
 Release to  public
19. SECURITY CLASS (This Report)

  Unclassified
                                                                           11. NO. OF PAGES
                                                                             197
20. SECURITY CLASS (This page)

  Unclassified
                                                                          22. PRICE
EPA Form 2220-1 (9-73)
                                             185
               U.S. GOVERNMENT PRINTING OFFICE: 1980—657-165/0053

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