PARTIAL   OXIDATION

                 OF SOLID ORGANIC WASTES
     This final report (SW-7rg)  on work performed under

                Research Grant No.  EC-00263

(formerly successive Grant Nos.  were SW-00022 and UI-00552)

          to the Rensselaer Polytechnic Institute

             was written by WILLIAM W.  SHUSTER

 and has been reproduced as received from the grantee with

   the exception of a minor change in the introduction.
     U.S.  DEPARTMENT OF HEALTH,  EDUCATION,  AND WELFARE
         Public   Health   Service
               Environmental  Health Service
             Bureau of Solid  Waste Management
                           1970

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  Public  Health Service  Publication No.  2133
LIBRARY  OF CONGRESS CATALOG  CARD  NO.  74-609260
    For sale by the Superintendent of Documents, U.S. Government Printing Office
                 Washington, B.C., 20402 - Price $1

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                               FOREWORD






     Recent applications of scientific and engineering knowledge to the




development of new products and processes have had significant effects




upon the health, comfort, and well-being of the Nation's people.  While




such technical advances are, of course, most desirable, they have at the




same time, ever increasing stresses upon man's environment.  One particularly




pressing problem is that of solid waste disposal.  Not only have changing




patterns in social structure affected the quantity of solid wastes, but




also the quality and composition have changed.  The introduction of




increased amounts of materials resistant to biological and chemical




degradation has made the disposal of solid wastes increasingly difficult.




     The approach used in the present work has been to consider the




possibilities of utilizing the large organic portions of domestic solid




wastes as building blocks for useful compounds through a process of




pyrolysis, and partial combustion.  Such an approach is entirely consistent




with the objectives of the Solid Waste Disposal Act of 1965,to study ways




for reducing the amount of solid waste and to consider the recovery and




utilization of potential resources in solid wastes.




     This report has been prepared to describe the approach that has been




used to produce useful products from the Nation's huge store of solid waste




materials.  The methods and techniques described and the results obtained




to date will be useful to other workers in the field in pointing the




direction to a potentially useful new method of solid waste disposal.







                                      RICHARD D. VAUGHAN, Director




                                        Bureau of Solid Waste Management
                                  

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                             Table of Contents
III.       Theoretical Considerations
I.         Introduction 	     1

II.        Background	     3

           A.  General	     3
           B.  Incineration 	     3
           C.  Pyrolysis  	 ..... 	     5
           D.  Gas Chromatography	     6
           E.  Infrared Spectroscopy  	     7
           A.  Partial Combustion 	      9
           B.  Fluidization	     11
           C.  Gas Chromatography	     12
           D.  Infrared Spectroscopy  	     14

IV.        Materials and Apparatus	     17

           A.  Materials	     17

               1.  Analytical Standards 	     17
               2.  Carrier Gases	     17
               3.  Indicating Papers  	     18
               4.  Reagents for the Analysis of Formaldehyde
                   and Methanol	     18
               5.  Reagents for Syringe Reactions 	     18

           B.  Apparatus	     18

               1.  Reactor System Equipment 	     20
               2.  Sample Collection Equipment  	     24
               3.  Analytical Equipment 	     24

V.         Experimental Procedure 	     27

           A.  Paper	     27

               1.  Reactor Operation  	     27
               2.  Gas Chromatograph Operation  	     29

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VI.
VII.
VIII,

IX.
                                                       Page

B.  Dried Sewage Sludge (Orgro)  	    32

    1.  Reactor Operation  	    32
    2.  Analytical Run	    33

C.  Dried Leaves	    37

    1.  Reactor Operation  	    37
    2.  Analytical Runs	    38

Results	    43

A.  Reaction Runs Using Paper	    43
B.  Reaction Runs Using Orgro	    53
C.  Reaction Runs Using Leaves	    67

Discussion	    85

A.  Studies with Paper	    85
B.  Studies with Orgro	    87
C.  Studies with Leaves	    89

Summary and Conclusions  	    95

Literature Cited 	    97
                               List  of Tables
Table  1       Table  of Infrared  Absorption  Frequencies
               for Liquid  Samples

Table  2       Reagents and Conditions  for Syringe  Reactions

Table  3       Feed Materials  Composition

Table  4-       Summary of  Paper Reaction Runs

Table  5       Summary of  Retention Times

Table  6       Summary of  Leaf Reaction Runs

Table  7       Identification  of  Chromatogram  Peaks for
               Pyrolysis of Leaves at 250 C-300C

Table  8       Summary of  Identified Reaction  Products
                                                        Page



                                                         16

                                                         40

                                                         43

                                                         51

                                                         52

                                                         69


                                                         84

                                                         96
                                    VI

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                              List of Figures

                                                                  Page

Figure  1     Cellulose Molecule                                   10

Figure  2     Reactor System Schematic                             19

Figure  3     Brass Reactor                                        21

Figure  4     Black Iron Reactor                                   22

Figure  5     Ceramic Reactor                                      23

Figure  6     Gas Sampling Apparatus                               31

Figure  7     Infrared Gas Cell Loading Apparatus                  34

Figure  8     Typical Preparative Gas Chromatograph
              Collection Trap                                      36

Figure  9     Chromatograph Run - Sample #8                        45

Figure 10     Chromatograph Run - Sample #9                        46

Figure 11     Chromatograph Run - Sample #11                       47

Figure 12     Chromatograph Run - Sample #8 + Acetic Acid          48

Figure 13     Chromatograph Run - Sample #11 + Formaldehyde        49

Figure 14     Chromatograph Run - Sample #11 + Formic Acid         50

Figure 15     Chromatogram of Organic Liquid Effluents from
              a Partial Oxidation of Dried Sewage Sludge           54

Figure 16     Chromatogram of Organic Liquid Effluents from
              a Pyrolysis of Dried Sewage Sludge                   56

Figure 17     Infrared Absorption Spectrum of Low-Boiling
              Effluents from Partial Oxidation Held at -78C
              and Evacuated to 1/2 Atmosphere                      57

Figure 18     Infrared Absorption Spectrum of Low-Boiling
              Effluents from Partial Oxidation Held at 0 C
              and Evacuated to 1/3 Atmosphere                      58

Figure 19     Infrared Absorption Spectrum of Low-Boiling
              Effluents from Partial Oxidation Held at 25C
              and Evacuated to 1/3 Atmosphere:  First
              Extraction                                           59
                                   vii

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Figure 20     Infrared Absorption Spectrum of Low-Boiling
              Effluents from Pyrolysis Held at -78C and
              Evacuated to 1/2 Atmosphere                          60

Figure 21     Infrared Absorption Spectrum of Low-Boiling
              Effluents from Pyrolysis Held at 0 C and
              Evacuated to 1/3 Atmosphere                          61

Figure 22     Infrared Absorption Spectrum of Low-Boiling
              Effluents from Pyrolysis Held at 25C and
              Evacuated to 1/3 Atmosphere:  First Extraction       62

Figure 23     Infrared Absorption Spectrum Using a Sodium
              Chloride Liquid Cell of an Unknown Liquid
              (approximately 95% Pure)                             63

Figure 24-     Infrared Absorption Spectrum Using a Sodium
              Chloride Liquid Cell of 99.9% Pure Toluene           64

Figure 25     Potassium Bromide Pellet of Unknown Salt             65

Figure 26     Potassium Bromide Pellet of Reagent-Grade
              Ammonium Carbonate                                   66

Figure 27     Infrared Absorption Spectrum of an Unknown
              Liquid Fraction (95% Pure)                           68

Figure 28     Chromatogram of Vapor Above Liquid Sample
              From Pyrolysis of Leaves Before Venting              70

Figure 29     Chromatogram of Vapor Above Liquid Sample
              From Pyrolysis of Leaves After Venting               71

Figure 30     Chromatogram of Vapor Above Liquid Sample
              and Acetic Anhydride                                 72

Figure 31     Chromatogram for Pure Methanol and Acetic
              Anhydride                                            73

Figure 32     Chromatogram of Vapor Above Liquid Sample
              and Sodium Hydroxide                                 74

Figure 33     Chromatogram of Vapor Above Liquid Sample
              and Potassium Permanganate                           75

Figure 34-     Chromatogram of Vapor Above Liquid Sample and
              Sodium Borohydride                                   76

Figure 35     Chromatogram of Vapor Above Liquid Sample
              and Sodium Borohydride Plus Ethyl Alcohol            77
                                   viii

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                                                                  Page


Figure 36     Chromatogram of Vapor Above Liquid Sample and
              Isopropyl Alcohol                                    78

Figure 37     Chromatogram of Vapor Above Liquid Sample and
              Acetone                                              79

Figure 38     Chromatogram of Vapor Above Liquid Sample and
              Hydroxylamine Hydrochloride                          80

Figure 39     Chromatogram of Vapor Above Liquid Sample and
              Concentrated Sulfuric Acid                           81

Figure 40     Chromatogram of Vapor Above Liquid Sample and
              Hydrogen Iodide and Sodium Bicarbonate               82

Figure 41     Chromatogram of Vapor Above Liquid Sample and
              7:3 Sulfuric Acid                                    83

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                               Acknowledgement






        The author wishes to recognize the assistance of Edward F.




Maziarz, Jr., Joel S, Gilbert, and Laurence K. Burnell in the technical




phases of this study.  In addition, thanks are given to various members




of the staff of the Chemistry Department at Rensselaer Polytechnic Insti-




tute for their advice and assistance in the analytical phases of this




work, and for the use of their infrared spectrometer.




        This investigation was supported by Public Health Service Grants




Nos. 1R01-SW-00022-01, 5R01-SW-00022-02 and 5R01-UI-00552-03.

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                                    Abstract






         A study has been made of the possibility of utilizing the organic




content of solid municipal waste by reforming high molecular weight organic




compounds into simpler compounds of economic interest.  Major components of




waste such as paper and leaves have been investigated.  In addition, a dried




sewage sludge used as a soil conditioner and containing a large amount of or-




ganic matter was also studied.




         Reforming of organic molecules in the solid waste was accomplished by




a process of partial combustion.  Finely divided waste was supported as a




fluidized bed in an air-nitrogen stream containing less oxygen than that re-




quired for complete combustion.  Heat was supplied electrically through the walls




of the reactor to supplement the exothermic heat of reaction.




         Gaseous products of reaction evolved from the reactor were condensed




and collected in a series of traps held at progressively lower temperatures.




The fractions obtained included a tar fraction, an aqueous solution, liquid




organics, and a fraction of uncondensed gases.  Analytical methods which were




applied and utilized in the examination and identification of major components




in the complex mixtures included wet chemical methods, gas chromatography used




in conjunction with peak attenuation and a syringe reaction technique, infrared




spectrescopy and mass spectroscopy.




         Runs were made in a temperature range of 250C to 1000C and with air-




nitrogen mixtures that ranged from 0% air to 100% air.  Products which were




obtained and identified included water, acetic acid, formic acid, formaldehyde,




methanol, acetone, toluene, acetaldehyde, methyl acetate, ethyl vinyl ether,




methane, carbon dioxide, carbon monoxide, propylene, ethylene, ammonia, ammonium
                                      xi

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carbonate and hydrogen.  Many of the same products were found in all runs made,




In general, runs with high air-nitrogen ratios favored the formation of more




highly oxygenated compounds , while low air-nitrogen ratio promoted the forma-




tion of hydrocarbons.
                                        xii

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                                Introduction






         One of the most pressing problems facing our nation at present is the




problem of disposing of the huge quantities of solid wastes which accumulate as




a by-product of our modern society.  Until fairly recently, people of this country




have not been particularly concerned with solid waste disposal.  In the past, it




has been common practice to dispose of refuse by the most expedient method at




hand.  Such a method might be open burning or the use of an open dump.




