CN113145147A - Supported molybdenum carbide catalyst, preparation method thereof and application of catalyst in selective production of phenol monomers by depolymerizing lignin - Google Patents
Supported molybdenum carbide catalyst, preparation method thereof and application of catalyst in selective production of phenol monomers by depolymerizing lignin Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 229920005610 lignin Polymers 0.000 title claims abstract description 70
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910039444 MoC Inorganic materials 0.000 title claims abstract description 36
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000000178 monomer Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 78
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 37
- 229910052742 iron Inorganic materials 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 238000011068 loading method Methods 0.000 claims abstract description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- 239000011733 molybdenum Substances 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 6
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 239000010902 straw Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000012691 depolymerization reaction Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 240000008042 Zea mays Species 0.000 claims description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 6
- 235000005822 corn Nutrition 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- -1 iron modified molybdenum carbide Chemical class 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000005255 carburizing Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 150000002431 hydrogen Chemical class 0.000 description 18
- 150000002989 phenols Chemical class 0.000 description 13
- 239000003921 oil Substances 0.000 description 8
- 238000011160 research Methods 0.000 description 6
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 4
- 238000007327 hydrogenolysis reaction Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 229910003178 Mo2C Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- QSZCGGBDNYTQHH-UHFFFAOYSA-N 2,3-dimethoxyphenol Chemical compound COC1=CC=CC(O)=C1OC QSZCGGBDNYTQHH-UHFFFAOYSA-N 0.000 description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 229960001867 guaiacol Drugs 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- OMONCKYJLBVWOQ-UHFFFAOYSA-N 1-ethoxy-2-methoxybenzene Chemical compound CCOC1=CC=CC=C1OC OMONCKYJLBVWOQ-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 239000005844 Thymol Substances 0.000 description 1
- 229940023019 aconite Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229960000790 thymol Drugs 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
- 239000002699 waste material Substances 0.000 description 1
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a supported molybdenum carbide catalyst, a preparation method thereof and application of depolymerized lignin for selectively producing phenolic monomers2And C crystal, wherein the loading amounts of nickel, iron and molybdenum elements are all 1-10 wt%. The preparation process comprises the following steps: s1, dissolving the ammonium molybdate precursor, adding activated carbon, stirring, and loading the ammonium molybdate precursor on an activated carbon carrier; s2 adding nickel nitrate and ferric nitrate precursor into S1, stirring to load nickel and ironOn an activated carbon carrier; s3, dehydrating the S2 product in an oil bath at the temperature of 60-80 ℃, drying at the temperature of 100-110 ℃, slowly heating to 600-800 ℃ in a hydrogen atmosphere, and performing carburization reaction to obtain the nickel and iron modified supported molybdenum carbide catalyst. In the preparation process, the formation of beta-Mo 2C crystals and nickel-iron alloy is promoted, the catalytic effect is enhanced, and when the catalyst is used for carrying out hydrogenation depolymerization on lignin, the yield of the obtained phenol monomer is higher than 35%.
Description
Technical Field
The invention belongs to the technical field of biomass energy conversion, and particularly relates to a supported molybdenum carbide catalyst for producing a phenol monomer through lignin depolymerization reaction, a preparation method and an application.
Background
With the increasing consumption of fossil energy, the production of high value-added products by using biomass instead of fossil energy is becoming a popular research direction. At present, the technology for producing platform compounds (furfural, levulinic acid and the like) by using cellulose and hemicellulose is mature day by day, but as another main component of biomass, the utilization of lignin still faces the problems of complex structure, easy polycondensation, low selectivity of target products and the like.
As a polymer with the second highest content in nature, lignin is a three-dimensional phenolic structure compound composed of three monomers. Currently, much research is focused on the use of lignin for the production of aromatics or naphthenes, although higher yields can be obtained, the high price of the catalyst hinders its development. Moreover, the removal of the oxygen-containing functional groups of the lignin by hydrodeoxygenation is a waste of resources. Therefore, the utilization of lignin for the production of phenolic compounds is a very promising and economical research direction.
