Pfi-253 178
THE CHEMICAL CONVERSION OF SOLID WASTES  TO USEFUL
PRODUCTS
OREGON STATE  UNIVERSITY
PREPARED FOR
ENVIRONMENTAL  PROTECTION AGENCY


APRIL 1974
                             DISTRIBUTED BY:
                                   TeeJinic&l Efiferasation Sereiss
                             U. S. DEPARTMENT OF  CQftH

-------
I. RU'ORT NO.
    EPA-670/2-74-027
      TECHNICAL REPORT DATA
(ricasc rea-V3)
                                            O.S. GOVf.lJiMUKT l'KlHTl!J(i OH'JCr.i 1974 - 717- %.-/'. Jlfl

-------
                                          EPA-670/2-74-027
                                          April  1974
        THE CHEMICAL CONVERSION OF SOLID WASTES

                  TO USEFUL PRODUCTS
                          By

James F. Barbour, Robert R.  Groner, and Virgil H.  Freed
         Department of Agricultural Chemistry
                Oregon State University
               Corvallis, Oregon  97331
                 Brant No. EP-R-00242
              Program Element No.  1DB314
                    Project Officer

                   Charles J. Rogers
     Solid and Hazardous Waste Research Laboratory
        National Environmental Research Center
                Cincinnati, Ohio  45268
        NATIONAL ENVIRONMENTAL RESEARCH CENTER
          OFFICE OF RESEARCH AND DEVELOPMENT
         U.S. ENVIRONMENTAL PROTECTION AGENCY
                CINCINNATI, OHIO  45268

-------
                   REVIEW NOTICE

     The National Environmental Research Center
Cincinnati has reviewed this report and approved its
publication.  Approval does not signify that the
contents necessarily reflect the views and policies
of the U.S. Environmental Protection Agency, nor
does mention of trade names or commercial products
constitute endorsement or recommendation for use.

-------
                        FOREWORD
     Man and his environment must be protected from the
adverse effects of pesticides, radiation, noise and other
forms of pollution, and the unwise management of solid
waste.  Efforts to protect the environment require a focus
that recognizes the interplay between the components of our
physical environmentair, water, and land.  The National
Environmental Research Centers provide this multidisciplinary
focus through programs engaged in

       studies on the effects of environmental contaminants
        on man and the biosphere, and

       a search for ways to prevent contamination and to
        recycle valuable resources.

     As part of these activities, this study describes the
use of solid wastes as raw materials for producing useful
products through the application of chemical and engineering
technology.
                            A. W.  Breidenbach, Ph.D.
                            Director
                            National Environmental
                            Research Center, Cincinnati
                           111

-------
                           TABLE OF CONTENTS
Subject


Introduction
Page


   1
Chemical Nature of The Constituents of Solid Wastes	   2

    Composition	   2

        Municipal Refuse	   2
        Industrial Wastes	   3
        Agricultural Residues	   3
        Glass	   4
        Plastics	   4
        References	  22
        Tables
          II. B. 1.  Composition of Typical Municipal Refuse
                     as Reported by Kaiser	  25
          II. B. 2.  Composition of Municipal Refuse Collected
                     in Various States as Reported by Hickman...  26
          II. B. 3.  Industrial Wastes by Categories	  27
          II. B. 4.  Estimate of Industrial Waste
                     Composition in Oregon	  28
          II. B. 5.  Composition of Poultry Manures	  29
          II. B. 6.  Composition of Manures of
                     Different Animals	  29
          II. B. 7.  Composition of Cereal Straws	  30
          II. B. 8.  Composition of Grass Seed Straws	  31
          II. 6. 9.  Composition of Some Typical Glasses	  32
          II. B. 10. Production and Sales of Plastics in  1970...  33


    Chemical Nature of Constituents	  34

        Cellulose	  34
        Plastics	  35
        References	  37
        Figure
          II. C. 1.  Schematic Diagram of The Cellulose
                     Molecule	  3'J
        Tables
          II. C. 1.  Products of Thermal Decomposition
                     of Cel lulose	  40
          II. C. 2.  Cellulose Derivatives and Their Uses	  41
          II. C. 3.  Solubility of Some Plastics  in
                     Selected Solvents	  42
          II. C. 4.  Effect  of Acids  and Bases on Certain
                     Plastics	  43
                                     IV

-------
Subject
Page
Chemical Processes	  44

    Crosslinking	  44

        Chemistry	  45
        Process	  49
        Experimental Results	  52
        References	  57
        Figures
          III. B. 1.  Schematic Diagram for Straw
                      Particleboard Formation	  59
          III. B. 2.  Effect of Wax Removal on Straw
                      Particleboard Physical  Properties	  60
          III. B. 3.  Increased Board Strength Brought About
                      by Increased Dsnsity	  61
          III. B. 4.  Effect of Pressing Time on
                      Modulus of Rupture	  62
          III. B. 5.  Increased Board Strength Caused by
                      Increased Resin Concentration	   63
          III. B. 6.  Relationship Between Density
                      and Thermal Conductivity	   64
          III. B. 7.  The Relationship Between Pressure
                      and Density	   65
          III. B. 8.  Showing the Influence of Density on
                      The Modulus of Elasticity	   66
        Tables
          III. B. 1.  Thermal Conductivity of Straw
                      Particleboard and Other Substances	   67
          III. B. 2.  Physical Properties of  Straw
                      Particleboard	   68
          III. B. 3.  Changes in Weight and Linear Dimension
                      of Boards Made From Various Materials
                      When Soaked in Water for 24 Hours	   69

    Nitrogen and Phosphorus Enrichment	   70

        Chemistry	   70
        Process	   73
        Experimental Results	   75
        References	   80
        Figures
          III. C. 1.  Schematic Diagram of The Nitrogen-
                      Phosphorus Enrichment Process	   81
          III. C. 2.  The Effect of Reaction  Time on  Nitrogen
                      Fixation in the  Reaction of Cellulose
                      and Urea	   82

-------
Subject                                                         Page
        Figures
          III. C. 3.  Effect of Reaction Temperature on
                      Nitrogen Concentration ....................  83
          III. C. 4.  Effect of Reactant Concentration on
                      Nitrogen Concentration ....................  84
          III. C. 5.  Effect of Catalyst Concentration
                      on Nitrogen Concentration .................  85
          III. C. 6.  Effect of Reaction Time on
                      Phosphorus Concentration ..................  86
          III. C. 7.  Effect of Reaction Temperature on
                      Phosphorus Concentration ..................  86
          III. C. 8.  Effect of Reactant Concentration on
                      Phosphorus Concentration ................ . .  87
        Tables
          III. C. 1.  Soil Test With Amino Cellulose ............  88
          III. C. 2.  Phosphorylation of Straw ..................  89
          III. C. 3.  Nitrogen and Phosphorus Enrichment
                      of Straw ..................................  90
          III. C. 4.  Soil Test With N-Enriched Paper ...........  91
          III. C. 5.  Soil Test With N and P Enriched Paper .....  92

    Acetylation of Wastes .......................................  93

        Chemistry ...............................................  93
        Process ..... ............................................  95
        Experimental Results ....................................  97
        References ..............................................  102
        Figures
          III. D. 1.  Schematic of Vapor Phase Acetylation
                      of Solid Wastes ...........................  103
          III. D. 2.  Schematic of The Fiber Process of
                      Acetylation of Solid Wastes ...............  104
          III. D. 3.  Schematic Diagram of The Solution
                      Process for Acetylation of  Solid Waste....  105
          III. D. 4.  Effect of Reaction Time on  The
                      Degree of Acetylation .....................  106
          III. D. 5.  Effect of Reaction Time, from 1 to  10
                      Minutes , on Degree of Acetylation .........  107
          III. D. 6.  Effect of Anhydride Concentration on
                      Acetyl Content ............................  108
          III. D. 7.  Showing The Realtionship Between
                      Catalyst and Degree of Acetylation
                      When Using Perchloric Acid ................  109

    Hydrogenation of Wastes ....... ..............................  110

       Chemistry ............. ...................................  110
                                   VI

-------
Subject
Page
        Experimental Results	 113
        References	 119
        Figures
          III. E. 1.  Gas Train for Analysis of The Head
                      Gas from the High Pressure Reaction
                      Apparatus	 126
          III. E. 2.  Carbon Monoxide Analysis System	 127
          III. E. 3.  Gas Chromatographjc - Mass
                      Spectrometric Analysis System	 127
        Tables
          III. E. 1.  Reaction Conditions and Products
                      of Hydrogenations	 128
          III. E. 2.  Showing the Amounts, in Grams, of Solid
                      Residue, Oil and Water Produced per Gram
                      of Cellulose Hydrogenated	 129
          III. E. 3.  Information From Standard Oil Company
                      Concerning A Sample of Oil From The
                      Hydrogenation of Waste	 130
          III. E. 4.  Showing the Crudely Determined Material
                      Balance of The Hydrogenation Reactions.... 131

    Etherification	 132

        Chemistry	 132
        Experimental Results	 133
        Discussion	 133
        References	 134
        Table
          III. F. 1.  Some Properties of Methyl and Ethyl
                      Ethers of Cellulose	 135

    Oxidation of  Cellulose	 136

        Chemistry	 138
        Experimental Results	 141
        Discussion	,	 142
        References	 144
        Figure
          III. G. 1.  Showing the Oxygen  Comsumption with
                      Time in The Chromic Acid Oxidation
                      of 1'ilter Paper	 148
        Tables
          III. G. 1.  Per^odate Oxidation	 149
          III. G. 2.  Persulfate Oxidation	 150
          III. G. 3.  Chromic Acid Oxidation	 150

    Pulping  of Straw	 151
                                       vn

-------
Subject
Page
        Chemistry	 151
        Disucssion	 152
        References	 153
        Figure
          III. H. 1.  Showing The Reduced Yield with Increased
                      Acid Concentration During Nitric
                      Acid Pulping	 154
        Tables
          III. H. 1.  Nitric Acid Pulping of Annual Ryegrass
                      Straw	 155
          III. H. 2.  Sodium Hydroxide Pulping of Straw	 155


Pilot Plant Studies	 156

    Economic and Engineering Analysis	 156

        Crosslinking	 156
        References	 162
        Figures
          IV. B. 1.  Block Diagram Showing The Particleboard
                     Process	 163
          IV. B. 2.  Schematic Diagram Showing The
                     Straw Particleboard Process	 164
        Tables
          IV. B. 1.  Resins Used in The Laboratory  Study
                     of Straw Particleboard	   65
          IV. B. 2.  Estimation of Fixed-Capital
                     Investment Cost	 166
          IV. B. 3.  Estimation of Total Product Cost	 167
                                    viii

-------
                       THE CHEMICAL CONVERSION

                            OF SOLID WASTES

                          TO USEFUL PRODUCTS
     In recent years, the problems associated with solid  waste  disposal have
become a national crisis.  This situation has developed because increasing
amounts of wastes are being produced each year and present  waste management
techniques are not adequate to prevent serious environmental  pollution.
More wastes are being produced because 1) our population  is increasing
and 2) because our per capita rate of waste generation is also  increasing.
In 1920, the per capita production of municipal, commercial and industrial
solid wastes was 2.0 pounds per day.  By 1969 this figure had risen to
5.3 pounds per person per day.  During this same period of time, the
population of the United States had increased from 106 million  to 200
million.  When agricultural wastes are added, the figures become higher
yet.  A study in California reve.ils that an estimated 70  million tons of
solid municipal, industrial and agricultural wastes were  generated in 1967,
an average of 20.2 pound per capita per day.  Agricultural  residues account
for 48.8% of this total, while municipal refuse accounts  for  32.0% and the
industrial wastes account for 19.2%.

     Over 80% of the solid wastes produced in the nation  are  disposed of  by
open dumping, landfilling, or sanitary landfilling, while about 10% are
incinerated, and the rest are composted, dumped at sea, or disposed of
in other ways.

     Although ocean dumping is practiced by many cities located near the
ocean, its practice is being discouraged because of problems  associated
with floating debris and destruction of sea life.  Several composting
processes have been developed which are capable of converting municipal
refuse to compost, but this technique of waste disposal has not been
successfully adopted because no market for the product has developed.

     Incineration is limited to those components of waste which are combust-
ible, however, this process can lead to severe air pollution.  The cost of
incineration is high, partly because of the need for air  pollution control
equipment.

     Landfilling costs are primarily determined by the haul distance and
cost of the land.  Leaching from a landfill can pollute surface and sub-
surface water, while anaerobic degradation produces methane gas.

     Although none of these management techniques are entirely  satisfactory,
at present there is no alternative.  One possible alternative is the
utilization of solid wastes as raw materials for the manufacture of useful

-------
products.  This technique would not only reduce the amount of waste
needing disposal, but would conserve our natural resources.

     The use of solid wastes as raw materials for the production of useful
products will depend primarily on the successful application of chemical
and engineering technology to waste disposal problems.  The objectives
of this study are to 1) identify the chemical nature of the constituents
of solid wastes, 2) investigate transformation processes, and 3) conduct
engineering and economic evaluations of pilot ph-jit operations.  The
results of this study will be useful in the development of a Solid Waste
Chemical Transformation Facility, which will be capable of receiving the
wastes produced in a community and disposing of them in an acceptable way.

     This report is divided into three sections:  Component Chemistry,
Chemical Processing and Pilot Plant Studies.  It contains detailed informa-
tion about a few, but does not include an exhaustive evaluation of all
wastes or processes known in this country.  This report is designed to be
the foundation for continued study of reutilization processes rather than
the culmination of a research effort.
        THE CHEMICAL NATURE OF THE CONSTITUENTS OF SOLID WASTES
Composition

     Municipal refuse:  Municipal refuse is composed of  a vast  array  of
products which have lo.t their usefulness and have been  discarded.  These
waste? include home w.istes, commercial wastes and city wastes.  While
home and commercial vastes are usually placed in a rjceptJjle for periodic
removal by a collection agency to a  landfill or incinerator, city wastes
usually collect elsewhere and require special handling and  disposal.

     Home wastes include such diverse products as glass  bottles, cans,
plastic toys, cellophane, paper, cardboard, nails, small appliances,  tools,
light bulbs, clothes, rubber products, wood, and food items.  If these
products are not separated into clashes such as metal, glass, paper,  etc.,
in the home, this waste becomes very heterogenous.

     Commercial wastes are generated by retail business  and institutions
such as hospitals, banks and schools.  Although these wastes are alao heter-
ogenous, they contain high percentages of office waste and  packaging  materials,

     City wastes include automobile  bodies, large appliances, tires,  dead
animals, demolition wastes, street sweepings, crankcase  oil and sewage
sludge.

     The composition of a s'-.nple of  municipal refuse reported by Kaiser
(13), is given in Table II. B. 1.  Hickman  (8) studied the  composition of

-------
municipal refuse from different states to determine if any wide variations
occur because of geographical location.  His results are listed in Table
II. B. 2.  Paper and paper products make up the largest single category of
these samples of wastes.

     Industrial wastes;  Industrial wastes include anything that is pro-
duced by an industrial operation that is not salvaged, sold as a by-
product, or used by another industry as a raw material.  Since industrial
firms are designed to prepare specific products from raw materials, the
wastes generated by each industry will vary depending on the nature of
the product and the process.

     The Oregon State Board of Health  (22) recently surveyed the industries
operating in Oregon to determine the types of wastes that were being pro-
duced.  Table II. B. 3. lists the types of wastes being discarded and
Table II. B. 4. lists the percent by volume being discarded by each industry.
Paper, wood and metals are the most common types of industrial solid waste
being discarded.

     Agricultural residues;  Agricultural residues include both animal and
crop wastes.  Since these wastes come from a wide variety of animals and
crops, no attempt has been made to include a comprehensive list of animal
and crop waste composition, however, representative data from the literature
is included.

Animal         Current annual production of animal wastes exceeds that from
wastes         any other section of the agricultural-industrial-domestic
complex, with about one-half of the 1.8 billion tons produced annually being
generated in confinement or feeding systems  (3).

     Although historically, animal wastes have been recycled through the
soil, the advent of inexpensive chemical fertilizers and increased labor
costs have made waste utilization uneconomical.  Consequently, wastes
from feed lot operations contribute to problems involving odors, insects,
dust, rodents, stream pollution, nitrification of surface and ground water
resources and eutrophication of surface waters.

     The composition of a sample of poultry manure is given in Table II.
B. 5. (31), while a comparison of the fertilizing values of a variety of
manures is given in Table II. B. 6.  (2).  Animal manures are characterized
by a high percentage of water and a significant concentration of plant
nutrients.

Crop           Straw is a solid waste of the cereal and grass seed industries.
wastes         While it is tilled into the soil in many areas, some crops,
notably perennials and some soils with a high clay content prohibit the
use of this practice.  In some regions, open field burning has been practiced
to sanitize the field and dispose of the straw, however, this practice
contributes to air pollution.  The primary obstacle to industrial utiliza-
tion of straw is the cost of harvesting and  storing the straw for year
around availability.

-------
     The exact composition of straw depends on a number of factors such
as type, age and climate, but the general composition of most straw is
similar.  Rice straw is one notable exception, in that it contains over
twice as much ash as most other straws.  The composition of some cereal
straws is listed in Table II. B. 7. (19), and the composition of some grass
seed straws is listed in Table II. B. 8. (29).  One can see that cellulose,
lignins and pentosans are the major components of straw.

     Glass;  Glass products are found in municipal and industrial refuse
and present two problems for waste utilization processes.  In milling
operations, glass is very abrasive and can cause excessive wear in metal
parts.  One hospital, in Salen, Oregon, now separates glass products prior
to hydropulping their wastes because excessive wear on the impeller had
made their disposal process uneconomical.  A second problem encountered
in chemical processing of wastes, is the chemical stability of glass.  If
glass is separated and collected in a concentrated form, what are the problems
involved in its reuse in the glass industry?

     Recent emphasis has been placed on the possibility of recycling
glass, and collection and delivery systems have been developed in
order to provide the glass industry with a supply of discarded j;*.ass.
Although the technology may be available for the reutilization o: some
glass, one major problem persists:  the variations in glass composition.
Each different type of glass, with its unique composition, has its own
uses.  Since physical and optical properties are determined by composition,
% heterogeneous mixture of glass may have limited value in a glass
recycling process.

     The compositions of several types of glass are listed in Table II.
B. 9. (16).  Ihese types are used for such diverse products as windows,
bottles, glasses, vacuum tubos, cookware, chemical apparatus, and safety
glass.

     Colored glass contains small amounts of metals or metal oxides not
listed in Table II. B. 9.  Rose colored window glass has been produced
by the addition of gold to the melt, yellow-green glass used for metal
sealing is produced by the addition or uranium oxide, deep blue glass is
produced by th? use of cobalt oxide, and green colored fruit jars are pro-
duced by use of iron oxide.

     The trade name of a glass is not indicative of its composition, since
nearly 150 different compositions of glass have been marketed under the
trade name of "Pyrex."

     Plastics:  It has been estimated that plastics make up only 1.3% of
the total annual waste produced in the U.S., however, the plastics industry
is growing.  Plastics present a special problem to waste disposal processes,
in that they do not readily decompose in landfills, and some contribute
to air pollution from incineration.  It is therefore felt that a review
of the chemical composition of plastics will be helpful in considering
the affect that plastics will have on chemical processes.

-------
     Plastics are polymers which can be molded or shaped.  Polymers are
long chain molecules formed by the bonding of smaller molecular units
called monomers:

                   n A     - - -    [A]n
                 monomer           Polymer

     If all of the molecules making up the polymers are the same, it is
called a homopolymer, but if two different molecules are used to make
the polymer, it is called a copolymer:

                    n A + n B   -  *    [A - B]n
                     monomer               Polymer

     Some polymers are formed by condensation (15:39), that is, a small
molecule is eliminated as the monomer reacts to form the polymer:

          n HO - A - OH  - -  H[0 - A]n OH + (n - 1)H20

     Many plastics are formed from resins which are solids or semi-solids,
composed of a complex, amorphous mixture of organic substances having no
definite melting point and no tendency to crystallize.  Thus, cellulose
and its derivatives could not be called resins, even though many of the
esters of cellulose are plastics.  Most resins are used in moldings,
laminates and coatings.  The use of resins has increased from about 2 million
pounds in 1920 to about 18 billion pounds in 1970,  The amounts o ", various
plastics produced and sold in 1970 are listed ait Table II. B. 10.  ,.27:66).
Polyethylene constitutes nearly a third of the njastics market while cell-
ulosics, once the leader, comprises only about .-'->.  Capstain  (20:25)
reports that there are more than 40 different i. allies of plastics and
sometimes hundreds of individual types in each family.  A brief review of
the composition of some of these plastics is presented here.

Polyethylene  Polyethylene was discovered in England in the early 1930 's
by a group of chemists who were carrying out high pressure reactions .  It
is formed by the polymerization of ethylene:
     In the high pressure process  (15,000 - 45,000  Ib./sq.  in.)  ethylene
reacts with itself, in the presence of a catalyst,  by  a free  radical  mech-
anism.  When this polymer has a low degree of side  chain branching, it  has
a tendency toward a crystalline structure, leading  to  a higher melting
point.  Its specific gravity ranges from 0.940  - 0.970, and it is  called
high density polyethylene.  Low density polyethylene,  with  a  specific
gravity range of 0.910 - 0.935, results when side chain branches are
present, producing steric hindrance which also  lowers  crystallinity,
softening point, and viscosity.

-------
     The polyethylene plastics are non-polar resins which possess a low
dielectric constant.  They are used in electrical applications, as coatinga
on cardboard milk and juice cartons, and for containers for such liquids
as milk, juice, detergent and bleach.

Polystyrene   Styrene wan first isolated in 1931 during the distillation
of fragrant balsams from certain plants.  Although coal tar was the first
commercial source of styrene, today it is produced by the dehydrogenation
of ethylbenzene (21:429):
                  CH2 " CH3
Fe23

650C
            Ethylbenzene                    Styrene

     Purification of styrene is difficult because of its tendency to
polymerize to polystyrene:
                                         Polystyrene

     The use of styrene as a monomer began after 1930 when it was dis-
covered that as little as 0.01% divinyl benzenj would produce a brittle
product through crosslinking.

     Three styrene copolymers have been developed for utilization because
of their properties.  Acrylonitrile-Butadiene-Styrene (ABS) resins are
used because they are tough, rigid and hard.  They are used in sewage,
drain and vent piping.  Styrene-Acrylonitrile (SA) copolymers are used
with a glass filler for strength.  Styrene-Butadiene Rubber (SBR) is used
as a synthetic rubber in automobile tires.

Polyvinyl      Vinyl polymers are characterized by the presence of the
chloride       vinyl group (Cl^Ct^).  When chlorine is attached, the
group becomes vinyl chloride (CH2=CC1}.  Polymerization under heat and
pressure with a catalyst produces a linear chain with a molecular weight
between 25,000 and 150,000 times that of the hydrogen molecule:
                n   CH2 = CHC1

                Vinyl Chloride
               - CHCl}n

       Polyvinyl Chloride
     This product is thermoplastic, but long exposure to elevated temp-
eratures results in degradation with subsequent  loss of hydrogen chloride

-------
gas.  It has many uses in construction, clothing, electrical, flooring,
home furnishing, packaging, toys, sporting goods, auto mats and seat
covers, credit and playing cards, and paint formulations.

     Polyvinyl butyral is used in automobile safety glass laminates and
polyvinyl acetate is used in the manufacture of adhesives.

Phenolics      The term "phenolic resin" includes a wide variety of pro-
ducts formed by the reaction of phenolic compounds with various aldehydes,
such as formaldehyde or furfural.  These reactions may be acid or base
catalyzed.

     The basic catalysts produce a one step reaction from which the resin
is called "resol" type resin.  The resol resins have short shelf life
because they continue to react in the storage container and dc not need
additional curing agents:
                        H2CO
                                OH-
- CH2OH
             Phenol  Formaldehyde  Methylol phenol
                   -CH2OH    Q
 i- CH'
     The intermediate of the acid catalyzed  reaction  is  also  methylol
phenol:
     The  two  step,  acid  catalyzed  reaction,  produces  a "novalak" resin,

-------
which requires additional crosslinkin,? agents such as aldehydes or hexa-
methylene-tetramine for curing when heated.  The reaction of the novalak
with the amine is a typical Mannich reaction:

                                      - CH_ - N - H,C -
     Phenolic plastics are widely used where heat resistance or electrical
insulation is needed.  Phenol -formaldehyde resins are used as binders  in
the plywood and particleboard industries.
Polypropylene     The polypropylene homopolymer doesn't have a very high-
impact resistance, therefore, much of the polypropylene exists as copolymers.
The monomer reaction is:
                                    H

                           *  CH. - C
                                >   i
     n H2C = C - CH3
                                    CH,
                                              H
                                              CH,
        Propylene
                 H
                 I
     -  CH-CH2  -  C =  CH2
                                                  n-x.
                                        Polypropylene
     In order to be useful, polypropylene must  contai'   iditives  such  as
antioxidants and ultra-violet  light  absorbers.  These plastics  are  used
in filament and fibers, transportation equipment,  appliances, electrical
wire and cable covering, housewares,  luggage  and cases,  packaging,  toys
and novelties.
Amino
Resins
               With a suitable catalyst, urea and formaldehyde  combine
               to form dimethylol-urea  (11:1022):
                     0
                     a
      2 HCHO  +  H2N - C -  NH2
                                OH'
                                U"
H
            0
            "
                                                            H
                                      -HO-C-N-C-N-C-OH
                                            II        II
                                            H   H       H   H
   Formaldehyde      Urea
                                             Dimethylolurea
     The methylolurea  can  be  combined  with  polyhydric  alcohols  by a con-
densation process or with  the acetals  produced  from the  initial reaction
of the alcohol  and  aldehyde.

     When an  acid catalyst is used,  urea  and  formaldehyde combine to form
methylene urea; which  polymerizes  into a  solid,  transparent,  brittle,
plastic mass:
                     0

    n HCHO + n H2N - C -
                                H* ^
           8
CH2 - NH - C - NTi
                                                               n H20

-------
     The properties of this polymer are usually modified by adding wood
flour or some other suitable extender.

     Malamine is produced by heating cyanamide (6:156):
       3 H2N - C = N
                                >  H2N - C
              Cyanamide
                             Melamine (Cyanuramide)
or by heating dicyandiamide in the presence of anhydrous ammonia and
methyl alcohol (17:245):
3 H,N - C - NH - C 5 N NHV Me
   2    ||
        NH
                              heat
         Di cyanamide
     The amino group of melamine then reacts with the formaldehyde molecule
to form the methylol group which takes part in the final polymerization
reaction.  Other amines which can be used to make amino plastics  include
benzoguanamine, ethyleneurea, thiourea and ana line.
Polyesters     One of the earliest polyester resins was of  the  glyptal
type, which was made from glycerine and phthalic  anhydride:
                     CH2OH
                   n CHOH
                     CH2OH
                                    0
                                    II
                                   -C-O-CH  -CHOH-CH20 -

-------
     Excess phthalic anhydride serves to crosslink polymer chains:
                          C  - 0  - CK,  - CH  - CH.,0- 
     To make a resin that is compatable with styrene, an unsaturated
polyester resin can be made by heating a mixture of phthalic anhydride,
maleic anhydride and propylene glycol.  By controlling the acidity, and
using an excess of propylene glycol, the polyester formed can be cut
with styrene.  The rigidity of the final product is controlled by varying
the ratio of aromatic anhydride to maleic anhydride, or by use of a more
flexible glycol such as diethyl glycol:
II
C
                   8
                       I
                       C
             200
                                      CH
                               0
                               II
0
II
0
II
                        -CH2-0-C  C-0-CH2-C-C-CH=CH-G
        2 n
                                                    2n
   CH2OH

   CHOH
   I
   CH OH
                                   10

-------
     Unsaturated polyester resins have dominated the reinforced plastic
market for many years because they are economical, easily fabricated,
lightly colored and have excellent physical properties.  They are used
for body putty, buttons, cultured marble, clay pipe seal, surface coating,
radomes, and boat hulls.
Coumarone      Coumarone resins are prepared by the polymerization of a
               mixture of benzofuran (coumarone) and indene below 2QfC
               using a suitable catalyst such as sulfuric acid.  Although
Indene
Resins
the polymerization of coumarone has not been studied extensively, as has
indene, the mechanism involved is probably similar:
        Indene
                              Polyindene
Coumarone
     These resins are used primarily in varnishes, rubber products,
linoleum, floor tiles and mastic for flooring.

Alkyd          Alkyd resins are formulated from polyesters.  An  ester  is
Resins         formed by the reaction of an alcohol with an  acid or anhydrid
By selecting a polyfunctional alcohol and a polyfunctional acid, a large
number of repeating units can be formed.  If the acid  is unsaturated as
with maleic acid or maleic anhydride,
                                   9
                                   8

                           Maleic Anhydride
                                               /

the resulting esters will be unsaturated.  Polyesters  are  formed by
the addition of an unsaturated monomer such as methacrylate,  styrene,
vinyltoluene, or trial lylcyanurate.  Although this mixture begins  to
react immediately upon contact, the reaction rate is extremely  low at
room temperature, so a catalyst is needed.  The  final  product is A
                                    11

-------
polyester that has been crosslinked at its sites of unsaturation by a
method similar to that used to crosslink the polyenes.

Epoxy          Epoxy resins are formed by reacting epichlorohydrin with
a polyhydroxy compound such as bisphenol-A in the presence of a catalyst:
n CIL - CH - CH.C1 + n HO -
   V
Epichlorohydrin
Bis-phenol A
                 - OH
                            H,C -  
-------
     Epoxy resins are used in protective coatings, reinforced plastics,
and bonding and adhesive:; for auto primers and plant maintenance.

Acetal         The molecular structure of the acetal plastics is that of
Plastics       a linear acetal, made up of chains of unbranched oxymethylene
               groups:
                    -  CH2  - 0  - CH2  - 0  - CHH
     The resin has high crystallinity and high melting point making it
a suitable replacement for metal in some applications.  Gears, foot
valves, bearings, ballcocks, and showerheads have been made from acetal
homo-and co-polymers.

Acrylic        Acrylic resins consist of long chain, linear molecules
Plastics       formed by the polymerization of acrylic or methacrylic
esters in the presence of a suitable catalyst:

CH2




i
^
1
- C 	
1
C = 0
1
0
1
CH3
     These products are noted for their light transmission, clarity, and
resistance to sunlight and weathering.  Modified acrylics have a much
higher impact strength than the general purpose acrylic.

     Some of the common trade names for acrylic plastic resins are Lucite,
Crystallite, Plexiglas, and Perspex.  They are used for aircraft canopies,
windows, instrument panels, searchlight covers, and aquariums.
               The  fluorocarbon plastics are analogs of the olefins with
               some of the hydrogens replaced by fluorine atoms.  The
Fluorocarbon
Plastics
reaction producing the polymer is similar to that used for the other
olefins:
  n CF2 = CF2 + n
                       - CF = CF
                                     Cat..
CF2  -
- CF - CF2--

  CF,
                                   13

-------
     These compounds exhibit chemical inertness, resistance to temperature
extremes, essentially no moisture absorption, low coefficient of friction,
low flamnability, and weather and oxidation resistance.

     Other similar plastics are the copolymer plastics and the chloro-
fluoro-carbon plastics.  These plastics have good electrical, thermal
and chemical properties which give them a wide range of uses.  One such
plastic, teflon, is used as a lining on cookware for non-sticking and
greaseless cooking, and in containers for highly corrosive materials.

Polyamide      Nylons are polyaciides formed by condensation of dibasic
Plastics       anines or by polycondensation of amino acids.  Nylon  6/6
(Nylons)       is made by condensation of a 6 carbon diamine and a 6 carbon
dibasic acid while nylon 6/10 is formed by condensation of a 6 carbon
diamine and a 10 carbon dibasic acid:
 n H2N-(CH2)6-NH2
   0        0
   II        II
HO-C-(CH2)4-C-OH
 Hexamethylene diamine     Adiptic  acid
                            0        0
 n H2N-(CH2)6-NH2 * n   HO-C-(CH2)8-C-OH
                          Sebacic  acid
                                                                  0
                                                                  n
 NH-(CH2)6-NH-C-(CH2)4-C+ 2nH20
                                    Nylon 6/6
                                          0
                            NH2- (CH2) 6-NH-(i- (CH2) 8-C
                             2nH,0
                                    Nylon 6/10
     Nylon 6  is made by  the hydrolysis  of e-caprolactam followed by con-
densation.
    I        ]      n  H20
  n N-(CH2)SC=0 	*- n NH2-(CH2)S-C-OH

    H
                    -HiO
           0

 -N-(CH2)5-C-

  H
     e-caprolactam is prepared  from cyclohexanonoxime which is produced by
the reaction  of hydroxylamine and cyclohexanone.   Benzene and phenol,
the byproducts of coke  plants,  can be converted to cyclohexanone.
                                   14

-------
     Copolymers of nylon offer a wide range of properties, while blends
and grafts are used within the plastic industry because they impart
toughness and desirable performance characteristics.

Polycarbonate  Polycarbonate plastics are prepared by ester exchange between
Resins         dialkylcarbonate and dihydroxyaromatic'compounds or by
phosgenation of a dihydroxyaromatic compound, such as bisphenol A:
  n  HO-
               -OH  +  n  COC12
                           Phosg
                        ene
                                          Polycarbonate
                                                                         2n HC1
     Polycarbonates are characterized by high impact strength, dimensional
stability, heat resistance, transparency, and other desirable properties.
They are used for airplane canopies and safety glass lenses where high
impact strength is required.

