CA2085513C - Resole resin products derived from fractionated organic and aqueous condensates made by fast-pyrolysis of biomass materials - Google Patents

Abstract

A process for preparing phenol-formaldehyde resole resins by fractionating organic end aqueous condensates made by fast-pyrolysis of biomass materials while using a carrier gas to move feed into a reactor to produce phenolic-containing/neutrals in which portions of the phenyl normally contained in said resins are replaced by a phenolic/neutral fractions extract obtained by fractionation.

Description

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$s for such phenolic materials as include black liquor from kxaft pulping and other pulping proaessas, wher~ the lignin is present in a stream which is commonly burned to recover praaess heat and chemicals.
Unfortunately, these lign~.ns are generally not vary reactive after recovery far a variety of reasons, such as high 25 molecular weight, chemical modification during recovery due to condensation reactions and the lik~, and lack of reproducibility cg properties. Various types of pyro~.ysis proces~aes have also been utixized, frequently yielding similar kinds of results; however, fast-pyrolysis, Which proC:eeds at temperatures between about, 450°C to about X00°C and has short vapor residence times in the ox-der of seconds has net been used.
Fast~~py'ralysis of biomass features the depolymerization of cellulosic, lignin, and hemicellulo$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 . . . . . . ~ . ..

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.

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.

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 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 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 C .
Density, @ 20 Heat Vaporization, kcal/mole (20C) 84 9.3 10.4 10.00 kcal/mole (b. 7.71 820 8.58 8.50 . .
p.) solubility, wt%
08 2.3 0.43 1.7 "0 '2 2.4 in water . 3.9 1.86 1.9 "0 '2 2.6 Watsr in .

Azeotrope 47 i4 28.7 24.3 44.0 24 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 Constant .

Solubility param.
1 8.4 8.46 8.57 s.55 8.5 8,8 Total . 6.6 7.67 7.49 ?.80 "7.8 pispe7csive comp.. 2.4 1..B 3.0 2.8 '3.4 Polar comp. . 4.8 3.1 2.0 2.0 2.0 ~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.

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 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~ _ 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 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.

~~~~~:~ ~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 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 ~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 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 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 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 i ~~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.
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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 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 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.

~~~~ ~~_<~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;

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) 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.

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.

Claims (102)

1. An improved process for preparing phenol-formaldehyde resole resins by fractionating organic and aqueous condensates made by fast-pyrolysis of biomass materials while using a carrier gas to move feed into a reactor to produce phenolic-containing /neutrals suitable for manufacturing phenol-formaldehyde resole resins, comprising:
admixing said organic and aqueous condensates with basic materials 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 to neutralize acidic components of said aqueous condensates and to render said acidic components and polar compounds less soluble in organic phase;
admixing said neutralized acid components of said aqueous condensates with an organic solvent having a solubility parameter of approximately 8.4 to 9.1 (cal/cm3)1/2 with a polar components solubility parameter in the 1.9-3.0 cal/cm3 range, and hydrogen bonding components in the 2-4.8 range to extract phenolic-containing and neutral fractions from the organic and aqueous phases into a solvent phase;
separating the organic solvent-soluble fraction having the phenolic-containing and neutral fractions from the aqueous fraction;

removing the organic solvent to produce said phenolic-containing and neutrals compositions in a form substantially free from said solvent; and substituting said phenolic-containing and neutrals composition for a portion of phenol in a phenol-formaldehyde resole composition.

2. A process for fractionating organic and aqueous condensates made by fast-pyhrolysis of biomass materials while using a carrier gas to move feed into a reactor to produce phenolic-containing/neutrals extract, wherein the neutral fractions have molecular weights of 100 to 800; said extract being suitable for a part of the phenol for manufacturing phenol-formaldehyde resole resins; said process comprising:
admixing said condensates with an organic solvent having a solubility parameter of 8.4 to 9.1 (cal/cm3)1/2 with polar components solubility parameter in the 1.9-3.0 cal/cm3 range and hydrogen bonding component in the 2-4.8 range to extract phenolic-containing and neutral fractions from said condensates into a solvent phase;
admixing said organic and aqueous condensates with basic materials selected from the group consisting of sodium hydroxide, sodium carbonate, sodium sesquicarbonate, potassium hydroxide, potassium carbonate, ammonium hydroxide, ammonium carbonate, lithium hydroxide, lithium carbonate, calcium hydroxide, calcium carbonate, magnesium hydroxide, magnesium carbonate, hydrates thereof, or mixtures thereof to neutralize acidic components of the condensates and to render said acidic components and polar compounds less soluble in organic phase;
separating the organic solvent-soluble fraction having the phenolic-containing and neutral fractions from the aqueous fraction; and removing the organic solvent to produce said phenolic-containing and neutrals compositions in a form substantially free from said solvent; and substituting said phenolic-containing and neutrals compositions for a portion of the phenol in phenol-formaldehyde resole composition.

