CN111036239A - Supported sulfide catalyst and preparation method and method for synthesizing γ-valerolactone - Google Patents
Supported sulfide catalyst and preparation method and method for synthesizing γ-valerolactone Download PDFInfo
- Publication number
- CN111036239A CN111036239A CN201911223596.0A CN201911223596A CN111036239A CN 111036239 A CN111036239 A CN 111036239A CN 201911223596 A CN201911223596 A CN 201911223596A CN 111036239 A CN111036239 A CN 111036239A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reaction
- kettle
- mos
- room temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 33
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 107
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000007787 solid Substances 0.000 claims abstract description 37
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 28
- 238000011068 loading method Methods 0.000 claims abstract description 26
- 238000004073 vulcanization Methods 0.000 claims abstract description 25
- 238000005470 impregnation Methods 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 26
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims description 25
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 238000011049 filling Methods 0.000 claims description 13
- 239000012263 liquid product Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 229940040102 levulinic acid Drugs 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 9
- 229940010552 ammonium molybdate Drugs 0.000 claims description 9
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 9
- 239000011609 ammonium molybdate Substances 0.000 claims description 9
- 239000007810 chemical reaction solvent Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- UAGJVSRUFNSIHR-UHFFFAOYSA-N Methyl levulinate Chemical compound COC(=O)CCC(C)=O UAGJVSRUFNSIHR-UHFFFAOYSA-N 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 7
- ISBWNEKJSSLXOD-UHFFFAOYSA-N Butyl levulinate Chemical compound CCCCOC(=O)CCC(C)=O ISBWNEKJSSLXOD-UHFFFAOYSA-N 0.000 claims description 6
- 229940005460 butyl levulinate Drugs 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910016002 MoS2a Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229940094933 n-dodecane Drugs 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 34
- 239000007789 gas Substances 0.000 description 26
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- -1 ammonium heptamolybdate tetrahydrate Chemical class 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a supported sulfide catalyst, a preparation method thereof and a method for synthesizing gamma-valerolactone. MoS for catalyst2a/B or A-MoS2The component A is one or more of metal nickel, cobalt and copper; b is a catalyst carrier; the Mo loading is 2-20 wt%, and the A loading in the catalyst is 0-10 wt%. Dissolving a precursor of an active component Mo and a soluble salt of the component A in deionized water, and soaking a carrier in the solution in equal volume; after the impregnation is finished, putting the black solid in an oven for drying; the powdery solid taken out is placed in a tube furnace in H2S/H2And carrying out temperature programming vulcanization in the mixed gas to obtain the catalyst. The catalyst is used for synthesizing gamma-valerolactone; the conversion rate of the ethyl levulinate and the yield of the gamma-valerolactone respectively reach 98.2 percentAnd 85.7 percent, and the conversion rate and the yield are greatly improved relative to the metal element supported catalyst.
Description
Technical Field
The invention belongs to the technical field of preparation methods and applications of novel catalysts, and particularly relates to a preparation method of a supported catalyst which takes molybdenum disulfide as a main active component and takes metals such as nickel, cobalt, copper and the like as second metals, and an application of the catalyst prepared by the method in the synthesis of gamma-valerolactone (GVL) from levulinic acid and esters thereof. In particular to a supported sulfide catalyst, a preparation method and a method for synthesizing gamma-valerolactone.
Background
With the development of industrial revolution, economic development is brought to people, and serious environmental pollution is brought to people, and due to the non-renewable property of primary energy sources such as fossil energy, people generally begin to seek clean, green and sustainable energy sources such as wind energy, solar energy, biomass energy and the like. Biomass energy is considered to be the only renewable energy source that can replace fossil energy to fuel. The biomass energy mainly refers to the absorption of CO by plants through photosynthesis2Various organisms are formed. Lignocellulose is the biomass resource with the most abundant content on the earth, and is mainly utilized through a sugar platform and a thermochemical platform, and the thermochemical platform mainly obtains some liquid fuels by means of cracking and the like; sugar platform refers to a number of platform compounds obtained by chemical or biological conversion, which can catalyze some high value-added products due to their functional groups. Gamma Valerolactone (GVL) is a typical platform compound. GVL can be used as a green solvent, can also be directly used as liquid fuel and the like, is very wide in application and has wide commercial market and application prospect.