Aiming at the production of phenolic compounds by lignin depolymerization, different conversion technologies can be divided into three types, namely pyrolysis, hydrogenolysis and hydrothermal depolymerization, wherein hydrogenolysis is the most promising conversion technology. Many studies have shown that hydrogen sources can react with unstable intermediates in the depolymerization of lignin, thereby stabilizing it and inhibiting the production of coke. On the other hand, however, the introduction of hydrogen source may also cause hydrogenation reaction of benzene ring, thereby reducing the yield of the target product.
In addition to the hydrogen source, the catalyst is also the key to the efficient depolymerization of lignin. At present, the preparation of phenolic compounds by catalyzing lignin depolymerization mostly uses a high-price noble metal catalyst, and active metals are introduced for modification so as to achieve the purpose of selective depolymerization: ouyangxinping et al disclose a catalyst in which Fe and Pd elements are supported on HZSM-5 molecular sieve, and the catalyst is used for lignin depolymerization, and the results show that the yield of bio-oil reaches 78.5 wt%, and the yield of monophenol compound reaches 27.9 wt% [ CN 109289903A ]; patent [ CN 107840786 a ] discloses a method for depolymerizing alkali lignin in a supercritical ethanol environment by using a nickel-gold bimetallic catalyst, wherein the relative content of guaiacol obtained by the method reaches 64.25%.
Research finds that the properties of the transition metal carbide are similar to those of platinum group metal, and the transition metal carbide can be used for replacing the application of the transition metal carbide in lignin depolymerization; wu et al found that molybdenum carbide promoted the cleavage of β -O-4 bonds, thereby promoting the depolymerization of alkali lignin by hydrogenation, and yielded aromatic monomer yields of 0.5163g/g [ Ind. Eng. chem. Res.2019,58, 20270-Aconite 20281 ]; meanwhile, researches show that the metal nickel can improve the catalytic effect and promote the depolymerization of the lignin model by increasing metal sites in the molybdenum carbide catalyst [ Fuel,2019,244, 528-containing 535 ]. However, no report on the depolymerization of real lignin by a catalyst with metal to improve the performance of a molybdenum carbide catalyst is available at present.
Disclosure of Invention
On the basis of the research, the invention provides a novel supported molybdenum carbide catalyst and a preparation method thereof, and the novel supported molybdenum carbide catalyst is applied to the actual lignin depolymerization to produce the phenol monomer.
The improvement idea of the invention is as follows: the nickel and iron are adopted to modify molybdenum carbide, nickel-iron alloy is formed between the nickel and iron, the formation of beta-Mo 2C crystal is promoted, the synergistic effect between the nickel and iron improves the catalytic effect, the lignin is promoted to be efficiently converted into phenolic compounds, and the production and use cost of the catalyst is reduced.
The invention aims at providing a nickel and iron modified load type molybdenum carbide catalyst; the second purpose is to provide a preparation method of the catalyst; the third purpose is to provide the application of the catalyst, which is used for the hydrogenation depolymerization of real lignin to produce phenolic monomers.
In the catalyst, the loading amounts of nickel, iron and molybdenum elements are 1-10 wt%, preferably 5 wt%.
In the catalyst, metallic nickelNickel-iron alloy is formed between iron and beta-Mo is formed at the same time2The C crystal and the synergistic effect of the two can promote the breaking of beta-O-4 bonds in the lignin, inhibit the hydrogenolysis of alkyl side chains and efficiently depolymerize the lignin, thereby obtaining high selectivity of phenolic monomers.
In a second aspect of the present invention, there is provided a method for preparing the supported molybdenum carbide catalyst, comprising the steps of: s1, dissolving the ammonium molybdate precursor in deionized water, adding activated carbon, and stirring to load the ammonium molybdate precursor on an activated carbon carrier; s2, adding the nickel nitrate and the ferric nitrate precursor into the mixture of S1, and stirring to load the nickel nitrate and the ferric nitrate on the activated carbon carrier; and S3, dehydrating the mixture obtained in the step S2 in an oil bath at the temperature of 60-80 ℃, drying at the temperature of 100-110 ℃, slowly heating to 600-800 ℃ in a hydrogen atmosphere, and performing carburization reaction to obtain the nickel and iron modified supported molybdenum carbide catalyst.
The preferred process conditions for the preparation method are as follows:
in step S1, the stirring time is at least 2 h; in step S2, the stirring time is at least 4 hours.