3. The process of claim 1, wherein said organic solvent is selected from the group consisting of ethyl acetate, butyl acetate, methylisobutyl ketone and mixtures thereof.

4. The process of claim 2, wherein said organic solvent comprises ethyl acetate.

5. The process of claim 4, wherein the extraction utilizing ethyl acetate solvent is performed at a pH of approximately 6 to 8.

6. The process of claim 5, wherein the extraction utilizing ethyl acetate solvent is performed at a pH of about 6.5 to 7.5.

7. The process of claim 1, wherein said basic material is in a relatively dry, solid state.

8. The process of claim 1, wherein said basic material is dry sodium bicarbonate.

9. The process of claim 1, wherein said basic material is dry sodium carbonate.

10. The process of claim 1, wherein said basin material is a dry, hydrated form of sodium carbonate.

11. The process of claim 1, wherein said basic material is dry calcium carbonate.

12. The process of claim 1, wherein said basic material is dry calcium hydroxide.

13. The process of claim 1, wherein sail basic material is an aqueous solution of sodium carbonate.

14. The process of claim 1, wherein said basic, material is a slurry of sodium bicarbonate.

15. The process of claim 1, wherein said basic material is a slurry of sodium carbonate.

16. The process as claimed in claim 1, wherein said basic material is a slurry of calcium carbonate.

17. The process of claim 1, wherein said basic material is a slurry of calcium hydroxide in a suitable liquid.

18. The process of claim 1, wherein said neutralized pyrolysis condensates and condensed carrier steam are admixed with acid organic solvent in a solvent-to-dry-pyrolyzed-feed ratio of between 1 to 5 by weight, including solvent used to wash condensing equipment and/or to transfer the condensates into a neutralization tank.

19. The process of claim 1, wherein said organic solvent is removed from a residual organic fraction by evaporation to provide a substantially solvent free phenolic-containing/neutrals composition.

20. The process of claim 1, wherein said fast-pyrolysis condensates are produced from biomass materials that are lignocellulosic materials.

21. The process of claim 20, wherein said lignocellulosic materials are selected from the group consisting of softwoods, hardwoods, bark of tree species, and grasses.

22. The process of claim 21, wherein said softwoods are selected from pine and redwood.

23. The process of claim 21, wherein said hardwood is aspen, oak or maple.

24. The process of claim 21, wherein said bark of tree species is Douglas fir.

25. The process of claim 21, wherein said grass is bagasse.

26. The process of claim 1, wherein said phenolic-containing/neutrals fraction compositions are capable of substituting from 5% to 75% of phenol in phenol-formaldehyde resins.

27. The process of claim 18, wherein said phenolic containing/neutrals compositions include a high phenolic, hydroxyl and aldehyde content.

28. The process of claim 18, wherein said organic solvent is evaporated from a residual organic solvent fraction, and said phenolic-containing/neutral composition is in a substantially solvent free condition to form a basis for resin applications of molding compounds and wood adhesives for plywood, particle board, strand board, fiberboard, and paper overlay applications.