         This situation has now changed.  With the rapid increases in population




during the past few decades, people are now crowding in on one another to the




point where it has become increasingly difficult to hide our refuse.  In addition




to the increase in total quantity of waste produced through population increase,




the quantity of waste produced per capita has virtually doubled since 1920 be-




cause of changes in our living standards.  Besides these changes in total quantity,




the chemical and physical composition of refuse has changed, which in general, has




complicated the problem of satisfactory disposal.  The introduction of new plastic




materials which are resistant to or completely unaffected by bacterial or chemical




action, has been on a scale to completely alter the approach to refuse disposal.




Changes of packaging techniques and the concept of the throw-away container have




introduced large quantities of materials which are difficult to handle in the




traditional disposal processes.  Thus, the need for considering totally new ap-




proaches to the problem is apparent.




         In the present study, the problem has been approached by considering




refuse not so much as material to be gotten rid of, but rather as a resource.




As we look at the composition of refuse we find that well over half of the ma-




terial is organic in nature, and as such, is made up largely of carbon, hydrogen

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and oxygen in about the proportions found in cellulose.  Thus, the possibility




exists of reforming the organic portion of solid wastes into useful  and economi-




cally attractive materials in much the same way that natural gas or petroleum




may be reformed.




         Consequently, studies have been made of the types of products which can




be obtained by reacting certain organic materials, commonly discarded at present




as solid wastes, with limited quantities of oxygen at highly elevated temperatures.




The purpose of such treatment is to reform the organic components of waste into




simpler organic compounds of economic interest.  The materials studied in this




work included paper, sawdust, leaves, and "Orgro", a dried sewage treatment plant




sludge.




         The principal efforts in this study have been directed towards developing




suitable laboratory equipment for reacting the materials, to collecting, separating




and identifying the products formed and to establishing relations between operating




conditions and the types of products obtained.

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                                   Background
A.  General
         A review of the history of waste treatment reveals that various heat




processes have been applied with varying degrees of success to the decomposition




of the organic components of solid waste materials.  In the majority of processes,




the prime objective has been to reduce the bulk of the material and to reform the




organics into relatively simple, stable compounds.  In such cases , it has been




found expedient to use large quantities of air in processes usually categorized




as burning or incineration.




         More recently, however, attempts have been made to heat solid wastes to




high temperatures in the absence of air.  Such a process, usually called pyrolysis,




has as its prime objective, the decomposition of the organic material to relatively




simple compounds which are economically attractive.




         A brief review of these processes, particularly as they apply to the




problem of recovery and utilization of components of solid waste, will be useful.




A short discussion of appropriate analytical techniques is also included.






B.  Incineration




         The use of equipment specifically designed to handle and burn refuse is




probably somewhat less than one hundred years old.  It is reported that attempts




were made to burn municipal refuse in England in 1874, but that combustion was




unsatisfactory because of large quantities of wet garbage incorporated in the




refuse.  In general, temperatures in the early incinerators were low, and the




heavy production and accompanying odors was a problem.  The use of auxiliary fuel




was found to be necessary for satisfactory combustion.




         Apparently, the first practical units in the United States were made at




various government installations.  These were followed by municipal incinerators




in a few of the larger cities at about the turn of the century and fairly wide




acceptance followed soon thereafter.

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         Early attempts were made to separate rubbish, garbage and ashes before


burning, and to utilize rubbish as a fuel for waste heat recovery.  In general,


these early attempts did not prove practicable because of the lack of operating

              4
dependability.


         Many types of designs have evolved over the years.   Recently, such im-


provements as continuous feed, mechanical stoking, facilities for fly ash removal,


air pollution control devices, and other automated features  have greatly increased

                                                               2 15
the efficiency and lowered the operating costs of incineration. '


         The disposal of sewage sludge by incineration has been attempted for quite


a few years.  This method has met with limited success , due  to problems encountered


with respect to smoke, odor, and weather conditions.    Initial attempts to burn


these filter cakes with conventional stoker furnaces have been generally unsuccessful


because of clinker formation and high ash percentage by dry  weight of solids in


the filter cakes.  This material, at best, can be considered only a very low-grade


fuel.  Special equipment has been designed to provide for improved incineration of


sewage sludge.  Today, sewage plant incinerators generally use either the flash

                                                                                  2
drying incineration process or the multi-hearth process for the burning of sludge.


         Attempts to utilize the heat of combustion of organic matter in solid


wastes for the generation of steam has been one way of seeking to reduce the cost


of disposal.  Such methods have been employed in a number of instances in several


European countries.  In some cases attempts have been made to recover salvageable


materials from incinerator residue, or to utilize the residue as a building

         4.
material.   The gaseous products evolved from incinerators are largely oxides of


carbon and water vapor.  The sulfur content of refuse is low so that sulfur dioxide


is usually not a serious air pollutant.  Similarly, nitrogen oxides production is


usually not a problem, because the temperatures are usually lower than that required.

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It has been reported that when the oxygen supply is deficient, additional products



are formed which are often considered to be nuisances.  These include:  carbon



monoxide, ammonia, benzene, aldehydes, ketones , phenols, organic acids and esters.



These compounds are valuable by themselves, and efforts have been made to separate


  ,         ^,    15
and recover them.





C.  Pyrolysis



         Some work has been reported where organic material has been burned, or



pyrolyzed, in the absence of oxygen.  Research performed by Dimitri, Jongedyk,



and Lewis who used destructive distillation along with fluidization for the break-



down of powdered hardwood has been described.  The sawdust was heated while sus-



pended in a stream of hot non-oxidizing gas.  A recovery system was used to separate



tar, acetic acid, methanol and other products from the outlet gas.  The described



system operated between 250 C and 380 C.  It was proposed that this system be com-



bined with a second stage operating at a higher temperature which would strip off



all residual volatile matter and leave a charcoal.



         Morgan, Armstrong and Lewis followed up this work in 1953, and they at-



tempted to add several refinements to the system along with making a more complete



analysis of the products.  As in the earlier work, an isothermal fluidized bed was



used.  The sampling train consisted of a water-cooled condenser, a mist trap, and



two containers filled with activated charcoal, for the recovery of solvent vapors.



These vapors were recovered by desorption under the influence of heat and vacuum,



followed by condensation in a trap cooled with methyl-ethyl ketone and dry-ice with



a clean-up trap cooled by liquid nitrogen.  The condensates were then tested by wet


                                                               Ofi
chemical analysis for the presence of acetic acid and methanol.

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         Of more recent origin is the work performed by Hoffman on the pyrolysis



of solid municipal wastes.  The material studied consisted of so-called "typical



San Diego solid wastes".  As pyrolysis progressed, the tars and heavier fractions



were condensed immediately outside the reactor in a tar trap.  The lighter frac-



tions were collected in receiving bottles submerged in dry-ice and acetone and



the gases trapped in a gas receiving balloon.  The gases evolved were analyzed by



gas chromatography and were found to consist of carbon dioxide, carbon monoxide,



methane, ethylene and ethane.  The volume proportions of these gases proved to be



dependent upon the temperature at which the reaction was run.  The inert residue


                                                                                20
proved to be sterile and appeared to have potential as a suitable fill material.





D.  Gas Chromatography



         A variety of gas chromatography techniques have proven valuable for analysis



of products from combustion processes.  The gas chromatograph has been used for



both qualitative and quantitative analyses of mixtures of known and unknown compounds,



         In 1960 Feldstein made a chromatographic analysis of incinerator effluents.



His work was confined to the analysis of low molecular weight hydrocarbons present



in the effluents.  He employed a multiple column system and a method of trapping



which allowed the collection and identification of a range of products.  The instru-


                                                                              12 39
ment was calibrated by injection of known quantities of standard hydrocarbons.   '



         Gas chromatography work on a polluted atmosphere by Bellar and others in



1962 substantiated Feldstein's analysis.   The trapping system described by



Feldstein had been used in earlier work by Brenner and Ettre with similar success


                                                Q

using silica gel as a trapping column adsorbent.



         Cvejanovich developed a chromatographic technique in.which three columns



in series were employed to separate C, through C_ paraffins and olefins as well as

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to give the quantitative determination of hydrogen, oxygen, carbon monoxide and



carbon dioxide.



         A chromatography study of the Los Angeles atmosphere was conducted by



Altshuller and Bellar in 1963 using silica gel to separate ethane, ethylene ,



acetylene, propane, propylene, n-butane, isobutane, n-pentane, and isopentane,



and a carbowax column for benzene, toluene, ethylbenzene, and m, p, and o-xylene.



A flame ionization detector was used during this analysis instead of the thermal



conductivity detector because of the greater sensitivity that was needed due to


                                                       3
the low concentrations of the impurities in the sample.



         The gas chromatograph has been used with some success for quantitative



work.  Maher employed a technique of measuring relative peak areas before and



after treatment of samples to remove olefins , aromatics and normal paraffins.  The



amounts by which the areas of peaks changed compared to the increase in the largest



component was taken as a measure of the component removed by this treatment.   This



proved somewhat satisfactory for the analysis of several hydrocarbon mixtures,



yielding information in terms of hydrocarbon types , but suffered limitations  asso-


                                                                                 23
ciated with the efficiency of the reagents used to remove the hydrocarbon groups.



         Hoff and Feit have described a technique for carrying out syringe reactions



using various reagents to remove or change functional groups.  This method provided


                                                                  19
information on the types of compounds present in organic mixtures.





E.  Infrared Spectroscopy



         Infrared spectroscopy has proven to be extremely useful in the qualitative


                                                                        42
and quantitative analysis of unknown compounds.  Yokum, Hein, and Nelson   were



successful in identifying methanol, acetaldehyde, and carbonyl sulfide in the



gaseous effluents from back yard incinerators.  They employed evacuated bulbs to

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collect these gases and loaded their contents into an infrared gas cell.  These
trapped gases were analyzed using an infrared spectrophotometer.  They found that
by drawing the vapors off the liquid effluents they were able to identify acetone,
methanol, benzene, and an ester.
                           31
         Sawicki and Hauser   were successful in identifying carboxylic acids and
aldehydes in air-borne particulates through the use of high resolution infrared
spectroscopy.  As a result of a detailed study of the behavior of known carboxylic
acids and aldehydes, it was possible to identify unknown mixtures of these compounds.
Similar studies were conducted on primary and secondary aliphatic amines by
        38                                                          V
Stewart.    Quantitative analyses were performed by Brattain, et al. , but were
limited to mixtures of known compounds due to the necessity of pure component trans-
mission measurements.
         A promising application to pollution studies has been the combined use
of gas chromatography (to separate and collect pure components of an unknown mixture)
                                                                                18
and infrared spectroscopy (to analyze the collected components).  Haslam, et al.
concerned themselves with the development of micro sampling apparatus and sample
                                                                      o c oc
handling techniques for these instruments.  Similar attempts by others   "   have
been made to solve these problems.
         A strong advantage to the use of infrared spectroscopy for the identifica-
                                                                 17
tion of complex organic materials has been demonstrated by Harms.    He suggests
that the infrared spectra of the pyrolysis products of complex organic molecules
could be used as a means of identification.  He demonstrates that the infrared
spectrum of the pyrolyzate can be used simply as a unique characterzing pattern,
without special regard for the actual chemical composition reflected in the spectrum.

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                           Theoretical Considerations





A.  Partial Combustion



         As is well known, most organic materials may be burned under conditions



of total combustion to yield such products as carbon dioxide, sulfur dioxide, oxides



of nitrogen and water vapor.  However, if the reaction occurs in a deficiency of



oxygen, the combustion is incomplete and a wide variety of products are formed.



         Some typical combustion reactions under both total and partial combus-



tion conditions are as follows :



         Total combustion
         Partial combustion




                   + 0  - > 2CO
              CO + H   - ^  HCHO (formaldehyde)



              CO + 2H0 - >  CH0OH (methanol)
                     Z          o



         Thus , even the simplest of hydrocarbons may yield a variety of products



under conditions of partial combustion.  As the complexity of the fuel increases,



so also does the variety of possible products increase.  In the case of a material



such as paper, a major component of domestic refuse, the list of possible products



is considerable.  In Fig. 1 is shown a representation of the cellulose molecule,



which is the chief constituent of paper.  As can be seen, this molecule is al-



ready partially oxygenated and it would be expected that a great variety of degrada



tion products should be possible .



