CN114426277A - Catalyst for degrading steam explosion lignocellulose material inhibitor and preparation method and application thereof - Google Patents
Catalyst for degrading steam explosion lignocellulose material inhibitor and preparation method and application thereof Download PDFInfo
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- CN114426277A CN114426277A CN202011185976.2A CN202011185976A CN114426277A CN 114426277 A CN114426277 A CN 114426277A CN 202011185976 A CN202011185976 A CN 202011185976A CN 114426277 A CN114426277 A CN 114426277A
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- 239000000463 material Substances 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 239000003112 inhibitor Substances 0.000 title claims abstract description 30
- 238000004880 explosion Methods 0.000 title claims abstract description 18
- 230000000593 degrading effect Effects 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 239000002023 wood Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 244000144730 Amygdalus persica Species 0.000 claims description 8
- 235000006040 Prunus persica var persica Nutrition 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 240000007049 Juglans regia Species 0.000 claims description 3
- 235000009496 Juglans regia Nutrition 0.000 claims description 3
- 235000020234 walnut Nutrition 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 241000219000 Populus Species 0.000 claims description 2
- 241000124033 Salix Species 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 239000003546 flue gas Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000001784 detoxification Methods 0.000 abstract description 14
- 238000000855 fermentation Methods 0.000 abstract description 10
- 230000004151 fermentation Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 22
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 18
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 13
- 230000002255 enzymatic effect Effects 0.000 description 13
- 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 9
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 235000019253 formic acid Nutrition 0.000 description 9
- 239000000413 hydrolysate Substances 0.000 description 9
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 9
- 229940040102 levulinic acid Drugs 0.000 description 9
- 239000012071 phase Substances 0.000 description 7
- 239000010902 straw Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229920005610 lignin Polymers 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 108010009736 Protein Hydrolysates Proteins 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 108010059892 Cellulase Proteins 0.000 description 4
- 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 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229940106157 cellulase Drugs 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 230000007071 enzymatic hydrolysis Effects 0.000 description 3
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012978 lignocellulosic material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010364 biochemical engineering Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003748 differential diagnosis Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- MHYCRLGKOZWVEF-UHFFFAOYSA-N ethyl acetate;hydrate Chemical compound O.CCOC(C)=O MHYCRLGKOZWVEF-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
- D21B1/00—Fibrous raw materials or their mechanical treatment
- D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
- D21B1/12—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
- D21B1/30—Defibrating by other means
- D21B1/36—Explosive disintegration by sudden pressure reduction
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Mechanical Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a catalyst for degrading a steam explosion lignocellulose material inhibitor and a preparation method and application thereof. The preparation method comprises the following steps: (1) placing the wood material in a reactor, and carrying out two-stage roasting treatment; (2) and (3) placing the material subjected to the second-stage roasting treatment in the step (1) in a muffle furnace, and performing gas-phase oxidation treatment to obtain the activated carbon catalyst. The activated carbon catalyst provided by the invention is used for detoxifying the steam exploded lignocellulose material, the detoxification efficiency is high, and the negative effects of inhibitors on enzymolysis and fermentation are reduced.
Description
Technical Field
The invention belongs to the field of biochemical engineering, and particularly relates to a catalyst for degrading a steam explosion lignocellulose material inhibitor, and a preparation method and application thereof.
Background
Lignocellulose has a complex structure, and the structural characteristics of the lignocellulose determine that the ethanol conversion needs to be pretreated. The steam explosion is used as a pretreatment method, can effectively realize the separation of chemical components of the lignocellulose, does not use or use less chemicals, has no pollution to the environment and low energy consumption, and is a lignocellulose high-efficiency separation technology which is developed more quickly, more effectively and with low cost in recent years.
During the steam explosion pretreatment process, due to the degradation of saccharides and lignin, a plurality of microbial growth inhibitors are released, including substances such as weak acid inhibitors (formic acid, acetic acid, levulinic acid and the like), furfural inhibitors (furfural and 5-hydroxymethylfurfural) and phenol inhibitors (vanillin, hydroquinone, 4-hydroxybenzoic acid) and the like. These inhibitors, in particular phenols, have a significant inhibitory effect on the subsequent enzymatic hydrolysis and microbial fermentation, and therefore should be detoxified before enzymatic hydrolysis and fermentation. The existing detoxification methods are more, and include physical detoxification, chemical detoxification, biological detoxification and the like.
