CN116676800A - Method for removing lignin from lignocellulose raw material by using molecular sieve and reaction device thereof - Google Patents
Method for removing lignin from lignocellulose raw material by using molecular sieve and reaction device thereof Download PDFInfo
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- CN116676800A CN116676800A CN202310863745.XA CN202310863745A CN116676800A CN 116676800 A CN116676800 A CN 116676800A CN 202310863745 A CN202310863745 A CN 202310863745A CN 116676800 A CN116676800 A CN 116676800A
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- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 86
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229920005610 lignin Polymers 0.000 title claims abstract description 65
- 239000002994 raw material Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 title claims description 49
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 71
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229960000583 acetic acid Drugs 0.000 claims abstract description 34
- 239000011259 mixed solution Substances 0.000 claims abstract description 33
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005485 electric heating Methods 0.000 claims description 9
- 230000002572 peristaltic effect Effects 0.000 claims description 6
- 238000010025 steaming Methods 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims 2
- 241001330002 Bambuseae Species 0.000 claims 1
- 239000011121 hardwood Substances 0.000 claims 1
- 239000011122 softwood Substances 0.000 claims 1
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 23
- 239000007787 solid Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229920001131 Pulp (paper) Polymers 0.000 description 14
- 229920002488 Hemicellulose Polymers 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- 244000166124 Eucalyptus globulus Species 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- -1 superoxide free radical Chemical class 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001397809 Hakea leucoptera Species 0.000 description 1
- 241000219071 Malvaceae Species 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960005191 ferric oxide Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002023 wood 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
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
-
- 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
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
Abstract
The invention discloses a method for removing lignin from lignocellulose raw material by using a molecular sieve, which comprises the following steps: and (3) placing the lignocellulose raw material into a mixed solution of hydrogen peroxide and glacial acetic acid, and adding a molecular sieve to the lignocellulose raw material after being steamed to obtain the lignocellulose raw material with lignin removed, wherein the molecular sieve is a FeY molecular sieve. The method of the invention adds hydrogen peroxide and acetic acid to produce synergistic effect with FeY molecular sieve, oxidizes toxic and nondegradable organic compounds, thereby achieving the purpose of removing or separating lignin, and the whiteness of the lignocellulose raw material treated by the method can reach 85ISO, thus obtaining the finished product with high whiteness and high lignin removal rate by a one-step method.
Description
Technical Field
The invention belongs to the technical field of biomass, and particularly relates to a method for removing lignin from lignocellulose raw materials by using a molecular sieve.
Background
In lignocellulosic feedstocks, the composition will generally comprise three parts: lignin, cellulose and hemicellulose. Wherein lignin, cellulose and hemicellulose are cross-linked with each other, and lignin is rigid and not easily corroded, and generally plays a supporting role in cells.
The traditional lignin removing method is a strong alkali removing method, but the treatment method has the problems of incapability of recycling waste liquid, metal ion residue phenomenon, environmental pollution and the like in the reaction process, the treated lignin raw material needs to be subjected to pretreatment such as pressurization, crushing and grinding, the process is complex, the maximum thickness of the treated raw material needs to be less than 0.5mm, lignin can be converted into lignin salt, the original structure of the lignin is changed, and the environment-friendly efficient recyclable chemical concept is not met.
Therefore, it is a problem to be solved by those skilled in the art to provide a method for removing lignin which has the advantages of simple treatment process, environmental friendliness, low production cost and high removal efficiency.
Disclosure of Invention
In view of the above, the invention provides a method for removing lignin from lignocellulose raw materials by using a molecular sieve, wherein hydrogen peroxide and acetic acid are added to generate synergistic action with FeY molecular sieve, so that toxic and nondegradable organic compounds are oxidized, the purpose of removing or separating lignin is achieved, the whiteness of the lignocellulose raw materials treated by the method can reach 85ISO, and a finished product with high whiteness and high lignin removal rate can be obtained by a one-step method; and the thickness of the processed lignocellulose raw material can reach 30mm, so that the lignocellulose raw material does not need to be crushed or ground into fine particles in advance, and the processing efficiency is greatly improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for removing lignin from a lignocellulosic feedstock utilizing a molecular sieve, the method comprising the steps of:
and (3) placing the lignocellulose raw material into a mixed solution of hydrogen peroxide and glacial acetic acid, adding a molecular sieve, and steaming to obtain the lignocellulose raw material with lignin removed.