The conventional catalysts applied to the reaction of preparing the GVL from the levulinic acid and the esters thereof can be divided into homogeneous catalysts and heterogeneous catalysts. For homogeneous catalysts, the presence of ligands is complicated; noble metals as active centers have problems of high cost, difficult recovery and the like, so people are increasingly turning to the research of heterogeneous catalysts. In the case of heterogeneous catalysts, impregnation, hydrothermal synthesis, coprecipitation, ionic precipitation, etc. can be generally employed. The preparation method of the catalyst directly influences the dispersion degree, the actual load capacity, the particle size distribution and the like of the active components of the catalyst, thereby influencing the activity of the catalyst. The preparation method of the single metal supported catalyst mainly adopts an impregnation method, and the catalyst prepared by the equivalent-volume impregnation method has the advantages of simple process and uniform active component loading. The hydrothermal synthesis method requires higher experimental temperature and pressure, and has certain requirements on a hydrothermal synthesis kettle; the coprecipitation rule requires strict control of reaction conditions
Therefore, the invention provides a catalyst prepared by an isometric impregnation method and application thereof in GVL synthesis. The preparation method of the catalyst has the advantages of simple preparation process, mild operation conditions and uniform active component loading, and the effect of the catalyst prepared by the method in the reaction of preparing GVL from levulinic acid and esters thereof is not inferior to that of the catalyst prepared by the traditional preparation method, even better.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an isometric impregnation method for synthesizing a series of single metal or double metal supported catalysts and application thereof in synthesizing GVL (global solution level) from levulinic acid and esters thereof, aiming at solving the problems of high cost of noble metals, complex preparation, harsh reaction conditions, easy loss of active components, uneven distribution of the active components and the like in the traditional impregnation method.
The technical scheme of the invention is as follows:
a supported sulfide catalyst with a structural formula of MoS2a/B or A-MoS2The component A is one or more of metal nickel, cobalt and copper; b is a catalyst carrier; the Mo loading is 2-20 wt%, and the A loading in the catalyst is 0-10 wt%.
The carrier B of the catalyst is AC, gamma-Al2O3、ZrO2、SiO2Molecular sieves, oxides or TiO2And (3) a carrier.
The preparation method of the supported sulfide catalyst adopts an impregnation method to support the precursor of the active component Mo and the soluble salt of the component A on the carrier, and specifically comprises the following steps:
(1) dissolving a precursor of an active component Mo and a soluble salt of a component A in deionized water to form a solution;
(2) after the components are fully dissolved, soaking the carrier in the solution in the step (1) in the same volume;
(3) after the impregnation is finished, putting the black solid in an oven for drying;
(4) the powdery solid taken out is placed in a tube furnace in H2S/H2And carrying out temperature programmed vulcanization in the mixed gas.
The precursor of the active component Mo is ammonium molybdate, and the soluble salt of the component A is nitrate or carbonate.
The dipping temperature in the step (1) is room temperature, and the time is 12-50h.
The drying temperature of the step (3) is 60-200 ℃, and the time is 1-24 h.
The step (4) H2S/H2The flow rate of the mixed gas is 20-100mL/min, wherein H2The volume fraction of S is 2-100%, and the vulcanization procedure is as follows: raising the temperature from room temperature to 800 ℃ at the speed of 2-20 ℃/min, maintaining for 2-5h, and cooling to room temperature under inert atmosphere.
The volume of deionized water for soaking the carrier in the same volume is the same as the pore volume of the carrier.
