CN117403462A - Method for comprehensively utilizing waste liquid from pulping by chemical mechanical method/sulfate method - Google Patents
Method for comprehensively utilizing waste liquid from pulping by chemical mechanical method/sulfate method Download PDFInfo
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- CN117403462A CN117403462A CN202311409091.XA CN202311409091A CN117403462A CN 117403462 A CN117403462 A CN 117403462A CN 202311409091 A CN202311409091 A CN 202311409091A CN 117403462 A CN117403462 A CN 117403462A
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- pulping
- waste liquid
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- furfural
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- 239000007788 liquid Substances 0.000 title claims abstract description 86
- 239000002699 waste material Substances 0.000 title claims abstract description 79
- 238000004537 pulping Methods 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 42
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 24
- 239000000126 substance Substances 0.000 title claims abstract description 19
- 238000010297 mechanical methods and process Methods 0.000 title claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 156
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229920005610 lignin Polymers 0.000 claims abstract description 47
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 37
- 230000008569 process Effects 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 65
- 238000010438 heat treatment Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000003265 pulping liquor Substances 0.000 claims 3
- 230000005226 mechanical processes and functions Effects 0.000 claims 2
- 238000001311 chemical methods and process Methods 0.000 claims 1
- 230000009471 action Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000284 extract Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000000605 extraction Methods 0.000 description 9
- 229920002488 Hemicellulose Polymers 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 239000002655 kraft paper Substances 0.000 description 5
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 244000166124 Eucalyptus globulus Species 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000002029 lignocellulosic biomass Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- 241000219000 Populus Species 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- 150000002972 pentoses Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical group CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
-
- 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
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/04—Regeneration of pulp liquors or effluent waste waters of alkali lye
Landscapes
- Paper (AREA)
Abstract
The invention belongs to the field of comprehensive utilization of lignocellulose raw materials, and provides a method for comprehensively utilizing pulping waste liquid by a chemical mechanical method/a sulfate method. The whole process fully utilizes the different chemical properties of the sulfuric acid at different temperatures, realizes different action effects of the sulfuric acid on all main components in the pulping black liquor by adjusting the treatment temperature, simultaneously extracts or prepares lignin, furfural and acetic acid, and realizes the high-value utilization of the black liquor.
Description
Technical Field
The invention belongs to the field of comprehensive utilization of lignocellulose raw materials, and particularly relates to a method for comprehensively utilizing pulping waste liquid by a chemical mechanical method/a sulfate method.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Lignocellulosic biomass feedstock is the most abundant renewable resource in nature, and about one hundred million tons of lignocellulosic biomass feedstock are used for pulping and papermaking each year worldwide. Woody biomass raw materials mainly consist of cellulose, hemicellulose and lignin. Cellulose in lignocellulosic biomass feedstock in the pulping and papermaking industry is used primarily for making paper, while a large amount of hemicellulose and lignin are dissolved in pulping effluent during pulping.
Hemicellulose is a heteromultimer composed of several different types of monosaccharides, with hemicellulose of broadleaf and grasses being mainly polysaccharides and hemicellulose of conifer being mainly polygalactoglucomannans. Lignin is a biopolymer with a three-dimensional network structure formed by connecting 3 phenylpropane units through ether bonds and carbon-carbon bonds, and contains rich active groups such as aromatic ring structures, aliphatic and aromatic hydroxyl groups, quinone groups and the like. Xylose, galactose, glucose, mannose and the like can be converted into important platform compounds such as furfural, 5-hydroxymethylfurfural and the like through a series of chemical reactions. Lignin is the only renewable resource in nature that provides aromatics and can be used to produce high heating value fuels and aromatics. The traditional pulping waste liquid treatment mode is to recycle chemicals and heat energy in the waste liquid by an alkali recycling method or discharge the waste liquid as waste water after biochemical treatment, which causes serious resource waste.
Therefore, there is an urgent need to establish a method for comprehensively utilizing the pulping waste liquid of the chemical mechanical method/the sulfate method, and efficiently extracting or preparing lignin, furfural, acetic acid and other products so as to improve the economic value of the pulping waste liquid.