In step S3, the oil bath temperature is preferably 60 ℃, and the drying temperature is preferably 105 ℃; the carburizing reaction conditions are as follows: heating the mixture from room temperature to 700 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 1.5h to obtain the nickel and iron modified supported molybdenum carbide catalyst.
In a third aspect of the present invention, there is provided a method for selectively producing phenolic monomers by depolymerizing lignin with a supported molybdenum carbide catalyst, comprising the steps of: fully mixing a catalyst, a lignin raw material and a solvent according to a certain proportion in a hydrogen gas atmosphere, heating to 240-280 ℃, carrying out a hydrogenation depolymerization reaction under the conditions of stirring and pressure, and reacting for 2-6 h to obtain a phenol depolymerization product. The phenol depolymerization product comprises phenol, methyl phenol, ethyl phenol, thymol, guaiacol, ethyl guaiacol, vanillin, dimethoxyphenol and other common monomers.
Preferably, the lignin raw material is organic solvent lignin separated from corn stalks by using an organic solvent, and the method comprises the following steps: 1) drying and crushing corn straws into powder of 40-80 meshes; 2) treating the straw powder at 70 ℃ for 20min by using a 3.94mol/L couple, wherein the liquid-solid ratio is 10:1 (mL/g); 3) after filtering the mixture, water was added in an amount of 4 times the volume of the filtrate to precipitate lignin, which was then filtered, washed to neutrality, and its moisture content was measured and used directly for depolymerization.
Preferably, the mass ratio of the catalyst to the lignin raw material is 1:1, and the solid-to-liquid ratio of the lignin raw material to the solvent is 1:40 (g/mL);
preferably, the solvent is a mixed solution of water and alcohol, and the volume ratio of the water to the alcohol is 3-9: 1. The alcohol is methanol, ethanol or propanol, preferably methanol, and the volume ratio of water to alcohol is 3-4: 1. Reducing the water content of the solvent favours the formation of phenolic compounds, but when the water/alcohol ratio is 3:1, the yield of phenolic compounds is compared with 4:1 does not vary much.
Preferably, the optimal temperature of the hydrogenation depolymerization reaction is 260 ℃, the optimal reaction time is 4h, and the reaction pressure is 3 Mpa. Lignin depolymerization is incomplete at low temperature, and phenolic compounds generated at high temperature are further decomposed, so that the yield is reduced; in terms of reaction time, the reaction time is not longer, but rather, the target product is polymerized again, thereby reducing the yield of the phenolic compound.
The invention has the following beneficial effects:
firstly, the molybdenum carbide catalyst provided by the invention is modified by adopting two metals of nickel and iron, nickel-iron alloy is formed between the nickel and the iron, and beta-Mo is formed at the same time2The C crystal and the synergistic effect of the two can promote the breaking of beta-O-4 bonds in the lignin, inhibit the hydrogenolysis of alkyl side chains and efficiently depolymerize the lignin, thereby obtaining high selectivity of phenolic monomers. Experiments prove that the yield of the obtained phenol monomer is higher than 35 percent by adopting the catalyst to carry out the hydrogenation depolymerization on the lignin.
Secondly, the nickel and iron are adopted to modify the catalyst, and compared with a method of modifying by adopting noble metal in the prior art, the method is beneficial to reducing the cost of the catalyst.
Thirdly, when the catalyst is prepared and used for lignin hydrogenation depolymerization, the reaction conditions are mild, the reaction raw materials and the process are simple, and the depolymerization product and the catalyst are simple to separate, so that the catalyst is environment-friendly and is beneficial to further expanding the trial production or popularization.
Drawings
FIG. 1 shows XRD test results of catalysts prepared in examples 1 to 4.
Detailed Description
The following embodiments are implemented on the premise of the technical scheme of the present invention, and give detailed implementation modes and specific operation procedures, but the protection scope of the present invention is not limited to the following embodiments.
The following examples illustrate the preparation of different types of supported catalysts with nickel, iron and molybdenum loadings of 1-10 wt% and compare the catalytic effects.
In the following examples, the lignin raw material used is straw lignin separated by a solvent, and the specific separation method is as follows: 1) drying and crushing corn straws into powder of 40-80 meshes; 2) treating the straw powder for 20min at 70 ℃ by using a 3.94mol/L p-toluenesulfonic acid solution, wherein the liquid-solid ratio is 10:1 (mL/g); 3) after filtering the mixture, water was added in an amount of 4 times the volume of the filtrate to precipitate lignin, which was then filtered, washed to neutrality, and its moisture content was measured and used directly for depolymerization.