Physical detoxification methods include rotary evaporation, solvent extraction, adsorption, and the like. Rotary evaporation can reduce low boiling point organic matters such as acetic acid and furfural, but at the same time, the concentration of non-volatile inhibitors is increased, so that the fermentation efficiency is reduced. The solvent extraction method has the defects of difficult solvent recovery and higher cost. The adsorption method can adsorb some fermentable sugar while removing inhibitors, so that the yield of fermentation products is reduced.
Chemical detoxification methods are mainly through chemical reactions, by chemical precipitation or by changing the pH and the ionization characteristics of some inhibitors. Of these, the most common is the use of excess Ca (OH)2And (4) pretreating acidolysis solution.
The biological detoxification method is to use some specific enzymes or microorganisms to act on the fermentation inhibitor, so as to reduce the toxicity of the inhibitor by changing the structure of the inhibitor. However, the cost of the enzyme is high, and the microorganism needs to be cultured and consumes the saccharides in the hydrolysate.
Cantarella M et al (composite of differential diagnosis methods for steam-expanded polyplastic wood as a substrate for the bioproduction of ethanol in SHF and SSF, Process Biochemistry, 2004, 39(11): 1533-1542) compared three methods of detoxification of dilute acid steam exploded aspen wood materials, including water rinsing, water-ethyl acetate two-stage extraction, excess Ca (OH)2Treatment, wherein an excess of Ca (OH)2The best treatment effect is achieved, enzymolysis is carried out after detoxification, the cellulose conversion rate is 88.4%, and the ethanol concentration of synchronous saccharification and fermentation is 24.6 g/L. But the methodHas disadvantages that the subsequent distillation step is liable to be unfavorable due to the precipitation of calcium ions, and the saccharide component is destroyed by an excessive amount of alkali.
CN102286545A discloses a method for removing soluble lignin which inhibits butanol fermentation from straw enzymatic hydrolysate, which comprises treating the straw enzymatic hydrolysate with activated carbon or treating the straw with alkaline hydrogen peroxide to remove fermentation inhibitors generated by the straw. The straw enzymatic hydrolysate is treated by active carbon, so that soluble lignin in the enzymatic hydrolysate can be removed, and the obtained enzymatic hydrolysate can be used for fermenting butanol after being supplemented with a nitrogen source; the alkaline hydrogen peroxide is adopted to treat the straws, so that lignin in the straws can be removed, and the generation of soluble lignin after enzymolysis is reduced. However, the above method is only for removing the lignin component therein, and does not involve removal of other inhibitors.
In conclusion, the invention provides a catalyst which is more beneficial to removing the steam explosion lignocellulose material inhibitor and a preparation method thereof, which are needed to be solved in the field.
Disclosure of Invention
The invention provides a catalyst for degrading a steam explosion lignocellulose material inhibitor and a preparation method and application thereof. The catalyst provided by the invention is used for detoxifying the steam exploded lignocellulose material, the detoxification efficiency is high, and the negative effects of inhibitors on enzymolysis and fermentation are reduced.
In a first aspect of the present invention, there is provided a process for preparing a catalyst for degrading an inhibitor of an evapotranspiration-exploded lignocellulosic material, comprising the steps of:
(1) placing the wood material in a reactor, and carrying out two-stage roasting treatment;
(2) and (3) placing the material subjected to the second-stage roasting treatment in the step (1) in a muffle furnace, and performing gas-phase oxidation treatment to obtain the activated carbon catalyst.
Further, in the step (1), the first stage of roasting treatment is carried out for 60-180 min at 300-1500 ℃, and the roasting atmosphere is nitrogen. The second stage roasting treatment is carried out for 20-60 min at 300-1500 ℃, and the roasting atmosphere is water vapor, flue gas and CO2Or air, preferably CO2。
Further, in step (1), the reactor may be a reactor commonly used in the art, such as a tube furnace.