The catalyst of the invention is used for a method for synthesizing gamma-valerolactone; the method is characterized in that the reaction of gamma-valerolactone is carried out in an intermittent high-pressure reaction kettle, a reaction internal standard substance is a thermostable organic substance n-dodecane, and a reaction solvent dissolves a substrate and a reaction product; the method comprises the following specific steps:
1) fully mixing a reaction substrate, a catalyst, an internal standard substance and a reaction solvent, adding the mixture into a reaction kettle, replacing gas in the kettle for 3-5 times by using gas before the reaction starts, and filling the pressure in the kettle to the target pressure of 0-5 MPa at normal temperature;
2) heating the reaction kettle to 100-300 ℃, wherein the stirring speed is 100-1500r/min, and the stirring time is 0-5 h;
the reaction substrate comprises levulinic acid, methyl levulinate, ethyl levulinate or butyl levulinate; the reaction solvent is water, 1, 4-dioxane, methanol, ethanol, isopropanol, n-butanol or sec-butanol.
3) After the reaction is finished, reducing the temperature, releasing the pressure, opening the kettle, and filtering the solid catalyst component to obtain a liquid product.
The concentration of the reaction substrate in the reaction solvent is 0.1-0.5 mol/L; the mass ratio of the reaction substrate to the catalyst is (1:1) - (10: 1).
In the former case, when levulinic acid is used as a reaction substrate, a noble metal ruthenium-based catalyst is generally used as a main component, and although the conversion rate and the yield are both more than 90%, the problems of complex ligand, high cost and difficult recovery exist. When the levulinic acid esters are used as reaction substrates, the catalyst is generally a transition metal simple substance loaded on a carrier, the conversion rate and the yield are both about 80%, but the problems of higher required hydrogen pressure ratio and metal loss exist.
The invention has the beneficial effects that:
1. the molybdenum and other metals adopted by the invention belong to transition metals, and the molybdenum and other metals have the characteristics of low price, convenience and easy obtainment.
2. The active ingredient can be distributed uniformly and highly dispersedly on the carrier by the isovolumetric impregnation method.
3. According to an XRD (X-ray diffraction) pattern, a molybdenum sulfide structure with better hydrogenation performance can be obtained by a programmed heating method, and the activity of the molybdenum sulfide structure is higher.
4. Compared with the traditional metal elementary substance supported catalyst, the supported sulfide catalyst is innovatively adopted in the research, the conversion rate and the yield are improved by about 10%, and meanwhile, the stability of the catalyst is improved.
5. The reaction solvent in the invention is a conventional organic solvent, and is environment-friendly and pollution-free.
Drawings
FIG. 1 is a loaded MoS2the/AC (10% Mo loading) catalyst and AC support spectra;
FIG. 2 is a diagram of a loaded MoS2/γ-Al2O3(10% Mo Supported) catalyst and gamma-Al2O3A carrier; MoS2/SiO2(10% Mo Supported) catalyst and SiO2XRD spectrum of the carrier.
Detailed Description
The invention will be described in more detail with reference to the following figures and embodiments, but the scope of the invention is not limited thereto.
Example 1
10 wt% MoS2Preparation of the AC catalyst:
(1) 0.8178g of ammonium heptamolybdate tetrahydrate are weighed out and dissolved in 8mL of deionized water,
(2) after ammonium molybdate is completely dissolved in deionized water, 4g of activated carbon (the pore volume of the activated carbon is the same as the volume of water) is added, the mixture is immersed for 30 hours at room temperature,
(3) after the impregnation is finished, the solid is placed in an oven and dried for 12h at 100 ℃, and then cooled to room temperature
(4) Putting the solid taken out into a tube furnace, and then carrying out temperature programming vulcanization, wherein the specific vulcanization process is as follows: heating to 500 deg.C at 10 deg.C/min, maintaining for 4H, cooling to room temperature under Ar atmosphere, and cooling to room temperature under H2S/H2The total flow rate is 60mL/min, H2The volume fraction of S is 60 percent, and MoS with Mo loading of 10 weight percent is obtained2an/AC catalyst. The XRD pattern 1 is MoS2the/AC spectrum, peaks of molybdenum disulfide can be observed at 2 θ 33 ° and 59 °.