Example 1 molybdenum carbide catalyst with 5% loading
0.92g (NH)4)6Mo7O24·4H2O was dissolved in 10mL of deionized water, and 9.5g of activated carbon was added and stirred for 2 h. The resulting mixture was then dehydrated in an oil bath at 60 ℃ and dried at 105 ℃ for 12 h. Then the obtained solid is put into a fixed bed reactor, and is heated to 700 ℃ from room temperature at the speed of 1 ℃/min under the atmosphere of hydrogen, and is kept for 1.5h for carburization reaction. After the reaction, the reactor is cooled to room temperature, then the catalyst is exposed in the air for 10min, and the obtained Mo2The loading of the molybdenum element in the C/AC catalyst is 5 wt%.
1.25g of lignin and 1.25g of Mo2C/AC catalyst in 50mL water/alcohol (4: 1)The reactants are mixed, then the mixture is placed into a 100mL autoclave, 3MPa hydrogen is filled in the autoclave, the reaction is carried out for 4 hours at 260 ℃, the liquid yield is 79.52%, and the phenolic monomer yield is 19.91%.
Example 2 nickel supported molybdenum carbide catalyst with 5% loading
0.92g (NH)4)6Mo7O24·4H2O was dissolved in 10mL of deionized water, and 9.0g of activated carbon was added and stirred for 2 h. Then adding Ni (NO) under stirring3)2·6H2O (2.47g) in water (10mL deionized water) was stirred for an additional 4 h. The resulting mixture was then dehydrated in an oil bath at 60 ℃ and dried at 105 ℃ for 12 h. Then the obtained solid is put into a fixed bed reactor, and is heated to 700 ℃ from room temperature at the speed of 1 ℃/min under the atmosphere of hydrogen, and is kept for 1.5h for carburization reaction. After the reaction, the temperature of the reactor is reduced to room temperature, then the catalyst is exposed in the air for 10min, and the obtained Ni-Mo2The loading amounts of nickel and molybdenum elements in the C/AC catalyst are both 5 wt%.
1.25g of lignin and 1.25g of Ni-Mo2The C/AC catalyst was mixed in 50mL of water/alcohol (4: 1) solvent, placed in a 100mL autoclave, charged with 3MPa of hydrogen, and reacted at 260 ℃ for 4h, giving a liquid yield of 84.75% and a phenolic monomer yield of 28.39%.
Example 3 iron-supported molybdenum carbide catalyst with a 5% loading
0.92g (NH)4)6Mo7O24·4H2O was dissolved in 10mL of deionized water, and 9.0g of activated carbon was added and stirred for 2 h. Then adding Fe (NO) under stirring3)3·9H2O (3.61g) in water (10mL deionized water) and stirring was continued for 4 h. The resulting mixture was then dehydrated in an oil bath at 60 ℃ and dried at 105 ℃ for 12 h. Then the obtained solid is put into a fixed bed reactor, and is heated to 700 ℃ from room temperature at the speed of 1 ℃/min under the atmosphere of hydrogen, and is kept for 1.5h for carburization reaction. After the reaction, the temperature of the reactor is reduced to room temperature, then the catalyst is exposed in the air for 10min, and the obtained Fe-Mo2The load amounts of iron and molybdenum in the C/AC catalyst are both 5 wt%.
1.25g of lignin and 1.25g of Fe-Mo2The C/AC catalyst was mixed in 50mL of water/alcohol (4: 1) solvent, then placed in a 100mL autoclave, charged with 3MPa of hydrogen, and reacted at 260 ℃ for 4h, giving a liquid yield of 88.16% and a phenolic monomer yield of 26.43%.
