CN103910903A - Application of molybdenum-based catalyst to prepare organic chemicals from lignin - Google Patents
Application of molybdenum-based catalyst to prepare organic chemicals from lignin Download PDFInfo
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- CN103910903A CN103910903A CN201310008112.7A CN201310008112A CN103910903A CN 103910903 A CN103910903 A CN 103910903A CN 201310008112 A CN201310008112 A CN 201310008112A CN 103910903 A CN103910903 A CN 103910903A
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- xylogen
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- molybdenum
- catalyzer
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 44
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000011733 molybdenum Substances 0.000 title claims abstract description 37
- 239000000126 substance Substances 0.000 title claims abstract description 20
- 229920005610 lignin Polymers 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 17
- 150000003624 transition metals Chemical class 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 3
- 239000011949 solid catalyst Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000002585 base Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- -1 gac Chemical compound 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical class OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000007810 chemical reaction solvent Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000007600 charging Methods 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229960001866 silicon dioxide Drugs 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 27
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 150000001491 aromatic compounds Chemical class 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000012263 liquid product Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 18
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 16
- 238000003763 carbonization Methods 0.000 description 10
- 239000004480 active ingredient Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 229960001867 guaiacol Drugs 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 238000003421 catalytic decomposition reaction Methods 0.000 description 7
- IGIDLTISMCAULB-UHFFFAOYSA-N 3-methylvaleric acid Chemical compound CCC(C)CC(O)=O IGIDLTISMCAULB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 150000003384 small molecules Chemical class 0.000 description 5
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N (2-methylphenyl)methanol Chemical compound CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- RBJLHYGZMJNFBK-HWKANZROSA-N ethyl (e)-hex-4-enoate Chemical compound CCOC(=O)CC\C=C\C RBJLHYGZMJNFBK-HWKANZROSA-N 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- YYZUSRORWSJGET-UHFFFAOYSA-N ethyl octanoate Chemical compound CCCCCCCC(=O)OCC YYZUSRORWSJGET-UHFFFAOYSA-N 0.000 description 3
- VTSFIPHRNAESED-AATRIKPKSA-N ethyl-3-hexanoate Chemical compound CCOC(=O)C\C=C\CC VTSFIPHRNAESED-AATRIKPKSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- GHDQBJLOOLNHCJ-UHFFFAOYSA-N (2,4,5-trimethylphenyl)methanol Chemical compound CC1=CC(C)=C(CO)C=C1C GHDQBJLOOLNHCJ-UHFFFAOYSA-N 0.000 description 2
- UFLHIIWVXFIJGU-ARJAWSKDSA-N (Z)-hex-3-en-1-ol Chemical compound CC\C=C/CCO UFLHIIWVXFIJGU-ARJAWSKDSA-N 0.000 description 2
- MEMBJMDZWKVOTB-UHFFFAOYSA-N 1-ethyl-2,4-dimethylbenzene Chemical compound CCC1=CC=C(C)C=C1C MEMBJMDZWKVOTB-UHFFFAOYSA-N 0.000 description 2
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 2
- AXIUBBVSOWPLDA-UHFFFAOYSA-N 2-ethyl-p-xylene Chemical compound CCC1=CC(C)=CC=C1C AXIUBBVSOWPLDA-UHFFFAOYSA-N 0.000 description 2
- KIKXGIRAIYTCRB-UHFFFAOYSA-N 2-methylpent-2-en-1-ol Chemical compound CCC=C(C)CO KIKXGIRAIYTCRB-UHFFFAOYSA-N 0.000 description 2
- ZLCSFXXPPANWQY-UHFFFAOYSA-N 3-ethyltoluene Chemical compound CCC1=CC=CC(C)=C1 ZLCSFXXPPANWQY-UHFFFAOYSA-N 0.000 description 2
- KMTDMTZBNYGUNX-UHFFFAOYSA-N 4-methylbenzyl alcohol Chemical compound CC1=CC=C(CO)C=C1 KMTDMTZBNYGUNX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- UFLHIIWVXFIJGU-UHFFFAOYSA-N hex-3-en-1-ol Natural products CCC=CCCO UFLHIIWVXFIJGU-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920005611 kraft lignin Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing organic chemicals from lignin. The method comprises: taking a catalyst employing a transition metal molybdenum as an active site to perform catalysis on reactions, heating to 230-350 DEG C, stirring to react for 0.5 h-12 h, after the reaction is finished, filtering out the solid catalyst, and performing rotary evaporation to obtain liquid products. The catalytic process of the technical scheme has extremely high product efficiency, the product total yield is up to 90%, the products comprise monophenols and other aromatic compounds used in large scale in industry, the added value is high, and the application has extremely good industrial application prospect.
