CN105237371A - Method for preparing vanillin by catalytic oxidative degradation of lignin - Google Patents
Method for preparing vanillin by catalytic oxidative degradation of lignin Download PDFInfo
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- CN105237371A CN105237371A CN201510778418.XA CN201510778418A CN105237371A CN 105237371 A CN105237371 A CN 105237371A CN 201510778418 A CN201510778418 A CN 201510778418A CN 105237371 A CN105237371 A CN 105237371A
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- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 235000012141 vanillin Nutrition 0.000 title claims abstract description 43
- 229920005610 lignin Polymers 0.000 title claims abstract description 31
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 25
- 238000010525 oxidative degradation reaction Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 239000011973 solid acid Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 52
- 235000013305 food Nutrition 0.000 claims description 40
- 239000007787 solid Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 239000001117 sulphuric acid Substances 0.000 claims description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 241001062009 Indigofera Species 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000026676 system process Effects 0.000 description 6
- 239000011949 solid catalyst Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical group OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 2
- -1 aliphatic organic compound Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- 241000732800 Cymbidium Species 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 241000775848 Syringa oblata Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003570 biosynthesizing effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000006652 catabolic pathway Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007515 enzymatic degradation Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- JJVNINGBHGBWJH-UHFFFAOYSA-N ortho-vanillin Chemical compound COC1=CC=CC(C=O)=C1O JJVNINGBHGBWJH-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KCDXJAYRVLXPFO-UHFFFAOYSA-N syringaldehyde Chemical compound COC1=CC(C=O)=CC(OC)=C1O KCDXJAYRVLXPFO-UHFFFAOYSA-N 0.000 description 1
- COBXDAOIDYGHGK-UHFFFAOYSA-N syringaldehyde Natural products COC1=CC=C(C=O)C(OC)=C1O COBXDAOIDYGHGK-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing vanillin by catalytic oxidative degradation of lignin, which comprises the steps of mixing lignin with a solid acid catalyst, adding a solvent, and carrying out oxidative degradation on the lignin under the condition that the oxygen pressure is 1-3 MPa to obtain a monoaromatic compound mainly containing vanillin; wherein the solid acid catalyst is heteropoly acid, salt or hydrate thereof, and the heteropoly acid is K6[CoⅡW12O40]、H6[CoⅡW12O40]、K5[CoⅢW12O40]、(NH4)3[CoMo6O24H6]、H3PW12O40Any one or more of them. The product of the invention is mainly aromatic hydrocarbon compounds, wherein the selectivity of vanillin is as high as 50-70%, and the yield reaches 0.5-6.4%. The lignin oxidative degradation reaction condition is mild, green and safe, the catalyst is convenient to recover, and the catalyst has high recovery rate and good reutilization property.
Description
Technical field
The invention belongs to lignin degradation technical field, be specifically related to a kind of method that vanillin food grade,1000.000000ine mesh is prepared in catalytic lignin oxidative degradation.
Background technology
Xylogen is that vegitabilia is only second to the cellulosic second largest natural polymer, primarily of the unbodied three-dimensional netted fragrant macromolecular compound that phenylpropyl alcohol alkyl structure unit (C9) is formed, accounting for the 15-30% of lignocellulose biomass quality, is the non-oil resource that occurring in nature uniquely can provide renewable compound aromatic base.The phenylpropyl alcohol alkyl C9 structural unit of xylogen, mainly comprise guaiacyl, Syringa oblata Lindl. base and p-hydroxybenzene, degradable is single aromatics or aliphatic organic compound under proper condition, as vanillin food grade,1000.000000ine mesh, syringaldehyde etc.But lignin structure is complicated and to form the of bondings such as C-C, C-O of its modular construction comparatively stable, and not easy fracture, causes the trans-utilization Study of way of xylogen to be made slow progress.Along with the exhaustion day by day of petroleum resources, and people are to the high request of environmental protection, and xylogen, with the cost of its low in price, abundant source, becomes the important channel of aromatic compound regeneration.