Silicones      Silicones are semi-organic polymers containing silicon,
oxygen, and an organic compound.  One method of preparation  is  to  reduce
quartz to silicon and react it with methylchloride.  This  product  is
then hydrolyzed to the polyorganosiloxane:
         2 RC1 + Si
                  Cl -
 n Cl -
R
I
Si
I
R
- Cl
n H2o
R
I
Si -
i

R(R
  I
 Si
  I
  R
                         Cl
- 0-  +.'2n 10
    Oichlorosilane
                       Polyorganosilane
     The silicones of greatest value  are resistant  to  weathering  and oxida-
tion, repellent to water, have good electrical  properties,  and  are  incom-
patablo with most organic polymers  (can be used as  mold  releases).

     Hydrolysis of the pure dichlorosilanes  can give only  linear  polymers
which are oils or greases  (21:605).   If trichlorosilanes are  hydrolyzed,
                                    15

-------
crosslinking of the chains after hydrolysis produces three dimensional
solid resins:
4n  RSiCl3  +  8n
   R    R
   I     I
0-Si-O-Si-h  +  12n HC1
   I     I
   OH   OH
      Trichlorosilane
r


0




0




R
1
- Si
1
0


- Si
1
R


OH
I
- 0 - Si-
1
R
R
1
- 0 - Si-
1
OH
-



m







n
     It follows that by changing the proportion of dichloro and trichloro-
silanes present, the properties of the silicone resin produced could be
varied.  Other molecules are introduced into the siloxane molecules to
modify the properties of the resin.  One of these molecules - fluorine -
has profound effects on the solubility of the silicone compounds.  These
fluorinated silicones are insoluble in almost all solvents and can be shown
as:                                                    

CH,-



CH3
Si - 0-
I
CH3


1
 Si - 0-
l
CH-
I '
CM,
i i
3
CH3
 Si -
CH,

n

CH3



Foam           Almost any plastic can be used to form a foam plastic
Plastics       (5, 7, 18, 26, 32, 33).  Although styrene and polyurethane
foams are probably two of the most widely recognized foams today,  cellulosic
foams have been used in the past.  Thermosetting plastics such  as  phenolics
(32) and ureas (7) produce light weight, brittle foams which are good heat-
resistant insulators.

     Foams may be rigid, semi-rigid, or flexible and ma; be formed with
                                  16

-------
or without skins.  The differences between the normal plastic and a foam
is the density, the residue left in the cells by the blowing agent, and
their uses.

     Blowing aeents may be low boiling solvents that evaporate rapidly 'to
caace foaming, or they may be nitrogen containing compounds, such as
azobisformamide, N-nitroso compounds, and sulfonylhydrazides, that decompose
to produce nitrogen.  A typical blowing agent is p-toluenesulfonyl semi-
carbazide:
                              - S - NH - NH - C - NH,
                                II                   i
                                0

One gram of this material produces 143-145 c.c. of gas at standard tempera-
ture and pressure (12).  The composition of the gas produced is 62% nitrogen,
30% carbon dioxide, and 4% carbon monoxide (5:27), the non-gaseous products
are toluene disulfide, ammonium sulfinate, and ammonium carbonate.

     Another blowing agent, which reacts with water, is sodium azodicarboxylate,
which decomposes to nitrogen in the following way (5:29):

        0           o                                0
2 NaO - C - N = N - C - 0 Na   + 4 II20  - *" 4 NaO - C - OH * 2 NH2-NH2 + NH2

        Sodium Azodicarboxylate

     The hydrazine formed can react further if lead peroxide is employed
as the curing agent, as shown by the following equation:


            H2N - NH2 + 2 Pb02  - * N2 + H20 + 2PbO


     The lead compounds present are potential health hazards.

Additives      Most plastics include some additives which impart desirable
properties to the product allowing a wider range of utilization.  Although
most additives are present in very low concentrations, they could affect
the  reaction rate or products of chemical processes.  A brief description of
some typical additives are given below.

     Plasticizers  are low melting solids oi" low volatile liquids, very
often esters which impart desirable qualities such as flexibility and
ease in  processing to the plastic.  Plasticizer molecules mixed with
the plastic  weaken the van der Waals forces, usually without reacting
with the polymer.

     Plasticizers are chosen with regard  for toxicity, odor, heat resistance
and solvent resistance as well as the product  flexibility, hardness, flam-
mability and utilization.  In addition, "he physical and chemical properties
of a particular plasticizer are important from a standpoint of color, handling,
acidity, moisture content and compatibility with the resin.
                                   17

-------
     Some general classes of plasticizers include phthalate esters, adipate
esters, azelate esters, sebacate esters, phosphate esters, epoxy esters,
biphenyls, ether derivatives, glycerol esters, glycol derivatives, petroleum
derivatives (mineral oil, etc.), polyesters, styrene derivatives, sucrose
derivatives, and sUlfonic acid derivatives.

     Ultraviolet absorbers are used to reduce polymer degradation caused by
ultraviolet light, with a wavelength between 400 and 290 mu, which has
sufficient energy to break ..most chemical bonds in organic molecules.  This
type of degradation results in crazing, color change, decreased strength
and loss of flexibility.

     Light energy can be disposed of by the molecule in one or more of the
following ways:
     a.  emit a photon - fluoresce and return to its original state,
     b.  give up its energy in the form of heat after distributing the
         energy over several bonds,
     c.  undergo a reversible photochemical change, give off heat, and
         return to its original state, and
     d.  transfer its energy to another molecule.  Ultraviolet absorbers
         work in two ways to protect the polymers from degradation by UV
         light; by absorbing  (screening) most of the incident light so the
         polymer does not acquire the excited state, and by acting as an
         energy transfer agent, absorbing most of the energy from the poly-
         mer molecule before  it can undergo alteration, thus quenching the
         excited state.  Most UV stabilizers are screening agents, but
         nickel and some of the heavy metals form complexes which act only
         as excited state quenches.

     Absorbers are selected with regard for their color, compatibility with
the plastic and plasticizer,  toxicity, and resistance to water and solvents.

     Typical classes of UV absorbers are benzophenones, benzotriazoles,
benzylidene malonates, salicylates, substituted acrylonitriles, organic
nickel, monobenzoates, and indole derivatives.  They are usually used in
concentrations of less than 2%.

     Colorants are classified as pigments  (inorganic and organic ) or dyes.
Pigments are finely divided solids which are dispersed in the system being
colored, while dyes are materials which dissolve in the resin.

     Colorants are chosen with regard for  cost, hue  (red, yellow, blue, etc.),
value  (degree of lightness and darkness),  chroma (intensity of a distinct
hue, degree of color departure from gray of same lightness), strength
(quantity of color when mixed with titanium dioxide will give a depth of
shade  equal to a given weight of some other color mixed with TiC^), and
opacity  (the measure of a colorants ability to stop  light transmission).

     Some colorants, such as  the cadmium sulfides, selenides, and cadmium
                                   18

-------
mercury compounds, could prove to be a problem in waste disposal systems
if they became concentrated or leached into the ground water.

     Antioxidants are used to combat oxidative degradation during processing,
manufacture, and storage.  They must be able to withstand the effects of
heating during processing.  In general, heat and light stabilizers are
not antioxidants.

     Typical antioxidants are alkylated phenols, alkyiated bisphenols,
alkylidene polyphenols, thio and dithio polyphenols, amines, organic
phosphates, and hydroquinones.

     Stabilizers are used to retard the rate of degradation caussd by heat,
light, oxidation, etc.  In view of the knowledge of degradation the perfect
stabilizer would be a compound that would screen ultraviolet light, absorb
free radicals, offer oxidation protection, react with resin impurities, and
protect against the disruption of double bonds, however, stabilizers should
not have detrimental effects on the clarivy of the product, be prone to
discoloration, plate out, or be toxic.

     Typical stabilizers are barium chloride powders or liquids, barium
cadmium zinc powders or liquids, barium carbonate, barium lead, barium
silicate complexes, calcium powders, some epoxides, nitrogen compounds,
phenols, phosphates, tins and ureas.

     Flame retardants, both additive and reactive types, are used to reduce
the hazards to life and property caused by flammable plastics  (1, 9, 10,
23, 24, 25, 28 30).  Certain chemical agents are known for their ability
to impart flame resistance, including the halogens  (chlorine, bromine,
fluorine), phosphorus, and antimony.  It is a common practice to use the
halogens in conjunction with phosphorous to formulate flame retardants.
Boron is used to a limited extent because of technical problems related to
compounds containing this element.

     Obviously, some resins have inherent flame resistance, such as poly-
vinylchloride and the flurorcarbons, but it is necessary to use flame
retardant additives with most plastics.  Some typical flame retardants
are the phosphate esters, chlorinated paraffins, halogenated phosphates,
halogenated aromatics, ammonium bromide, antimony oxide, zinc borate,
bromine containing polyyois, and tetrabromo-bisphenol A.

     Fillers and extenders are used for reinforcement, reducing the required
amount of resin to lower the product cost, and to add beauty or strength as
with the addition of marble chips to vinyl flooring.  Almost all fillers
give a small amount of reinforcing  action when added to polymers.  While
most fillers are inert, there is evidence that there may be strong attraction
between some fillers and the functional groups in some resins.
The major types of fillers are:
     a.  Silica products such as sand, quartz, or diatomaceous earth, and
         pyrogenic silica products  such as fumed coloidal silica,
                                    19

-------
     b.  Silicates including mica, kaolinite, talc, and asbestos, as well
         as the synthetic silicates such as calcium and aluminum silicate,
     c.  Glass in the form of flakes, spheres, fibers and even microballons,
     d.  Metal oxides such as alumina, magnesia, and titania,
     e.  Other inorganics such as barium sulfate, silicon carbide and
         molybdenum disulfidc,
     f.  Metals such as bronze, aluminum, lead and stainless steel which
         are added primarily for beauty,
     g.  Carbon black for all types of elastomers and
     h.  Organic fillers such as wood flour, pulp, etc.

     Fiber reinforcement is attained with cellulose fibers, synthetic
fibers, dacron, orlon or nylon, carbon fibers, glass fibers, asbestos
fibers, metallic fibers and ceramic fibers.

     Processing aids are used to control viscosity, stabilize an emulsion,
provide lubrication during processing, assist a mold release, prevent
blocking and adhesion, or improve the formation of a filled molding
compound.

     The viscosity depressants are not the same as the plasticizers, but
are used to lower the viscostiy of the plastisol without the use of
additional plasticizer.  Quite often the compounds will be ethoxylated
fatty acids.

     The parting or mold release agents can be sprayed directly on the mold
or incorporated into the plastic itself.  Examples are waxes, silicones,
fluorocarbons, and soaps.  Their purpose is to prevent the plastic from
sticking to the mold.

     Emulsifiers and compounds that help preserve the resin in a heter-
ogenous system of one immiscible liquid dispersed in another.  They may
be anionic, cationic, cr non-ionic in nature  and in the case of water
emulsions, they could be detergents.

     Internal lubricants are somewhat like the mold release agents in that
their raaior function is to prevent the plastic or rubber from sticking to
the processing equipment.  Very commonly the  internal lubricants are waxes
or metallic soaps.

     Anti-blocking agents are designed to prevent two surfaces from per-
manently adhering to each other.  These anti-blocking agents must have
partial compatibility and yet exude from the  surface under desired con-
ditions to perform their function.  Again, the blocking agents are often
waxes, oils, salts of fatty acids, and even polymers.

     Silane coupling agents  (14) improve the  coupling between the  inorganic
reinforcement agent and the organic polymer.  This  is generally  carried
out through a chemical reaction or series of  chemical reactions.  A very
small anuunt of "he right silane will give a  large  improvement in  the
product, especially in the cases where the additives are koalin  clays,
silicas, and silicates.
                                   20

-------
     Other additives include the peroxides, for generation of free radicals
to crosslink unsaturated compounds; and the anti-static compounds which may
be amines, ammonium compounds or anionic compounds designed to bleed off
static electric charges.
                                   21

-------
                              References
 1.   Andrews,  W. R., A. D. Cianiolo, E. G. Miller, and W. L. Thompson,
          "Plastic Foams as a Flame Penetration Barrier",  Journal
          of Cellular Plastics.  4(3):102-108  (1968).

 2.   Benne, E. J., C. R. Hoglund, E. D. Longnecker, and R. L. Cook,
          Michigan State University Bulletin 231, Agricultural Experiment
          Station, Cooperative Extercion Service, East Lansing, Michigan
          1961.

 3.   Beyer, H. C.,  "New Developments in Federal Animal Waste Disposal
          Programs".  Presented at the Animal Waste Disposal Workshop,
          Oregon State University, December 2, 1970.

 4.   Bruins, Paul F.,  Epoxy Resin Technology, Interscience Publishers,
          London, 1969.

 5.   "Cellular Plastics",  Proceedings of a conference, Natick, Massachussets,
          April 13-15, 1966; National Academy of Science? Publication 1462,
          National Research Council, Washington, D.C., 19o7.

 6.   Degering, E. F.,  Organic Chemistry, College Outline Series 6th edition,
          Barnes and Noble, Inc., New York, 1958.

 7.   Ferrigno, T. H.,  Rigid Plastic Foams, Second edition, Reinhold
          Publishing Corporation, New York, 1967.

 8.   Hickman,  H. L. Jr.,  "Characteristics of Municipal Solid Wastes",
          Scrap Age, 26,  (February, 1969).

 9.   Hilado, C. J., P. E. Burgess Jr., and W. R. Proops,  "Bromine,
          Chlorine, and Phosphorus Compounds as Flame Retardants in
          Rigid Urethane Foams",  Journal of Cellular Plastics, 4(2),
          67-78  (1968).

10.   Hilado, C. J., W. C. Kuryla, R. W. McLaughlin, and W. R. Proops,
          "Boron and Antimony Compounds as Flame Retardants in Rigid
          Polyurethane Foams",  Journal of Cellular Plastics, 6(5),
          215-220   (1970).

11.   Hodgins,  T. S., and A. G. Hovey,  "Urea-Formaldehyde Film Forming
          Compositions",  Industrial and Engineering Chemistry,
          3,  9  (1938).

12.   Hunter, B. A, and M. J. Kleinfeld, Rubber World, 155(3), 84
           (December, 1965).

13.   Kaiser, E., "Chemical Analyses of Refuse Components", p. 87,
          Proceedings of_ the_ 1966 National Incinerator Conference.
          ASME, New York, 1966.
                                   22

-------
14.  Kanner, B., and T. G. Decker, "Urethane Foam Formation  Role of
          the Silicone Surfactant",  Journal of Cellular Plastics,
          5(1). 32-39  (1969).

15.  Kaufman, M., Giant Molecules, Doubleday Science Series, Doubleday,
          Garden City, New York, 1968.

16.  KohJ, W. H., Materials Technology for Electron Tubes, p. 4,
          Reinhold Publishing Corporation, New York, 1951.

17.  Kresser, T. J., Polyolefin Plastics, Van Nostrand Newhold, New York, 1969.

18.  Lubitz, H. H., "Minicel Polypropylene Foam", Journal of Cellular
          Plastics, 5(4). 37-40  (1968).

19.  Miller, D. F., "Composition of Cereal Grains and Forages",
          National Academy of Sciences, National Research Council
          Publication 285, Washington, D.C., June, 1958.

20.  Modern Plastics Encyclopedia 1969-1970, Vol. 46, No. 10A, McGraw-Hill,
          Inc., New York, 1969.

21.  Noller, C. R.,  Textbook of Organic Chemistry, 2nd edition, W. B.
          Saunders Co., Philadelphia, Pa., 1958.

22.  "Industrial Solid Waste Survey, Oregon, 1970",  Oregon State Board
          of Health, Solid Waste Section, 1970.

23.  "arrish, D. B., and R. M. Pruitt, "The Thermal Stability of Flame
          Resistant Flexible Urethar.e Foams", Journal of Cellular
          Plastics, 5(6), 348-357   (1969).

24.  Pitts, J. J., P. J. Scott, and Powell, D. C., 'Thermal Decomposition
          of Antimony Oxychloride and Mode of Flame Retardancy",
          Journal of Cellular Plastics, 6(1), 35-37  (1970).

25.  Pruitt, R. A., "Self Extinguishing Characteristics of Flame Resistant
          Flexible Urethane Foam", Journal of Cellular Plastics,
          262-266 (1970).

26.  Schutz, C. A., "Urea Formaldehyde Foan for  Insulation",  Journal of
          Cellular Plastics, 4(2),  37-40  (1968).

27.  "The Statistics for 1970",  Modern Plastics, 48(1). 65-71  (1971).

28.  Tilley, J. N., H. G. Dadean, H. E. Regmore, P. H. Waszeciak, and
          A. A. R. Sayigli, "Thermal Degradative  Behavior cf  Selected
          Urethane Decompositions",  Journal of_ Gellular Plastics,
          4(2), 56-66  (1968).

29.  Unpublished Data  from the U.S.D.A. Utilization Laboratory, Albany,
          California.
                                   23

-------
30.  Way, D. H. and C. J. Hilado, 'The Performance of Rigid Cellular
          Plastics in Fire Tests for Industrial Insulation", Journal
          of Cellular Plastics, 4(6), 221-228 (1968).

31.  Wehunt, K. E., H. L. Fuller, and H. M. Edwards, Jr., 'The Nutritional
          Value of Hydrolyzed Poultry Manure for Broiler Chicks",  University
          of Georgia Agricultural Experiment Station, Journal Paper
          No. 114, 1960.

32.  Wheatley, S. J., and A. J. Mullett, "Foam Plastic Insulation for
          High Temperature and Shock Protection", Journal of Cellular
          Plastics, 6(3), 112-118 (1970).

33.  Woolard, D. C., "Expandable ABS", Journal of Cellular Plastics,
          4(2), 16-21 (1921).
                                    24

-------
Table II. B. 1.  Composition of Typical Municipal Refuse as Reported by

                             Kaiser  (13).
         Category
Paper
   Corrugated paper boxes
   Newspaper
   Magazine paper
   Brown paper
   Mail
   Paper food cartons
   Tissue paper
   Wax cartons
   Plastic coated paper

Moisture

Garbage
   Vegetable food wastes
   Citrus rinds 6 seeds
   Meat scraps, cooked
   Fried fats

Glass, Ceramics, Ash

Vegetation
   Ripe tree leaves
   Flower garden plants
   Lawn grass green
   Evergreen

Metals

Miscellaneous
   Wood
   Plastics
   Rags
   Leather goods
   Rubber compositoon
   Paint and oils
   Vacuum cleaner catch
   Dirt

Total
 Weight Percent
23.38
 9.40
 6.80
 5.57
 2.75
 2.06
 1.98
 0.26
 0.76
 2.29
 1.53
 2.29
 2.29
 2.29
 1.53
 1.53
 1.53
 2.29
 0.76
 0.76
 0,38
 0.38
 0.76
 0.76
 1.53
          53.46
           9.05
           8.40
           7.73
           6.85

           7.62
          99.90
                                   25

-------
   Table II. B. 2.  Composition of Municipal Wastes



Collected in Various States as Reported by Hickman  (8).



                   wt.% (wet basis)



 CALIFORNIA  NEW JERSEY  TENNESSEE  ARIZONA  ILLINOIS  OHIO  NEW YORK
Paper
Food
Metal
Glass
Wood
Misc.
54
15
7
2
2
2
51
10
8
4
4
4
46
26
11
11
1
5
43
22
10
8
2
1
42
14
9
6
-

42
28
9
8
3
3
40
10
8
-
7
3
                           26

-------
Tabia II. B. 3.  Industrial Wastes by Categories
Rubber-Plastics
Shredded rubber
Tires
Foam Rubber
Plastic wastes
Fiberglass wastes
Rubber Scraps

Mixed Sludges
Treatment plant
sludge
Lagoon sludge
Settling basin
sludge
Fruit -Vegetable
Wastes
Fruit wastes
Vegetable wastes
Dough wastes
Grain wastes

Glass Wastes
Glass bottles




Paper Waste
Corrugated
Paper bags
Paper drums
Office waste
Cafeteria waste
Washroom waste

Wood Waste
Bark
Lumber
Pallets
Sawdust
Sanding dust
Wooden crates
Wooden boxes
Trimmings
Skids

Sand and Stone
Wastes
Bricks
Tailings
Tiles
Sand
Concrete
Ashes
Metal Wastes
Banding
Strapping
Metal Scraps
Buckets
Barrels
Cans
Wire
Turnings
Burnings
Slag
Animal Wastes
Animal offal
Hair
Feathers
Hides
Leather scrap
Bones
Shells
Paunch
Fish
Seafood



Petro-Chemical
Wastes
Waste Inks
Paints
Oils
Solvents
Thinner
Resins
Glues
Asphalt
Pesticides
Herbicides
Textile Wastes
Rags
Upholstery scrap:
Drapery scraps
Apparel scraps
Canvas  burlap
Cotton 5 wool
Textile bags




                        27

-------
                         Table  II.  B.  4.   Estimate of Industrial Waste Composition in Oregon
                                                     Volume Percent
to
oo
Meat Processing
Electric Machinery
Dairy Products
Misc. Food Processes
Printing 5 Publication
Petroleum 5 Allied
Scientific Instrument
Ordnance
Non-Elec. Machinery
Processed Foods
Apparel Products
Rubber 5 Plastics
Chemical  Allied
Transportation
Misc. Manufacturing
Cannery  Frozen
Textile Mills
Furniture
Stone, Clay 5 Glass
Seafood Processing
Fabricated Metals
Primary Metals
Wood Products
Paper & Allied
Leather Manufacture
Paper
Waste
97
97
96
94
94
92
88
85
82
70
69
69
60
58
57
56
54
52
44
43
43
30
27
25
14
Wood
Waste
3
1
>1
1
4
5
5
11
13
>1
1
13
27
40

3
2
39
40
13
43
7
65
4
2
Metal
Waste
>1



1

1
1
3
5
1
1
8
1

2
1
4
5
10
14
15
6
1
4
                                                   Animal  Textile    Petro-
                                                   Waste   Waste      Chemcl
                                                                                        Fruit   Rubber   Sand,  stn
                                                                                        Vegtbl  Plastic  Glass, Ash
                                                                                                    1
                                                                                                    3
                                                                        >1
                                                                        28
                                                                         1
                                                                        42
                                                                         3
                                                                                           23
                                                                                           39
                                                               33
                                                               72
>3
                             2
                             2
                             1
                            16
43


 1

 1


 1

 3
                                                                                                             11
                                                                                                            47

-------
          Table II. B. 5.  Composition of Poultry Manures

                         wt.% (air dry basis)
                                       Hen Manure          Broiler Manure

Moisture                                   4.29
Ash                                       23.28                 20.83
Crude Fiber                               12.15
Ether Extract                              1.38
Crude Protein                             19.94                 32.21
True Protein                              10.13                 11.42
Calcium                                    6.50                  S.50
    Table  II. B. 6.  Composition of Manures of Different Animals

                                 wt.%

                            Water      Nitrogen      Phosphorus  Potassium

Chicken                      54            1.56         0.40        0.35
Dairy cattle                 79            0.56         0.10        0.50
Fattening  cattle             80            0.70         0.20        0.45
Hog                          75            0.50         0.14        0.38
Horse                        60            0.69         0.10        0.60
Sheep                        65            1.40         0.21        1.00
                                    29

-------
Table II. B. 7.  Composition of Cereal Straws



               wt.%, dry basis
Component
Dry matter
Cellulose
Lignin
Pentosans
Crude protein
Crude fat
Crude fiber
Ash
Sulfur
Sodium
Chlorine
Calcium
Phosphorus
Potassium
Magnesium
Iron
Oat
rain. - max.
\
83.9 -
40.1
13.4 -
2.0 -
0.8 -
33.3 -
4.9 -
0.20 -
0.23 -
0.70 -
0.13 -
0.15 -
0.20 -
0.16 -
0.018-
95.2
15.8
8.6
3.2
54.0
12.9
0.27
0.53
0.85
0.40
0.43
2.41
1.43
0.056
Rice
min. - max.
38.8
17.7
2.8
8.7
27.6
14.0
\
0.31

O.lr
0.06
1.10
0.07
- 93.4

- 6.2
- 2.3
- 38.3
- 20.1



- 0.38
- 0.15
- 1.51
- 0.18
Wheat
min. - max.
82.8 -
35.3 -
12.4 -
1C. 2 -
1.5 -
1.0 -
36.4 -
3.5 -
0.13 -
0.06 -
0.21 -
0.10 -
0.04 -
0.12 -
0.05 -
0.007-
99.1
63.9
15.1
12.8
6.9
3.7
51.5
11.1
0.29
0.23
0.34
0.42
0.51
1.95
0.70
0.017
                       30

-------
           Table II. B, 8.  Composition of Grass Seed Straws

                            wt.%, dry basis
           Fine Chewings    Merion     Highland    Perennial    Annual
Component     Fescue       Bluegrass   Bentgrass   Ryegrass    Ryegrass
Crude protein
Crude fiber
Crude fat
Crude pectin
Ash
Total sugars
Reducing sugars
Pentosans
Lignin
Cellulose
5.2
45.1
1.8
1.1
7.0
0.20
0.17
27.1
10.2
45.2
9.1
36.6
2.1
1.6
5.4
2.49
1.74
24.0
8.7
41.6
4.6
39.4
1.9
1.7
2.7
2.01
0.96
24.8
9.0
44.2
5.5
41.2
1.8
2.3
6.7
0.68
0.43
22.0
8.8
42.3
4.5
40.2
1.4
1.8
6.6
4.05
3.25
23.7
8.6
42.8
                                31

-------
Table II. B. 9.  Composition of Some Typical Glasses.



                         Wt%

TYPE
Soft Soda



Lead


Borosilicate


Special
Extra Hard



1
2
3
'A.
5
6
7
8
9
10
11
12
13

Sl
70
69
69
73
56
57
63
71
30
73
22
54
58

2
.5

.3
.6
.5

.1

.5

.6
.5
.7

B22 A1
1
4
3
1.2
1
1
0
13.7 7
12.9 2
16.5
37 23
7.4 21
3 22

22 Pb
.8

.1

.5 29
.5 29.4
.28 20.22
.4
.2
6
.7
.1
.4
C 0
N T
CaO
6
5
5
5
0
0
0
0


10
13
5
.7
.8
.6
.37
.2
.2
.94
.3



.5
.9
E N T
Na2
16
17
16
17
5
4
7
5
3

6

1
.7
.5
.8
.23
.6
.1
.6
.3
.8
4.5
.5

.1
K20
0.8
1.9
0.6

6.6
7.3
5.54
2.4
0.4

0.2

0.2
MgO BaO Ma23
3.4
1.6
3.4
3.67
0.6
0.4
0.88




3.5
8.4

-------
      Table II. B. 10.  Production and Sales of Plastics in 1970
Plastic



Polyethylene, low density



Polystyrene ft copolymers



Polyvinylchloride  copolymers



Polyethylene, high density



Phenolic?



Polypropylene



Urea and Melamine



All other vinyls



Polyesters



Alkyds



Coumarone-indeme



Cellulosics



Epoxy



Miscellaneous



Total
Production
4300
3350
3150
^
1700
1075
1010
710
650
645
604
340
180
165
1722
19600
Sales
4180
3323
3050
1625
888
985
638
600
613
300
350
175
155
1618
18500
                                     33

-------
Chemical Nature of  the  Constituents

     Cellulose.  Cellulose  is  a polysaccharide which yields  only glucose
upon hydrolysis.  There is  general agreement  among workers  in the field
that cellulose  is composed  predominately  of 3 1,4  linked D-glycopyranose
units,  Figure II. C.  1.

     The reactions  of cellulose resemble  those of  the simple sugars.   Since,
however, all but one  of the potential  reducing groups of the glucose  residue
(the one terminating  unit of the open  chain)  are involved in glycosidic link-
ages between individual members of the chain, cellulose lacks the pronounced
reducing power  of most  of the  sugars.   The chief reactions  of cellulose are
those of its hydroxyl groups.

     All glucose residues except one (the other terminating unit) possess three
free hydroxyl groups, the one  in the C-6  position  being of primary nature and
those in the C-2 position and  the C-3  position being of secondary nature.
These free hydroxyl groups  react as  alcohols  to form addition compounds
with alkalies and certain complex salts.   Under certain conditions they also
react with sodium metal to  form compounds (comparable to the alcoholates)
called  cellulosates.  Furthermore, the hydroxyl groups of cellulose react
to  form esters  and  ethers,  and on oxidation are converted stepwise into
carbonyl and carboxylic groups.

     The reaction product of cellulose and sodium  hydroxide, called alkali
cellulose, is used  in the production of cellulose  xanthate and cellulose ethers.
A variety of cellulose  ethers  can be prepared by reacting alkali cellulose with
various alkyl chlorides. Similarly  a  variety of cellulose esters can be pre-
pared by reacting cellulose with various  organic acid anhydrides.

     Acid hydrolysis  of cellulose produces glucose which can be converted to
hexsne  by reduction with hydrogen iodide  and red phosphorus or to sorbitol by
reduction with  sodium amalgam.

     Cellulose  can  be degraded both  thermally and  chemically.  The main products
of  thermal decomposition are carbon, carbon dioxide, and water.  Some of the
other products  formed are acetic acid, acetone, formic acid, formaldehyde,
furfural, hydroxymethylfurfural, ethene,  carbon monoxide, and methane.  A
summary of the  quantity of  products  produced by the thermal decomposition of
cellulose  (9^ ;ire  listed in Table II.  C.  1.

     The er.d product  of the hydrolysis of cellulose is glucose, but continued
chemical action on  the  glucose results in the formation of hydroxymethylfurfure
which produces  levulinic acid  and formic acid.  Oxalic acid can be produced
from cellulose  by  alkaline  oxidation  (5)  or nitric acid oxidation  (15).  Under
some  conditions the alkaline degradation of cellulose can result in complex
fragmentation reactions producing formic, ace;tic,  glycolic, and lactic acids
 (16).

      Cellulose  derivatives  are used for a variety  of purpoi.es.  Some of the
uses  of cellulose  derivatives  are listed in Table II. C. 2.
                                   34

-------
     Plastics.  Most plastics are generally chemically inert, however, each is
affected to some degree by certain organic solvents, acids, and bases.  In
addition, all plastics degrade at elevated temperatures.

     The solubility of some plastics in organic solvents is listed in Table
II. C. 3.  The plastics which appear to be most resistant to attack by
solvents are the nylons, urethanes, polyethylene, fluorocarbons, and chlorinated
polyethers.

     The effect of acids and bases on certain plastics is listed in Table
II. C. 4.

     As with wood, paper, or other combustible materials, at elevated temp-
eratures, plastics degrade to form combustible gases, non-combustible gases,
and a char.  If an oxidizing agent is present, the combustible gases will
burn when heated above their ignition point.  However, in the case of halogenated
or flame retardant treated plastics the combustibility of the plastic is nil
unless the temperature is raised much higher than the normal combustion temp-
erature.  The halogenated plastics produce acid gases such as hydrogen chloride.

     The urethane plastics show a great variation in properties.  Urethane foam
from tertiary alcohols may decompose at a temperature as low as 50CC, while
urethanes of many primary alcohols change only slowly at 150C.  According to
Saunders (2:127) there are essentially three types of reactions that can take
place during the thermal decomposition of urethane:
     1)  a dissociation to alcohol and isocyanate,

                      0
             R - NH - C - OR'  	*    R'OH + R-N = C = 0


     2)  formation of a primary amine and an olefin, and

             q
    R - NH - fc - 0 - CH2 - CH2R'  	-   RNH2 + C02 + R1 - CH = CH2


     3)  secondary amine formation.


                 RNH - C - OR  	*   R - NH - R + CO,
The two reactions  likely to occur with  isocyanates  at  elevated  temperature  are
the formation of the  carbodiimide and trimerization to an  isocyanate.
                                   35

-------
              2R-N =
               R - N = C = 0
 RN = C = NR + C02
   Carbodiimide

         9
R - N
    I
    C

- R
                                         Isocyanurate

     When polyethylene is pyrolyzed  (4) at 300 and SOOC in oxygen and wet
or dry carbor. dioxide, the products  contain carbon dioxide, carbon monoxide,
hydrogen, saturated and unsaturated  aliphatic hydrocarbons, benzene, toluene,
and polycyclic aromatic compounds.

     The pyrolysis (not combustion)  of polyvinyl chloride  (8) produces hydrogen
chloride, saturated and unsaturated  aliphatic hydrocarbons, methyl and ethyl
chlorides, and aromatic compounds.

     Other studies of the products of plastic degradation have been conducted
by Cerceo (3), Way and Hilado  (14),  Pruitt (12), Pape, et al.  (10), Parish
and Pruitt (11), and others  (1, 6, 7).
                                   36

-------
                               References
 1.   Andrews,  W.  R.,  A.  D.  Cianiolo,  E.  G.  Miller,  and W.  L.  Thompson,
           "Plastic Foams  as  a Flame  Penetration Barrier," Journal  o
           Cellular Plastics,  4(5).  102-108 (1968).

 2.   "Cellular Plastics,"   Proceedings of a Conference, Natick Massachusetts,
           April  13-15,  1966.   Publication 1462, National  Academy of Sciences,
           National Research  Council, Washington, D.C., 1967.

 3.   Cerceo,  E.,  "Effect of Time on  the  Infrared Spectra of Epoxy Pyrolyzates,'
           Industrial and  Engineering Chemistry, Product Research and Develop-
           ment,  9_, 96-100 (1970).

 4.   Chaigneau, M., and  G.  LeMoan,  "Pyrolysis of Plastic Materials.  IV.
           Polyethylene,"   Annales  Phannaceutiques Francaises, 28(6),
           417-423 (1970).

 5.   Heuser,  E.,  The Chemistry of Cellulose, p.  490,  John Wiley and  Sons
           Inc.,  London, 1944.

 6.   Hilado,  C. J., P. E.  Burgess, Jr.,  and W. R. Proops,  "Bromine,  Chlorine,
           and Phosphorus  Compounds  as Flame Retardants in Rigid Urethane
           Foams,"  Journal of Cellular  Plastics, 4(2), 67-78 (1968).

