Note: Descriptions are shown in the official language in which they were submitted.
CA 02085513 2001-08-14
RESOLE RESIN PRODUCTS DERIVED FROM
FRACTIONATED ORGANIC AND AQUEOUS CONDENSATES
MADE BY FAST-PYROLYSIS OF BIOMASS MATERIALS
CONTRACTUAL ORIGIN OF THE INVENTION
The United States Government has rights in this invention under
Contract No. DE-AC02-83CH10093 between the United States
Department of Energy and the Solar Energy Research Institute, a Division
of the Midwest Research Institute.
BACKGROUND OF THE INVENTION
1. FIELD OF THE INVENTION
The invention relates to the production of phenolic type
resole resins from biomass materials and, more particularly, to the
treatment of fast-pyrolysis oils derived from lignocellulosic materials to
make phenolic type resole resins. Specifically, the present invention
relates to taking phenolics/neutrals fractions (PIN) and rendering them
suitable for the production of phenolic type resole resins, subsequent to
obtaining said fractions from fast-pyrolysis oils derived from
lignocellulosic materials.
2. DESCRIPTION OF THE PRIOR ART
Adhesive resins such as resoles are utilized in a wide
variety of applications, inclusive of which is the bonding of wood layers to
manufacture plywood, and a variety
~~~~~ ~...'~
~L composite boards. However, certain disadvantages axe I
t
attendant to existing techniques fox manufacturing these
. i
different types cø phenolic resins,
For ~xample, phenol has bean traditionally derived
from petroleum-based products; however, the prod~.xctian of
petroleum-bas~:d phenol is quite expensive, and efforts ~.n the
industry in recent years have been to at least partially
substitute the phenol in such resins with inexpr~nsive phenols
derived from wood~based products or extracts. More
specirically, phenols derived from bark, wood chips and the
like havs~ bean looked at as a potential substitute for
petrol~um-based phenol in such res~.ns.
The pyrolysis of biomass, and in particular
lignocellulosi.c materials, is known to produce a complex
1.5 mixture of phenolic compounds, In naturQ, lignin acts as an
adhesive to bind the cellulose fibers togethEr. Therefore,
lignin and lignin-derived material Erom wood would appear to
be a natural starting point fox the development of biomass-
based adhesive resins. sourc$s for such phenolic materials
as include black liquor from kxaft pulping and other pulping
proaessas, wher~ the lignin is present in a stream which is
commonly burned to recover praaess heat and chemicals.
Unfortunately, these lign~.ns are generally not vary
reactive after recovery far a variety of reasons, such as high
25 molecular weight, chemical modification during recovery due to
condensation reactions and the lik~, and lack of
reproducibility cg properties. Various types of pyro~.ysis
2
proces~aes have also been utixized, frequently yielding similar
kinds of results; however, fast-pyrolysis, Which proC:eeds at
temperatures between about, 450°C to about X00°C and has short
vapor residence times in the ox-der of seconds has net been
used.
Fast~~py'ralysis of biomass features the
depolymerization of cellulosic, lignin, and hemicellulo$ic
polymers which p~'oduces an oil having a relatively low
molecu7.ar Weight and which has con$iderable chemical activity
1,p under proper conditions. Crude pyrolysis oil apparently
undergoes a limited amount of repolymerization due to
condensation. Hovrever, the thermal stability of fast-
pyralysis oils at room temperature is qualitatively guita good
imparting a gioad shelf life for the oils, although at 100°C
g5 the crude oils solidify overnight. Solidified pyrolysis oils
axe characterized by their low strength and brittlenass. 'fhe
potential of pyrolysis products for use in adhesive resins is
not a new concept, as indicated above, but the efficient and
Cost-affective reduction of th us approach to practice has been
20 an elusive goal over many years.
The gel~eral approach of producing phenols from
biomags has previously been to purify the phenolic fraatiana
present in the pyrolyeis oils by the use of solvents to
part~.tian the constituents by differences in solubility and
~5 reactivity. different variations of salvente, reagents, and
sequence of extractions have been developed in the past, and
this has resulted in different partitioning coefficients for a
' _
~~~~~~3
couple of hundreds of chemical comp~uhds kridwn to be in
pyrolysis oils, and therefore produced extracts having
differing relative compositions. Another significant
difference between various reseaxah efforts pertaining to this . .
area in the past has been the type of pyxolysis process used
to produce the ails used as feed 'in the extraction process.
xhese include updraft gasification, entrained fast-pyr4lysis,
ana fluidized bed fast-pyrolysis, all at atmospheric
pressures, as well as slow, high pressure liquefaction
1p proaesses~ In addition, both hardwoods and softwoods have
been used as faedstock in the past for the oil farming
processes. These differences in extraction and pyrolysis
processes, coupled with the differences in feedstock, yield
different materials as products. Thus, the usefulness of a
particular extract as ari adhesive component is quate
different, one from the other.
U.S. Patents No. 4,209,647 and 4,223,465 disclos~
methods for recovering phenolic fractions from oil obtained
fram pyrolysis of licjnocellulosic materials and the suhseqvaent
use of that fraction in making of phenol-formaldehyde resins.
However, these processes use pyrolysis oils which are usually
formed at i1.1-defined temperatures and which have undergone
phase separation cracking and soma condensation, and suffer
from very low yigldg.
Zg ~ number of other patents including U.S. Patents No.
2,172,415, No. 2,203,x17, No. 3,469,354, No. 3,309,356 and No.
4,508,BB6 as well as ~apaness Patent No. 38-16895 all disclose
_ 4 _
~~~~~z~ j
a variety of processes far recovering phenolic fractions from
oils derived from biomass materials and derived resources such
as wastes. These processes vary in the particular procedures
and technique: utilized to ultimately separate the phenolic~
fractions as well as the procedures utilised to derive the~~o'il
from the biomass ox' other feed material. Koweverd they all
have a~ common thread linking them in that the ultimate end
product is a phanolio fraction, which is dessired tQ be as pure
as possible. This phgnolic fraction is then utilized to
produce phenol-formaldehyde thermosetting resins. The phenol
substitutes usually were slower than phenol derived from
petroleum-based products. The complex procedures disclosed in
these references to produce relatively pure phenolic fractions
are not particularJ,y economical. Thus, there is still a need
L5 for a process designed to produce pyrolysis oils from
lignocallulosic materials and then extract a phenolic
composition from such oils which is capable of functioning as
efficiently as petroleum°basad phenols in the formation of
phenol-formaldehyde. resins and which is less expensive to
produce,
$nbIM.ARX OF THE TD1VENTION
Accordingly, it is one object of the present
invel7tion to provide phenolic type resole xes~.ns, it1 which 'the
phenol content is i.n part replaced by a phenolic°aompounds~
ac~ntair~i.ng/nautral fractians (P/N) from fast pyrolysis oils
derived from lignocelXulosic materials.
Another c~b~ect of the present invention is to
provide inexpensive adhesive compositions comprising pherioliC
type resole xesing, in whi,-ch the phenol content is in part
replaced by a p/N fraction from fast-pyrolysis oils derived
from lignoceXlulosic materials.
p,nother object of the pr~sent invention is to
provide phenolic compounds-~c~anraining/neutxal fractions
extract, wherein the neutral fractions have molecular weights
of prom 10a-800.
1p The foregoing and other objects in accordance with
the present invention, as embodied and broadly descri)aed
herein, i.s accomplished by: admixing said ails with an organic
solvent having a solubility parameter of approximately 8.~-9.1
[cal/cm3~~~ polar components in the ~..8-3.0 range and hydrogen
bonding components xn the 2-4.8 range; separating the organio
solvent-soluble fraction containing the phenolic compounds-
containing/neutral fractions Erom said mixture and admixing it
with water ts~ extract water--saLuble materials therefrom
separating the organic solvent-soluble fraction from said
z0 water fraction and admixing said sa~.vent fraction with an
ac(ueous alkali metal bicarbonate solution to extract strong
organic acids and highly polar compounds from said solvent
fractions and separating the residual organic solvent soluble
fraction and removing the organ~.c ~sal.vant therefrom t4 produce
said phenolic campounds/neutral fractions extract,
Ths obae~cts in accordance w~.th the present
invention, ass embodied and broadly dagcribed herein, Can
~ P .
a . . . . . . ~ . ..
CA 02085513 2001-08-14
further be accomplished by: admixing said oils which contains organic
and aqueous condensates with basic materials in a relatively dry, solid
state, which basic materials may be selected from the group consisting of
sodium hydroxide, sodium bicarbonate, sodium carbonate, sodium
sesquicarbonate, potassium hydroxide, potassium bicarbonate, potassium
carbonate, ammonium hydroxide, ammonium bicarbonate, ammonium
carbonate, lithium hydroxide, lithium bicarbonate, lithium carbonate,
calcium hydroxide, calcium carbonate, magnesium hydroxide, magnesium
carbonate, hydrates thereof, or mixtures thereof, and chosen to be able to
neutralize acidic components of the condensates and to render such
acidic components and other polar compounds less soluble in the organic
phase; admixing said neutralized condensates with an organic solvent
having at least a moderate solubility parameter and good hydrogen
bonding capability, said organic solvent has a solubility parameter of
approximately 8.4 to 9.1 (cal/cm3)~ with polar components in the 1.9-3. 0
range and hydrogen bonding components in the 2-4.5 range, utilizing said
solvent to extract phenolic-containing and neutral fractions from the
organic aqueous phases into the solvent phase; separating the organic
solvent-soluble fraction having the phenolic-compounds-containing and
neutral fractions from the aqueous fraction; and removing the organic
solvent therefrom to produce said phenolic-compounds-containing and
neutrals compositions in a form substantially free from said solvent.
-7-
J
~~'~~~::~3
s~ar~ DESCR~rx~xorr os xx~ n~nwaNaa
The accompanying drawi.~xgs which are incorporated in
and form a part of the specification illustrate preferred
embodiments oP the present invention, and together with the
description, serve to explain the principals of the invention.
In the drawings:
Fig. 1 ie a flow diagram l~llustrating the process of
the present invention
Fig. 2 is a graph illustrating shear stress strength
of resin adhesives produced using the phenol and P/N end
products og the present invention compared to a commercial
product; and
Fag. 3 is a graph illustrating wood failure test
results of xesole adhesive resins produced using the phenol
and P/N and products of the process of the present invention
compared to a commerai.al adhesive product.
Fig. 4 is a graph Showing the time/texnperatuxe
relationship for the preparation of resole reins according to
one aspect of the invention.
Fig. 5 is a gx'aph showing the time/temperature
rela~.i.onship for the pxeparatian of resole xesins aGCOrding to
another aspect of th~ invention.
Fig. ~ is a graph of gel times far rasoles.
Fig, 6 is a graph of gel times for regolee versus
thermal treatment severity.
CA 02085513 2001-08-14
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
During the course of studying the problem of producing
inexpensive but effective phenolic compositions from biomass, it was
discovered that certain polar organic solvent having at least a moderate
solubility parameter, moderate degree of polarity, and good hydrogen
bonding capabilities were capable of extracting both phenolic compounds
and neutral fractions from fast-pyrolysis oils. Moreover, it was discovered
that this extraction technique was equally effective for fast-pyrolysis oils
of
differing starting materials. Thus, it was discovered that the present
invention may be utilized with pyrolysis oils derived from redwood, pine
sawdust, bark, grasses, softwoods as well as certain hardwoods with very
little differences in the final results.
Apparently, the fast-pyrolysis process preserves the delicate products in
monomeric and oligomeric states. A key factor in the process of the
present invention is that the oils derived from the lignocellulosic materials
must be done so utilizing a fast-pyrolysis. Fast-pyrolysis is generally
known in the art, and such a technique has been specifically disclosed in
an article entitled, "Production of Primary Pyrolysis Oils in a Vortex
Reaction", American Chemical Society Division of Fuel Chemistry
Preprints, Vol. 32, No. 2, pp. 21-28 (1987). Thus, details of such fast-
pyrolysis techniques need not be specifically repeated and disclosed
herein. Oils from other fast-pyrolysis concepts are
_g_
also good fesdstocks. Such concepts are referenced in "Fast-
Pyrolysis of Pretreated Wood and Cellulose", Ibidem, pp. 29-35
(198?), a»d "Preliminary Data for Scale up of a 8iamass
Vacuum 1?yrolysis Reactor", Ibidem, pp. 12-20 (198?}; "The Role ,
of Tempasatura in the Fast-Pyralysis of Cellulose and Wood",
industrial Engineering chemistry ~tesearch", Vol. 27, pp. 6-15
(1988), and "Oil From Bioms.ss by Entrained flow Pyrolysis",
Biotechnology and Bioengineering symposium, No. 14, pp. 15-20
(1984).
7.0 in general, in such fast-pyrol.ysis the particulate
biomaas~ solids enter tangentially at high velocities into a
vortex reactor tube which has an internal surfaoe design that
guides the centrifuged spuds into a tight helical pathway on
the reactor wall. This results in a very high heat transfer
Z5 to the wood or other feedstock particles which allows mild
cleavage of the polymeric components of the faedstock.
Conseg~lently, high yields (greater than 55%} of dry woads and
bark oils are generally obtained. Xf the feedstock is not
fully pyrolyzed, the solids enter a recycle laop located at
20 the end of the vortex reactor. After attrition to a powder, ,
char part~.c~les elute with the vapor stream and are isolz~tad in
a char cyclone The PjN sam~al.es numbers L-30 were produced
using th~.s concept of fast pyxolysis with steam or nitrogen as
carrier gas for the process.