Disclosure of Invention
In order to solve the problems, the invention provides a method for extracting lignin and preparing furfural and acetic acid by using chemimechanical/sulfate pulping waste liquid as a starting material. Firstly, acidizing pulping black liquor by using an acid solution and catalyzing lignin-carbohydrate complex (LCC) degradation to obtain high-purity lignin, and then acidolysis by using sulfuric acid and catalyzing hemicellulose in the black liquor to be converted into furfural and acetic acid. The whole process fully utilizes the different chemical properties of the acid solution at different temperatures, realizes different action effects of the acid solution on all main components in the pulping black liquor by adjusting the treatment temperature, simultaneously extracts or prepares lignin, furfural and acetic acid, and realizes the high-value utilization of the black liquor.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a method for comprehensively utilizing a chemimechanical/kraft pulping effluent, comprising:
filtering or centrifuging pulping waste liquid, and adding acid to form acidified waste liquid;
heating the acidified waste liquid to 100-120 ℃ and preserving heat to degrade lignin-carbohydrate complex LCC, and carrying out solid-liquid separation to respectively collect separated lignin and clear liquid;
placing the clear liquid in a closed container, heating to evaporate steam containing furfural and acetic acid, condensing, and collecting the evaporated liquid;
separating furfural and acetic acid from the distillate;
the pulping waste liquid is black liquor from sulfate pulping or waste liquor from chemimechanical pulping.
Wherein, the black liquor from the sulfate pulping process is used for extracting lignin from the black liquor from the sulfate pulping process by means of an alkali recovery system, and various organic matters in the waste liquor are utilized for producing furfural and acetic acid.
In some embodiments, the pH of the acidified waste liquid is from 1 to 4.
In some embodiments, the incubation time is 10-50min (chemimechanical pulping effluent) or 0.5-2h (kraft pulping black liquor).
In some embodiments, the temperature is maintained for 0-20 minutes in a sealed container heated to 150-220 ℃.
In some embodiments, the closed vessel is vented at a rate of 2 to 10% waste volume/min.
In some embodiments, the gassing, water injection and heating are stopped when the volume of the furfural-containing liquid is 0.5-1.5 times the volume of the starting liquid in the autoclave.
In the present application, the method for obtaining furfural and acetic acid by purification and separation from the reaction distilled liquid is not particularly limited, and those skilled in the art can select from various methods in the prior art according to the actual circumstances.
In some embodiments, the acid solution used for adding the acid is at least one of sulfuric acid, hydrochloric acid, and phosphoric acid.
In some embodiments, when the pulping waste liquor is kraft pulping black liquor, the remaining liquor in the closed container is introduced into a kraft pulping black liquor alkali recovery system;
when the pulping waste liquid is prepared by the pulping waste liquid chemical mechanical method, the residual liquid in the closed container is concentrated and desalted for adjusting the pH of the pulping waste liquid.
In a second aspect of the invention, there is provided furfural and acetic acid produced by the above-described process.
In a third aspect of the invention, there is provided the use of chemical pulping black liquor and chemical mechanical pulping waste liquor in the preparation of furfural and acetic acid.
The beneficial effects of the invention are that
(1) For the black liquor from the sulfate pulping process, the invention firstly uses sulfuric acid to acidify the black liquor and catalyze the degradation of lignin-carbohydrate complex (LCC) to obtain high-purity lignin, then uses sulfuric acid acidolysis and catalyzes the conversion of hemicellulose in the black liquor into furfural and acetic acid, and finally prepares and recovers sodium sulfide by means of a traditional black liquor alkali recovery system. The whole process fully utilizes the different chemical properties of the sulfuric acid at different temperatures, realizes different action effects of the sulfuric acid on all main components in the pulping black liquor by adjusting the treatment temperature, simultaneously realizes the utilization of reaction residues by depending on a pulping black liquor alkali recovery system, not only realizes the high-valued utilization of the black liquor, but also has the advantages of environmental protection and low production cost.
(2) For the pulping waste liquid of the chemical method mechanical pulp, the invention adopts the acid liquor to acidify the pulping waste liquid to promote the acid precipitation of lignin in the waste liquid, and simultaneously is used as a catalyst to catalyze the hydrolysis of glycan in the waste liquid into monosaccharide and acetic acid to further catalyze the conversion of five-carbon sugar into furfural, thereby reducing the dosage of chemical reagents and greatly reducing the production cost. The invention maintains the temperature to treat lignin suspension at a lower temperature, damages lignin-carbohydrate complex (LCC), and improves the purity of extracted lignin. The residual liquid after the reaction is finished can be recycled to adjust the pH of the pulping waste liquid, so that the recycling is realized.
(3) The preparation method is simple, has strong practicability and is easy to popularize.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention will now be described in further detail with reference to the following specific examples, which should be construed as illustrative rather than limiting.
In the following examples, the mass fraction of concentrated sulfuric acid was 72%.