Example 4 Nickel and iron Supported molybdenum carbide catalyst with 5% load
0.92g (NH)4)6Mo7O24·4H2O was dissolved in 10mL of deionized water, and 8.5g of activated carbon was added and stirred for 2 h. Then adding Ni (NO) under stirring3)2·6H2O (2.47g) and Fe (NO)3)3·9H2O (3.61g) in water (10mL deionized water) and stirring was continued for 4 h. The resulting mixture was then dehydrated in an oil bath at 60 ℃ and dried at 105 ℃ for 12 h. Then the obtained solid is put into a fixed bed reactor, and is heated to 700 ℃ from room temperature at the speed of 1 ℃/min under the atmosphere of hydrogen, and is kept for 1.5h for carburization reaction. After the reaction, the temperature of the reactor is reduced to room temperature, then the catalyst is exposed in the air for 10min, and the obtained Ni-Fe-Mo2The load capacity of nickel, iron and molybdenum in the C/AC catalyst is 5 wt%.
1.25g of lignin and 1.25g of Ni-Fe-Mo2The C/AC catalyst was mixed in 50mL of water/alcohol (4: 1) solvent, then placed in a 100mL autoclave, charged with 3MPa of hydrogen, and reacted at 260 ℃ for 4h, giving a liquid yield of 89.56% and a phenolic monomer yield of 35.53%.
FIG. 1 shows the XRD test results of the above four catalysts, and it can be seen that the addition of nickel and iron metal can promote beta-Mo in the catalyst2The formation of C crystals and nickel-iron alloy, the synergy of the two is helpful for the liquefaction of lignin and the formation of phenolic monomers.
Example 5 a nickel, iron supported molybdenum carbide catalyst with a loading of 1%,
0.18g (NH)4)6Mo7O24·4H2O was dissolved in 10mL of deionized water, and 9.7g of activated carbon was added and stirred for 2 h. Then adding Ni (NO) under stirring3)2·6H2O (0.49g) and Fe (NO)3)3·9H2O (0.72g) in water (10mL DI water) and stirring was continued for 4 h. The resulting mixture was then dehydrated in an oil bath at 60 ℃ and dried at 105 ℃ for 12 h. Then the obtained solid is put into a fixed bed reactor, and is heated to 700 ℃ from room temperature at the speed of 1 ℃/min under the atmosphere of hydrogen, and is kept for 1.5h for carburization reaction. After the reaction, the temperature of the reactor is reduced to room temperature, then the catalyst is exposed in the air for 10min, and the obtained Ni-Fe-Mo2The loading amounts of nickel, iron and molybdenum elements in the C/AC catalyst are all 1 wt%.
1.25g of lignin and 1.25g of Ni-Fe-Mo2The C/AC catalyst was mixed in 50mL of water/alcohol (4: 1) solvent, then placed in a 100mL autoclave, charged with 3MPa of hydrogen, and reacted at 260 ℃ for 4h, giving a liquid yield of 80.26% and a phenolic monomer yield of 21.89%.
Example 6 nickel and iron supported molybdenum carbide catalyst with a loading of 10%,
1.84g (NH)4)6Mo7O24·4H2O is dissolved in 10mL of deionized water, and 7g of activated carbon is added and stirred for 2 h. Then adding Ni (NO) under stirring3)2·6H2O (4.94g) and Fe (NO)3)3·9H2O (7.22g) in water (10mL DI water) and stirring was continued for 4 h. The resulting mixture was then dehydrated in an oil bath at 60 ℃ and dried at 105 ℃ for 12 h. Then the obtained solid is put into a fixed bed reactor, and is heated to 700 ℃ from room temperature at the speed of 1 ℃/min under the atmosphere of hydrogen, and is kept for 1.5h for carburization reaction. After the reaction, the temperature of the reactor is reduced to room temperature, then the catalyst is exposed in the air for 10min, and the obtained Ni-Fe-Mo2The load of nickel, iron and molybdenum in the C/AC catalyst is 10 wt%.
1.25g of lignin and 1.25g of Ni-Fe-Mo2The C/AC catalyst was mixed in 50mL of water/alcohol (4: 1) solvent, then placed in a 100mL autoclave, charged with 3MPa of hydrogen, and reacted at 260 ℃ for 4h, giving a liquid yield of 89.01% and a phenolic monomer yield of 33.89%.
Compared with the examples 1-6, the catalytic effect of the nickel or iron modified molybdenum carbide catalyst is obviously improved under the same loading amount, but the catalytic effect is not as good as that of the nickel and iron modified catalyst; under the condition that nickel and iron are modified simultaneously, the catalytic effect is optimized along with the increase of nickel and iron loading capacity, and when the nickel, iron and molybdenum loading capacity is 5%, the catalytic effect is the best, and along with the promotion of loading capacity, the catalytic effect begins slowly to descend on the contrary.