Description
Technical field
The present invention relates to the method for biomass to liquid fuel and organic chemicals conversion, more particularly, relating to xylogen one step catalytic decomposition is the process of the organic chemicals including alcohols, ethers, phenylcarbinol class, phenols, monocycle aromatic compounds.
Background technology
In recent years, due to the exhaustion day by day of the Nonrenewable resources such as coal, oil, Sweet natural gas, the exploitation of renewable resources have been become to our instant task.Biomass resource is renewable resources the most widely on existing nature, comprise the materials such as Mierocrystalline cellulose, hemicellulose and xylogen, wherein Mierocrystalline cellulose and hemicellulose are utilized widely, exceed 25% xylogen and be not used widely so far and account for biomass total amount, not only cause the waste of resource, also caused environmental pollution.
The transformation technology of xylogen is much studied, and the method for having reported comprises pyrolysis, basic hydrolysis, supercritical water conversion etc.But above method severe reaction conditions, product yield is very low.Therefore research and develop the extensive concern that a kind of quick, efficient, green lignin conversion method is subject to scholars.Xylogen is the three-dimensional macromolecular compound being formed by connecting by C-C and carbon-oxygen bond by phenylpropyl alcohol alkanes structural unit, contain the multiple organo-functional groups such as hydroxyl, methoxyl group, carbonyl and carboxyl, if just interconnective C-C key C-O key between monomer can be disconnected to the small molecules product can in a large number with high added value.But because xylogen is extremely complicated net high-polymer, steady chemical structure, is decomposed into small molecules very difficult; In addition xylogen also contains a large amount of functional groups, and the small molecules intermediate producing in degradation process again extremely easy repolymerization is macromolecular cpd, therefore, by the micromolecular compound that is converted into of the efficient highly selective of xylogen, has suitable challenge.Not yet having at present any report is to carry out efficient catalytic lignin degrading with catalyst with base of molybdenum.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of technique of utilizing the coupling of reaction solvent and catalyzer to carry out catalyzed degradation xylogen is provided, single step reaction is translated into the micromolecular compound of high added value, to realizing the recycling of xylogen.
Technical purpose of the present invention is achieved by following technical proposals:
A kind of method of being produced organic chemicals by xylogen, carry out according to following step: after xylogen, catalyzer and reaction solvent are mixed, add in closed reactor, pass into gas, be warming up to 230-350 ° of C, stirring reaction 0.5h-12h, after reaction finishes, filter out solid catalyst, rotary evaporation, obtains product liquid.
In such scheme, xylogen used comprises that alkali lignin (Kraft lignin), sulfuric acid xylogen (Klason lignin), milled wood lignin quality (Milled wood lignin) and organic solvent xylogen (refer to Jiang Ting great, " xylogen ", Chemical Industry Press, January in 2009 the 2nd edition, 88-98).
In such scheme, after encloses container, need oxygen wherein to be got rid of, pass into gas and elect rare gas element (as nitrogen, argon gas, helium) or hydrogen as.
In such scheme, can also adopt continuous solid body, two bursts of chargings of liquid or slip charging reactor, adopt the method for continuous still battery (or reaction distillation), process is carried out continuously.
In such scheme, the solution that reaction solvent selects deionized water, ethanol, water and ethanol to mix with arbitrary proportion, for example volume fraction of ethanol is 10-50%.