         Because of the increased complexity in the composition of leaves and saw-



dust, it would be expected that the variety of compounds resulting from the partial



combustion of these materials would be correspondingly greater.  Likewise, dried

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  'CM
O
                                            w
                                            O
                                            w
                                            J
                                            O
                                            s
                                        P-i
                O
                 I
                                             O
                                             J
                                             w
                                             O
                     10

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sewage sludge contains a myriad of organic compounds, and heat treatment might



be expected to yield a product mixture of tremendous complexity.  Through



partial combustion somewhat simpler organic compounds are potentially possible.



For instance, hydrocarbons that are present may oxidize to mixtures of alcohols



which in turn might oxidize to aldehydes and ketones.  Further oxidation would


                                          25 2 8 34-
result in the corresponding organic acids.  '  '





B.  Fluidization
         Chemical reactions between solid and gaseous materials may often be carried



out most conveniently in a fluidized bed.  The process of fluidization involves



bringing a fluid into intimate contact with a bed of finely divided solids at a



velocity sufficient to keep the solids in suspension.  At fluidization, the rate



of fluid flow through the bed will be such that the pressure across the bed, due



to frictional drag on the particles, will equal the effective weight of the bed.



When a fluidized bed is examined at this point, it is found to be in a turbulent



state.  It bubbles and boils and the solids move about in an erratic manner.



         A fluidized bed has three characteristics that make it desirable for use



in a reactor system.  The first is that the violent agitation and rapid redistribu-



tion of solids in a fluidized bed results in the elimination of hot spots in the



reaction zone.  This allows for close control over reaction temperatures.  Secondly,



the large gas-solid contact area makes a fluidized bed reactor an efficient system



for catalytic and non-catalytic reactions.  Lastly, the solids can be handled con-



veniently by pneumatic systems when they are in a fluidized state.  If the solids



have to be introduced and removed from the reaction bed, this can often be done



conveniently since the solids can be pumped into and out of the system like a fluid.



         There are several limitations of a fluidized bed reactor, primarily as-



sociated with non-ideal flow.  The ramification of non-ideal flow is that reactor





                                        11

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size increases much more rapidly than for plug flow reactions for high conversions.



In addition, the extent of deviation from plug flow must be determined by experi-


                                      22
ment to adequately design these units.





C.  Gas Chromatography



         The analysis of organic mixtures can be performed in a gas chromatograph.



The sample, either liquid or vapor, is injected into a vaporizer which generates a



"plug" of vapor which is then swept into a packed column by an inert carrier gas.



Separation of the components in the column results from the differences in the



multiple forces by which the column materials tend to retain each of the components.



The nature of the retention may be absorption, solubility, chemical bonding, polar-



ity, or molecular filtration, but in any event, the column retains some compounds



longer than others.  Upon emerging from the column, the gases immediately enter a



detector.  In the thermal conductivity detector, the difference in thermal conduc-



tivity of the product stream and a reference stream is used to generate a signal



which is amplified and used to cause a pen deflection in a strip chart recorder.



         The selection of a suitable packing material which will effectively



separate the unknown sample components is critical to the successful use of gas



chromatography.  Besides being dependent on the material used as a column packing,



the separation achieved is strongly dependent in the manner in which a column is



packed.



         Gas chromatography, while being an excellent analytical tool, suffers



from two limitations in its application to pollution studies.  The first limitation



is that if components of a wide boiling range or different characteristics are



present in the sample, the analysis often cannot be carried out in one run because



it is very hard to find "general" chromatographic columns.  The second limitation



is that although gas chromatography shows an extremely high sensitivity, it is not
                                         12

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high enough for ranges of compounds in concentrations such as are commonly of
                                  Q T 1 0*7 QQ
interest in air pollution studies.  '   '   '    While these two shortcomings may
be formidable in some cases, they can often be overcome.  The problem of a wide
variety of compounds can often be overcome by temperature programing.  In this
technique, the column is kept at a low temperature until all low boilers have been
eluted.  Then the column temperature  is linearly programed which accelerates the
elution of the higher boiling components.  The sensitivity problem can be solved
by collecting the samples using a concentration technique.
         The gas chromatograph can often be used for quantitative as well as quali-
tative work.  The length of time that a component is in a column, called its re-
tention time, is specific for any particular compound and solid phase under the
                           21
same instrument conditions.    This time may, therefore, be used for qualitative
identification of the component.  A homologous series of organic compounds will
yield a straight line or smooth curve when some property of the compounds is
plotted against retention time on semi-logarithmic paper.  The retention time on
the log scale may be plotted against  carbon number, molecular weight or boiling
point.  With an unknown sample, this plot can be used for tentative identification.
Confirmation of a tentative identification from retention times with a particular
column packing may be accomplished by duplicating the separation on another column
using a different packing.  Confirmation may also be made by adding a small amount
of the suspected component to the mixture and rechromatographing.  If the peak of
the component is increased, then more positive identification has been made.  This
is known as the peak attentuation technique.  Complications may arise when compo-
                                                                               21 37
nents having similar properties are present.  Then peak interference may occur.   '
         Quantitatively, the height of the elution peak or the area under the peak
is approximately proportional to the amount of the component that produced it.
The peak height is influenced by the temperature of the column or any other factor
                                       13

-------
that affects the activity of the adsorbent.  Since the area under an elution peak



is practically independent of the sample size, it is generally a more satisfactory



quantitative measurement than peak height.  The area can be computed by any of a



number of ways.





D.  Infrared Spectroscopy



         Infrared spectra originate primarily from the vibrational stretching and



bending modes within molecules.  Most organic and inorganic compounds have charac-



teristic absorption wavelengths in the infrared region.  A scan of the infrared



region presented as wavelength versus absorbance (or transmittance) is called an



infrared spectrum.  This spectrum is a powerful tool for the study of molecular



structure.  Both qualitative and quantitative measurements are possible with an



infrared spectrophotometer.  In addition, a match between the infrared spectrum



of an unknown material and the spectrum of a reference sample is almost without


                                        M-l
equal as an empirical proof of identity.    It is quite unlikely that any two com-



pounds have the same response in the infrared region.



         Although an infrared spectrum is a characteristic of a specific compound,



certain functional groups of atoms give rise to absorption bands at or near the



same frequency regardless of the structure of the remainder of the molecule.  It



is the presence of these characteristic group frequencies that enables one to



examine an unknown compound and pick out its key functional groups.  A table of the



more commonly used functional group absorption frequencies appears in Table  1.



These frequencies were taken from reference (35) but appear in almost any text



covering infrared spectroscopy.



         To realize the full potential of infrared spectroscopy in qualitative



analysis, a large collection of properly indexed reference spectra of known com-



pounds must be readily available.  Even though there are enormous amounts of





                                        14

-------
spectra available, the problem is that present indexing and retrieval systems




suffer from shortcomings, and the spectra that are available vary widely in




quality and the manner in which they are presented.
                                        15

-------
                                    TABLE 1

                   TABLE OF  INFRARED ABSORPTION FREQUENCIES

                              FOR LIQUID SAMPLES
     Type  of Compound

      General
Characteristic Group
    Vibrations	

  C-H Stretching
  C-H Bending
  C=C Stretching
  C=C Stretching
Frequency (Microns)
   3.3
   6.8
   6.0
   4.4
3.5
7.3
6.25
4.8
      Alcohols  and
      Phenols
  0-H Stretching
  0-H Bending
  C-0 Stretching
   2.7 - 3.1
   7.0 - 7.5
   7.9 -10.0
      Ketones
  C=0 Stretching
   5.35- 6.5
      Aldehydes
  C-0 Stretching
  C-H Stretching
   5.7
   3.5
6.0
3.7
      Carboxylic
      Acids
  0-H Stretching
  C-0 Stretching
   2.8
   5.6
2.9
5.9
      Nitriles
  C=N Stretching
   4.4 - 4.5
*These frequencies have been taken from Reference (35).
                                        16

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                             Materials and Apparatus






A.  Materials




    1.  Analytical Standards




         The analytical standards used in the peak attenuation technique were




all analytical reagent grade compounds.  They were used in conjunction with the




research gas chromatograph in an attempt to analyse samples for their presence.




These standards included:




                  Alcohols - methanol, ethanol, propanol, isopropanol,




                       butanol, isobutanol, pentanol, and hexanol




                 Acids - formic, acetic, propionic, butyric, and




                       valeric acids




                 Aldehydes - formaldehyde, acetaldehyde, and




                       propionaldehyde




                 Ketones - acetone and butanone




                 Paraffins - methane, ethane, propane, and butane




                 Miscellaneous - carbon dioxide, carbon monoxide,




                       nitrogen, benzene, toluene, xylene , carbon




                       tetrachloride, and carbon disulfide




         The gases listed in these last two categories, with the exception of




nitrogen, were obtained from the Matheson Company in lecture bottles.  The nitrogen




gas was purchased from the Linde Division of Union Carbide.  The liquid standards




were obtained from the Fisher Scientific Company.





    2.  Carrier Gases




         Helium, nitrogen, and air were used as carrier gases and were obtained




from the Linde Division of Union Carbide.  The nitrogen was used as a carrier gas




in the preparative gas chromatograph and in the reactor during the pyrolysis






                                      17

-------
reactions.  The helium was used in the research gas chromatograph, and the air




was used in the reactor during the partial oxidation reactions.





    3.  Indicating Papers




         Accutint was used to determine the pH of several of the liquid samples




that were collected.  The entire range of this indicating paper proved to be use-




ful.  This paper is a product of Anachemia Chemicals, Ltd.  At a later stage of




the research Alkacid test paper by Fisher Scientific was employed.





    4.  Reagents for the Analysis of Formaldehyde and Methanpl




         The two reagents required in the analysis of formaldehyde were chromo-




tropic acid and concentrated sulfuric acid.  The former was purchased from




Matheson Coleman and Bell, and the latter acquired from the Fisher Scientific




Company.




         The analysis of methanol required the use of potassium permanganate,




sodium bisulfite, chromotropic acid, sulfuric acid, and pyrogallol.  These were




all obtained from Matheson Coleman and Bell with the exception of the sulfuric




acid.





    5.  Reagents for Syringe Reactions




         The reagents used for the syringe reactions included the following:




concentrated sulfuric acid, hydrogen iodide, sodium borohydride, potassium




permanganate, hydroxylamine-hydrochloride, acetic anhydride, sodium hydroxide and




hydrochloric acid.  The reagents were obtained from Matheson Coleman and Bell




with the exception of the acids and sodium hydroxide which were obtained from




Fisher.






B.  Apparatus




         A schematic diagram of the apparatus used is shown in Fig. 2.
                                      18

-------
                                                                o
                                                                I-H
                                                                H
                                                                O
                                                                CO

                                                                s
                                                                w
                                                                H
                                                                CO
                                                                >-"
                                                                CO
                                                                o
                                                                H
                                                                O
19

-------
    1.  Reactor System Equipment




         Three separate reactors were used at various times for this work.   They




were generally similar in overall dimensions but differed in materials (brass ,




iron and ceramic) and in some details.  Diagrams of the three reactors are




shown in Figs.3,4 and 5.




         Each reactor was approximately two inches in diameter and 24 inches in




length.  A metal flange at the bottom was used to join the reactors to a 12 inch




entrance section.  A 100 mesh brass screen was supported between the flanges




which in turn supported the bed of material in the reactor.  A 1/4 inch side




arm was connected to the reactor near the top to allow removal of product gases.




A similar arm was provided on the iron reactor for removal of solid residue.