Example 2
2 wt% MoS2/γ-Al2O3Preparation of the catalyst:
(1) 0.164g of ammonium heptamolybdate tetrahydrate is weighed out and dissolved in 3.6mL of deionized water,
(2) after the ammonium molybdate is completely dissolved in the deionized water, 4g of gamma-Al is added2O3(γ-Al2O3Pore volume is the same as water volume) at room temperatureThe lower part is dipped for 12 hours,
(3) after the impregnation is finished, the solid is placed in an oven and dried for 1h at 60 ℃, and then cooled to room temperature
(4) Putting the solid taken out into a tube furnace, and then carrying out temperature programming vulcanization, wherein the specific vulcanization process is as follows: heating to 250 deg.C at room temperature of 2 deg.C/min, maintaining for 2H, cooling to room temperature under Ar atmosphere, and cooling to room temperature under H2S/H2The total flow rate is 20mL/min, H2The volume fraction of S is 2 percent, and MoS with the Mo loading of 2 weight percent is obtained2/γ-Al2O3A catalyst. The XRD pattern 2 is MoS2/γ-Al2O3The spectrum, peaks of molybdenum disulfide can be observed at 2 θ ═ 33 ° and 59 °.
Example 3
20 wt% MoS2Preparation of VB catalyst:
(1) 1.6356g of ammonium heptamolybdate tetrahydrate are weighed out and dissolved in 6.4mL of deionized water,
(2) after ammonium molybdate is completely dissolved in deionized water, 4g of VB (the volume of the VB pore is the same as that of water) is added, the mixture is immersed for 50 hours at room temperature,
(3) after the impregnation is completed, the solid is placed in an oven and dried for 24h at 200 ℃, and then cooled to room temperature
(4) Putting the solid taken out into a tube furnace, and then carrying out temperature programming vulcanization, wherein the specific vulcanization process is as follows: heating to 800 deg.C at 20 deg.C/min, maintaining for 5H, cooling to room temperature under Ar atmosphere, and cooling to room temperature under H2S/H2The total flow rate is 100mL/min, H2The volume fraction of S is 100 percent, and MoS with Mo loading of 20 weight percent is obtained2a/VB catalyst.
Example 4
2 wt% MoS2/SiO2Preparation of the catalyst:
(1) 0.164g of ammonium heptamolybdate tetrahydrate is weighed out and dissolved in 1.6mL of deionized water,
(2) after ammonium molybdate is completely dissolved in deionized water, 4g of SiO is added2(SiO2Pore volume is the same as water volume), impregnated at room temperature for 12h,
(3) after the impregnation is finished, the solid is placed in an oven and dried for 1h at 60 ℃, and then cooled to room temperature
(4) Putting the solid taken out into a tube furnace, and then carrying out temperature programming vulcanization, wherein the specific vulcanization process is as follows: heating to 250 deg.C at room temperature of 2 deg.C/min, maintaining for 2H, cooling to room temperature under Ar atmosphere, and cooling to room temperature under H2S/H2The total flow rate is 20mL/min, H2The volume fraction of S is 2 percent, and MoS with the Mo loading of 2 weight percent is obtained2/SiO2A catalyst. The XRD pattern 2 is MoS2/SiO2The spectrum, peaks of molybdenum disulfide can be observed at 2 θ ═ 33 ° and 59 °.
Example 5
10 wt% MoS2/ZrO2Preparation of the catalyst:
(1) 0.8178g of ammonium heptamolybdate tetrahydrate are weighed out and dissolved in 1.4mL of deionized water,
(2) after ammonium molybdate is completely dissolved in deionized water, 4g of zirconium dioxide (the pore volume of the zirconium dioxide is the same as the volume of water) is added, the mixture is immersed for 30 hours at room temperature,
(3) after the impregnation is finished, the solid is placed in an oven and dried for 12h at 100 ℃, and then cooled to room temperature
(4) Putting the solid taken out into a tube furnace, and then carrying out temperature programming vulcanization, wherein the specific vulcanization process is as follows: heating to 500 deg.C at 10 deg.C/min, maintaining for 4H, cooling to room temperature under Ar atmosphere, and cooling to room temperature under H2S/H2The total flow rate is 60mL/min, H2The volume fraction of S is 60 percent, and MoS with Mo loading of 10 weight percent is obtained2/ZrO2A catalyst.