In such scheme, the mass ratio of reaction raw materials xylogen and solvent is (1:200)-(1:10), the mass ratio of xylogen and catalyzer is (1:1)-(200:1), under room temperature 20-25 ° of C, in reactor, gas original pressure is 0-6MPa, and stirring velocity is 100r/min-1500r/min.
In such scheme, each optimal process parameter is as follows: the mass ratio of reaction raw materials xylogen and solvent is (1:100)-(1:80), the mass ratio of xylogen and catalyzer is (10:1)-(100:1), under room temperature 20-25 ° of C, in reactor, gas original pressure is 0-6MPa, stirring velocity is 100r/min-1500r/min, be warming up to 260-300 ° of C, stirring reaction 2h-6h.
In such scheme, described catalyzer is catalyst with base of molybdenum, selecting transition metal molybdenum is active metal, adopt loaded catalyst or unsupported catalyst, wherein in loaded catalyst, the charge capacity of active metal is 1-80wt% of catalyzer total quality (quality of active metal and carrier and), is preferably 5-30wt%.
Described loaded catalyst can be represented by the formula: A
xb
y/ C loaded catalyst, wherein A is transition metal molybdenum; B is carbon, phosphoric or oxygen element; C is support of the catalyst, comprises aluminum oxide (Al
2o
3), gac (AC), silicon-dioxide (SiO
2), silicon carbide (SiC) and other are commonly used for the material of support of the catalyst, wherein 0 < x≤2,0≤y≤3, preferably 1≤x≤2.
Described unsupported catalyst can be represented by the formula: A
xb
yunsupported catalyst, wherein A is transition metal M o; B is carbon, phosphoric or oxygen element, wherein 0 < x≤2,0≤y≤3, preferably 1≤x≤2.
Above-mentioned catalyst with base of molybdenum preparation process is as follows:
Described loaded catalyst is prepared in the following way
The wherein preparation method of supported transition metal carbide catalyst
(1) soluble salt that contains active ingredient molybdenum is dissolved in to (massfraction of ammoniacal liquor is 10%) in ammoniacal liquor, adopts the method for incipient impregnation to load on carrier, then at the 80-150 DEG C of dry catalyzer precursor that obtains
(2) method of temperature programming carbonization for this precursor, can prepare different transition metal carbide (P.P.Aegerter et al, Journal of Catalysis, 1996,164,109 – 121).
The preparation method of loaded transitional metal phosphide catalyst: by soluble in water the soluble salt of Secondary ammonium phosphate and active ingredient molybdenum, then flood, the dry catalyzer precursor that obtains, this precursor is being carried out under hydrogen atmosphere to temperature programming reaction, can prepare transition metal phosphide catalyst (P.A.Clark et al, Journal ofCatalysis, 2003,218,78-87).
The preparation method of supported transitional metal oxide catalyst: the soluble salt that contains active ingredient molybdenum is dissolved in to (massfraction of ammoniacal liquor is 10%) in ammoniacal liquor, adopt the method for incipient impregnation to load on carrier, then be dried and obtain catalyzer precursor at 80-150 DEG C, if precursor is placed in to N
2in atmosphere, be warming up to 500 DEG C, calcining 4h, the catalyzer obtaining is designated as the MoO of load
3catalyzer; If by precursor in H
2in atmosphere, keep, after 12h, being down to room temperature at 350 DEG C, do not re-use CH
4/ H
2carbonization, the catalyzer obtaining is designated as the MoO of load
2catalyzer.
The preparation method of carrier-borne transition metal catalysts: the soluble salt that contains active ingredient molybdenum is dissolved in to (massfraction of ammoniacal liquor is 10%) in ammoniacal liquor, adopt the method for incipient impregnation to load on carrier, then be dried and obtain catalyzer precursor at 80-150 DEG C, precursor is placed in to H
2in atmosphere, be warmed up to 650 DEG C, reduction 4h, the catalyzer obtaining is designated as the Mo catalyzer of load.