25 Alterrlativs methods to produce primary pyrolysis
oils thought to be similar to fast-pyrolysis include fast-
pyrolysis in f luidized beds and in entrained flow reaatars.
-.10
3~
bne example utilizing a fl.uidized bad reactor to
produce a P/N material is sample #~1, as shown in Table III.
a fluidized bed was operated at 2.~ kgJh and was heated by hot
gases. P/N sample #31 was produced with a South Boston
Southern pine feed, under conditions similar to those of
samples #17 and #20, and the reactor was operated by
circulating recycled gases instead of the steam used in the
fast pyralysi.s reactor.
Examples utilizing oils from an entrained glow
1o reactor are P/N samples #32 and #33, as shown in xable IxI.
An entrained flow reactor operating at 3o kg/h was heated
using sand as the heat transfer medium to generate two samp7.es
fron Maple I and II, which were produced using different
residence times in the reactor. These samples were prepared
1.5 in the low thermal severity range, as these ranges are known
to be employed for the production of flavor compounds that
provide oornmerGialiy useful fXavor extracts. In this
pyrolyzer, recycled gases from pyrolysis are exec used instead
of steam as carrier gases.
2o Utilizing the process of the present invention, the
pyrolysis oils are fractionated in a unique way which produces
a combined phenalics and neutral fraction of high phenolio
hydroxyl and aldehyde content. In genez'al, a polar organic
solvent is added to the oils to s$paraGe the phenol and
25 nautrt~l fractions from Said oils. The organic solvent-soluble
travtion is then admixed with water to extract water-~soluh7.e
materials, and then further w2~shad with an aqueous alkali
° - X1 -
~~~~~~z~
metal Bicarbonate so~.ution to extract strong organic acids and
highly polar' oompounds. 1'he residual argania solvent-soluble
fraction containing the phenol and neutral. fractions is than
~.solated, and the organic solvent is removed, preferably by
evaporation, to produce a phe~nolic compounds-containing
composition having most of the phenolics and neutral fractions
of the oxiginal raw oils. The yield of the phenolics and
neutrals fraotion in the extract is about 30~ of the fast-
pyrolysis oil derived from sawdust and about 50~ of the o~.l
derived from bark.
In prior art phenol-producing processes, the
procascas ended only after the phenolic-containing
compositions were generally reduced to purified phenolics
only, with the neutral fractions also being removed. 8y
neutral fractions, it is meant those compounds which are flat
solubilizad by a strong base such a.s sodium hydroxide, and
have molecular Weights of approximately 100-800. such neutral
fractions include carbonyl compounds, furfural-type compounds
and the like. ~t was apparently previously believed that such
neutral. fractions must also be extracted in order to provide a
phenOliGS composition which may be utilized as a substitute
for petroleum based phenol in the production of phenol-
formaldehyde adhesive resins. xt has bean discovered,
however, that by utilizing the process of the present
invention, the resultant composition containing both phenolics
and neutral fractions function dust as well as and in same
aspects better than a relatively pure phenol composition in
Z2 -
the production of phenol-formaldehyde resins because, since
the compositions have aldehyde groups, mucr~ less forma~.dehyda
is needed to make these formulations. Reduced formaldehyde
levels lead to minimization of potential environmental
problems. In addition, the economics are such that, it is
substantially less e~cpensive to manufaoture the combined
phenolics and neutral. fraction composition. Maxeover, by
utilizing the entire Erection whioh includes phenolic
compounds and neutral compQUnds as feedstocks for resins, it
1p was found that this prevented the pyrolysis~derived reactive
phenalics from undergoing air oxidation under alkaline
conditions, which is what prevails when one isolates and
purifies the phenolics fraction alone. This latter air
oxidation which can be a problem is a type of condition that
15 prevails in many prior art techniques and is accomplished by
ar:l-x acta~~!-.. sri th aquc~ouc ~nri> »m hyr3rnxi r7P fiAl Ut 1 One . end
a~:companied by tho ~o~rmatx.on of insoluble tars and reduced
yields of phenolios.
Znvestigat~-one of the fractionation scheme of the
Zp pxesettt invention as genez'ally desori,bed above utilizing pine
fast-pyrolysis oils were carried out employing a number of
different solvents to determine the preferred and optimum
solvents and the requirements thereof. In general, the whole
oil was first dissolved in the organic solvent preferably in
an oil:solvent ratio of 0.5:1'to 1:3 Jpy weight. The oi9~ was
initially fi~.ltared to separate char which is carried over from
the pyrolys~.s reactor operations. Upon standing, the ,
,.. . , . . , ..' ~. 3 ~ - , . . . ~ ,
~~~~ ~:~3
salvent/oil mixture then aeparat~as into two phases, the
solvent-soluble phase and the solvent-insoluble phase.
One require~ment~for the argania solvent is that the
solvent and water exhibit low mutual solubi:Xity. pxef~rab~.y,
acceptable solvents include these with solubilities that are
not mare than about 1.o grams of solvent in 100 grnms of water
and about 3 grams of water in 100 grams solvent, in terms of
mutual solubility. xhus, this solvent requirement eliminates
all lvw-molecular-weight alcohols (methanol, ethanol,
1b propanol.) that axe infinitely soluble in water, mathyl-
ethylketone, the carboxylic acids (formic, acetic and
propionic) which area infinitely soluble ih water, and ma~thyl
form2~te. The classes of solvents that would be acceptable
only from a pure mutual. solubility paint of view include
a.5 hydrocarbons (aliphatic, aromativ), higher alcohols (greater
than G carbon atoms), higher ketones (greater than 5 carbon
atoms), esters (greater than 2 carbon atoms), atherg,
polychl4xinated hydrvcaxbons, and higher nitrites (greater
than 4 carbon atoms).
20 Another requirement for the organic solvent which
further limits potential candidates is that the solvent must
have a low boiling p4xnt or a law-boiling point axeotrope.
The preferred boiling point is around 100°G, although thi: is
,, , somewhat relative. Yet another~requirament for the oxganic
25 s4lvent is that the solvent have some degree of polarity,
preferably high polarity, as well as high hydrogen bonding
capability in addition to a moderate-ta-good,solubility
.. , . . . .. ;.. , ~ '. . .. lq ,-., ...:: , .,. . .,
~~~'J ~~.
parameter. The salubility parameter is defined as a measure
of all 'the intermolecular forces present in the solvent. They
overall solubility parameter is aompogad of camponentfi due to
dispersive forces, polax Forces (caused by a high dipole
moment in the molecule), and hydrogen bonding capability.
These three-companent Hansen parameters are determined in
accordance with an axticle commencing on page 141 of the "CRC
Handboak of Solubility pararceters and Other Gohasion
Parameters" by Allan F.D2. Sarton, 1983. Solubility
parameters, maasures in [cal/cm~~'~, range from 5-7 fox
hydrocarbons and nanwpolar solvents, to 14.5 for methanol and
z3.4 For water-highly polar substances. Thus, low boiling
point ethers, such as diethyl ether, are excluded from being
prefexrgd solvents since they have very low solubility
parameters (7.4j and very low polar components (1.4).
Hydrocarbons are also excluded as preferred solvents beaa~ase
of thair very low polar components and ovarall low solubility
parameters.
It has been found that the preferred group of
solvents For use in the present invention include acetate and
propionate esters, methyl alkyl katones and ethyl alkyl
kaCanes. More speoific.preferred organic solvents are listed
below in Table Z, the most preferred being ethyl acetate due
to its availability, relatively~low solubility in water, arid
high oil solubility. The most preferred range fox solubility
parameters includes 8.4-9.1 with polar components in the 1.8-
3,0 range and hydrogen bonding components in i:he 2.4-5 xange.
15 :. . ,.
2~~~~~,~
Additional acceptable solvents are the isomers of those listed
in Table 1. Mixtures of esters arQ also acceptable as are
mixtures of the higher ketones. .Ternary solvent systems.also
are possible, primarily mixtuxas of estate and high molecular
s weight ethers such as diisopropylether to reduce the boiling
point, T3owavor, the moa preferred solvents for use with the
present invention era ethyl acetate, as indicated above, as
well as butyl acetate and methylisobutylketone.
B I
Methyl Ethyl
Ace er s Ketones ~$.~ona
a te ~sr
~ _~
Ethyl Propyl Butyl i-autyl i-Amyl i-PropylEthyl
Property 1 102.1 116.2 100.2 114.2 86.14 86.14
88
Mol. Wt . 101.5 126.1 116.5 144 92 102.0
Boiling Point, 77.1
C
(at 760 rnmHg)
90 0.89 0.8$ 0.80 0.88 0.81 O.B1
0
C .
Density, @ 20
Heat Vaporization,
kcal/mole (20C) 84 9.3 10.4 10.00
73 06
7 8
kcal/mole (b. 7.71 820 8.58 8.50 . .
p.)
solubility, wt%
08 2.3 0.43 1.7 "0 '2 2.4
8
in water . 3.9 1.86 1.9 "0 '2 2.6
94
2
Watsr in .
Azeotrope
47 i4 28.7 24.3 44.0 24
9
Water wt% . 82.2 90.2 87.9 94.? B2.9
boiling point, 70.38
C
Dielectric
02 6.00 5.01 13.11 17.0
5
Constant .
Solubility param.
1 8.4 8.46 8.57 s.55 8.5 8,8
9
Total . 6.6 7.67 7.49 ?.80 "7.8
44
7
pispe7csive comp.. 2.4 1..B 3.0 2.8 '3.4
6
2
Polar comp. . 4.8 3.1 2.0 2.0 2.0
4
5
~i-Honding comp. .
As indicated above, the preferred solvent is ethyl
aCatate, and the process of the present ~.nvention will
hereinafter be described in farms of utilizing ethyl acetate
as the solvent. However, it should be understood that any of
the identified solvents may be utilized in the f ol~.owing
.. . ~ _ x 6 _
described process. As previously indicated the whale oil is
dissolved in the ~thyl acetate at a preferred pH of about 2-~
and then filtered. Upon standing, the ethyl acetate/pyrolysis
oils mixture separates into two phases. Chemical
spaatrogcopic analyBis revealed that the ethyl acetate-
insoluble fraction contains carbohydrate and carbahydrate~
derived products. The ethyl acetate-soluble fraction,
containing the phenolics/neutrals fractions, is then separats~d
and washed with water to remove the remaining water-soluble
carbohydrate and carbohydrate-derived materials, preferably in
a 1.6 to 1:1, water: oil weight ratio. The ethyl acetats-
soluble fraction is then gurther extracted with an aqueous
metal bicarbonate solution, preferably a 5% by weight aqueous
solution of sodium bicarbonate. The pH of the b3.carbariate
extraction solution is preferably maintained at approximately
8-9.5, and a 6:1 to o.5:1 bicarbonate solution: oil weight
ratio ~.s preferably utilixed. The aqueous bicarbonate layer
extracts the strong organic acids and highly polar compounds,
and the remaining ethyl acetate-soluble layer contains the
phenols and rieutxal fractions. This ethyl acetate-soluble
lay~r is then separated, and the ethyl acetate solvent is
evaporated using any known evaporation technique, including
vacuum"evaporatl.on technic~uea,~ The drieQ.phenalics/neutrals
'fraati~on.typically contains 0.5-1% of water with traces of
~thyl acetate. Table TI illustrates typical yields for
vafious pine sawdust fast-pyrolysis oils and fractions of oils
1'~
.. . .. '
ob~.ained duxing diøfarent test runs as wall as fnr l~c~uglas fit
bark fait.-~pY~'olysia oiis.
TABhE Ir
y~.elds for Vaxious Pyrolysis ails
--
Wt % Yi.elc~~of ly7rolysisOils B~qpr3on Dry, Char-Fx~o
Oil
pYrr~ly~ic EtaAc Water' w4rganic Yt7enollcs/N~u~
Oil Znsol poi. r~~iu~
Pine sawdust 42,8 24.7 5.7 21.3 .
Pine sawdust 28.2 39 6.1 26.7'
Combined pineoils 22~$ Zw 9 s~ 25
pine sawdust 41 27.2 6.3 28
Douglas f~.r bmrk 0 12.5 15 Ph$riolics: NsUtrals:
Solids: 2.9 47.8 15.6
Douglas firWark d ND* ~-9 Phenolic-s: Neutrals:
Solids: 4.8 50.8 17
'Phenolics: 1.6.5; Neutrals: 9.5
bphe,noliac: 7.6.5; Neutrals: 6.0
°Water s~olublGS by dif f el'enGe
°From two condenser
°EtOAG insoluble~s by dif f arenas
*NOt hetermined
As indioated in Table ZI, the aqueous alkali metal
bi.oarbonate solution utili2ed to ex~.ract stxong organic acids
and highly polax compounds further purifies the
phenolitss/neutxals fractions. While any suitable alkali metal
bicarbonate solutit~n m2:y be utilized, the preEerrdd solution
~.g selected from sodium biCaxbonate, potassium bica~'bona~te,
lithium bi.cax'bonate and ammonium bicarbonate, with sodium
bioaxbonate being the preferred and most optimal solution.
- 18 --
frog, thQ aqueous bicarbonate solution, it is possible to
isolate a fraction rich in organic acids as a by-product. In
this instance, the aqueous layer can be neutralized, for
example wl.th 50% by weight o~ phosphoric acid (although other
acids can be used) saturated with sodium chloride, and
extracted with ethyl acetate. It is possible to than
evaporate the solvents and isolate the remaining fractions as
well.
The phenolics/neutral fraction can be further
Zractionated into isolated phenolica and neutrals if desired.
