EP0211558A2 - Procédé de digestion de matière lignocellulosique - Google Patents
Procédé de digestion de matière lignocellulosique Download PDFInfo
- Publication number
- EP0211558A2 EP0211558A2 EP86305606A EP86305606A EP0211558A2 EP 0211558 A2 EP0211558 A2 EP 0211558A2 EP 86305606 A EP86305606 A EP 86305606A EP 86305606 A EP86305606 A EP 86305606A EP 0211558 A2 EP0211558 A2 EP 0211558A2
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- EP
- European Patent Office
- Prior art keywords
- line
- lignin
- water
- liquor
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000012978 lignocellulosic material Substances 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229920005610 lignin Polymers 0.000 claims abstract description 48
- 150000002148 esters Chemical class 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 63
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 20
- 239000002023 wood Substances 0.000 claims description 19
- 239000008346 aqueous phase Substances 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 13
- 238000004061 bleaching Methods 0.000 claims description 10
- 230000029087 digestion Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 150000002895 organic esters Chemical class 0.000 claims 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 23
- 229920002678 cellulose Polymers 0.000 abstract description 8
- 239000001913 cellulose Substances 0.000 abstract description 8
- 230000001079 digestive effect Effects 0.000 abstract description 7
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 238000004537 pulping Methods 0.000 description 19
- 239000012074 organic phase Substances 0.000 description 14
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 10
- 238000010411 cooking Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000605 extraction Methods 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 235000000346 sugar Nutrition 0.000 description 6
- 150000008163 sugars Chemical class 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920002522 Wood fibre Polymers 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002025 wood fiber Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241001263092 Alchornea latifolia Species 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241000218657 Picea Species 0.000 description 1
- 208000036366 Sensation of pressure Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940000425 combination drug Drugs 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
Definitions
- a number of pulping processes have been utilized in the past to separate cellulose fiber from wood and other lignocellulosic materials.
- the conventional pulping processes use inorganic chemicals, such as sodium, calcium, magnesium, ammonia, or sulfur as sulfides or sulfates, in water. Since lignin is insoluble in water, the most successful processes in the past have modified the lignin to water soluble alkali lignins or lignosulfonates.
- the Kraft and sulfite processes have been widely used commercially and these processes are geared to the use of recycling systems for the recovery of the inorganic chemicals. However, there has been a notable lack of success in utilizing the organic residue from these processes.
- the inorganic chemicals and the organic residues are concentrated as spent liquors. These spent liquors are burned to recover or destroy the inorganic chemicals. It is a major concern and financial burden on the pulping industry to purify the air and water effluents from the concentration and burning operations required to recover the pulping chemicals.
- lignin solvents such as acetic acid, formic acid, acetone, dioxane, polyglycols, alcohol, glycerol, phenol, and the like.
- the solvents are utilized to dissolve the lignin from the lignocellulosic material.
- these processes have proven to be unattractive for industrial application due to the high cost to make up and recover the solvents and the lower quality pulp produced.
- United States Patent No. 3,553,076 discloses a method of pulping using acetic acid.
- the presence of excess water is shown to be detrimental to producing good quality pulp due to the hydrolyzing of the cellulose and slowing down the rate of delignification.
- concentrations of acetic acid of greater than 50% by weight are used.
- wood chips normally contain about 50% by weight of water, so the amount of acetic acid required to achieve the high concentrations is excessive.
- United States Patent No. 4,100,016 discloses a method of pulping utilizing ethanol as the lignin solvent. In this process a 50% by weight aqueous solution of ethanol is utilized as the cooking liquor. Due to the high concentrations of alcohol required the recovery system is expensive, and due to high alcohol losses it is necessary to contend with government restrictions to assure that the alcohol does not leave the mill.
- the invention is directed to an improved process for digesting lignocellulosic material, and more particularly to a pulping process which reduces the amount of water in the digestion to reduce the hydrolysis of the cellulose, as well as accelerating the delignification and providing a more economical chemical recovery system.
- a lignocellulosic material such as wood chips is introduced into a digester with a cooking liquor composed of an ester, an organic lignin solvent and water.
- the ester is produced from an aliphatic alcohol having 1 to 4 carbon atoms in the molecule and an aliphatic acid having 1 to 4 carbon atoms in the molecule, while the lignin solvent is preferably either an organic acid, containing 1 to 4 carbon atoms in the molecule, or an alcohol containing 1 to 4 carbon atoms in the molecule, or a mixture thereof.