The invention utilizes the characteristic of easy-to-obtain electrons of transition metal (Fe) and the synergistic effect of the transition metal (Fe) with hydrogen peroxide and acetic acid to generate hydroxyl (& OH), organic free radical (R-C.) and superoxide free radical (& O) in situ 2- ) And singlet oxygen 1 O 2 ) And (3) separating lignin from the lignocellulose raw material by using high-activity substances, thereby solving the problem that the lignin in the lignocellulose raw material is difficult to treat when removing high-pollution waste liquid in the pulp production process.
Preferably, the concentration of the hydrogen peroxide is 20-50%, and the concentration of the glacial acetic acid is 95-99%;
the mass ratio of the hydrogen peroxide to the glacial acetic acid is 1:0.2-4.5.
Preferably, the concentration of the hydrogen peroxide is 30%, and the concentration of the glacial acetic acid is 99%.
Preferably, the mass ratio of the lignocellulose raw material to the mixed solution is 1:1.0-3.0.
Preferably, the molecular sieve is FeY molecular sieve, and the molar ratio of the effective components in the molecular sieve is 0.5Na 2 O：0.167Al 2 O 3 ：1SiO 2 ：22.5H 2 O：xFeSO 4 ：yH 2 O 2 (x＝0～0.01，y＝0～0.15)。
Preferably, the mass ratio of the molecular sieve to the mixed solution is 1:50-5000.
Preferably, the thickness of the lignocellulosic feedstock is from 0 to 30mm.
Preferably, the parameters of the cooking are: the temperature is 40-90 ℃, and the reaction time is 2-6h.
Preferably, the temperature is 60 ℃.
Preferably, the filtrate obtained after the steaming is dried to obtain lignin.
Preferably, the lignocellulosic feedstock is selected from at least one of pine, eucalyptus, basswood and fir, and the delignified lignocellulosic feedstock is used in pulp production.
Preferably, the lignocellulose raw material is any one of bamboo, needle wood and broad-leaved wood.
The reaction device comprises a reaction kettle, wherein the top of the reaction kettle is provided with a feed inlet and an exhaust port;
the bottom of the side wall of the reaction kettle is provided with a first circulation port which is connected with a second circulation port arranged at the upper part of the first circulation port through a peristaltic pump;
a discharge hole is formed in the middle of the bottom of the reaction kettle, and electric heating devices are arranged on two sides of the discharge hole;
the top is equipped with the stirring rake in the reation kettle, the stirring rake top the reation kettle lateral wall is equipped with molecular sieve layer.
Preferably, the electric heating device comprises an electric heating sleeve and rock silicate cotton.
Preferably, the exhaust port is connected with the water tank.
Adding stirring paddles into the reaction kettle to accelerate the reaction, wherein a discharge port is arranged at the bottom of the reaction kettle; a peristaltic pump is additionally arranged outside the reaction kettle to accelerate the reaction of the mixed solution in the reaction kettle, and an electric heating sleeve and rock silicate cotton are additionally arranged outside the reaction kettle to heat and preserve heat; in the reaction process, the FeY molecular sieve is filled in a 500-mesh 316L stainless steel mesh layer, and the molecular sieve can be recycled.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a method for removing lignin from lignocellulose raw materials by using a molecular sieve, wherein lignin, cellulose and hemicellulose are crosslinked with each other in the plant lignocellulose raw materials, and the lignin has rigidity and is not easy to corrode and generally plays a supporting role in cells, but due to the lignin polyhydroxy structure, when the lignin is treated by an alkaline method, new groups are added to the lignin to become lignin salt which is dissolved in water, so that the original structure of the lignin is damaged. Under acidic conditions, lignin usually maintains the original structure, so that the invention utilizes the synergistic effect generated by glacial acetic acid, hydrogen peroxide and FeY molecular sieve and the characteristic of easy-to-get electrons of transition metal to generate hydroxyl (& OH), organic free radical (R-C) and superoxide free radical (&O 2- ) And singlet oxygen 1 O 2 ) The lignin removal rate of the equal-high active substances in the lignocellulose raw material can reach 94% and the hemicellulose removal rate reaches 91% within 6 hours, the method does not generate waste water, and the whiteness of the treated fiber can reach 85ISO; the method can not generate waste water and destroy the original structure of lignin, and the solution can be reused, thereby reducing environmental pollution.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and the drawings in the description are only embodiments of the present invention.