Example 6
20 wt% MoS2/TiO2Preparation of the catalyst:
(1) 1.6356g of ammonium heptamolybdate tetrahydrate are weighed out and dissolved in 3.2mL of deionized water,
(2) after ammonium molybdate is completely dissolved in deionized water, 4g of TiO is added2(TiO2Pore volume is the same as water volume), impregnated at room temperature for 50h,
(3) after the impregnation is completed, the solid is placed in an oven and dried for 24h at 200 ℃, and then cooled to room temperature
(4) The withdrawn solids are placed in a tube furnace,and then carrying out temperature programming vulcanization, wherein the specific vulcanization process is as follows: heating to 800 deg.C at 20 deg.C/min, maintaining for 5H, cooling to room temperature under Ar atmosphere, and cooling to room temperature under H2S/H2The total flow rate is 100mL/min, H2The volume fraction of S is 100 percent, and MoS with Mo loading of 20 weight percent is obtained2/TiO2A catalyst.
Example 7
2 wt% MoS2Preparation of SAPO-34 catalyst:
(1) 0.164g of ammonium heptamolybdate tetrahydrate is weighed out and dissolved in 4mL of deionized water,
(2) after ammonium molybdate is completely dissolved in deionized water, 4g of SAPO-34 (the pore volume of SAPO-34 is the same as the volume of water) is added, the mixture is immersed for 12 hours at room temperature,
(3) after the impregnation is finished, the solid is placed in an oven and dried for 1h at 60 ℃, and then cooled to room temperature
(4) Putting the solid taken out into a tube furnace, and then carrying out temperature programming vulcanization, wherein the specific vulcanization process is as follows: heating to 250 deg.C at room temperature of 2 deg.C/min, maintaining for 2H, cooling to room temperature under Ar atmosphere, and cooling to room temperature under H2S/H2The total flow rate is 20mL/min, H2The volume fraction of S is 2 percent, and MoS with the Mo loading of 2 weight percent is obtained2SAPO-34 catalyst.
Example 8
Ni-MoS with Ni content of 0.1 wt% and Mo content of 2 wt%2Preparation of the AC catalyst:
(1) 0.164g of ammonium heptamolybdate tetrahydrate and 0.2g of nickel nitrate are weighed, dissolved in deionized water,
(2) adding 4g of active carbon after complete dissolution, soaking for 50h at room temperature,
(3) after the impregnation is completed, the solid is placed in an oven and dried for 24h at 200 ℃, and then cooled to room temperature
(4) Putting the solid taken out into a tube furnace, and then carrying out temperature programming vulcanization, wherein the specific vulcanization process is as follows: heating to 800 deg.C at 20 deg.C/min, maintaining for 5H, cooling to room temperature under Ar atmosphere, and cooling to room temperature under H2S/H2The total flow rate is 100mL/min, H2The volume fraction of S is 100 percent, and the Ni loading amount is 0.1 percent by weight and the Mo loading amount is obtainedIs 2 wt% of Ni-MoS2an/AC catalyst.
Example 9
Co-MoS with Co loading of 5 wt% and Mo loading of 10 wt%2Preparation of the AC catalyst:
(1) 0.164g of ammonium heptamolybdate tetrahydrate and 10g of cobalt nitrate are weighed, dissolved in deionized water,
(2) adding 4g of active carbon after complete dissolution, soaking for 50h at room temperature,
(3) after the impregnation is completed, the solid is placed in an oven and dried for 24h at 200 ℃, and then cooled to room temperature
(4) Putting the solid taken out into a tube furnace, and then carrying out temperature programming vulcanization, wherein the specific vulcanization process is as follows: heating to 800 deg.C at 20 deg.C/min, maintaining for 5H, cooling to room temperature under Ar atmosphere, and cooling to room temperature under H2S/H2The total flow rate is 100mL/min, H2The volume fraction of S is 100 percent, and the Co-MoS with the Co loading capacity of 5 weight percent and the Mo loading capacity of 10 weight percent is obtained2an/AC catalyst.