This can be accomplished by utilizing a !3~ by weight solution
of sodium hydroxide in a volume ratio of 5:1 of
solution:extract, The aqueous layer is then acidified to a pH
of about 2 utilizing ~ 50a solution of phosphoric acid
13 (although other acids can be us~sd). It is than saturated with
sodium chloride and extracted with ethyl acethte. Evaporation
of the solv~nt leads to the isolation of the phenolics
fraction; evapoxatic~n of the in~.tial ethyl acetate solution
treed from phenolics leads to the neutrals fraction. Tt
should be noted, however, that the present invention does hat
require this separation of the phenol from the neutral
fractions, and it is in fact th~.s aspect of the present
invention which makes the present proaeaa ao economical. In
the past, as previously indicated, the phenalics hav~a always
been the desired end-product, and sodium hydroxide has
typically been utilised in such process treatment, this is
unneoessary with the process of the present invention, since
° 1.~ °
~J~~~:~a
it has been discovered that the combined phenolics and
neutrals fraction composition is sufficiently pure to functimn
by itself in the formation of adhesive resins.
The process of the present invention can be operated
in both batch made as we~~.Z as in a continuous mode. In the
batch mod~ embodiment, the whole ails are extracted with ethyl
acetate and then washed with water. Following the water wash,
the composition i~c then washed with the aqueous sodium
bicarbonate to eliminate the acidic components, which come
from pyrolysis of the ca~:bahydrate fxaatian and would be
deleterious to the resins. In a Goritinuous operation, the
pyrolysis oils is preferably extracted simultaneously with
water and ethyl acetate, and then th~a ethyl acetate's soluble
fraction is extracted countercurrently with the aqueous
biaarbon$t~a so~.ution. The whole ethyl acetate fraction, which
includes both phenoXic and neutrals compounds, is then
utilized as a fesdsctock far resins after solvent evaporation.
EXAMFLE I
1.0 kg of Bast-pyrolysis oil derived from pine
sa~adeast was dissolved into 1 kg op ethyl acetate. After
filtration of the solution, this solution than separated into
two easily identified and separated phases: The ethyl
acetate-soluble phase was ~Ghen isolated, and 0.8 kg r~~P water
was added to thfs phase. They re~sulti.ng water-soluble fraction
was isolated and saved for further p~cocessing. 2 kg of 5~
sodium biaarboriats solution was then added to trig ethyl
.. , r 20
5d~~e~,
acetate-soluble fraction, and the aqueous phase therefrom was
saved for further processing. This aqueous phase was the
acids-salable fraction. The resulting washed ethyl acetate-
s~oluble solution, containing the phenol and neutral fractions,~~.
was then solvent evaporated to remove the ethyl acetate
solvent. The yla~.a of phanoliaa/~autralw woo 3i~ by weight
based on the dry oil.
The remaining ethyl acetate-insoluble ~x~,ct~,on was
solvent ~vapoxated and yielded a weight percent of the
starting dry oil. The aqueous Wash yield after solvent
evaporatiar~ was 39 we~.ght percent of the oil. The aqueous
bicarbonate solut~.on was neutralized with a 50% phosphoric
acid solution, and after saturation with sodium chloride, the
organic phase was extracted into ethyl acetate. After solvent
evapaxation, the acids fraction yield was approximately ?
Weight percent. Fig. 1 illustrates this mass balar~ae of the
various fractions resulting from this Examp~.e x utilizing the
process of the invention.
Z o ~~tpL$ z a
9.5 kg of tast~pyrolysis oils derived from pane,
sawdust were dissolved into 10 kg of ethyl aoetat~a. After
filtration, this solution settled,ihto two eas~.Xy.identified
tend separated phases. 1,8 kg of water was then added to the
2~ ethyl aastrite-soluble phase, and this solution was then
separated into two easily identified and separated phases,
~'he resulting water-soluble fraction was saved for gurther
- 2 ~, .-
~~,~ ,~. ~.~~
ic.~~~~
processing, and the other ethyl acetate-soluble fraction was
then t~dmixed with 8.9 kg of a 5% sodium biaarbanata solution.
The aqueous phase of this,solution was then separated and
saved for further prccessingr which was the acids»soluble
fraction. The resulting washed ethyl acetate-soluble
solution, containing the phenolicsjneutral fraction was
separated, and the solvent was then evaporated. 'fhe yield of
the phenoli.cs/neutral fraction was 30% by weight based on dry
oil.
Using a procedure similar to that described E~bove in
Example T, the mass balance of the fractionation was
determined as follows: the ethyl aaetata insoluble fraction
comprises 27. weight percent, the Water-soluble fraction
comprises 31 weight percent, and the Qrganic acids comprise
~.5 7.2 weight perC~ant.
~XAM1~LE xII
The fraot~.onation of Douglas fir pyrolysis products
which are solids at roam temperature, Was similar to that
2p described for pine. 4.6 kg of Douglas fir fast-pyrolysis
product wars dissolved iota 9.8 kg, of ethyl acetate solution.
No ethyl acetate insoluble fractfon was observed. The whole
eollutiOn was then extracted with 12 kg of a 5 weight percent
aqueous sodium bicarbonate solution. The ethyl. acetate--
25 solublelsoluGi.on aonta~.ned 6B~weight percent of phenolias and
neutrals. ~'he phenols and neutrals were then separated by
extraction with 11 kg of a 5 weight percent agueous solution
' - Z2 -
a
ap sodium hydroxide. From the ethyl acetate solution, 17
weight percent Op neutrals were obtained. The alkaline
aqueous solution containing the phenolics was aC~.dified with
a0% phosphoric acid (although other acids could have been
uged~, Tni$ solution was then saturated With sodium chloride
and extracted with ethyl acetate to yield 5f~.8 weight percent
for the phenolics fractipn upon solvent evaporation. Tn the
extraction with aqueous bicarbonate solution, n precipitate
was foamed (5 weight peicent~ along with the soluble acids
la fraction of 1.9 weight percent. The data por the fractionated
materials axe provided in Table IX above.
EXAMPLE IV
Fast-pyralysig oil derived tro:~ pine sawdu$t also
Fractionated on a continuous basis. Th3.s continuous process
utili~ad, but is not limited to, a 6-stage system of mixer
tanks and settling tanks. The oil, ethyl acetate and water
were mixed and allowed to settle, with the organic phase being
gent on to mult~.~$tage extraction with 5 weight percent
20 aqueous radium bicarbonate solution with each eXtraCtion stage
having a separate Settler tank. The bicarbonate extraction
was 7cun countercurrent to the Elow of the organic phase. The
aqueous fxaations, that is the combined ethyl acetate
inso3.uble and water-soluble fractions, the aqueous biGarbonat.e
25 aolutaon, and the organic phase were all colleoted and
processed as described above, Conditions of the extraction
included the tolxowinq: oil flown water flow] ethyl: acetate
a
23
flaw, and aqueous bicarbonate flow rates were 7.0, 6, a4 and 33
mLjmin, respectively. It shau~.~1 be rioted, however, that the
countercurrent continuous wxtraction presses is not limited to
these f low rates. The yield of phenolics/heutrals ~xaGtivns
composition was about 20% based on the oil flaw rats and
phenolics/neutrals isolated fractions. A total of 2D kg of
oil. was fractionated in this way. Variations in flow rates
and number of settler and mixer tanks, howevex, can yield
different proportions o~ materials. Phase separation was
readily accomplished within the settlers.
Analysis of the products for intermediate stages of
extraction revaalsd that 1-3 stages of bicarbonate extraction
may be used. Turning from the Examples given above, the
fractiona~.ion scheme described above allowed the isolation of
2Z% to 31% of the starting pine oils as a phenolics/neutrals
fraction, or overall. yields of 12-21% based on starting dry
wood. This Exaction consisted of approximately 73% phsnolias,
extraa~able from sodium hydxaxide solution from an ethyl
acetate solution, and 27% neutrals. The total yield of
20 phenol~.cs~neutrals fraction isolation is reproducible as shown
by the runs in TablQ rx above.
The typical oil contained 6.2% phenolic hydroxyl and
0.4% carboxylic acid contents by wei5~ht ranges. Ranges of
5.5-6.5% phenoliC hydroxyl and 0.1-0.6% carboxylic acid
25 contents are expected for the different staxting g~edstocks,
The phenoliasjneutrals Exaction included about 6.6% phenolic
hydroxyl content and na carboxylic acid content. Expected
24 _
2~~~~ ~.
ranges for phe.nolics/neutral~s era 6.0-12% dep~nding on the
feed. 'the acids fraction iriGludad about 9.2% phenoiics and
0.9% carboxylic acid contents. Ranges far various feedstoe~;g
are 5-10% for phenolics and o.5-3% carboxylic acid contents.
In characteri2ing the resultant phenol camposition$,
the apparent molecular weight distributions"obtained from gel
permeation chromatography an polystyrene-divinylbenzene
copolymer gels (50 Angstrom) with tetrahydrofuran as solvent,
indicated that the phenolics fraction had components ranging
from the manomeric substituted phenols around 150) to
olic~omers (up to several thousand in molecu~,ar weig$t), The
acids 2nd neutrals had the low~st moleGUlar weight components.
From molecular beam mass spectra of the phanolics/neutrals
fractions, a number of ph~:noli.o compounds were detected:
~.5 guaiacol (2-methoxyphenol) m/z 124j catechols m/z 110; isomers
of substituted 2-methoxyphenols with a7.ky1 groups such as
methyl (mJz 138), vinyl (m/z 150), 3-hydroxy-propen(1)-yl (m/z
180), allyl (m/z 164), hydraxyethyl (mJz 168), and ethyl (m/2
x.52), most likely in the p-position. In addition,
2o Carbohydrate-derived compounds were present such as furfural
alcohol and a number of ether furfural derivatives.
From proton nuclear magnetic resonance spectrum of
the phenoiics/nautrals Exaction, of the total intensity, the
arr~mat~.c protons (S.5°~-0 ppm) , constituted 52%, the e~lj,phatia
25 (1.5-3.5 ppm} about 20%, and the methaxy region and oxygenated
and side~°chain region (3. 04.2 ppm) constituted 30%, This was
in a.gxeement with the description from the molecular beam mass
- a~ _
CA 02085513 2001-08-14
spectra of mixtures of phenolics with substituted groups. The carbon-13
nuclear magnetic resonance spectra confirmed this data.
Bark derived phenolics have a very high phenolic hydroxy
content (7.4-11.5%) depending on pyrolysis conditions (steam to nitrogen
carrier gas) and therefore are very suitable for adhesive formulation
replacing phenol at greater than a 50% level.
As previously indicated, a principal purpose of producing the
phenolics/neutrals fractions is to provide a substitute for pure phenol in
the production of resins and the like. Specifically, resoles, which are
phenol-formaldehyde resins formed under alkaline conditions for gluing
wood, were produced and compared to resoles utilizing standard
formulations of commercially available phenol.
Of the various fractions of pyrolysis oil, only the
phenolics/neutrals fractions gave positive gel test under the above
conditions. In preliminary gel testing of the phenolics/neutrals extract,
one gram of paraformaldehyde was arbitrarily added to 4 grams of the
extract. The pH of the extract was adjusted by adding 0.2-1.0 mL of 50%
by weight sodium hydroxide. There appeared to be a strong buffering of
the pH by the extract at a pH 9.5. CascophenT"" 313 was used for
comparison. At 0.5 mL of added sodium hydroxide, the gel time of the
phenolics/neutral fraction was much shorter than that of the
CascophenT"", with a gel time of only 29% that of CascophenT"" at
124°C,
At 112°C, it was 34%, while at 101 °C it
-26-
CA 02085513 2001-08-14
was 46% of CascophenT"". At the original pH of 3 of the
phenolics/neutrals fractions, there was no gelling of the mixture even at
132°C with the same amount of added paraformaldehyde.
Resoles have also been made utilizing a 50% replacement
of phenol with the phenolics/neutral fractions produced by the process of
the present invention. Fig. 2 discloses a comparison of sheer stress
strength between CascophenT"" and resoles produced with the
phenolics/neutrals fraction of the present invention. Specimens were
tested after a cold water soak (rightmost bar) and met test requirements.
As can be seen from Fig. 2, the CascophenT"" showed a shear stress
strength in psi of approximately 700, while the resole with the
phenolics/neutral fraction produced from the present invention showed a
strength of approximately 800 psi, significantly higher than CascophenT""
Moreover, the resole produced from the phenolics/neutrals fraction of the
present invention illustrated a cold soak strength of approximately 600,
which is considerably higher than the standard 500 which has generally
been set for existing products such as the CascophenT"". The tests
performed used the British standard 1204; Part 1:1964, and the testing of
10 specimens per evaluation. Thus, Fig. 2 illustrates the fact that the
shear strength of resins produced by substituting 50% of the phenols
therein with the phenolics/neutral fraction produced from the present
invention are in fact stronger than phenol-formaldehyde resins utilizing
pure phenol.
- 27 -
~~~~~:~ ~3
It has been found that useful resins may be obtained
by substituting from about 25 to about 75 weight percent of
the phenol normally present in a-resole resin with the PJN
fraction of the invention. Resins have been prepaxed with
from about 5 t4 about 75% by weight, and this is preferred.
~iawever, about 15 to about 50% by weight is most preferred.
Referring to xig. 3, wood failure tests axe compared
between the Cascophen and resoles having the
phen4lics/neutrals fractions produced from the present
invention. To interpret Fzg. 3, it should be understood that
i.t is pregexred to have a wood failure, not a resin failure.