 7.   Hilado,  C. J., W. C.  Kuryla, R.  W.  Mclaughlin,  and W. R. Proops,
           "Boron and Antimony Compounds as Flame Retardants  in Rigid
           Polyurethane  Foams,"  Journal of Cellular Plastics, 6(5),
           215-220 (1970).

 8.   LeMoan,  G.,  and M.  Chaigneau,  "Pyrolysis of Materials in Plastics.  I.
           Polyvinyl Chloride (PVC).   Characterization of Possible Volatile
           Toxic  Compounds,"   Annales Phannaceutiques Francaises,' 27(2)  97-
           101 (1969).

 9.   Nikitin,  N.  I., The Chemistry of Cellulose and Wood, Translated by
           J.  Schmorak,  Israel Program for Scientific Translations,
           Jerusalem, 1966.

10.   Pape, P.  G., J. E.  Sanger, and R. G. Nametz, "Tetrabromophthalic
           Anhydride in  Flame Retardant  Urethane Foams," Journal of
           Cellular Plastics, 4(11),  438-442  (1968).

11.   Parrish,  D.  B., and R. M. Pruitt, "The Thermal Stability of Flame
           Resistant Flexible Urethane Foams,"  Journal of Cellular
           Plastics. 5(6), 348-357 (1966).
                                   37

-------
12.   Pruitt, R. M.  "Self-Extinguishing Characteristics of FJame Resistant
          Flexible Urethane Foam," Journal of_ Cellular Plastics, 6(6),
          262-266 (1970).

13.-  Tilley, J. N., H. G. Nadeau, H. E. Reymore, P. H. Waszliciak, and
          A. A. R. Sayigh, "Thermal Degradative Behavior of Selected
          Urethane Foams,"  Journal of Cellular Plastics, 4(2), 56-66 (1968)

14.   Way, D. H., and C. J. Hilado, "The Performance of Rigid Cellular
          Plastics in Fire Tests for Industrial Insulation,"  Journal
          Of Cellular Plastics, 4J6J_, 221-228 (1968).

IE.   Webber, H. A., "The Production of Oxalic Acid from Cellulosic
          Agricultural Materials," Iowa Engineering Experiment Station
          Bulletin 118, Iowa State University, Ames, Iowa, 1934.

16.   Whistler, R. L. editor, "Cellulose" Volume III, p. 161, Methods
          in_ Carbohydrate Chemistry, Academic Press, New York, 1963.
                                   38

-------
    H-C-H
       c-

   1/&


  /\9H
 HO    C-
       I
       H





*0
H),

c
I
OH









OH
1


H-C-H
H
1
A P 
/ \ /\
' \ /OH
C

c 
1
H-C-H
1
OH
OH
1
-C
\r
A
c o


.




\
r





1
1
 
/H
>
\,H
c 
1
H





-o
y
Hv/H
-c
i
OH






H
I
0 C 	
\/OH
H\H
c 
1
H-C-H
1
OH
n



OH
I
-C
\'
/\
0 OH




Figure II. C. 1. Schematic Diagram of a Cellulose Molecule.

-------
    Table II. C. 1.  Products of Thermal Decomposition of Cellulose





                         Cotton      Pine Pulp    Spruce Pulp     Birch Pulp



carbon                    38.8         36.9          34.9            33.4



carbon dioxide            10.4         12.8          11.9            11.1



ethene                     0.2          0.2           0.2             0.4



carbon monoxide            4.2          3.4           3.9             3.5



methane                    0.3          0.3           0.2             0.5



methanol                   0.0          0.0           0.1             0.0



acetone                    0.1          0.1           0.1             0.2



acetic acid                1.4          2.2           2.8             3.9



other organic comp.        5.1          4.2           8.5             7.7



tar                        4.2          4.8           6.3             9.6



water                     34.5         34.2          30.0            29.4
                                  40

-------
         Table II. C. 2.  Cellulose Derivatives and Their Uses
        Compound



ethyl cellulose







methyl cellulose
sodium carboxymethyl cellulose



benzyl cellulose



ethyl hydroxyethyl cellulose








cellulose nitrate



sodium cellulose sulphate
cellulose acetate
cellulose xanthate
        Uses



plastics, lacquers, sheeting,



varnishes, adhesives.



adhesives, latexes, emulsions,



foods, sheeting, cosmetics,



Pharmaceuticals.



colloid, thickener.



coatings, plastics, lacquers.



emulsifier, thickener,



stabilizer.



lacquer, plastic,  explosives.



gelatin films,  glues, paints,



textiles, sizing,  paper,



coating.



yarn, photographic films,



sheeting, plastics, coatings



membrane.



fiber, cellophane, plastics,



sponges.
                                  41

-------
Table II. C. 3.  Solubility of Some Plastics in Selected Solvents.





























Methanol
Ethanol
i-Propanol
n-Propanol
sec-Butanol

n-Butanol

Methyl -isocutyl carbinol
Ethylene glycol
Monoethyl Ether
Ethylene glycol
Monobutyl ether
Acetone
Ethylene glycol monoethyl
Ether Acetate
Methyl Ethyl Ketone
Ethyl Acetate
iso-Propyl Acetate
sec-Butyl Acetate
n-Propyl Acetate
Methyl-i-Butyl Ketone
n- Butyl Acetate
n-Amyl Acetate
Ethyl Ether
Methyl Amyl Acetate
Hexyl Acetate
Isophorone
Benzene
n-Hcptane
Toluene
Xylene
Chlorinated Hydrocarbons
zct>T3>*o>nnm -nponoT3ms<<-l->-ceH-O
PXP rtOH-AH-H- HOrt t - o
3 X M 3*n33A32O*-X OS > D O G D A
A 0* XPPAP-P03C^ 2CO3'V'UIA>-
O (--Hit rt p. A O* A A-tAH-AAil-'
3 AO*A<>(DI-"IH-3 rtXrtO >- C
p 3OP.H-nO'>-hi->Ci
rt A3 3 H H-3 PprtH-noi-O
A T3X XPOAP.13 OIAO-AAOI/I
O !- h- C O- A 3* H A rf rt Ul A
t-pCTSA X PPA
X > rt 0* > A 3 t- >rtrt
AOAA>-- O P OAA
r  u> H  !- rt Ai
3* rt X H- A rt 03
A P ft. O PC
H rt rt rt
A AX
H
n P
O rt
a A
o
s
A


JO PO
A A
I/I VI
H- !-
W Ul
rt rt
P P
3 3
rt rt
rt rt .
0 0
a a
o o
w ui
rt rt

rt

<0
0
tX>

O
H'
O
p
o
H-
P.




X
X
X
X




A
rt
H
CD
5-
**<
P.
o
p
tJ
rf
P



x tr
o
X <
X
00
x o
o
x n
x
x
x



X
X
X
X
X X



50 jo
A A
I/I U)
(J. H.
VI Ul
rt rt
P P
y 
rt rt
rt rt
0 0
3 9
VI Ul
rt rt


















X












X X


X

X
X X
X X
X X
X X
X
X
X

X
X X
XXX
X X

X X
X X












X

\J V
^\ r*
X X

XXX
X X
XXX
XXX
XXX
XXX
XXX
XXX
X
XXX
XXX
XXX
X X

X X
X X
X
X
X
X
X

X

X
X

X

X
X X

X X
X
X
X
X
X
X
X



XXX
X


X
X
X












XXX
X X

XXX
XXX
X
X X
X X
X X
X X
X X
X X

X X
XXX
X


X


X X
X

X
X

X

X
X X

X X

XXX
X X

X X
X X
X X
X X
X X
X X
X X
X X
X X
X
X
XXX
X

X
X

                                42

-------
Table II. C. 4.  Effect of Acids and Bases on Certain  Plastics.
Plastics
Polypropylene
Polystyrene
Polycarbonate

Pherroxy
Vinyl Butyral
Polyvinyl dichloride
Urethane Elastomers
Acetal
Acrylic
Ethyl Cellulose
Cellulose Acetate
Chlorinated Polyether
Fluorocarbons
Nylons
Polyethylene
Diallyl Phthalate
Furan
Melamine FormaJdehyde
Phenol -Formaldehyde
Polyacrylic ester
Polyesters
Silicons
Urea-formaldehyde
Epoxy Cast Resins
Aliyl Res in
Phenol :s
weak
acids
resistant
none
none

none
slight
none
dissolves
resistant
slight
slight
slight
none
none
resistant
resistant
none
none
none
slight
swells
slight
none
slight
none
none
none
strong
acids


attacked

resistant
slight
none
dissolves
attacked

decomposes
decomposes

none
attacked

slight

decomposes

swells
attacked
slight
decomposed
attacked

slight
Effect of
oxidizing
acids
attacked
attacked







attacked


attacked


attacked

attacked

decomposed





attacked
decomposed
weak
alkalies
none
none
limited
resistance
resistant
slight
none
dissolves
resistant
slight
none
slight
none
none
none
resistant
none
none
none
slight
swells
attacked
none
slight
none
none
slight
strong
alkalies
resistant
none
attacked

resistant
slight
none
dissolves
resistant
slight
slight
decomposes
none
none
none
resistant
slight
slight
attacked
decomposes
swells
attacked
slight
decomposed
slight
none
decomposes

-------
                          CHEMICAL PROCESSES
     As indicated earlier, cellulose is the single component that appears
in the greatest amounts in most solid wastes.  The reactions reported
herein are primarily reactions involving cellulose because reclaiming and  
veuse of this cellulose would remove about half of the solid waste disposed
c' annually.

     Of the many reactions possible with cellulose the primary groupings
studied are crosslinking, nitrogen and phosphorus enrichment, esterification,
hydrogenation, etherification, oxidation, and pulping.

     The process which shows the greatest potential and will be persued to
finish first is crosslinking.  Crosslinking can help solve two problems at
once:  The disposal-reutilization of solid waste, and shortage of satisfactory
building materials.

     Hydrogenation is probably not economically feasible at present,
however, with the rapidly dwindling petroleum supplies this may soon
become not only economical, but essential.

     Nitrogen and phosphorus enrichment would allow the waste to be returned
to the soil as a combination soil conditioner and fertilizer.  Composting
alone, does not give a product that has appeal to the market because of
the lack of plant growth stimulants.

     Esterification and etherification lead primarily to plastics.  Cellulose
plastics are at present being replaced by the petro-chemical plastics, and
therefore are a waning market.  One new field that may require more
cellulose is reverse osmosis, used in purifying water.

     The products of partial oxidation may have great potential, but the
time required to produce dialdehyde cellulose is so great that the economics
of this process appear unsatisfactory.

     Pulping may be developing again.  Our dwindling forests, new pulping
methods, and new straw storage methods may overcome the economic barriers
that have blocked the use of straw for pulping.  Reclaiming paper and adding
straw pulp could greatly reduce the demands on our forests and alleviate
air pollution at the same time.

Crosslinking

     Since cellulose is a polymer containing chemically active hydroxyl groups,
crosslinking between chains should be one means of producing a solid material.
The crosslinking agents would have to be polyfunctional compounds capable of
uniting with the cellulose hydroxyls of more than one cellulose chain.  The
fabric industry has evaluated the use of polycarboxylic acids, such as succinic
acid, oxalic acid, and citric acid, to crosslink cotton cloth for improvement
                                  44

-------
of its properties (4).  Crosslinking may also be possible with  an  alkyl  dihalide,
resulting in ether linkages, but no known experimentation has been attempted.
A third possibility for crosslinking involves use of  isocyanates,  which  react
with hydroxyls to produce carbamate esters.  This reaction  is the  basis  for
rigid and soft polyurethane foam using  liquid polyls.  The reaction  of
cellulose with isocyanates has been studied by Schnecbeli  (14),  Ellzey  (6),
and Hobart (11).

     A variety of cellulosic wastes can be used to make a solid board using  isocya-
nate resins including wood, straw, and  paper, and although  each of these wastes
has been used in the  laboratory to prepare small samples, extensive testing  has
been accomplished only with straw particleboards.  Therefore this  report will
primarily show results achieved with straw.

     Chemistry:  An isocyanate compound contains the  functional group
-N=C=0 (-NCO), while  diisocyanates contain two functional groups per  molecule
and polyisocyanates contain many functional groups on a long chain resin.
In order to achieve crosslinking between two cellulose molecules,  at  least
two functional groups per molecule are  required.

     Isocyanates react with compounds which contain  an active hydrogen  such  as
alcohols, phenols, amines, amides, ureas, acids, and  water. These reactions
ordinarily take place without catalysts or high temperatures (3),  but
catalysts may be required when steric hindrance is a  factor.

     A brief review of isocyanate chemistry is presented here.   More  detailed
information about the synthesis and use of isocyanates is reported by
Saunders and Slocombe (13).

     Aromatic isocyanates are usually more reactive  than aliphatic isocyanates
(3), and electronegative groups on the  aromatic ring  enhances reactivity,
while electropositive groups reduce the reactivity.

Reactions        Water will react with  isocyanates  (I) as  shown in Reaction
                 T:fk=alkyl or aryl group)

                       RNHCOOH  RNH2 + COj                       [1]

                           II     III

                 RNCO * RNH-CO-HNR                                [2]

                  I          IV

     The carbamic acid  (II) that is formed decomposes readily  to produce an
amine (III) and carbon dioxide.  If a base is present, this reaction  will
proceed no further; however, in the absence of  a base, the  amine (III)  will
react with the isocyanate  (I) to form a substituted  urea  (IV)  as shown  in
reaction 2.
                                  45

-------
     The rate of reaction of isocyanates with water depends on  the  particular
isocyanate involved, for example octadecyl isocyanate  can be  emulsified
and will be stable for as much as a day while others react much more  readily.

     Alcohols will react with isocyanates  (I) as shown in reaction  3:

          R-NCO + R'OH * R NHC 0 OR1                              [3]

            I      V         VI

     The carbamate ester (VI) which is formed is sometimes called
a urethane.  The reaction of primary alcohols is fairly rapid but
tertiary butyl alcohols react slowly, probably due to  steric  hindrance,
and must be catalyzed.  Phenolic compounds react as aromatic  alcohols, but
their reaction rates with isocyanates are  extremely slow and  must be
catalyzed.

     Halogen, acids (VII) react with isocyanates as shown in reaction  4:
(x is a halogen)

          RNCO + HX * RNH-COX                                     [4]

           I     VII    VIII

This reversible reaction produces a monosubstituted carbamyl  halide (VIII),
which is stable at room temperature but not at. elevated temperatures.
The reaction between isocyanates (I) and organic acids (IX) is  shown  in
reaction 5:

          RNCO + R'COOH -* RNHCOOCOR1                              [5]

           I       IX          X

The anhydride (X) which is formed decomposes to form an amide (XI)  and
carbon dioxide as shown in reaction 6:

          RNHCOOCOR' + RNHCOR' + C02                              [6]

               X         XI

     Cellulose should react with isocyanates because of the three hydroxyl
groups on each anhydroglucose unit, however Bayer  (2)  speculated  that
cellulose would not react with isocyanates because of  the  "water  of
crystallization" left in carefully dried cellulose.  He theorized that  only
substituted ureas would be present in the  reaction mixture.

     More recently, however, Hearon, et. al.  (8,9), studied the reaction
of aliphatic and aromatic isocyanates with dried cellulose  and  cellulose
acetate, and found that the acetate groups could be removed by  hydros/sis,
and the resulting cellulose carbamate was  soluble  in organic  solvents.
                                  46

-------
     In addition, the isocyanate-cellulose reaction has been  studied  by
Hearon and Lobsitz (10), Schneebeli  (14), Eckert  (5),  Ellzey  (7),  Hobart
(11), and Volozhin (15).  llearon and  Lobsitz  studied  the  aryl carbamates
of cellulose including chlorophenyl carbamate and reported that  the completely
carbamylated product is soluble in a  variety  of organic solvents,  but not
in methanol or ethanol.  Schneebeli studied the reaction  of phenyl
isocyanate, in anhydrous pyridine, with cellulose which had been dried at
105C.  Using x-ray study, nitrogen determination, and water  sorption, he
determined that the carbamate esters  are  actually formed  and  concluded
that the isocyanate reacts first with the available hydroxyl  units, then
penetrates into the.crystalline structure of  cellulose to react  with  other
hydroxyl units.

Reactions with     Isocyanates react  with hydrogen atoms  attached  to
Hydrogen attached  nitrogen in such compounds as  amines,  amides, ureas, and
To Nitrogen        carbamates, but the reaction rates are affected by
nuclear substituents and steric hindrance.

     Amines (XII) will react with isocyanates as  shown in reaction 7:

          R NCO + R'NH2 -* R NHCONItR1                              [7]

           I       XII      XIII

The product is a substituted urea  (XIII).

     Aliphatic amines are generally more  reactive than aromatic  amines
which are more reactive than pyrrole, but these reaction  rates are especially
affected by steric hindrance caused by ortho-substitution of  the phenyl
ring.  The reaction of isocyanates which  contain  N-H  bonds is governed
primarily by how basic or nucleophilic the N-ll bond is;  isocyanate reactivity
decreases approximately in the order  (1)

            4(-N02) > 3(-N02) > 3(-OCH3)  > H  > 4(-CH3) >  4(-OCH3)

whc-ds amine activity tends to increase  in the same  order.

     Amides (XV) will react with isocyanates  as shown in  reaction  8:

                   0          99
          RNCO + R-C-N1L -* R'-C-N-fc-NR                            [8]
                       ^        H    II

           I       XV          XVI

The reaction product is a substituted biuret  (XVI).

     Urea  (XVII) being a diamide will react with  isocyanates  as  shown in
reaction 9:
                                   47

-------
          RNCO + H2NCONH2 > RNHCO NHCONH2                         [9]

           I       XVII         XVIII

Again, the reaction product is a substituted  biuret  (XVIII).

     Carbamates  (XIX) will react with  isocyanates  as  shown in reaction 10:
          RNCO + R'NHCOOR" > RNHCO-N-COOR"
                                   R'
                                                  [10]
            I
      XIX
       XX
     The reaction product  is an  allophanate  (XX)  which decomposes at elevated
temperatures to produce two isocyanates  (XXI,  XXII)  and an alcohol (XXIII)
as shown in reaction 11:
          RNHCO-N-COOR"
t'
 XX
RNCO + R'NCO + R"0'l
[11]
                             XXI
        XXII   XXIII
This reaction is reversible, however,  and  upon cooling the allophanate may
again be formed.

Kinetics and          The electronic  structure of isocyanates is approximated
Mechanisms of         in reaction  12,  with the possible resonant structures
Isocyanate Reaction   shown  as:

          R._N=C=0:  *-*  R-N-C=0:  -*  R-N=C-0:                   [12]
Isocyanate reactivity  is affected  by the  composition of the aryl or alkyl
group, R.

     The hydroxyl groups of  alcohol  may catalyze the reaction between alcohols
and isocyanates according  to Arnold  et. al.  (1), reaction 13.  (Ar=aryl)
          Ar-NCO + ROH
              Ar-NCO
                                 ROH
 k3
ROH
                Ar-NHCOOR + ROH
[13]
     It is clearly  seen  that  alcohol  with  its  slightly basic oxygen can act
as its own basic  catalyst,  while  phenols,  being more acidic or less basic,
do not catalyze themselves  as well,  and therefore, need the aid of a
basic catalyst in order  to  have reasonably fast reaction times.  In addition,
phenols have the  resonance  form shown in reaction 14, which tends to lessen
their basicity even more.   The result is a reaction rate about equal to
the very sterica'ly hindered  t-butyl  alcohol.
                                  48

-------
                     -OH <-*  !<(}>= 0-H                           [14]
     The hydrogen attached to the nitrogen of amines will react with
isocyanates to form a substituted" urea.   In fact, methyl isocyanate reacts
nearly 200 times faster with an amine group than it does with hydroxyl
groups.  In a mixture of alcohol and water, the rmine  formed would tend to
catalyze the reaction of the isocyanatg: with both the  hydroxyl groups of water
and of the alcohol, but the amine would also react with the isocyanate to
form a substituted urea.

     Process:  A schematic diagram of the process is shown in Figure III. B.  1
Baled straw is milled to reduce the particle size, and is dried to reduce
the water content.  The fines are removed by screening and the isocyanate
resin is applied by air spraying.  The mixture is pressed into a  solid
board with a heated-platen hydraulic press.  The boards are then  finished
and stored.  If the straw contains 15% moisture, and 5% resin is  applied,
120 pounds of baled straw will be needed to produce 100 pounds of finished
board with 5 pounds of trim.  Theoretically the trim could be passed
through the process again but no allowances were made  in the diagram for
this operation.

     A discussion of some of the variables involved in each step  of the
process is given below.

Straw     Theroetically, any straw could be used in this process  to form
Type      a straw purticleboard, but differences in composition and
structure may affect both the physical properties and  appearance  of the
board.  The only differences in physical properties that have been
measured thus far show that the physical properties of cascade fescue
and hard fescue are significantly lower than the physical properties of
annual ryegrass when the three straws are processed in the same way
(Figure III. B. 2.).  Differences in appearance are also noticeable
between such straws as annual ryegrass, cascade fescue, hard fescue,
and highlight fescue.  Both the size (width) of the straw stalk and the
color of the particles contribute to these differences.

     Differences in wax content might also contribute  to differences
in physical properties, since it has hp*n shown that the removal  of
wax from the surface of the straw particle improves the strength  of
straw particleboard (see Figure III. B. 2.).

Particle       The straw particle size can be reduced  by passing  the straw
Size           through a mill; the average particle size being determined
by the size of the holes in the screen.

     Straw particleboard strength is directly affected by particle size
because small particles, having more surface area, tend to pack more tightly
and collect more resin, while the tensile strength of  longer particles
is also a factor.
                                  49

-------
     Differences in the handling characteristics of straw particles have
also been noticed; short particles flow more easily than longer particles,
but produce a board of lower strength.

Moisture       Moisture content is an important variable for two reasons;
Content        the reaction of water with the isocyanate resin, and the
vaporization of the water during the pressing cycle.

     Although no direct measurements have been made, there is no
apparent detrimental effect on the board physical properties by the
presence of a small amount of water in the straw, that is, strong boards can
be produced whether the water is removed prior to application of the
resin or during the pressing operation itself, however, the temperature
profile of the board in the press will be different i: the two cases.
In addition, it is presumed that any water in the straw would react with
the resin over a period of time if the resin-straw mixture were being
stored prior to utilization.

     Any gas that is produced in the board during the pressing operation
must be allowed to escape prior to releasing the pressure or delamination
(blows) will occur.

Resin          Three variables involving the r^sin may affect the board
physical properties; resin type, resin concentration, and resin application
method.

     A variety of isocyanate resins are available industrially including
4,4'-diphenyl methane diisocyanate, polymethylene polyphenylisocyanate,
tolylene 2,4-diisocyanate, hexamethylene diisocyanate, and m-xylylene
diisocyanate.  The reaction rates of these compounds with cellulose and
with water are unknown, however, straw particlebcards have been made
in the laboratory with tolylene 2,4-diisocyanate  (with dibutyltin diacetate
catalyst), 4,4'-diphenylmethane diisocyanate, and polymethylene poly-
phenylisocyanate .

     Resin concentration should have a direct effect on the board physical
properties, unless the breaking strength is determined by other factors
such as the internal cohesion of the straw particle.  Although the effect
of changes in resin concentration on board physical properties has not
been completely evaluated, preliminary tests have shown that the board
strength increases as the resin concentration increases.

     The technique of resin application will affect the distribution of
the resin on the straw particles.  Lehmann  (12) hai shown that the
distribution of resin is the most important factor in the strength and
stability of wood particle boards.  He has also shown that fine atomization
of the resin and a suitable period of application were  ti
-------
solvent can also be used to reduce the resin viscosity and improve the
atomization, but boards produced in this manner do not have the strength
of those made with the undiluted resin.

     A uniform application of resin could also be attained by soaking
the straw in a solvent solution of the resin.

Pressing       The straw-resin mixture forms a solid board when it is
subjected to heat and pressure for an adequate length of time.  Variables
in the pressing operation include pressing time, pressing temperature,
pressure, and speed of closing.  Although the speed of closing can be
adjusted to change the ratio of the modulus of rupture to the internal
bond in a wood particleboard process, no evaluation of this variable
has been made in this study.

     Pressing time is measured from the time the press reaches maximum
pressure, or from the time the press is closed if stops are used.
The time must be long enough for the center of the board to heat up and
complete the reaction, but should not be too long because degradation
may occur.  Preliminary studies have shown that board strength increases
with an increase in pressing time up to a point, and then decreases.
The optimum pressing time is determined by the pressing temperature.

     The effect of pressing temperature on t.h? physical properties of
the straw particleboard has not been determined, but will affect the
temperature profile within the board and the degradation rate of board
components.  The temperature must be high enough to allow the reaction
to be completed, but should not be too high because the straw will
undergo thermal decomposition.  Preliminary tests have shown that the
range of allowable temperatures is 250-400F, with 325-3SOF being most
desirable.

     The pressure exerted on the straw particles will determine the thickness
and density of the resulting board unless stops are used.  An increase
in pressure results in a decrease in thickness and an increase in
density.  When stops are used the pressure is no longer a variable, as
long as the press can be closed, and the density will be determined by
the amount of straw being used, and the thickness will be determined by
the stops.  However, a higher density board will require a higher
pressure for closure, and the effects of higher pressure on physical
properties can be measured in terms of the effects of higher density.
In general, the strength of a straw particlebourd increases as the
density increases regardless of whether the thickness or the weight of
the board is held constant.

Finishing      The finishing operations that are required will depend on
the techniques being used in the pressing operation.  If the boards
are pressed in a mold, the edges will be firm and no trimming will be
required; however, if the boards are pressed with unrestrained edges,
they will be soft and will need to be trimmed.  In addition, it may
be desirable to provide the board with a paint, lacquer, or vinyl finish.
                                  51

-------
     Experimental Results;  Three sizes of straw particleboard samples have
been prepared for evaluation, a laboratory test sample measuring 4  1/2 inches
by 4 1/2 inches, a standard test sample measuring 12 inches by 12 inches, and
a commerical test sample measuring about 4 feet by 8 feet.  All of  these
samples were prepared from baled straw that had been stored in an open
shed for at least six months.  The results of these tests are listed below.

Laboratory     These samples were prepared using a manually operated,
Test Samples   heated-platen (5 inch by 8 inch), hydraulic press and a
2-piece mold designed to produce a 4 1/2" x 4 1/2" x 3/8" board.  Although
these samples were too small to allow the use of ASTM standard testing
procedures for the determination of physical properties, non-standard
tests were used to show differences rather than absolute values.

     The Modulus of_ Rupture  (MOR) is influenced by the board density
as shown in Figure III. B. 3.  These samples were prepared at 350C
using 3% isocyanate resin.  This straw was milled on a hammermill with
1/4" screen and was dried prior to the resin application.  The optimum
pressing time for these conditions is five minutes.  The MOR increases
with increasing density.

     Figure III. B. 4. shows the effect of pressing time on MOR for samples
prepared at 340C using 3% isocyanate resin.  This straw was milled on
an Abbe mill with 3/16" screen and was dried prior to the application
of the resin.  The optimum pressing time for these conditions is two
minutes or less, and again the MOR was higher for the boards produced with
higher density.

     Figure III. B. 5. shows the effect of resin concentration on MOR
for samples prepared at 300F.  This straw was milled on a hammermill with
a 1/4 inch screen and was not dried prior to application of the resin.   In
addition, a small amount of  acetone was used in the resin to lower  its
viscosity and the straw-resin mixture was stored in a plastic sack
for about 24 hours prior to pressing.  The optimum pressing time for
these conditions is four minutes, except for a resin concentration  of
1.25%, then it is five minutes or longer.  At two minutes pressing  time
the optimum resin concentration is 2.0%, while for pressing times of
three, four, and five minutes the optimum resin concentration is 1.5%.

     The thermal conductivity of straw particleboard was determined and
compared to samples of wood  particleboard, asbestos, and air.

     Since heat transfer through a_jnaterialgby conduction is governed
by the Fourier equation, -r-  = kA -r where -jr- is the rate of heat flow,
A is the area of contact perpendicular to neat flow, ^- is the temperature
gradient through the material and k is the thermal conductivity constant
for the material, the thermal conductivity constant for a test material
(k) can be determined byapplying heat to one side of a  stack which  includes
materials with known k's, and measuring the temperature gradient through
the stack:
                                  52

-------
          d
          dt s Vt  &


                    kt

     Experimentally, a stack containing plates of aluminum, straw
particleboard, and copper was placed in a heated platen hydraulic press.
The lower platen was heated to 230F and the top platen was held at room
temperature.  Pressure was applied to the stack to insure good contact
between the layers in the stack.  After 20 minutes the temperature profile
through the stack was measured with iron-constatan thermocouples.  In
addition to straw particleboard, samples of particleboards made from
Sander dust and municipal refuse were evaluated and also samples of commercial
wood particleboard, asbestos, balsa wood, air, and loose straw.  The
results of these tests are listed in Table III. B. 1.

     The relationship between density and thermal conductivity constant
is shown in Figure III. B. 6.  Although no clear relationship is evident,
the thermal conductivity appears to increase slightly with increase in
density.  A more significant factor appears to oe the classification of
the straw.  At approximately the same density, the thermal conductivity
increases as the particle size increases, with the exception of the fines.
However, the boards with the lowest conductivities were prepared from
heterogeneous straw with the fines removed.

     Although straw particleboard seems to be a better thermal insulator
than most of the other materials measured, a comparison with insulating
materials has not been computed.

     The water absorption properties of several samples of straw particle-
board were measured to determine if changes in processing variables
affected the  p.ter absorption properties.  Since this test was not
conducted according to the ASTM standard, only the differences in
weight and length measurements were observed.  The boards used in this
test were 4 1/2 inches square and about 3/8 inch thick.  Weight and length
measurements were made prior to and after soaking under 1 inch of water
for 24 hours.

     The water absorption properties of straw particleboards appear to be
affected by the type of resin used, the resin concentration, the moisture
content of the straw prior to pressing, and the density of the board, but
not by variations in resin application procedures.

Standard       These samples were prepared using an automatic hydraulic
Test Samples   press with steam heated platens  (24 inch by 24 inch).  The
straw mat was hand formed between two stainless steel caul plates,  12
inches by 12 inches, and placed on the lower platen.  The press closing
time was about 30 seconds.  The first series of samples were prepared by
                                  53

-------
applying constant pressure; variations in pressure resulted in variations
in the density and thickness of the boards produced.  The second series
of samples were prepared using stops to achieve a thickness of 3/8 inch.
Variations in density were produced by variations in the quantity of
straw used in the mat.  The boards were trimmed to 11 1/2 inches by 11
1/2 inches, providing an adequate sample for physical testing using ASTM
procedure D-1037-64.  The physical properties of these test samples are
listed in Table III. B. 2.

     The density of the boards is determined primarily by the level of
pressure applied, when stops are not used.  The relationship between
pressure and density is shown in Figure III. B. 7.  When a constant pressure
of over 1000 p.s.i. was applied for over one minute, "blows" appeared in
the board.  Although an alternative technique of allowing the straw mat
to heat up for two minutes at 200 p.s.i. prior to application of the
higher pressure prevented the "blow" formation, this technique also
affected the physical properties of the boards including the density.

     Board density is also affected by the pressing time.  The effect of
pressing tine on board density is also shown in Figure III. B. 7.
Time apparently has a greater effect on board density at high pressure
(1000 p.s.i.) than at low pressures (200 p.s.i.).

     The Modulus of_ Rupture is affected by the removal of wax from the
straw.  Figure III. B. 2. shows the effect of wax removal on MOR for
three kinds of straw.  The removal of wax from the straw results in a
significant increase in MOR, but loss in water swell properties.

     The Modulus of Elasticity (MOE) is influenced by board density as
shown in Figure III. B. 8.These samples were prepared with 5% isocyanate resin.
An increase in density results in an increase in MOE.  Variations in
Figure III. B. 8. may be caused by variations in average particle length.

     The MOE is also affected by the removal of wax from the straw.
Figure III. B. 2. shows the effect of wax removal on MOE for three kinds
of straw.  The removal of wax from the straw results in a significant
increase in MOE, but this effect is not as great as the effect on MOR.

     The internal bond values listed in Table III. B. 2. are not
indicative of the actual strength of the boards since the separation during
testing occured at the metal surface and not within the board; therefore,
it is not possible to show the effects of changes in board density or
thickness on the I.E.

     Figure III. B. 2. shows the effect of wax removal on the I.E.
for three kinds of straw.  The removal of the wax results in a significant
increase in the I.E.
                                   54

-------
     The water absorption properties of several different materials,
pressed under varying conditions are shovm in Table  III.  i. 3.  Reproducibility
of results, holding all parameters constant, is indicated by samples 2
and 9.  Variation of resin type produced the results shown in samples 1,
11, and 15.

     As one can see from samples 5, 6, and 7, or 9 and  11, resin concentration
has small influence on water absorption properties.  Density also has only
a. small influence as shown in samples 1 and 8.

     Samples 18 and 19 were cut from a single sheet  of  commercial wood
particleboard for use as a comparison with laboratory products.  Eight
percent PAPI on straw gives about the same water absorption properties
as the 6-8% resin used in the wood counterpart as can be  seen by comparing
samples 18 and 19 with samples 2 and 9.

     The samples made from paper were inferior, possibly  because of the
lack of wax "sizing".  Sizing is added to wood particleboard, but because
of the natural wax in straw there is no need to add  sizing to straw
particleboard.

     In general one can summarize by noting that increased density and
increased resin concentration reduce the swell caused by  water  absorption
in straw particleboard.  The polyisocyanate resin, Mondur MRS,  appears to
give slightly better moisture stability characteristics than the other
resins tested.  Paper might be used as a fiber source if  wax is added
to decrease the water absorption.