- the lignin solvent is miscible in both the ester and the water and the three components of the liquid composition are characterized by the ability to form a separate organic phase and aqueous phase under certain concentrations limits.
- the cellulosic material is maintained in the digester at a temperature of 0°C to 230°C for a sufficient time to solubilize the lignin in the ester and solvent.
- the liquid composition is then discharged from the digester and flashed to atmospheric pressure causing cooling. Cooling of the liquid will reduce the solubility of the lignin in the organic components with the result that a portion of the solubilized lignin will precipitate and be suspended in the water phase.
- the liquid is then transferred to a separation vessel where the organic phase, containing dissolved lignin, and the aqueous phase containing suspended particles of liquid, are separated.
- the organic phase containing dissolved lignin is returned to the digester for a succeeding digestive cycle, while the aqueous phase is further treated to remove residual organic materials and separate the lignin from the water.
- the delignification operation is accelerated over conventional processes utilizing inorganic chemicals.
- the major portion of the organic materials i.e. the ester and acid solvent, are separated in the organic phase from the water and are recycled back to the digester. This greatly simplifies the recovery system for the organic materials.
- the process of the invention also employs lower cooking temperatures for given pressures in the digestive zone and the time required to produce pulp having commercially acceptable properties is reduced.
- the process of the invention eliminates the use of sulfur compounds which cause series environmental pollution problems.
- the bleaching process can be substantially simplified by introducing bleaching chemicals into the washing cycle for the pulp.
- lignocellulosic material such as wood chips
- Wood is composed essentially of cellulose, hemicellulose and lignin with small quantities of extractives and minerals, the relative quantities of which vary depending on the wood species.
- An ideal pulping operation would be one that would modify the wood structure and/or separate the structure into its component parts and enable those parts to be reassembled as products that maximize the benefits derived from the individual physical and chemical properties of the component parts.
- the digesting liquor is composed of an ester, an organic solvent for lignin and water.
- the ester is formed from an aliphatic acid and alcohol each containing one to four carbon atoms in the molecule.
- Specific examples of esters that can be used are methyl acetate, ethyl acetate, propyl acetate and butyl acetate made from reacting the appropriate alcohol with acetic acid. Similar products can be made from formic, propionic and butyric acids. Lignin is soluble in the ester but to a lesser degree than in the organic solvent.
- the lignin solvent can be an organic aliphatic acid containing 1 to 4 carbon atoms, such as formic, acetic, propionic, or butyric acid, or an ali phatic alcohol containing 1 to 4 carbon atoms, such as methanol, ethanol, propanol and butanol, or mixtures of the acid and alcohol.
- the digesting liquor has the following composition in weight percent: Ester 1% - 98% Acid or Alcohol 1% - 90% Water 1% - 80%
- a preferred compositional range for the liquor utilizing an acid as the solvent is as follows: Ester 5 - 95% Acid 5 - 80% Water 10 - 60%
- compositional range for the liquor containing an alcohol as the solvent is as follows: Ester 5% -95% Alcohol 10% - 45% Water 10% - 60%
- Wood chips contain approximately 50% by weight of water and the specific composition of the cooking liquor falling within the above ranges is determined by the desired spent liquor composition which takes into account the liquid to wood ratio and the water content of the wood.
- the liquor is used in a weight ratio of about 1:1 to 20:1 with respect to the wood chips.
- acetic acid is soluble in both ethyl acetate and water, while ethyl acetate has only limited solubility in water.
- concentrations of acetic acid under about 22% by weight, the liquid composition will separate into two phases, an organic phase and a second aqueous phase.
- concentration of acetic acid under 40% by weight, so that when the liquor is discharged from the digester it can be made to separate into two phases as will hereinafter be described.
- Fig. 2 is a flow sheet showing a batch pulping system incorporating the invention.
- the wood chips or other biomass is fed to a digester 1 through line 2, while the digesting liquor contained in tank 3 is pumped through lines 4 and 5 to the lower end of digester 1.
- the digesting process is carried out at a temperature of 0°C to 230°C and preferably at a temperature of about 100°C to 200°C. If an elevated temperature is utilized, the liquor being introduced to digester 1 can be heated by steam in a heat exchanger 7.
- the digestion is carried out for a time sufficient to substantially delignify the lignocellulosic material, usually ranging from about 1 minute to 16 hours.
- the temperature and time are dependent upon the quality desired, the yield of pulp and the quantity and quality of the by-products to be produced.
- gaseous products discharged from the upper end of digester 1 through line 8 are passed through a heat exchanger 9 to cool the gases and are then delivered to a chemical recovery unit 10.