It is presoma that the preparation of described unsupported catalyst adopts the soluble salt that contains active ingredient molybdenum, specifically:
The wherein preparation method of non-loading type transition metal carbide catalyst, using the soluble salt that contains active ingredient molybdenum as presoma, by the method for temperature programming carbonization, can prepare different transition metal carbides (T.Miyao, Applied CatalysisA:General165 (1997) 419-428; J.S, LEE; Journal of Catalysis125 (1990), 157--170; Changhai Liang, Chem.Mater.14 (2002), 3148-3151).
The preparation method of non-loading type transition metal phosphide catalyst: using the soluble salt that contains active ingredient molybdenum as presoma, mix with Secondary ammonium phosphate, under hydrogen atmosphere, carry out temperature programming reaction, can prepare non-loading type transition metal phosphide catalyst (C.Stinner, R.Prins, and Th.Weber, Journal of Catalysis191 (2000), 438-444).
The preparation method of non-loading type catalyst of transition metal oxide: using the soluble salt that contains active ingredient molybdenum as presoma, if precursor is placed in to N
2in atmosphere, be warming up to 500 DEG C, calcining 4h, the catalyzer obtaining is designated as unsupported MoO
3catalyzer; If by precursor in H
2in atmosphere, keep, after 12h, being down to room temperature at 350 DEG C, do not re-use CH
4/ H
2carbonization, the catalyzer obtaining is designated as unsupported MoO
2catalyzer.
The preparation method of non-loading type transition-metal catalyst: using the soluble salt that contains active ingredient molybdenum as presoma, precursor is placed in to H
2in atmosphere, be warmed up to 650 DEG C, reduction 4h, the catalyzer obtaining is designated as unsupported Mo catalyzer.
Catalyst with base of molybdenum is applied in by xylogen and is produced in the method for organic chemicals, the reaction product liquid that obtains is after chromatography-mass spectroscopy separation and confirming, (X-coordinate is the residence time (min) to obtain the total ion current figure of the Gc-ms of the reacted product liquid of alkali lignin, ordinate zou is intensity), as shown in Figure 1.For each product the qualitative analysis in total ion figure, mainly contain alcohols (for example n-hexyl alcohol, 3-hexenol, 2-ethyl butanol, 2-methyl-2-pentenol), ester class (for example n-caproic acid ethyl ester, 3-hexenoic acid ethyl ester, 4-hexenoic acid ethyl ester, 3 methylvaleric acid ethyl ester, 3-octylenic acid ethyl ester, ethyl octylate), single phenols (for example 2-methoxyphenol, 4-methyl, 2-methoxyphenol, 4-ethyl, 2-methoxyphenol, 4-propyl group, 2-methoxyphenol), phenylcarbinol class (for example phenylcarbinol, 2-methylbenzyl alcohol, 4-methylbenzyl alcohol, 4-ethylbenzene methyl alcohol, 2, 4, 5-trimethylbenzene methanol), arene (for example dimethylbenzene, 3-methyl-ethyl benzene, 2, 4-dimethyl ethylbenzene, 2, 5-dimethyl ethylbenzene), as shown in the table:
Compared with prior art, the present invention has the following advantages (beneficial effect):
1. raw material wood element is the abundant biomass of nature reserves, its wide material sources, the xylogen etc. that comprises by-product in the black liquor, cellulosic ethanol industry of pulp industry discharge can be used as reaction raw materials, has advantages of that raw material sources are extensive, with low cost.
2. catalyzer is taking transition metal molybdenum as active centre, and molybdenum is the abundant elements of nature reserves, and catalyzer is with low cost.
3. adopt water or ethanol to be reaction solvent, environmentally friendly, pollution-free, in reaction process, do not use any mineral acid, alkali, avoid common problem of environmental pollution in biomass processing technique.
4. in lignin molecule structure, be with phenyl ring part to obtain monocycle aromatic product, a chain portion obtains six carbon alcohols and ester class, and Atom economy is better, meets the requirement of Sustainable development.