29. The process of claim 1, wherein said process is a series of batch processes.

30. The process of claim 1, wherein said process is a series of continuous processes.

31. The process of claim 1, wherein said process is a mixture of batch and continuous processes.

32. The process of claim 1, wherein said neutralization is a batch process and the extraction is a continuous process.

33. A resole resin containing the phenolic-containing and neutral fraction produced by the process of claim 1.

34. A process for fractionating organic and aqueous condensates made by fast-pyrolysis of lignocellulosic materials while using a carrier gas to move feed into a reactor to produce a phenolic-containing/neutral composition suitable for manufacturing phenol-formaldehyde resole resins, said process comprising:
admixing said organic and aqueous condensates with materials that neutralize acidic components of the condensates and render said acidic components and other polar compounds less soluble in an organic phase;
admixing said neutralized condensates with ethyl acetate to extract phenolic-containing and neutral fractions from the organic and aqueous phases into an ethyl acetate phase;
separating ethyl-acetate-soluble fraction having phenolic-containing and neutral fractions from an aqueous fraction;
removing the ethyl acetate solvent from the organic phase to produce said phenolic-containing and neutrals compositions in a form substantially free from ethyl acetate; and substituting said phenolic-containing and neutrals composition for a portion of phenol in a phenol formaldehyde resole composition.

35. The process of claim 34, wherein the carrier gas is noncondensible recycled gas.

36. The process of claim 34, wherein extraction utilizing ethyl acetate solvent is performed at a pH of approximately 6 to 8.

37. The process of claim 34, wherein extraction utilizing ethyl acetate solvent is performed at a pH of 6.5 to 7.5.

38. The process of claim 34, wherein said neutralizing material is in a relatively dry state and is 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, or hydrates thereof, or mixtures thereof.

39. The process of claim 34, wherein said neutralizing material is in a relatively dry state and is sodium bicarbonate.

40. The process as claimed in claim 34, wherein said neutralizing material is in a relatively dry state and is sodium carbonate or hydrates of sodium carbonate.

41. The process as claimed in claim 34, wherein said neutralizing material is in a relatively dry state and is sodium sesquicarbonate.

42. The process as claimed in claim 34, wherein said neutralizing material is in a relatively dry state and is calcium carbonate.

43. The process as claimed in claim 34, wherein said neutralizing material is in a relatively dry state and is calcium hydroxide.

44. The process as claimed in claim 41, wherein said neutralizing material is in a slurry form in a suitable liquid.

45. The process as claimed in claim 34, wherein said neutralizing material is in an aqueous solution and is selected from the group of sodium hydroxide, sodium carbonate, sodium sesquicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, lithium hydroxide, lithium carbonate, lithium bicarbonate, ammonium hydroxide, ammonium carbonate, or mixtures thereof.

46. The process of claim 34, wherein said neutralized pyrolysis condensates and condensed carrier steam are admixed with ethyl acetate solvent in a solvent-to-dry-lignocellulosic-feed ratio of between 1 to 5 by weight, including solvent used to wash condensing equipment and/or to transfer the condensates into a neutralization tank.

47. The process of claim 34, wherein said ethyl acetate is removed from a residual organic fraction by evaporation to provide a substantially solvent free phenolic-containing/neutrals composition.

48. The process of claim 34, wherein said lignocellulosic materials are selected from the group consisting of: softwoods, hardwoods, bark, and grasses.

49. The process of claim 48, wherein said softwoods are pine and redwood.

50. The process of claim 48, wherein said hardwoods are aspen, oak and maple.

51. The process of claim 34, wherein said phenolic-containing compositions include phenolic and neutral fractions therefore present.

52. The process of claim 34, wherein said phenolic-containing/neutrals fraction compositions are capable of substituting for up to 75% of phenol in phenol-formaldehyde resole resins.

53. The process of claim 42, wherein said phenolic-containing/neutrals compositions include a high phenolic hydroxyl and aldehyde content.

54. The process of claim 46, wherein said ethyl acetate solvent is evaporated from a residual organic fraction, and said phenolic-containing/neutral composition is in a substantially solvent free condition to form a basis for molding compounds and adhesives for wood bonding.

55. The process of claim 34, wherein a portion of said organic solvent/pyrolysis condensate not extracted into an organic solvent-soluble fraction is further processed utilizing zeolite catalysts to form gasoline.