Vanillin food grade,1000.000000ine mesh, is also called Vanillin or 4-hydroxyl-3-methoxylbenxaldehyde, is a kind of widely used edible spices, mainly in food, daily use chemicals, tobacco industry as fixative and correctives, also can be used for medicine intermediate, plant growth promoter, sterilant etc.Vanillin food grade,1000.000000ine mesh route of synthesis has natural extract, biosynthesizing and chemosynthesis.Wherein, the vanillin food grade,1000.000000ine mesh more than 98% on domestic and international market is synthetic.Because xylogen method produces vanillin food grade,1000.000000ine mesh, abundant raw material, technique are simple, condition is easy to control, and at present, countries in the world produce vanillin food grade,1000.000000ine mesh in this way and account for more than half.Therefore, build the lignin degradation system of efficient economy, improve productive rate and the selectivity of the aromatic compounds such as vanillin food grade,1000.000000ine mesh, realize the higher value application of xylogen, have wide prospect.
The degradation pathway of xylogen mainly contains catalytic pyrolysis, hydrolysis, oxidation, hydrogenation etc., also has photochemical catalysis or enzymatic degradation etc. in addition.Wherein, the liquefied fraction of catalytic pyrolysis xylogen is up to 50%, but temperature that cracking adopts is high, and energy consumption is large, and easily generation coke makes catalyst deactivation, is difficult to recycling.Hydrolytic lignin transformation efficiency and speed of reaction are all lower.Compared to above two kinds, the oxidation of xylogen and hydrogenation depolymerization are with its cheap cost, relative relatively mild condition, high conversion and receiving much concern.Hydro-reduction process inevitably can lose some oxygen-containing functional groups makes product quality reduce, and adopts oxidative degradation xylogen, can obtain the polyfunctional monomer of higher yields, reaches the object producing the fine chemicals such as aldehyde or acid.The oxidative degradation of xylogen is mainly carried out under alkaline condition (pH>12) and High Temperature High Pressure, and improves the productive rate of organic molecule by introducing oxide catalyst.The catalyzer of current catalytic lignin oxidation is mainly metal catalyst, and the metal center adopted is mainly Cu, Co, Ru etc., and oxygenant is mainly O
2and H
2o
2(Chinese science: chemistry, 2015,45,510-525).Wherein copper sulfate receives much concern with its good catalytic activity and lower cost, but it reclaims difficulty, easily causes secondary pollution.
Solid acid catalyst heteropolyacid and salt thereof show very high catalytic activity in a lot of reaction system, are therefore subject to very large attention at catalytic field.Heteropolyacid and salt thereof are made up of the transition metal of multiple easy transmission electronics usually, as Co, Mo, W, V etc., can accept multiple electronics, be good redox catalyst, and its oxidation-reduction quality carries out systematically modulation within a large range by change component and ratio thereof.
Summary of the invention
The method of vanillin food grade,1000.000000ine mesh is prepared in the catalytic lignin oxidative degradation that technical problem to be solved by this invention is to provide a kind of efficient economy.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A method for vanillin food grade,1000.000000ine mesh is prepared in catalytic lignin oxidative degradation, is mixed by xylogen with solid acid catalyst, adds solvent, under oxygen pressure 1 ~ 3MPa condition, carry out oxidative degradation to xylogen, obtains the single aromatic compounds based on vanillin food grade,1000.000000ine mesh;
Wherein, described solid acid catalyst is heteropolyacid and salt thereof or its hydrate, and described heteropolyacid is specially K
6[Co
iIw
12o
40], H
6[Co
iIw
12o
40], K
5[Co
iIIw
12o
40], (NH
4)
3[CoMo
6o
24h
6], H
3pW
12o
40in any one or a few.
Wherein, described xylogen comprises any one or a few the mixture in enzymolysis xylogen, alkali lignin, sodium lignosulfonate, organic solvent type xylogen.
Wherein, xylogen mixes according to mass ratio 1:0.1 ~ 0.5 with solid acid catalyst.
Wherein, described solvent is water, sodium hydroxide solution, methyl alcohol or ethanol, and the add-on of solvent is 20 ~ 50mL/1g xylogen.Wherein, described sodium hydroxide solution, the concentration of its solute sodium hydroxide is 0.1 ~ 3mol/L.
Wherein, the temperature of reaction of oxidative degradation is 80 ~ 180 DEG C, and the reaction times is 1 ~ 24h.