5. catalytic process has very high product yield, under the reaction conditions of optimizing, small molecules organic products total mass yield exceedes 100%, this is because of solvent molecule and the lignin depolymerization small molecules useful molecule of combination generation again, as n-caproic acid ethyl ester, 3-hexenoic acid ethyl ester, 4-hexenoic acid ethyl ester, 3 methylvaleric acid ethyl ester, 3-octylenic acid ethyl ester, ethyl octylate.And product comprises the aromatic compounds such as single phenols of industrial large use, and added value is high, has good prospects for commercial application.
Brief description of the drawings
Fig. 1 is the total ion current figure (X-coordinate is the residence time (min), and ordinate zou is intensity) of the Gc-ms of the reacted product liquid of alkali lignin.
Embodiment
Further illustrate technical scheme of the present invention below in conjunction with embodiment, molybdenum source adopts Ammonium Heptamolybdate, adopts commercial Tianjin to recover the ammoniacal liquor of reagent company, is configured to the solution of 10wt%.
The preparation of embodiment 1 catalyzer
Take Ammonium Heptamolybdate and be dissolved in ammonia soln, then incipient impregnation, to gac (AC) carrier of acidification, after 120 DEG C of oven drying 12h, carries out temperature programming carburizing reagent by catalyzer precursor, and concrete reaction process is: at H
2in atmosphere, 0.5g precursor is placed in to crystal reaction tube and is warmed up to 350 DEG C, keep 12h.Then gas is switched to volume fraction and is 15% CH
4/ H
2, be warming up to 590 DEG C, keep 2h, be then down to fast 25 DEG C of room temperatures.The catalyzer that the molybdenum charge capacity obtaining is 30wt%, is expressed as Mo
2c/AC (30wt%Mo
2c/AC).
The preparation of embodiment 2 catalyzer
Method for preparing catalyst is with embodiment 1, and difference from Example 1 is, changes the concentration of ammonium molybdate in steeping fluid, or through repeatedly flooding, can obtain the catalyzer of different loads amount.As the charge capacity of Mo is respectively the Mo of 1wt%, 5wt%, 10wt%, 15wt%, 20wt%, 30wt%, 50wt% and 80wt%
2c/AC catalyzer.
The preparation of embodiment 3 catalyzer
Method for preparing catalyst is with embodiment 1, and difference from Example 1 is, changes gac (AC) carrier into aluminum oxide (Al
2o
3), silicon-dioxide (SiO
2) or silicon carbide (SiC) carrier, can obtain loading on the catalyzer of different carriers.As Mo
2c/Al
2o
3, Mo
2c/SiO
2, Mo
2c/SiC catalyzer.
The preparation of embodiment 4 catalyzer
Method for preparing catalyst is with embodiment 1, and difference from Example 1 is, makes final carbonization temperature into 560 DEG C, 620 DEG C, 650 DEG C, 680 DEG C, 710 DEG C, 740 DEG C, obtains the Mo of different crystalline phases
xc
y/ AC, wherein 0 < x≤2,0≤y≤1, x is 1,1,2,1,2,2; Y is 1,0,0.5,0.8,0.2,0.6.
The preparation of embodiment 5 catalyzer
Method for preparing catalyst is with embodiment 1, and difference from Example 1 is, precursor is placed in to N
2in atmosphere, be warming up to 500 DEG C, calcining 4h, the catalyzer obtaining is designated as MoO
3/ AC.
The preparation of embodiment 6 catalyzer
Method for preparing catalyst is with embodiment 1, and difference from Example 1 is, precursor is in H
2in atmosphere, keep, after 12h, being down to room temperature at 350 DEG C, do not re-use CH
4/ H
2carbonization, the catalyzer obtaining is designated as MoO
2/ AC.
The preparation of embodiment 7 catalyzer
Method for preparing catalyst is with embodiment 1, and difference from Example 1 is, precursor is placed in H
2in atmosphere, be warmed up to 650 DEG C, reduction 4h, the catalyzer obtaining is designated as Mo/AC.