The method for calculating lignin extraction rate and acetic acid yield of pulping waste liquid comprises the following steps:
(1) The lignin extraction rate calculation method comprises the following steps:
since the lignin precipitation amount in the waste liquid is influenced by the lignin concentration and pH in the waste liquid, the lignin precipitation mass m is selected when the pH of the waste liquid is=1 1 As a reference.
Lignin extraction%m/m 1 *100
Wherein m is lignin precipitation quality.
(2) The method for calculating the acetic acid yield comprises the following steps:
(1) determination of total sugar content in pulping waste liquor: a certain amount of pulping waste liquid is taken, the pH=7 of the waste liquid is regulated by dilute sulfuric acid, and 1mL of filtrate is taken out after filtration and placed in a pressure-resistant bottle. 70uL of sulfuric acid with mass fraction of 72% and 0.93mL of deionized water were added to the pressure-resistant bottle to make the concentration of sulfuric acid in the waste liquid 4%. The pressure-resistant bottle is placed in an oil bath pot at 121 ℃ and is kept for 60 minutes. The concentration of pentose in the waste liquid was determined using ion chromatography. Finally converting to obtain the concentration of pentose in the digestion waste liquid after acidolysis of C 1 (g/L)。
Total sugar content m in pulping waste liquor Total sugar (g)＝C 1 *V 1 Wherein V is 1 And (L) is the volume of pulping waste liquid.
(2) Determination of acetic acid concentration C in the distillate Using liquid chromatography Acetic acid (g/L)。
Acetic acid production m Acetic acid (g)＝V 2 *C Acetic acid is used as a solvent for the acetic acid, wherein V2 is the volume of distilled liquid
(3) Production rate alpha of acetic acid prepared from pulping waste liquid Acetic acid (％)＝m Acetic acid /m Total sugar *100。
Example 1
Pouring 500mL of filtered waste liquid from eucalyptus chemimechanical pulping into a pressure-resistant bottle, adjusting the pH value of the waste liquid to be 2 by using sulfuric acid with the mass fraction of 72%, heating the acidified waste liquid to 120 ℃, and preserving the temperature for 10min. Centrifuging at 4000rpm to separate out lignin from the waste liquid; placing the acidified and centrifuged chemical mechanical pulp waste liquid into a high-pressure reaction kettle, and adjusting the heating rate of the reaction kettle to heat the reaction kettle to 180 ℃ for 30 min; after heat preservation for 5min, opening and adjusting an exhaust valve of the reaction kettle, directly introducing steam rich in furfural and acetic acid into a condensing tube and collecting the steam in a glass tube, and adjusting the exhaust valve to enable the collection rate of condensate to be 20 mL/min; and opening the exhaust valve of the reaction kettle and simultaneously opening the switch of the high-pressure water sample device to ensure that the water inlet rate of the reaction kettle is equal to the condensate collecting rate. And when the volume of the condensate is 500mL, closing the reaction kettle air release valve and the high-pressure water inlet, and stopping heating. Purifying and separating the reaction distillate to obtain furfural and acetic acid.
The lignin extraction from pulping effluent and the production of furfural and acetic acid are significantly affected by the lignin content and total sugar content in the effluent. The yield of final lignin was 93%, the purity 92%, the yield of furfural was 76%, and the yield of acetic acid was 21%.
Example 2
500mL of eucalyptus chemimechanical pulp waste liquid is poured into a pressure-resistant bottle, the ph=2.5 of the waste liquid is adjusted by using concentrated sulfuric acid, and the acidified waste liquid is heated to 110 ℃ and kept for 20min. Filtering the acidified waste liquid to obtain acid-separated lignin in the waste liquid; placing the filtered chemical mechanical pulp waste liquid in a high-pressure reaction kettle, and adjusting the heating rate of the reaction kettle to heat the reaction kettle to 170 ℃ for 30 min; after heat preservation for 10min, opening and adjusting an exhaust valve of the reaction kettle, directly introducing steam rich in furfural and acetic acid into a condensing tube and collecting the steam in a glass tube, and adjusting the exhaust valve to enable the collection rate of condensate to be 25 mL/min; and opening the exhaust valve of the reaction kettle and simultaneously opening a switch of the high-pressure water inlet device to ensure that the water inlet rate of the reaction kettle is equal to the condensate collecting rate. And when the volume of the condensate is 750mL, closing the reaction kettle air release valve and the high-pressure water inlet, and stopping heating. Purifying and separating the reaction distillate to obtain furfural and acetic acid.