Example 10
Cu-MoS with Cu loading of 10 wt% and Mo loading of 10 wt%2Preparation of the AC catalyst:
(1) 0.164g of ammonium heptamolybdate tetrahydrate and 23g of copper nitrate are weighed, dissolved in deionized water,
(2) adding 4g of active carbon after complete dissolution, soaking for 50h at room temperature,
(3) after the impregnation is completed, the solid is placed in an oven and dried for 24h at 200 ℃, and then cooled to room temperature
(4) Putting the solid taken out into a tube furnace, and then carrying out temperature programming vulcanization, wherein the specific vulcanization process is as follows: heating to 800 deg.C at 20 deg.C/min, maintaining for 5H, cooling to room temperature under Ar atmosphere, and cooling to room temperature under H2S/H2The total flow rate is 100mL/min, H2The volume fraction of S is 100 percent, and the Co-MoS with the Co loading capacity of 10 weight percent and the Mo loading capacity of 20 weight percent is obtained2an/AC catalyst.
Example 11
MoS2Use of the/AC catalyst:
1) dissolving 0.1mol/L ethyl levulinate and 0.125mol/L dodecane in 20ml isopropanol, then weighing 0.1g of catalyst, fully mixing, adding into a reaction kettle, replacing gas in the kettle with gas for 3 times before the reaction starts, and filling the pressure in the kettle to a target pressure of 1MPa at normal temperature;
2) heating the reaction kettle to 220 ℃, wherein the stirring speed is 1000r/min, and the stirring time is 2 h;
3) after the reaction is finished, the temperature is reduced, the pressure is released, the kettle is opened, solid components in the kettle are filtered, and meanwhile, liquid products are obtained and used for gas chromatography analysis. The conversion of ethyl levulinate was calculated as (initial moles of ethyl levulinate-remaining moles of ethyl levulinate)/(initial moles of ethyl levulinate) x 100%. The yield of the product was calculated as (moles of product/Nc)/(initial moles of ethyl levulinate) x 100%, where Nc is (moles of product formed from 1mol of substrate)/mol.
MoS prepared in example 12The result of the reaction of the/AC catalyst on the synthesis of GVL from ethyl levulinate was that the conversion of ethyl levulinate was 98.2% and the yield of GVL was 85.7%.
Example 12
MoS2Use of the/AC catalyst:
1) dissolving 0.3mol/L levulinic acid and 0.125mol/L dodecane in 20ml isopropanol, then weighing 0.025g of catalyst, fully mixing, adding into a reaction kettle, replacing gas in the kettle with gas for 4 times before the reaction starts, and filling the pressure in the kettle to the target pressure of 0MPa at normal temperature;
2) heating the reaction kettle to 100 ℃, wherein the stirring speed is 100r/min, and the stirring time is 0 h;
3) after the reaction is finished, the temperature is reduced, the pressure is released, the kettle is opened, solid components in the kettle are filtered, and meanwhile, liquid products are obtained and used for gas chromatography analysis. The conversion of ethyl levulinate was calculated as (initial moles of levulinic acid-remaining moles levulinic acid)/(initial moles levulinic acid) x 100%. The yield of the product was calculated as (moles of product/Nc)/(initial moles of levulinic acid) x 100%, where Nc is (moles of corresponding product formed from 1mol of substrate)/mol.
Prepared as in example 1MoS2The result of the reaction of the/AC catalyst on the synthesis of GVL from levulinic acid was that the conversion of ethyl levulinate was 10.2% and the yield of GVL was 0.3%.