- chemical recovery unit 10 the gaseous products of the digestion, such as methanol, methyl acetate, furfural, and the like, are separated from the ethyl acetate, acetic acid and water vapors and discharged through line 11.
- the recovered ester, acid and water are recyled from chemical recovery unit 10 through line 12 and returned to digester 1.
- the liquor is discharged from the lower end of digester 1 through line 14 and delivered to a flash tank 15 which is at approximately atmospheric pressure.
- the flashing to atmospheric pressure will reduce the temperature of the liquor.
- the digester is operating at a temperature of 180°C and a pressure of150 psi, flashing to atmospheric pressure will reduce the temperature to about 100°C.
- the vapors resulting from the flashing are conducted through line 16 to the chemical recovery unit 10, while the liquid is discharged through line 17, and passes through screens 18 to remove fibrous material.
- the liquid then flows through line 19 to a primary phase separation tank 20.
- the liquor will be separated into two phases, an organic phase consisting primarily of the ester and acid and an aqueous phase consisting primarily of water.
- the concentration of the acetic acid in the digester is below 22%, the liquid will separate into the two phases. If the concentration of acetic acid in the digester 1 is maintained above 22% so that a two-phase separation will not occur, additional quantities of water and/or ethyl acetate can be added to the liquid after flashing to reduce the acetic acid concentration to a value below 22% so that the phase separation occurs in tank 20. If additional water is supplied, it can come from the bottom of the raffinate solvent recovery column 27 through line 33 or evaporator condensate through line 50.
- lignin As the lignin is less soluble in the organic components at a lower temperature after flashing than at the higher digesting temperature, a portion of the lignin will separate or precipitate from the organic phase and be suspended in the aqueous phase in tank 20.
- the organic phase consisting primarily of ethyl acetate and acetic acid with dissolved lignin, is then returned through line 21 to line 4 and recycled to digester 1.
- the aqueous phase consisting primarily of water containing suspended particles of lignin and also containing a limited amount of the ester and acid with lignin dissolved in the organic components, is then discharged from separator 20 through line 22 and is cooled to 20°C at cooler 22A and fed to centrifuge 34 where the suspended lignin is removed.
- the aqueous liquid is then introduced into the upper end of an extraction column 23 through line 35 or recycles back to primary phase separator 20.
- the extraction column which is operating at a temperature of about 20°C, acts to separate the water from the organic components.
- the organic components consisting of the ester and acid, are discharged from the upper end of column 23 and introduced into the central portion of an extract solvent recovery column 25 through line 24, while water is discharged from the lower end of column 23 through line 26 and is fed to a raffinate solvent recovery column 27.
- ester and acid are separativelyed by distillation and the acid containing dissolved lignin is discharged from the lower end of column 25 through line 28 and is returned to the liquor storage system 3.
- the ester is discharged from the upper end of column 25 through line 29 and is conducted through line 30 back to liquor storage system 3.
- a portion of the ester can be recycled from line 30 through line 31 to the lower end of extraction column 23 to aid in separating the organic components from water.
- column 27 the residual ester is separated from the aqueous phase and the ester is discharged from column 27 through line 32 which is connected to line 30, while the water containing dissolved sugars is discharged from the lower end of column 27 through line 33 to an evaporator 36 where a portion of the water is evaporated and the residue is delivered to a burning unit 37.
- the lignin recovered from the centrifuge 34 is conducted through line 38 to the burner unit 37.
- the burner unit 37 By burning the lignin and the residue from the evaporation, steam and electrical power can be generated for industrial use.
- the pulp in digester 1 is washed with the digester liquor.
- the liquor from storage system 3 is fed through lines 4 and 6 into the central portion of the digester and the liquor is drained from digester 1 through line 39 to a holding tank 40.
- the liquor in tank 40 is then returned to line 4 through line 41.
- the washing aids in removing residual lignin and sugars from the pulp.
- the pulp in digester 1 is subjected to a hot water wash.
- hot water in line 42 is fed to pulp recovery system 43 where it is used on pulp washers, then it is discharged from recovery system 43 through line 44 to line 4.
- the hot water, after entering the digester through line 6, is discharged through line 14 to flash tank 15.
- the washing water flows through line 17 and through screens 18 where it is transferred through lines 45 and 46 to secondary phase separator tank 47.
- separator tank 47 the residual organic materials, i.e. the ester and acid will separate as an organic phase from the water.