FIG. 1 is a block diagram of a reaction apparatus of the present invention;
wherein, 1-reation kettle, 2-feed inlet, 3-gas vent, 4-discharge gate, 5-peristaltic pump, 6-first circulation mouth, 7-second circulation mouth, 8-stirring rake, 9-net post, 10-electric heater unit, 11-water tank.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As shown in figure 1, the invention provides a reaction device for removing lignin from lignocellulose raw materials, which comprises a reaction kettle 1, wherein the top of the reaction kettle 1 is provided with a feed inlet 2 and an exhaust outlet 3; the exhaust port 3 is connected with the water tank 11;
the bottom of the side wall of the reaction kettle 1 is provided with a first circulation port 6, the first circulation port 6 is connected with a second circulation port 7 arranged at the upper part of the first circulation port 6 through a peristaltic pump 5, and two sides of the peristaltic pump 5 are respectively provided with a switch valve; a discharge hole 4 is formed in the middle of the bottom of the reaction kettle 1, and electric heating devices 10 are arranged on two sides of the discharge hole 4, and each electric heating device comprises an electric heating sleeve and silicate rock wool;
a stirring paddle is arranged at the inner top of the reaction kettle 1, and a molecular sieve layer is arranged on the side wall of the reaction kettle above the stirring paddle; mesh 500 mesh 316L stainless steel mesh;
the reaction flow of the device is as follows: the catalyst is filled into a stainless steel mesh layer, then raw materials are placed into a reaction kettle through a feed inlet, an electric heating device and a stirring device are turned on, a peristaltic pump and a switching valve are turned on to circulate reaction solution, the reaction of the mixed solution in the reaction kettle is accelerated, after the reaction is completed, a discharge port is opened to take out lignocellulose raw materials, and meanwhile, a water tank is used for collecting waste gas generated by an exhaust port.
Example 1
A method for removing lignin from lignocellulose raw material by using a molecular sieve, which comprises the following specific steps:
(1) Preparation of molecular sieves: at room temperature, naOH and NaAlO are added into silica sol 2 Adding Fenton reagent after stirring for 3H, wherein the Fenton reagent is a mixed reagent of iron and hydrogen peroxide, and the molar ratio of hydrogen peroxide to ferric sulfate is H 2 O 2 :FeSO 4 =15:1, stirring in a water bath at 80 ℃ for 9 hours, filtering, washing with deionized water, and drying at 80 ℃ to obtain a FeY molecular sieve; feY molecular sieve has a molar composition of 0.5Na 2 O：0.167Al 2 O 3 ：1SiO 2 ：22.5H 2 O：0.01FeSO 4 ：0.15H 2 O 2, Packaging and granulating the FeY molecular sieve, wherein the granule diameter is 2mm, and the molecular sieve content is 60%.