The metal reactors had black iron reducers at top and bottom.  The bottom reducer




connected to the inlet gas line.  In the brass reactor, the top reducer allowed




the introduction of a thermocouple well the length of the reactor.  In the iron




and the ceramic reactor, the top of the reactor was connected to an injection




feed system.  This system consisted of two 1 1/2 inch brass gate valves separated




by a 10 inch section of 2 inch iron pipe.  A 1 1/2 inch black iron nipple con-




nected the lower valve to the reducer at the top of the reactor, and an identical




nipple was connected to the upper valve.  A rubber stopper fitted tightly with




an aluminum plunger was forced to fit tightly into the upper nipple.  This enabled




feed to be injected into the reaction zone while the reactor was at operating




temperature.




         Heat was supplied to the reactors by heating tape.  A model BIH-62 1/2




heating tape manufactured by the Briskeat Company was found to be satisfactory and




capable of heating the reactor to 2000 F.  Current was controlled by a Powerstat.




         The reactors were insulated by a high temperature pipe lagging to prevent




undue heat losses.
                                       20

-------
Exit Port
                24
                 10"
                              III
                              I''

                          FIGURE 3




                        BRASS REACTOR
                                               2  x 7/8" Reducer
                                               Insulation
                                               Combustion Chamber
                                               Thermocouple Well
                                               Bolted Flanges
                                               2 x 7/8" Reducer
                             21

-------
2 x iJg" Reducer
        Exit Port
                                                              Gate Valve
                                                          Feed Reservoir
                                                          1%" Gate Valve
                                                          Combustion Chamber
                                                          Thermocouple Location
                                                          Insulation
                                                          Exit Port
                                                           Bolted  Flanges
                                                           2  x  7/8"  Reducer
                                    FIGURE  i*




                               BLACK STEEL  REACTOR
                                      22

-------
23$ x 7/8" Reducer
       Exit Port
                                FIGURE 5




                            CERAMIC REACTOR




                                    23
IV Gate Valve






Feed Reservoir






IV Gate Valve
                                                         Insulation
                                                         Combustion Chamber
                                                         Thermocouple Location
                                                         Exit Port
                                                         Sand
                                                         Glass Wool
                                                         2% x 7/8" Reducer

-------
         Reaction temperatures were measured by chromel-alumel thermocouples




made and calibrated in the laboratory.  These were used in conjunction with an




L and N Potentiometer, Model 8691.




         Air and nitrogen streams were measured by two model 2-1355 Sho-Rate




rotameters manufactured by Brooks Instrument Division of Emerson Electric Company.




They were calibrated by a Precision Scientific wet test gas meter.




         As shown in Fig. 2, a Lucite pilot plant was connected in parallel with




the reactor.  This was periodically used as an indicator of the type of fluidiza-




tion obtained under a particular set of operating conditions.




         The solids fed to the reactor were fluidized by a mixture of nitrogen




and air.  Nitrogen was fed from a cylinder and air was supplied from an oil-less




air compressor.  In later runs cylinder air was used.  The gases were blended to




provide the desired oxygen concentration and feed to the bottom of the reactor.





    2.   Sample Collection Equipment




         The product gas stream leaving the top of the reactor was passed to a




water-cooled Liebig condenser.  Here the high boilers were condensed and collected




in a flask connected to the condenser.  From here the product stream passed




through a series of glass traps maintained successively at lower temperatures.




Each trap was immersed in a cold bath held in a Dewar thermos flask.  Icewater,




dry ice, and dry ice-acetone mixtures were used in the cooled baths.  In some runs,




the gases from the traps were passed through a column packed with silica gel made




of 2 feet of 1/4 inch copper tubing.  Gases were adsorbed in this unit for subse-




quent analysis.






    3.   Analytical Equipment




         Much of the analytical work was done on a Model 5751A research gas




chromatograph manufactured by Hewlett Packard.  This instrument was equipped with
                                       24

-------
both dual flame ionization and thermal conductivity detectors.  A Model 7128A




strip chart recorder was used in conjunction with this unit.  This recorder had




two channels and one disc integrator.




         On some tests a Hewlett Packard, Model 775, Prepmaster gas chromatograph




was used to fractionate the liquid samples.  This unit had a built-in strip chart




recorder, and the capability of completely automatic operation.




         Several column packings were used for both the analytical and preparative




instruments.  Most of the work was done with Polypack-1, manufactured by Hewlett




Packard, and Porapak Q or Porapak N, both manufactured by Waters Associates.




         A soapfilm flowmeter having a 10 ml scale was used in conjunction with




a stop watch to determine the volumetric flow rate of carrier gas through the




analytical columns in the research gas chromatograph.  Carrier gas flow in the




preparative unit was measured using the built-in rotameters.




         A Perkin Elmer, Model 137, sodium chloride spectrophotometer was used




for all of the infrared analyses, including gas, liquid and solid analyses.   The




sample holders included a 10 cm gas cell, several sodium chloride liquid cells,




and a potassium bromide pellet holder.  The pellets were formed by use of an




evacuable potassium bromide die.




         A collection system was fashioned for use with the preparative gas  chro-




matograph in order to eliminate excess sample transferrals between collection in




gas chromatograph and final analysis in the infrared spectrophotometer.  This




system consisted of special collection cells called Extrocells , Model 195918;




plugs for these cells to prevent evaporation, Model 195919; polystyrene packs to




hold the cells while centrifuging the sample into the small slit in the bottom of




these cells, Model 195924; a cell mount to fit the sodium chloride spectrophotom-




eter, Model 1954-79; and a cell holder that slides the Extrocell into the cell
                                      25

-------
mount, Model 195929.  This equipment was manufactured by the Scientific Instru-




ments Division of Beckman Instruments.
                                       26

-------
                             Experimental Procedure


         During the course of this study three classes of materials were examined

as potential sources of useful products.  In chronological order in which they

were studied, they were 1) finely divided paper, 2) Orgro, dried sewage sludge

from the Schenectady N. Y.  sewage treatment plant, and 3) finely divided dried

leaves.  Since these materials differed somewhat in their properties, somewhat

different techniques of handling and of analysis were required.  Consequently, the

procedures used for each material are considered in order.


A.  Paper

    1.  Reactor Operation

         Most of the runs on paper were made using printed newspaper.  A few runs

were made with ink-free unused newspaper but no significant differences were noted

and no distinction between runs appeared to be justified.

         A considerable effort was devoted to finding a suitable way of preparing

the paper so that it could be fluidik,ed.  It was found that because of its low

density, rather large particle sizes were required for good fluidizations.  Particles

in the size range of 5 to 10 millimeters were generally satisfactory.  Smaller sizes

tended to clump together and fluidized erratically.

         Unheated runs were made in the transparent pilot column to determine opti-

mum particle size, and gas velocity as a function of reactor batch size.

         Several methods were used to prepare the paper sample.  A Waring blender

was found to reduce the paper to a convenient size and was used in some runs.  A

conventional kitchen meat grinder was also found to produce satisfactory samples.

Other methods of preparation were found to be less effective.  The sample size

varied between 15 and M-0 grams.  In most runs the sample was taken as 15 grams.

During later runs larger samples were taken to see if sample size had any effect on

results.
                                        27

-------
         Once the sample size was decided upon and the sample prepared, it was

loaded into the cold reactor by removing the reactor cap and dropping the sample

in by hand.  After the reactor was loaded, it was connected into the line and

sealed against leaks.  Silver Goop, a sealant distributed by the Crawford Fitting

Company, was found to be a reasonably good sealant under the conditions encountered.

         The Dewar flasks, in which the liquid and gas traps were immersed, were

filled with the appropriate cooling medium and allowed to come to equilibrium.

The flows of air and nitrogen were then established to give both the desired total

flow for good fluidization and the desired air to nitrogen ratio.  The ratios

studied varied from total air or a complete combustion run, to total nitrogen or a

pyrolysis run.

         Once the bed was fluidizing properly and base measurements were recorded,

the electrical heating coils in the reactor were turned on.  The temperature in

the reactor was measured at intervals with the chromel-alumel located in a well at

the centerline of the reactor.

         A reaction run usually lasted from 2.5 to 3.0 hours.  As the run progressed

the temperature rose fairly steadily to about 400 F.  At this point an evolution

of smoke was usually noted and the temperature rose rapidly.  The maximum tempera-

ture attained depended upon how much heat was supplied to the heating coils , the

size of sample and the gas flow rate, but usually was in the range of 860 F to

1100F.

         After a run was completed, the heat to the reactor was discontinued, and

after a brief cooling period the gas flows were stopped.  The cooling baths were

removed from the liquid traps and the traps were allowed to come to room tempera-

ture.  While remaining connected to the system, nitrogen was passed through the

trap to purge any low boilers to the gas trap which remained at the low temperature.

The remaining liquid sample was then transferred to a labeled test tube, the pH

determined, and the tube stored in a dry-ice chest for subsequent analysis.  The
                                       28

-------
gas trap was sealed and removed from the system and likewise stored in the dry-




ice chest.  After cooling, the reaction residue was removed and weighed.





    2.  Gas Chromatograph Operation




         Basic to the successful operation of the chromatograph was the selection




of suitable columns for the constituents.  After considerable investigation,




columns with dimensions of 4 ft. by 1/4 in. diameter, packed with Porapak Q, were




selected.




         For all runs , helium was used as a carrier gas since it gave fewer peak




inversions.  As a general procedure, the gas flow was established, once the columns




were in place, and the system checked for leaks.  The flows through the reference




column and the operating column were balanced by means of a soap film flowmeter and




maintained at 50 cc/min.




         A number of standardization runs were made by sending various liquids and




gaseous samples of known materials through the chromatograph at different tempera-




tures.  This provided a relationship between retention time and molecular weight




for these materials.  All of the liquid samples were of analytical reagent grade.




The liquid samples were injected into the chromatograph with a 10 microliter




syringe and the retention times were measured at 150 C, 175 C and 200 C.  Results




are shown in a later section.




         Gaseous standards were also processed in a similar manner, but injected




by a special technique developed for gases, and described later..  An oven tempera-




ture of 100 C was used during these runs, since the gases tended to move through




the column at a faster rate than the liquid samples.  Results are given in a later




section.




         The analysis of liquid samples from reaction runs were made as soon after




being obtained as possible.  In preliminary analyses, oven temperature was maintained




at 200 C and several runs made until suitably reproducible chromatograms were ob-




                                        29

-------
tained.  It became apparent that many of the same components were being obtained




in virtually all of the reaction runs, although in different proportions.  Conse-




quently , it was decided to make programmed runs in subsequent work to achieve




better separation of components.  In these runs the temperature was raised at a




constant rate of 10 C/min from a temperature of 150C to 200C during the course




of the analysis.  Based upon the results from previously determined standards, it




was possible to make postulations regarding the identity of several of the compo-




nents.  To substantiate these postulations, a peak attenuation technique was tried,




in which a small amount of the suspected component was added to the original sample




and its effect upon the resulting chromatogram observed.  This method was tried




with numerous pure materials as indicated in the results.




         Attempts were made to apply infrared spectroscopy to the identification




of unknowns in the liquid samples.  Results, however, were inconclusive with the




samples tested in this part of the study.




         A limited number of analyses were made on the gases which were not con-




densed in the liquid traps.  The sampling apparatus shown in Fig. 6 was used to




collect the off-gases and to allow their introduction to the gas chromatograph.