- the organic phase is delivered from the upper end of tank 47 through line 48 to line 19 where it passes through the primary phase separator 20, while the aqueous phase is discharged through line 49 and is returned to line 4 for recycling of the wash water.
- Condensate from the evaporation process can be delivered through line 50 to line 49 to add to the wash water.
- the pulp is flushed from digester 1 through line 51 to the pulp recovery system 43 where it is discharged through line 52 to other processing operations.
- the pulp can be bleached with hydrogen peroxide or other bleaching chemicals during the digesting operation. More specifically, the bleaching chemicals can be introduced into the hot water during the water washing cycle so that the pulp can be bleached in the digester to thereby eliminate the expensive bleaching equipment which is normally required in conventional pulping processes.
- Fig. 3 illustrates the invention as utilized in a continuous pulping process.
- Wood chips or other biomass are introduced through line 53 to a feed system 54 and the wood chips are continuously fed from feed system 54 through line 55 to the upper end of digester 56.
- Digester 56 will normally operate at a temperature in the range of 100°C to 200°C.
- the digesting liquor as described in connection with the batch process of Fig. 2, can be a com bination of ethyl acetate, acetic acid and water.
- the liquor is contained in liquor storage system 57 and is continuously fed through line 58 to the central portion of digester 56.
- a portion of the liquor is continuously recirculated through external line 59 and can be heated by passing through heat exchanger 60 in heat transfer relation to steam or other heating medium.
- the digesting liquor is continuously withdrawn from the digester through line 61 and flows to a flash tank 62 where the liquor is flashed to approximately atmospheric pressure.
- the reduction of pressure will volatilize the volatile components and cause a substantial reduction in the temperature of the liquor.
- the volatilized components resulting from the flashing are discharged from tank 62 through line 63 to the volatile chemical recovery system 64.
- recovery system 64 the highly volatile components such as methanol, methyl acetate, furfural and the like, are separated from the vaporized liquor and are discharged through line 65.
- the residual liquified liquor is then discharged from system 64 through line 66 and is returned to the wood chip feed system 54.
- the liquor being returned through line 66 can be preheated by passing through a heat exchanger 67 in heat exchange relation with the volatilized products flowing through line 63.
- the spent liquor is discharged from flash tank 62 through line 68 and passes through screens 69 to remove the fibrous material and then flows through line 70 to the phase separator tank 71 which operates in a manner similar to separator tank 20 of the first embodiment.
- the components of the digesting liquor are adjusted in concentration either in the digester or in tank 62, screens 69 or tank 71 so that a phase separation occurs in tank 71.
- liquor separates into an organic phase, which contains primarily the ester and acid with dissolved lignin, and an aqueous phase which contains precipitated lignin along with a minor amount of the organic components which, in turn, contain dissolved lignin.
- the organic phase is discharged from the separator tank 71 through line 72 and is continuously fed to the digester 56 through line 58, while the aqueous phase is discharged from the phase separator 71 through line 73 and cooler 100 to centrifuge 80 where the precipitated lignin is removed from the water.
- the water is discharged from centrifuge through line 81 and is pumped to the extraction column 74, while the lignin discharged from centrifuge 83 is fed to a burning unit 84, similar to burning unit 37 of the previous embodiment.
- Extraction column 74 operates in a manner similar to column 23 and serves to separate the aqueous phase from residual organic phase.
- the residual organic phase consisting of the ester and acid with dissolved lignin, is discharged from the upper end of extraction column 74 through line 75 and a portion of the organic components are fed to the central portion of extract solvent recovery column 77, while the remaining portion of the organic components pass through line 78 and is returned to the liquid storage system 57.
- column 77 the acetate and acetic acid are separated by distillation and the acetic acid is discharged from the lower end of column 77 through line 86 and is returned through line 78 to the liquor storage system 57, while the ester is discharged from the upper end of column 77 through line 87 and is recycled to extraction column 74 through line 88 or is returned to storage system 57 through lines 88 and 78.
- the pulp can be washed with hot water to remove residual spent liquor and lignin from the pulp.
- the water is introduced into recovery system 94 through line 96 and the water flows through lines 95 and 97 to the lower end of the digester 56 and is circulated from the digester through line 61 to the flash tank 62 and phase separator 71, as previously described in the first embodiment.
- the pulp is then flushed from digester 56 through line 98 to pulp recovery system 94 and then can be conveyed through line 98 for further processing in a conventional manner.
- the refined, bleached pulp product leaves in line 99.