Wherein, described K
6[Co
iIw
12o
40] solid acid catalyst prepares in accordance with the following steps:
(A1) by 19.8gNa
2wO
42H
2o is dissolved in 40mL deionized water, is adjusted to pH7 with Glacial acetic acid, obtains solution A, 2.5g (CH
3cO
2)
2co4H
2o is dissolved in 12mL deionized water, obtains solution B; Solution A is placed in flask, boils and slowly add the solution B of 80 DEG C of preheatings and stir afterwards in oil bath pan, produce blackish green solution, after boiling 20min, filtered while hot obtains filtrate;
(A2) by the saturated CH of 20mLpH7
3cOOK solution slowly adds the filtrate that step (A1) obtains, stir and produce green solid, filter after being cooled to room temperature, with being dissolved in 40mL2M sulphuric acid soln by solid after filtrate washing solid 2 times, 50 DEG C are stirred 15min, produce black and blue color solution, filter, obtain liquor C, condensing crystal, obtain K
6[CoW
12o
40] 16H
2o solid heteropoly acid salt.
Wherein, described H
6[Co
iIw
12o
40] solid acid catalyst prepares in accordance with the following steps:
By 1.0gNa
2wO
42H
2o, 0.1gCoCl
26H
2o, 0.12g (CH
3cO
2)
2co4H
2the mixing of O and 0.06g1,3-propylene diamine is dissolved in 15mL water, is adjusted to pH2, moves in reactor after magnetic agitation 1h with 6MHCl, reacts 4 days at 160 DEG C, i.e. obtained H
6[Co
iIw
12o
40] 2.5H
2o solid heteropoly acid.
Wherein, described K
5[Co
iIIw
12o
40] solid acid catalyst prepares in accordance with the following steps:
(A1) by 19.8gNa
2wO
42H
2o is dissolved in 40mL deionized water, is adjusted to pH7 with Glacial acetic acid, obtains solution A, 2.5g (CH
3cO
2)
2co4H
2o is dissolved in 12mL deionized water, obtains solution B; Solution A is placed in flask, boils and slowly add the solution B of 80 DEG C of preheatings and stir afterwards in oil bath pan, produce blackish green solution, after boiling 20min, filtered while hot obtains filtrate;
(A2) by the saturated CH of 20mLpH7
3cOOK solution slowly adds the filtrate that step (A1) obtains, and stirs and produces green solid, filter after being cooled to room temperature, with being dissolved in 40mL2M sulphuric acid soln by solid after filtrate washing solid 2 times, 50 DEG C are stirred 15min, produce black and blue color solution, filter, obtain liquor C;
(A3) liquor C is heated to boiling, adds 10gK in batches
2s
2o
8, after solution is turned yellow by indigo plant, stop heating, ice bath cooling obtains yellow needle-like crystals, filters, obtains K
5[Co
iIIw
12o
40] 20H
2o solid heteropoly acid salt.
Wherein, described (NH
4)
3[CoMo
6o
24h
6] solid acid catalyst prepares in accordance with the following steps:
2.74gCoCl
26H
2o is dissolved in 15mL water, adds 1mLH
2o
2obtained solution D, then by 15g (NH
4)
6mo
7o
244H
2o is dissolved in 150mL water obtained solution E; Solution E is heated to boiling, solution D slowly instills in solution E, obtains green-blue crystals, then uses 80 DEG C of distilled water recrystallizations, obtain (NH after evaporation concentration, cooling
4)
3[CoMo
6o
24h
6] 7H
2o solid heteropoly acid salt.
Wherein, described H
3pW
12o
40can directly commercially.
Beneficial effect: the product that the inventive method obtains is mainly compound fragrant hydrocarbon, wherein vanillin food grade,1000.000000ine mesh selectivity is up to 50 ~ 70%, and productive rate reaches 0.5 ~ 6.4%.In the present invention, lignin oxidation's degradation conditions is gentle, green safety, and catalyzer is convenient to reclaim, and has high-recovery, and reusing is good.
Accompanying drawing explanation
Fig. 1 catalytic lignin oxidative breakdown product makings figure.
Fig. 2 vanillin food grade,1000.000000ine mesh standard mass spectrum.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, the content described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
The xylogen used in following examples is enzymolysis xylogen, obtains the residue after cellulase degradation from corn cob and stalk.