The gases were adsorbed in a silica gel column cooled in a dry ice-acetone bath




as shown.  When an analysis was desired, the carrier gas used in the chromatograph




was diverted to flow through the column which was heated in boiling water.  Thus,




the adsorbed gases were carried into the instrument and analysed.  Most runs were




carried out by running the chromatograph at 100 C for 20 minutes, followed by a




program in which the temperature was raised to 200 C at a rate of 10 C/min.  The




helium flow was directed through the trap for 1 minute and then by-passed the trap




for the remainder of the run.  Standard gas samples were introduced into the gas




stream through a septum just ahead of the silica-gel trap.
                                       30

-------
                                                                      s
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                                                                      3     co     6
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c
w
w
IT)
O<
 0)  w
rH  
 (1)  rH
 0)  rcJ
iz;  >
                                                                                                               a
                                                                                                               
                                                                                                                      Pk
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a
<
CO

                                                                                                       w
                                                                                                       nS
                                                                          0)     4i
                                                                          H      o.
                                                                          (0  6  W)
                                                                          O  O  O
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                                                  H
                                                  H
                                                   0)
                                                                                  O
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                                                                                 ^2
                                                                                 O
                                                        31

-------
B.  Dried Sewage Sludge (Orgro)




    1.  Reactor Operation




         In early attempts to fluidize Orgro, it was found that considerable




channeling took place because of the heterogeneous nature of the dried sewage




sludge.  Good fluidization was obtained by screening out fines smaller than 60-




mesh, and mixing the remainder with about an equal volume of glass beads or sand




of approximately the same mesh size.  To prevent the loss of a small amount of




fines present in the solids mixture, a glass wool plug was inserted in the exit




gas port.




         It was found that a 2 inch layer of coarse sand supported on a 100 mesh




screen at the bottom of the bed acted as an excellent gas distributor to the bed,




and also acted as a gas preheater because of its high heat capacity.  This sand




did not fluidize at gas velocities required for the runs.




         In a reaction run, the solid mixture was introduced into the reactor to




give a static reaction mixture bed depth of approximately 1 foot.  Upon adjust-




ment of the gas flows to the desired values, the bed usually expanded by an addi-




tional 2 inches.  This height, combined with the sand height above the brass




screen brought the total height of the bed to within a few inches of the exit port.




         The desired carrier gas flow, and the desired ratio of air to nitrogen,




were made by making appropriate adjustments to the gas rotameter settings.  Air




was supplied from a compressor in the early runs, but the supply was later replaced




by cylinder air because of a smoother flow.  Temperatures in the range of 900 F




to 1900F were studied.




         In the early runs, using the brass reactor, the procedure followed was




exactly as described for the batch runs using paper.  Later, when the black iron




reactor and the ceramic reactor were used, attempts were made to develop a procedure

-------
for making continuous runs.  A continuous feed of solid mixture was pumped to




the reactor, and solid residue was continuously removed.  This worked well with




a cold reactor, but with a hot reactor, the inlet and exit lines quickly plugged.




Consequently, a procedure for semi-continuous runs was  evolved.  Here, a batch




of feed was introduced into the reactor from a feed reservoir on top of the




reactor by opening the valves on top of the reservoir.  A plunger aided in in-




troducing the feed quickly to the gas stream flowing in the hot reactor.  This




procedure was adopted for all runs with the iron reactor and the ceramic reactor.




         Gases evolved from the reactor were sent through a series of traps held




at successively lower temperatures and liquid fractions were collected in each




trap.  After a run was completed, the gas flows were discontinued and the reactor




cooled.  The traps were sealed and the contents held at a low temperature for




subsequent analysis.





    2.  Analytical Run




         The samples collected in the traps held in the dry ice-acetone baths




were found to contain absorbed gases.  It was found convenient to analyse these




gases by use of an infrared spectrophotometer.  To load the gas cell with the




absorbed gas, an apparatus shown in Fig. 7 was used.   The infrared cell and




connecting system was evacuated by a vacuum pump.  A collection trap immersed in




its cold bath and containing the desired sample was connected to the system, and




the pump then isolated from the system.  The valve at the top of the trap was




opened slowly to allow some of the gases to enter the system.  When the pressure,




as indicated by the gauge, reached 1/2 atmosphere absolute, the valves on the gas




cell and the trap were closed.  The system was then vented to atmospheric pres-




sure, the infrared cell disconnected, and an infrared spectrum of the gas was




determined.  The cell was then reattached to the system, the vent closed and the




system pumped down again so that the cell could be reloaded.  The trap for this



                                      33

-------An error occurred while trying to OCR this image.

-------
portion of the run was placed in ice water.  The above procedure was followed




except that the run was discontinued when the pressure reached 1/3 of an atmos-




phere.  The cell was again removed for another spectrophotometer determination.




This procedure was repeated once more with the trap at room temperature.




         Liquid samples were collected in each of the traps for all runs.  The




samples in the dry ice-acetone cooled traps usually separated into an aqueous




layer and an organic layer.  Many analytical methods were attempted with each




sample, but most proved unsatisfactory because of the complexity of the mixtures.




Mass spectroscopy was attempted but merely resulted in a spectrum of almost every




conceivable mass number.  Wet chemical methods were attempted but indicated that




there were interferences present.  The most satisfactory technique was the use of




gas chromatography in conjunction with infrared spectroscopy.




         The aqueous samples were analyzed qualitatively using a research gas




chromatograph.   The resultant chromatogram showed one large peak for water, fol-




lowed by a large number of other compounds of relatively low concentration.  When




the organic layer was run on this chromatograph under the same conditions, it was




indicated that the same compounds present in the aqueous layer were also present




in the organic layer.  Since this organic sample was too complex to analyse using




infrared spectroscopy without further refinement, fractions were collected using




a preparative gas chromatograph.




         The collection traps furnished with the preparative unit were too large




to be used with the collected samples.  A special trap was devised, as shown in




Fig. 8, which proved quite satisfactory and allowed collection efficiencies of




about 90%.  The technique used to separate and collect components was basically




the following:   first, approximately 3 microliters of the unknown mixture were




injected into the analytical side injection port to see what type of separation
                                       35

-------
                       Vapor Entrance
  Connection to
  Manifold
Pyrex Glass Tube
       Glass Wool
                             UJ
                                     Vapor Exit
                                            Silicone Elastomer
                                            Septum Material
                                            1/16" Outside Diameter
                                            Stainless Steel Tubing
                                            Electrocell or Test Tube
                          FIGURE 8

    TYPICAL PREPARATIVE GAS CHROMATOGRAPH COLLECTION TRAP
                              36

-------
could be achieved.  Then, the oven temperature was programmed at several rates




until a suitable separation was found.  When the right conditions were decided




upon, the preparative side of the unit was adjusted to duplicate these conditions.




It was found that the most efficient operating conditions were an injection port




temperature of 210 C, a column oven programmed from 110 C to 240 C at 2.5 C/min.




and a detector temperature of about 250 C.  The column oven programming rate was




delayed 4- minutes after injection of the sample to further increase separation.




         The collection traps were attached to the manifold of the chromatograph




and placed in dry ice-acetone baths.  Four of these traps were employed to collect




pure components, and a fifth was used to collect the remaining mixture.  The col-




lection valve was operated manually in such a way as to collect the same components




in each trap on successive sample injections.  Only the four components which ap-




peared to be in the largest concentrations were collected in these first four




traps.  Two injections of one ml. each were thought necessary, and by subsequent




inspection of the collection traps, this was verified.  The collected fractions




were then rechromatographed to check for purity.  This was accomplished by ex-




tracting approximately one microliter of a collected fraction and injecting it




into the analytical side of the chromatograph.  If the resulting chromatogram




proved to be free of impurities , the sample was then put in an infrared liquid




cell and run on the infrared spectrophotometer.




         In addition to the technique described above for component identification,




the peak attenuation method previously described was also used.







C.  Dried Leaves
    1.  Reactor Operation




         All of the work on this material was carried out in the black iron




reactor under essentially isothermal conditions.  The operational procedure was
                                      37

-------
similar to that employed during the Orgro runs.  The feed mixture was prepared



by grinding leaves in a Waring blender and blending the finely divided solids



with an equal volume of glass beads.  This mix was introduced into a hot reactor



from the feed reservoir, and the gas flow adjusted to give the desired fluidiza-



tion.  Runs were made at 500F and 1500F.  Evolved gases were collected in



series of cold traps, described for the Orgro runs, and held at trapping tem-



peratures for analysis.





    2.  Analytical Runs



         The research chromatograph was used extensively in this phase of the



work.  Helium was used as the carrier gas at a rate of 60 cc/min.  The column



packing was  Porapak  Q.  Liquid samples were programmed at 2 C/min and gas



samples were programmed at 4 C/min.


                                                                     19
         A technique of syringe reactions, described by Hoff and Feit   was used



as an aid in product identification.  This technique involved conducting reac-



tions between products and certain reagents in a syringe, and then observing



the chromatogram of the resulting reaction product mix.  By observing changes



in the chromatograms of the original samples one may draw conclusions as to com-



pounds or functional groups that are present.  In making a run, the sample in the



trap was allowed to warm at room temperature for 30 minutes.  This allowed a



saturated vapor above the liquid and insured uniformity in the samples.  An eye-



dropper bulb acted as a septum on the trap.  Vapor samples were withdrawn by



inserting the needle of a syringe through the septum.  The reagents for the re-



action had previously been distributed on the walls of the syringe.  After drawing



a sample into a prepared syringe, it was set aside for 3 minutes to allow reaction



to occur.  The sample was then injected into the chromatograph for analysis.
                                      38

-------
The reagents used and the conditions required for the reaction are given in




Table 2.  To supplement the data obtained by the syringe reaction technique,




peak attenuation was also used to aid in component identification.
                                      39

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                                                                         41

-------

-------
                                     Results


         The composition of paper and leaves  used as feed materials to the

reactor in these studies is shown in Table 3.  No analyses for the dried sewage

sludge were given because of extreme variability of samples.


                                     Table 3

                           Feed Materials Composition

                                                 Percentages	
                                           PaperLeaves
51.21
5.85
41.14
0.04
0.12
1.57
55.72
5.37
28.72
4.20
0.11
5.88
           Moisture                         4.07
             (as received)

           Ultimate Analysis (dry)

                 C


                 H2

                 2

                 N2
                 S

                 Ash


         Material balances on the system invariably gave low product yields be-

cause of the small size of the initial charge and leaks which were inevitable to

reactor operation.

A.  Reaction Runs Using Paper

         The products obtained from the partial combustion of paper were classified

into three groups in accordance with the trap in which the products were found.

High boiling compounds having a viscous, tarry appearance were obtained in the

first two traps, cooled respectively by water at room temperature, and by ice-

water.  These traps did an excellent job of removing the tars and prevented them
                                      43

-------
from contaminating the other traps in the system.  In the third trap a liquid




fraction was obtained having a color varying from a pale straw color to a rather




intense yellow.  This trap was immersed in a dry ice-acetone bath and was de-




signed to accomplish the removal of any water vapor and other high boiling prod-




ucts formed from the reaction.  Low boiling products were collected in the silica




gel trap at the end of the collection train.




         The small amount of high boilers which was obtained in most runs , and




the high viscosity of this fraction made analysis most difficult.  Attempts to




determine the components in this group were made but no definitive results were




obtained.




         Principal efforts were directed towards identifying products present in




the liquid fraction.  Gas chromatography proved to be the most effective method




available.   Porapak Q was found to be a good column packing for separation of




components.  While the combustion reaction was carried out under varying propor-




tions of air and nitrogen, the same compounds appeared to be formed in each case




but in differing proportions.   A summary of the operating conditions investigated




for various runs, together with the sample size and amount of residue obtained,




is given in Table 4.




         As an aid in identifying the product materials , the retention times for




a number of pure materials, thought possibly to be present, were determined.