56. The process of claim 34, wherein said process is a series of batch processes.

57. The process of claim 34, wherein said process is a series of continuous processes.

58. The process of claim 34, wherein said process is a mixture of batch and continuous processes.

59. The process of claim 34, wherein said neutralization is a batch process and said extraction is a continuous process.

60. An adhesive resin having the phenolic-containing and neutrals fraction produced by the process of claim 37.

61. A process for fractionating organic and aqueous condensates made by fast-pyrolysis of lignocellulosic materials while using steam as a carrier gas to move feed into and char out of a reactor to produce a phenolic-containing/neutral composition suitable for manufacturing phenol-formaldehyde resole resins, said process comprising:
admixing said organic and aqueous condensates with dry sodium carbonate to neutralize acidic components of the condensates to a pH of between about 6.5 and 7.5 to render such acidic components and other polar compounds less soluble in an organic phase;
admixing said neutralized condensates with ethyl acetate in a weight ratio of ethyl acetate solvent to dry lignocellulosic feed of between 1 and 5 to extract phenolic-containing and neutral fractions from organic and aqueous phases into an ethyl acetate phase;
separating an ethyl-acetate-soluble fraction having the phenolic-containing and neutral fractions from the aqueous fraction;
removing the ethyl acetate solvent to produce said phenolic-containing and neutrals compositions in a form substantially free from ethyl acetate; and substituting said phenolic-containing and neutrals compositions for a portion of phenol in a phenol-formaldehyde resole composition.

62. The process of claim 34, wherein said phenolic-containing and neutrals fractions are used as a basis to produce plywood, particle board, strand board, fiber board, paper overlay, and other applications of resole resins.

63. A process for fractionating organic and aqueous condensates made by fast-pyrolysis of lignocellulosic materials while using steam as a carrier gas to move feed into and char out of a reactor to produce a phenolic-containing/neutral composition suitable for manufacturing phenol-formaldehyde type resins, said process comprising:
admixing said organic and aqueous condensates with dry sodium bicarbonate to neutralize acidic components of the condensates to a pH
of between 6.5 and 7.5 to render said acidic components and other polar compounds less soluble in the organic phase;
admixing said neutralized condensates with ethyl acetate at a ratio of between 1 and 5 kg ethyl acetate per kg of dry feed to extract phenolic-containing and neutral fractions from the organic and aqueous phases into a ethyl acetate phase;
separating an ethyl-acetate-soluble fraction having a phenolic-containing and neutral fractions from an aqueous fraction;
removing ethyl acetate solvent to produce said phenolic-containing and neutrals compositions in a form substantially free from ethyl acetate; and substituting said phenolic-containing and neutrals compositions for a portion of phenol in a phenol-formaldehyde resole composition.

64. The process of claim 1, wherein the carrier gas used is noncondensible recycled gases, but where sufficient water is present in the condensates of fast-pyrolysis to form an aqueous phase and an organic phase, and wherein said aqueous phase is sufficiently large to extract water soluble organic compounds from the organic phase and to serve as an ionizing media for material used to neutralize acidic organic compounds present.

65. The process of claim 34, wherein the carrier gas used is noncondensible, but where sufficient water is present in the condensates of fast-pyrolysis to form an aqueous phase and an organic phase, and wherein said aqueous phase is sufficiently large to extract water soluble organic compounds from the ethyl acetate phase and to serve as ionizing media for material used to neutralize acidic organic compounds present.

66. The process of claim 61, wherein the carrier gas used is noncondensible, but where sufficient water is present in condensates of-fast-pyrolysis to form an aqueous phase and an organic phase, and wherein said aqueous phase is sufficiently large to extract water-soluble organic compounds from the ethyl acetate phase and to serve as an ionizing media for the sodium carbonate used to neutralize the acidic organic compounds present.

67. The process of claim 62, wherein the carrier gas used is noncondensible, but where sufficient water is present in condensates of fast-pyrolysis to form an aqueous phase and an organic phase, and wherein said with the aqueous phase is sufficiently large to extract the water soluble organic compounds from the ethyl acetate phase and to serve as ionizing media for the sodium bicarbonate used to neutralize acidic organic compounds present.

68. The process of claim 17, wherein said organic solvent is evaporated in a way as to produce a product having sufficient water remaining to provide a lower viscosity for ease of handling.

69. The process of claim 46, wherein said organic solvent is evaporated in a way as to produce a product having sufficient water remaining to provide a lower viscosity for ease of handling.