Commercial     Two commercial samples were prepared  in  a  5 foot by 9 foot
Test Samples   multi-opening press to evaluate the engineering  factors
involved in industrial production of full sized sheets  (4 foot  by 8 foot).
The straw was milled in a hammermill with screen openings larger than
1/2 inch diameter, and was dried in a tray drier at  65C  for 24 hours.   The
isocyanate resin was applied at 5% to 1600 gram batches of straw, and
the mixture was stored in plastic bags for 24 hours  prior to pressing.
Approximately 35 pounds of treated straw were used in each board.

     The straw mat was hand formed on an aluminum caul  plate and the plate
was lifted onto a conveyor belt for feeding into the press.  Paper was
used on the top and bottom of the mat to prevent sticking to the platens.
The platens were heated to about 325F and the pressing time was about
5 minutes.  A constant pressure of over 1000 p.s.i.  was applied.

     When the pressure was released, the boards delaminated severely,
although the two layers appeared to have good cohesion.  Wide variations
in thickness were observed; this resulted from the hand forming operation.
The straw does not flow readily and is difficult to  form  into a uniform
mat.  The paper that was used stuck to the straw particleboard  on both
sides hut most of it could by removed by soaking it  with  water  and scraping
                                   55

-------
it with a spatula.  The soft edges were trimmed and the resulting board
showed no major defects except for the delamination.  No physical properties
were measured.

     In order to produce full sized sheets for physical testing, a
mechanical mat forming device should be used, and if resin sticking is a
factor, release paper should be employed.  In addition, the pressing
conditions should be adjusted to prevent delamination.
                                   56

-------
                              References
 1.   Arnold,  R.  G.,  J. A. Nelson and J. J. Verbank, "Recent Advances in
          Isocyanate Chemistry", Chemical Reviews, 57, 47-76 (1957).

 2.   Bayer,  0.,  "Das Di-isocyanate-Polyadditionsuerfahren (Polyurethane)",
          Angewandte Cheinie, A59_, 257-288 (1947).

 3.   Chadwick, D.  H., and E. E. Hardy, Kirk-Othmer Encyclopedia of Chemical
          Technology, Vol. 12, pp. 45-64, John Wiley and Sons,  Inc., 1967.

 4.   "Citric Acid  Crosslinks Cellulose", Chemical and Engineering News,
          40(49),  42 (1962).

 5.   Eckert,  P., and P. Herr, "Formation of Bridged Compounds in Cellulose
          Fibers with Diisocyanates", Kuntseide und Zellwolle,  25, 204-210
          (1947).

 6.   Ellzey,  S.  E.,  and C. H. Meek, "Reaction of Aryl Isocyanates with Cotton
          Cellulose.  I.  Variables in Reaction Using Phenyl Isocyanate",
          Textile  Research Journal, 32_, 1023-1029  (1962)

 7.   Ellzey,  S.  E. Jr., C. P. Wade, and C. H. Mack, "Reactions  of Aryl
          Isocyanates with Cotton Cellulose.  II.",  Textile Research
          Journal. 32_, 1029-1033  (1962).

 8.   Hearon,  W.  M.,  G. D. Hiatt, and C. R- Fordyce, "Carbamates of Cellulose
          and Triacetate; Preparation", Journal of The Aoerican Chemical
          Society, 65_, 829-833 (1943).

 9.   Hearon,  W.  M.,  G. D. Hiatt, and C. R. Fordyce, "Carbamates of Cellulose
          Acetate.  II.  Stability Towards Hydrolysis",  Journal of The
          American Chemical Society, 6S_, 833-836 (1943).

10.   Hearon,  W.  M. and J. L. Lobsitz, "Aryl Carbamates and Cellulose
          Acetates", Journal of The American Chemical Society,  70,
          296-297  (1948).

11.   Hobart,  S.  R.,  H. H. McGregor, and C. H. Mack, "Reaction of Aryl
          Isocyanates with Cotton Cellulose.  IV.  Reactions Via Phenyl
          N-Aryl Carbamates", Textile Research Journal, 38, 824-830
          (1968).

12.   Lehmann, W. F., "Improved Particleboard Through Better Resin Efficiency",
          Forest Products Journal, 15, 155-161 (1965)

13.   Sauniers, J.  H., and R. J. Slocomb, "The Chemistry of Organic
          Isocyanate", Chemical Reviews, 43, 203-218  (1948)
                                  57

-------
14.  Schneebli, "Etude de 1'addition de 1'isocyanate de Phenyle sur les
          Fonztions Alcool de la Cellulose", Acadamie Des Science,
          Comptes Rendus, 254, 738-740 (1952).

15.  Volozhin, A. I., 0. P. Kozmina, and S. N. Danilov, "Synthesis and
          Properties of N-substituted Carbamic Esters of Cellulose",
          Zh. Prikl. Khim, 37(12), 2761-2763  (1964); Institute of Paper
          ChTmists, Abstract Bulletin, 36:183  (1965).
                                   58

-------
      en
      to
i

I
*
s
        Straw

        Ra 1 gs
                  Wire
Figure III. B. 1.  Schematic Diagram for Straw  Particleboard Formation.

-------
   7 -I
                                                                              140
                                                                              120
                                                                             100
                                                                             to
                                                                             JO
                                                                              60
                                                                             o

                                                                             o
                                                                             CO
                                                                              20  -
    Unextracted
Extracted
Unextracted     Extracted
Unextracted
Extracted
Figure III. B.  2.   Effect of Wax Removal on Straw Particleboard Physical Properties.

-------

     I
         7 '
         6 '
         5 -
         4 -
         3 
         2 -
         1 '
                                                   A A
                      4-
                      30          40           50
                              Density  (Lbs./Cu.Ft.)
60
Figure III. B. 3.  Increased Board Strength Brought About by  Increased
                   Density.  Point A Indicates Increase of  Strength
                   Because of Longer Fibers.
                                  61

-------
        5000
        4000
i-i
*j

I
o
O
        3000
        2000
         1000	


                2                  3                  4


                                       Time (Min.)



 Figure III.  B. 4.  Effect of Pressing Time on Modulus of Rupture.
                                   62

-------
 cr
 (A
 in
 3
 o
 o
 o
 o
 (H
 I
 o
 IA
 O
                                     Resin (%)
Figure III. B. 5.   Increased  Board Strength Caused by Increased  Resin
                    Concentration.
                                   63

-------
  Ib
  o
us
s
  C
  3
  H

  ri
  O
  U
<
6
4)
          90
          80
        70
          60
          50
                O
              20
                                   O
                       o
                              30
                                                          Heterogeneous
                                                          Mixture
                                                          Hetrogeneous
                                                          Mixture
                                                          Fines Removed
                                                  40
                                                                       SO
                                  Density  (Lbs./Cu.  Ft.)

Figure III. B. 6.  Relationship Between Density  and Thermal Conductivity.
                                   64

-------
u.
in
3
H
V)
64  '



62



60  '



58  



56



54



52


50  
o   48


    46  '


    44  -



    42


    40


    38  '


    36
                               5 Min.
               12       3456      789


                            Pressure (100 Lbs./Sq. In.)


  Figure  III.  B.  7.   The Relationship Between Pressure and Density.
                                                                 10
                                   65

-------
   600
   500  '
x  400

rl
U
H

in
(8
fH
UJ

<4H
O


3
I
    300
    200
    100
20       30
                                      40
50
                                                                    60
                                       Density

       Figure III.  B. 8.  Showing the Influence  of Density on the Modulus of
                          Elasticity.
                                         66

-------
    Table III. B. 1.  Thermal Conductivity oi- Straw Particleboard
                      and Other Substances
Sample             Thickness,            Density,                    k
	                 in.               Ib/cu.ft.            BTV/hr.(ft2)(F/ft.)

  Straw particleboard, heterogeneous mixture
  1                 0.247                  30.0                    0.76
  2                 0.255                  27.5                    0.84
  3                 0.231                  28.2                    0.76
  4                 0.238                  25.4                    0.95
  5                 0.232                  23.8                    0.79
  6                 0.243                  20.8                    0.73
  7                 0.25D                  30.8                    0.78
  8                 0.267                  31.7                    0.80

  Straw particleboard, classified
Fines
  9                 0.237                  30.4                    0.73
 10                 0.245                  45.0                    0.85
 11                 0.298                  49.6                    1.08
 12                 0.215                  34.6                    0.83
Medium length
 13                 0.233                  30.4                    0.59
Medium/coarse length
 14                 0.229                  30.9                    0.66
Coarse
 15                 0.228                  30.4                    0.71
  Heterogeneous, but with fines removed
 16                 0.244                  40.0                    0.61
 17                 0.224                  33.0                    0.52
  Loose straw
 18                 0.360                   3.7                    0.78
  Balsa wood
 19                 0.225                                          0.67
  Commercial wood particleboard
 20                 0.367                                          1.12
  Asbestos
 21                 0.250                                          1.20
  Sander dust
 22                 0.216                                          1.57
  Municipal refuse
 23                 0.294                                          1.72
  Air
 24                 0.360                                          1.01
                                   67

-------
                              Table III.  B. 2.  Physical Properties of Straw Particleboard
CO
      2
      3
      4
      S
      6
      fj
      i
      8
      9
Sasiple
  No.

  1 (w)
   '(*)
    (w)
    (w)
    (w)
    (w)
    (w)
    (w)
    (w)
 10 (w)
 11 (w)
 12 (w)
 13 (w)
 14 (w)
 15 (w)
 16 (w)
 17 (w)
 18 (w)
 19 (u)
 20 (w)
 21 (u)
 22 (w)
 23 (u)
Straw
Type
AR
AR
AR
AR
AR
AR
AR
AR
AR
AR
AR
AR
AR
AR
AR
AR
AR
AR
AR
HF
HF
CF
CF
Temp.,
F
V^*i^^H^^^^^M
344
343
344
345
347
346
344
344
345
349
344
340
358
346
350
354
354
325
525
325
325
325
325
Press . ,
psi
216
216
216
540
540
540
1080
200/1080
200/1080
200/2160
200/2160
216
216
216
216
216
216
stops
stops
stops
stops
stops
stops
Time,
min.
1
3
5
1
3
5
1
2/1
2/3
2/1
2/3
1
3
5
1
3
5
4
4
4
4
4
4
Ave. Density,
   Ib/ft *

    37.4
    37.6
    37.8
    48.1
    54.9
    55.8
    57.6
    55.0
    58.2
    61.3
    63.8
    37.2
    39
    40
    36
    37
                                                              .7
                                                              .7
                                                              .4
                                                              .4
                                                            41.0
                                                            44
                                                            44
                                                            44
                                                            43.8
                                                            44.7
                                                            36.4
                                                                         Ave. Thickness,
                                                                              in.
0.220          2190
0.212          2369
0.208          2276
0.173          4520
0.141          5680
0.148          6892
0.137          6740
0.148          4477
0.137          4655
0.132          5375
0.133          2696
0.149          2621
0.135          3642
0.136          2990
0.069          2603
0.070          3588
0.066          5818
0.333          4318
0.334          3873
0.335          2408
0.336          31S6
0.337          1662
0.331
MOE,
1000 psi
308
341
338
545
672
780
772
580
669
718
746
367
341
443
364
434
607
626 t
565
498
438
450
258
IB,'
psi
61
82
84
90
130
110
88
65
94
66
94
68
98
80



, 103
61
116
6S
80
32
f

(s)


(s)
(s)
(s)
(s)
(s)
(s)
(s)
(s)

(s)
(s)









    1   (w) means extracted,  (u) means  unextracted
    2   (AR) means annual ryegrass,  (HF)  means  hard fescue, (CF) means cascade fescue
    3   (s) means surface failure

-------
Table III. B. 3.   Changes in Weight and Linear Dimensions  of Boards Made  From
            Various Materials When Soaked in Water for 24  Hours.
Substance

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
13
19

Straw
Straw
Paper
Sanderdust
Sanderdust
Sanderdust
Straw
Straw
Straw
Paper
Straw
Straw


Straw
Straw
Straw
Wood particle
Wood particle
Treatment

Dried 110C/15 hr.
Field run (9% H2<3)
Ground  dried



Abbe treated
110/15 hr.
Field run (9% H20)
Ground  dried
Air dry after spray



Air dry 65C
HO0/ 15 hr.
Air dry 65 C
Commercial
Conunercial
Resin
Type
PAP I
PAP I
PAP I
PAP I
PAP I
FAPI
PAPI
PAP I
PAPI
PAPI
P-F
PAPI


MRS
MRS
MRS


Wt. %
5.5
8
8
3
4
5
5
5
8
8
5
10


5
5
5


Density
Dry (g/cc)
0.81
0.98
0.66
C.65
0.6S
0.71
0.82
0.66
1.01
0.66
0.99
0.94


0.62
0.60
0.69
0.63
0.64
                                                                Dimensional  Change
                                                               Length  %      Weight
                                                               0.866
                                                               0.347
                                                               0.435
                                                                2.
                                                                2.
                                                                2.
 .34
 .54
 .34
0.868
0.866
0.347
0.435
1.04
0.433
                                                               0.86
                                                               0.605
                                                               0.605
                                                               0.343
                                                               0.343
58
28
46
46
42
36
49
56
30
33
67
22
               37
               25
               38
               43
               34

-------
Nitrogen and Phosphorus Enrichment

     The use of solid wastes as soil conditioners and fertilizers is hindered by
their low concentration of plant nutrients, especially nitrogen, phosphorus,
and potassium.  Since the soil is an ideal location for the disposal of large
quantities of solid wastes, it seems reasonable to consider enriching
solid wastes with plant nutrients in order to make land disposal more
attractive.  For wastes containing large amounts of cellulose this can be
done chemically by preparing cellulose derivatives that contain nitrogen,
phosphorus, and potassium.  The water-holding capacity of these organic  
materials, their insolubility in water, and their slow rate of degradation
would be additional desirable characteristics.  Since nitrogen and
phosphorus are the two main plant nutrients required, this report will
be limited to consideration of these.  Potassium can be added to some
cellulose derivatives which have ion exchange properties.

     Chemistry:  Many cellulose derivatives can be produced which contain
nitrogen and/or phosphorus.  A more extensive discussion of the chemistry
involved in their formation entitled "Cellulose Compounds Containing
Nitrogen"  (2), can be found in a report prepared by J. F. Barbour; however,
the present report will be limited primarily to consideration of the
cellulose-urea and cellulose-phosphoric acid reactions.

Nitrogen       Cellulose derivatives containing nitrogen can be prepared
Enrichment     by reacting cellulose with urea, ammonia, or nitric acid.
In each case the concentration of nitrogen in the product will depend on
the extent of the reaction.

     Urea reacts with cellulose under the influence of heat.  Extensive
research on the cellulose-urea reaction has been conducted by the textile
industry for the purpose of improving the crease resistance of cotton
fabrics.  When a mixture of urea (I), cellulose and a catalyst are heated,
the product contains chemically fixed (water insoluble) nitrogen, presumably
in the form of cellulose carbamate  (II), as shown in reaction 1:

                             CuCl,
          Cell-OH + NH2CONH2   -* ^ Cell-OCONH2 + NHj              [1]

                       I              II

When this reaction is conducted in a closed chamber, the nitrogen content
of the product is very low, indicating that the reaction is inhibited.
Nuessle (8) concludes that the urea decomposes into cyanic acid  (HNCO)
and ammonia (NH_) and that the ammonia must be removed in order for the
reaction to proceed; however at low temperatures cyanic acid  (III) can
trimerize to form cyanuric acid (IV), as shown in reaction 2:
                                  70

-------
3 Cell - OH +     |
                                          H
                                      ,^-N,
                                 0 = C       "C = 0
                  3 HNCO - -       j         |
                                 H - N.       N - H
                                      ^C-^                    [2]
                                          0

                   III                    IV

which can react with cpllulo e to form the cyanic acid ester  (V)  as
shown in reaction 3:
                                                         0
                                            3 Cell - 0 - 5 - NH,  [3]
                         IV                            V
     Ammonia, under heat and pressure will react with cellulose to form
"amino cellulose" as shown in reaction 4:

          Cell-OH + NH3 -" Cell-NH2 + H20                          [4]

                             VI

     "Amino" cellulose has been studied in relation  to its  fertilizing
properties by Davis, et.al,  (4), who describes the conversion  of  ammoniated
peat to usable nitrates in the soil.  They indicate  that the amount of
nitrogen available  .s a function of the temperature  at which the  cellulose-
ammonia reaction takes place and that some of the nitrogeneous materials
formed are soluble in water and some are not.

     When cellulose is soaked in annydrous liquid ammonia,  the fibers
are swollen and remain swollen when the ammonia is removed  by heating at
105C.  X-ray diffraction studies  (3) have shown that the airaronia is not
bound to the cellulose at regular  intervals and presumably  amino  cellulose
is not formed.

     Anderson (1) reports that mineral acids, such as 8.25% sulfuric acid,
can be used to hydrolyze the hemi-cellulose before reaction with  ammonia.
When hydrolyzed cellulose was treated with ammonia at a temperature
slightly above room temperature, the product contained 7.4% nitrogen
which was 84% water soluble.  When the hydrolyzed cellulose was treated
with ammonia at 249C the product  contained 9.5% nitrogen which was 17.6%
water soluble.  When the reaction  temperature was raised to 300C, the
product contained 4.6% nitrogen, none of which is water soluble.
The product of the low temperature reaction was nearly as good as ammonium
                                  71

-------
sulfate when used as a fertilirer, but the other products had a  lesser
effect on plant growth.

     Nitric acid will react with cellulose to produce nitrate  (VII)  as
shown in reaction 5:

          Cell-OH + HNO,   -   Cell-ONO, + H.O                    [5]
                       O                   i

                         H,SO.
                          2  4      VII

Complete nitration of the cellulose molecule results in  cellulose
trinitrate.  Cellulose nitration can be achieved, with a  mixture  of nitric
and sulfuric acids, nitric and phosphoric acids, nitric  acid and acetic
anhydride, or nitric acid and methylene chloride.  When  sulfuric acid is
used, the process is very rapid with most of the reaction occurring  in
the first few minutes because the nitric acid readily penetrates into the
cellulose micelle.

     Cellulose nitrates can be modified to produce carboxy-cellulose
nitrates, cellulose nitrosyl sulfates, and cellulose nitroethyl  ethers.

     Cellulose nitrates are extremely flammable, and when confined,  are
considered explosives.  They are used in the manufacture of smokeless
powder and rocket propellants as well as in plastics, films, and lacquers.

Phosphorus     When cellulose is treated with phosphoric acid, the ester
Enrichment     cellulose phosphate  (VIII), is produced as shown  in
reaction 6:

          Cell-OH + H3P04   -   Cell OPO(OH)2 + H20               [6]

                                    VIII

     Nikitin (7) claims that two reaction products are possible  with
cellulose and phosphoric acid, one being an addition product, that is
easily hydrolyze-J by water and the other being the ester which is unaffected
by water, consequently, phosphorus fixation can be determined by measuring
the phosphorus concentration of the reaction product after washing with
water.

     Cellulose derivatives containing phosphorus can also be prepared by
reacting cellulose with ammonium phosphate, phosphorus tri- and  oxy-
chlorides, monophenyl phosphate, phosphorus pentoxide, and alkali-metal
salts of phosphoric acids.

     Gallagher  (5) reports that sodium phosphate acts as a crosslinking
agent forming dicellulose phosphate  (XIX) as shown in reaction 7:
                                 72

-------
          2 Cell-OH + NaH,PO.   -   Cell-OPO-Cell                 [7]
                         ^  4             ONa

                                           XIX

     The addition of phosphorus to cotton cloth has been studied  extensively
by the textile industry in order to achieve a flameproofing property.
An extensive summary of the chemistry and uses cf fire retardants is
given by Lyons (6) .

Nitrogen and   When cellulose is reacted with a mixture of urea and
Phosphorus     phosphoric acid, the product is cellulose ambonium phosphate
Enrichment     (XX) or cellulose amide phosphate (XXI), depending on the
reaction temperature, as shown in reaction 8:
                                        under
          Cell-OH + NH2CONH2 +
                                        over
     Since cellulose phosphate has ion exchange properties, other  cations
can be added to the compound, such as potassium, iron, or calcium.

     Process :  A schematic diagram of the process  is given in Figure  III.
C. 1.

     The solid waste containing cellulose is milled to reduce the  particle
size and then soaked in a water solution of the appropriate reagents.
If only nitrogen enrichment  is desired, the solution will contain  urea
and a catalyst, probably cupric chloride.  If both nitrogen and phosphorus
enrichment are dasired the solution will contain urea and phosphoric
acid.  After soaking, the excess  solution is removed by  filtration.   The
wet mixture is dried and then heated to the reaction temperature.
Following the reaction, the  product is washed with water to remove any
water soluble product or unused reactants.  The product  is then dried
and stored.  A discussion of some of the variables in the process  is
given below.

Solid          Any solid waste containing cellulose could theoretically
Waste          be used in the process to produce a nitrogen and/or
phosphorus enriched product  with  fertilizing properties; however,  the
nature of the impurities will affect the efficiency of the reaction,  for
example the fillers, sizing, wax, and ink that are added to paper  used
in magazines may reduce the  availability of cellulose hydroxyl units  for
reaction.
                                  73

-------
Milling Of     Solid wastes can be milled to reduce the particle size for
The Haste      easier handling and to increase the available surface area
for chemical reactions.  Milling can be accomplished by use of a number of
pieces of equipment such as hammermills, shredders, raspers, and hydro-
pulpers.

Soaking In_     The soaking step is designed to produce a uniform mixture
The Reagent    of the reactants, and although water is the common solvent,
Solution       other solvents might be used.  Although the time required
for complete mixing is not great, chemical reactions during this step may
affect the concentration of reagents in the cellulose after pressing.
Since the solvent mixture can be recycled, the amount of chemicals and
solvent added each time will equal the amount of chemicals and solvent
entrained in the cellulose.

     This process could be a batch or continuous operation.

     If uniform mixing of the reactants with the cellulose is not
required, such as would be the case if the reaction were vapor phase,
then soaking and filtering would not be required.

Filtering Tp_   The excess solution can be removed from the cellulose by
Remove Excess  filtering, filter pressing, or by centrifuging, depending
Reagents       on which method provides the best wet/dry ratio.  When this
ratio is" high, more heat will be required to remove the solvent.  The
reactant concentration in the solvent will have to be adjusted in order
to attain the appropriate concentration of nitrogen and phosphorus in the
cellulose.

Drying To      Tne purpose of'this step is to remove the excess solvent
Remove The     carried along in the cellulose.  Although this step could
Solvent        be included in the first part of the heating step, it may
be desirable to recycle the solvent or to collect a component of the
reaction gases.  Pre-drying will allow a better measure of the actual
reaction time, but reactions may also occur at the drying temperature.
Drying, if it is used, can be accomplished in a variety of ways, such
as tray, rotary drum, vacuum, and radiant heat drying.

Heating Tp_     This step provides the temperature for completion of
Promote The    reaction.  The reaction temperature and reaction time
Reaction       will probably both affect the speed and extent of the reaction
These factors will also have ar. effect on the degradation rate of the
organic components of the waste, which may influence the physical
and chemical properties of the product.

Washing Tp_          When a water-insoluble product is desirable, washing
Remove Unre icted    will be required, after the reaction is completed,
Materials           to remove unused reagents and water soluble reaction
products.  These compounds can be recovered for reuse by drying, or the
                                   74

-------
water solution could be reused in the soaking operation.  In actual
practice, it may be beneficial to leave some water soluble plant
nutrients in the final product to provide an immediate stimulus to the
plant growth.  The fixed nutrients would then become available as the
enriched cellulose slowly degraded.

     Experimental Results;  In the laboratory, samples of newspaper and
straw have been treated with ammonia, nitric acid, urea, and phosphoric
acid to give products with varying concentrations of nitrogen and.
phosphorus.  Several different techniques were used for mixing and
heating the reactants.  Nitrogen and phosphorus concentrations were
measured before and after water washing to detemdne the levels of
fixed nutrients in the product.  Selected samples of these products
were then tested in a greenhouse soil test to determine if they possessed
fertilizing properties comparable to commercial fertilizers.  The long
range or "slow release" fertilizing properties have not been evaluated
as yet.

Nitrogen       Urea, was reacted with cellulose in a series of experiments
Enrichment     to determine the affects of changes in reaction variables
on the degree of nitrogen fixation in the cellulose of newspaper.

     The effect of reaction time on nitrogen fixation is shown in
Figure III. C. 2.  Shredded paper was soaked in a 40% solution of urea
for two hours and the excess solution was removed by filtration to give
a wet/dry ratio of 4.5.  The wet paper was dried for 16 hours at  110C
and then divided into eight parts ivhich were reacted at 150C for varying
times up to 17 hours.  The level of nitrogen fixation increases as the
reaction time increases, however, the maximum level of fixation was not
determined initially.  The maximum fixation possible under these  conditions
was later determined  (Curve B) using a 50% urea solution ard a 4.4
wet/dry ratio.  This paper, was dried at 110C for 20 hours and then divided
into eight parts.  The longest reaction time was 42 hours.  The maximum
nitrogen concentration attained in the reaction product was about 13%.
If on the average one cyanic acid molecule reacted with one anhydroglucose
unit, it would produce a nitrogen concentration of 7.0%, while two cyanic
acid molecules/anhydroglucose unit would result in a nitrogen concentration
of 11.3%, and three cyanic acia molecules/anhydroglucose unit would
result in a nitrogen concentration of 14.4%.  The maximum fixation
achieved, then, was on the average 2.5 nitrogen molecules per anhydroglucose
unit; however it is very  likely that prolonged exposure of the cellulose
to the heat resulted in some cellulose degradation so the nature  of
the chemical bonding involving the nitrogen cannot be specified with
certainty.

     The catalyst cupric  chloride, at 5% of the weight of urea, has  a
definite influence on the rate of nitrogen fixation as shown in Figure
III. C. 2.  The paper was soaked in a 50% urea solution for two hours and
pressed to a wet/dry ratio of 4.4.  The paper was dried at  110C  for
                                  75

-------
20 hours prior to being heated to the reaction temperature.  Four percent
nitrogen fixation was achieved during the drying operation.  The rate
of nitrogen fixation was initially greater than with no catalyst, but
this rate decreased after about 4 hours.

     The reaction temperature will affect the nitrogen fixation as  shown
in Figure III. C. 3.  Each sample contained 25 gins, of shredded paper  that
had been soaked in a 19% urea solution and pressed to a wet/dry ratio
of 4.  The mixture was dried in the reaction flask and the reaction time
was measured from the time the mixture reached the reaction  temperature.
Heat was applied by use of a fluidized sand bath and the flask was  rotated
to aid heat transfer within the flask.  The reaction time for all states
was 1 hour.  The level of nitrogen fixation increased as the reaction
temperature increased.

     The urea concentration (measured as moles urea/mole cellulose)
in the reaction mixture has a definite influence on the nitrogen fixation
as shown in Figure III. C. 4.  Each sample was prepared with 25 gms. of
shredded paper soaked in a urea solution.  The urea concentration was
varied from sample to sample, and each sample was pressed to give a
wet/dry ratio of 4.  The reactions were carried out in a rotating
flask heated by a fluidized sand bath.  A copper chloride catalyst  was
used at 10% concentration  (based on weight of urea) and the  mixtures
were heated at 190C for 1 hour.

     An increase in urea concentration resulted in an increase  in
nitrogen fixation, however, the 1 hour reaction time may have been
the limiting factor in the 155C curve.

Catalyst       The effect of catalyst concentration  (expressed  as % of
Concentration  the weight of urea used) on nitrogen fixation is shown
in Figure- III. C. 5.  Each state contained 25 grams of paper which  had
been soakct4 in a solution containing varying concentrations  of  catalyst
and dried at 110C for 20 hours.  The reactions were  carried out  in a.
rotating flask heated by a fluidized sand bath.

     The mixture was heated to 155C for 1 hour.  Since  a nitrogen
fixation of about 2% was; expected with no catalyst, it appears  that
even small concentrations of catalyst  (0.1-1.0%) have some  effect on
the nitrogen fixation attained, but no effect was noted  for  concentrations
over 5%.  In comparing Figure  III. C. 2. and Figure  III. C.  5., we  find
less nitrogen fixed in Figure  III. C. 5.  This may be caused by a lack of nitrogen
available. This work needs co be re-run using greater urea  concentrations.

Ammonia        "Amino" cellulose was prepared from newspaper by reacting
shredded paper with ammonia in a Parr high pressure bomb at  elevated
temperatures.  The reaction temperature and pressure  were varied, but
it was impossible to maintain  the same reaction time  for all runs because
of gas leaks.  The results of  this test are  listed  in Table  III.  C. 1.

     It is not possible  to know what  contribution each of the  variables
                                    76

-------
made to the increase in nitrogen enrichment, but apparently the reaction
does not proceed readily at room temperature.

Nitric         Nitric acid mixed with sulfuric acid was used to prepare
Acid           cellulose nitrate containing 2.9%N from filter paper.  No
attempt was made to evaluate the effect of variables on the degree of
nitrogen fixation.

Phosphorus     Four samples of straw were soaked in a 21.5% phosphoric
Enrichment     acid solution and drained to achieve a wet/dry ratio of 4.
The wet straw was heated in an oven'at 100C for 64 hours.  Two samples
were washed with water prior to the phosphorus concentration determination.
The results are listed in Table III. C. 2.  Although some phosphorylation
has taken place, it is equivalent to an average of only one phosphate
group per two anhydroglucose units.

Nitrogen and   Both nitrogen and phosphorus can be chemically fixed to
Phosphorus     cellulose by reaction with urea and phosphoric acid.  Although
Enrichment     other reactions could also be used to accomplish this,
this was the only reaction used in this study.  Both straw and paper
were used as a source of cellulose for these reactions.

     Annual ryegrass straw was soaked in a phosphoric acid/urea solution
and filtered to remove the excess solution,  to prepare samples with a
wet/dry ratio of 4.0.  The filtrate from the first sample was replenished
and used for the second sample.  This procedure was repeated except for the
fifth sample, which was soaked in the filtrate without replenishing.
The five samples were heated in an oven for 2 hours after drying.  One
half of each sample was washed in water.  The results are listed  in Table
III. C. 3.  On the average they contained 3.5% phosphorus and 5.0% nitrogen
or 3.2 moles of nitrogen/mole phosphorus even though excess phosphorus and
nitrogen were available.

     Newspaper can be enriched with nitrogen and phosphorus by soaking
the paper in a 40/30/30 wt./wt./wt. solution of urea/85% phosphoric acid/
water and filtering the paper to give a 4.9 wet/dry ratio.  Khen  the mixture
is heated to 155C for three hours and washed with water.  The product
contains 5.0% nitrogen and 4.4% phosphorus.

     Some of the variables in the process which might affect the  nutrient
concentration are predrying, reaction time, reaction temperature, and reactant
concentration.

     The effect of predrying the reaction mixture on nitrogen and phosphorus
fixation was determined by soaking two samples of paper in the urea/acid
solution.  One sample was predried for 20 hours at  110C while the other  sample
was dried in the reaction chamber.  Both samples were heated to  166C for
160 minutes and then washed.  The predried  sample contained 6.1%  nitrogen
and 3.5% phosphorus while the  other sample contained 5.9% nitrogen and
3.6% phosphorus.  These results show that predrying the wet paper did not
affect the results.
                                    77

-------
     The effect of reaction time on nitrogen and phosphorus fixation is
shown in Figure III. C. 6.  Samples of shredded newspaper were soaked
in a 40/30/30 solution of urea/85% phosphoric acid/water and pressed
to a wet/dry ratio of 4.7.  The reactions were conducted at 155C in a
rotating flask heated by fluidized sand bath.  After washing, the nitrogen
and phosphorus concentrations were determined.

     Over the range used, the phosphorus concentration is not affected
by reaction time, but the nitrogen concentration increased slightly
with the longer reaction times.

     The effect of reaction temperature on ritrog^n and phosphorus fixation
is shown in Figure III. C. 7.  Samples of shredded newspaper were soaked
in a 40/30/30 solution of urea/85% phosphoric acid/water and pressed to
a wet/dry ratio of 4.0.  Each sample was predried at 110C for 16'hours
prior to being heated at the reaction temperature for 1 hour in an oven.
After washing, the nitrogen and phosphorus concentrations were determined.

     The reaction temperature has a negligible effect on the degree of
phosphorus fixation although the nitrogen fixation increased at higher
temperature.  Apparently most of the reaction occurred during the drying
step.  This is surprising considering Nuessle's suggestion that the
urea (m.p. 133C) acts as a solvent for the reaccion.

     The effect of reactant concentration on nitrogen and phosphorus
fixation is shown in Figure III. C. 8.  Samples of shredded paper were
soaked in a 40/30/30 solution of urea/85% phosphoric acid/water and
pressed to a wet/dry ratio of 3.0.  The urea/phosphoric acid weight ratio
was constant at 4/3 for each soaking solution.  After predrying the mixtures
were heated to 150C for 3 hours.  After washing the nitrogen and phosphorus
concentrations were determined.  The degree of nitrogen and phosphorus
fixation increases as the reactant concentration increases, but there  is
obviously an upper limit to the amount of nitrogen and phosphorus that
can be chemically united to cellulose.

Soil           These tests were conducted using No. 10 size cans  filled
Test's          with soil.  A mixture of the various ryegrasses was used
because of the response of these grasses to nitrogen in the soil.  Enough
commercial fertilizer or enriched waste was used to provide 50 pounds  of
nitrogen per acre.  Approximately two weeks after the initial planting,
the grass was cut to a uniform height, and the grass clippings were weighed.
The grass was then cut each week for the duration of the test period.
The total glass production from each state is the total of the weekly
productions.  All cans received the same amount of water and each can
had holes in the bottom for drainage.  In each series of tests, two control
states were included, one with no fertilizer  added and one with a sample
of commercial fertilizer providing 50 pounds  of nitrogen per acre.