The different conditions of the depolymerization reaction of the nickel-iron-loaded molybdenum carbide catalyst with the nickel, iron and molybdenum loading amounts of 5 wt% are compared, and the specific reference is made to examples 7-13.
Example 7
1.25g of lignin and 1.25g of Ni-Fe-Mo2The C/AC catalyst was mixed in 50mL of water/alcohol (4: 1) solvent, placed in a 100mL autoclave, charged with 3MPa of hydrogen, and reacted at 240 ℃ for 4h, giving a liquid yield of 75.38% and a phenolic monomer yield of 21.11%.
Example 8
1.25g of lignin and 1.25g of Ni-Fe-Mo2The C/AC catalyst was mixed in 50mL of water/alcohol (4: 1) solvent, then placed in a 100mL autoclave, charged with 3MPa of hydrogen, and reacted at 280 ℃ for 4h, giving a liquid yield of 91.54% and a phenolic monomer yield of 26.66%.
Example 9
1.25g of lignin and 1.25g of Ni-Fe-Mo2The C/AC catalyst was mixed in 50mL of water/alcohol (4: 1) solvent, then placed in a 100mL autoclave, charged with 3MPa of hydrogen, and reacted at 260 ℃ for 2h, giving a liquid yield of 70.15% and a phenolic monomer yield of 19.56%.
Example 10
1.25g of lignin and 1.25g of Ni-Fe-Mo2The C/AC catalyst was mixed in 50mL of water/alcohol (4: 1) solvent, then placed in a 100mL autoclave, charged with 3MPa of hydrogen, and reacted at 260 ℃ for 6h, giving a liquid yield of 82.43% and a phenolic monomer yield of 27.34%.
Example 11
1.25g of lignin and 1.25g of Ni-Fe-Mo2The C/AC catalyst was mixed in 50mL of an aqueous solution and then placed at 100mL autoclave, charging 3MPa hydrogen, reacting at 260 ℃ for 4h, obtaining liquid yield of 74.56% and phenolic monomer yield of 19.55%.
Example 12
1.25g of lignin and 1.25g of Ni-Fe-Mo2The C/AC catalyst was mixed in 50mL of water/alcohol (6: 1) solvent, then placed in a 100mL autoclave, charged with 3MPa of hydrogen, and reacted at 260 ℃ for 4h, giving a liquid yield of 83.25% and a phenolic monomer yield of 29.39%.
Example 13
1.25g of lignin and 1.25g of Ni-Fe-Mo2The C/AC catalyst was mixed in 50mL of water/alcohol (3: 1) solvent, then placed in a 100mL autoclave, charged with 3MPa of hydrogen, and reacted at 260 ℃ for 4h, giving a liquid yield of 89.77% and a phenolic monomer yield of 36.34%.
From the above, it is found that when the Ni-Fe-Mo2C/AC catalyst is used for carrying out the lignin depolymerization reaction, the effect is best when the metal loading is 5%, the water-alcohol volume ratio is 3:1 or 4:1, the reaction temperature is 260 ℃, and the reaction time is 4 hours.
Analysis has found that reducing the water content of the solvent favours the formation of phenolic compounds, but when the water/alcohol ratio is 3:1, the yield of the phenolic compound is not greatly changed from 4: 1; in the aspect of temperature, the reaction temperature is too low, lignin is not depolymerized completely, and the phenolic compounds generated at high temperature are further decomposed, so that the yield is reduced; in terms of reaction time, the reaction time is not longer, but rather, the target product is polymerized again, thereby reducing the yield of the phenolic compound.
From the above examples, the catalyst of the present invention uses a nickel and iron metal modified molybdenum carbide catalyst to promote the formation of β -Mo2C crystal and nickel-iron alloy, enhance the effect of the catalyst, and achieve the purpose of preparing phenolic compounds by high-efficiency conversion of lignin. The invention uses solvent lignin as raw material, and has wide source; the catalyst is a non-noble metal catalyst, has the remarkable advantages of simple process, mild conditions, low catalyst cost and the like, and is simple to separate a depolymerization product from the catalyst and environment-friendly.