70. The process of claim 61, wherein said ethyl acetate is removed by evaporation in a way to produce a product having sufficient water remaining to provide a lower a viscosity for ease of handling.

71. The process of claim 62, wherein said ethyl acetate is removed by evaporation in a way to produce a product having sufficient water remaining to provide a lower viscosity for ease of handling.

72. The process of claim 68, wherein said organic solvent is partially or wholly evaporated by direct contact with steam.

73. The process of claim 69, wherein said organic solvent is partially or wholly evaporated by direct contact with steam.

74. The process of claim 70, wherein said ethyl acetate is partially or wholly evaporated by direct contact with steam.

75. The process of claim 71, wherein said ethyl acetate is partially or wholly evaporated by direct contact with steam.

76. The process of claim 1, wherein the organic solvent is recovered from the aqueous phase by evaporation.

77. The process of claim 42, wherein the organic solvent is recovered from the aqueous phase by evaporation.

78. The process of claim 61, wherein the ethyl acetate is recovered from the aqueous phase by evaporation.

79. The process of claim 62, wherein the ethyl acetate is recovered from the aqueous phase by evaporation.

80. The process of claim 76, wherein heat for evaporation is supplied by direct contact with steam.

81. The process of claim 77, wherein heat for evaporation is supplied by direct contact with steam.

82. The process of claim 78, wherein heat for evaporation is supplied by direct contact with steam.

83. The process of claim 79, wherein heat for evaporation is supplied by direct contact with steam.

84. The process of claim 1, wherein pyrolysis vapors are subjected to subsequent controlled thermal treatment after their formation to minimize the formation of precipitates during the neutralization and/or extraction steps.

85. The process of claim 35, wherein pyrolysis vapors are subjected to subsequent thermal treatment after their formation to minimize formation of precipitates during the neutralization and/or extraction steps.

86. The process of claim 61, wherein pyrolysis vapors are subjected to subsequent thermal treatment after their formation to minimize formation of precipitates during the neutralization and/or extraction steps.

87. The process of claim 62, wherein pyrolysis vapors are subjected to subsequent thermal treatment after their formation to minimize formation of precipitates during the neutralization and/or extraction steps.

88. The process of claim 1, wherein the aqueous phase is decanted and neutralized separately from the organic phase and then admixed with the organic phase to neutralize the organic phase.

89. The process as claimed in claim 29, wherein the aqueous phase is decanted and neutralized separately from the organic phase and then admixed with the organic phase to neutralize the organic phase.

90. The process of claim 61, wherein the aqueous phase is decanted and neutralized separately from the organic phase and then admixed with the organic phase to neutralize the organic phase.

91. The process of claim 56, wherein the aqueous phase is decanted and neutralized separately from the organic phase and then admixed with the organic phase to neutralize the organic phase.

92. The process of claim 5, wherein a part or all of the solvent used in the extraction is added prior to the neutralization.

93. The process of claim 34, wherein a part or all of the ethyl acetate solvent is added prior to neutralization.

94. The process of claim 54, wherein a part or all of the ethyl acetate solvent is added prior to the neutralization.

95. The process of claim 56, wherein a part or all of the ethyl acetate solvent is added prior to neutralization.

96. The process of claim 1, wherein steam recycled gases plus steam on an inert gas is the carrier gas.

97. The process of claim 1, wherein said organic solvent also exhibits low mutual solubility with water.

98. The process of claim 1, wherein said organic solvent is selected from the group consisting of acetate esters, methyl ketone, ethyl ketones and mixtures thereof.

99. The process of claim 1 wherein said fast-pyrolysis oils are produced from lignocellulosic materials.

100. The process of claim 2 wherein said biomass materials are lignocellulosic materials selected from tree group consisting of softwoods, hardwoods, pine sawdust, bark, grasses and agricultural residues.

101. The process of claim 1 wherein said phenolics/neutrals fractions extract replaces 5% to at least 50% by weight of the phenol in said phenol-formaldehyde resole resins.

102. The process of claim 1 wherein said phenolics/neutral fractions extract replaces 5% to at least 25% by weight of the phenol in said phenol-formaldehyde resole resins.