     It is presumed that when the nitrogen in the treated waste is readily
available to the plant, the growth rate will  be comparable to the state
                                   78

-------
containing commercial fertilizer, while when the nitrogen in the treated
waste is not immediately available to the plant, the growth rate will be
comparable to the state containing no fertilizer.  Finally when the
enriched waste has a deleterious influence on plant growth, the growth
rate will be less t'aan the control with no fertilizer.  The "slow release"
of the treated waste was not determined by this series of tests.

     The results of these tests are presented below.

     Nitrogen enriched samples of waste cellulose were used in the soil
tests.  The tests were conducted on samples enriched with urea, ammonia,
and nitric acid.

     The effect of nitrogen enriched paper resulting from the reaction
of urea and cellulose on plant growth is listed in Table III. C. 4.
The use of the nitrogen enriched paper raised the plant growth rat .
slightly, on the average about 75% as much as the commercial fertilizer;
however, two samples showed an exceptionally high effect, over 90% as
much as the commercial fertilizers.  Apparently the reaction product of
the dry mixture is different than the product that results when the
urea is dissolved, at least it appears to be more readily available to
the plant.

     The effect of amino cellulose on plant growth is  listed in Table III.  C.  1.
Two of the samples apparently had a deleterious effect on the plant
growth rate.  The product that had been reacted at the highest pressure  and
temperature raised the plant growth rate about 40% as  much as the commercial
fertilizer.

     The use of cellulose nitrate did not appreciably  affect the plant
growth rate.

     The nitrogen and phosphorus enrichment influence  on the plant growth
rate is listed in Table III. C. 5.  The use of these samples resulted in
a significant increase in plant growth, on the average 130% as much as
that produced by the commercial fertilizer.
                                    79

-------
                             References.
1.  Anderson, J. W., "Preparation of Nitrogenated Fertilizers by
         Treatment of Cellulosic Materials with Ammonia", Iowa State
         Journal of Science, 26_, 158-159 (1952).

2.  Barbour, J. F., "Cellulose Compounds Containing Nitrogen", Report of
         The Department of Agricultural Chemistry, Corvallis, Oregon
         June, 1951.

3.  Barry, A. J., F. C. Peterson, and A. J. King, "Interaction of
         Cellulose and Liquid Ammonia", Journal of The American
         Chemical Society, 5, 333-337  (1936).

4.  Davis, R. 0. E., R. R. Miller, and W. Scholl, "Nitrification of
         Ammoniated Peat and Other Nitrogen Carriers",  Journal of
         The American Society of_ Agronomy, 27_, 729-735 (1935).

5.  Gallagher, D. M., "Phosphorylation of Cotton with Inorganic Phosphates",
         American Dyestuff Reporter. 55(10), 23-25 (1964).

6.  Lyons, J. W., The^ Chemistry and Uses of Fire Retardants, Wiley-
         Interscience, New York, 1970.

7.  Nikitin, N. I., The Chemistry of Cellulose and Wood, Isreal Program
         for Scientific Translations, Jerusalem, 1966.

8.  Nuessel, A. C., "A Note on The Reaction Between Urea and Cellulose",
         American Dyestuff Reporter, 53(2), 26-27 (1964).
                                  80

-------
                                                 .Solution
CD
              Waste
                       -*
Soak
Filter
Heat
Wash
  Dry
Storage
                                                               Concentrate
        Figure III.  C.  1.   Schematic  Diagram of the Nitrogen-Phosphorus Enrichment Process.

-------
00
K)
                                    10
                                                            (B) No Catalyst
15
20        25
  Time  (Hours)
30
35
40
45
                  Figure III. C.  2.  The Effect of Reaction Time on Nitrogen Fixation in the Reaction of Cellulose and Urea

-------
         4.




      Of


        3
      2
      g
      00
      s
          140
150         160         170         180

       Reaction Temperature,  C
190
figure III.  C.  3.   Effect  of Reaction  Temperature on Nitrogen Concentration.
                                  83

-------
   0           0.5         1.0         l.S         2.0         2.5       3.0



                     Urea Concentration, Mole Ration  Urea/Cellulose



Figure III. C. 4  Effect of Reactant Concentration on Nitrogen Concentration.



        Time = 1 hr.
                                 84

-------
      00
      in
I
 01234567

                                     Catalyst Concentration,  % Urea Wt.


Figure III.  C.  5 Effect of Catalyst Concentration on Nitrogen Concentration.   (Cupric Chloride)

-------
   6 
(-1
*j

v
u

o  .,
u  4
                                       Phosphorus
              1         234         56         7



                        Reaction Time (Hours)



      Figure  III.  C.  6  Effect  of Reaction Time on Phosphorus Concentration
o
H   J^

s

g  31
u
c

5
    no
                                  Phosphorus
             120
, 160
                                                             170
                                                                      180
                      130       140        1?0



                   Reaction Temperature (C)



Figure III. C. 7  Effect of Reaction Tpmporsture on Phosphorus Concentration
                                   86

-------
2
2
>
g
u
  0            0.2         0.4         0.6         0.8        1.0

         Phosphoric Acid Concentration, Mole Ratio  H,P04/Ce]lulose


Figure III. C. 8  Effect of Reactant Concentration on Phosphorus Concentration
                             87

-------
           Table III.  C.  1.   Soil  Test With Amino Cellulose
State i I
Reaction Pressure, P.S.I.
Reaction Temperature, C
Reaction Time, min.
N Concentration (unwashed), %
Production, gms.
N Concentration, (washed), %
Production, gms.

132
23
900
0.8
10.5
0.3
5.7

900
90
10
1.7
17.6
0.9
7.1

980
185
30
4.1
13.5
3.1
10.2

2700
300
60
11.2
12.4
10.5
12.4
Standards



     No Fertilizer    9.5 gms.,  nono anaonium phosphate 31.4 gms.
                                   88

-------
Table III. C. 2.  Phosphorylation of Straw
Straw weight, grams
Phosphoric Acid, grains
Reaction Temperature, C
Reaction Time, hours
Product Weight, grains
Product Weight (washed) , grams
Phosphorus Concentration, weight \
20
15.3
110
64
26.6

20.8
20
15.2
110
64
26.6
11.7
3.1
20
14.8
110
64
26.6

21.7
20
14.6
110
64
26.6
12.0
3.2
                      89

-------
     Table III. C. 3.  Nitrogen and Phosphorus Enrichment of Straw


Sample      Phosphorus Concentration, Wt. %      Nitrogen Concentration, Wt. %
              Unwashed            Washed           Unwashed          Washed
1
2
3
4
5
13.3
13.3
11.8
12.3
11.5
3.4
4.8
2.5
3.8
2.9
14.5
14.3
12.8
13.9
14.9
5.6
4.8
4.1
5.5
5.1
                                   90

-------
                                        Table  III. C.  4.   Soil  Test Kith N-Enriched Paper





              Reaction Time,  (hrs)              50         110         111



              Reaction Temperature,  (8C)       155        -       155      155       -       145      145 '     145



              Washed, Unwashed  (w,u)            ww         uww         uuw



              Nitrogen Concentration,  (%)       3.8      0.1       10.2      1.6     0        12.2     12.2       1.7



              Grass Production,  (grams)         10.3     36.6       32.4     43.9     8.9      24.1     32.5     42.4



              Standards



jo               No Fertilizer                   8.5     33.2       33.2     33.2     8.5       8.5     14.4     33.2



                Commercial Fertilizer      "    28.1     46.5       46.5     46.5    28.1      28.1     36.3     46.5

-------
                  Table III. C. 5.  Soil Test  With N and P Enriched Paper
State



Reaction Time, (hrs)



Reaction Temperature, (C)



Washed, unwashed, (w,u)



Nitrogen Concentration,  (%)



Phosphorus Concentration,  (%)



Grass Production, (grams)



Standards



  No Fertilizer



  Commercial Fertilizer
1
1
155
w

7.3
4.6
35.3
14.4
36.3
2
4
155
u
i
13.1
1.1.7
31.5
6.5
31.5
3
4
155
w

5.1
8.7
63.4
6.5
31. ':
4
4
155
w

5.1
8.7
27.8
11.5
31.0
5
0.5
190
u

11.4
8.8
37.1
14.4
36.3
6
0.5
190
w

6.6
6.4
32.7
14.4
36.3
7
0.5
190
w

6.6
6.4
27.4
8.5
28.1

-------
Acetylation of Wastes

     The first recorded acetylation of cellulose has been  credited  to  Schutzen
berger (4:61) in 1865.  However, the sulfuric acid  catalyst used reacted
with the cellulose to form sulfate esters.  These groups cause  the  product
to be unstable.  Later it was found that by using a hydrolysis  step, the
acetate could be converted to a more useful form.

     A typical reaction scheme for the commercial production  of cellulose
acetate can be shown as

                              cellulose

       acetic acid  catalyst      4-    acetic  anhydride

                            esterification

                                   4-

                         water in acetic acid
                              hydrolysis

                                    4-

                              filtration

                                    4-

                          wash  and  stabilize

                                    4

                             dewater and dry

                                    +

                         screening and packaging

     Chemistry;  There  are  several  methods  of esterification that can be
used to acetylate  cellulose in  the  laboratory.   Since cellulose contains
hydroxyl  (OH)  groups, it must be considered to be an alcohol, and will be
denoted by the usual symbol ROH.  The acid  will be noted as R-^-OH.
                                                               0
Reactions That  In general there are four  reactions that can be used to
Produce ITsters  produce an ester.  These reactions can be shown as:
                                    93

-------
     1.  The reaction of an acid chloride with an alcohol

             0
             ii
           R-C-C1 + R'OH * RCOOR' * HC1

     ?..  An acid plus an alcohol using a basic catalyst

             0
             '<                  +
           R-C-OH + R'OH + Base ^ RCOOR1 + H20

     3.  An acid plus an alcohol using an acid catalyst


                                y.1
           R-C-OH + R'OH + Acid  ^  RCOOR' + H.O
                                 V2
     4.  An anhydride plus an alcohol

             0   0
             n   n
           R-C-0-C-R + R'OH * RCOOR' + RCOOH

     Reaction three is usually used commercially to produce  cellulose  acetate.
As shown, the reaction is reversible, and the velocity  (v) of  each  reaction
depends on the rate constant and the concentration of the reactants and
products.

           V1 = kx (RCOOH) (R'OH)

           V2 = k2 (RCOOR') (H20)

It is  easily seen that by using an excess of acetic anhydride  to  remove the
water, the reaction will be forced toward the formation  of the ester RCOOR'.

     It has been found that when using sulfuric acid catalyst, S% by weight  of
the cellulose, a very rapid reaction takes place at the  beginning of the
esterification producing sulfate esters.  Because of the large concentration
of acetic acid, a transesterification occurs replacing  the sulfate  groups
with acetyl groups.  Some sulfate groups remain even after long reaction
times.  A hydrolysis step is employed to remove the sulfate  groups.
Acetic acid, containing enough water to make the final  solution to  about
0.5% water, is added to the reaction mixture.  This water not  only
hydrolyzes the sulfate groups but destroys the excess anhydride as  well.
This hydrolysis step should be fairly short, i.e., about 5 hours  or less
because it has been found  (2) that long hydrolysis times reduce the acetyl
content and again increase the sulfate content.

     The usual laboratory procedure for preparing cellulose  acetate for
esterification would be to soak the cellulose in water  and replace  the
                                    94

-------
absorbed water with glacial acetic acid.  This requires large quantities
of water and acid, and has been replaced in industry by simply soaking
the cellulose with acetic acid for 1-2 hours before acetylatJon takes place.

     Several publications have reported the preswelling of the cellulose
with various materials to insure a more complete reaction.  A fairly
recent paper by Klenkova et. al. (1) reported the preparation of  cellulose
triacetate with high degrees of polymerization  (1100-1150).  They used
methylamine or ethylenediamine to preswell the cellulose.  The amines
were subsequently removed with organic solvents then with acetic  acid.
It is doubtful that this complicated process will be used by industry.

     Malm et. al. (3) studied the far hydrolysed cellulose acetates, i.e.,
cellulose acetate with a large portion of the acetyl groups removed by
hydrolysis.  They found the products to be soluble over a wide range of
acetyl content if they varied the water to acetone ratio in the solvent.
For example a 1:1 mixture of water and acetone  (they did not state whether
this was mole %, weight %, or volume %) was capable of dissolving
cellulose acetates with an acetyl content from about 16 to 35%.

Catalysts Used           Numerous acids and acid salts have been  used in
In Esterifications       the laboratory to produce cellulose acetate.
Typically one finds zinc chloride, perchloric acid, sulfonic acids,
various halogen acids, and sulfuric acid being used as catalysts.
Commercially sulfuric acid is used because of its reasonable cost and lack
of corrosion of the equipment used.  Its use does require the hydrolysis
step however.

     Basic catalysts are usually limited to pyridine or basic salts such
as sodium acetate.

Recovery Of         Stannett (5:40) tells us that solvent extraction,
Excess Reagants     followed by solvent distillation, is used to  reclaim
the dilute acetic acid produced by the precipitation step of the  acetylation
process.  She suggests the use of ethyl acetate as a solvent because ethyl
acetate removes excess water as an azeotropic mixture.  The ethyl acetate
is next to distill, and finally the acetic acid is removed at the bottom
of the column.

     There are several alternate =civents that  could conceivably  be used,
but will not be listed here.

     Process:  Acetylation has been conducted on a laboratory scale using
the vapor phase,  fiber, and solution processes.

Vapor         A schematic diagram of the vapor  phase process is shown in
Phase         Figure  III. D. 1.  The cellulosic waste is placed in  an oven
and hot air  containing acetic anhydride vapors  is circulated through the
oven.  Since acetic acid is formed by  the reaction,  it  can be condensed
from the exit gases.  A catalyst, such as pyridine, must be used  to
swell the fibers.  Although this acetylation process does not produce a
                                   95

-------
high degree of acetylation, it does improve dimensional stability in paper
and wood, and in laboratory tests it has produced adequate acetylation in
ground paper to form a solid disc on pressing.

     Solid waste moisture content and nature of the solid waste will be
important in this process since the anhydride reacts with water to form
acetic acid and since the anhydride is being transported in the air.  The
waste should be dried and ground because reduction in particle size will
increase the surface area and promote faster and more complete acetylation.

     Catalyst selection is important in rate of reaction, cost, and recovery,
Pyridine is not the only catalyst that has been used in this process, but
it does have some advantages, in particular it is easily volatilized, and
it readily expands the cellulose fibers.  The catalyst concentration will
undoubtedly have sorce effect on the availability of cellulose hydroxyl
groups f^r reaction.

     Reaction temperatures must be controlled to maintain the greatest
yield at the least cost.  If the reaction temperature is set below the
boiling point of acetic anhydride (~140C), then the condensation of anhydride
on the cellulose will facilitate the reaction; however, if the temperature
is above the boiling point of acetic acid, (~118C), then the acid formed
will immediately be vaporized.  Since the boiling point of pyridine is
about HS^C, it will remain in the vapor state at these conditions.  Reaction
temperatures above 140C would insure that the anhydride remained in the
vapor state.  In a batch reaction, the temperature could be maintained
above 140C after the reaction to remove the excess anhydride.

     The reaction time will determine the degree of acetylation until
the reaction is complete.  The rate at which anhydride and catalyst is
carried to the oven will be determined by the air flow and air temperature.
The acetylation rate will be influenced by the oven temperature
and the availability of the cellulose hydroxyls.  Sufficient reaction
time will be needed to produce an acetyl content that will allow the
cellulose to have thermoplastic properties.

The Fiber      is schematically shown in Figure III. D. 2.  The dry
Process        cellulosic waste is reacted with a solution containing
acetic anhydride, a catalyst, and a solvent.  Acetic acid and cellulose
acetate are produced by the reaction.  The reaction solution is separated
from the acetylated waste solids.  The solvent and catalyst are reclaimed
for reuse,  leaving the acetic acid as a by-product.  The acetylated
waste is then washed and dried.  This process can be used to prepare
the triacetate by repeated acetylations of the product.

     The solid waste must be dr/.  Although the particle size is not as
important as in the vapor phase process, a reduction in particle size may
facilitate waste handling.  The anhydride is carried to the cellulose by
the solvent, but the product iloes not dissolve in the acetylation solution.

     Perchloric acid serves as a good catalyst for this process since it
does not combine with the cellulose, however it can be a hazard under some
conditions.  Catalyst concentration will influence the rate of the
reaction.

                                   96

-------
     Several organic solvents have been evaluated for this process
including toluene, methylene chloride, and ethylene chloride.  The solvent
prevents the cellulose acetate from dissolving and carries the acetic
acid away.  The solvent can be reclaimed for reuse by removing the acetic
acid.  The degree of acetylation will be determined primarily by the
concentration of acetic anhydride used in the acetylating solution.

     This reaction will proceed at room temperature but normally a
temperature of about 50eC is employed.  Since the reaction is exothermic,
the reaction temperature rises during the reaction and often reaches
50CC without the addition of heat.  The reaction proceeds rapidly and a
complete reaction is usually achieved in less than 10 minutes.

     After the reaction is complete, the acetylating solution can be
separated from the cellulose acetate by filtration or by centrifuging.
Since some solvent, remains in the cellulose acetate, an alcohol wash is
used instead of water.  Ether can be used to remove the alcohol or it
can be evaporated.  The resulting cellulose acetate is normally dried at
60C.

Solution       A schematic diagram of the solution process is shown in
Process        Figure III. D. 3.  The solid waste is reacted with a solution
containing acetic anhydride, acetic acid, and a catalyst, usually sulfuric
acid.  The cellulose acetate produced dissolves in the acetylating
solution.  Any solids left in the mixture can be removed by filtration.  The
cellulose acetate is precipitated in water, and if it is passed through
tiny holes, it will form threads of the cellulose acetate polymer.  The
solid is separated by filtration and any combined sulfate is neutralized
by addition of sodium carbonate.  After further washing, the at?tate is
dried.

     The solid waste composition is least important in this process,
since the acetate produced goes into solution.  Of the three processes,
impurities which influence the reaction will have the most effect in
this one, however inert solids can be removed by centrifugalion or filtration.

     The catalyst used in the laboratory was perchloric acid although
sulfuric acid is normally used.  The catalyst concentration will affect
the nature of the product, since the sulfuric acid is a combining catalyst
and until hydrolyzed *he product is actually a mixed ester.

     Experimental results:  Cellulose acetate has been prepared  in the
laboratory from samples of commercial refuse, paper, and straw.  Three
acetylation processes have been used; vapor phase, fiber, and solution.

Vapor Phase    Two samples of paper were acetylated using the vapor phase
Process        process.  Hot dry air  (120C) was passed through  acetic
anhydride to pick up vapors then was passed through a flask  containing
the paper.  The catalyst, pyridine, was dissolved in the anhydride.
The reaction was allowed to continue  for 2 hours at  120C and then the
                                   97

-------
excess anhydride was driven off at 150C for 12 hours.  After washing
and drying the paper was compressed with 2,000 p.s.i. at 350F to form
a plastic disc.

     The weight gain for each of the two samples was 22% and 31%,
respectively, approximately equal to that expected for formation of  the
monoacetate (26%).

Fiber          A study of the effect of variables on the degree of acetylation
Process        in the fiber process conducted using various samples  of
cellulosic wastes.  The results of these tests are reported below.

     Cellulose swelling with water or other chemicals speeds the reaction.
Presumably, when the cellulose is "activated", or swollen, prior to
reaction with the acetic anhydride, the internal cellulose hydroxyls
are made available to the anhydride.  The effect of swelling the fibers
on the extent of acetylation was determined using 2 samples of filter
paper.

     One sample was soaked in water and the water was then replaced  by
acetic acid prior to reaction with the anhydride.  The other sample
was dried at 110C prior to reaction.  Both samples were acetylated
using perchloric acid as the catalyst.  The activated sample resulted in
a gain in weight of 56% while the non-activated sample resulted in a gain
in weight of 55%.  Both products were soluble in a 90:10 wt./wt. dichloromethane/
methanol solution.  A 52% increase in weight would be equivalent to  the
formation of cellulose diacetate.  Under these reaction conditions,  soaking
the cellulose did not affect the degree of acetylation achieved.

     In a similar test, using toluene as the solvent, a different result
was obtained.  When no acetic acid was present in the toluene and the paper
was not preswollen, cellulose acetate with only 12% acetyl content was
produced after 20 minutes reaction time, compared to an acetyl content of
23% when DCM was used as the solvent.

     When acetic acid was added to the toluene a cellulose acetate with
28% acetyl was obtained after only 2 ninutes reaction time.

     When the cellulose was preswollen with water and the water replaced
with acetic acid, the reaction in toluene produced an acetate with 35%
acetyl, while the reaction in DCM produced an acetate with 30% acetyl.

     From this evaluation it appears that "activating" the cellulose does
have an influence on the degree of acetylation achieved; however, the
effect is different for different solvent systems.  In addition, the presence
of acetic acid in the solvent influences the degree of acetylation,
although this effect is also different for different solvent systems.

     Reaction time influences the degree of acetylation as shown in  Figure
III. D. 4.  This evaluation was conducted with a sample of commercial
paper waste obtained from a Seattle bank.  The waste was dewatered with
                                   98

-------
acetic acid and reacted with a solution containing toluene, perchloric acid,
and acetic anhydride.  After the reaction was complete, the solid acetate
was separated by centrifuging.  Ethanol was used to remove the toluene and
the cellulose acetate was washed in water and dried.  Under the conditions
of this test, changes in the reaction time did not affect the degree of
acetylation.

     A second evaluation was conducted to determine the effect of changes
in time from 1 to 10 minutes.  The results of this test are shown in
Figure III. D. 5.  Although the degree of acetylation increases with
increasing time, a plateau occurred at about 5 minutes reaction time.
This plateau corresponds to a degree of substitution of about 1.5 - 1.8.
It appears that the introduction of the third acetyl group is somewhat
more difficult than the first two.

     Anhydride concentration affects the degree of acetylation as shown in
Figure III. D. 6.  This evaluation was conducted with a sample of
commercial paper waste obtained from a Seattle bank.  The waste was
dewatered with acetic acid and reacted with a solution of toluene, perchloric
acid, and acetic anhydride.  After the reaction was complete, the solid
cellulose acetate was separated by centrifuging.  Ethanol was used to remove
the toluene and the cellulose acetate was washed with water and dried.
An increase in the anhydride concentration resulted in an increase in
the decree of acetylation but only 50-70% of the .anhydride reacted.

     A second evaluation conducted with newspaper confirmed these results.
Based on these findings, an anhydride concentration of 2 moles anhydride/
mole cellulose would be required to produce the monoacetate, which is
the level required in order to impart a thermoplastic property into the
product; however, cellulose acetate with .209- acetyl can be prepared
withouth any anhydride.  Two reactions conducted with acetic acid only,
for 1 minute and 14 hours respectively, resulted in products with acetyl
concentrations of 13% and 20% respectively, however the physical properties
of these products were not determined.

     A reaction temperature increase will increase the degree of acetylation.
An evaluation of this effect was conducted using a sample of commercial
paper waste obtained from a Vancouver brewery.   It was uewatored with
acetic acid and reacted for 5 minute.; with a solution containing 150 ml
toluene, 15 ml acetic anhydride, and 0.15 ml perchloric acid.  Cellulose
acetate samples with 41.6% and 39.0% acetyl respectively were produced.

     Catalyst concentration will influence the degree of acetylation as
seen In Figure III. D. 7.these reactions were  carried out using a sample
of commercial paper waste from a Vancouver, Washington brewery.  The water
was replaced with acetic acid and the reaction was conducted with a solution
of toluene, acetic anhydride, and perchloric acid for  1? minutes at 25C.
The acetic anhydride concentration was 3.7] moles anhydride/mole cellulose.
The acetyl concentration is reduced when the catalyst concentration is
reduced below 1% of the acetic anhydride weight.
                                   99

-------
     The product that was.obtained with the use of DCM as solvent exhiMts
extremely good flow properties in the plastic state.  This flow property
is not exhibited by acetate made with toluene or made by the solution process,
however, removal of the DCM is a problem.

     Solvents used in conjunction with the acetylation reaction have a
pronounced affect on the results.  Since toluene prevents dissolution of
the cellulose acetate, it is a solvent only in that it holds the anhydride
and catalyst in solution.  Because the cellulose does not dissolve in the
reaction mixture, the acetate can easily be recovered from the reaction
mixture by filtration or centrifugation.  The solvent mixture can then be
recycled or subjected to a reclamation process.  The solids from this
process need less water for washing because methanol, which is at least
in part reclaimable, is used to remove the residual toluene and acids.

     Following separation, the reaction mixture can be distilled and the
distillate returned to the system as a starting material for further
acetylations.  The first portion of the distillate contains an acetic
acid-toluene azeotrope, boiling at 104C.  As the toluene is depleted,
the temperature of the distillate increases and there is more anhydride
present.  When the acetic acid has completely distilled, acetic anhydride
can be recovered.

     The methanol used for the wash is more difficult to reclaim.  Traces
of acetic acid and acetic anhydride washed from the acetate react with
the methanol to form methyl acetate.  When this mixture is distilled,
the first portion contains methanol, methyl acetate and toluene, then as
the toluene is exhausted, the raethanol-methyl acetate azeotrope distills.
Finally, as the methyl acetate is exhausted, the pure luethanol can be
reclaimed by di  illation.  The methanol-methyl acetate azeotrope could be
converted to methyl acetate, which would have utilization as a solvent for
introducing the plasticizers into the cellulose acetate.

     When dichloromethane (DCM) is used instead of toluene, the reaction
mixture becomes very gummy and is not filterable, however the solid can be
separated by centrit'uging.

     The waste source has a strong influence on the maximum acetyl concentration
obtainable.  Filter paper, produces a white powder with up to 44% acetyl
content.  This material can be formulated and ca^ndered into transparent
sheets.  As the impurities in the starting material are increased, the
product loses its transparency and becomes darker in color.

     Newspaper, which contains some lignins produces a  light brown
cellulose acetate with 42% acetyl content, while municipal refuse produces
a dark brown cellulose acetate with 36% acetyl content.  This latter
sample of municipal refuse was obtained from the Black-Clav/son Company
in Ohio, ar.d still contained small pieces of inorganic  residue although
most of the metal and glass had been removed.
                                    100

-------
Solution       Cellulose acetate was prepared from paper and straw
Process        using the solution process, but an extensive evaluation of
this process was not undertaken since the vapor phase and fiber processes
appear to be better suited for chemical treatment of waste cellulose to
produce cellulose acetate.

     Straw, when acetylated gives a product which is dark brown, brittle,
and contains straw components that are not dissolved.

     Paper was used in a series of tests to evaluate the effect of
changes in catalyst concentration on the degree of acetylation when using
samples of newspaper as the source of cellulose.  The amount of catalyst,
perchloric acid, was varied from 0.16% to S% by volume, based on the volume
of acetic anhydride used.  One series of samples was prepared at a reaction
time of 1 minute while another series was prepared at a reaction time of
30 minutes.

     Perchloric acid, while somewhat more hazardous to use than sulfuric
acid, was chosen as the catalyst because it eliminated the need for
hydrolysis between the acetylation and the precipitation steps in the
solution reactions.  Perchloric acid does not form esters with the
cellulose as sulfuric acid does.  The sulfate esters not only lower the
degree of acetylation of the final product, but because of their acid
nature, these esters cause hydrolysis of the acetate esters when exposed
to atmospheric moisture.
                                   101

-------
                              References
1.   Klenkova, N. I., 0. H. Kulakova, N. D. Tsimara, N. A. Matveeva, and
     E. M. Khlebosolova, "Preparation of Cellulose Triacetates of High
     Degree of Polymerization", Journal of Applied Chemistry of U.S.S.R.,
     41_, 592 (1968).

2.   Malm, C. J., L. J. Tanghe, and B. C. Laird, "Preparation of Cellulose
     Acetate, Action of Sulfuric Acid", Industrial anc[ Engineering
     Chemistry, 3, 77  (1946).

3.   Malm, C. J., K. T. Barkey, M. Salo, and D. C. May, "Far-Hydrolyzed
     Cellulose Acetates", Industrial and Engineering Chemistry, 49, 79  (1957).

4.   Schutzenberger, P., "Action de 1'acide acetique anhydre sur la cellulose",
     Academic de_ Sciences, Comptes Rendes, 01, 485 (1865).

S.   Stannett, V., Cellulose Acetate Plastics, Temple Press Ltd., London  (1950).
                                   102

-------
o
w
                     Solid Waste
                                                       Acetic Anhydride

                                                           Pyridine
                                                         vapor
   phase
Oven
                                                          Acetic Acid
Pressing
         Figure III. D. 1.  Schematic of Vapor Phase Acetylation of Solid Waste.

-------
       Acetic Anhydride
          Solid Waste
Acetic Anhydride
    Catalyst
     Solvent
   Acetylation
                                                                 Acetic Acid
Catalyst
Solvent
 Filter
->J   Acetic Acid
         Wash
          and
          Dry
                                                                                             Storage
Figure III.  D.  2.   Schematic Diagram of The Fiber Process  of Acetylation  of Solid Wastes.

-------
o
in
               Solid Waste
                                 Acetic Anhydride

                                  Acetic Acid

                                    Catalyst	
                                      I
Reactor
                                                                    Reclaim
                                           Water

Filter
|
Solids



i

Hydroli.se and

Precipitation



Acetic Acid
i

Filter
1

                                     Storage
                       Dry
Wash.
Stabilize
                                                                                                   Na2C03
         Figure  III. D. 3.'  Schematic Diagram of The Solution Process for Acetylation of Solid Waste.

-------
     60
     50
c

-------
     50
     40
g
+J
X
4-)

u
   30-
      20
                                                                        -f-
                                                                                     8
                                                                                                      . DS=3
                                                                                                        DS=2
                                                                                                     DS-1
              1234567


                               Time (minutes)


Figure  III.  D.  5  Effect of Reaction Time, from 1 to 10 Minutes, on Degree of Acetylation.
10

-------
                 12            345



           Acetic Anhydride Concentration, (Mole ratio Anhydride/CelluJose)



Figure  III.  D.  6  Effect of Anhydride Concentration on Acetyl Content.
                                108

-------
o
US
          V
         O
         X
         *->
         u
         u
              50
              40
              30
              20
              10
                          I
                                         1.0                      2.0                     3.0


                                  Mi111liters of  70% HC104 Mixed with 60 ml.  of Acetic  Anhydride
          Figure  III. D.  7.  Showing the Relationship  Between Catalyst and Degree of Acetylation  When

                            Using Perchloric Acid, with a Reaction Time of One Minute.

-------
Hydrogenation of_ Wastes

     "Future Fuels; Where From" was the title of an article  (30) describing
one of the problems facing this nation.  It is felt t'.i,  this problem  can
be partially solved along with the problem of the refuse crisis, by  converting
the wastes to gas and oil through hydrogenation.  Liquid fuels  are easier
to transport and presumably have a higher energy value  than  the solid
fuels.

     In 1966 a preliminary literature search concerning the  problem  of
our fuel shortage was undertaken.  It was found that Glover  (38) and Linsly
(62) both reported that the use of gas and oil was outstripping the
development of new reserves.  They stated that this condition had existed
since 1958.  By 1970 the news media had taken up the hue and cry about
the energy crisis (34, 84).  Even the oil journals were admitting that
the demand was increasing so rapidly that by 1990 the  world  demand for oil
would be 100 million barrels per day (90).

     By 1967 some people were beginning to look toward controlled nucleai
reactors as a source of electric power which would relieve some of the
strain on the gas, oil, and coal reserves  (86, 87).  Other are  convinced
that conversion of coal to oil and gas is the answer to the  energy shortage
(27, 28, 29, 70).  A relatively new concept is the atomic "mining" of  a
gas and oil from oil shale and oil sands.  (69, 71).  Thermal processing of
shale and sand is being examined in attempt to bolster our sagging reserves
(31).

     In the past 5 years there has been no reported gain in  the reserves to
production ratio for either gas or oil.  In fact the reserves to production
ratio is still reported to be declining  (40).

     Chemistry:  Man in his search for an understanding of the  world in
which he lives has done much toward finding the answer to how coal and
oil could have been formed.  In 1913, Heuser  (44) found that a  coal-like
substance was formed in the digester system at a pulp  mill.  In 1922
Willstatter and Kalb  (88) studied the reduction of carbohydrates  and lignins
by the action of hyclriodic acid and red phosphorus.   In 1923, Fischer
and Tropsch found that iron acting as a catalyst would produce  hydrocarbons
from carbon monoxide and hydrogen  (80).

     Berl and his co-workers published several papers  on the formation of a
coal-like substance from celluiosic compounds, and the conversion  of this
"coal" and carbohydrates to oil  (10, 11, 12,  13,  14,  15,  16, 17,  and 18).
They reported that the most positive results  toward  coal formation  resulted
when the material was treated under pressure  in  an alkaline  medium  (13).
The "protoproduct" was subsequently treated with  "ferrum reductum"  and
iodine under 100 atmospheres of hydrogen  (16,  17) to  produce an oil.  In
another article Berl  (15) postulated the formation of aromatics and  polycyclic
aromatics from carbohydrate molecules.  Other  references to  Berl  and his
co-workers would have to include the journals  Papier-Fabrikant  (18:141-149)
and Zcitschrift fur Physikalische Chemie  (14:71-93).
                                   110

-------
     About 1935 there was a flurry of work reported by Boomer et al.
(21, 22, 23, and 24), in which they hydrogenated various substances in
tetralin and similar media.  It was reported that the "oil" from the treatment
of grain screenings was very odorous, acid, contained conjiderable oxygen
and darkened rapidly (24:353).