The preparation of embodiment 8 catalyzer
Take Secondary ammonium phosphate and Ammonium Heptamolybdate and be dissolved in the aqueous solution, then incipient impregnation is to gac (AC) carrier of acidification, and after 120 DEG C of oven drying 12h, 500 DEG C of calcining 5h, obtain catalyzer precursor.At H
2in atmosphere, precursor is risen to 650 DEG C, keep 2h, be then down to fast room temperature.The catalyzer obtaining is designated as MoP/AC.
Embodiment 9 xylogen catalytic degradations
By 1.0g xylogen (purchased from the alkali lignin of Sigma company), 0.5g Mo
2c/AC catalyzer and 100ml ethanol join in 300ml reactor, pass into air in nitrogen replacement reactor, then rushing hydrogen to reactor original pressure is 2MPa, is warming up to 280 DEG C, stirring reaction 2h, after reaction finishes, suction filtration, revolves steaming, gets product liquid at gas chromatograph-mass spectrometer (GC6890-MS5973, Agilent company) on carry out qualitative analysis, carry out quantitative analysis in gas-chromatography after adding internal standard substance.Chromatogram adopts HP-5ms, 30m × 0.25mm × 0.25 μ m capillary column.Liquid product yield calculates with (product quality)/(xylogen quality) × 100%, and wherein the product quality in ester class yield only calculates carboxy moiety, does not comprise CH
3cH
2o part quality.In product yield, alcohols comprises n-hexyl alcohol, 3-hexenol, 2-ethyl butanol, 2-methyl-2-pentenol; Ester class comprises ethyl hexanoate, 3-hexenoic acid ethyl ester, 4-hexenoic acid ethyl ester, 3 methylvaleric acid ethyl ester, 3-octylenic acid ethyl ester, ethyl octylate; Single phenols comprises 2-methoxyphenol, 4-methyl, 2-methoxyphenol, 4-ethyl, 2-methoxyphenol, 4-propyl group, 2-methoxyphenol; Phenylcarbinol class comprises phenylcarbinol, 2-methylbenzyl alcohol, 4-methylbenzyl alcohol, 4-ethylbenzene methyl alcohol, 2,4,5-trimethylbenzene methanol; Arene comprises m-xylene, p-Xylol, 3-methyl-ethyl benzene, 2,4-dimethyl ethylbenzene, 2,5-dimethyl ethylbenzene.
Embodiment 10
Mo
2c/AC, Mo/AC, MoO
2/ AC, MoO
3/ AC catalyzer to xylogen catalytic decomposition Performance Ratio, in table 1.Reaction conditions is with embodiment 9.
Table 1: different catalyst with base of molybdenum to xylogen catalytic decomposition Performance Ratio
As can be seen from the table, catalyst with base of molybdenum can effectively improve each product yield, wherein Mo
2c/AC catalyst activity is the highest.
Embodiment 11
Mo
2c/AC, Mo
2c/Al
2o
3, Mo
2c/SiO
2, Mo
2c/SiC, Mo
2the comparison of C catalyzer to xylogen catalytic decomposition performance, in table 2.Reaction conditions is with embodiment 9.
Table 2: the comparison of different catalysts carrier to xylogen catalytic decomposition performance
As can be seen from the table, by Mo
2c loads on carrier can obviously improve each product yield, wherein uses gac (AC) carrier, and product yield is the highest.
Embodiment 12
30wt%Mo
2c/AC, 20wt%Mo
2c/AC, 10wt%Mo
2the comparison of C/AC catalyzer to xylogen catalytic decomposition performance, in table 3.Reaction conditions is with embodiment 9.
Table 3: the comparison of different catalysts charge capacity to xylogen catalytic decomposition performance
As can be seen from the table, the Mo of different loads amount
2c/AC catalyzer all has good product yield, wherein 30wt%Mo
2the product total recovery that C/AC catalyzer obtains is the highest.
Embodiment 13
Under different carbonization temperatures, Mo
xthe comparison of C/AC catalyzer to xylogen catalyzed conversion performance, in table 4.Except carbonization temperature difference, reaction conditions is with embodiment 9.