Further, in the step (1), the wood material is at least one of walnut shell, peach shell, coconut shell, poplar, bamboo, willow and the like, and preferably peach shell.
Further, in the step (2), the conditions of the gas phase oxidation treatment are as follows: treating at 150-650 deg.C for 2-10 h in air or oxygen.
In a second aspect of the invention, there is provided an activated carbon catalyst for degrading a steam exploded lignocellulosic material inhibitor prepared by the above method.
In a third aspect of the invention, an application of the activated carbon catalyst is provided.
Further, the application specifically comprises:
putting the steam exploded lignocellulose material into a reactor, adding water, and stirring; feeding H to the reactor2O2Adding the activated carbon catalyst into the solution, and treating for 20-120 min under the conditions that the temperature is 20-80 ℃ and the pH value is 2-7; and then heating to 50-100 ℃, introducing air into the reactor, and continuously treating for 20-120 min to obtain the detoxified material.
Further, the steam-exploded lignocellulose material can be obtained by conventional steam explosion methods such as dilute acid steam explosion, steam explosion and the like.
Further, the reactor may be a conventional reactor in the art, such as a cylindrical reactor, provided with an air intake duct at a lower portion thereof.
Further, the steam exploded lignocellulosic material is preferably placed in a wire mesh drum with a stirring device and then placed in the reactor.
Furthermore, the amount of the added water can meet the requirement of reaching 2/3-3/4 of the position of the reactor.
Further, said H2O2The mass concentration of the solution is 10-35 wt%. In the reaction system, the H2O2The addition amount of the solution is 0.02-0.6 ml/L.
Further, the temperature ratio of the treatment under air is H2O2The temperature of the treatment carried out under the solution is at least 30 ℃ higher.
Furthermore, the flow rate of air is 0.1-1.2L/min relative to a reactor with an effective volume of 1L.
Further, the detoxified material is filtered, dehydrated, pH adjusted and then subjected to enzymolysis, and the concentration of glucose and various inhibitors in the enzymolysis liquid can be determined. The pH value is adjusted to 4-7. The enzymatic hydrolysis may be carried out using conventional enzymatic methods in the art.
Compared with the prior art, the invention has the following effects:
(1) the invention adopts wood material to be burnt at high temperature and CO2The activated carbon catalyst with better stability, better strength and more active groups such as carbonyl, carboxyl and the like is prepared by high-temperature treatment and gas-phase oxidation.
(2) The activated carbon catalyst prepared from hard wood materials such as peach kernels, walnut shells and the like has good stability and strength, the structure and the surface area of holes can be kept in the using process, and the using performance of the activated carbon catalyst can be further improved through gas phase oxidation.
(3) At the early stage is catalytic H2O2Treatment of inhibitors, late stage of catalytic O2Treating the inhibitor to facilitate more inhibitor degradation and reduce H2O2And (4) using the amount.
(4) The use of acid and alkali reagents is reduced, the action time is short, the pollution is reduced, and the energy consumption is saved.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. Wherein, in the present invention, wt% means mass fraction.
Example 1
(1) Placing 25g of peach core in particle shape in a tube furnace, introducing nitrogen, calcining at 950 deg.C for 70min, introducing CO2Treating at 850 deg.C for 30 min;
(2) placing the material obtained in the step (1) in a crucible, placing the crucible in a muffle furnace, standing for 5 hours at 300 ℃ in an air atmosphere, and performing gas phase oxidation treatment to obtain an activated carbon catalyst;
(3) putting 200g of dilute acid steam explosion lignocellulose material into a metal wire mesh drum with a stirring device, then putting the metal wire mesh drum into a 1L drum type reactor, adding water until the dilute acid steam explosion lignocellulose material reaches the 2/3 position of the reactor, and installing an air inlet duct at the lower part of the drum type reactor;
(4) starting a stirring device to fully mix the dilute acid steam-exploded lignocellulose material with water;
(5) 0.5mLH was added2O2(mass concentration is 30%), adding 0.5g of the activated carbon catalyst prepared in the step (2), and treating for 30min at the temperature of 30 ℃ and under the condition that the pH value is 3;
(6) adjusting a temperature button to enable the temperature of the reactor to reach 80 ℃, opening an air valve, controlling the air flow rate to be 0.5L/min, and treating for 60 min;
(7) and (4) filtering and dehydrating the material obtained in the step (6), adjusting the pH value to 5, carrying out enzymolysis, and determining the concentrations of glucose and various inhibitors in the enzymolysis liquid.