     Kurihari and Yoshioka (59) reported the production of gasoline by
hydrogenation of the oil produced from the hydrogenolysis of a mixture of
peat and tetralin.  Hcnze, Allen, and Wyatt (43) treated cotton hull
fibers with base then hydrogenated the product.  They found that 7%
base gave the best results.  Geerards et al. (37) reported the hydrogenation
of carbohydrates.

     More recently Ichikawa et al. (49) formed C^-Cg hydrocarbons from CO
and H2 by using electron donor-acceptor complex films as catalysts.

     Appell, Wender, and Miller of the Bureau of Mines reported the
conversion of urban refuse to oil using the water-gas shift to hydrogenate
paper (2).  They reported a yield of 41% oil.  This oil from paper had a
relatively high, 20%, content of oxygen (2:4).

     Much work has been done in the field of partial hydrogenation of
carbohydrates.  In most cases the products are polyalcohols although
hydroxyketones have been reported by Gurkan (41).  Belandin et al.  (6,
7) used Ruthenium on a carrier in the presence of mineral acids to produce
sorbitol.  Van Ling and Vlungter  (85) produced polyalcohols, reporting
the analysis of these polyols by gas chromatography and paper chromatography.
Haidegger et al.  (42) produced sorbitol by the reduction of glucose with
ammonia synthesis gas.

     Kasehagen (55) obtained a patent for the production of glycerol from
reducible sugars.  A year  later Van Ling and Vlungter  (85) also reported
the formation of glycerol thiouyh the hydrogenolysis of saccharides.
Bizhanov et al.  (19) reported the use of a catalyst, consisting of nickel,
aluminum, and iron with about 2% manganese added, to hydrogenate monosaccharides.

     Lignin and lignin containing compounds have been hydrogenatod by
several methods.  Besides  the earlier mentioned work of Berl and his
co-workers we find th?.t Peterson  (68) obtained aldehydes, acids, and
phenolic compounds from the hydrogenolysis of bark using Raney nickel as
the catalyst.  Rieche et al.  (76) used MnC^-Fe^Os to hydropenate lignin.
Matsukura and Sukakibara  (65), and Ohta and Sukakibara  (65) examined the
products from the hydrogenolysis of protolignin and reported finding
substituted phenylpropane  and substituted phenylpropanol.  Pepper  and Lee
(67) have reported a study of catalysts tor lignin hydrogenolysis.

Temperaturs    Blackwood, McCarthy, and Cullis  (20) published a paper on
Effects        their study of the carbon-hydrogen reaction with coke
and chars.  They stated that the  reaction of coal with hydrogen was
                                   111

-------
dependant on temperature treatment history and not on the source of the
coal.  They were primarily interested in gasification rather than liquefaction
of the coal.

     Dehydrogenation was noted by Benson and O'Neal  (9:515) while studying
the kinetics of the reaction of alkyl iodides with hydrogen iodide.  They
noted that the alkyl iodides are unstable at elevated temperatures, possibly
forming free radicals.  Raley et al.  (75), Mullineaux and Slaugh  (64) and
Slaugh et al. (79) conducted a study of high temperature dehydrogenation
of hydrocarbons using iodine as a catalyst.  They concluded that the reaction
probably proceeded through an aliphatic free radical mechanism.  H&dgson
(45) also studied the reaction of iodine with various organic compounds
at high temperatures and found that a dehydrogenation occurs at temperatures
above 350C.  Adelson et al. (1) published the kinetic data for reaction
rates and the rate constant for the dehydration of isopentane by iodine
in the presence of oxygen at 500C.  They postulate  19 steos in the reaction.

     Pyrolysis products are similar to many of those found in the hydrogenations
referred to earlier in this paper.  Many listed products which were very
similar to those listed by Hurd (48:270-289) for destructive distillation
of cellulesic compounds.  Hurd (48:282) lists alcohols, acids, ketones,
aldehydes, phenolics, hydrocarbons, gases, water, and charcoal as the
products of destructive distillation.

     Goos (39:846-850) lists 213 compounds from the  destructive distillation
of wood, including such items as hydrocarbons, aldehydes, amines, esters,
ketones, acids, anhydrides, alcohols, and phenols.   Hoffman  (47) pyrolyzed
municipal refuse at 900, 1200, 1500, and 1700F.  He published values for
gas, pyroligneous acids, and ch?r produced, as well  as an analysis of
the composition of ths gas.

     Orphey and Jerman (66) studied the liquid condensates from the
pyrolysis of municipal refuse reporting aldehydes, ketones,  chloroform,
acids, water, aromatics, and phenolic compounds.  Jerman and Carpenter
(53) reported the analysis of the gaseous components from the pyrolysis
of solid municipal refuse.  They found H2, 02, N'2, CH4, CO 0)2, C2H4 and
C2H, to be present.  They also reported a wide variation in  the gas
composition from one sample to another, for example  the amount of CH4
reported ranged from 0.2 to 16.14 volume percent.

     Arseneau  (3) studied the competitive reactions  in the thermal
decomposition of cellulose and concluded that in the range of 200-280C
depolymerization occurs.  He suggests that one reaction of cellulose at
elevated temperature might be shown as:

                            H      H

          Cellulose - H,0 - C=C  "*" C-C
                              I  "  I  I!      .  __	'
                              OH   H  0  .-
                                   112

-------
Arseneau's work supported the  earlier work of Kilzer and Broido  (56).

Catalysts Used      Bowen and others, in 1925, reported that the  thermal
In_ Hydrogenations   decomposition of cellulosics was not influenced by
the presence of hydrogen unless a nickel catalyst was used  (25).  Fierz-David
and Hannig (36) substantiated these findings, buc reported  that even with
nickel catalyst there were aldehydes, ketones, arid phenols  in the "oil".
Bowen and Nash published again in 1926 saying that nickel on alumina was
an excellent catalyst.  They reported yields of oil up to 45.6 per cent,
using nickel oxide catalyst.  In their analysis they found  9.21%  phenol,
6.41% base, and an oil which, while not identified, was reported  to have
a "paraffin like" smell.

     For many years hydrogenation of coal to form an economical,  liquid
fuel has been a challenge.  Cochrait and Sayer  (32) in 1959  reported that
the results of the work at Billingham indicated this process was  not
economically realistic.  Yet in 1967, Chemical and Engineering News
(70:96-98) carried an editorial stating that a method for converting coal
to gasoline was in the final stage of development.  They gave son;e very
interesting economic and engineering figures which indicated that at best
the process would be marginal.  Laying and Hellwig (60) have reported
on the H-Coal process.  Coal hydrogasification  (8), hydrogenation (58, 54),
and fluid bed hydrogenation (89) were all subjects of publications in
1970.  Struck et al. (81) studied the kinetics of hydrocracking of coal
extract using molten zinc chloride catalyst.  Hodgson  (46)  used a combination
of catalysts for the hydreconversion of coal.  Lee et al.  (61) published
on the heat of reaction of hydrogen and coal, Szucs  (82) found that iodine
promotes the catalysts used in the hydrogenation of coal.   Jachh  (51)
states some of the problems found in the hydrogenation of coal.

     Schlinger and Jesse  (77), Flinn and Sachsen  (35), Bae  (4), and
Schultz and Linden  (78) all have used hydrogen treatment of oil shale
for oil recovery.

     Quader and Hill (73, 74) have published on their study of the hydro-
cracking of coal tar, as has Janardanerao et al.  (52).  An  editorial  in
Chemical Tn^ineer  (50:50) stated that iodine catalyst improves coal tar
hydrogenation.

     Experimental Results:  A large number of reactions were carried  out
under varied conditions.  The use of different  catalysts, various wastes,
and two separate gas mixtures was employed.

Catalysts           Several catalysts and catalyst combinations have  been
Used III             used  in the laboratory for  the study of the hydrogenation
Hydrogenation       of refuse.  Raney nickel, palladium, iodine,  hydriodic
acid, stannous chloride,  tetrahydronaphthalene, and  carbon  monoxide-water
have all been used singly or in combinations to attempt hydrogenation.   The
greatest yield of hydrocarbon oils was obtained using hydriodic acid.
                                   113

-------
With Raney nickel, palladium, tetrahydronaphthalene, and the C
reactions, sizable quantities of oxygen containing compounds were found
to be present in the "oil".  These oxygen compounds included groups such
as alcohols, ketones, acids, phenols and so on.  With hydriodic acid the
amount of oxygen containing material was greatly reduced.  Some phenols
were present, especially in wastes such as bark, straw, etc., which
contain lignins.

     Recovery of the cata]yst from the hydriodic acid runs has been given
a cursory examination.  In run W6-70-27 about 62% of the HI was recovered
in the water layer separated from the oils.  Some of the iodine appears
to be in the form of organic halides, and some has been found as nearly
insoluble material in the solid residue.  This latter material may be
polymeric in nature with iodine incorporated into the macromolecules.

Materials      A wide spectrum of waste materials have been examined to
Treated        determine their potential as sources of oil and gas, for
fuel, and of petrochemicals.  Because municipal refuse is more than half paper,
work was started using a fairly pure grade of filter paper, then news print
was used for comparison, and finally waste bark and straw were examined.

     Waste wood from the timber industry is a problem in the Pacific
Northwest, and since much wood is dumped in landfills by the construction
industry the feasibility of hydrogenating wood and wood by-products such
as bark was examined.

     In some seasons large amounts of leaves and grass clippings are
hauled to landfills by the collection agencies.  Locally there is a
problem with grass seed straw being burned; the examination of straw as
a source of oil and gas was therefore undertaken.

     Rubber tires are becoming a great problem especially since many
landfills now refuse to accept these carcasses.  Upon treatment under
hydrogenation conditions a gas and an oil were obtained.  About 50 weight
percent of the rubber was found to be inert materials such as carbon
black, fillers, metal and so on.  It may be possible to return the inert
materials to the industry for reuse.

     Polyethylene was treated in the high pressure hydrogenation apparatus.
Although some of the other wastes contain small amounts of plastic, only
polyethylene was specifically treated.  The results were not gratifying.
At the reaction temperatures used, the only results noticeable were the
melting and fusing of the pieces of plastic into one solid mass.

Head Ga       After a brief examination of the oils from several hydrogenation
Analysis       runs it was  decided to examine the head gas in detail first
since the gas was less complex.  The main components of the gas were
carbon dioxide  (C02), carbon monoxide (CO), methane  (0114), hydrogen  0^)
and variable amounts of light hydrocarbons, C2-C5, of both olefinic and
aliphatic nature.  In reporting the information the methane and  light
hydrocarbons are simply reported as hydrocarbons.
                                  114

-------
     Comparison of the head gas compositions from a series of  runs  to
determine the effects of hydrogen and of catalyst are  shown  in Table
III. E. 1.  If one looks at run W6-70-28 using CO and  1^0 for  hydrogenation,
one finds a high CO content in the head gas as would be expected because
of the excess CO introduced.  The same is true of the  hydrogen in the
hydrogenation runs.

     Since large volumes of gas were used, a collection train  was set  up,
Figure III. E. 1., for the gross examination of the gas and  a  gas chromatograph
was used for the more careful analysis of the component content of  gas.
However, since hydrogen was used as the carrier gas, and a hydrogen flame
detector was on the chromatograph, determination of the hydrogen present in
the gas samples was not possible by the gas chromatographic  process.

     Figure III. E. 1. represents the gas trapping and analysis train.
A is the connection to the bomb.  1B_ is a base filled bubble  scrubbing  trap
for the trapping of carbon dioxide.  Trap C_ is cooled  by a dry ice-acetone
refrigerant, while traps D_ and E_ are cooled by liquid  nitrogen.  Point  F_
is a gas sampling port where samples are taken periodically  for gas
chromatographic or carbon monoxide analysis, Figure III. E.  2.  The gas
buret, G, indicates the uncollected gas which is primarily hydrogen.

     Figure III. E. 2. represents the carbon monoxide  analysis train which
consists of two traps filled with ammoniacal cuprous chloride  solution
described by Bach, Dawson, and Smith (5).  A 200 milliliter  gas tight  syringe
was used to remove samples from the gas collection train in  Figure  III.  E.  1.
point F_ and transfer the gas for introduction at point F_ in  Figure  III.  E.  2.
The cuprous chloride solution was standardized with known mixtures  of  gases
generated in this laboratory.

     Figure III. E. 3. represents the gas chromatographic -  mass spectrometric
analysis system.  The gas chromatograph could be used  directly in conjunction
with the mass spectrometer or used independently when  desired.  Samples
were removed from the gas trapping system at point F_,  Figure III. E. 1.  by  a
gas tight syringe and subsequently injected at point F_ on the  chromatograph,
Figure III. E. 3.                                                       '

     After the gas from the bomb has been released through the gas  train,
the valve at A_, Figure III. E. 1. is closed and the refrigerants are
removed to allow, the CO, CH4 and hydrocarbon gases to  be measured and  the
analysis recorded.

     Gas chromatography of the head gas was accomplished using a Varian
1500 gas chromatograph equipped with a 20 foot long, 1/8 inch  diameter
aluminum column packed with S% SE-30 silicone rubber on Chromasorb  W
60/80 mesh.  The oven temperature was maintained at 35C throughout the
sampling of the head gas.  Standards v
-------
Oil            One of our very early hydrogenations was of the relatively
Analysis       complex material, wheat straw.  A sample of the oil was
injected onto the gas chromatographic column and the resulting chromatogram
revealed 66 peaks.  One can quickly see that the oil from these hydrogenations
is very complex and difficult to identify.

     A less complex material, glucose, was chosen since this is one of
the basic units of cellulose.  The chromatogram at the oil from hydrogenation
of this material gave 59 peaks of which 9 could be considered to be major
peaks.  This again confirms the complexity of the oil.

     A sample of oil from Douglas Fir bark was sent to Standard Oil
Company and their results are given in Table III. E. 3.  They stated  in
the cover letter that small amounts of material were distilling at 600F
so that a dry point could not be accurately determined.

     When subjected to normal extraction analysis, the oil from the
hydrogenation of hospital waste was found to contain primarily hydrocarbons
with very small amounts of ketones, aldehydes, and phenols, and trace
quantities of acids and amino acids.

     Oil from paper contained mostly hydrocarbons, although traces of
alkylhalides as well as small amounts of phenolic compounds were detected.
Berl et al. (15) postulated that aromatic and phenolic compounds could
be formed by the dehydration of glucose type molecules.

     Grass straw produced an oil containing alcohols and alkylhalides in
small quantities; with the majority of the oil being hydrocarbons.  A
modified FIA (Fit rescent Indicator Absorption) anclysis  (33) of the  oil
from straw indicated the presence of aliphatics, aromatics, and small
quantities of olefinic-compounds.

     Volume percents were not determined since the apparatus we were  using
was not of the smaller dimensions indicated by Knight  and Groennings
(57:1950).  The silica gel used was Davidson 923, 100-200 mesh, to meet
ASTM standard D 1319-61T, and was purchased from Fisher  Scientific Co.

     The oil from the CO-l^O treatment of straw contained considerable
amounts of strong acid, amino acids, aldehydes, ketones, alcohols, and
phenols.  By thin layer chromatogiaphy and gas chromatography five of the
seven phenolic compounds were tentatively identified as:  p-cre-ol,
p-ethyl and p-methyl guaicol, p-ethyl and p-propylphenol.  Standards  were
not available to match the other compounds present.

     Oil produced from treatment of straw with hydrogen  and tetrahydronaphthalene
(THN) contained large quantities of naphthalene and THN.  Gas  chrom..ttgraphy
in conjunction with the mass spectrometer led  to the  identification  of
benzene, toluene, cyclohexane,  l-methyl-2-ethyicyclopentane, n-butyl
benzene, l-methyl-2,3-dihydroindene.   Several  additional  compounds  have
not been definitely identified but most had a peak  at  mass  31 which  is
                                    116

-------
indicative of the presence of a primary alcohol  -r-ouping.  Upon examining
the identified compounds one can see that there  s  a possibility these all
came from rearrangement and breakdown of the THN.   It  is suggested that
any further work with this material should include  a treatment of THN
without any waste being present.

     Table III. E. 2. gives the weight of residue per  weight of cellulose,
the weight of water per weight of cellulose, the weight of the oil produced,
and the percentage of oil found in various boiling  ranges.  The products
from run W6-70-28 were very similar to those from the  reaction with hydrogen
without catalyst present, including the percentages of oil found in each
boiling range.

     The oils from the carbon monoxide  (CO)-water reaction, the hydrogen
only run, the water only run, and the HI run were all  similar in qualitative
composition.  Although the quantitative analysis has not been completed,
the preliminary work indicates similarities in several of these oils.

     The amount of carbon monoxide and carbon dioxide  found in the gas,
when methyl iodide was used as a catalyst, was greatly reduced but the
amount of oil was not appreciably increased.

     The oil samples were run either on the Varian  1520 or on a Varisn
1200 gas chromatograph which can be used in conjunction with the mass
spectrometer.  The mass spectrometer is a V;i; 'an M.A.T. CH7.

     The columns used were each 20 feet long by  1/8 inch outside diameter
aluminum tubing.  One column was packed with 8%  SE  30  silicone rubber on
Chromasorb W 60/80 mesh.  The other column vas packed  with  10% carbowax
20M on Chromasorb W 60/80 mesh.

     The temperature was programmed according to the  liquid phase and the
boiling range of the oil.  The crude oil was run on the SE-30 packed
column, and the temperature was programmed from  50  to  200C at 4 per minute.'

Material       The material balance was examined for  several of the runs,
Balance        Table III. E. 4.  If one looks at the  oxygen balance, that
is oxygen in versus oxygen out, one finds an oxygen loss for all hydrogenations
except W6-70-23 and W6-70-27.  Since the oxygen  balance was primarily
determined for the head gas and water, we must assume  that  the remainder
(loss) is to be found in the oil.  This is substantiated by the finding of
aldehydes, ketones and phenols in the oils.

     Run W6-70-23 is difficult to explain because of  the large apparent
gain in carbon.  The carbon balance was determined  by gas  analysis and
by calculating the oil to be totally composed of hydrocarbons.  Any oxygen
in the oil would therefore appear as an apparent gain in carbon  in the
oil.  It becomes apparent that a full material balance is  impossible
unless the oil is quantitated for C, H, N, S, and 0.
                                   117

-------
     It does appear that the oil produced in run W6-70-27, hydrogenated  ii
the presence of hydriodic acid, contains little oxygen.  The  5.4%  loss
of carbon in the carboi, balance may well fall within the limits  of experin
error for the handling techniques.  The variations  in  carbon  balance  in
runs W6-70-24, W6-70-26, W6-70-29, and W6-70-30 would  indicate about
5% error was probable.
                                    118

-------
                             References
 1.  Adelson,  S.  V.,  G.  M.  Adelson-Velshii,  V.  I.  Redeneev,  I.  G  Kalsnelson,
          and  V.  I.  Nikonov,  "Mechanism of The  Dehydration of Isopentane
          by Iodine  in the  Presence of Oxygen," Chemical Abstracts,
          73_:44640r  (1970).

 2.  Appell, H. R.,  I. Wender,  and R. D. Miller, "Conversion of Urban
          Refuse  to  Oil," U.S.  Bureau of Mines  Technical Progress Report
          No.  25, May 1970.

 3.  Arseneau, D. F., "Competitive Reactions in The Thermal  Decomposition
          of Cellulose," Canadian Journal of Chemistry, 49_,  623-638  (1971).

 4.  Bae,  J. H.,  "Some Effects  of Pressure on Oil-shale Retorting,"
          Society of Petroleum Engineers of  AIME Journal, 9, 287-292
          (1969).

 5.  Bach, B.  B., J.  V.  Dawson, and D. W. L. Smith, "Preparation of  Anmoniaca
          Cuprous Chloride," Chemistry and Industry, 1279-1280   (1953).

 6.  Balandin, A. A., N. A. Vasgunina, G. S. Barysheva, and S.  W. Chepigo,
          "The Hydrogenation of Polysaccharides", Chemical Abstracts,
          51_:14260f   (1957).

 7.  Balandin, A. A., N. A. Vasgunina, S. V. Chepigo, and G. S. Barysheva,
          "Hydrolytic Hydrogenation of Cellulose", Chemical Abstracts,
          54_:7140f  (1960).

 8.  Benson, H.  E.,  "Coal Hydrogasification", Chemical_ Abstracts,
          7:123748u  (1970).

 9.  Benson, S.  K.,  and E.  J. O'Neal, "The Kinetics of The Reaction of
          Alkyl  Iodides with Hydrogen Iodide",  Journal of_ Chemical
          Physics, 34_, 514-520  (1961).

10.  Berl, E., and A. Schmidt,  "Uber die Entstehen der Kohlen.   II.
          Die Inkoholen von Cellulose und Lignin in Neutralem Medium",
          Justus  Liebigs Annalen Per Chcmig, 493, 97-123  (1932).

11.   Berl, E., and A. Schmidt,  "Uber die Entstehen der Kohlen.   III.
          Die Inkohlen von Harzen und Wachsen in Neutralem Medium",
          Justus  Liebigs Annalen Per Chemie, 493, 124-135   (1935).

12.   Berl, E., and A. Schmidt,  "Uber die Entstehen der Kohlen.   IV   Die
          Verschwelung der Kunstlichen Kohlen", Justus Liebigs Annalen
          Per Chemie, 493,  135-152   (1932).

13.   Berl, E., and A. Schmidt,  "Uber die Entstehen der Kohlen.   V.  Die
          Inkohlen von Cellulose und Lignin in Alkalishem Medium",
          Justus  Liebigs Annalen Per Chemie, 496, 283-303   (1932).

                                    119   *

-------
14.   Berl, E., and R. Breiranann, "Uber die Einwirkung von Wasserstuff
          auf Holz, Kohle, und Aktive Kohle Uber die Methansynthese",
          Zeitschrift fur Physikalische Chemie, A 162, 71-93   (1932).

15.   Berl, E., A. Schmidt, H. Biebesheimer, and W. Dienst, "Die Entstehung
          von Erdol, Asphalt, und Stein Kohle",  Naturwissenschaften,
          20, 652-655  (1932).

16.   Berl, E., and H. Biebesheimer, "Zur Frage der Entstehung der Erdols",
          Justus Liebigs Annalen Per Chemie, 504, 38-61  (1933).

17.   Berl, E., and W. Dienst, "Zur Frage der Entstehung der Erdols.  II.",
          Justus Liebigs Annalen Der Chemie, 504, 62-71  (1933).

18.   Berl, E., "Cellulose als Grundstoffe der Steinkohle und Erdolbildung",
          Papier-Fabrikant, 31_, 141-14y  (1933).

19.   Bizhanov, F. B., D. V. Sokolskii, U. I. Yunosov, and A. M. Khisametdinov,
          "Monosaccharide Hydrogenation Catalyst",  Chemical Abstracts,
          73_: 45787k  (1970).

20.   Blackwood, J. D., D. J. McCarthy, and B. D. Cullis, "The Carbon-
          Hydrogen Reaction with Coke and Chars",  Australian Journal
          of Chemistry, 20_, 2525-2528  (1967).

21.   Boomer, E. H., and J. Edwards, "Hydrogenation in Tetralin Medium.
          I.  Destructive Hydrogenation of Bitumen and Pitch", Canadian
          Journal o_f Research, 13B. 323-330  (1935) .

22.   Boomer, E. H., and J. Edwards, "Hydrogenation in Tetralin Medium.
          II.  Destructive Hydrogenation of Coal in Tetralin and With
          a Mixture of Related Compounds",  Canadian Journal of Research,
          13B, 331-336   (1935).

23.   Boomer, E. H., G. H. Agrue, and J. Edwards, "Hydrogenation of Cellulose
          and Wood",  Canadian Journal of Research, 13B, 337-342   (1935).

24.   Boomer, E. H., and J. Edwards, "Hydrogenation in Tetralin Medium.
          IV.  Destructive Hydrogenation of Grain Screenings",  Canadian
          Journal of Research, 15B, 343-350  (1935).

25.   Bowen, A. R., H. G.  Shatwell, and A. W. Nash, "The Thermal Decomposition
          of Cellulose under Hydrogenation Conditions", Journal of The
          Chemical Industry, 44_, 507T-511T   (1925).

26.   Bowen, A. R., and A. W. Nash, "The Thermal Decomposition  of Cellulose
          and Lignin in The Presence of Catalysts and Hydrogen Under
          Pressure",  Fuel in Science and Practice, 5, 138-142   (1926).

27.   Bowen, A. R., and A. W. Nash, "The Thermal Decomposition  of Coal  in
          The Presence of Catalysts and Under Hydfujgen Pressure",
          Fuel in Science and Practice, 5, 361-364   (1926).
                                   120

-------
28.  Byrd, R. C., "Coal to Gasoline at Competitive Prices", Mining Congress
          Journal, 53, 56-58  (1967).

29.  Cameron, R. J., "Comparative Study of Oil Shale, Tar Sands and Coal
          as Sources of Oil", Journal of Petroleum Technology, 21, 253-259
          (1969).                                              ~"~

30.  Cardello, R. A., and F. B. Sprow, "Future Fuels; Where From?"
          Chemical and Engineering Progress, 65, 63-70   (1969).

31.  Chambers, P. S., "Bureau of Mines Researches Way to Oil Shale Development",
          Chemical Abstracts, 72_:113402n  (1970).

32.  Cochran, C., and E. W. Sayer, "Hydrogenation at Billingham in
          Retrospect",  Industrial Chemist,, 35_, 221-225  (1959).

33.  Griddle, D. W., and R. L. LeToumeau, "Fluorescent  Indicator Absorption
          Method for Hydrocarbon - Type Analysis",  Analytical Chemistry,
          23, 1620-1624  (1951).

34.  "Energy Shortage Worsens", Time, 96_, 62-63  (1970).

35.  Flinn, J. E., and G. F. Sachsel, "Exploratory Studies in The Process
          for Converting Oil Shale and Coal to Stable Hydrocarbons",
          Industrial and Engineering Chemistry Process Design, 7,
          143-149  (1968").

36.  Fierz-David, H. E., and M. Manning, "Distillation of Cellulose,
          Wood and Similar Substances Under Hydrogen Pressure With
          Catalyst",  Helvetica Chemica Acta, 8_, 900-923   (192S).

37.  Geerards, J. J. Th. M., 0. W. Van Kreuelen, J. F. Demkes; F. Meulenbeld,
          and H. I. Waterman, "Hydrierend Aufschlissung von Kohlenhydraten",
          Erdol und Kohle, 11_, 11-12  (1958).

38.  Glover, P. N., "United States Future Gas Requirements and Supply",
          Journal of Petroleum Technology, 1, 43-47   (1966)

39.  Goos, A. W.  "The Thermal Decomposition of Wood", Chapter 20,
          Volume 2, Wood Chemistry by L  E. Wise and E.  C. Jahn  (editors),
          2nd edition, Reinhold Publishing Co. New York  (1952).

40.  Grinnell, B. M., "Natural Gas at Any Price",  Journal of  Petroleum
          Technology, 22_, 937-940  (1970).

41.  Gurkui, H. H., "Catalytic Hydrogenation of Cellulose To Produce
          Oxygenated Compounds", U.S. Patent 2,488,722  (November  22,
          1949).  Chemica] Abstracts, 44:5590i   (1950).

42.  Haidegger, E., P. Isotvan, G. Istovan, and J. Karoi/i, "Production
          of Sorbitol by The 'Jse of Ammonia Gas",  Industrial and  Engineering
          Chemistry, Process Design and Dcv    "ent, 7_,  107-110   ^168)1
                                   121

-------
43.  Genze, H. R., B. B. Allen, and B. W. Wyatt, "Catalytic Hydrogenation
          of Cotton Hull Fiber", Journal of Organic Chemistry, 7, 48-55
          (1942).

44.  Heuser. E., "Kunstliche Kohle aus dea Holz dampfer",  Zeitschrift
          fur Angewandte Chemie, 26_, 393-396  (1913).

45.  Hodgson, R. L., "High Temperature Reactions of Iodine with Various
          Organic Compounds", Tetrahedron, 24(13), 4833-4838  (1968).

46.  Hodgson, R  L., "Hydroconversion of Coal with Combinations of
          Catalysts", Chemical, Abstracts, 73:37234n (1970).

47.  Hoffman, D. A., "Pyrolysis of Solid Municipal Wastes", Summary
          Report at Engineering Foundation Research Conference.
          Solid Waste Research and Development University School,
          Milwaukee, Wisconsin (July 23-28, 1967).

48.  Hurd, C. D., "Carbohydrate, Wood and Coal", Cahpter 11,  pp. 270-289,
          Pyrolysis o Carbon Compounds, The Chemical Catalog Company,
          Inc., New York, 1929.

49.  Ichikawa, M., M. Sudo, M. Soma, T. Onishi, and K. Tamaru, "Catalytic
          Formation of Hydrocarbons", Journal of_ The^ American Chemical
          Society, 91^, 1538-1539  (1969).

50.  "Iodine Catalyst Improves Coal Tar Hydrogenation", Chemical
          Engineer, 76_, 50  (1969).

51.  Jachh, W., "Problems of Hydrogenation of Coal", Erdol und Kohle,
          23, 334-337 (1970).

52.  Janardanaro, M., G. S. SaJvapati, P. Srikanthareddy and  R. Viadyeswarar,
          "Hydrocracking of Loi. Temperature Coal Tars.   I-  Hydrocracking
          of Low Temperature Cc  ' Tars Boiling in Tha Range of 230-280C
          Under Pressure", Erdo.  ^id Kohle. 23. 20-25  (1970).

53.  Jerman, R. I., and I.. R. Carpenter, "Gas Chromatographic Analysis
          of Gaseous Products from The Pyrolysis of Solid Municipal  Waste",
          Journal of_ Gas Chromatography, 6_, 298-301  (1968).

54.  Johanson, E. S., S- C. Schuman, H. Stotler, and R. H.  Wolk,  "Coal  is
          Catalytically Hydrocracked", Chemical Abstracts,  73_:57818j
           (1970).

55.  Kasehagen, L., "Hydrojjenolysis of Reducible Sugars  *o  Obtain  a High
          Percentage of Glycerol", U.S. Patent 3,396,199  (06  August
          1968).  Chemical Abstracts. 69j786C9z  (1968).

56.  Kilzer, F. J., and A.  Broido, "The Nature of Cellulose Pyrolysis",
          Pyrodynamics, 2(2-3) ,  151-163  (1965)   Chemical Abstracts,
          63:8599a  (1965).
                                   122

-------
57.  Knight, H. S. and S. Groennings, "Fluorescent Indicator Adsorption
          Method for Hydrocarbon Type Analyses.  Application To Traces
          and Heavier Distillates", Analytical Chemistry, 28,  1949-1954
          (1956).

58.  Krichko, A. A., "Catalytic Hydrogenation of Coal", Chemical -Abstracts,
          72;123747t (1970).

59.  Kurihari, K., and A. Yoshioka, Society of The Chemical Industry
          of Japan. 44_, 250  (1941).

60.  Layng, E. T., and K. C. Hellwig, "Liquid Fuels From Coal  by The
          H-Coal Process", Mining Congress Journal, 55_, 62-67  (1969).

61.  Lee, A. L., H. L. Feldkirchner, F. C. Schora, and J. J. Henry,  "Heat
          of Reaction of Hydrogen and Coal", Industrial and Engineering
          Chemistry, Process Design and Development, l_t 244-249  (1968)7

62.  Lindsly, R. R., "Review of U.S. Oil and Gas Production -  1965",
          Journal of_ Petroleum Technology, 18, 947-949  (1966).

63.  Matsukura, M., and A. Sukakibara, "Hydrogenolysis of Protolignin.   IV."
          Chemical Abstracts. 73_:26796w  (1970).

64.  Mullineaux, R. D., and J. D. Raley, "High Temperature Reactions  of
          Iodine and Hydrocarbons.  II.  Aroinatization",  Journal  of The
          American Chemical  Society, 85, 3178-3180  (1963).

65.  Ohta, M., and A. Sakakibara, "H' drogenolysis  of Protolignin.   III."
          Chemical Abstracts. 73_: 267.1?  (1970).

66.  Orpjiey, R. d., and R. I. Jerman, "Gas Chromatographic Analysis  of
          Liquid Condensates from The Pyrolysis  of Solid Municipal Waste",
          Journal of_ Chromatographic Science, , 672-674  (1970).

67.  Pepper, J. M., and Y. W. Lee,  "Lignin and Related  compounds.   I. A
          Comparative Study  of Catalysts for Lignin Hydrogenolysis",
          Canadian Journal of_ Chemistry, 4_7, 723-727  (1969).

68.  Peterson, Wm. E., "Hydrogenation ar.a Hydrogenolysis Products  From
          Bark Phenolic Acids", Master of Science  Thesis, Oregon State
          University, Corvalli,s Oregon  1964.

69.  "Plowshare Closer to Commercialization", Chemical  and  Engineering News,
          7_,  38-39  (1969).

70.  "Project  Gasoline in Final Development Stage", Chemical  and Engineering
          News, 45_, 96-98+  (1967).

71.  "Project  Rulison; more  Hope  for Success", Chemical  and Engineering
          News, 47_,  10-12  (1969).

72.  "Pyrolytic Decomposition  of  Solid  Wastes",  Public  Works.  99(8),
          82-83 and  160  (1968).

                                    123

-------
73.  Quader, S. A., and G. R. Hill, "Catalytic Hydrocracking; Hydrocracking
          of Low Temperature Coal Tar", Industrial and Engineering Chemistry,
          Process Design and Development, , 450-455 (1969) 

74.  Quader, S. A., and G. R. Hill, "Catalytic Hydrocracking, Mechanism
          of Hydrocracking Low Temperature Tar", Industrial and Engineering
          Chemistry, Process Design and Development, 8_, 456-461 (1969)

75.  Raley, J. H., R. D. Mullineaux, and C. W. Bittner, "High Temperature
          Reactions of Iodine with Hydrocarbons.  I.  Dehydrogenation",
          Journal of_ The American Chemical Society, 85, 3174-3178  (1963).