These times are given in Table 5.  By matching retention times of components with




those of known samples, a number of products have been identified with a reasonable




degree of certainty.  These products included water, formaldehyde, acetic acid and




formic acid.  These tentative identifications were substantiated by adding small




amounts of the suspected pure components to the original samples and observing




the changes produced in their chromatograms.  These results are shown quite graph-




ically in Figures 9-14.  The presence of acidic compounds was verified by the low







                                      44

-------
   20
    16
   12
o
           Chromatograph Run
           Flow = 50 cc/min
           Temp.
           Packing - Porapak Q
                                                 =  150-200C @ 10C/min
                                           Sample  #8
a
rH
0)
    8
           0
     4           6
Retention Time (min)
8
10
                                  45
                                     FIGURE

-------
    20
    16
    12
                                       Chromatograph Run
                                       Flow =50 cc/min
                                       Temp.  = 150-200C @ 10C/min
                                       Packing - Porapak Q

                                       Sample #9
g
a)    8
cu
            0
   4           6
Retention Time (min)

     FIGURE 10
     46
8
10

-------
  20
   18
                                            Chromatograph Run
                                            Flow = 50 cc/min
                                            Temp. = 150-200C @  10C/min
                                            Packing - Porapak Q
                                            Sample
   12
o
bO
H
01
JS
0)
o.
8
                                    4            6
                             Retention Time (min)
                                                          8
10
                                  FIGURE 11
                                    47

-------
  20 r
   16
                                                   Chromatograph Run
                                                   Flow =50
                                                   Temp.
                                                   Packing - Porapak
                cc/min
            = 150-200C @
10 C/min
   12
                                                   Sample #8 + Acetic  Acid
 o
bfl
H
 a)  8
P..
                              Retention Time
   6
(min)
                                                             8
 10
                                    FIGURE 12
                                      48

-------
  20
   16
  12
                                             Chromatograph Run
                                             Flow  -  50  cc/min
                                             Temp. = 150-200C @ 10C/min
                                             Packing -  Porapak Q


                                             Sample  #11 +  Formaldehyde
u
bfl
H
0)
O-i
   8
                                    I
                  I
           0
     4            6
Retention Time (min)
8
10
                                   FIGURE 13
                                  49

-------
  20 r
   16
   12
                                             Chromatograph Run
                                             Flow = 50 cc/min
                                             Temp. = 150-200C @  10C/min
                                             Packing - Porapak Q
                                             Sample #11 t Formic Acid
-p
a
*<-\
(U
SJ
s
8
                                    4           6
                             Retention Time (min)
                                                          8
10
                                   FIGURE
                                   50

-------
            Table 4




Summary of Paper Reaction Runs
Sample
No.
1
2
3
4
5
6
7
8
9
10
11
12
Sample Size
Grams
15
15
15
20
20
20
25
30
35
40
40
40
Air:N
Ratio
2:1
2:1
1:1
00
0
2:1
0
3:1
00
00
2:1
3:1
Residue
Grams
3.5
0.7
1.4
0.1
6.7
6.0
7.3
6.2
7.0
10.0
10.4
10.0
Temperature
C
458
480
532
534
534
523
546
529
580
532
558
548
Liquid
pH
2.5
2.5
3.5
3.5
3.0
2.5
3.0
2.5
3.0
3.0
3.0
3.0
            51

-------
                                       Table 5

                             Summary of Retention Times
                       Porapak Q
Compound 150 C
Air 0.5 min
Water 0.90
Alcohols
Methanol 1.70
Ethanol 3.50
Iso-
propanol 8.20
n-
propanol
Butanol
Acids
Formic
Acetic
Propionic
Butyric
Aldehydes
Formal-
dehyde
Ketones
Acetone 7.40
But an one
175C
0 . 5 min
0.80

1.25
2.40
3.70
4.70
10.40

2.15
4.30
9.30
14.80

8.20

3.50
7.00
200C
0.5 m:
0.60

0.90
1.45
2.10
2.50
5.10

1.45
2.55
5.00
9.60

4.20

2.05
3.75
Porapak N
                                                3.10

                                                6.70


                                                9.30


                                               12.70
                                                9.60
  1.90

  3.75


  6.05


  8.45
                                                           8.50
  5.45

 10.60
 1.30

 2.20


 3.35


 4.20

 8.70




 4.35

 6.55

12.70
 2.90

 5.60
Note:  - indicates that the compound wasn't run at this temperature either
         because of poor separation or lengthy retention time.


       Flow = 50 cc/min
                                         52

-------
pH of these liquid samples which ranged from 2.5 to 3.5.  Specific values are




given in Table 4.  The presence of the above products was tentatively confirmed




in several samples by wet chemical methods.  These analyses also suggested the




presence of methanol.




         A limited amount of work was done on the gas adsorbed in the last trap.




Chromatography showed the presence of at least nine components in this gas.




Methane was found in all cases, together with carbon dioxide, carbon monoxide




and formaldehyde.





B.  Reaction Runs Using Qrgro




         The products of reaction obtained in the first trap, which was water




cooled, were found to be high viscosity, high-boiling tars.  Because of the small




quantity and the difficulty of handling,little progress was made in analysis of




this fraction.




         The second trap which was cooled by ice-water contained a liquid which




was over 95% water.  The small amount of organic matter present was roughly sim-




ilar in composition to the material in the third trap.  The third trap which was




cooled by dry ice-acetone contained the bulk of the organic products.  This




material was liquid at the trap temperature but also contained dissolved gases




which were analysed.




         A chromatogram of the separation obtained using the preparative gas




chromatograph is shown in Fig. 15.  The sample treated was 1.0 cc of the organic




layer collected in the dry ice-acetone trap from the partial oxidation of Orgro.




Not all of the eluted peaks have been shown in this figure.  Those that occurred




after 46 minutes were quite small and were not collected due to their low con-




centration.  There were a total of 34 peaks that could be discerned.  The compo-




nents that were collected in preparative collection traps were those at retention

-------An error occurred while trying to OCR this image.

-------
times of 14-, 16, 33 and 37 minutes.  The other components were collected in the



by-pass trap.  These four fractions were run on an infrared unit to be discussed



later.



         Fig. 16 is a chromatogram of the organic layer collected in the dry ice-



acetone trap from a pyrolysis run using Orgro.  Nitrogen was used as the fluidizing



medium and no air was added.  This chromatogram shows remarkable similarities



to the chromatogram in Fig. 15.  These two chromatograms represent the planned



extremes in operating conditions, i.e., those of partial oxidation and pyrolysis.



         Figs. 17, 18 and 19 represent the infrared work done with the absorbed



gases resulting from the partial oxidation of Orgro.  As described previously,



these gas samples were taken at sequentially higher bath temperatures and loaded



into a 10 cm path length infrared gas cell.  The spectra obtained were interpreted


                           29
in terms of published data.    The presence of carbon dioxide, propane, methanol,



and acetone is indicated.



         Figs. 20, 21 and 22 represent the results comparable to the above for the



absorbed gases resulting from the pyrolysis of Orgro.  These spectra indicate the



presence of carbon dioxide, carbon monoxide, methane, ethylene, propane and ammonia.



         Fig. 23 is an infrared absorption spectrum of the fraction collected in



one of the preparative collection traps at a retention time of 14 minutes , after



being rechromatographed.  An infrared spectrum of pure toluene was determined, as



shown in Fig. 24.  The striking similarity confirms the presence of toluene.



         Considerable quantities of a white salt was recovered by addition of



acetone to the aqueous layers.  This salt appeared to sublime at a temperature



of 60 C with the evolution of a strong odor of ammonia.  This information suggested



that the salt was ammonium carbonate.  An infrared spectrum of ammonium carbonate,



shown in Fig. 26, confirms this suspicion.
                                      55

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         An infrared spectrum of a fraction obtained by the chromatographic



separation of a liquid sample at a retention time of 16 minutes is shown in



Fig. 27.  Absorbance values suggest the presence of an unknown nitrile.




C.  Reaction Runs Using Leaves



         A summary of operating conditions and product yields for runs using



dried leaves is shown in Table 6.   Results in this table were included for both



pyrolysis and partial combustion runs at relatively low temperatures (270 CI-



SCO C).  In addition, pyrolysis runs at high temperatures (500 C-1000 C) were



also included.



         Again, the water-cooled first trap yielded a small amount of high



boiling, viscous tar which could not be conveniently analyzed.  The second trap



yielded an aqueous solution of water-soluble organics.  Upon analysis with the



gas chromatograph, this solution was found to contain besides water, methanol,



formaldehyde and acetic acid.



         The third trap, cooled by dry ice-acetone mixture, contained the bulk



of the organics.  The gas chromatograph, used in conjunction with the syringe


                                              19
reaction technique described by Hoff and Feit,   was found to be most effective



in identifying major constituents  in this fraction.



         In Fig. 28 is shown the complexity of a typical pyrolysis product sample.



Fig. 29 shows the same sample that has been vented and allowed to reach equilibrium



at room temperature.  The loss of dissolved gases and low boilers from this sample



is apparent.  The same type of results were obtained with partial combustion runs,



differing only in the magnitude of individual peaks.  The analytical work in this



section was confined to vented samples, such as the one whose chromatogram is



given in Fig. 29.  The chromatograms which resulted from reactions between this



sample and various reagents are shown in Figs. 30-41.  In Table 7, a summary



is given of the products which have been identified by these reactions , together



with the identity of the major peaks in Fig. 29.


                                     67

-------
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     o   o 
-------
                                 Table 6

                      Summary of Leaf Reaction Runs
Sample   Sample Size   Air:N    Residue   Liquid Products   Temperature
  No.       Grams      Ratio     Grams         Grams            C
            136.8        0       85.6           2.3          250-300


            142.3        0       94.0           7.4          250-300


            155.0       1:1      90.3           3.8          250-300


            168.0       1:1      99.2           5.0          250-300


             62.1        0       23.4           6.2          500-1000


             73.2        0       25.1           6.9          500-1000
                                 69

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                                     Table 7
               Identification of Chromatogram Peaks for Pyrolysis
                            of Leaves at 250C-300C

                                 (see Figure 29)
                     Peak                         Material
                   A,B,C,D                   unknown

                      E                      water

                     F,l                     unknown

                      2                      raethanol

                      3                      formaldehyde

                      4                      an ester

                    G,H,5                    unknown

                      6                      acetaldehyde

                      7                      acetone

                      8                      methyl acetate

                    I,J,9                    unknown

                     10                      ethyl vinyl ether

                    11-20                    unknown
NOTE:  Peaks identified by numerals were considered in the analysis; those
       designated by letters were not involved in identification.
                                       84

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                                   Discussion






A.  Studies with Paper




         All of the work with paper was done in the brass reactor.  This apparatus




performed fairly well but did suffer from certain limitations.  Leaks were a




continual problem that made accurate material balances almost impossible.  This




problem was particularly severe where screwed joints were required to introduce




or remove material from the reactor.  The use of Silver Goop sealant eventually




reduced this problem but did not completely eliminate it.  Problems also existed




in making satisfactorily tight joints between metal and glass equipment in the




temperature ranges encountered.  This was fairly well solved by the use of




Swagelok quick-connect fittings, but breakage of glass connections continually




was a problem.  Some corrosion of the reactor was observed.  Flakes of oxide were




observed on the walls and had to be removed periodically.




         From the results shown in Table 4, it appeared that the degree of reac-




tion of the sample decreased as the size of the initial charge was increased.  A




charge of 20 grams seemed to be optimum for reasonable decomposition.  Even this




size sample, however, gave more residue than could be accounted for from the ash




originally present in the charge.




         The size of the equipment used in this work represented a limitation on




the accuracy of quantitative results.  The small sample charge resulted in corres-




ponding small yields of products.  This , in turn, made it difficult to separate




components produced in partial combustion and pyrolysis reactions.  Consequently,




major emphasis has been directed towards the identification of major materials




produced.  The use of the gas chromatograph has been most helpful for this purpose.




Good chromatograms were obtained from both liquid and gaseous samples.  Comparison
                                      85

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of these chromatograms with those obtained from standard samples of known



materials run under identical conditions provided indications of possible product



components.  Spiking of product samples with pure samples of suspected components



resulted in the attenuation of peaks corresponding to these materials.  This



technique provided additional information for the identification of individual



materials.  Wet chemical analysis provided still further information as to the



identity of products.