Example 13
MoS2Use of the/AC catalyst:
1) dissolving 0.1mol/L methyl levulinate and 0.125mol/L dodecane in 20ml isopropanol, then weighing 0.5g of catalyst, fully mixing, adding into a reaction kettle, replacing gas in the kettle with gas for 3 times before the reaction starts, and filling the pressure in the kettle to a target pressure of 5MPa at normal temperature;
2) heating the reaction kettle to 300 ℃, wherein the stirring speed is 1500r/min, and the stirring time is 5 h;
3) after the reaction is finished, the temperature is reduced, the pressure is released, the kettle is opened, solid components in the kettle are filtered, and meanwhile, liquid products are obtained and used for gas chromatography analysis. The conversion of methyl levulinate was calculated as (initial mole of methyl levulinate-remaining mole of methyl levulinate)/(initial mole of methyl levulinate) x 100%. The yield of the product was calculated as (moles of product/Nc)/(initial moles of methyl levulinate) x 100%, where Nc is (moles of product formed from 1mol of substrate)/mol.
Example 14
MoS2Use of the/AC catalyst:
1) dissolving 0.1mol/L butyl levulinate and 0.125mol/L dodecane in 20ml isopropanol, then weighing 0.1g of catalyst, fully mixing, adding into a reaction kettle, replacing gas in the kettle with gas for 3 times before the reaction starts, and filling the pressure in the kettle to a target pressure of 1MPa at normal temperature;
2) heating the reaction kettle to 220 ℃, wherein the stirring speed is 1000r/min, and the stirring time is 2 h;
3) after the reaction is finished, the temperature is reduced, the pressure is released, the kettle is opened, solid components in the kettle are filtered, and meanwhile, liquid products are obtained and used for gas chromatography analysis. The conversion of butyl levulinate was calculated as (initial moles of butyl levulinate-remaining moles of butyl levulinate)/(initial moles of ethyl levulinate) x 100%. The yield of the product was calculated as (moles of product/Nc)/(initial moles of butyl levulinate) x 100%, where Nc is (moles of product formed from 1mol of substrate)/mol.
Example 15
MoS2Use of the/AC catalyst:
1) dissolving 0.1mol/L ethyl levulinate and 0.125mol/L dodecane in 20ml methanol, then weighing 0.1g of catalyst, fully mixing, adding into a reaction kettle, replacing gas in the kettle with gas for 3 times before the reaction starts, and filling the pressure in the kettle to a target pressure of 1MPa at normal temperature;
2) heating the reaction kettle to 220 ℃, wherein the stirring speed is 1000r/min, and the stirring time is 2 h;
3) after the reaction is finished, the temperature is reduced, the pressure is released, the kettle is opened, solid components in the kettle are filtered, and meanwhile, liquid products are obtained and used for gas chromatography analysis. The conversion of ethyl levulinate was calculated as (initial moles of ethyl levulinate-remaining moles of ethyl levulinate)/(initial moles of ethyl levulinate) x 100%. The yield of the product was calculated as (moles of product/Nc)/(initial moles of ethyl levulinate) x 100%, where Nc is (moles of product formed from 1mol of substrate)/mol.
MoS prepared in example 12The result of the reaction of the/AC catalyst on the synthesis of GVL from ethyl levulinate was that the conversion of ethyl levulinate was 91.1% and the yield of GVL was 22.2%.
Example 16
MoS2Use of the/AC catalyst:
1) dissolving 0.1mol/L ethyl levulinate and 0.125mol/L dodecane in 20ml ethanol, then weighing 0.1g of catalyst, fully mixing, adding into a reaction kettle, replacing gas in the kettle with gas for 3 times before the reaction starts, and filling the pressure in the kettle to a target pressure of 1MPa at normal temperature;
2) heating the reaction kettle to 220 ℃, wherein the stirring speed is 1000r/min, and the stirring time is 2 h;
3) after the reaction is finished, the temperature is reduced, the pressure is released, the kettle is opened, solid components in the kettle are filtered, and meanwhile, liquid products are obtained and used for gas chromatography analysis. The conversion of ethyl levulinate was calculated as (initial moles of ethyl levulinate-remaining moles of ethyl levulinate)/(initial moles of ethyl levulinate) x 100%. The yield of the product was calculated as (moles of product/Nc)/(initial moles of ethyl levulinate) x 100%, where Nc is (moles of product formed from 1mol of substrate)/mol.