Thus, if the wood fails, the resin is deemed to bs good, and
if the resin fails, it is deemed not to be gpod since the
resin has actually separated. Thus, it is desirable to have a
higher wood failure percent in order to show resin strength.
Referring to Fig. 3, it should be clear that the Cascophen
samples had a wood failure of approximately 3s%, while the
resin produced by substituting 50% of the phenolic portion
with the phenolics/neutral traction from pyrolysis oils was
well. over 50%, illustrating a significant digferenCe in resin
strength capabi~.ity. Moreover, the sold soak test xesults
illustrated that the resole having the phenolics/neutxals
fraction produced fxom the present invention had a cold soak
rating .the same as a non-cold soak rating of the Cascophen.
'thus, these tests fuxther indicated that resole resil~s
produced by substituting 50% of the phenol with the
phenoll~as/neutra7.s fraction produced from the present
- 28 -
a
2~~~j.~~
invention are cons3.darat~ly batter in function and strenc2th
than standard cammercielly available products. The tests
performed used the 8xitish standazd 1204: part 1:1964, and
testing of ~0 specimens per evaluation.
g With respect to the economic benefits of the pres~nt
invention, historical petrol~um derived phenol casts range
from $0.Z8 t~r~ $0.45 peY pound (1981-7.991] depending an
petroleum casts and the stt~ts of the economy, part.iau~.arly
housing, the mayor market segment that employs resole ph enalic
resins. xhe average cost of phenoX in these past eleven
years ie $0.34/pound. Prior to the present invention, the main
aampetition has been the l5.gnin-derived substitutes from
commercial pulping processes. Kraft lignins have to be made
chen~ical3.y mare reactive to replace phenol in phenol-
formaldehyde resins with similar performance. These
commercial products are sold as resin co-reactants, and their
price ranges from $0.33-$0.85 per pound depending on the
reactivity needed (based on kraft lignins). Less expensive
products are available from the process of the present
2a invention and are co-reactants with the ability to replace
about 50% of the phenol in phenol-formaldehyde resins as
described above. Indications are that for molding compounds,
plywood, particle boa~'d, oxi.ented board, paper ov~erlt~ys and
other,si.milar adhesive resins, 50% phenol raplacemer~t would
provide a very similar performance to the commercial phenolic
adhesives, and in fact would give a better perEorrnance as
illustrated and described above in Fags. 2 and 3. Mawever,
2~~~~:~~
there is a significant cost reduction factor in that the
phenol-formaldehyde fractions produced from the P/N
corngo$ition of the present invention have an amartixed cost
projection at approximately $i~.16 per pound compared to $0.30
to $0.40 per pound for commercial phenol. If the
lignocellulasic starting matsrit~l is bark, this cost is even
less because the yie~.d of phenolics from the bark is higher
then that of sawdust or pine. Plant sizes were 250 to 1000
tars of feedstock per day, 15% return on capital, plant life
~0 of 20 years, and waste sawdust at $10.b0 per dry ton.
Ass described above, the mast developed application
fox the end products oP the present invention is the
rep7.acement o~ 50% and potentially more of phenol in phenal-
farmaldehyde resins fox use as molding compounds, foundry, and
she7.1 r,~oldings. Other potential applications for the
resulting product of the process of the present invention
include the replavement of phenol in softwood and hardwood
plywood resins, the insulation market, composite board
adhesives, laminated beams, flooxing and decking, industrial
particle board, wet-formed hard boards, wet-farmed insulation
boards, structural panel board, and paper overlays.
Alternative adhesive systems from the carbohydrate-rich
fractions of the. present invention could also be made.
~n addition, another product that can ba derived
from the othar fractions of the pyrolysis oils is an aromatic
gasoline. Massage of vapors of these compounds over zealite
Catalysts pxoduces high oetane gasoline, as more clear7.y
-- 30
~D~~~:~~
discus5~ed in "Low-pressure upgrading of Pr~.mary F~yrolysis Oils
form Bicmass and organic Waste", in Energy from 8iomass and
Wastes, E~.sevier Applied Science Publishers, London, pp. 801
$30 ( 1.966) . . .
g A final advant$ge to the present invention is that
about one-thixd of the usual amount of Formaldehyde employed
in conventional phenolic adhesives is necessary iri producing
adhesives wherein 50% of the phenol is substituted with
phanolics/neutra7. fracti.ans provided by the present invention.
1a Sinee~ there is significant environmental concern over
formaldehyde emissions from resins, the products resulting
from the proaesg of the present invention therefore becomes
very important from this context.
As can be seen from the above, a novel process for
~.5 ' ~ractionating fast--pyrolysis pi.ls to produce phenplic
compounds-containing composit~.ans having P/N fractions
coritzsined therein suitable for manufacturing phenol-
formaldehyde resins are disclosed. The process ie simple and
economic, and can. be used in eithex batch or continuous mode
2p operations. Th~ resulting P/1~ composition can be subsequently
utilized to produce xesole resins of comparable or superior
performance charaCtariatias relative to standard phenol-
forma~.dehyde rev,ins yet the pyrolysis~deri.ve~d phenolic
geedstocka are projected to cost less than half of the cost of
petro~.et~m~derived phenol. Moreover, these resulting resins
have numerous different types of applications, and the coast
benC~fit3t alone are significant.
' - 31
EXAMPLE '~' (stun 109)
Using 24 kg of dxx, Colorado pine sawdust as geed
for the fast pyrc~lysis vortex reactor w~.th steam as the
carrier gag at a steam-to-biomass ratio o~ 3..5, 60.2 kg of
pyrolysis aonder,sates (including water) were prepared, which
had both an aqueous and an oxgariic phase. The average
measured temperature. of the carrier steam was 700°C at 98
ps~,a, upstream of the supersonic nozzle in the ejector. The
average measured temperatures of the vortex reactor wall ware
610°G in the first third, 608°C in the middle third and
626°C
in the 7.ast third of the reactor. Ir~t~ediatsly downstream of
the vortex pyralysis reactor was a char cyclone, followed by a
long, heated transi~er tuba (the pxocess stream had a gaseous
residence time of about 0.9 seconds in this tube), a second
char cyclone, arid then the first condenser. The average
measured t.amperatures of the pyx~plysis process stream at the
entrance to the transfer line and at the six equally spaced
locations down the transfer line were 493, 544, 526, 502, 489,
496, and 495QC.
~'o remove the residual organic phase from the
condensate co7.lection eguipment, 1 kg of ethyl acetate was
used {the weight of the wash ethyl. acetate is ~.ncluded 3.n the
candansate weight). These condansates were similar to those
used iri Example 1V, but also included the condensed oarrier
steam. The organic phase. was relatively viscous, which could
coat the glass membrane of the pH electrodes, and thus cause
32 _
~~:<~
erroneous pH measurements. Tha aqueous phase (56.?. kg) was
d.acanted a.nd slowly neutralized by the addition of 2.2 kg of
dxy, solid sodium bicarlaonate until an indicated pH of 6.B was
readied. This avoided the fouling tendencies of the pH
electrode by the organic phase during the addition of ~ha
sodium b~.carbonate. ~'he neutralized aqueous material was
mixed overnight, at which time the measured pH had risen to
7,5 (due to the loss of dissolved carbon dioxide). Tha
organic phase was dissolved in 5 kg of ethyl acetate to
~.0 facilitate transfer tram its container to the mixer. Tha
o:gari~.d solution was then ma.xed into the previously
neutralized aqueous phase to result in a slightly lowered pH
of 7,3, which rose to 7.4 after mixing overnight. Thus, the
previou$ly neutralized aqueous phase solution w~.s used to
neutralize the small am4unt of acidity present in the organic
phase, This minimized the loss of ethyl acetate in the
evolved carbon dioxide.. NQ significant formation of an organic
precipitate was reported during the neutralization and
extxaation ~sequenast.
The extraction of the phenoXiC~cantaining/neutrals
could have been accomplished in any oP a number of ways known
to one e~killed in the art, but in thin aaao, the xsautrelixed,
two-phase suspension was than m~atorod into a liguid extraction
system having counter-current flow through three mixer-
settlera in series. Each mixer had a volume of 250 mL~ and
each settler had a volume of 3000 mL. The neutraliz~d feed
was fed at ~0 mL per minute and the ethyl acetate solvent eras
-- 3 3 -
fed at 35 mL per minute, although these rates era riot meant to
be limiting. The phenolics and neutrals (P/N} materials wez°e
extracted into the organic phase w~,th the use of U.7 volume of
ethyl acetate per volume of mixed-phase neutrnlizad
oonde.nsates: A total of 2.6 kg of ethyl acetate bras used per
kg of dry wood feed. The ethyl acetate was evaporated from
the organic phase to result in about the same yield of P/N
material as was obtained in E~,ample TV, 0.17 kg PJN per kg dry
wood Egad.
1a
EXAMPLE VI (Run 116)
In an integrated, commercial application, it is
anticipated that the aqueous phase, containl.ng the neutralized
organic acids and other water soluble organias, may be
incinerated in a furnace. This wou~.d both dispose of the
contaminated water, as w211 as, recover the sodium
bicarbonate. However, from such a furnace, it is well known
that the sodium salt recovered is soda ash (sodium carbonate)
rather than sodium bicarbonate. An additional process step is
required to convert the recovered sodium carbonate to sodium
bicarbonate, i,.a, carbon dioxide gas ~.s bubbled through an
aqueous solution of sodium carbonate. This additional step
is expensive as evidenced by the fact that the commerciaX
value of sodium bicarbonate is about three times that of
sodium carbonate. 'this carbonation process requires the
add~.tion of a large amount of watex td form the aqueous
solution, due to the relatively small solubility of sodium
- 34
ra
~~ ~1~ ~ t~ e.f .~.
bicarbonate in water. As discussed above, this additional
wet~r is c~etr3mental to the operability of the process. In
addition to being cheaper, only half as muoh sodium oarbanate
is required to neutralize a given amount of aczdic material
Compared to soditam bicarbonate on a molar basis (0.63 times
lsss on a weight basis). Coupled with the lower cost per
pound of sodium carbonate, this lowers the cost of the raw
materials by a factor of 5 to neutralize with sodium carbonate
rather than sodium bicarbonate.
X0 Therefore, it would be advantageous to bs able to
use the cheaper radium carbonate to neutralize the pyrolysis
candansates. However, the pH of aqueous sodium carbonate is
much higher ~t 7.1,6, as compared to that of sodium bicarbonate
at only 6.4. It was expected by those skilled in the art,
that some of the rihenalic constituents of the pyrolysis
condensates would react with the sod~.ur,~ carbonate to form
sodium phenolates, which era water soluble and therefore would
not be as well extracted into the ethyl acetate solvent phase.
In additit~r~, base-catalyzed condensation reaction, that are
0 not advantageous, could take place at a higher pH, thus
altering the proportion of low- and high-molecular weight
phenolic products in the material.
however, it has been found that by slowly adding
dry, basic sodium carbonate to the acidic pyrolysic
caridensates until only a pH of about 7 is reached, that the
phenalic oonstituents axe still primarily extracted into the.
organic solvent phase, rather than forming the water-soluble
-- 3 ~
~~~~~a~~.
phenolates. This unexpected observation al~aw~s the use o~ the
more basic sodium carbonate, or other basic matera.als that may
be advantageous to replace the sodium biaarbonatc in the
neutralization process, which could result in a significant
cost savings or rather advantages.
Sixty-nin~ kg of pyrolysis oondensr~tes (including
water) were formed by the fast pyrolysis of 27 kg of dry
Colorado pine sawdust in the vortex reactor using steam as the
carri~r gas at a steam-to-dry--aawdust ratio of 1,2 to 1.8 and
at a sawdust feeding rate 4f 11 to 16 kg per hau~c~ ~'he steam
was at 88 peia and 700°C prior to expansion through the
supersonic orifice of the ejector at the entrance of the
vortex reactor. The walls of the vortex r~:actor were at a
nominal 625°C to result in an average pyrolysis stream exit
temperature of 530°C. In the transfer line between the two
Char cyclones, the average measured gas temperature at the
entrance and at six equally spaced locations were 498, 520,
52'7, 500, 490, 463, and 455°C, respectively. The gas phase
residence time in the transfer lire was at~out 0.4 se~c411da.
To aid in equipment cleanup 4 )cc~ of ethyl acetate
wars added. An additional 9 kg of ethyl acetate was added to
transfer the organic phase into the mixer for neutralization.
Foic neutralization, 1.5 kg at dry sodium carbonate wag added
to the two-phase suspension to result in an init~.al pH o~ 6.8.
After two days, the pH had dropped to 6.2 and an additional
0.1 kg of sodium carbonate was added to result in the final pH
of 6.8. Care was taken during the neutralization to keep the
a
- 36
pH electrode clean and the calibration was checked aftex each
use. The amount of solid precipitate was 0,026 kg per kg of
sawdust fed. Although any of sevexal well known methods of
extraction could have been utilized, this neutralized m$:texial
was then extracted in the three-$tag$ counter current .'
extraction system described in Example v. The total, Weight, of
ethyl acetate used was 3.p kg per kg of dry weed fed. The
yield of P/p~ material was 21 % by weight of the feed, higher
than that obtained in Examble V, but similar to yields
s0 obtained itt batch mode operation.