(2) 78.08g of hydrogen peroxide (30%) and 165.09g of glacial acetic acid (99%) are weighed and mixed to obtain a mixed solution, namely the mass ratio of the hydrogen peroxide to the glacial acetic acid is 1:2.1; taking 2.43g of FeY molecular sieve and 122g of eucalyptus chips (50 x 10mm, water content is lower than 55%) with the mass ratio of lignocellulose raw material, mixed solution and molecular sieve being 50:100:1; soaking lignocellulose raw materials in the mixed solution for 20min, adding FeY molecular sieve, heating to 60 ℃ within 20min, keeping the temperature for 4h, and cooling to room temperature after the reaction is finished;
carrying out solid-liquid separation on the reacted solution to obtain a molecular sieve, raw material solids and liquid, wherein the molecular sieve can be reused; drying the liquid at 80 ℃ to obtain solid powder, namely lignin; in the reaction process, glacial acetic acid can be recycled through condensation and reflux; the separated solids are uniformly decomposed by a grinder or a beater to prepare paper pulp, wherein the whiteness of the paper pulp can reach 85ISO, the lignin removal rate is 94%, and the hemicellulose removal rate is 91%;
example 2
(1) Preparation of molecular sieves the same as in example 1
(2) Mixing 175.38g of hydrogen peroxide (30%) and 62.22g of glacial acetic acid (99%) to obtain a mixed solution, wherein the mass ratio of hydrogen peroxide to glacial acetic acid is 1:0.35; and then taking 2.37g of FeY molecular sieve and 118.8g of eucalyptus chips (50 x 10mm, water content is lower than 55%) with the mass ratio of lignocellulose raw material, mixed solution and molecular sieve being 50:100:1. Soaking lignocellulose raw materials in the mixed solution for 20min, adding FeY molecular sieve, heating to 60 ℃ within 20min, keeping the temperature for 4h, and cooling to room temperature after the reaction is finished;
carrying out solid-liquid separation on the reacted solution to obtain a molecular sieve, raw material solids and liquid, wherein the molecular sieve can be reused; drying the liquid at 80 ℃ to obtain solid powder, namely lignin; in the reaction process, glacial acetic acid can be recycled through condensation and reflux; the separated solid is uniformly decomposed by a grinder or a beater to prepare paper pulp, wherein the whiteness of the paper pulp can reach 85ISO, the lignin removal rate is 94%, and the hemicellulose removal rate is 91%.
Example 3
(1) Preparation of molecular sieves the same as in example 1
(2) 78.08g of hydrogen peroxide (30%) and 165.09g of glacial acetic acid (99%) are weighed and mixed to obtain a mixed solution, namely the mass ratio of the hydrogen peroxide to the glacial acetic acid is 1:2.1; and then taking 2.43g of FeY molecular sieve and 122g of eucalyptus chips (50 x 30mm, water content lower than 55%) with the mass ratio of lignocellulose raw material, mixed solution and molecular sieve being 50:100:1. Soaking lignocellulose raw materials in the mixed solution for 20min, adding FeY molecular sieve, heating to 60 ℃ within 20min, keeping the temperature for 4h, and cooling to room temperature after the reaction is finished;
carrying out solid-liquid separation on the reacted solution to obtain a molecular sieve, raw material solids and liquid, wherein the molecular sieve can be reused; drying the liquid at 80 ℃ to obtain solid powder, namely lignin; in the reaction process, glacial acetic acid can be recycled through condensation and reflux; the separated solids are uniformly decomposed by a grinder or a beater to prepare paper pulp, wherein the whiteness of the paper pulp can reach 85ISO, the lignin removal rate is 94%, and the hemicellulose removal rate is 91%;
example 4
(1) Preparation of molecular sieves the same as in example 1
(2) 200.0g of hydrogen peroxide (30%) and 40.0g of glacial acetic acid (99%) are mixed to obtain a mixed solution, namely the mass ratio of the hydrogen peroxide to the glacial acetic acid is 1:0.2; and then taking 2.40g of FeY molecular sieve and 120.0g of eucalyptus chips (50 x 30mm, water content lower than 55%) with the mass ratio of lignocellulose raw material, mixed solution and molecular sieve being 50:100:1. Soaking the lignocellulose raw material in the mixed solution for 20min, adding a FeY molecular sieve, heating to 60 ℃ within 20min, keeping the temperature for 4.5h, and cooling to room temperature after the reaction is finished;
carrying out solid-liquid separation on the reacted solution to obtain a molecular sieve, raw material solids and liquid, wherein the molecular sieve can be reused; drying the liquid at 80 ℃ to obtain solid powder, namely lignin; in the reaction process, glacial acetic acid can be recycled through condensation and reflux; the separated solids are uniformly decomposed by a grinder or a beater to prepare paper pulp, wherein the whiteness of the paper pulp is 85ISO, the lignin removal rate is 94%, and the hemicellulose removal rate is 91%;