Table 4: the comparison of catalyzer to xylogen catalyzed conversion performance under different carbonization temperatures.
As can be seen from the table, the Mo of different carbonization temperatures
xc/AC catalyzer all has good product yield, and the product total recovery wherein obtaining at 590 DEG C of catalyzer is the highest.
Embodiment 14
Under differential responses solvent, Mo
2the comparison of C/AC catalyzer to xylogen catalyzed conversion performance, in table 5.Except reaction solvent difference, reaction conditions is with embodiment 9.
Table 5: under differential responses solvent, Mo
2the comparison of C/AC catalyzer to xylogen catalyzed conversion performance
As can be seen from the table, use deionized water to make solvent, only have single phenol in product, selectivity is better.Use ethanol to make solvent, product total recovery is the highest.
Embodiment 15
Mo under different hydrogen pressure
2the comparison of C/AC catalyzer to xylogen catalyzed conversion performance, in table 6.Except the pressure difference of hydrogen in reaction, reaction conditions is with embodiment 9.
Table 6: the comparison of different hydrogen pressure to xylogen catalyzed conversion performance.
Embodiment 16
Mo under the differential responses time
2the comparison of C/AC catalyzer to xylogen catalyzed conversion performance, in table 7.Except reaction times difference, reaction conditions is with embodiment 9.
Table 7: the comparison of differential responses time to xylogen catalyzed conversion performance
Embodiment 17
Under gas with various atmosphere, use Mo
2the comparison of C/AC catalyzer to xylogen catalyzed conversion performance, in table 8.Except atmosphere difference, reaction conditions is with embodiment 9.
Table 8: the comparison of gas with various atmosphere to xylogen catalyzed conversion performance
Embodiment 18
N
2under atmosphere, the differential responses time is used Mo
2the comparison of C/AC catalyzer to xylogen catalyzed conversion performance, in table 9.Except the reaction times is different and change atmosphere into 0MPaN
2outside, reaction conditions is with embodiment 9.
Table 9:N
2under atmosphere, the comparison of differential responses time to xylogen catalyzed conversion performance
On the basis of above-described embodiment, changing xylogen is sulfuric acid xylogen (Klason lignin), milled wood lignin quality (Milled wood lignin) and organic solvent xylogen, carries out catalytic production alcohols, ester class, single phenols, phenylcarbinol class and arene organic products in the condition of getting rid of oxygen.In the time being prepared, can also adopt continuous solid body, two bursts of chargings of liquid or slip charging reactor, adopt the method for continuous still battery (or reaction distillation), process is carried out continuously, the mass ratio of reaction raw materials xylogen and solvent is (1:200)-(1:10), preferably (1:100)-(1:80); The mass ratio of xylogen and catalyzer is (1:1)-(200:1), preferably (10:1)-(100:1); In loaded catalyst, the charge capacity of active metal is 1-80wt% of catalyzer total quality (quality of active metal and carrier and), is preferably 5-30wt%; Temperature of reaction is selected 250-350 ° of C, preferably 260-300 ° of C, and stirring velocity is selected 100r/min-1500r/min.
Above the present invention is done to exemplary description; should be noted that; in the situation that not departing from core of the present invention, the replacement that is equal to that any simple distortion, amendment or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (10)
1. catalyst with base of molybdenum is being produced the application in organic chemicals by xylogen, it is characterized in that, after xylogen, catalyzer and reaction solvent are mixed, add in closed reactor, pass into gas, be warming up to 230-350 ° of C, stirring reaction 0.5h-12h, after reaction finishes, filters out solid catalyst, rotary evaporation, obtains product liquid
Wherein after encloses container, need oxygen wherein to be got rid of, pass into gas and elect rare gas element or hydrogen as; The solution that reaction solvent selects deionized water, ethanol, water and ethanol to mix with arbitrary proportion; Described product liquid is alcohols, ester class, single phenols, phenylcarbinol class or arene.