EX,~1M T I (stun 7.25)
Using 125 kg of Southern pine sawdust, 258 kg og
pYrolysis condensates (including water) were produced using
steam as the carrier gas at 1 to 1.1 kg steam per kg of dry
sawdust in the vertex pyrolysis reactor. The feed rate was 18
to 20 kg dry feed per hour. The pyrolysis te~.~peratures were
as in the above examples, eXaept that the average measured
temperature of the pyrolysis stream at the e~.it of the vertex
2a reactor was 500°G (stud. dev. of 11°Cy and in the transfer
litre, between the primaxy and secondary char cyclones, the
avexags measured temperatures at eight locations were 93B~C.
To mere completely recover the condensed material from the
equipment, 11.9 kg of ethyl acetate was used.
Two samples were made from the condensates produced.
The first eampl.e contained 87 kg 4g condensates. The aqueous
phase was decanted and neutralized to a pH of 7.9 from an
s
37
i
1
~~t'~r..~..
G,~~.~~
j.n~itial pH of 2.7 with 1.8 kg dx'y sodium carbanata. To the
I_
organic phase, 28.5 kg df ethyl acetate was added to make a
very low viscosity solution. This solution was then added to
the previously neutrall.zad aqueous phase to make the two-phase
suspension to feed to the conti.r~uoc~s flow, countercurrent .
extraction system. After mixing the two phases together, a
significant amount of salad precipitate formed, which was
skfmm~ad off grorn the top at the suspension. Although, the
extraction could be carried out in any of several manners, in
this case, the extraction system consisted of three
mixer/sattlsrs in series, w~.th the mixers having a volume of
750 mL and the settlers having a volume of 3000 mL. The feed
rates were 300 mL per minute for the neutralized feed and 210
mL per minute for the ethyl acetate, although one skilled in
the axt secoc3nizes that one could vary these rates
considerably and stiX1 obtain a usable product.
The second sample of 179 kg of pyrolysis condensates
(including water) was mixed with 63 kg of ethyl- acetmte to
keep 'the organic phase fluid and easily suspended in the
z0 mixer. This two-phase cusp~nsion was then neutralised from an
in5.tial pH of 2.9 to a final pH of 6.8 by the addition cg 4.0
kg of sodium carbonate. At this time a solid precipitate
floated to the tap of the suspension, where it was skimmed
off. 'fhe amount of precipitate recovered from the second
sample of this example was judged to be proportionately
similar to that observed in the first sample. Thus,
demonstrating that the order of neutralization re~.ati,ve to the
- ~8 -
~~~~~:~.3
addition of ethyl acetate did not have a marked affect an the
preparation of the aondensgtes for extraction nor on the
formation of the solid precipitate, which must be removed
prior to extraction to avoid operational problems. The
recovered precipitate was found to be about 6 wt ~ of the...
sawdust feed.
Although any number of different methods could have
been used to contact the neutralized suspension in
oauntexaurrent Ylow with ethyl acetate solvent, a three-stage
mixerJsettlsr system was used having the same dimensions and
nominal Ilow rates noted for the other sample described above
in this example.
2'he organic phase was mixed with that from aevera?
other batches to result in an average yield of phenolics-
containing/neutrals of 0.19 kg per kg of dry feed.
~XAtdPLE VIII (Run 121 )
Usfng steam as the carrier gas in the vortex
pyrolysis xeactor, ~5 kg of dry southern pine sawdust was
pyrolyaed to produce 77 kg of condensates (including water),
xhe carxier gays to sawdust weight ratio was 1.2 at a sawdust
tending rate of 15 kg per hour. The average steam temperature
was 690°C fiedsured upstream of the ejector noazle at 9p Asia.
Tha average temperatures measured in the vortex xaactor vrall
were 570°C in the first third, 600°C iri the mi.ddla third, and
630°C in the last third. Tha measuxed average temp~rature of
the pyro~,ysis process stream as it exited the vortex reactors
3~ -
~~~a:~.
was d95°C with a standard deviation of 4°C (1~8 measurements).
~'he transfex line between the primary char cyclone and the
secondary char cyclone was heated and the av~srage measurs~d
temperatures of the pyrolysi,s stream wars 505°C (128
measurements at each of 6 axial locations with a standaxd
deviation of 23°C) with a Calculated residence time of 0,4
seconds. However, sinoe chemical kineti.os are exponenti$1
with temperature, zt is important to recognize that it is the
instantaneous temperatures of the pyrolysis process stream,
not the overall average temperature, that are important. The
average temperatures at the exit of the vortex reactor, the
transfer line entrance, and the six equally spaced locations
of the transfer line itself were 500, 485, 525, 530, 515, 505,
490, and 477°C respectively. .
A 49 kg sample of the mixed suspension of
condensates wa$ neutralized and extracted. To aid in the
transfer of the thick organic phase and to lower the viscosity
of the ~rgantc phase during neutralization, 16 kg of ethyl
acetate was added to the two-phase suspension prior to
neutralization. To neutralize the suspension to a pI~ of 6,9
from the initial pH off' 2.7 required 1.1 kg of sodium
carbonate. Only a very small amount of solid precipitate,
0.0009 kg pex kg sawdust, was observed after the
neutralizatian (t~bout 65 times less than for example VII).
Apparently the higher process temperatures during the
residence time in the heated transfer line waxe sufficient to
achieve a thermally induced change in matexial, which
' - 40
~~~a ~~
atherwis~e would have produced a solid material, which would
have precipitated in the extraction step. This change.
presumably lowered the molecular weight or otherwise made that
material, which would have precipitated, mare soluble in the '
S ethy7~ acetate/water solvent systelu.
Although any number of different methods could have been used
to contact the neutralized suspension in countercurrent flow
with ethyl acetate solvent, a three-stage mixex/settler system
was used having the same dimensions and nominal flow rates
noted for Example VII.
EX ALE YX (Run 133)
~n all of the above examples, the sawdust feed had
been completely dried at lob°C and was fed to the vortex
reactor while still at about this te~uperature. Thie results
iri an equilibrium moisture content ~.n the feed of less than
1%. In a commercial process, it may not be feasible to
achieve this low level of moisture, although it may be
desirable to do so in order to minimize both the heat required
for pyxo~.ysis and the amount of waste water for d~,sposal. To
evaluate the effect of residual moisture in the feed, the
moisture i.n the as-received sawdust was measured az~d then
adju$ted to result in 8 ~ moisture in the feed. Ta avoid
23 moisture losses prior to pyrolysis, the Feed was riot
preheated, but rath~ar fed at ambient temperature into the
vortex reactor. The vortex reactor was operated as in the
' - 41 -
~0~ i~.~
above examples, but with 39.5 kg of Southern p~.ne 6a~~rdu5t fed
at a 3.ower xate of 12.9 kg per hour and a steam-to-biamass
ratio of 1.~. The haated.tranrfer nine was maintained at a
Very uniform, measured temperature of 5o0°C within 11~C~.~
Although any number of different methods could have
been used to contact the neutralized suspension ~;n
countercurrent flow with ethyl acetate solvent, a three-stage
mixer/settle~r system was used having the same dimensions and
nominal flow rates noted for Example VII.
~iJLITT~NAL FRAC'~IONATI9 EXAMPLES
This information is summarized in Tables xly, IV,
and V, which a~.so cantains examples of fractivnativn of other
materials prepared similarly. zn addition to the thermal
severity conditions (temperature/time), the extract~.vn
severity is another important parameter varied. It is
represented by the pH of the neutralization step, which is an
approximate measure ~.n the non-aqueous solvents-containing
solutions employed.
Most of the examples of resol~s prepared an the new
procedures are from runs 121-140.
' w 42 -
~p ~ M n Gt a~ r1 M m a~ o~ a~ n ~D ~ ~~ V' ~r ~a' O w mn o~ M 57 O u~ w n
. . r . . . . . .
~,r-ncvo~ererriccoaoNrraa~r.,:~r:cv rv co wr~W nHN~~
M M M M M f'7 M t'1 M M V' M M M M M M M M M M M (~t 4 t'') V' M n1 cp r~?
N 0p !D h~ M h~ C~ PI r~i O ~~I d ~ O N N N N N f'~ O~ C. T ~1 Cp H M h~ d' In
a a v a . a a a r r r
r vD 60 us a en m ID ~o r 1~ h ~ ewo ve vri vo us ID uW n ui t- ~ wo w r vo
pp t~ In u5 rD tt9 v-1 r1 Ch 111 h M 111 C r~~1 CO 00 40 ef'
a . a a r r r a a a a r r .
M tf5 sr pt !W !1 r1 ri N M r-1 Ifs c~ r1 H n-1 N ..~1 r1 O N 1~~ eI1 t~ H H O
d
O ~ I
W -! 1 M ~0 Ob O~ N W n I~~ N Qr N W M O~ Ov 1f1 00 t? O 00 1'1
tD 1 r N ~ .-i N r1 Iff u'1 .-1 N r-1 '.1 ~ N C7 h n ~1' IA a ~'f M Vw0 us v1
G~ d' (~
1
I
I I ~ d H ~ x = x
!V 1 I ~ '" p~'e ~ C4 W (y P. Ae ~ '$ ''h "L ?'. N ~ ~ '.1: Die F. ~ ~' A~ ar
I h. I 1 I I I I I 1 1 1 W pe W W W W U 1 1 I d t0 et .-~ Vr ~p M
V ~ ~ O N a, al d' N a O r1 M N H I ( 1 I I I .-i n rn M cr W r1 W
i oo In~amr-leownrn 1 1 drmc~ a~r~h ~c r~ .ap$dooo
1 N r1 I I 1 1 I I I ~? a ID t~ 1a 00 a0 ap tp I 1 I I I 1 I i ( I
fx. R~ aIP I D H 1 ? > aC YJ 1i ?C i4 1 1 I 1 1 1 ~ 7 I H H H H ~ M n7 <~I r7
eh rh
H .~ ~ ~ H M ~ H H W I~~1 H M H '.~' ~ 9C ?C bC ~C 'r~ w N N N N N N
W C yG st >a >a av >C x ~C at sc ~C ac Dt ~ m n n n t~- n n
H ,~r~ I
phi 1 I .
W ~ dl I I
N I
ti 1 I t~CJUUU U U G Uc,7t,~UC~4
0 0 a o 0 0 ! 4 0 0 0 0 o a
1 Lt9 Iff tA u5 eA uS M uW f1 :l7 N u1 1J1 IA ~' ,.
~CG193~QI ~ ~U O~ ~ ~ 1
I o 0 o a a ~ ~ a a a Q,
~W P : 1 CICI~~.Nd~a~e~a~~~a~.~-.y~~'~e~y~~ ~ ~C iJx'
I I o 0 4~ e~ ~ oar 0v Ip ~ ~ ~ ~ a wa..~ h. W w W o ~. ~.. ~. ~, ~-., w.
I I l!) lff °,9 .? > r~ ''.~' °3 J 'J r~ ~ ~ ~ r~'' e'J r~ ? ''J
d. ? J' .~ W 9 .~ ? ? ? ?
mw~rr~n;xacmxc~~ccawma;c~~asx x a x vrxczxsxxx
g . ~a~~sw~w~ww~w~~aa~~~w~~~ ~ ~ d~wwwww
1 I N
W ~~ I y y! W W to W f~ Gv 1~ ~ w W W 6r 44 ~e ~ W P4 P4 h. C! w
1y ~ . ~ roro . . . . m
H t 1 ~ ix1 U is V U U U U U U U 10 a1 U U U U U I,1 C7 U U Pa U U C7 U b U
I ~ a a >a la t, t.~ a N >.I N NN N a H a w w 1~ >H o ~ f.~
a,.iWminU~ ~U~~~~~UU V UUL U U ~ul~ ~U~~
per, ~ ~~~aC~a~A~OACOGOOGG~AGGt d p ~~OCA~~A
°~ ~ ~
N 0~A N W N N N N ~ E~'f N N N ~ ~ ~ N ~ ~-.; V7 ~-1 IA ~ N 171 N N N
jf~ \ 14h hnl.-1 ~...1 ~ y
U In~.l 1 ~ ~. ..~~.I ~..G~ a a..~.t..~~ a.~ ~..~a ~~.~1 ~ a.i a.~~ a ~x a ~ ~
C ~ ~ 1e
I ~,wa,p,a.wa~s~nrae~~wa~wwwwwa~n.~ w~ tea ~wwa~,~s~~
a
~~~~uV~~~~~~~t°nu°ee°nc°nu°~v°Wv.degr
ee.uxsna~c~~v°~c°nHt~t~o
d 0~ C~ a9~ h~ 1~~ h t~ l'~~ C~~ t~ Oo Ov
1 1 1 I 1 1 I I ! 1 1 1 1 1
O 1 O T'1 (~ p~ M eD ~D ~C CO 00 00 H h- H H .-t .-1 r1 .-i .i N M b' C ll1 n
!-~ n G7
W 11 O ri i e"1 N d C 0 W W r"'1 H H r4 H N N N N N N N N M t~'e M Qy f~ M f~l
M M Q
H (~ I~ I~;, ~i ~ 11 W r1 .1 r1 f1 11 r1 r.1 '-t r1 11 r1 vi r~1 H r1 ri r1
e~~I r~~1 r~e rw .1 H ri r1 H r-i
m' ~ I
n ~ ~ ~ al
Fe ~ ~ i ri N M e1~ !l! ~G i'~ CC Q? O ri N M Vr It1 tD n GO G~ C? e-1 N P'i
d' U7 i9 t~ OD Q~ O
sd H r~d rd si r1 r1 ~~~1 r1 H N N N N N N N N N N M
Q r Ln 6 Ic1 O u1 a
r1 N N cy1 r1
~d~ i~:~~
..