         Examination of the chromatograms made on liquid samples shows many



similarities for total combustion, partial combustion and pyrolysis runs.  It



appears that many of the same products are present in all cases but in different



proportions.  For instance, the results in Table M- show that all liquid samples



had a low pH indicating the presence of acid products.  It was thought quite



possible that acetic acid might be present, and consequently a chromatogram was



run on pure acetic acid.  This resulted in a chromatogram with three distinct



peaks.  These same peaks also appeared in liquid samples.  Three peaks have also



been observed for formic acid and these peaks also occur in the liquid samples



with one or two of the last peaks coming close to or overlapping some of the



acetic acid peaks.  Based upon other work,  '   methanol was considered likely



to be present.  However, the concentration of water is such that the large water



peak probably obscures the methanol peak during most of the runs.  Methanol is



known to have a short retention on the column packing used and trails water by


                                                         13
only a few seconds.  The colorimetric method of Feldstein   seemed to confirm



the presence of methanol although some interferences were present.



         As mentioned previously, a number of gases were formed in each run.



Methane, carbon dioxide, carbon monoxide and formaldehyde were definitely identi-
                                      86

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fled and there were strong indications that propylene, ethylene and hydrogen




were also present.  The production of these gases increased with higher reaction




temperatures, with a corresponding decrease in oxygenated products.   This is




consistent with previous observations.




         It is felt that the condition of the reactor wall may have  had an ef-




fect upon the combustion reactions, particularly with regards to the kinetics.




It was observed that the wall surface tended to flake and may have influenced




the reaction.  This is consistent with observations by Albright.   It was noted




that the time required for a batch reaction decreased for subsequent runs under




similar conditions provided that no alterations were made to surface conditions.




Carbonaceous deposits tended to accumulate, probably the result of polymerization




of products formed.  These deposits may well have a catalytic effect on subsequent




reactions.





B.  Studies with Orgro




         As mentioned previously, the brass reactor used in the paper studies was




not entirely satisfactory, because of the necessity of removing the  cap each time




the reactor was charged.  This resulted in leaks and placed undue strain on




metal-to-glass connections.  In addition, considerable flaking on the inner sur-




face was noted, presumably due to corrosion.  Consequently, for the  work with




Orgro, a new reactor was provided made of black iron pipe.  This reactor also had




provisions for adding and removing material in a semi-continuous manner without




drastic disturbance to operating conditions.  It was found, however, that leaks




continued to be a problem and that some corrosion was occurring.  To obviate




these difficulties, a few runs were made with a ceramic reactor.  A  technique was




developed for supporting the fluidized mass on a bed of glass wool and sand which
                                      87

-------
eliminated leaks at the point where the supporting screen had previously been
held between flanges.  Leaks still occurred at inlet and outlet ports, and more
importantly through the porous ceramic walls.  Consequently, in all subsequent
runs, the black iron reactor was again used, and efforts were continued to
minimize leaks.
         The combined use of preparative gas chromatography and infrared spec-
troscopy was effective in analyzing the products formed.  It would have been even
more effective if larger samples had been available for analysis.  With the small
samples available, it was most important to have a column packing that had a high
capability of separating the components.  A considerable amount of experimentation
was required to find optimum analytical conditions.
         Porapak Q was able to separate the components fairly well up to a reten-
tion time of 18 minutes, as shown in Figs. 15 and 16.  It was for this reason
that major attention was given to the collection and analysis of the significant
peaks at 14- and 16 minutes.  The fractions corresponding to these peaks were col-
lected in the preparative traps and were run on the infrared unit.  The purity of
both of these collected fractions was approximately 95%.  The infrared spectrum
of the fraction with a retention time of 14 minutes compares very closely with
that of pure toluene as shown in Figs. 23 and 24.  The extraneous peaks can largely
be attributed to the sample collected at a retention time of 16 minutes which is
shown in Fig. 27.  It is believed that a slight amount of contamination may have
occurred in the preparative unit through cross-leakage at the collection valve.
         The infrared spectrum shown in Fig. 27 is probably that of a nitrile, as
indicated by the sharp absorbance at 2250 cm  .  It would also appear that the
compound has a ring structure, because of the characteristic absorbance in the
range between 1700 to 2000 cm   .  The remaining structure is so complex that no
further conclusions seem valid.
                                      88

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         It might be noted that the organic liquid samples which were collected




seemed to be rather unstable.   Care was exercised to keep samples in dry ice-




acetone baths until analysed.   Even in these baths they gradually turned darker,




and upon long standing turned into a brown tarry mass.




         The infrared analysis of the salt precipitated from the aqueous layers




appears to be conclusive.   The unknown salt corresponds in every way to ammonium




carbonate.  The carbonate  decomposes at 60 C which explains why the salt appeared




to sublime at that temperature when a melting point determination was attempted.




The correspondence between Figs. 25 and 26 is almost exact.




         An interesting observation was the similarity between the chromatograms




of the organic samples resulting from the pyrolysis of Orgro and the organic




samples resulting from partial oxidation of Orgro.  It had been expected that




much greater differences would occur.  The similarity is evident in a comparison




between Figs. 15 and 16.  One reason for this may be that the residence time in




the reactor was too short  for a complete reaction to take place.




         The gas phase infrared results indicate a much stronger difference be-




tween pyrolysis and partial oxidation.  Figs. 17, 18 and 19 indicate that the




gaseous products formed in the partial oxidation of Orgro include carbon dioxide,




propane, methanol and acetone.  Figs. 20, 21 and 22 indicate that the gaseous




products formed in the pyrolysis include carbon dioxide , carbon monoxide, methane,




ethylene, propane and ammonia.  The vapor of acetone seems to be present also,




but due to the strong absorbance of the ammonia, its presence is uncertain.





C.  Studies with Leaves
         As shown in Table 6 , both partial combustion and pyrolysis runs were




made using a feed of a fluidized mixture of dried leaves and glass beads at tem-




peratures in the range of 250 C-300 C.  In addition, pyrolysis runs in the range





                                      89

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of 500 C-1000 C were made.  Attempts to make high temperature partial oxidation




runs were not successful because of the extremely fast reaction which became




virtually an explosion.  It was almost impossible to collect product samples




under these conditions.




         All samples were analyzed in the same chromatographic column packed




with Porapak Q.  The same flow rates and temperature program, as previously des-




cribed, was used for all samples.




         The sample, whose chromatogram is shown in Fig. 29, will serve as an




example of the application of the syringe reaction technique to the identifica-




tion of products.  This sample was obtained from the pyrolysis of leaves at




250 C-300 C and the results obtained on it are typical of other runs.




         It is noted in Fig. 29 that four major peaks occurred in a short time




period.  Presumably two of these peaks are carbon dioxide and nitrogen.  Peak E




is for water.  These materials were not involved in the identification of other




compounds.




         The first reaction investigated was a reaction with acetic anhydride.




As seen from Table 2 acetic anhydride will react with alcohols to form acetate




esters, reducing or eliminating alcohol peaks and increasing the corresponding




ester peak.  Fig. 30 is a chromatogram of the sample after such a reaction.  The




attenuation used with the instrument was changed to assure that peaks were all




properly recorded.  The dotted peaks indicate the original chromatogram before




reaction.  It is noted that peak 2 has disappeared following reaction while peak




8 has increased and a new peak has appeared between peak 8 and peak 9.  The posi-




tion of the eliminated peak indicates the presence of methanol.  Then, either the




enlarged peak or the new peak must be methyl acetate.  It can be shown that pure




methanol vapor reacted with acetic anhydride yields methyl acetate and acetic




acid, as shown in Fig. 31.  Here it can be seen that the methanol peak is gone



                                      90

-------
and peaks for methyl acetate and acetic acid appear at the same positions as




they do in Fig. 30.  Further, if the reaction is done in two steps so that the




product of the acetic anhydride reaction is reacted with sodium bicarbonate , the




second peak, acetic acid disappears.  This allows the identity of the acetic




acid peak in Fig. 31 and, therefore, in Fig. 30.  The identity of the methanol




peak was verified by spiking with pure methanol which resulted in the enlargement




of the methanol peak.  The proposed methyl acetate peak 8 was verified by reaction




with sodium hydroxide.  Sodium hydroxide completely removes esters and forms cor-




responding alcohols which are partly removed by the reagent.  Fig. 32 does indicate




that methyl acetate has been removed.




         Sodium hydroxide also removed peak 4.  If this is indeed an ester, it




probably is a formate.  Also, peak 18 appears to be enlarged as a result of the




reaction.  This is the region in which n-propyl alcohol would appear if present.




If this is n-propyl alcohol, then the ester may be propyl formate.  There is no




other supporting evidence with regard to peak M-.




         If a vapor sample of reagent grade formaldehyde is injected into the




chromatograph which is programmed initially at 70 C and increased at a rate of




2-4 C/min after injection, two peaks emerge close together, but not overlapping,




after approximately 10 minutes.  The first can be shown by peak attenuation to be




methyl alcohol which acts as a preservative for the formaldehyde solution.  If




1/2 cc of formaldehyde solution vapor is combined with 8 cc of vapor from the




unknown mixture, peak 3 becomes noticeably enlarged.  This result not only in-




dicated that peak 3 is formaldehyde but also enhances the evidence that peak 2




is methanol.




         Two reagents were used to identify aldehydes.  The first was a saturated




solution of potassium permanganate; the second was sodium borohydride.  Both
                                     91

-------
reduce aldehydes and ketones to alcohols.  Fig. 33 was obtained after reacting




a 10 cc vapor sample from the liquid product and potassium permanganate.  It may




be seen that peak 3, previously postulated to be formaldehyde, has been eliminated.




Reaction with sodium borohydride also removes peak 3 as seen in Fig. 34-.  The




product peak of methyl alcohol was itself reduced by the reagent since lower pri-




mary alcohols are soluble in the reagent.  Reaction with sodium borohydride re-




vealed that a new peak appeared just ahead of peak 6 in a region in which ethyl




alcohol might be expected.  Another 10 cc sample reacted with sodium borohydride




and spiked with 2 cc of ethyl alcohol gave a very large ethyl alcohol peak as shown




in Fig. 35.  Either the large new peak was ethyl alcohol or was being covered by




ethyl alcohol spike.  If the peak was ethyl alcohol, it may be inferred that its




source was acetaldehyde, given by peak 6.  This was confirmed by spiking a 9 cc




vapor sample with 1 cc of isopropyl alcohol which showed in Fig. 36 that a shoulder




developed to the left of peak 8.  Another sample, shown in Fig. 37, spiked with




0.25 cc of acetone showed that peak 7 was greatly enlarged.  Considering that iso-




propyl overlapped methyl acetate in peak 8, it is not unreasonable to find that




acetaldehyde and acetone overlapped.  Several other items of information were ob-




tained from the sodium borohydride reaction shown in Fig. 34-.  It was noted that




peak 9 was eliminated in this reaction and that a new peak appeared between peak




8 and where peak 9 formerly had been.  Peak 11 which appeared as a tail on peak 10




in Fig. 29 was markedly reduced by the sodium borohydride reaction.  Peaks 6,7




and 15 were all decreased while peaks 12, 13 and 19 appeared to be larger.  This




may be evidence that peak 15 is a ketone or aldehyde and that peaks 12, 13 and 19




are corresponding alcohols.




         An effort was made to identify peak 10.  A vapor sample was reacted with




hydroxylamine hydrochloride to produce the chromatogram shown in Fig. 38.  A





                                       92

-------
comparison of peak 10 in Fig. 38 with peak 10 in Fig. 32 representing the sodium




hydroxide reaction with peak 10 in the original sample showed that peak 10 was




untouched by hydroxylamine hydrochloride, and untouched by sodium hydroxide.