example 5
(1) Preparation of molecular sieves the same as in example 1
(2) 43.64g of hydrogen peroxide (30%) and 196.36g of glacial acetic acid (99%) are mixed to obtain a mixed solution, namely the mass ratio of the hydrogen peroxide to the glacial acetic acid is 1:4.5; and then taking 2.40g of FeY molecular sieve and 120.0g of eucalyptus chips (50 x 30mm, water content lower than 55%) with the mass ratio of lignocellulose raw material, mixed solution and molecular sieve being 50:100:1. Soaking the lignocellulose raw material in the mixed solution for 20min, adding a FeY molecular sieve, heating to 60 ℃ within 20min, keeping the temperature for 4.5h, and cooling to room temperature after the reaction is finished;
carrying out solid-liquid separation on the reacted solution to obtain a molecular sieve, raw material solids and liquid, wherein the molecular sieve can be reused; drying the liquid at 80 ℃ to obtain solid powder, namely lignin; in the reaction process, glacial acetic acid can be recycled through condensation and reflux; the separated solids are uniformly decomposed by a grinder or a beater to prepare paper pulp, wherein the whiteness of the paper pulp is 85ISO, the lignin removal rate is 94%, and the hemicellulose removal rate is 91%;
example 6
(1) Preparation of molecular sieves the same as in example 1
(2) 78.08g of hydrogen peroxide (30%) and 165.09g of glacial acetic acid (99%) are weighed and mixed to obtain a mixed solution, namely the mass ratio of the hydrogen peroxide to the glacial acetic acid is 1:2.1; and then taking 0.049g of FeY molecular sieve and 122g of eucalyptus chips (50 x 30mm, water content is lower than 55%) with the mass ratio of 50:100:0.02 of lignocellulose raw material to the mixed solution to 1:5000 of molecular sieve to the mixed solution. Soaking lignocellulose raw materials in the mixed solution for 20min, adding FeY molecular sieve, heating to 60 ℃ within 20min, keeping the temperature for 6h, and cooling to room temperature after the reaction is finished;
carrying out solid-liquid separation on the reacted solution to obtain a molecular sieve, raw material solids and liquid, wherein the molecular sieve can be reused; drying the liquid at 80 ℃ to obtain solid powder, namely lignin; in the reaction process, glacial acetic acid can be recycled through condensation and reflux; the separated solids are uniformly decomposed by a grinder or a beater to prepare paper pulp, wherein the whiteness of the paper pulp can reach 85ISO, the lignin removal rate is 94%, and the hemicellulose removal rate is 91%;
example 7
(1) Preparation of molecular sieves the same as in example 1
(2) 78.08g of hydrogen peroxide (30%) and 165.09g of glacial acetic acid (99%) are weighed and mixed to obtain a mixed solution, namely the mass ratio of the hydrogen peroxide to the glacial acetic acid is 1:2.1; and then taking 2.43g of FeY molecular sieve and 244g of eucalyptus chips (50 x 30mm, water content lower than 55%) with the mass ratio of lignocellulose raw material, mixed solution and molecular sieve being 100:100:1. Soaking the lignocellulose raw material in the mixed solution for 20min, adding a FeY molecular sieve, heating the lignocellulose raw material and the mixed solution to a mass ratio of 1:1, heating the lignocellulose raw material to 60 ℃ within 20min, keeping the temperature for 6h, and cooling to room temperature after the reaction is finished;
carrying out solid-liquid separation on the reacted solution to obtain a molecular sieve, raw material solids and liquid, wherein the molecular sieve can be reused; drying the liquid at 80 ℃ to obtain solid powder, namely lignin; in the reaction process, glacial acetic acid can be recycled through condensation and reflux; the separated solids are uniformly decomposed by a grinder or a beater to prepare paper pulp, wherein the whiteness of the paper pulp can reach 85ISO, the lignin removal rate is 94%, and the hemicellulose removal rate is 91%;
comparative example 1
The difference between comparative example 1 and example 1 is that the lignocellulose-removing solution is prepared by a conventional method, namely, the raw materials are sodium hydroxide and sodium sulfite, 26.0g of sodium hydroxide and 13.1g of sodium sulfite are mixed in 260g of deionized water to prepare 2.5mol/L sodium hydroxide and 0.4mol/L sodium sulfite solution, the solution is reacted for 6 hours at 103 ℃, the lignin removal rate is 43%, the temperature required by the method is high, a large amount of sodium ions remain in the solution, the solution cannot be recycled, and the related data result is shown in Table 1.