N N O
SD vD v0
r~1 47 r~
t1 .~1 N
O
LO N d' ~ "~ V ' II .-dl
u~min ice., ~ ~ w H~ 0.4 ro ~ a ro~~~o~LH
roL'' M k H QI fn a ~ 0 O w a 1,l
N
ro H dC ~ H b ~' N ~ ~I ~~ 4 N ~ a y~ b ~ 0J ~k ~
~ o a a 5 w o v1 r.r H a o m ~a .~~ m
x a~ m~.arov~~ a~ ~~oc~ . ~~N.~ Gg~ro~a
H ~ w N ~'~ x y v Tt ao N ,~ ~ .-I I b
m .a ~c a al a ..-r r~ m w a I sr
O O ~ X ~ I ~ H O 1~ .a a rC 1a p ~ N .,~ .-1 N
I I ~ Nq ~.a d' a 'O or a .N d ea ~ N G a~ a -a ~p
w .1 x m al a a ~ a ~ ~ ~n o o ~ w
xcc~ sam.~ ~,.~ woroa W ~-~m~,~uH
N N N . I m m 'CJ ~~1 .. .-I '~y 0! N N ,'t II ro C .~ it Cl O
t'~ C~ P pt N ro ' s~ Fi .C 01 H b .~ G> .-1 N W
~d b .~ u1 y H -.~ ..~1 H ..1 .b r1 U .~ Z G b
w ns ~-°'1 ~ - ~ w ~ '..~' ~ ve ~ b ~' y
01 H ~~-~ Ir 0 ~ d i7 c K w .
.p w x ,c ~ ~ H ro Ci ~ ~ ~a tr m a 4r ~ uo
N'~..~y~NdQ~ mmWm H~ d~b~ bNb~~r-i
Q, H M t! .~ .-r 01 ' ~ ~ W O 1 O U C N f:
41 r5' N ri ~.i .O ~'I C: Ci W 1.1 1 , L. -.a p 1,1 ..-1 'O
x as.~ m a.~.~ao~~ a., x xGN
~..N~ vbrCwH W~ dw v t~ o ~~a ro v
p, .,~ r1 O o ~a .-i N ~ w a) ~ w C ~ ~ 5 I
N of b ~ ?' tr ~.d O ~ ,~ 0 v m ~ a
a v v 4r N .-~ d ~ b ~ C O ~ .c ~ a ..I N a
o o a ,Q ?9 C iJ :1 01 v G H C ~ N G C4 C ~ s ~t
N N ~, ~r >., ~ ~ M w a o .c N .~ v s~ o ~, ~, o ~ Ic +~
in u1 u~ C7 ~..v W ,~a 1n .-,I .1~ N N .~1 0 4 ~~~ d O ~ r1
Y4 .Q 0f ?.~~i Q ~ ~ ~ dl iT. +t ~ ~ m ,O i~ .~ .~ a, ~ t
i
d ~ r~~1 ~~ N ~ C G ~ ~ ~ ~ ~ ~ ~ ~ 7
t7 Z CI~ d! W H .~.~ 0. 'O H ~ ~ n ,,.1 d ..1
p ~ °G3 ~ ~~ ' O GI o O ~t W O a ;' '~ ~ ~ ~~ 1~ ~
~ .~ ,c w ~ N ~ o ~' s~ ro a m .-I
i + + + ~~ ~~ ~ x ao w o" d +~ ~ I +~ w ,, a ~ a a~ s n .u tr "
~ ri ..1 H and O c~t ~ ~ ~! .C m 0 C s
I W fG 1! ~ G U GI O N U' r1 l'1 W ~ i4 ?. ' N '°' ~ ~-~-1 .1.1
~ m a cr ~ ~~~ N ~ o .-~ o ~ x v .N ~' q ~ ~ .c ~ .~ a ~~
r.,.a tnrl v ~ xw ~,~
I~u~o~a ~;~''~~~'~qI~°m rm,°~~o~r"a o ,~ .,~~v roo~u a
p, ~ Ol f7 H C C ..d C C ~d ~.9 N 0
I ~ ~ w ~ ,~ri N ~ i1 C ~ a a V U~ ~ SJ~ r.~ >w ~ a a m to ,>a
UGG OC~a~C'.~~ ~~NII~Dy~~.C~~~ ~ ~ ~~~ ..~~C~~
..i m N ~M p~ ~ Cp dl ~ ~ O Z. 4J 'Jr ~ 6'1 ~~ y'
ft ~ ~1~~00 C~~~'~.IOeuDW4r ~~~'~pd ~Ilf~~p
r a m a -~a m a ~~ ''''~~I
El YI ~~d ~~~ P4 v~ ~ ~r1 ~ 'j ~ 1u ~1~1 'Ci ~F~ G M
'~, ..a ..i m W ~ A. GI td W QI b ' .L1 N
N N r~ 0 ~ v ~~ ~ G v t~ N II N p ~~
~t ca M H .~ ~r .. ..1 .a . a .- C d,
" N ~ ~ m ~ ~ H ' ~ a ao ;-y '~ m ro a ~~
N N a' a~ 0 4 w .~ ~ ~d r.1 .a ~
N ro ro v 4 ,c ..r '.~ i~ a is r >,a
11 M N ~ ~ x ~y ~ ~' ~ W '' ~ C ~ ~ a,c ~ y a'6 ~
~ro ~~~a ~.~ a. ~ ~~~' ~ t~ ~o~oao w~'n,~w'~y
.~1 N M
MMM
p ' ~1 O 1i7 C 1t1 O
,.I rt N N ! ~ ~ a'
~~~~'~~:~3
0
v ., ~' w
a s a ~' a +~ c ~, .
V ~ I J.O.~ of ~c fir v ~ w N ~ d d a ~
o W ~ ~ fA ti +1 rt1 N 3 a ~ ~ N ~ ro 0
u'~w~~x,,vp,°~~~bu ~cxu.-vain' oro
+~ ~ 0 rr W H ro H .N U .V ~ ~ ~ 1~ y
t, x '~ ~ °~ a a ~ .roc i~ .'°a ~- cc .~ .a
0 II ~.-ml.l ~~ ~ ~ O N b ~ O x a ~ ~ ~-~ N V
a m .u p .~+~.~ °~ a.~ac .x v ~~a
id O ~ ~ .N w ~ ~ U 0 b ~ C9
b ~F1 O Sd N N ro ~.' 'a w
a ~ ~ec 0 ~ ~, ca a w ~.a1 m C
.1 ro .N ~ d~
4~ i~ 41 r0 0 07 01 .-r ~ ~ 'pa w . .al La1 x
m v N >J ~~ ~t a a a a
H GI c ~ .s; ~ d! w ~ C x b v ~v fi >, ~
w IR ~ ~~ b ~ ~ ~ W ~ O b..~01 ~ 'r9 a ~ ~ ~t
4~1 W ~ ~ .~.~ N w ~ s~ 0 ~ y ~ G a ~ ~ ~~ ~I
01 D ~ v N'M N 0 0! ~ ~ N .~r ~a ~ a
a p .~y sr w w O d 0 C4 m Cue H C1 0! x I
~''.a r .-I ,a m ao v w a ~-- d a ~a
.e.~~ a wLI savr m o wrov v o
d~1 ~"~ 11 '~ D 1a c~ ~4 G t~l 4 N a.1 f.i L.1 C ro r~ d
O tp ~ri a d 9i N r-a (~ t0 la Cl U
1r W N L~~ 4H I!! Of fl,.C UI d 1.1 u7 ~b ro ..1
ftl ,.t fQ ~ is.~ ~V ~~ b G'Hl w .,fir d U tn o
U II 3r.INCdIG~~~
> v~ ~~u ~ vas w a ~ a ~~ ..~ c
0G ri 16 C L Ol N ~ Q y
Ya G~ O CSI d~N ~.1 ~ ~ ~ ~' D ,~ ~ ~ 0~ divl ~.V.1 ~ ~ t=.
a w a ~ .~' ~I ~ ..r ''° ~ r~ a, ~' ~ N ~ a ~ .,
ca u1 rev ~v a bvo.a v
~ ~.~t ~ w ro y, ~ p.r .u ~ ,-~ o v °~m ro o ~''' a ~ ~~~ a
,e ~ .u s:a ~ an ro ~ ~.~ .~ ~ v ~r ~S' a
!d jJ r1 ~ IC 11 J~ ~1.' ~~ U if al ~~)
~., H I uo ~t a ro a~ s~ N ~.I ~.a al
~,,~ro~~ ~~ ~ v ai ro ~- w:° ~
a ar H ~. De ~d m ~ , 0 ~ ~ e1 w
w~au ~~~~u~~~N ~~ ~s~ bG
ab~~.~~mv~~w.°~'~ v"'~u°~ro~ ~'~~.I .,
h'~ ~,~ 0~ ~~~ ~~ v ~I ~ N.a c a H
o~va~°~~~rod~ pox ~~ ~ -~
tl~ a~ ~ $ ~ 3 f~~ ~4 ~ d ~r d~ v! w P, rtl '3 a4 W $ t4
tc~ o ~ ~ o u1
r1 ri N
-
~C
a
w
rv
00
n
~
,n v
o
M
r.,
.p,
w
M
N
v,
f
~
~
l'~
f~~
f~
rv
h
'~O
d
~
f
I
.
~'
h
r
v
w -
r
,
I~
t
r
f
"
f
~
h
a
7 0
~ L
'C oa
j;'!
Ptr.I'~flN
tAN~OO.
.n
~D
aOt'!N'Onl-O
fi
. ~
v ri
C v.
~ v
fi
co
t~
vi
f~
O fi
o vi
O N
c0
O
p w
O P
a
V
,
_
c ,..
O a
O n
O b.
~~
~ v?
- N
nev,fi~n
~o
~
i
ia
V
1r
f
v
n1 O
'v.O~tir-V
o.GCirvvivi~lr~W
n.
,~
ni
U
O O
O O
r p
O ~D~
V P
O h
O ~O
v.
f~
N P
M rv
O' o.
f'
f~
O
V O
4
O ~~
~ fi
r h
'a
~C
N ~
~ CI
~I
V ~
O
f~
U.
~
r
~
~
w
P
'~
~I
~
~1
f
i
h
~
O
ri
0
0
.. it N
~ f!
~
.
fl
~
C
_
m
H
P
~
~
U ~ ~f
00
w1
H
P
Y
h
N
~V
a
V
a
?
N
'i1
N
Y7
a
V
~
V
O
~ h 1
S O
O
C
O
C
O
O
O
4
O
O
O
O
O
O
'
O
,~ o ~
. P p
<s ~ O
O
, a
a ? 04
5~
v, p~.
..- t~1
n
~
~
y
d
H
~
P
~
Nt
V1
!1
~
V ti ~ ~ f!y r'1H
' h-.f'1O
r
--
M
f1
V
Q
0
a
a
'1
r1
N
Y
a
V
a
-1
V
't
ft
J
~Lcu V
N
'v v vv','~.ONO~~ vico
o'.~ondr-~~~i-nw~
a
:~
~ OaaaaeoPO~'~~ o n
r v'!v,
0
aw"
~
~ f n
- t
~l
.
o.~a
a
V
v
r
h
a
v
v
v~
v
n
~
0 p v v n
a
p
a
v
vW
x H
~
0
,00 m
r-onrv~~~~~wwh~Va~o~~~ t'~
M
w
v
a
'
v
c = n M !
i r
o
~
r!
r!
r~
c-!
r1
r!
r
r~!
~
o
v
s
U
,
h .
PG
O
o a fl~ ~ ~ ~ !_~.:~'? e~~'~~r~!~ r ~ ~ 2_
1fW"'
~
w ;'
O
f N ."....O ~ O O
I f!! n!O fie d
fn
N
rvM r,~s~n~oP _ _ i" ,:,,n ,;,r, ~~fi~ f~
o d d v. f
~
w h
o;n r; < 4 .
~ .
~ b z x r
o
o -
E~'
o p ~ ~ z x
o, ~...,.;
w
w
r
r,r;fi
~ '
a o o: r-r-ri
r.v~ r ~ ' e~~,
> ..:
~
& E .
F
o
~ i3 ~
j
~I V ~ ,p.,f V CO
b ~ o d ~ o
a
i
~
R
p'v1 h p!~h
~
Y~V 41 h
1
7
H
m
~
t
~r
Ov
r ~ r a
o ,
s~.
o
'
: c'' '' .
~ ~
. .
~
~ b
jt ~. Nt~~N ~
Q
w
~~~~ ~~.3
,, nv w
1
g
o,v o009 v a. rANS t t7.e w ~ a v, va
o
ca. oon ~o~o , ~d ~dr c ~o ~dN t:r.t~''
r r
W
'
v~ oov oo~n r.o~ en r ~ v ~ ~ o~. ~n
v, rna oa eo00 0o r 'r~l..
ti~ 1 W O tb O G1 O O p G G G , ,
r
1.., .
G p
et~
o ~ ~ ~ ~ o ~ a a
z ~ ~ . a . t ~ . 4 O p C O o O C1O O P CO 9
p w
7 a ~ ~
1 41 h p ~ _ ('I~ .A.nwq,~ p ~ ~ P r
v c o a o 0 0 0 0 0 o d o o d o t~a ca a o.
X .-.
'e3 ~ t
u
, '
f
~1d vhO d r- ~ ~ .PV W r1 r W O v r~ o W7
Ca ~n~ ~ ~ Y1c, d f1 P oo v;~ O r1O ci .