- the system was heated to 170°C for 2 hours. After heating, the ethyl acetate/acetic acid, water solution containing the dissolved lignin, other extractives and dissolved sugars and polysaccharides were drained from the wood fiber and the wood fiber washed first with fresh liquor in the same proportions as the cooking liquor and then with acetone.
- the yield of pulp, Kappa number and pulping conditions are shown in Table I.
- Example II Additional experiments were carried out as described in Example I but at different cooking times as shown in Table II. A high yield pulp was obtained with a short cooking time and a post-refining stage as shown in the following table.
- Example III Additional tests were carried out as described in Example I but with different ratios of the three primary components of the cooking liquor, namely, ethyl acetate/acetic acid/water, and at different times and temperatures as shown in Table III.
- the two-phase liquid - liquid separation, in or outside of the digestive zone is controlled by the concentration of the individual components, i.e. the ester, lignin solvent and water.
- concentration of the individual components i.e. the ester, lignin solvent and water.
- the invention reduces the time required to produce pulp having acceptable chemical and physical properties and permits the use of lower cooking temperatures for given pressures in the digestive zone.
- the system also results in the production of higher yield pulps and higher strength pulps.
- the pulping system eliminates the use of sulfur compounds which cause serious environmental pollution problems.
- the invention also facilitates bleaching of the pulp, for the bleaching chemicals can be added to the water wash so that the bleaching can be carried out without the need for the expensive and complicated auxiliary bleaching equipment.
Landscapes
- Paper (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US75959185A | 1985-07-26 | 1985-07-26 | |
| US759591 | 1985-07-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0211558A2 true EP0211558A2 (fr) | 1987-02-25 |
| EP0211558A3 EP0211558A3 (fr) | 1987-05-27 |
Family
ID=25056238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86305606A Withdrawn EP0211558A3 (fr) | 1985-07-26 | 1986-07-22 | Procédé de digestion de matière lignocellulosique |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0211558A3 (fr) |
| JP (1) | JPS6269893A (fr) |
| CN (1) | CN86105219A (fr) |
| AU (1) | AU6049386A (fr) |
| BR (1) | BR8603731A (fr) |
| DK (1) | DK353886A (fr) |
| FI (1) | FI863069A7 (fr) |
| NO (1) | NO863018L (fr) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3830993A1 (de) * | 1987-09-14 | 1989-04-06 | Shell Int Research | Verfahren zum aufschliessen lignozellulosehaltigen materials |
| EP0325891A1 (fr) * | 1988-01-25 | 1989-08-02 | Kunz Holding Gmbh & Co. Kg | Procédé pour obtenir une pâte de cellulose blanchie |
| EP0485150A1 (fr) * | 1990-11-06 | 1992-05-13 | Biodyne Chemical Inc. | Procédés de lessivage, extraction de lignine et composition pour ces procédés |
| US5730837A (en) * | 1994-12-02 | 1998-03-24 | Midwest Research Institute | Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars |
| AT404478B (de) * | 1996-02-02 | 1998-11-25 | Impco Voest Alpine Pulp Tech | Celluloseherstellung |
| EP2489780A1 (fr) * | 2011-02-16 | 2012-08-22 | Rheinisch-Westfälisch-Technische Hochschule Aachen | Procédé intégré pour le fractionnement sélectif et la séparation de la lignocellulose en ses principaux composants |
| US10767308B2 (en) | 2014-07-09 | 2020-09-08 | Virdia, Inc. | Methods for separating and refining lignin from black liquor and compositions thereof |
| US11053558B2 (en) * | 2012-05-03 | 2021-07-06 | Virdia, Llc | Methods for treating lignocellulosic materials |
| WO2022125709A1 (fr) * | 2020-12-09 | 2022-06-16 | Virdia, Llc | Procédés d'extraction de lignine |
| WO2024017949A1 (fr) * | 2022-07-19 | 2024-01-25 | Katholieke Universiteit Leuven | Raffinerie de biomasse lignocellulosique |