76.  Rieche, A., L. Redinger and K. Lindenhayn, "Hydrogenation of  Lignin",
          Brenstoffe Chemie, 47 (U), 326-330  (1966).

77.  Schlinger, W. G., and D. R. Jessie, "Hydrotorting Oil Shale",
          Industrial and Engineering Chemistry, Process Design and
          Development. 7_, 275-277  (1968).

78,  Schultz, E. B. Jr., and H. R. Linden, "From. Oil Shale to Production
          of Pipeline Gas by Hydrogenolysis",  Industrial and Engineering
          Chemistry, Sl_, 573-576  (1956).

79.  Slaugh, L. H., R. D. Mullineaux, and J. H. Raley, "High Temperature
          Reactions of Iodine with Hydrocarbons.  III.  Rearrangement  of
          Aliphatic Free Radicals", Journal of_ The American Chemical
          Society, 85_, 3180-3183  (19637!

80.  Storch, H. H., N. Golumbic, and R. B. Anderson.  The Fischer-Tropsch
          and Related Synthesis, John Wiley and Sons, Inc., New York  (1951).
                                                                    t
81.  Struck, R. T., W. E. Clark, C. W. Zielke, and  E. Gorin, "Kinetics of
          Hydrocracking of Coal Extract Wtih Molten Zinc Chloride  Catalyst
          in Batch and Continuous  Systems", Industrial and Engineering
          Chemistry, Process Design and Development, 8_, 546-551  (It/69).

82.  Szucs, M., "Hydrogenation of  Hungarian Coals in Oil Suspension",
          Chemical Abstracts, 50_:6019d  (1956).

83.  Texaco Development Corporation, "Purification  of Hydrogen  for Recycle",
          French Patent 1,562,026.  Chemical  Abstracts, 73_:27360m  (1970).

84.  "U.S. Moves Toward Fuel Crisis",  U.S. News, 69_, 26-28  (1970).

85.  Van  Ling,  C., and J. C. Vlungter,  "Catalytic Hydrogenation of Saccharides.
           II.   Formation  of  Glycerol", Journal  of Applied Chemistry,  19,  43-45
           (1969).

86.  Weinberg,  A. M.,  "Uranium and Coal; Rivals or  Partners'1, Mining Engineer,
           19,  46-49  (1967).
                                   124

-------
87.  Weinberg, A. M., "Uranium, Coal  - Rivals  or Partners", Mechanical
          Engineer, 89, 34-35  (1967).

88.  V.'illstatter, R., and L. Kalb, "Uber die Reduktion von Lignin und von
          Kohlenhydraten tnit Jodwasserstoffesaure und Phosphor",
          Chemische Berichtc,  55_, 2637-2653  (1922).

89.  Wolk, R. H., and E. S. Johanson, "Catalytic Fluidized Bed  Coal
          Hydrogenation", Chemical Abstracts,  73_:37233m  (1970).

90.  "World Deamnd to Reach 100 Million Barrels Per  Day  by 1990", World
          Oil, 170 61 (1970).

91.  "Process Converts Animal  Wastes  to Oil",  Chemical and Engineering
          News. 49(33). 43  (1971).
                                   125

-------
               "iF^
O\
                                                               7
     Figiire III. E. 1.  Gas Train for Analysis of the Head Gas from the High Pressure Reaction Apparatus.

-------
                                   H
Figure III. E. 2.  Carbon Monoxide Analysis System.
Figure III. E. 3.  Gas Chromatographic - Mass Spectrometric Analysis System.
                                   127

-------
                           Table III. E. 1.  Reaction Conditions and Products of Hydrogenations
                        Hydrogenation Statstics
Gaseous Products  (Moles/Mole of Cellulose)
Is)
co



Run
23
24
25
26
27
28
29
30
31
'3
o
*3
 *
*4
O

100
107.7
92.7
93.7
94.9
93.4
116.2
93.1
93.5
in
tn
rt

1000 H2
950 H2
None
950 H2
850 H2
1000 CO
None
None
None
t <
in
X
rt

rt

None
25 CH3I
None
None
25 HI
25 1% H2CO.
25 HI
50 H20
None
u
o
1
01
2
4
E-
370
355
395
375
350
j 350
370
365
400
4>
oa
o
ti
o
X
I
1.32
0.085
0.001
2.98
1.41
0.522
0.158
0.0

bon Monoxide
t->
at
CJ
2.42
0.663
0.001
0.332
0.175
1.45
0.219
0.171

bon Dioxide
t->
0)
U
0.398
0.405

0.955
0.750
1.02
0.560
0.595

rocarbons
^O
X

0.208
0.995
1.46
0.526
0.512
0.039
0.329
0.254


-------
     Table III. E. 2.  Showing the Amounts, in Grains, of Solid
Residue, Oil and Water Produced per Gram of Cellulose Hydrogenated
             Run      Residue      Water       Oil
23
24
26
27
28
29
30
0.347
0.341
0.316
0.179
0.318
0.585
0.392
0.157
0.236
0.175
0.374
-
0.069
0.107
'
0.013
0.066
0.135
0.079
0.008
0.016
                                129

-------
       Table III. E. 3.  Information Received from Standard Oil
                 Company Concerning A Sample of Oil
                    From The Hydrogenation of Waste.
     PROPERTIES	VOLUME PERCENT

Gravity, "API                                      31.3
  Specific Gravity, 60F                            0.8692
  Pounds per Gallon                                 7.24
Mixed Aniline Point, F                            90
Distillation, D-86, F
  Initial Boiling Point                           128 *F
   5% Recovered                                   170
  10%    "                                        208
  20%    "                                        263
  30%    "                                        300
  40%    "                                        326
  50%    "                                        354
  60%    "                                        380
  70%    "                                        405
  80%    "                                        430
  90%    "                                        465
  95%    "
  Dry Point
                                   130

-------
 Table III. E. 4.  Showing the Crudely Determined
; Material Balance of The Hydrogenation Reactions.
                 Material Balance












Run
23
25
26
27
28
29
30

c
H

e
o
rt
U
<4H
0
in
V
_o
3.70
.438
3.46
3.51
, 6.29
4.30
3.44

3
o

e
0
(4
rt
U
4-t
O
V)
O
1
4.81
.441
3.201
3.32
4.45
4.47
3.67
H

C
0>
00
s
a
S
<44
O

%
5.91
3.92
4.66
6.66
4.26
5.36
5.65
o

c

t>o
2
a
X
<
o
in
V
o

4.19
3.07
6.55
1.71
1.94
3.84

c
H

c
0
60
fr
0
SH
O
M
V
1
3.08
3.3?
2.8f
4.17
7.11
4.83
5.65

^
0

e:

>j
o
*w
o
tn
V
1
3.00
2.021
2.201
4.20
2.853
2.26
4.01
                        131

-------
Etherification

     Methyl, ethyl, benzyl, and other ethers of cellulose are important
in the production of textiles, cosmetics, medicines, films, and various
plastic objects.  For the product to be technically useful as a p - stic
item, it must regain a certain degree of hardness after being formed by
fluid or plastic flow.  Forming depends on applying the right conditions
of temperature and pressure to the cellulose ether, which must have been
formulated to give the desired properties to the product.

     Some cellulose ethers may be considered to be, in a sense, internally
plastici'ed by their constituents.  The degree of internal plasticizing
appears to be proportional to the size of the substituent group, and is
quite pronounced in the case of the benzyl ether of cellulose.  The higher
alkyl ethers appear to have an increasing degree of softness and yet
they exhibit an increasing tensile strength with the increased size of
the substituent group.

     The most common of the alkyl ethers of cellulose are ethyl and methyl
cellulose.  They are found in plastics, lacquers, sheeting, melts, varnishes,
adhesives, therapeutic eye drops, and cosmetics.  As plastics, they are
useful as both soft and rigid plastics because they are tough.  They find
uses in both molded and cast objects.  Some of the properties of methyl and
ethyl cellulose are shown in Table III. F. 1.  While varying degrees of
substitution change the solubility pattern of these compounds, they can
be made insoluble by crosslinking with bifunctional compounds such as:
citric acid, glyoxal, and dimethyl urea.

     Chemistry;  According to Ni! *in's interpretation (3:328-9) of the
work of several authors.  The mono-benzyl ether of cellulose is formed by
treating cellulose with 15-25% sodium hydroxide solution and heating at
1COC with benzyl chloride.  The use of 40-50% sodium hydroxide will form
the disubstituted product if the reaction is started in a less concentrated
base.  This reaction is completed in less than eight hours at 100C.
At 130C the reaction takes 2-3 hours.

     The benzyl cellulose has a softening point between 145 and 170C
(293-338F) depending en the properties of the product.  Benzyl cellulose
with a degree of substitution of 2.3 is used for the plastics industry  (3:330),

     The methyl ether can be made by treating soda cellulose with methyl
chloride or dimethyl sulfate  (4).  The ethyl ether is made by essentially
the same method (4).  For both ethyl chloride, b.p. 12.2C, and methyl
chloride, b.p. -24C, an autoclave is necessary to carry out the reaction
without loss of the halide.

     Mixed ethers have been prepared  (1) by treating soda cellulose with
mixtures of benzyl chloride and diethyl sulfate.  The product is suitable
for making filaments and films.
                                    132

-------
      Cyanoalkyl cellulose is prepared by treating soda cellulose with
 acrylonitrile (2).

      Carboxy ethers have been prepared (5) by treatment of soda cellulose
 with chloroacetic acid.

      Hydroxy alkyl  ethers have been prepared (6) from soda cellulose and
 ethylene oxide or chlorohydrin.  These compounds are used in coatings,
 extrusions, and binders  for pigments.

      Experimental Results:  Several samples of the benz>* ether of cellulose
 were prepared by treating soda cellulose with benzyl chloride under
 reflux (TM20C).  The soda cellulose was prepared by soaking the cellulose
 in 30% sodium hydroxide  aqueous solution for 1 hour.  Soda cellulose made
 from Whatman #40 filter  paper was treated with benzyl chloride for 2 hours
 to yield an orange  product.  This orange material was pressed at 300F,
 2000 Ibs/in^ for 4  minutes to form a hard disk without any indication of
 extrusion from the mold.  A second experiment was conducted with the reaction
 time increased to 6 hours.  Again the product was orange with an odor of
 aromatic compounds.  On  pressing, this mate-rial formed a yellow-brown
 translucent disk.

      Straw was treated to form the benzyl ether by the same method.  The
 reaction time was four hours.  The product was pressed at 32SCF for 4
 minutes at 2000 Ibs/in2  to form a hard fibrous disk.  From 10 grams of straw
 only 6 grams of product  were recovered.  The product from a second run
 using straw, when pressed at 325F for 2 minutes at 1000 Ibs/in^, tended
 to extrude from the mold.  Straw fibers were visible in this plastic.

      A sample of sulfuric acid lignin was treated with sodium hydroxide
 followed by benzyl  chloride in the same manner as noted earlier.  When
 pressed, the product was bonded but did not flow.  Fibrous particles were
 seen in this material also.

      A sample of glucose was treated in the same manner.  The product was
 a yellow liquid which would not crystallize.

      Discussion;  Several cellulose ethers are used commercially at present.
 If these are used for plastic molding or casting purposes there is reason
'to believe that the purity of the cellulose source does not have to be
 exceedingly high for many of these products.

      Pure cellulose, in the form of filter paper, appears to give a product
 in which the plastic properties can be controlled more easily than with
 the impure straw.  The benzyl ethers of sugars in the straw are thought to be
 the cause of the increased plasticity and flow properties of the second run.

      When glucose was treated, the benzyl ether was recovered as a yellow
 oily substance which would not readily crystallize.  Such a material could
 easily act as a plasticizer.
                                     133

-------
                              References
1.  Dreyfus, H., "Benzyl-ethyl Cellulose Ethers,"  Chemical Abstracts,
          17:2505'  (1923).

2.  Hutchinson, W. M., "Carboxycellulose Ethers,"  Chemical Abstracts,
          4:10319a  (1950).

3,  Nikitin, N. I., The Chemistry of Cellulose and Wood, Isreal Program
          for Scientific Translations, Jerusalem 1966.

4.  Ott, E., H. M. Spurlin, and M. W. GraffHn, "Cellulose and Cellulose
          Derivatives", Volume 5, Hi^h Polymer Series, 2nd edition,
          Interscience Publishers, Inc., New York 1954.

5.  Waldeck, W. F., "Carboxymethyl Cellulose",  Chemical Abstracts,
          44_:7538f  (1950).

6.  Ward, K., Jr., A. J. Morak, R. H. Giliespie, and M. H. Voelker,
          "Hydroxyethylation of Linters Pulps.  II.  Effect of Alkali
          Concentration,"  The Journal of The Technical Association of
          The Pulp and Paper IndustrieVTTappi)", 51(5), 2T8-Hi (19687.
                                    134

-------
            Table III. F. 1.  Some Properties of the Methyl

                     and Ethyl Ethers of Cellulose.


Ethyl

  Degree of substitution                     Property

     2.60-2.8                                  Soluble in hydrocarbons

     2.20-2.58                                 Thermoplastic; soluble in common
                                                 organic solvents

      .8-1.7                                   H20 soluble; difficult to control


Methyl

     2.4-2.8                                   soluble in polar organic solvents

     1.6-2.0                                   soluble in cold H20

      .1- .9                                   soluble in 4-10% of NaOH

  Made insoluble with crosslink by bifunctional compounds.
                                   135

-------
Oxidation of_ Cellulose

     Because of the similarity, in respect to chemistry, between dialdehyde
cellulose (DAC) and dialdehyde starch  (DAS), derivitives of dialdehyde
starch have been included in this report.  One finds upon examination of
the literature that most of the derivitive preparation has been done with
DAS, but structural examinations through infrared spectroscopy have been
carried out on DAC.  DAC and DAS seem  to undergo all of the reactions
typical of aldehydes.  DAS is commercially prepared by The Miles Chemical
Works using an electrolytic production of periodate.

     Several reactions of dialdehyde polysaccharides (DAP) with nitrogen
compounds have been studied.  Kuznetsova et al.  (23) reacted DAC in aqueous
solutions at room temperature during 24 hours, or at the boiling point of
the mixture in 4 minutes, to give a series of amino compounds.  Thermal
stability varied, but generally decreased in the following order:

          m - p - 0;2N)2C6H4 > N2H4 >  o - (NHp2 C^

The stricture of the products was determined to be
          tyHR
          C


  X\c_0/

      CH2OH
        la
Roqovin et al. (35) reacted DAC with aromatic amines to synthesize Schiff-Type
bases (Ic above) which were useful in preparation of chemically colored
cellulose fibers from various diazo compounds.  A patent  (39) exists
for the condensation of o-aminophenol with a dialdehyde.  This type of
compound is useful as tuberculostats and intermediates for the preparation of
medicines and dyes.

     Patents exist on the reactions of DAP with melamine  and other triazines.
The uses so far have been in papermaking.  These reactions impart wet
strength and dimensional stability to paper.

     Honeyman end Holker (18) reacted DAC with several amines and hydrazine
derivatives, but reported the reaction to be incomplete in all cases.
The products remained alkali sensitive making them of no  value to the textile
industry.  Material treated with urea was wrinkle and flame resistant, while
the thiosemicarbazide is resistant to attack by most fungi.

     DAC undergoes reaccion with the hydrazides.  With phenylhydrazine a
phenylformazan, He, is formed showing that the DAC reacted to give one
of the two possible hemi acetals, Ha and lib,  (28).
                                  136

-------
     Q'2
  A\
  /  o   V    ^ _ ^
     J   /     ^     ^
   C-J HC           
  OH      0                                                 /    
  OH        '                    0   OH                   OH   N-NHph

      Ha                            lib                      He
            Hemi-acetal forms                               formazan

     DAS has been left standing in liquid ammonia to produce a  compound
containing two nitrogen atoms per dialdehyde unit (40) .   The product  decomposed
on standing, because of the unstable nature of the a-amino  alcohol,  Ilia,
formed.  It is possible for the reaction


                  RCH(OH)NH2    "H2fc.. R  - CH = Nil

                      Ilia                 Illb

to occur.   From I lib one can obtain I He.

                  Illb
            3R  - CH = NH
     The dioxime of DAC is readily formed.   Reduction of the dioxime  gives
the aiaine, while dehydration gives the nitrile.   A literature search  has
not revealed the formation of the nitrile from DAC using the cyanide  ion.

     Rogovin (36) states that the diamino derivatives, from the reduction
of the oxime, can be used to initiate grafting of monomers, particularly of
the cyclic type.

     DAP acetals have been produced and are used in coating and laminating
applications.  DAP-phenol derivatives (29)  are used in resins and adhesives.
Several patents  (2, 3, S, 22) cover the production of dialdehyde polysaccharide-
urea resin.  These products have applications as adhesives, wet strength
agents for paper, and textile finishing agents.   The resin formed is
a thermo-setting resin.  A casein-DAS resin has been prepared and tested
for use as a plywood bonding agent (42).
                                  137

-------
     A general reaction of aldehydes with epoxides  (40) might be found to
be useful, since a patent covering aldehyde-epoxide copolymers formation  > '
using poly(hydrocarbyl aluminum) catalyst does e
-------
     The C02 yield and increased weight loss noted with increasing
degree of oxidation are considerably greater for periodic acid than for
metaperiodate oxidations  (7).  Periods of a week or more are necessary
for production of a high degree of oxidation in cellulose.  Acid
hydrolysis does not play an  important part in the oxidation of cellulose
by periodic acid.  The possibility of acid attack during the metaperiodate
oxidation is ruled out by the low hydrogen ion concentration in the
raetaperiodate solutions.

     The properties of dialdehyde cellulose are markedly different from
those of cellulose, for instance the strength of the dialdehyde cellulose
is slightly lower than that  of cellulose.  Periodic acid oxidized
cellulose shows an increased hygroscopicity over that found in cellulose.
Treatment of cellulose sheets with periodic acid results in pronounced
shrinkage in area, but increased thickness.  The introduction of two
aldehyde groups into the anhydroglucose unit of cellulose produces
considerable decrease in stability of the glucosidic bond to the action
of alkali.  All of these differences are brought about because the
periodate ion can penetrate  the ordered as well as the disordered areas
of cellulose to produce the  dialdehyde cellulose.  The production of
periodate oxidized cellulose can be found in references 14, 15 and 43.

     Preparation of metaperiodate solution is accomplished by adding
sodium hydroxide to periodic acid in the proportion of one mole of
base to one mole of acid, or by dissolving recrystallazed salt in
distilled water.  The final  solution used in the oxidation of cellulose
to dialdehyde cellulose is usually 0.1 Molar in metaperiodate.

Lead          Lead tetraacetate in glacial acetic acid oxidized glycols
Tetraacetate  to pairs of carbonyl groups at rates which were greater
for cis than trans configurations and were dependant upon the particular
glycol.

     Detrick (9) made a thorough study of the oxidation of wood pulps
by Pb(OAc)4 and found that there was a selective oxidation of mannose
units.  In addition, a smaller but significant removal of xylose units
occurs.  In his oxidation of pulp, Detrick treated dry pulp with acetic
acid at 50C to activate the pulp.  Preheated lead tetraacetate in
glacial acetic acid was then added and the reaction allowed to proceed.
Ten hours was found to be about the minimum reaction time.  The reaction
was quenched using a solution of potassium iodide, and sodiun acetate
in distilled water.  Quenching can also be accomplished using oxalic acid.

     The type of pulp used,  affects the length of time needed to reach a
certain level of oxidation.  A minimum of about seven hours is required to
reach 0.2 atoms of oxygen consumed per anhydroglucose unit.

     Abdel-Akher  (1) oxidized various polysaccharides using a lead tetraacetate
and sodium acetate solution.  The reaction Mixture was kept in the dark
at 25C for 15 - 45 days  with an occasional shaking and addition of
lead acetate.  The insoluble residue was removed by centrifugation,
Vashed with acetic acid,  water, ethanol, acetone, and ethyl ether, then
                                   139

-------
dried in vacu to give 88 - 95% partially oxidized polysaccharide.  With
cellulose he achieved 17.21% dialdehyde units.
     Vargha (41) states that red lead, Pb304, can be used in many cases
to replace lead tetraacetate.

Peroxydisulfate   Heidt (16), in a review article of the oxidation
of cellulose to dialdehyde cellulose, indicates four possible oxidants:
periodate, lead tetraacetate, peroxydisulfate, and perbismuthate.  At
the time of the article (1945) no work had been reported using peroxy-
disulfate.  A review of the literature by Menghani  (27) in 1969 indicated
that the oxidation of diols by persulfate had not been reported.  A
literature search has not turned up any reported work since that time.

     Rusznak, Kantouch, and Khalil (38) studied the oxidation of
cellulose with sodium persulfate at 50-70C, pH 4 - 10, and with solutions
of persulfate ranging in strength from 0.05 - 0.3 N.  The oxygen consumed
(determined by titration with acidic ferrous sulfate) in the oxidation
increased with increasing time, pH, temperature, and persulfate concentration.
At pH 8 and 70C, oxygen was released faster than the rate of oxidation
of cellulose with a subsequent evolution of oxygen.

     Work done by Menghani (27) indicates that in the oxidation of
ethanediol using persulfate with silver ion  as catalyst, the rate of
persulfate disappearance depends on both the persulfate and silver ion
concentrations.

     Oxygen causes an inhibition period with peroxydisulfate which is
dependant on the amount of dissolved oxygen present.

Perbismuthate  Perbismuthate is a rapid acting oxidizing agent, but there
is a drawback to its use with cellulose:  Perbismuthate is a relatively
insoluble brown powder, whose reduced form Bi(OH)3  is also poorly
soluble.  These properties render perbismuthate cf  little value for use
in oxidizing cellulose or other insoluble substances  (16).

Chromic Acid and    The early stages of the oxidation of cellulose by
Chromic Anhydride   chromic acid produces dialdehyde cellulose.

     Cotton oxidized by chromic acid falls into a powder when the oxygen
consumption reaches about 0.4 atoms per anhydroglucose unit  (8).  Chromic
acid oxidation does not lead to marked swelling as  does the periodate
oxidation.  Chromic acid confines its attack to the disordered regions of
the cellulose fiber.  It also leads to an increase  in hygroscopic ity
which is not as high as in the periodic acid oxidations.  Both chromic
acid oxidized and periodate oxidized cellulose show a decrease in tensile
strength, but in the latter stages of oxidation the chromic oxidized
cellulose has a much lower tensile strength  (32).
                                    140

-------
     Feher  (10) proposed an industrial application of electrolytic
oxidation with chromic acid of starch using the method of Mehltratter
and Wise (26), but found the method inconvenient.  He then proposed
the use of potassium dichromate in strongly acid medium.  The product
contained 60% dialdehyde and only 4-5% -COOH groups.

     Gladding and Purves (13) did an extensive study on the use of
chromic anhydride dissolved in acetic acid-acetic anhydride, and in
sulfuric acid, on cellulose.  The acetic acid solvent was found to be
more efficient in producing carbonyls and about 10 times faster than sulfuric
acid solution.

t-Butyl        Oxycelluloses containing aldehyde groups in the C-6
Chrpmate       position are prepared from cellulose or partially
substituted cellulose, at 20 - 70C, in an acetic anhydride solution of
of t-butyl chromate (37).  The fibrous products are white and stable
when stored in the absence of light and oxygen.  They are useful for
surface coatings and finishes on textiles through cross-linking reactions.

Hypobromite    Oxidation of cotton by hypobromite in concentrated alkaline
hypobromite solutions is non-selective and approaches wet conbustion  (11).

Hypochlorite   In alkaline solutions, where the effective oxidant is the
hypochlorite ion, the reaction is very slow and gives rise to an acidic
oxycellulose with little reducing power (43).  In mildly acidic solution,
pH 3 - 5, in which the effective oxidant is undissociated hypochlorous
acid, the reaction is again slow but gives rise to a highly reducing
oxycellulose containing fe* acidic groups.  In neutral solutions the
rate of reaction is at its maximum, and oxycelluloses with both acidic
and reducing properties are produced.

Hydrogen       Oxidation by hydrogen peroxide is essentially the same
Peroxide       as hypochlorite, but during the oxidation of cellulose
the glycol grouping at C-2 and C-3 are attacked simultaneously, resulting
in the formation of two aldehyde groups (43).

Nitrogen       Nitrogen dioxide is a more or less specific reagent which
Dioxide        oxidizes primary hydroxyl groups in cellulose to carboxyl
groups (31).  Cellulose may be oxidized by gaseous nitrogen dioxide,
by the liquid tetroxide, or by solutions of nitrogen tetroxide in inert
solvents.

Chlorine       Chlorine dioxide, in acid medium, does not react with
Dioxide        cellulose (31), however in any other media it leads to
oxidation of aldehyde groups to carboxyl groups.  This oxidation involves
both the terminal hemiacetal groups and aldehyde groups formed by the
oxidation of cellulose by other oxidizing agents.

     Experiment.   .esults:  There are several oxidative materials that
may be used to },.oduce dialdehyde cellulose.  For several reasons, we
elected to work with periodate, chromic acid, and persulfate oxidations
first.  Periodate oxidations are well documented and there is little
doubt that it is fairly specific for vicinal hydroxyl cleavages.  Nikitin
                                   141

-------
(31) does note however, that about 10% of the primary  (C-6) hydroxyls
are oxidized during the reaction.

     Basically, there are two ways of determining the  degree of oxidation
of the sample:  by measuring the fall in the concentration of the oxidative
material, or by reacting the carbonyl units in the product with a reagent
that is specific for such groups.  Neither method appears  ;o be
exceedingly accurate.  The decrease in oxidative agent does not mean
that only the aldehyde is formed nor are many aldehyde specific reagents
completely reacted because of the stereochemistry of the cellulose.
Hydrolysis of the cellulose to glucose units would obviously lead to
higher yields of oxime because of additional aldehyde  units available.

     Chromic acid oxidation is not as selective as the periodate method,
but a comparison was run using the method of Whistlor  (43).

     A comparison of our kinetics and those of Whistler was made.
Whistlers method was modified by buffering to pH = 5 by the addition of
acetic acid and sodium acetate for use with samples 1  and 2.  A large
discrepancy was found between the oxygen consumption and the amount of
carbonyl present by oxime formation for samples 1 and  2, Table III. G. 1.
An interesting phenomenon is the apparent increase in  periodate concentration
in the first two days.  This work was not repeated to  confirm this observation.

     The large amount of hydroxylamine consumed in oxime format  vn  ?or
samples 1 and 2 indicates oxidation of the C-6 carbon  probably took place.

     Table III. G. 2. contains the results of the persulfate oxidation
experiments.  Ammonium persulfate was used as the oxidizing agent, and
the reaction times ranged from 15 minutes to two days  using various catalysts.
The most noticable change was the loss of weight of the cellulose.
Oxime analysis indicates few carbonyl groups were formed.  The pH was
maintained at 2 except when a buffer was added.  At a  pH of 2 one
would expect hydrolysis of the cellulose to glucose which probably
accounts for some of the weight loss.

     The chromic acid hydrolysis was carried out using the method of
Whistler (43).  Figure III. G. 1. shows the oxygen consumption versus
the reaction time.  Table III. G. 3. gives the data from this work,
comparing the titrametric (oxygen consumption) analysis with the analysis
by oxime formation.  One can readily see that the data indicates carboxy
unit formation rather than carbonyl formation.

     Alkaline degradation of the oxidized cellulose was observed
when the pH was allowed to become too high during oxime formation.

     Discussion:  There are a number of oxidizing agents capable of
converting cellulose to dialdehyde cellulose  (DAC) or  carboxyl cellulose.
At present there are not enough uses known for this substance to justify
spending much time examining this process.
                                   142

-------
     The conversion of cellulose to DAC has many interesting possibilities
if the reaction rate could be increased to make the process economically
feasible.  DAC, made from waste paper, could possibly be used as the
basis for resins for water purification, for resins to be used by the
plastics industry, paint industry, and many other applications.

     Because of the long periods of time needed for the formation of
DAC, this material was only briefly examined in this laboratory.

     Cellulose peroxides were not examined, but hold a special interest
because of their potential use as initiators for graft polymerization.

     In general the formation of DAC was found to be better with the
periodates, as the literature suggested, than with other oxidizing agents.
However at present this does not look like an economically feasible
method for handling the large quantities of wastes necessary for the
solution of the problems of pollution in this country.
                                   143

-------
                              References


 1.   Abdel-Akher,  M.,  "Oxidation of Polysaccharides with Lead Tetraacetate",
          Journal  of Chemistry UAR, 6(1),  107-118 (1963).  Chemical Abstracts,
          63_:7090g (1965).

 2.   Borchert,  P.  J.,  "Preparation of Urea-Dialdehyde Starch Derivatives",
          U.S.  Patent  3,001,979 (September 26, 1961) (Miles Laboratories).
          Institute of Paper Chemistry Abstract Bulletin, 32_:41S5 (1962).

 3.   Borchert,  P.  J.,  "Dialdehyde Polysaccharide-Urea Resin Dispersions",
          Canadian Patent 691,461 (July 28, 1962) (Miles Laboratories).
          Institute of_ Paper Chemistry Abstract Bulletin, 35;. 3801 (1965).

 4.   Borchert,  P.  J.,  "Dialdehyde Polysaccharide-Acrylamide Derivatives",
          U.S.  Patent  3,100,203 (August 6, 1963) (Miles Laboratories).
          Institute of_ Paper Chemistry Abstract Bulletin, 34:9112 (1964).

 5.   Borchert,  P.  J.,  ''Dialdehyde Polysaccharide-Urea Derivatives",
          U.S.  Patent  3,177,250 (April 6,  1965) (Miles Laboratories).
          Institute of Paper Chemistry Abstract Bulletin, 36_:1971 (1965).

 6.   Cremonesi, P., and L.  D'Angiuro, "Graft Copolymerization of Methyl
          Methacrylate on Cellulose Initiated by Catalytic Decomposition
          of Cellulose Peroxides", Cellulose Chemistry ami Technology,
          3(6). 599-611 (1969).  Institute of Paper Chemistry Abstract
          Bulletin, 4Jjl933 (1970).

 7.   Davidson,  G.  F.,  "The Progressive Oxidation of Cotton Cellulose by
          Periodic Acid and Metaperiodate Over a Wide Range of Oxygen
          Consumption", Journal of The Textile Institute, 32, T109-T131
          (1941).

 8.   Davidson,  G.  F.,  "The Progressive Oxidation of Cotton Cellulose by
          Chromic Acid Over a Wide Range of Oxygen Consumption",
          Journal of_ The Textile Institute, 32_, T132-T148  (1941).

 9.   Detrick R. W., "The Oxidation of ICCA Pulps With Lead Tetraacetate",
          The Journal of_ The Technical Association of The Pulp and Paper
          ImTustrTlTappi), 45(7), 654-638 (1960).

10.   Feher,  I., "Oxidation of Starch to Dialdehyde Starch", Bor-es
          Cipotech, 11(21. 33-36 (1961).  Chemical Abstracts, 55_:25305a
          (1961).

11.   Fossen, P. V., and E. Pacsu, "Cellulose Studies.   III.  Hyperoxidation
          of Cellulose with Concentrated Sodium Hypobromite Solutions.
          A Simple Method for The Determination of Hypobromite and Bromate
          Ions in The Presence of Each Other", Textile Research  Journal,
          16, 163-170 (1946).
                                  144

-------
12.   Frostick, F. C. Jr., and B. Phillips, "Resins From 1,2:5,6
          Diepoxycyclooctane", U.S. Patent 3,065,209  (November 20, 1962).
          Chemical Abstracts, 5:P10357b (1963).

13.   Gladding, E. K., and C. B. Purves, "Estimation of Carbonyl Groups
          in Chromic Anhydride Oxystarch and Oxycellulose by Means of
          Hydroxylami-ne", Paper Traded Journal, 116(4), 26-31 (1943).

14.   Guthrie, R. D., "The Dialdehyde from Periodate Oxidation of Carbohydrates",
          Volume 16, pp. 105-157, Advances in Carbohydrate Chemistry,
          Academic Press, New York, 1961.

15.   Head, F. S. H., "Effect of Light on The Reaction Between Periodates
          and a-glycols", Nature, 165, 236-237 (1950).

16.   Heidt, L. J., E. K.Gladding, and C. B. Purves, "Oxidants That Promote
          The Dialdehyde Cleavage of Glycols, Starch, and Cellulose",
          Paper Trade Journal, 121(9), 35-43 (1945).

17.   Hobart, S. R., C. H. Mack, and C. P. Wade, "The Wrinkle Recovery
          Properties cf Acethyhrazide Disulfide Crosslinked Dialdehyde
          and Dialcohol Cottons", Textile Research Journal, 36(1),
          30-27 (1966).

18.   Honeyman, J., and J. R. Holker, "Some Derivatives of Periodate
          Oxycellulose", Textile Rundshau, 16, 561-570 (1961).
          Chemical Abstracts, S6_:5000h  (1962).

19.   Ide, F., and M. Nakatsukak, "Graft Copolymerization of Dialdehyde
          Starch", Chemistry of Hi.gh^ Polymers  (Tokyo)  (Kobunshi Kagaku),
          21(225), 49-56 (19647.  Institute of_ Paper Chemistry^AbstracY
          Bulletin, 3S_:1800  (1964).

20.   Imperial Chemical Industries Ltd., "Bis(amidinohydrazones)",
          British Patent 819,587 (September 9, 1959).  Chemical
          Abstracts, S4_:P3513c  (1960).

21.   Imperial Chemical Indsutries, Ltd., "Cellulose Derivatives",
          British Patent 1,081,732  (August 31, 1967).  Chemical
          Abstracts, 67;P110241v (1967).