V
' 'h.C~~ i"1N tJN h7r1 t1 r1hl : TIri rM1 a
r1
t
L.
n W
.' ~., w ~ o ~ e'~ot' ~~ ~ ~ g ~ o
tiC
Q r1G >. d M N CVR V'h V ~ Y1 f0P0 1Dh O
C 1 I I O o O O c O O O V o O o Ci d t
C~,
m V CJ .
x V
A d D A ~ n ~ ~ A A ~ Q A ~ O
d ~ ~ a,.o ~ o. rvo, a rt o w a n ~nr- rvr .a
O O D 4 O ~ O
~ O ~ O C ~ p O
L t O O ~ O Q 6 D O e5O G O O G CiO p 9 t
V7 ~ ~ ~ ri C d
~ ~
P eoOn 19~ t-J ~ v h
rA' ~ Y ~ ~ tf V1~ O 1 ~ ~ M O F7 P ~D
~ ~ I 0 , , 9~ W ,
O 15O N N i V 3 V N Y 1 i
8 r ! f H e I c c O
~
p p v r;~C;h ~ r, v~o, v,o; ~tov m Eo a f a~ t th
e~ ; 'n
,awN ~ ~ l~~lN V~1N ~ ~ h M M ~ N P A M ~
_ V r f
E~ ~ ~ 0. I ~Y
~ ~ U ~ .~ c a v a V ~ n H ~ ~ ~ H
. C f
N
v s
x
o s ~ ~ ~ ~ ~ ~~ ~ ~ ~ ~ n
N
Q'D: O_vt_A0v_A
.~ ~ M P1 aTM b ~ 6 t~ t~P1 1n!tSM Po1~ ~ ~ ~
r1
r1 t
m 'I
x
t
o,o.ar;Maw p a
Wd ~d w r- W o ~a.
B
w
P ~ b ~ M
O C O o O O O C7 O
7 ",
o~ s
p a o a o 0 0 0 o H
a
'>
"- ~ Y: °: °~ °~ c a: .°:
ci o o ti d d o a o
d T '~f~ ~ tN~l ~ ~~-~ ' _~
O O d O O O Q Q ii
r ~ I
~, < ~ < G~
i Q ~ V ~ a
0 0
o a o ~ ~ o I t 1
G O A d D ,~~." a g
8 rv o t~ ac rs e~~
O ~ ~ ~ O ~ . ~ V a
o O O o P O O O F1 c
m
_ _
w ~ A~
? " . a ~R
w z ~ ~ ~y
~ evq ~ rte.. c~ r. ,~,
~t a .. .- ... o f d o w
M h H N ~~ tV $ pNy
'~ ~ 1 ! $ .'$ ~ ~ 5
n ~ ~n Q .~ -~ '° ~ a °° $ f
C ~ ~e
''
$ G.1 . .~ ~ ~ ~ . ~ P
4
1 1 ~ p 4 4 11 W
,~~,.a'-~l~~gr ~~ ~ ~'u:i.ao ~°~~~a."
- _
C N f tp°~ M M ~ _
a ,°~.~iG~.''~..~~~'~'rQ.'.v
l CZ I"
r
l ~~ 1~ :~
~ ~ C
d O O C7 Q O O O O O
O O O d d O n
0~ ~ l1'1 M
U1
C'
1
Q1
r1 M t'1 C~ G~ CY
G1 t0
~ ~C vD 10 v0 u1 N ~0 d'
U O U1 Y1 t0 U1 N ;
~ ~f7
,ri
i~
61
N
W
U
px', 1C7 O V1 D ts1 S? a ~N1
.~ O ~l1 u1 N O tn u1 .-~1
41 u'1 U
U Ep N ll1 h sh lTi O r~
t'~ ~D O N 1 U1 d' G)
O Id
h ppep d~~NaON Tr.~~O~r ~
l'r1~
b
N
ro~
~ ~
W O 2
~ N
~
'
~
~
O
~
a' ON
h-
0000
0p
G
pN0
C
0
-1
W -f
-1
-1
1
~ r O
e Q
'
,
~ r1 r1 .
Q)
O
d
'
~
~
O .d V ~ T1
~ u1 M o tl1 t,7 V1 tn w .
0 4 o tt1 tJ1 u1
Y'
y l1 O O
1
dr M O f" M O O GO f"1 N '"~ d
~ N 0' ,1 M ih Il1 N
~ '0' ''
'C m r yc av n o0 t~ ~
OI r r Wo n ~o co
G Ip ~ e
G ~
U~ ~ 0 r
~ v
~
U
p, 'd ra
H v
R~~ ~o
'~
C7 O .al' M O t0 ri ~ r1
~I n C9 N h O U1
~ O
H rf
i9
~'
,1J ~ . . . . ~ . . . . .
r-1 ~ . . .
Id ~ N N !~ ~O d' '4' u1 N 0~
O 1 '~ r (' N r r1 r1
'1 ~
M
1
'
~' 1 ~ ~
M w N
V
M
M M r"~ M M M ~
d d dJ al
d N O
,~ r1
Id
O
L '
i~ p
oN ~" ~
i ..t rl
.-1
C
n r Q, cwn r m ~0 o O 0
a ~C 1-~ r vo 0
.~ w
a a
a 1a 00 0o v r~ w r~ rwn m U 1
'd p ~ ~r d r C ?v
l ~ ?~
N
~
tJ) ~ r1 M ~ al' s1' eY ~ ,
G .~,. d' M' V' Q d at ~ i
41 ~
~d
'
. . p
..
~
O
4
N 1
U
U
w a
R >
O 3
0 ~ Id>t tf5 O O O O O "y~ r O
Ov t0 00 m 1t~ ,~ U
7 N G~ O G~ CO 00 ..
GC t0 h '
(J CI ih r r
1 41 W f1 d' rP d' ~ ~ C
~r a d~ ~ N o
~ G
~ .,r u -..
-11
.
0
~
d
R Irt
~
0 ~
V
it ~
. c
~
1r ,p
O ~ ~
O
~G O O p o ~ O
~
a' v O O O O v ~ ~ ~
-w.1 m o~ o M 'a N ~ a
a a~ so t
l d
d
r ~ TS ~
. ~ o
' ~' V' V' CD
'
'
'
.', V y ri
u7 V r1 S-1
d d 41 rt
i(1 tf1 'a
0 ~
~ m
o
t
A
~
'-1 I 1 ~ h
w L
~
, ~ r I
, -t ~
~ 0
O l
i~
H M 0 d
W ~
b
N "~ $ 3 d ,p ~
~ O q ~ ~
~ ' x" N
:-I rr w h N ~? ~ ~
1!1 4 O O Q ~ ~'
~. ( y I , row .
d I c ,y . a
o~ .rvoo.o.o.-m,~nln~n~n xx ~a
y ~u
, f ~C~ata'~wwuslnu~~neW ~ x ~.t~n
ntn~ o ~
,
o ~ ~ n ~t
"
ro
~
H ~ a ~
oo
~
w a
N
anonN.ru~oov~o~~nu~rnoocorn v '~d'~O
wa
. ~ yp h- r n t~. ~o e0 ~ ., ~
~D t~ N w to ~D ~D r~ . ~
O v.1
O
x ~
pp
w NNUVI
r~ r1
~/ -l
r-1 P
r1
l N
1
'
i
p,~ QI A r1 f'' V~ CO . ~
V' .-i ll1 t0 C'7 r -
itf ~D ~T 'd
~ ~C
a~
.r .~ .-1 r ~o r .r d w
~r mwn u9 ,r ~ ~O 4a
o 'C w
a 1
1 I
I .
co N 1 1 I 1 I I I cG
I R
1 .~r~ av w S-~ H GL
t~ M r~ th M M r~ O
e~i r, O
iJ
O
h r ~
'N
'
~
'
y
~ ~ ~
~ to ! N A
- t ~
C~ Y~ t !! Ul
f ~ ~
D
~
'~ c. h. G~ C1 0~ : ~ '
1 t1
w
w
N O P~
N ~-i ri ~-1 4 Lx
l-~
P~
-~ N (1 41 1
O 0) 1
1
~ h
a
'
- Ci
, .1-.".
U O
r t w ~
.-1 N M d W N
,~ x
N ~ ~'t t"D M P'! ro
t'1 f''f f"1 N1 M ~
d' ~i' ~' d' a
.-t .-~ ~ .-1 ~ .a
.-1 P.a .-r .-i .-1
~1 ~ ~
2~.~c~~ ~:~z~
Table. Vx presents a compaxison of pyrolysis/
neutralization conditions with gel times and reso7.e
viscosities far 25% and 5t7% phenol replacement with PN
product. Hate that sever2~~. repetitions of the px°eparations
have bean :nade~, with viscosities that vary within acce~ptabla
ranges for plywood manufacture as well as for other resole
applications such as d variety oP composit~ boards and paper
overlays.
The P/td products from the ails of Samples ,~31, 32
l0 and 33 are compared with those from similar materials, in
which the thermal severity of the treatment varied and the
properties of these materials are assembled in Table xzr,
whereas the conditions of ertraation are detailed in xable V.
These comparisons were investigated in order to
ascertain:
A) Whether other oils from different fast pyroly2er
reactors were suitable to produce PJN products for resole
formationp
B) whether gel times and resin properties depend on
species -- bath within the Southern pine family and r~utside;
and
C) whether c~el times/rssin properties correlate
with the method of production of P/N products, i.e.,
fractioriatian condi.tions.~
To obtain ariswera to guestion B) above, pines from
South Boston, Monticello and Russelville were investigated in
order to observe the characteristics of products from these
' - 51 -
' sources cornpar~d to feedstooks of Colox°ado pines and Douglas
Fir bark. Examples of other specie$ are Oak and Maple.
Tn order to assess the resole formation with resins
that would permit assessment of differences betr~e~,n
fractionation methods, resins were prepared at. two levels of
phenol substitution; i.e,, 25% and 50% by weight.
PROCEDURE
ease was added in two stages, with a large excess in
id the first addition, in which base and formaldehyde were added,
and a second addition of less sodium hydroxide. The final
viscosity was controlled in cooking each resin, so that the
resulting resin would be in a range deemed feasible for a
plywood resin as w~11 as composite boards {particle board,
oriented board, and strand board) and paper overlays, Table
~lX shows the resole viscosities and gal times at ~.
An illustration is: to 29.1, g P/N (equivalent to
2~%j~ 7o g of phenol, 20 g NaoH (5p$ wt) and 143 g of
formaldehyde . (37%) were added -.-. temperatures and viscosity
2~ were followed as a function of time; a second addition of half
of the initial amount of NaOH is added while t~-,e v~.sGOSity is
controlled. For the example with the resin fxc~m run 132, the
final viscosity achieved was TU (59o cps) and the gel time at
120~C Was 112 seconds for the first measux'emant and 117
seconds for the second one, resin reproduofbility was gaol
for gel times and less accurate for viscosity which could vary
widely with cooking conditions as shown in three examples of
S2 -
Table VI; cooking conditions are key to achieving the
desirable viscosity and gel times. The corresponding resin at
50% substitution gave gel times of 8s and 9z s~oonds and a
viscosity of 8so ceps. i~henol gel tines and viscosities
under the same conditions that the substituted resins were
prepared were '7~ and 81 seconds and ~7o cps. Using half ot~ .
the amount of base added in the first step and a similar
arnaunt in the second step, these numbers increase to 115 and
7.10 seconds and 550 cps. while these latter conditions mre
Zo more normal Eor plywood resin preparation, it should be kept
in rind that the goal is to demonstrate differences between
fractionated materials and not necessarily to optimize each
pr~apaxation .
The viscosities demonstrated in these preparations ;could be
15 suitable for a variety of applications ranging From plywood to
various composite boards and paper overlays.
In order to ascertain whether the F/td materials
reacted with formaldehyde and/or phenol, representative
resoles were 'taken to partial cure, such that the extraction
20 of the not fully reacted materials could be observed and the
extracts oharaGterized. These extracts were compared to then
pure phenol resins. From a 3-minute cure in a hot plate (3 g
sample), the materials were ground up and golubilized
seguentially in water and tetrahydrofuran. one gram of the
x5 partially cured resole was extracted overnight with 30.0 mL cf
water (shaken table) at room temperature; the a,gueaus
solution was separated and freeze dried for extractives
- 53
determination. The residue was dried overnight and
resuspended in THF for further assessment of solubilization of
intermediates (30 mL/g).
The phenol resoles produced roughly 8% of
extractable organic materials. FTIR speatxum of the ertract
had main absorption peaks at (absorption given in parenthesis)
765 (.13), 802 (.08), 831 (0.09), 1017 (.~.4), 1300 (.35), 1354
{.36), 1446 (1.16), 1603 (0.6), and 1697 (.1)Cm'~. These
absorption peaks are characteristic of oligomeric phenolic
struCtureg bonded by GHQ groups, having methylpl groups.