| US11993624B2 (en) | 2013-05-03 | 2024-05-28 | Virdia, Llc | Methods for preparing thermally stable lignin fractions |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017086887A2 (fr) * | 2015-11-16 | 2017-05-26 | Ptt Global Chemical Public Company Limited | Procédé de fractionnement de biomasse lignocellulosique |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2024689A (en) * | 1934-02-16 | 1935-12-17 | Celanese Corp | Production of cellulose from ligno-cellulosic materials |
| US3553076A (en) * | 1968-01-22 | 1971-01-05 | Weyerhaeuser Co | Non-catalytic process for the production of cellulose from lignocellulosic materials using acetic acid |
| JPS6044430B2 (ja) * | 1978-09-22 | 1985-10-03 | 東洋紡績株式会社 | 合成高分子成形品の耐溶融加工方法 |
| JPS5846176A (ja) * | 1981-09-10 | 1983-03-17 | 帝人株式会社 | ポリアミド合成繊維の撥水撥油加工方法 |
| JPS59163474A (ja) * | 1983-03-04 | 1984-09-14 | 旭化成株式会社 | 抗菌性を有するポリアミド系繊維製品の製造法 |
| JPS61102492A (ja) * | 1984-10-23 | 1986-05-21 | ユニチカ株式会社 | 染色堅牢度向上方法 |
-
1986
- 1986-07-22 EP EP86305606A patent/EP0211558A3/fr not_active Withdrawn
- 1986-07-24 AU AU60493/86A patent/AU6049386A/en not_active Abandoned
- 1986-07-25 BR BR8603731A patent/BR8603731A/pt unknown
- 1986-07-25 FI FI863069A patent/FI863069A7/fi not_active Application Discontinuation
- 1986-07-25 NO NO863018A patent/NO863018L/no unknown
- 1986-07-25 DK DK353886A patent/DK353886A/da not_active Application Discontinuation
- 1986-07-26 JP JP61176542A patent/JPS6269893A/ja active Pending
- 1986-07-26 CN CN198686105219A patent/CN86105219A/zh active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3830993A1 (de) * | 1987-09-14 | 1989-04-06 | Shell Int Research | Verfahren zum aufschliessen lignozellulosehaltigen materials |
| GB2209772A (en) * | 1987-09-14 | 1989-05-24 | Shell Int Research | Process for pulping lignocellulose-containing material |
| GB2209772B (en) * | 1987-09-14 | 1991-05-15 | Shell Int Research | Process for pulping lignocellulose-containing material |
| EP0325891A1 (fr) * | 1988-01-25 | 1989-08-02 | Kunz Holding Gmbh & Co. Kg | Procédé pour obtenir une pâte de cellulose blanchie |
| EP0485150A1 (fr) * | 1990-11-06 | 1992-05-13 | Biodyne Chemical Inc. | Procédés de lessivage, extraction de lignine et composition pour ces procédés |
| US5730837A (en) * | 1994-12-02 | 1998-03-24 | Midwest Research Institute | Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars |
| AT404478B (de) * | 1996-02-02 | 1998-11-25 | Impco Voest Alpine Pulp Tech | Celluloseherstellung |
| EP2489780A1 (fr) * | 2011-02-16 | 2012-08-22 | Rheinisch-Westfälisch-Technische Hochschule Aachen | Procédé intégré pour le fractionnement sélectif et la séparation de la lignocellulose en ses principaux composants |
| WO2012110231A1 (fr) * | 2011-02-16 | 2012-08-23 | Rheinisch-Westfälische Technische Hochschule | Processus intégré de fractionnement sélectif et de séparation de la lignocellulose en ses composants principaux |
| US11053558B2 (en) * | 2012-05-03 | 2021-07-06 | Virdia, Llc | Methods for treating lignocellulosic materials |
| US11993624B2 (en) | 2013-05-03 | 2024-05-28 | Virdia, Llc | Methods for preparing thermally stable lignin fractions |
| US10767308B2 (en) | 2014-07-09 | 2020-09-08 | Virdia, Inc. | Methods for separating and refining lignin from black liquor and compositions thereof |
| WO2022125709A1 (fr) * | 2020-12-09 | 2022-06-16 | Virdia, Llc | Procédés d'extraction de lignine |
| WO2024017949A1 (fr) * | 2022-07-19 | 2024-01-25 | Katholieke Universiteit Leuven | Raffinerie de biomasse lignocellulosique |
Also Published As
| Publication number | Publication date |
|---|---|
| FI863069A0 (fi) | 1986-07-25 |
| NO863018D0 (no) | 1986-07-25 |
| AU6049386A (en) | 1987-03-19 |
| FI863069L (fi) | 1987-01-27 |
| EP0211558A3 (fr) | 1987-05-27 |
| DK353886D0 (da) | 1986-07-25 |
| BR8603731A (pt) | 1987-03-10 |
| CN86105219A (zh) | 1987-02-25 |
| FI863069A7 (fi) | 1987-01-27 |
| JPS6269893A (ja) | 1987-03-31 |
| NO863018L (no) | 1987-01-27 |
| DK353886A (da) | 1987-03-20 |
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