The differences between comparative examples 2-7 and example 1 are the differences in the use and proportions of the lignocellulosic feedstock, the mixed solution and the molecular sieve, the specific parameters and results are shown in Table 1,
table 1 raw material ratios and results of examples 1 to 7 and comparative examples 1 to 7
As can be seen from the above table, the invention utilizes the synergistic effect of glacial acetic acid, hydrogen peroxide and FeY molecular sieve and the characteristic of easy-to-get electrons of transition metal to generate hydroxyl (OH), organic free radical (R-C.) and superoxide free radical (O) in situ 2- ) And singlet oxygen 1 O 2 ) The lignin removal rate of the equal-high active substances in the lignocellulose raw material can reach 94% and the hemicellulose removal rate reaches 91% within 6 hours, the method does not generate waste water, and the whiteness of the treated fiber can reach 85ISO; the method can not generate waste water and destroy the original structure of lignin, the solution can be reused, the environmental pollution is reduced, the raw materials are not required to be crushed and ground, the thickness of the raw materials can reach 30mm at most, and the method has remarkable progress.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for removing lignin from a lignocellulosic feedstock using a molecular sieve, the method comprising the steps of:
and (3) placing the lignocellulose raw material into a mixed solution of hydrogen peroxide and glacial acetic acid, adding a molecular sieve, and steaming to obtain the lignocellulose raw material with lignin removed.
2. A method for removing lignin from a lignocellulosic feedstock utilizing a molecular sieve according to claim 1 wherein the concentration of hydrogen peroxide is in the range of 20-50% and the concentration of glacial acetic acid is in the range of 95-99%;
the mass ratio of the hydrogen peroxide to the glacial acetic acid is 1:0.2-4.5.
3. A method for removing lignin from a lignocellulosic feedstock utilizing a molecular sieve according to claim 1 wherein the mass ratio of the lignocellulosic feedstock to the mixed solution is in the range of 1:1.0 to 3.0.
4. The method for removing lignin from a lignocellulosic feedstock utilizing a molecular sieve according to claim 1 wherein the molecular sieve is a FeY molecular sieve wherein the molar ratio of the active components in the molecular sieve is 0.5Na 2 O：0.167Al 2 O 3 ：1SiO 2 ：22.5H 2 O：xFeSO 4 ：yH 2 O 2 ，x＝0～0.01，y＝0～0.15。
5. A method for removing lignin from a lignocellulosic feedstock utilizing a molecular sieve according to claim 1 wherein the mass ratio of the molecular sieve to the mixed solution is in the range of 1:50 to 5000.
6. A method for removing lignin from a lignocellulosic feedstock utilizing a molecular sieve according to claim 1 wherein the lignocellulosic feedstock has a thickness in the range of 0 to 30mm.
7. A method for removing lignin from lignocellulosic feedstock utilizing molecular sieves according to claim 1 wherein the parameters of the digestion are: the temperature is 40-90 ℃, and the reaction time is 2-6h.
8. A method for removing lignin from lignocellulosic feedstock utilizing molecular sieves according to claim 1 wherein the filtrate obtained after digestion is dried to lignin.
9. A method for removing lignin from a lignocellulosic feedstock utilizing a molecular sieve according to claim 1 wherein the lignocellulosic feedstock is any one of bamboo, softwood and hardwood.
10. The reaction device of any one of claims 1-9, comprising a reaction vessel, wherein a feed inlet and an exhaust port are provided at the top of the reaction vessel;
the bottom of the side wall of the reaction kettle is provided with a first circulation port which is connected with a second circulation port arranged at the upper part of the first circulation port through a peristaltic pump;
a discharge hole is formed in the middle of the bottom of the reaction kettle, and electric heating devices are arranged on two sides of the discharge hole;
the top is equipped with the stirring rake in the reation kettle, the stirring rake top the reation kettle lateral wall is equipped with molecular sieve layer.
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| CN103635628A (en) * | 2011-06-30 | 2014-03-12 | 纳米绿色生物炼制公司 | Catalytic biomass conversion |
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