Tha amount of ~?xtraatives under similar conditions
of partial cure of the p/N~phenol (50%) resoles varied from
15.8$ {oak, high severity sample) to 23% for three sampJ.es of
intermediate severity samples of southern pins to 30-60% for
the low severity southex-n pine sample. The FTIR spectra of
these extracts oil not resemble those of tha original, P/N
produatt~, but produced the following key spectral features:
peak posi.t~.on ,in cm's (absorbance) 766 ( .26) ; .773 ( . 28) , 881
{.09), 1044 (.33), 1258 (.295), 1355 (1.26), 1368 (1.1), 1413
(.74), 1446 (.94), 1629 (2.2). Thess characteriatirs ors Very
dissimilar to the original 1~/N material and are signifinant~.y
increased ,~.n, the resole in the '760-880 cm's range,
characteristic of methylene groups; tha dominant pack St.1629
cm' xa ahaxactexistic of multiply substituted phenyl rings,
_ 54 _
and the disappearance of the 1512 cm'', which characterizes the
neat P/N pxt~ducts due to the aromatic skeletal rang vibrations
typical of aromatic structures with at least three zing
hydrogen atoms and increase i.rt the 162 cm~ peak, indicating
multiple substitution. The fingerprint region 1000-1400 cm"'
of the P/N product has also changed appsaranae drastically,
suggesting that the P/N product has reacted with
phenol/formaldehyde to produce oligomexs that contain methylol
groups and methylene-bonded phenyl compounds. Very little
unrebcted material can be detected by FTIR. The 1?/N materials
reacted and produasd oligomers/polymers. Reaction conditions
in the preparation of the P/t~1 products influence the ~xtettt of
reaction, thus providing a tool fox reactivity assessment of
the P/N products. ,
RESULTS AND INTERPRETATION
Important parameters in thermal severity are:
1) pyro7.ys~,s reactor temperature arid vapor
residence time (including vapor x-asidenca time in the reactor
2o and recycle xoop, as it is a very di:~ficult parameter to
calculate and the temperature is assumed constant, although
thex~ were small variations from experiment to ~xperiment);
2) temperature and zesidence time in the vapor
axacker (these were measured experimentally ~- ari average
vapor cracker temperature was used here); and
3) sequence of condensation temperatures (less
severe ttaan the above ones and assumed constant).
'rhermai Beverit~
Effeots oil time and temperature can be jointly
observed to pravide a guidelfor the production o~ the P/N
product as far as acceptable time/temparature profiles are
concerned. This treatment is based on severity concepts i~n
the literature that have been utilised in pulping,
Fractionation of lignocallulosics, and other pracessas [e. g.,
K, ~. Vroom, "The "H" factor: A means o~ e::pressing ccaoking
times and temperatures as ~, single variable", Pulg and Paper
Magazine of Canada, vol. 58, pp. 226-231 (1965); R. P. Overand
and ~. Chornet, "FracGi.onataon of Lignacellulosics by Steam
agueous pretreatment", Phil. Txansacti.on o:f the Royal Society
London, A, val. 321, pp. 523-536, 1987].
A reaction ordinate, the severity factor, is defined
as RW = exp[ (T, - T~) /w J *r~t, where T~ is the reaction
temperature, Tb is the base temperature (a temperature at which
the reactions are negligible), of ~.s the duration of the
reaction, and w is an exparimenta3 parameter, related td the
activation energy, and equal to ~6 or 1T degrees K in the
present case (26 kcal/mol and 29.8 kcal/mol, respectively for
pyrolysis and vapor thermal cracking). The severity results
era approxxmat,e, whil~ the thermal cracking results are
,experimental and more reliable than those sst~,mated fc~r the
pyrolysis step alone. The base temperature was chosen at
2Ua°C. Table VI shows the results of these calculations for
several Southern pittea and for oak.
- 56 -
~~~~ ~~_<~i
Therma~Z seve7rity - pH
The effect of the neutralization was added by
including the pH at which,that operation was carried oat. The
treatment follpwed literature xeferences: H. L. Chum, ~. K.
Johnson, and s. K. Hlack, "organosolv Pretreatment for ~ .
E:~zyr~atic ~tydrolysis of Poplars. II. Catalyst Effects and the
Combined Severity Parameter," ~,nd. sna. Chem. Res, Vol.
156-162, 1990; H. L. Chum, S. K. Black, I7. K. Johnson, and
R. P. Overend, "Pretreatment - CataJ.yst Effects and the
la Combined Severity Parameter" Auu~~ ~~ oo Vim,-~j ot,~t~ no , , Vol .
24/25, pp. 1-14, 1990. This combined severity parameter is
also shown in TablQ VI.
The two initial points in the table are approximate
since the severity was calculated as an average of pyrolysis
cvt~ditions from xuns 122-127, and therefore, these numbers
should be considered approximate. The actual parameters are
better known in runs 131--140.
By using factor analyses of the FTIR results, the
thermal severity, and the pH, a good norrelation can be
obsexve~d between the speCtxal properties and these variables,
which i.ec illustrated in Figure A.
The correlation includes factors 3 and 4, vrhich
contain wave number6 of 1711 and 7.263 cm''. These wavenumbers
axe associated with C~0 stretches in conjugated C~C systems
and C-o-CHI in the P/N products. Those frequencies axe
Chemically quite sensible for corralations since the higher
the amount of mathoxyl groups left, the r~lower the reactivity;
- 57 -
2~~~~.~~
the higher the G=ar C~C systems content, the higher the
reactivity. The correlatzo:~ observed involves
spectrax Factors*saverity - 4*spectral factors*pH~
and produces a correlation coefficient around 0.6.
Theraforg, t.he~rmal cracking severity - pH are
representative a~ the overcall severity of the production of
P/2J materials, and this ordinate is used in Table 'VZ.
ANALY8E5 0~' GEL TIMEB/VZSC06ZTY AS A k'UNCTION OF TIiDRMA~L
SEVERITY ANA THE COt4aINED THERMAL 6EVERITYJPH
The thermal severity permits grouping of the
relative gaverity of the preparation of these var~ous samples
from a thermal point of view only (see Figure B). The nunbers
used indicate the xun employed and can be cross-checl~;ed with
conditions in Tables VI and Tzz-V:
High Severity Group (44-45)
135 (45) ~ 137-139 (44.7) ~ x.30 (44.6) - 7.40 (oak, 44.6)
Intermediate Sewexity Gxoup (41-44)
131 (MantiCello, 43.'x) ~ 134 (43) ~ 133 (Wet South Boston,
42.6)
Low Severity Group (<42)
132 (Russelville, 41..5) > 121-127 (39, poor calculation since
it is averaging seven runs -- the number has at 7.aast a t 4
' - 58 -
error}a this group of samples could easily be in a higher
severitx group.
With the exception of samples from run 130, and the
trail from low severity runs, 121~127 and 132, all materials
make resoles of gel times from 50-80 seconds, which are equal
to or smaller than that for phenol, as displayed in figure H
or Table 'J1. The gel. times {where the first number represents
50% substitution, and the second number represents 25%
substitution) are as lollows:
High severity Group (at constant pH 7~0.1)
135 (73.5, 56.5) < 137-139 (72.5, 100.5} ~ 130 (117.5, 85.5)
> 140, oak (63, 85.5)
Intermediate severity Group
(pH of samples varied -~ average 7.4~0.4)
131 pH 7.4 {63.5, 97} a I34 pH 5.9 (88.5, 87) a 133 pH 7.8
as t7s, $~y
This group of samples of similar thermal severity
illustrates the very goad reproduvibility obtained from
different Southern pines, including one sample (133) which was
at 7% moisture content versus dried feed. Samples from
Monticella, South Bostan dry, arid South Boston wet were
obtained under similar reactor conditions and oalcuJ.ata to be
in the same thermal se~~erity group. The diffexence.s in pH
.- 59 -
p.r r" A
appeax td be responsible for s4me of the trends seen. The
average gel time at 50% substitution is 7?~12 and at 25%
substitution ie $f~~~ B°th'°f these values axe within two
standard deviations from the mean gel. time of 80 seconds for
phenol alone. Standard deviation for single measurements is
~3 seconds.
Low Severity Group
132 p1~ 7.3 (90.3, 114.5) ; 121-7 pa 6.9 (93.5, 78.a; 70, $2)
It should be noted that the RusselvillE sample,
which had a significantly loner thermal severity gave a rr~sole
with gel times that were significantly higher than the
previous samples. This fact suggests that severity parameters
can be used for c~peratic~naZ control of py:olysisJthermal
cracking.
A~.1 resoles at 50% substitution have gel. times that
were smaller than pr equal to 80 seconds {with the exception
of three samples from runs 130, x.32, and 121°-x.2? (Master
Batch) which gave gal times of 117.5, 93,5, and 90.3,
respectively). The outlier~s tend to be in the low severity
area. The Ax~.Btach P/N sample had a higher severitx than the
. carresponding Master Batch because of a higher temperature-
time profile duxing s°lvent evaporation, ~rhich lands suppoxt
to the idea that the higher severity samples appear to give
equal. or smaller gel times than phena~. alone.
° - ~Q -
The thermal severzty correlations parallel the
eyaractives removed from the partially cured resoles:
run 140 (oaX), severity 49. G, 7.6~$% extractives
runs x37-9 at pH 2.3 Ox 6.9, severity 44. G, 23.5% extractives
run 13f, severity 42.6, 24% extractives y
run x,21-127, XX-84 MB, severity 38.9, 28% extractives .
run 125.127, Aristech samples, severity 38.9, 68a extractives,
xn general terms, the higher the severity of the thermal '
process, the lower the amount of extractives removed from the
partially cured resole.
At 255 substitution, only the P/N pzoduced at the
highest tnerrnal severity has a gel time significantly smaller
than 80 seconds (56 seconds). Next, identical within 5
seconds, are the samples with high severity (oak, 85.5
seconds, runs 230, 133, and 7.37 139 at the highest severity,
with 77 seconds). Higher than 85 seconds are samples: 130,
7.31, 134, 137-9 dt pH 6.9 and 7.7, and ~iaterloo, three of
which have intermediate severity.
Ten PjN substituted samples gave higher resole gel
time at 25~ substitution th$n at 50~, while four ~rrere lower,
and appears to indicate a hi.r~hex reactivity between i'/N
species than P/N-phe~nol species reacted with formaldehyde or
with their own reactivs groups.
When the pH is inalude:d into the severity parameter
estimation, the following r~xe the groupings:
- 67. -
~~ i~~3
High sevexi.ty GHdup (42)
13789 pH 2.5 (42)
Intsrmediate Severity Group (35-38)
s i35 (3s.i) 2.137-9 pH 6.9 (37.7) - lao (oak, 37.7) : a3o
(37.q) ~ 137-~ pH 7.7 (37) Z 131 (Monticello, 36.3) ~ 134
(56.1) >_ 133 (Wet South Eoston, 34.1}
Lo~~r Severity Group (<35)
132 (Fusselville, 34) ~ 121-127 (poor calculation Since it is
averaging seven runs ~-- the number 32 can have at least a *4
error); these twa samples may easily be in a higher severity
group.
With exception of the sample frog: run 130, the
groupings lead to materials of very similar gel times, as
displayed in Table VI. mhe gel times (first number 50%,
second number 25% substitution levels) are as fo~.lovas;
2o High Severity Group
137-9 pii 2.5 (71, 77)
Intermediate Severity Group
135 (73.5, 56.5) < x.37-139 pH 6.9 (72.5. 100.5) < 1q0 (63,
85.3) ~ 13a (19.7.5, 85.5) ' 137-9 pH 7.7 (74, 92.5) > 131
(63.S, 97) = 134 (88.5, 87) < 133 (78, 85)
-- B2 -
2~~ ~G~:~3
Low Severity Group
132 (90.3, 114.5) ; 12i-7 (93.5, 78.x; ?0, 82)
~rQm these comparisons, it appears that: pH enables
one to see more differences between samples than would have
been seen when applying the thermal severity test alonee
(except for extraatable.s content), and that the samples with
variable pti follow a trend, although both the therl~al severity
calculations and the pN determinations in non-aqueous/ae~ueous.
1O wadia offer substant~.a~. experimental errors:
137-9 pH 2. r (7X, 77) < 137-139 pH 6.9 (72.5, 7.03.5) ~ 7.3'7-9
pH 7.7 (74, 92.5)
These resu~.ts suggest that the dominant factor is
thg thermal severity, but pH control allows an additional
degree of control of the suitability of the material Por,
replacement of phenol ir. phenol jforma~7.dehyde resins.
the viscosity of the resoles can be also grouped iri
an analogous manner. Hoarever, the resole advancement and i.ts
Viscosity can be controlled during cooking.
From the foregoing data, it can ba seen that many of
the samples prepared can replace 25~ or 50$ of phenol in
resoles.
Z5
It is possible to guide the conditions of P/N
product preparation such that the PjN-containing reso7,e$ have
' - 63 -
aoceptablo gel times and viscosities. The pH should be near
6.9t0.5, although a wider range of pH can be used between 2.3-
7.7. The impact of the use~of a pH 2.3 material is that more
water teachable material can be incorporated into the resin,
however, there axe no detectable differences in partially
cured resoles extractables from these samples prepared at pH
2,3 or 6.9, within the experimental error. Haiaever, the
higher pM is not desirable because it tends to farm more
precipitate in the neutralization/extraction steps (see Table
Tv) .
The maple samples at 50% replacement have lower gel
times than phenol. These samples gave higher viscosity
resoles; however, since these runs are with maple, it is more
difficult to assess the viscosity/gel tine relationship with
25 the unknown thermal treatment conditions. The second sample
has a more acceptable gel time at 25~t substitution, and the
decrease in resole viscosity is parallel to that observed in
the other samples.
The oak sample is a good example of a high severity
p/N product that can be employed with acceptable properties at
25$ and significantly better gel tames at 50% relative to
phenol.
A wide range of P/N praduats has been prepared that
is suitable fox replacement of phenol in resole resins. The
inhQrent reactivity of the material is us~ad to best advantage
by substituting 50% of phenol by the F/N material versus the
lower level Qf substitution. zntermediata to high severity
' - 6 4 ~-
~i !" ~,
c:anditions ax's best for the productioh of faster curing
matgrial$ at 50% substitution. The tranc9 appearing from the
data is that by increasing the severity further, the viscosity
of the result,S~g resole may be affected.
- G5