Embodiment 1:
Prepare solid catalyst heteropolyacid salt K
6[Co
iIw
12o40] 16H
2o, step is as follows: Na
2wO
42H
2o (19.8g) is dissolved in 40mL deionized water, regulates pH=7, obtains solution A, (CH with Glacial acetic acid
3cO
2)
2co4H
2o (2.5g) is dissolved in 12mL deionized water, obtains solution B; A liquid is placed in flask, boils in oil bath pan and slowly add the B liquid of 80 DEG C of preheatings and stir afterwards, produce blackish green solution, boil filtered while hot after 20min.By the saturated CH of pH=7
3cOOK solution (20mL) slowly adds filtrate, stirs and produces green solid, filter after being cooled to room temperature, with being dissolved in 40mL2M sulphuric acid soln by solid after filtrate washing solid 2 times, 50 DEG C are stirred 15min, produce black and blue color solution, filter, obtain liquor C, condensing crystal, obtain K
6[Co
iIw
12o40] 16H
2o solid heteropoly acid salt.
Embodiment 2:
Prepare solid catalyst heteropolyacid salt K
5[Co
iIIw
12o
40] 20H
2o: on embodiment 1 basis, is heated to boiling, adds K in batches by C liquid
2s
2o
8(10g), after solution is turned yellow by indigo plant, stop heating, ice bath cooling obtains yellow needle-like crystals, filters, obtains K
5[Co
iIIw
12o
40] 20H
2o solid heteropoly acid salt.
Embodiment 3:
Prepare solid catalyst heteropolyacid H
6[Co
iIw
12o
40] 2.5H
2o: by Na
2wO
42H
2o (1.0g), CoCl
26H
2o (0.1g), (CH
3cO
2)
2co4H
2o (0.12g), 1,3-propylene diamine (0.06g) mixing is dissolved in 15mL water, is adjusted to pH=2, moves in reactor after magnetic agitation 1h with 6MHCl, reacts 4 days at 160 DEG C, i.e. obtained H
6[Co
iIw
12o
40] 2.5H
2o solid heteropoly acid.
Embodiment 4:
Prepare solid catalyst heteropolyacid salt (NH
4)
3[CoMo
6o
24h
6] 7H
2o catalyzer: CoCl
26H
2o (2.74g) is dissolved in 15mL water, adds 1mLH
2o
2obtained solution D, then by (NH
4)
6mo
7o
244H
2o (15g) is dissolved in 150mL water obtained solution E; E liquid is heated to boiling, D liquid slowly instills in E liquid, after evaporation concentration, cooling, obtain green-blue crystals.Use 80 DEG C of distilled water recrystallizations again, obtain (NH
4)
3[CoMo
6o
24h
6] 7H
2o solid heteropoly acid salt.
Embodiment 5:
By enzymolysis xylogen 0.5g, embodiment 1 gained catalyzer K
6[Co
iIw
12o40] 16H
2o0.1g, water 20mL, be placed in autoclave, excluding air, passes into 2MPa oxygen, reacts 10h at 100 DEG C.Stop heating, stop stirring after being down to room temperature, filter, filter residue and drying is weighed, and filtrate is extracted with ethyl acetate 3 times.Ethyl acetate is steamed except desolventizing through revolving, and obtain oil product, drying is weighed.Oil product 2mL ethyl acetate is dissolved again, sampling analysis.The qualitative and quantitative analysis of product adopts gas chromatography combined with mass spectrometry (GCMS) technology, with vanillin food grade,1000.000000ine mesh standard substance for external standard carries out quantitative analysis.Vanillin food grade,1000.000000ine mesh productive rate and selective calculation method as follows, the results are shown in Table 1.
Embodiment 6-9:
Adopt the condition of embodiment 5, difference is, in embodiment 6, catalyzer is K
5[Co
iIIw
12o
40] 20H
2o, in embodiment 7, catalyzer is H
6[Co
iIw
12o
40] 2.5H
2o, in embodiment 8, catalyzer is (NH
4)
3[CoMo
6o
24h
6] 7H
2o, in embodiment 9, catalyzer is H
3pW
12o
40.Vanillin food grade,1000.000000ine mesh productive rate and selectivity are in table 1.
Under table 1 differing temps, catalyzed oxidation lignin degradation is selectivity and the productive rate of vanillin food grade,1000.000000ine mesh
Can be found out by form, [Co
iIw
12o
40]
6-(NH
4)
3[CoMo
6o
24h
6] prepared by chinese cymbidium to catalytic lignin oxidative degradation have higher catalytic activity, but the former has better selectivity to product vanillin food grade,1000.000000ine mesh.
Embodiment 10:
Adopt the condition of embodiment 5, difference is, in embodiment 10, temperature of reaction replaces with 80 DEG C.After reaction, system process and product analysis method are with embodiment 5, and vanillin food grade,1000.000000ine mesh productive rate and selectivity are in table 2.