Carrying out enzymolysis according to a conventional mode, specifically: adding Shandongze cellulase, hydrolyzing at 50 deg.C for 120 hr, and centrifuging to obtain enzymatic hydrolysate. Detecting the content of 5-hydroxymethylfurfural, furfural, levulinic acid, formic acid, acetic acid and total phenol in the enzymatic hydrolysate, wherein the removal rate of 5-hydroxymethylfurfural after detoxification is 78%, the removal rate of furfural is 80%, the removal rate of levulinic acid is 83%, the removal rate of formic acid is 88%, the removal rate of acetic acid is 85% and the removal rate of total phenol is 74%.
Example 2
(1) Placing 20g of peach core in particle shape in a tube furnace, introducing nitrogen, calcining at 900 deg.C for 90min, introducing CO2Treating at 900 deg.C for 30 min;
(2) placing the wood material prepared in the step (1) into a crucible, placing the crucible into a muffle furnace, standing for 6 hours at 350 ℃ in the air atmosphere, and performing gas phase oxidation treatment to obtain an activated carbon catalyst;
(3) putting 200g of dilute acid steam explosion lignocellulose material into a metal wire mesh drum with a stirring device, then putting the metal wire mesh drum into a 1L drum type reactor, adding water until the dilute acid steam explosion lignocellulose material reaches the 2/3 position of the reactor, and installing an air inlet duct at the lower part of the drum type reactor;
(4) starting a stirring device to fully mix the dilute acid steam-exploded lignocellulose material with water;
(5) 0.4mLH was added2O2(mass concentration is 30%), adding 0.4g of the activated carbon catalyst prepared in the step (2), and treating for 30min at the temperature of 30 ℃ and under the condition that the pH value is 3;
(6) adjusting a temperature button to enable the temperature of the reactor to reach 80 ℃, opening an air valve to enable the air flow rate to be 0.4L/min, and treating for 60 min;
(7) and (4) filtering and dehydrating the material obtained in the step (6), adjusting the pH value, carrying out enzymolysis, and determining the concentrations of glucose and various inhibitors in the enzymolysis liquid.
Carrying out enzymolysis according to a conventional mode, specifically: adding Shandongze cellulase, hydrolyzing at 50 deg.C for 120 hr, and centrifuging to obtain enzymatic hydrolysate. Detecting the content of 5-hydroxymethylfurfural, furfural, levulinic acid, formic acid, acetic acid and total phenol in the enzymatic hydrolysate, wherein the removal rate of 5-hydroxymethylfurfural after detoxification is 88%, the removal rate of furfural is 84%, the removal rate of levulinic acid is 94%, the removal rate of formic acid is 94%, the removal rate of acetic acid is 92% and the removal rate of total phenol is 84%.
Example 3
(1) Placing 20g of peach core in particle shape in a tube furnace, introducing nitrogen, calcining at 900 deg.C for 100min, introducing CO2Treating at 900 deg.C for 45 min;
(2) placing the wood material prepared in the step (1) into a crucible, placing the crucible into a muffle furnace, standing for 8 hours at 350 ℃ in the air atmosphere, and performing gas phase oxidation treatment to obtain an activated carbon catalyst;
(3) putting 200g of dilute acid steam explosion lignocellulose material into a metal wire mesh drum with a stirring device, then putting the metal wire mesh drum into a 1L drum type reactor, adding water until the dilute acid steam explosion lignocellulose material reaches the 2/3 position of the reactor, and installing an air inlet duct at the lower part of the drum type reactor;
(4) starting a stirring device to fully mix the dilute acid steam-exploded lignocellulose material with water;
(5) 0.45ml of H was added2O2(mass concentration is 30%), adding 0.48g of the activated carbon catalyst prepared in the step (2), and treating for 30min at the temperature of 30 ℃ and under the condition that the pH value is 3;
(6) adjusting a temperature button to enable the temperature of the reactor to reach 80 ℃, opening an air valve to enable the air flow rate to be 0.5L/min, and treating for 60 min;
(7) and (4) filtering and dehydrating the material obtained in the step (6), adjusting the pH value, carrying out enzymolysis, and determining the concentrations of glucose and various inhibitors in the enzymolysis liquid.