From the data of Hoff and Feit this indicated that peak 10 was limited to paraf-




fins, olefins, benzene or ethers.  Reaction with concentrated sulfuric acid showed




that the peak was removed as seen in Fig. 39.  Reaction with hydrogen iodide fol-




lowed by sodium bicarbonate reagents also eliminated all peaks as seen in Fig.




M-0.  These reactions indicate that peak 10 is one of five ethers.  Sulfuric acid




diluted 7:3 removes peak 10 as shown in Fig. 41.  This reaction reduces the choice




to three ethers:  ethyl vinyl ether, tert-butyl methyl ether, or tert-butyl ethyl




ether.  Reaction with potassium permanganate removes about 80% of peak as shown




in Fig. 33.  Hoff and Feit reported 100% removal for ethyl vinyl ether, 10% re-




moval for tert-butyl methyl ether and 11% removal for tert-butyl ethyl ether.




Since the above results do not conform exactly to any of these three, the evidence




is uncertain.  It is believed, however, to be reasonably strong evidence of the




presence of ethyl vinyl ether.




         It is recognized that the syringe technique has limitations and tends




to be somewhat subjective.  It is felt, however, that the method lends strong




support to other information and techniques.
                                      93

-------

-------
                             Summary and Conclusions






         It appears that a considerable potential exists for reforming the or-




ganic portion of a number of solid waste materials into lower molecular weight




compounds having significant economic value.  The process of partial combustion,




which utilizes less than the amount of air required for complete combustion, is




effective in reforming paper, the organic portion of a dried sewage sludge, and




dried leaves.




         It was found that fluidization was an effective technique for bringing




finely divided solid waste material into contact with the desired air-nitrogen




mixture.  In these studies, pyrolysis in which no air was used, was considered




to be a limiting case of partial combustion.  In cases where the organic waste




material was very finely divided, the presence of an inert solid such as sand or




glass beads helped to stabilize the fluidized bed and minimized channeling or




slugging.




         Four broad classifications of products were obtained from the reactions,




namely:  1) tars, 2) an aqueous mixture, 3) an organic fraction, and 4) a mixture




of gases.  Tars represented a relatively small portion of the total products




formed, and decreased with increasing temperature.  Products contained in the




tars were not identified.  The aqueous fraction was largely made up of water plus




water soluble organics.  The organic fraction contained a complex mixture of at




least 35 materials including dissolved gases.  The gaseous products were materials




not condensed at the dry ice-acetone bath temperature.  A summary of products




identified with reasonable certainty is included in the following table.
                                      95

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                                     Table 8
                     Summary of Identified Reaction Products
  Paper
Water
Acetic Acid
Formic Acid
Formaldehyde
Methanol
Methane
Carbon Dioxide
Carbon Monoxide
Propylene
Ethylene
Hydrogen
  Orgro
Water
Methanol
Acetone
Toluene
A Nitrile
Propane
Methane
Carbon Dioxide
Carbon Monoxide
Ethylene
Ammonia
Ammonium Carbonate
   Leaves
Water
Carbon Dioxide
Carbon Monoxide
Formaldehyde
Methanol
Acetone
Acetaldehyde
Methyl Acetate
Ethyl Vinyl Ether
         The compounds found in partial combustion runs and pyrolysis runs were
remarkably similar.  As a generalization, oxygenated compound predominated in
partial combustion runs, and hydrocarbons predominated in pyrolysis runs.
         The problems of chemical separation and analysis were formidable and
many products known to be present remained unidentified.  The techniques used
included wet chemical methods , gas chromatography in conjunction with peak at-
tenuation and syringe reaction techniques, infrared spectroscopy, and mass
spectroscopy.
                                       96

-------
                                Literature Cited


 1.  Albright, L. F. , "Partial Oxidation of Light Paraffins,"  Chemical
     Engineering, 74, 15, 197-202 (1967).

 2.  Allan, L. B. , "Incineration as a Method of Sewage  Sludge  Disposal,"
     Municipal Utilities Magazine, 46-51 (Nov.  1954).

 3.  Altshuller, A. P. and Bellar, T. A., "Gas  Chromatograph Analysis of
     Hydrocarbons in the Los Angeles Atmosphere," Journal of the  Air
     Pollution Control Association, 13, 2, 81-87 (1963).

 4.  American Public Works Association, Municipal Refuse  Disposal,  Public
     Administration Service, 140-165 (1966).

 5.  Anger, V. S. and Ofri, Z., "The Detection  of Phenols by the  Gerngross
     Color Reaction with Tyrosine," Analytical  Chemistry, 203, 5, 350-354
     (1964).

 6.  Bellar, T., Sigsby, J. E., demons, C.  A.  and Altshuller, A. P., "Direct
     Application of Gas Chromatography to Atmospheric Pollutants,"  Analytical
     Chemistry, 34, 7, 763-765 (1962).

 7.  Brattain, R. R. , Rasmussen, R. S. and Cravath, A.  M., "A  Spectrophoto-
     metric Method for the Analysis of Multicomponent Mixtures and  Its  Infra-
     red Application," Journal of Applied Physics, 14,  418-428 (1943).

 8.  Brenner, N. and Ettre, L. S., "Condensing  System for Determination of
     Trace Impurities in Gases by Gas Chromatography,"  Analytical Chemistry,
     31_, 11, 1815-1817 (1959).

 9.  Cvejanovich, G. J., "Separation and Analysis of Mixtures  of  Hydrocarbons
     and Inorganic Gases by Gas Chromatography," Analytical Chemistry,  34, 6,
     654-657 (1962).

10.  Dimitri, M. S., Jongedyk, R. P. and Lewis, H. C.,  "Distillation of
     Fluidized Hardwood," Chemical Engineering, 124-125 (Dec.  1948).

11.  Ettre, L. S., "Application of Gas Chromatographic  Methods for  Air  Pollu-
     tion Studies," Journal of the Air Pollution Control  Association, 11, 1,
     34-43 (1961).

12.  Feldstein, M. , "Study on the Analysis of Hydrocarbons from Incinerator
     Effluents with a Flame lonization Detector," Journal of the  Air Pollution
     Control Association, 12, 3, 139-141 (1962).

13.  Feldstein, M. , "The Colorimetric Determination of  Formaldehyde and Methanol
     from Combustion Sources," Symposium on  Air Pollution Control,  ASTM Special
     Technical Publication No. 281, 23-26 (1960).

14.  Feldstein, M., Coons, J. D., Johnson, H. C. and Yocom, J.  E.,  "The Collection
     and Infrared Analysis of Low Molecular  Weight Hydrocarbons from Combustion
     Effluents," Industrial Hygiene Journal, 374-378 (Oct.  1959).
                                       97

-------
15.  Flood, Leo P., "Air Pollution Resulting from Incineration  -  Its Reduction
     and Control,"  Journal of Air Pollution Control Association,  9_, 1, 63-68
     (1959).                                                     ~

16.  Haldj A., Statistical Theory with Engineering Applications,  John Wiley
     and Sons, Inc., New York (1952).

17.  Harms, Donald  L., "Identification of Complex Organic  Materials by Infra-
     red Spectra of Their Pyrolysis Products,"  Analytical  Chemistry, 28,  8
     1140-1155 (1953).

18.  Haslam, J., Jeffs, A. R. and Willis, H. A.,  "The  Collection  of Fractions
     from the Gas Chromatograph and Their Identification by  Infrared Spectros-
     copy," Analyst, 86^, 4-4-53 (1961).

19.  Hoff, J. E. and Feit, E. D., Anal. Chem. ,  36_, 6,  1002 (1964).

20.  Hoffman, D. A., "Pyrolysis of Solid Municipal Wastes,"  Paper presented at
     the Engineering Foundation Research Conference on Solid Waste Research
     and Development (July 1967).

21.  Kaiser, Rudolf, Gas Phase Chromatography,  Vols. 1, 2, 3, CRC Press,
     Cleveland, Ohio (1963).

22.  Levinspiel, 0., Chemical Reaction Engineering, John Wiley  &  Sons, Inc.,
     New York (1962).

23.  Mahar, T. P. ,  "Semi-Quantitative  Analysis  of Hydrocarbon Mixtures by Gas
     Chromatography Without Complete Separation of Components," Journal of
     Gas Chromatography, 355-362 (Oct. 1966).

24.  Miller, Franklin, Scherberger, R. , Brockmyre, H.  and  Fassett, W. , "Deter-
     mination of Acetic Acid in Air,"  American  Industrial  Hygiene Quarterly,
     17_, 221-224 (1956).

25.  Minkoff, G. J. and Tipper, C. F.  H., Chemistry of Combustion Reactions,
     Butterworths Scientific Publications, London (1962).

26.  Morgan, L. W., Armstrong, G. M.,  Jr. and Lewis, H. C.,  "Distillation of
     Hardwood in a Fluidized Bed," Chemical Engineering Progress, 49, 2,  98-101
     (1953).

27.  Morris, R. A.  and Chapman, R. L., "Flame lonization Hydrocarbon Analyzer,"
     Journal of the Air Pollution Control Association, 11, 10,  467-489  (1961).

28.  Morrison, R. T. and Boyd, R. N.,  Organic Chemistry, Allyn  and Bacon, Inc.
     Boston  (1962).

29.  Raymond, H. P., Fletcher, A. N. and Gantz, C., "Catalog of Infrared  Spectra
     for Qualitative Analysis of Gases," Analytical Chemistry,  28, 8, 1218-1239
     (1956).
                                       98

-------
30.  Ruch, W. E., Chemical Detection of Gaseous  Pollutants,  Ann Arbor  Science
     Publishers , Inc. (1966).

31.  Sawicki , E. and Hauser, T. R. , "Infrared Spectral  Detection  of Carboxylic
     Acids and Aldehydes in Air-Borne Particulates,"  Analytical Chemistry,  31,
     4 (1959).

32.  Sawyer, C. N. , Chemistry for Sanitary Engineers, McGraw-Hill Book Company,
     Inc., 67-77 (1960).

33.  Selby, S. M. , Standard Mathematical Tables , Chemical Rubber  Company,
     Cleveland, Ohio (1967T.

34.  Shirley, D. A., Organic Chemistry, Holt, Rinehart, and  Winston, New York
     (1964)

35.  Silverstein, R. M.  and Bassler, G. C., Spectrometric Identification of
     Organic Compounds,  John Wiley  Sons, Inc. , New  York (1967).

36.  Sloane, H. J. , Johns, T, , Ulrich, W. F.  and Cadman, W.  J., "Infrared
     Examination of Micro Samples - Application  of a  Specular Reflectance Sys-
     tem," Applied Spectroscopy, 19, 4 (1965).

37.  Sproul, 0. J. , Caskey, J.  W. and Ryckman, D.  W., "Organic Pollutant Analy-
     sis by Gas Chromatography," Industrial Water and Wastes, 139-145  (Sept.-
     Oct. 1962).

38.  Stewart, James E.,  ''Vibrational Spectra of  Primary and  Secondary  Aliphatic
     Amines," Journal of Chemical Physics, 30, 5,  1259-1265  (May  1959).

39.  Tuttle, W. M. and Feldstein, M., "Gas Chromatographic Analysis  of Incinera-
     tor Effluents," Journal of the Air Pollution Control Association, 10,  6,
     427-430 (1960).

40.  West, P. W., Sen, B.  and Gibson, N.  A.,  "Gas-Liquid Chromatographic
     Analysis Applied to Air Pollution,"  Analytical Chemistry, 30,  8,  1390-1397
     (1958).

41.  Willard, H.  H., Merritt, L. L., Jr.  and Dean, J. A., Instrumental Methods
     of Analysis, D. Van Nostrand Company, Inc., New  York (1966).

42.  Yokom, J. E., Hein, G. M.  and Nelson, H.  W.,  "A  Study of the Effluents
     from Back-Yard Incinerators," Journal of the  Air Pollution Control Associa-
     tion, 6,2, 84-89 (1956).
                                      99

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