2. catalyst with base of molybdenum according to claim 1 is being produced the application in organic chemicals by xylogen, it is characterized in that, the method that described reaction can be selected to adopt continuous solid body, two bursts of chargings of liquid or slip charging reactor or adopt continuous still battery or reaction distillation, carries out process continuously.
3. catalyst with base of molybdenum according to claim 1, produced the application in organic chemicals by xylogen, is characterized in that, described xylogen comprises alkali lignin, sulfuric acid xylogen, milled wood lignin quality or organic solvent xylogen; Described rare gas element is nitrogen, argon gas or helium.
4. catalyst with base of molybdenum according to claim 1, produced the application in organic chemicals by xylogen, is characterized in that, in the solution that described water and ethanol mix with arbitrary proportion, the volume fraction of ethanol is 10%-50%.
5. catalyst with base of molybdenum according to claim 1 is being produced the application in organic chemicals by xylogen, it is characterized in that, the mass ratio of reaction raw materials xylogen and solvent is (1:200)-(1:10), the mass ratio of xylogen and catalyzer is (1:1)-(200:1), under 20-25 ° of C of room temperature, in reactor, gas original pressure is 0-6MPa, and stirring velocity is 100r/min-1500r/min.
According to the catalyst with base of molybdenum described in claim 1 or 5 being produced the application in organic chemicals by xylogen, it is characterized in that, each optimal process parameter is as follows: the mass ratio of reaction raw materials xylogen and solvent is (1:100)-(1:80), the mass ratio of xylogen and catalyzer is (10:1)-(100:1), under room temperature 20-25 ° of C, in reactor, gas original pressure is 0-6MPa, stirring velocity is 100r/min-1500r/min, be warming up to 260-300 ° of C, stirring reaction 2h-6h.
According to the catalyst with base of molybdenum described in claim 1 or 5 being produced the application in organic chemicals by xylogen, it is characterized in that, described catalyzer is catalyst with base of molybdenum, selecting transition metal molybdenum is active metal, adopt loaded catalyst or unsupported catalyst, wherein in loaded catalyst, the charge capacity of active metal is 1-80wt% of catalyzer total quality.
8. catalyst with base of molybdenum according to claim 7, produced the application in organic chemicals by xylogen, is characterized in that, in loaded catalyst, the charge capacity of active metal is 5-30wt% of catalyzer total quality.
9. catalyst with base of molybdenum according to claim 7, produced the application in organic chemicals by xylogen, is characterized in that, described loaded catalyst can be represented by the formula: A
xb
y/ C loaded catalyst, wherein A is transition metal molybdenum; B is carbon, phosphoric or oxygen element; C is support of the catalyst, comprises aluminum oxide, gac, silicon-dioxide, silicon carbide, wherein 0 < x≤2,0≤y≤3, preferably 1≤x≤2.
10. catalyst with base of molybdenum according to claim 7, produced the application in organic chemicals by xylogen, is characterized in that, described unsupported catalyst can be represented by the formula: A
xb
yunsupported catalyst, wherein A is transition metal M o; B is carbon, phosphoric or oxygen element, wherein 0 < x≤2,0≤y≤3, preferably 1≤x≤2.
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| CN201310008112.7A CN103910903B (en) | 2013-01-08 | 2013-01-08 | Application of the catalyst with base of molybdenum in organic chemicals are produced by lignin |
| EP13870898.7A EP2975015A4 (en) | 2013-01-08 | 2013-12-26 | Use of catalyst of subgroup vi element for preparing organic chemical product from lignin |
| CA2897545A CA2897545A1 (en) | 2013-01-08 | 2013-12-26 | Use of catalyst of subgroup vi element for preparing organic chemical product from lignin |
| PCT/CN2013/090604 WO2014108031A1 (en) | 2013-01-08 | 2013-12-26 | Use of catalyst of subgroup vi element for preparing organic chemical product from lignin |
| US14/791,999 US9789473B2 (en) | 2013-01-08 | 2015-07-06 | Use of catalyst prepared with a subgroup VI element for the production of organic chemicals and fuels from lignin |
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