The lignin extraction from pulping effluent and the production of furfural and acetic acid are significantly affected by the lignin content and total sugar content in the effluent. The yield of final lignin was 88%, the purity was 90%, the yield of furfural was 73%, and the yield of acetic acid was 21%.
Example 3
500mL of wheat straw chemimechanical pulp waste liquid is poured into a pressure-resistant bottle, the pH=2 of the waste liquid is adjusted by using the reaction waste liquid, and the acidified waste liquid is heated to 100 ℃ and is kept for 30min. Filtering the acidified waste liquid to obtain acid-separated lignin in the waste liquid; placing the filtered chemical mechanical pulp waste liquid in a high-pressure reaction kettle, and adjusting the heating rate of the reaction kettle to heat the reaction kettle to 185 ℃ for 30 min; when the temperature of the reaction kettle is raised to 185 ℃, immediately opening and adjusting an exhaust valve of the reaction kettle, directly introducing steam rich in furfural and acetic acid into a condensing tube and collecting the steam in a glass tube, and adjusting the exhaust valve to enable the collection rate of condensate to be 20 mL/min; and opening the exhaust valve of the reaction kettle and simultaneously opening a switch of the high-pressure water inlet device to ensure that the water inlet rate of the reaction kettle is equal to the condensate collecting rate. And when the volume of the condensate is 500mL, closing the reaction kettle air release valve and the high-pressure water inlet, and stopping heating. Purifying and separating the reaction distillate to obtain furfural and acetic acid.
The lignin extraction from pulping effluent and the production of furfural and acetic acid are significantly affected by the lignin content and total sugar content in the effluent. The yield of final lignin was 93%, the purity was 90%, the yield of furfural was 76%, and the yield of acetic acid was 23%.
Example 4
Pouring 1000mL of filtered poplar sulfate pulping black liquor into a beaker, regulating the pH value of the black liquor to be 2 by using concentrated sulfuric acid, heating the acidified black liquor to 120 ℃ and preserving the heat for 0.5h, and then filtering the black liquor to obtain acid-separated lignin; placing the delignified black liquor into a high-pressure reaction kettle, and adjusting the heating rate of the reaction kettle to heat the reaction kettle to 185 ℃ for 40 min; after heat preservation for 5min, opening and adjusting an exhaust valve of the reaction kettle, directly introducing steam rich in furfural and acetic acid into a condensing pipe and collecting the steam in a glass pipe, and adjusting the exhaust valve to enable the condensate collecting rate to be 50mL/min; and opening the exhaust valve of the reaction kettle and simultaneously opening the switch of the high-pressure water sample device to ensure that the water inlet rate of the reaction kettle is equal to the condensate collecting rate. And when the volume of the condensate is 1200mL, closing the reaction kettle air release valve and the high-pressure water inlet device, and stopping heating. Purifying and separating the reaction distillate to obtain furfural and acetic acid. And finally, introducing the reaction residual liquid rich in sodium sulfate and sulfuric acid into a pulping black liquor alkali recovery system to realize the recovery and utilization of the reaction residual.
The lignin extraction from pulping effluent and the production of furfural and acetic acid are significantly affected by the lignin content and total sugar content in the effluent. The yield of final lignin was 93%, the purity 92%, the yield of furfural was 75%, and the yield of acetic acid was 20%.
Example 5
Pouring 1000mL eucalyptus kraft pulping black liquor into a beaker, adjusting the pH=2.5 of the black liquor by using 72%, heating the acidified black liquor to 100 ℃ and preserving the temperature for 1.5h, and centrifugally separating acid lignin in the black liquor; placing the delignified acidified black liquor in a high-pressure reaction kettle, and adjusting the heating rate of the reaction kettle to heat the reaction kettle to 180 ℃ for 30 min; when the temperature of the reaction kettle is increased to 180 ℃ and the temperature is kept for 10min, an exhaust valve of the reaction kettle is opened, steam rich in furfural and acetic acid is directly introduced into a condensing pipe and is collected in a glass pipe, and the exhaust valve is regulated to enable the collection rate of condensate to be 50mL/min; and opening the exhaust valve of the reaction kettle and simultaneously opening a switch of the high-pressure water inlet device to ensure that the water inlet rate of the reaction kettle is equal to the condensate collecting rate. And when the volume of the condensate is 1500mL, closing the reaction kettle air release valve and the high-pressure water inlet device, and stopping heating. Purifying and separating the reaction distillate to obtain furfural and acetic acid. And finally, introducing the reaction residual liquid rich in sodium sulfate and sulfuric acid into a pulping black liquor alkali recovery system to realize the recovery and utilization of the reaction residual.