Embodiment 11:
Adopt the condition of embodiment 5, difference is, in embodiment 11, temperature of reaction replaces with 110 DEG C.After reaction, system process and product analysis method are with embodiment 5, and vanillin food grade,1000.000000ine mesh productive rate and selectivity are in table 2.
Embodiment 12:
Adopt the condition of embodiment 5, difference is, in embodiment 12, temperature of reaction replaces with 120 DEG C.After reaction, system process and product analysis method are with embodiment 5, and vanillin food grade,1000.000000ine mesh productive rate and selectivity are in table 2.
Embodiment 13:
Adopt the condition of embodiment 5, difference is, in embodiment 13, temperature of reaction replaces with 130 DEG C.After reaction, system process and product analysis method are with embodiment 5, and vanillin food grade,1000.000000ine mesh productive rate and selectivity are in table 2.
Embodiment 14:
Adopt the condition of embodiment 5, difference is, in embodiment 14, temperature of reaction replaces with 150 DEG C.After reaction, system process and product analysis method are with embodiment 5, and vanillin food grade,1000.000000ine mesh productive rate and selectivity are in table 2.
Embodiment 15:
Adopt the condition of embodiment 5, difference is, in embodiment 15, temperature of reaction replaces with 180 DEG C.After reaction, system process and product analysis method are with embodiment 5, and vanillin food grade,1000.000000ine mesh productive rate and selectivity are in table 2.
Under table 2 differing temps, catalyzed oxidation lignin degradation is selectivity and the productive rate of vanillin food grade,1000.000000ine mesh
In table, data declaration temperature of reaction is to K
6[CoW
12o40] 2.5H
2the catalytic activity of O solid heteropoly acid salt has great effect.During temperature > 130 DEG C, vanillin food grade,1000.000000ine mesh productive rate and selectivity sharply decline, and makings assay products mostly is P-hydroxybenzoic acid and carbon number is the fatty acid of 5 ~ 7.Can be found out by trend in table, when temperature of reaction is 120 DEG C, solid acid catalyst catalytic activity is optimum, and vanillin food grade,1000.000000ine mesh productive rate is up to 6.43%, and selectivity is greater than 65%.
Claims (10)
1. the method for vanillin food grade,1000.000000ine mesh is prepared in a catalytic lignin oxidative degradation, it is characterized in that, xylogen is mixed with solid acid catalyst, add solvent, under oxygen pressure 1 ~ 3MPa condition, oxidative degradation is carried out to xylogen, obtain the single aromatic compounds based on vanillin food grade,1000.000000ine mesh;
Wherein, described solid acid catalyst is heteropolyacid and salt thereof or its hydrate, and described heteropolyacid is specially K
6[Co
iIw
12o
40], H
6[Co
iIw
12o
40], K
5[Co
iIIw
12o
40], (NH
4)
3[CoMo
6o
24h
6], H
3pW
12o
40in any one or a few.
2. the method for vanillin food grade,1000.000000ine mesh is prepared in catalytic lignin oxidative degradation according to claim 1, it is characterized in that, described xylogen comprises any one or a few the mixture in enzymolysis xylogen, alkali lignin, sodium lignosulfonate, organic solvent type xylogen.
3. the method for vanillin food grade,1000.000000ine mesh is prepared in catalytic lignin oxidative degradation according to claim 1, and it is characterized in that, xylogen mixes according to mass ratio 1:0.1 ~ 0.5 with solid acid catalyst.
4. the method for vanillin food grade,1000.000000ine mesh is prepared in catalytic lignin oxidative degradation according to claim 1, it is characterized in that, described solvent is water, sodium hydroxide solution, methyl alcohol or ethanol, and the add-on of solvent is 20 ~ 50mL/1g xylogen.
5. the method for vanillin food grade,1000.000000ine mesh is prepared in catalytic lignin oxidative degradation according to claim 4, it is characterized in that, described sodium hydroxide solution, and wherein the concentration of sodium hydroxide is 0.1 ~ 3mol/L.
6. the method for vanillin food grade,1000.000000ine mesh is prepared in catalytic lignin oxidative degradation according to claim 1, it is characterized in that, the temperature of reaction of oxidative degradation is 80 ~ 180 DEG C, and the reaction times is 1 ~ 24h.