Carrying out enzymolysis according to a conventional mode, specifically: adding Shandongze cellulase, hydrolyzing at 50 deg.C for 120 hr, and centrifuging to obtain enzymatic hydrolysate. Detecting the content of 5-hydroxymethylfurfural, furfural, levulinic acid, formic acid, acetic acid and total phenol in the enzymatic hydrolysate, wherein the removal rate of 5-hydroxymethylfurfural after detoxification is 82%, the removal rate of furfural is 81%, the removal rate of levulinic acid is 90%, the removal rate of formic acid is 91%, the removal rate of acetic acid is 90% and the removal rate of total phenol is 79%.
Comparative example 1
Compared with example 1, a comparative catalyst was obtained except that the vapor phase oxidation treatment of step (2) was not performed when preparing an activated carbon catalyst.
Carrying out enzymolysis according to a conventional mode, specifically: adding Shandongze cellulase, hydrolyzing at 50 deg.C for 120 hr, and centrifuging to obtain enzymatic hydrolysate. Detecting the content of 5-hydroxymethylfurfural, furfural, levulinic acid, formic acid, acetic acid and total phenol in the enzymatic hydrolysate, wherein the removal rate of 5-hydroxymethylfurfural is 51%, the removal rate of furfural is 58%, the removal rate of levulinic acid is 72%, the removal rate of formic acid is 75%, the removal rate of acetic acid is 78% and the removal rate of total phenol is 55%.
Claims (10)
1. A method for preparing a catalyst for degrading a steam explosion lignocellulose material inhibitor comprises the following steps:
(1) placing the wood material in a reactor, and carrying out two-stage roasting treatment;
(2) and (3) placing the material subjected to the second-stage roasting treatment in the step (1) in a muffle furnace, and performing gas-phase oxidation treatment to obtain the activated carbon catalyst.
2. The method of claim 1, wherein: in the step (1), the first stage of roasting treatment is carried out for 60-180 min at the temperature of 300-1500 ℃, and the roasting atmosphere is nitrogen; the second stage roasting treatment is carried out for 20-60 min at 300-1500 ℃, and the roasting atmosphere is water vapor, flue gas and CO2Or air.
3. The method of claim 1, wherein: in the step (1), the wood material is at least one of walnut shells, peach shells, coconut shells, poplar, bamboo and willow, and preferably peach shells.
4. The method of claim 1, wherein: in the step (2), the gas phase oxidation treatment conditions are as follows: treating at 150-650 deg.C for 2-10 h in air or oxygen.
5. An activated carbon catalyst obtainable by the process according to any one of claims 1 to 4.
6. Use of an activated carbon catalyst according to claim 5, wherein: putting the steam exploded lignocellulose material into a reactor, adding water, and stirring; feeding H to the reactor2O2Adding the activated carbon catalyst into the solution, and treating for 20-120 min under the conditions that the temperature is 20-80 ℃ and the pH value is 2-7; and then heating to 50-100 ℃, introducing air into the reactor, and continuously treating for 20-120 min to obtain the detoxified material.
7. Use according to claim 6, characterized in that: the reactor is a cylindrical reactor, and an air inlet duct is arranged at the lower part of the cylindrical reactor.
8. Use according to claim 6, characterized in that: said H2O2The mass concentration of the solution is 10-35 wt%; in the reactionSaid H in the system2O2The addition amount of the solution is 0.02-0.6 ml/L.
9. Use according to claim 6, characterized in that: the flow rate of air is 0.1-1.2L/min relative to a reactor with an effective volume of 1L.
10. Use according to claim 6, characterized in that: the temperature ratio of the treatment under air is H2O2The temperature of the treatment carried out under the solution is at least 30 ℃ higher.
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