22.   Kuznetsova, N. Y., G. A. Timokhiva, and V. I. Ivanov, "Amino
          Derivatives of Cellulose", U.S.S.R.  Patent  203,665 (October 9,
          1967).  Chemical Abstracts, 68_:96946r (1968).

23.   Kuznetsova-Lenshiva, N., G. A. Timokhiva, N.  Zhavoronkov, and V. I.
          Ivanov, "Synthesis and Structure of  Some Nitrogen Containing
          Derivatives of Dialdehyde Cellulose", Chemical Abstracts,
          70:5300c  (1969).

24.   Livshits, R. M., and I. A. Rogovin, "Synthesis of Graft Copolymers
          Using Pentavalent  Vanadium",  Institute of Paper Chemistry
          Abstract  Bulletin, 33:1801  (196271
                                  145

-------
25.  Marvel, C. S., and II. W. Hill, Jr., "Polyazines", Journal of The
          American Chemical Society, 72_, 4819-4820 (1950).

26.  Mehltratter, C. L., and C- S. Wise, "An Electrolytic Process for
          Making Sodium Periodate", Industrial and Engineering Chemistry,
          5JU 511-514 (1959).

27.  Mehghani, G. D., and G. V. Bakore, "Kinetics of Oxidation of Ethanediol
          by Peroxydisulfate Catalyzed by Silver Ions", Zeitschrift fur
          Physikalische Chemie, 241(3-4), 153-159, (1969).

28.  Mester, L., "The Formazan Reaction in Proving The Structure of Periodate
          Oxidized Polysaccharides", Journal of_ The American Chemical
          Society, 7T/.5452-5455 (1955).

29.  Miles Laboratories Inc., "Dialdehyde Polysaccharide-Phenol Derivatives",
          British Patent 932,657  (July 31, 1963) Institute of Paper
          Chemistry Abstract Bulletin, 34_: 7367 (1964).

30.  Muratora, U. M., A. Yuldashev, R. V. Perlina, M. I. Ismailova, and
          Kh. U. Usmanov, "Reaction of Dialdehyde Cellulose with
          Trialkyl Phosphites", Institute of Paper Chemistry Abstract
          Bulletin, 4:8673  (197077^

31.  Nikitin, N. I., The Chemistry of Cellulose and Wood, pp. 155-179,
          Israel Program for Scientific Translations  Ltd., Jerusalem,
          1966.

32.  Ott, E., and H. M. Spurlin, Volume V, Part 1, pp. 165-167,
          Cellulose and Cellulose Derivatives, Interscience Publishers
          Inc., New York, 1954.

33.  Puzyrev, S. A., E. Ya.  Pechko, B. B. Gutman, and A. E. Gushchin,
          "Oil and Oil Filters", Chemical Abstracts,  66_:48154t  (1967).

34.  Roches, P., and G. Edel, "The Action of Semicarbazide and of
          Thiosemicarbazide  on Cellulose Oxidized With Periodic Acid",
          Institute of_ Paper Chemistry Abstract Bulletin, 33:1806  (1962).

35.  Rogovin, Z. A., N. A. Yashunskaya, and V. Bcgslovski, "Preparation
          of Chemically Dyed Fiber", Chemical Abstracts, 46_:4235g  (1952).

36.  Rogovin, Z. A., L. S. Galbraikh,  and A. I. Polakov, Encyclopedia
          of_ Polymer Scicr :o and Technology, 3_, 291-306  (1964).

37.  Roth, C. B.,  "Oxycelluloses", U.S. Patent 2,758,111  (August 7,  1956).
          Chemical Abstracts, 51:713g  (1957).
                                   146

-------
38.  Rusznak, I., A. Kantouch, and M. Khalil, "Reaction of Cellulose
          and Peroxydisulfates", Kolpr Ert, 10(1-2), 38-49 (1968).
          Chemical Abstracts, 68;96724s (1968).

39.  Schafer, W., R. Wegler, and Domagk, "Anils of Dialdehydes",
          (Farbenfabriken Bayer Akt-Ges.)> German Patent 1,007,729
          (May 9, 1957).  Chemical Abstracts, 5:21812b (1959).

40.  Sloan, J. W., B. T. Hofreiter, R. L. Mellies, and I. A. Wolff,
          "Properties of Periodate Oxidized Starch", Industrial and
          Engineering Chemistry, 48(7), 1165-1172 (1956).

41.  Vargha, L., "Red Lead as a Selective Oxidant", Nature, 162,
          927-928 (1948).

42.  Weakly, F. P., M. L. Ashby, and C. L. Mehltratter, "Casein-
          Dialdehyde Starch Adhesives for Wood", Forest Products
          Journal, 15(2), 51-55  (1963).

43.  Whistler, R. L. (editor) "Cellulose", pp. 164-180, Volume  III,
          Methods Iii Carbohydrate Chemistry, Academic Press, New York,
          1963.

44.  Yashungkaya, A. G., N. N. Shorygina, and Z. A. Rogovin, "Preparation
          of Dialdehyde Cellulose and Its Esters", Chemical Abstracts,
          44_:835i (1950).

45.  Zenftman, H., and D. Calder, "Difluoraminated Dialdehyde Cellulose
          and Nitric Acid Esters Thereof", U.S. Patent 3,426,013
          (February 4, 1969).  Institute of_ Paper Chemistry Abstract
          Bulletin, 39:9853  (1969).
                                    147

-------
             140
         in
         8   120
         1-4
         tie
         o
         o
         i
         *j
         0)
         C
         oo
         g
         I
         s
         oo
             100
              80
              60
              40
              20
                            1          2345

                                         Time (days')
Figure III. G. 1.  Showing  The  Oxygen Consumption With Time in The Chromic
                   Acid Oxidation of Filter Paper.
                                   148

-------
                 Table III. G. 1.  Periodate Oxidation


Sample I    lOg filter paper; 1 N NaI04; 1 liter of soln; 2/7/72-2/17/72

            20 mis of HOAc-NaOAc buffer pH 4.

  Days         123456789    10

Oxygen
  Consumption      1.8  6.9 11.1   -    -  21.4   -  24.7  25.7

% Conversion
  (Oxime)                                                 >100%


Sample II   20g paper; 5 N NaK>4; 1 liter of soln; 2/7/72-2/17/72

            20 nls of HOAc-NaOAc buffer pH 4.

Days           1    23456789    10

Oxygen
  Consumption            .9  2.6       -   7.8   -   9.9  10.8

% Conversion
  (Oxime)                                                 >100%

                                                               i

Sample III  20g paper; S N NaI04; 1 liter of soln; 2/8/72-2/21/72

            no buffer

Days           1    2    3    4    S    6    7    8    9    10    11    12    13

Oxygen
  Consumption 2.9  5.0  6.4   -    -   9.2   -  10.6 11.2	13.2

% Conversion
  (Oxime)                                                                    77%
                                    149

-------
Time (min)
    Table III.  G.  2.   Persulfate Oxidation
      pH  Catalyst     % Conversion  Weight Loss (gm)
20
30
60
120
2 days
120 min
120 nin
15
30
2
2
2
2
2
2
2
4
4
Ag
Ag
Ag
Ag
Ag
Fe*
_
Ag+
AE*
                                         0
                                         0
                                         0
                                         6.2

                                         0
                                         0
                                         0
                                         0
                                             0
                                             0
                                             0
                                              .3
                                              .1
                                              .33
                                             0
                                             0
                                             0
Days
   Table III. G. 3.  Chromic Acid Oxidation


lOg paper: 30gm Na2Cr207 5 11 mis cone. H2S04 per liter; 2/4/72-2/9/72

   1234
Oxygen
  Consumption

% Conversion
  (Oxime)
        -  92.6 136.8


                 15
                       150

-------
Pulping of_ Straw


     For many years straw was pulped in this country, and in other countries
it is still pulped.  Why is straw no longer used for pulp in this country?
Some sources say that the straw pulp mills would not modernize, while this
did not impair the quality of the product, tha cost per unit of product was
forced upward until these mills priced themselves out of existence.  Others
say that straw storage is too much of a problem.

     With our forests being depleted the time has come to re-evaluate straw
and waste paper as a source of pulp.  If this pulp is unsatisfactory for
paper it may still be satisfactory for cardboard cartons, chemical inter-
mediates, or wrapping paper.

     The Institute of Paper Chemistry (9) has compiled a bibliography listing
articles and books covering cereal straws as a source of cellulose for paper-
making.  The original publication has been supplemented twice  (7)  i8). These
articles are primarily concerned with papermaking and not with growing,
harvesting, economics, or extraction of the straw.

     Straw can be pulped by nearly any pulping process, however, these are not
necessarily economical.  The high silica content of straw can cause problems
in boilers, while the low bulk density can reduce equipment capacity.

     Straw lignins can be removed from the cellulose by nitric acid pulping
or by the soda process.  Laboratory evaluation has shown that both of these
methods are effective in producing pulp from grass seed straws.  A third
method, holopulping (5), which is supposed to have less pollution than the
Kraft process has not been investigated yet.

     Chemistry:  Th- re are several methods available for pulping cellulosic
materials, among these are the sulfite process, the sulfate  (Kraft) process,
soda process, nitric acid process and the holocellulose process.

Nitric Acid    The nitric acid pulping process  (1), (2),  (3),  (4) consists
Pulping        of treating straw with hot nitric acid to oxidize and nitrate
the lignin.  The lignin is then dissolved by a dilute sodium hydroxide solu-
tion.

     In the laboratory bentgrass and fescue straw treated with 10% nitric acid
at 70C for 1 hour followed by a 2% sodium hydroxide treatment for 1 hour at
90C resulted in 29% and 30% pulp respectively.  Three similar runs with
annual ryegrass resulted in an average yield of 26%.  Because  less concen-
trated acid should result in less degradation, a series of runs were made to
determine the effect of nitric acid on the pulp yield.  The alpha cellulose
content of the pulp from each run was measured.  These results are shown in
Table  III. H. 1., and Figure III. H. 1.   As expected, the pulp yield increased
with decreased acid concentration.
                                  151

-------
     Linear extrapolation to zero nitric acid concentration indicates that
sodium hydroxide alone should result in a 41.5% yield of pulp with 83.5% alpha
cellulose.

Sodium         In a series of runs straw was pulped in IN, 3N, and 6N sodium
Hydroxide      hydroxide at 70C for 1 hour.  The resulting pulp yields were
Pulping        38.5, 38.2 and 35.7% respectively.  Another sample was treated
with IN sodium hydroxide for 2.5 hours at 70C.  The pulp yields for all runs
are shown in Table III. H. 2.  The 6N sodium hydroxide treated straw became
gummy and hard to handle.

     The Forest Research Laboratory of The School of Forestry at Oregon State
University then did some additional work with straw using the "Soda Process"
(4).  They reported yields between 50% and 60% using 16% (4N) chemical.  The
tensile, burst, and fold strengths compared favorably with the commercial
soft wood Kraft papers.

     Discussion!  As stated earlier, pulping can be accomplished by the use
of one of several methods.  The "soda process" has been shown to be satisfactory
for making pulp from straw.  Because the use of sulfur compounds has been
eliminated there is practically no smell to mills using the soda process.
The holopulping process which was not examined in this laboratory reportedly
(5) is more economical than the Kraft process.

     The main drawbacks to using straw are all expressed in economic terms. The
information from pulping of grass seed straws is minimal.  More work in this
area, improved techniques for handling and storing straw, and the dwindling
forests may soon bring straw back into the field of pulp production.
                                  152

-------
                              References
1.  Brink, D, L., "Pulping Process Studies. I. Aspects of an  Integrated
          Nitric Acid Pulping Process,"  Journal of The Association of
          Pulp and Paper Industry, 44(4). 256-262~7l96l") 

2.  Brink, D. L.; Vlamis, J.; and Merriman, M. M., "Pulping Process Studies.
          II.", Journal of The Association of Pulp and Paper  Industry. 44(4)
          263-270 (1961)

3.  Brink, D. L.; Merriman, M. M.; and Schwerdtfeger, E. J.,  "Pulping
          Process Studies. III."  Journal of the Association  of Pulp
          and Paper Industries, 4Jj](457~315-326~Tl9625

4.  Bublitz, W. J., "Pulping Characteristics of Oregon Seed Grass Residues.
          I."  Journal of The Association of Pulp and Paper Industries, 53(12),
          2291-2294 (1970):

5.  "Holopulping to Cost Chemicals Market," Chemical and Engineering News,
          47(21), 30-32 (May 19, 1969).

6.  Kalisch, John H., "Nitric Acid Pulping. A New Rapid-Cycle Process,"
          Journal of_ The Association of Pulp and Paper Industry, SO(12),
          44A-51A (19675".

7.  Roth, L., and Weiner, J.  Papermaking Materials, I_. Cereal Straws, The
          Institute of Paper Chemistry, Appleton, Wisconsin,  Bibliographic
          Series, Number 171, Supplement 1 1963.

8.  Roth, L. and Weiner, J.  Papermaking Materials. I_. Cereal Straws, The
          Institute of Paper Chemistry, Appleton, Wisconsin,  Bibliographic
          Series, Number 171, Supplement II 1968.

9.  West, C. J., Papermaking Materials. JL Cereal Straws, The Institute of
          Paper Chemistry, Appleton, Wisconsin Bibliographic  Series, Number
          171  (1949)
                                  153

-------
     45
     40
 4)
 H
(X
r-4
3
     35
     30
     25
                                  4           6


                                  Nitric Acid (%)
                                                                     10
Figure III. H. 1.  Showing The Reduced Yield with  Increased Acid

                   Concentration During Nitric Acid Pulping.
                                   154

-------
    Table III. H. 1.  NITRIC ACID PULPING OF ANNUAL RYEGRASS  STRAW





Run                                  A       B      C         D
Wt. Dry straw, gms.
Concentration HN03, wt. %
Reaction time at 80C, hrs.
Concentration NaOH, wt. %
Dissolving time at 90C, hrs.
Wt. Pulp, gms.
Pulp yield, dry basis, %
Alpha cellulose, %
Beta cellulose, %
Alpha cellulose yield, %
Table III. H. 2
NaOH
Run Cone. (N)
1 1
2 3
3 6
4 3
100.0 100
7.5 4
1 1
2.0 2
1 1
31.5 35
31.5 35
85.5 84
10.4 9
26.9 30
Sodium Hydroxide
Cooking
Time (hr.)
1
1
1
2.5
.0 100.0 100.0
.8 3.8 2.9
1 1
.0 2.0 2.0
1 1
.9 36.8 37.3
.9 36.8 37.3
.5 84.7 84.5
.4 7.6 8.1
.3 31.2 31.5
Pulping of Straw
Cellulose
yield (wt. %)
38.5
38.2
35.7
42.5
100.0
1.9
1
2.0
1
39.2
39.2
84.0
8.0
32.9







                                  155

-------
                           PILOT PLANT STUDIES
 Economic and Engineering Analysis

      Each year industry produces thousands of products which are useful in
 society, but when they lose their usefulness they become solid waste, which
 must be transported to a disposal site.  In the the early years of our
country, when the population was sparce, it was easy to find disposal
 sites.   Today serious waste disposal problems exist because disposal sites
 are no  longer readily available and the amount of waste is increasing be-
 cause of our increased population and our convenience packaging of consumer
 goods.   Improper disposal methods have contributed to environmental pollution.
 It is essential that we develop and utilize acceptable waste management
 systems.

      One alternative to the present method of burial and burning is
 reutilization of our wastes.  A large portion of our wastes should be
 treated as raw materials for the production of new, usable products.  Using
 solid wastes as raw materials would conserve our natural resources, and at
 the same time reduce the amount of waste that needs disposal.

      Although the main economic factors of the reutilization processes
 are the Capital Investment and The Total Product Cost, other economic factors
 to be considered when waste is involved include:  resource conservation,
 social  resistance to change, industry survival, and environmental pollution.
 These factors will be discussed in relation to a process designed to use
 waste straw to make a solid particleboard through isocyanate crosslinking.

      Crosslinking:  Straw, the hollow stalks or stems of some agricultural
 crops,  is a solid waste of agriculture; more specifically, in Oregon,
 straw is a solid waste of the grass seed and cereal industries.  When
 the grass seed or cereal grains are harvested, the straw is normally
 left in the field.  When the straw is not subsequently removed, a reduction
 in crop yields usually occurs the subsequent year.  Straw can be removed
 by bailing or by tilling (plowing under) with two exceptions; perennial
 crops are not tilled for the life of the stand, and .some heavy clay soils
 inhibit the normal degradation processes,  (undecomposed straw has been
 unearthed after 2 years of burial).

      In the mid 1940"s when blind seed fungus  (Glocotima temulenta) was
 infecting 90% of the perennial ryegrass crop of Western Oregon, open field
 burning was recommended as a field sanitation measure  (1).  Burning proved
 to be effective in controlling disease and served as an inexpensive means
 of residue disposal.  In addition, burning served to kill weed seeds on
 the soil surface, reduce fertilization requirements, increase seed yields,
 reduce fire danger, partially control insects and rodents, and release
 minerals back to the soil.  This practice was later adopted for other crops
 as well, until in 1970, approximately 300,000 acres were burned.
                                    156

-------
     The major disadvantage of open field burning is that it contributes to
air pollution.  According to a study by Boubel (1), particulate emissions
average 15,6 Ib/ton of fuel burned.  Carbon monoxide, hydrocarbons, and
nitrogen oxides are also produced.  Normally, these products would be dis-
persed in the upper atmosphere, but meterological studies have revealed
that the climatic conditions in the Willamette Valley are not always
conducive to smoke dispersion (3:23).  During these times, particulate and
gaseous emissions are held near the ground, resulting in decreased visibility
and increased human annoyance.

     The increasing acreage and tonnage of crop residue being burned,
coupled with the increase in population and the limitations of natural
atmospheric ventilation in the Willamette Valley, have led to a legis-
lative decision to ban field burning after January 1, 1975.  This decision
will necessitate the development of alternative cultural practices for
field sanitation if Oregon is to retain its position as a major world
supplier of grass seeds.  In 1968, Oregon produced 41% of all U.S. grass
and legume seeds on 308,000 acres at a sales value of $31 million.  Eighty
one percent of this was produced in the Willamette Valley.  Virtually all
of the U.S. ryegrass production is from 134,000 acres in the Willamette
Valley.  This yield has a value of nearly $13 million (2).

     A state supported research program is being conducted at Oregon State
University to develop alternative cultural practices to replace open field
burning.  One alternative is the use of a mobile field sanitizer, a machine
capable of burning crop residues with less resultant air pollution, but
the physical removal of some of the straw will probably be required.  The
industrial utilization of this straw for the production of useful products
will conserve a natural resource, provide an acceptable disposal method, and
could provide the farmer with an economic return to help defray the added
costs of straw removal.  Denmark  (4) has studied the production of a straw
particleboard, and since straw particleboard is one product with potential
for industrial utilization in home construction and finishing, furniture,
and decorative articles, this process is being studied at Oregon State
University as part of a research program supported by the Environmental
Protection Agency, State of Oregon, and Oregon Seed Council.

Engineering    This analysis is designed to identify the major factors
Factors        that contribute to the total product cost.  A capacity of
100 tons/year of product has been selected to provide information for a
small pilot plant.  This size of plant could be operated by tv/o employees
using readily available equipment and the product could be used to evaluate
physical properties and to determine market potential.  Operative information
could be used for scale-up analyses.  Since it is anticipated that modifica-
tions will be proposed to reduce both capital investment and total product
cost, this analysis is presented as a starting point for the development-
of a process to utilize .-aste straw.

     A schematic design of the process is shown in Figures  IV. B. 1. and  IV.
B. 2.  The plant would be constructed in a 40' x 40' steel building on a
concrete pad.  Adequate storage area is available for the year's supply of
straw.
                                   157

-------
     The straw will be removed from the field and stored in 50-pound ha?as,
held with 2 strands of wire or string.  The straw will be fed into a nri.l.
The milled straw will be carried by air to a cyclone separator where the
straw will be collected and the air will pass out of the top carrying the
fines.  The fines will be collected in a bag.

     If drying is required prior to the resin application, the straw will
be fed through a dryer and into a rotary mixer for the resin application.
Scales will be used to determine the resin concentration.  Liquid resins
such as polyisocyanates, U. F., and P. F. will be applied by spraying with
compressed air.  Solid resins such as acrylics or bakelite will be physically
mixed prior to pressing.  The straw/resin mixture will be pressed into a
solid particleboard with a heated platen press.  The density and size of
the board will be determined by the quantity of straw used and the pressure.
The board will be cut to finished size with a saw and a finish coat will be
applied if desired.  The waste material will be returned to the mill for
recycling.  The finished product will be stored for later utilization.

     The following equipment is readily available for utilization in the
plant with a capacity of approximately 100 tons of product/year.

     A hammermill of the type similar to a Ward's Model 6A hammermill with
a changeable screen is adequate for reducing the straw particle size.   It
has an approximate capactiy of 150 pounds/hour.  The straw is carried by
air to a cyclone separator where the chopped straw is collected.  A cloth
bag can be utilized to filter the dust from the air.  Approximate cost,
$260.00.

     The dryer may be a rotary drum, fluid bed, or tray dryer, a more
economical way of drying might involve circulating hot air through the
cyclone separator.  The heater, fan, and ducts could be fabricated for  less
than $50.00.  The dryer is left out of this schematic because laboratory
experimentation indicates that for some resins, the presence of water
vapor is not detrimental.

     The mixer can be any one of several types of commercially available
ribbon blenders or rota-cone blenders with sprayers which can be used to achieve
a good spray coating of resin on the straw particles.  This equipment is
availabJe in both small and large sizes but a suitable size for this plant
would cost approximately $5,000.00.  Continuous resin application would
be possible using a Day Centri-Flo mixei which can process over 600
pounds/hour.

     A direct reading scale would be utilized to determine the resin con-
centration.  Since batch sizes would be approximately 5 pounds or multiples
thereof and resin concentrations could vary  from 5 -  10%, a 10-25 Ib. scale
with 2 ounce markings or 0.1 pound markings would be needed.  Only one
scale would be needed with a container for transferring the straw from  the
cyclone to the mixer and from the mixer to the press.  Approximate cost,
$50.00.
                                   158

-------
     An automatic hydraulic press with heated platens 24.5 inches square
wouldfFe ideal for producing a 24 inch square board, however, the cost would
be over $8,000.00.  Manual presses are not available as a stock item at this
size.  Although normally a one-opening press, alterations could be made to
convert it to a multiple opening press in order to increase its capacity.

     A small table saw could be used to cut the boards to finished dimension;
approximate cost, $50.00.  The waste scraps would be fed back into the process
at the mill.  The finished product would be stored for transportation to a
sales center or for utilization in making straw particleborrd products.

     The equipment mentioned here would be useful for a manually operated
batch pilot plant.  A study of the results of variations in process variables
on the properties of the product could be conducted, and the design
for a larger automated plant could be established.  In addition,
a market study could be conducted to determine the market value of the
product.

Economic       The  industrial utilization of straw would be greatly
Considerations enhanced if a profitable process could be developed.
Profitability depends primarily on the cost of processing and the value
of the product.  It is important to identify the contribution that the
various aspects of processing make to the total cost so that efforts can
be made to reduce the total cost of processing.  It is also important to
identify the value of the product in its most likely applications.  This
may necessitate the production of finished products for retail sales
evaluation.

     A sample estimation of fixed capital investment and total product
cost for a 100 ton/year pilot plant using polyisocyanate resin is given
in Table IV. B. 2. and Table IV. B. 3.  No additional equipment would be needed  to
produce boards with other resins.  This plant would be manually operated
by two men.                                                                       ;

     Indirect costs and general expenses are estimated based on the assumption
that this plant would be a part of a larger business enterprise requiring
some supervision and overhead expenses.  If, for example, ten such plants
were located near grass seed farms to reduce transportation costs, super-
vision, clerical, sales, and maintenance support could be shared.  These          
costs, then are listed at 1/10 of the total estimated cost for the larger
business enterprise.

     The plant would be operated for 8 hours/day and 250 days/year. Since
capacity is rated at 200,000 pounds of product/year, the average daily
production rate would be 800 pounds or 100 pounds/hour.

     The unit production cost is estimated at $0.15/lb product or $4.80
for a 4' x 8' x 1/4" r-heet with a density of 48  lb/ft-3.  If the press
could be modified into a multiple opening press with no change in capacity
or operating cost, the cost for a sheet 4' x 8' x 1/8" could be reduced
to $2.40.
                                   159

-------
     The value of a straw particleboard made with polyisocyanate resin
has not been determined as yet, however, it has general appeal for use as
decorative interior home paneling.  The cost of wood paneling ranges from
$2-8 for a 4* x 8' x 1/8" panel depending on quality and finish.

     The value of straw particleboard for utilization in lamination or
furniture construction is difficult to estimate without a market survey
using actual samples, however, it is presumed that consumer acceptance will
be sufficient to establish a value higher than the estimated production
cost, even though the margin of profit will be low at this production rate.
The unit production cost could be lowered by automation and by increasing
plant capacity through the use of larger machines since operating labor
accounts for 47% of the total product cost.  The use of lower resin concen-
tration or a different, less expensive resin, assuming no change in physical
properties, would make a slight reduction in the production cost since resin
costs account for 15% of the production cost.  The cost of the straw accounts
for only 6i of the cost of the product.
*
Resins         In the laboratory, six different resins have been received
Examined       in order to evaluate the preparation of a solid board from
straw; bakelite, acrylic, transoptic powder, phenol-formaldehyde, urea-
formaldehyde, and isocyanate.  The resin cost and the physical properties
of the product will be important factors in developing an industrial process.

     Bakelite is a synthetic resin made from formaldehyde and phenol.  It
was obtained in solid form and was ground to a powder prior to utilization.
Four colors have been used; black, red, green, and amber.  The powdered
resin and milled straw were physically mixed prior to pressing at 350F.

     Acrylic resin was obtained as a ground-up white solid.  Physical
mixing and pressing at 350F produced a solid board.  The resin becomes
transparent as it fuses.

     Transoptic Powder, a finely ground solid, initially becomes fluid
as it is heated under pressure.  Continued heating of a straw/powder
mixture produces a solid board.  This resin also becomes transparent upon
fusion.

     Phenol-formaldehyde is one of the resins used in wood particleboard
manufacture.  It is normally sprayed onto the particles in a water solu-
tion.  The water is driven off during the heating and pressing cycle when
the phenolic compound and the formaldehyde polymerize.

     Urea-formaldehyde is also used in wood particleboard manufacture.
It is sprayed onto the particles in a water solution.  A low pH is needed
to trigger the polymerization reaction and since wood contains acid groups
it is a very effective resin when used with wood.  Since straw appears to
be neutral, it may not be as effective without adding an acidic compound.
                                   160

-------
     Polyisocyanate resins are used in conjunction with polyalcohols in the
production of polyurethane plastics.  It was initially surmised
that the cellulose of straw could be utilized as the polyalcohol and
that a solid product should result if a polyisocyanate resin were mixed
with straw particles and heated under pressure.  The term polyisocyanate
includes both diisocyanates and polyisocyanates in this report.

     Since the polyisocyanate resins are liquid at room temperature, they
can be sprayed onto the straw particles.  Solvent application  is also
possible using DCM, acetone, toluene, or benzene.

     A list of the resins obtained for straw particleboard formation is
provided in Table IV. B. 1.
                                    161

-------
                              References
1.  Boubel, R. W., E. F. Darley, and E. A. Schuch, "Omissions From Burning
          Grass Stubble and Straw,"  Journal of the Air Pollution Control
          Association, 19_, 497-500 (1969^.

2.  Middlemiss, W. E., and R. 0. Coppedge, "Oregon's Grass and Legume Seed
          Industry in Economic Perspective," Cooperative Extension Service,
          Oregon State University, Corvallis, Oregon, Special Report 284,
          April 1970.

3.  "Research Relating to Agricultural Field Burning," Agricultural Experi-
          ment Station and Air Resources Center, Oregon State University
          Corvallis, Oregon, February 1971.

4.  Personal Communication:  Finn Rexen, Forskningsinstituttet for Handels-
          O.G.  Industriplantcr; 6000 Kolding, Holbergsvej 10, Denmark.
                                   162

-------
                                                          Waste

Wire
or
String
i

Baled
Straw
i

1^

i  	 1- 	
Fines | Resin Water
' Water ! | ^
t i i
Size ) Product
Reduction *" Drying 7"*" Mixing * Formation *" Finis

;hing
i
Figure IV.  B.  1.   Block Diagram Showing  the  Particleboard Process.

-------
      Straw Bales
         Wire
                                                         Waste
                           Fines
                        Bag
\  /
 \  /
   
          Air
         I"-	t      i
         LZ3=TT=
Cyclone       I  I
Separator     I  I

              Liquid
              Resin
                   wywwwvi
                   Rotary
                    Mixer
                                                                      t    ,,,  -3
                                                                                                Saw
                    Mill
                                        Scales
                             Scales
                                                                              Press
                                                           1
                                                                                                Storage
Figure IV,  B.  2.  Schematic  Diagram of Straw Particleboard Plant.

-------
 Table IV. B. 1.  Resins Used in The Laboratory Study of Straw Particleboard
Identification Used
In This Report	
      Chemical Composition
Vendor
Bakelite
Acrylic
Trans-optic powder
PF
UF
TKI
PAPI
Isonate 125M
MR
MRS
Phenol-formaldehyde                     Buehler
Polyacrylic esters                      duPont
                                        Buehler
Phenol-formaldehyde                     Borden
Urea-formaldehyde                       Borden
Tolylene 2,4 diisocyanate               Aldrich
Polymethylene polyphenylisocyanate      Upjohn
Diphenylmethane diisocyanate            Upjohn
4,4 diphenylmethane diisocyanate        Mobay
4,4 diphenylmethane diisocyanate        Mobay

      (others available)

dianisidine diisocyanate                Carwin
tolidine diisocyanate                   Carwin
Hexamethylene diisocyanate              Mobay
m-xylyene diisocyanate                  Carwin
2,4 tolylene diisocyanate               Allied
4,4' diphenylmethane diisocyanate       duPont
                                    165

-------
      Table IV.  B.  2.   ESTIMATION OF FIXED-CAPITAL INVESTMENT COST

                                  Dollars
  Plant Description:

  Capacity:
Straw Particleboard - Pilot Plant

100 tons/year product
  I.   Direct Costs

      A.   Equipment                                            21,510
          1.  Purchased Equipment                       13,410
              a.   Mill w/motor           260
              b.   Cyclone separator       40
              c.   Dust collector          10
              d.   Scale                   50
              e.   Mixer w/sprayer      5,000
              f.   Press                8,000
              g.   Saw                     50
          2.  Installation (35% P.E.)                    4,700
          3.  Instruments 6 Controls (6% P.E.)             800
          4.  Piping (10% P.E.)                          1,300
          5.  Electrical (10% P.E.)                      1,300

      B.   Buildings                                             5,200
          1.  Steel Building 40' x 40'  w/concrete pad    4,000
          2.  Doors, Windows, etc.                       1,200

      C.   Service Facilities n/a

      D.   Land                                                    200

 II.   Indirect Costs

      A.   Engr. fi Supervision  (1/10 of 10% D.C.)                  270
      B.   Const.  5 Contractor Fees  (10% D.C.)                   2,700
      C.   Contingency (5% F.C.I.)                               1,600

III.   Fixed Capital Investment

 IV.   Working Capital (10% T.C.I.)

  V.   Total Capital Investment

   Peters, Max. S., and Timmerhaus, Klaus D., "Pilot Design and
      Economics for Chemical Lngineers", P. 140, McGraw-Hill,
      New York, 1968.
                                                 26,910
                                                  4,570
                                                  31,480

                                                   3,500

                                                  34,980
                                     166

-------
            Table IV. B. 3.  ESTIMATION OF TOTAL PRODUCT COST1

                                  Dollars


  Plant Description:      Straw Particleboard - Pilot Plant

  Capacity:               100 tons/year product


  I.   Manufacturing Cost                                                    27,660
      A.  Direct Production Costs  -..                               23,780
          1.  Raw Materials                               6,240
              a.  Straw ($15.00/ton)   v  1,740
              b.  Resin ($0.45/lb)        4,500
          2.  Operating Labor (2 men)                    14,000
          3.  Supervisory  Clerical (10% of O.L.)        1,400                  x
          4.  Utilities                                   1,400             ,..-'"'
              a.  electricity             1,200
              b.  phone                     100
              c.  water                      50
              d.  waste disposal             50
          S.  Maint., S Repairs (1/10 of 10% F.C.I.)         310
          6.  Operating Supplies  (0.5% of F.C.I.)            ISO
          7.  Laboratory Charges  (1/10 of 20% O.L.)          280
          8.  Patents  Royalties (assume none)
      B.  Fixed Charges                                             2,380
          1.  Depreciation                                1,440
              a.  equipment (10% P.E.)    1,340
              b.  buildings (2% value)      100
          2.  Taxes  (2% F.C.I.)                              630
          3.  Insurance (1% F.C.I.)                          310
          4.  Rent  (n/a)
      C.  Plant Overhead (5% T.P.C.)                                1,500

 II.   General Expenses                                                       3,080
      A.  Administrative Costs (1/10 of 5% T.P.C.)                    180
      B.  Distribution and Selling (1/10 of 10% T.P.C.)               300
      C.  Research and Development (1/10 of 5% T.P.C.)                150
      D.  Financing  (7% T.C.I.)                                     2,450

III.   Total Product Cost                                                    30,740

          Unit Cost  $30,740      =  $0.15/lb
                     200,000 Ibs.

   Peters, Max S., and Tinunerhaus, Klaus, D., "Plant Design  and  Economics
      for Chemical Engineers", P. 141, McGraw-Hill, New York,  1968.
                                     167

-------

-------