While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the invention is not limited thereto, and that various changes and modifications may be made without departing from the spirit of the invention, and the scope of the appended claims is to be accorded the full scope of the invention.
Claims (10)
1. The supported molybdenum carbide catalyst is a nickel and iron modified molybdenum carbide catalyst, nickel-iron alloy is formed between metal nickel and iron, and beta-Mo is formed at the same time2C crystal, wherein the loading amounts of nickel, iron and molybdenum elements in the catalyst are all within the range of 1-10 wt%.
2. The supported molybdenum carbide catalyst of claim 1, wherein:
wherein, in the catalyst, the loading amounts of nickel, iron and molybdenum elements are all 5 wt%.
3. A process for preparing a supported molybdenum carbide catalyst according to claim 1 or 2, comprising the steps of:
s1, dissolving the ammonium molybdate precursor in deionized water, adding activated carbon, and stirring to load the ammonium molybdate precursor on an activated carbon carrier;
s2, adding the nickel nitrate and the ferric nitrate precursor into the mixture of S1, and stirring to load the nickel nitrate and the ferric nitrate on the activated carbon carrier;
and S3, dehydrating the mixture obtained in the step S2 in an oil bath at the temperature of 60-80 ℃, drying at the temperature of 100-110 ℃, slowly heating to 600-800 ℃ in a hydrogen atmosphere, and performing carburization reaction to obtain the nickel and iron modified supported molybdenum carbide catalyst.
4. The method of preparing a supported molybdenum carbide catalyst according to claim 3, wherein:
in step S1, the stirring time is at least 2 h; in step S2, the stirring time is at least 4 hours.
5. The method of preparing a supported molybdenum carbide catalyst according to claim 3, wherein:
in the step S3, the oil bath temperature is 60 ℃, and the drying temperature is 105 ℃;
the carburizing reaction conditions are as follows: heating the mixture from room temperature to 700 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 1.5h to obtain the nickel and iron modified supported molybdenum carbide catalyst.
6. A method for selectively producing phenolic monomers by depolymerizing lignin using the supported molybdenum carbide catalyst of claim 1 or 2, comprising the steps of:
fully mixing a catalyst, a lignin raw material and a solvent according to a certain proportion in a hydrogen gas atmosphere, heating to 240-280 ℃, carrying out a hydrogenation depolymerization reaction under the conditions of stirring and hydrogen pressure, and reacting for 2-6 h to obtain a phenol depolymerization product.
7. The method for selectively producing phenolic monomers by depolymerizing lignin with the supported molybdenum carbide catalyst according to claim 6, wherein:
the method comprises the following steps of (1) separating the lignin raw material from the corn straws by using an organic solvent, wherein the lignin raw material is the organic solvent lignin which is separated from the corn straws by using the organic solvent, and the method comprises the following steps:
A. drying and crushing corn straws into powder of 40-80 meshes;
B. treating straw powder for 20min at 70 ℃ by using 3.94mol/L p-toluenesulfonic acid solution, wherein the liquid-solid ratio is 10mL:1 g;
C. after filtering the mixture, water was added in an amount of 4 times the volume of the filtrate to precipitate lignin, which was then filtered, washed to neutrality, and its moisture content was measured and used directly for depolymerization.
8. The method for selectively producing phenolic monomers by depolymerizing lignin with the supported molybdenum carbide catalyst according to claim 6, wherein:
wherein the mass ratio of the catalyst to the lignin raw material is 1:1, and the solid-liquid ratio of the lignin raw material to the solvent is 1g:40 mL;
the solvent is a mixed solution of water and alcohol, the alcohol is methanol, ethanol or propanol, and the volume ratio of the water to the alcohol is 3-9: 1.
9. The method for selectively producing phenolic monomers by depolymerizing lignin with the supported molybdenum carbide catalyst according to claim 8, wherein:
wherein the volume ratio of water to methanol is 3-4: 1.
10. The method for selectively producing phenolic monomers by depolymerizing lignin with the supported molybdenum carbide catalyst according to claim 6, wherein:
wherein the temperature of the hydrogenation depolymerization reaction is 260 ℃, the reaction time is 4h, and the reaction pressure is 3 Mpa.
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