7. the method for vanillin food grade,1000.000000ine mesh is prepared in the catalytic lignin oxidative degradation according to claims 1, it is characterized in that, described K
6[Co
iIw
12o
40] solid acid catalyst prepares in accordance with the following steps:
(A1) by 19.8gNa
2wO
42H
2o is dissolved in 40mL deionized water, is adjusted to pH7 with Glacial acetic acid, obtains solution A, 2.5g (CH
3cO
2)
2co4H
2o is dissolved in 12mL deionized water, obtains solution B; Solution A is placed in flask, boils and slowly add the solution B of 80 DEG C of preheatings and stir afterwards in oil bath pan, produce blackish green solution, after boiling 20min, filtered while hot obtains filtrate;
(A2) by the saturated CH of 20mLpH7
3cOOK solution slowly adds the filtrate that step (A1) obtains, stir and produce green solid, filter after being cooled to room temperature, with being dissolved in 40mL2M sulphuric acid soln by solid after filtrate washing solid 2 times, 50 DEG C are stirred 15min, produce black and blue color solution, filter, obtain liquor C, condensing crystal, obtain K
6[CoW
12o
40] 16H
2o solid heteropoly acid salt.
8. the method for vanillin food grade,1000.000000ine mesh is prepared in catalytic lignin oxidative degradation according to claim 1, it is characterized in that, described H
6[Co
iIw
12o
40] solid acid catalyst prepares in accordance with the following steps:
By 1.0gNa
2wO
42H
2o, 0.1gCoCl
26H
2o, 0.12g (CH
3cO
2)
2co4H
2the mixing of O and 0.06g1,3-propylene diamine is dissolved in 15mL water, is adjusted to pH2, moves in reactor after magnetic agitation 1h with 6MHCl, reacts 4 days at 160 DEG C, i.e. obtained H
6[Co
iIw
12o
40] 2.5H
2o solid heteropoly acid.
9. the method for vanillin food grade,1000.000000ine mesh is prepared in catalytic lignin oxidative degradation according to claim 1, it is characterized in that, described K
5[Co
iIIw
12o
40] solid acid catalyst prepares in accordance with the following steps:
(A1) by 19.8gNa
2wO
42H
2o is dissolved in 40mL deionized water, is adjusted to pH7 with Glacial acetic acid, obtains solution A, 2.5g (CH
3cO
2)
2co4H
2o is dissolved in 12mL deionized water, obtains solution B; Solution A is placed in flask, boils and slowly add the solution B of 80 DEG C of preheatings and stir afterwards in oil bath pan, produce blackish green solution, after boiling 20min, filtered while hot obtains filtrate;
(A2) by the saturated CH of 20mLpH7
3cOOK solution slowly adds the filtrate that step (A1) obtains, and stirs and produces green solid, filter after being cooled to room temperature, with being dissolved in 40mL2M sulphuric acid soln by solid after filtrate washing solid 2 times, 50 DEG C are stirred 15min, produce black and blue color solution, filter, obtain liquor C;
(A3) liquor C is heated to boiling, adds 10gK in batches
2s
2o
8, after solution is turned yellow by indigo plant, stop heating, ice bath cooling obtains yellow needle-like crystals, filters, obtains K
5[Co
iIIw
12o
40] 20H
2o solid heteropoly acid salt.
10. the method for vanillin food grade,1000.000000ine mesh is prepared in catalytic lignin oxidative degradation according to claim 1, it is characterized in that, described (NH
4)
3[CoMo
6o
24h
6] solid acid catalyst prepares in accordance with the following steps:
2.74gCoCl
26H
2o is dissolved in 15mL water, adds 1mLH
2o
2obtained solution D, then by 15g (NH
4)
6mo
7o
244H
2o is dissolved in 150mL water obtained solution E; Solution E is heated to boiling, solution D slowly instills in solution E, obtains green-blue crystals, then uses 80 DEG C of distilled water recrystallizations, obtain (NH after evaporation concentration, cooling
4)
3[CoMo
6o
24h
6] 7H
2o solid heteropoly acid salt.
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| CN113773187A (en) * | 2021-10-28 | 2021-12-10 | 吉林农业大学 | Method for preparing vanillin from straw lignin under normal pressure condition |
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| CN116196950B (en) * | 2023-02-16 | 2024-05-24 | 北华大学 | Synthesis method of bimetal doped heteropolyacid catalyst and application of bimetal doped heteropolyacid catalyst in lignin conversion |
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