The lignin extraction from pulping effluent and the production of furfural and acetic acid are significantly affected by the lignin content and total sugar content in the effluent. The yield of final lignin is 88%, the purity is 90%, the yield of furfural is 70%, and the yield of acetic acid is 21%.
Example 6
Pouring 1000mL of poplar sulfate pulping black liquor into a beaker, regulating the pH value of the black liquor to be=3 by using 72% sulfuric acid, heating the acidified black liquor to 90 ℃ and preserving the heat for 3 hours, and filtering the acidified black liquor to obtain acid lignin in the black liquor; placing the acidified black liquor after filtration in a high-pressure reaction kettle, and adjusting the heating rate of the reaction kettle to heat the reaction kettle to 185 ℃ for 30 min; when the temperature of the reaction kettle is raised to 185 ℃, an exhaust valve of the reaction kettle is opened and regulated, steam rich in furfural and acetic acid is directly introduced into a condensing pipe and is collected in a glass pipe, and the exhaust valve is regulated to enable the collection rate of condensate to be 30mL/min; and opening the exhaust valve of the reaction kettle and simultaneously opening a switch of the high-pressure water inlet device to ensure that the water inlet rate of the reaction kettle is equal to the condensate collecting rate. And when the volume of the condensate is 1000mL, closing the air release valve of the reaction kettle and the high-pressure water inlet, and stopping heating. Purifying and separating the reaction distillate to obtain furfural and acetic acid. And finally, introducing the reaction residual liquid rich in sodium sulfate and sulfuric acid into a pulping black liquor alkali recovery system to realize the recovery and utilization of the reaction residual.
The lignin extraction from pulping effluent and the production of furfural and acetic acid are significantly affected by the lignin content and total sugar content in the effluent. The yield of final lignin is 85%, the purity is 90%, the yield of furfural is 65%, and the yield of acetic acid is 20%.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for comprehensively utilizing waste pulping liquor from a chemical mechanical process/a sulfate process, comprising the steps of:
filtering or centrifuging pulping waste liquid, and adding acid to form acidified waste liquid;
heating the acidified waste liquid to 100-120 ℃ and preserving heat to degrade lignin-carbohydrate complex LCC, and carrying out solid-liquid separation to respectively collect separated lignin and clear liquid;
placing the clear liquid in a closed container, heating to evaporate steam containing furfural and acetic acid, condensing, and collecting the evaporated liquid;
separating furfural and acetic acid from the distillate;
the pulping waste liquid is black liquor from sulfate pulping or waste liquor from chemimechanical pulping.
2. The method for comprehensively utilizing chemical mechanical process/sulfate process pulping effluent according to claim 1, wherein the pH of the acidified effluent is 1 to 4.
3. The method for comprehensively utilizing the waste liquid from the chemimechanical/sulfate process pulping according to claim 1, wherein the holding time is 10-50min or 0.5-2h.
4. The method for comprehensively utilizing the waste liquid from the chemimechanical/sulfate pulping process according to claim 1, wherein the waste liquid is heated to 150-220 ℃ in a closed container and is kept for 0-20min.
5. The method for comprehensively utilizing waste liquid from chemimechanical/sulfate pulping process according to claim 1, wherein the air release rate of the closed container is 2-10% of the volume/min of the waste liquid.
6. The method for comprehensively utilizing the waste liquid from the chemimechanical/sulfate pulping process according to claim 1, wherein the gas release, the water injection and the heating are stopped when the volume of the liquid containing furfural is 0.5 to 1.5 times of the volume of the initial liquid in the high-pressure reaction kettle.
7. The method for comprehensively utilizing waste liquid from chemimechanical/sulfate pulping process according to claim 1, wherein the acid solution used for adding acid is at least one of sulfuric acid, hydrochloric acid and phosphoric acid.
8. The method for comprehensively utilizing the waste chemimechanical/sulfate pulping liquor according to claim 1, wherein when the waste pulping liquor is the sulfate pulping black liquor, the residual liquor in the closed container is introduced into a sulfate pulping black liquor alkali recovery system;
when the pulping waste liquid is prepared by the pulping waste liquid chemical mechanical method, the residual liquid in the closed container is concentrated and desalted for adjusting the pH of the pulping waste liquid.
9. Furfural and acetic acid produced by the process of any one of claims 1-8.
10. Application of black liquor from pulping by sulfate process and waste liquor from pulping by chemical process in preparing furfural and acetic acid.
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