MoS prepared in example 12The result of the reaction of the/AC catalyst on the synthesis of GVL from ethyl levulinate was that the conversion of ethyl levulinate was 72.8% and the yield of GVL was 50.9%.
Example 17
MoS2Use of the/AC catalyst:
1) dissolving 0.1mol/L ethyl levulinate and 0.125mol/L dodecane in 20ml 1-butanol, then weighing 0.1g of catalyst, fully mixing, adding into a reaction kettle, replacing gas in the kettle with gas for 3 times before the reaction starts, and filling the pressure in the kettle to the target pressure of 1MPa under the normal temperature condition;
2) heating the reaction kettle to 220 ℃, wherein the stirring speed is 1000r/min, and the stirring time is 2 h;
3) after the reaction is finished, the temperature is reduced, the pressure is released, the kettle is opened, solid components in the kettle are filtered, and meanwhile, liquid products are obtained and used for gas chromatography analysis. The conversion of ethyl levulinate was calculated as (initial moles of ethyl levulinate-remaining moles of ethyl levulinate)/(initial moles of ethyl levulinate) x 100%. The yield of the product was calculated as (moles of product/Nc)/(initial moles of ethyl levulinate) x 100%, where Nc is (moles of product formed from 1mol of substrate)/mol.
MoS prepared in example 12The result of the reaction of the/AC catalyst on the synthesis of GVL from ethyl levulinate was that the conversion of ethyl levulinate was 98.4% and the yield of GVL was 8.7%.
Example 18
MoS2Use of the/AC catalyst:
1) dissolving 0.1mol/L ethyl levulinate and 0.125mol/L dodecane in 20ml 2-butanol, then weighing 0.1g of catalyst, fully mixing, adding into a reaction kettle, replacing gas in the kettle with gas for 3 times before the reaction starts, and filling the pressure in the kettle to the target pressure of 1MPa under the normal temperature condition;
2) heating the reaction kettle to 220 ℃, wherein the stirring speed is 1000r/min, and the stirring time is 2 h;
3) after the reaction is finished, the temperature is reduced, the pressure is released, the kettle is opened, solid components in the kettle are filtered, and meanwhile, liquid products are obtained and used for gas chromatography analysis. The conversion of ethyl levulinate was calculated as (initial moles of ethyl levulinate-remaining moles of ethyl levulinate)/(initial moles of ethyl levulinate) x 100%. The yield of the product was calculated as (moles of product/Nc)/(initial moles of ethyl levulinate) x 100%, where Nc is (moles of product formed from 1mol of substrate)/mol.
MoS prepared in example 12The result of the reaction of the/AC catalyst on the synthesis of GVL from ethyl levulinate was that the conversion of ethyl levulinate was 99.0% and the yield of GVL was 97.9%.
Example 18
MoS2/γ-Al2O3The application of the catalyst comprises the following steps:
1) dissolving 0.1mol/L ethyl levulinate and 0.125mol/L dodecane in 20ml isopropanol, then weighing 0.1g of catalyst, fully mixing, adding into a reaction kettle, replacing gas in the kettle with gas for 3 times before the reaction starts, and filling the pressure in the kettle to a target pressure of 1MPa at normal temperature;
2) heating the reaction kettle to 220 ℃, wherein the stirring speed is 1000r/min, and the stirring time is 2 h;
3) after the reaction is finished, the temperature is reduced, the pressure is released, the kettle is opened, solid components in the kettle are filtered, and meanwhile, liquid products are obtained and used for gas chromatography analysis. The conversion of ethyl levulinate was calculated as (initial moles of ethyl levulinate-remaining moles of ethyl levulinate)/(initial moles of ethyl levulinate) x 100%. The yield of the product was calculated as (moles of product/Nc)/(initial moles of ethyl levulinate) x 100%, where Nc is (moles of product formed from 1mol of substrate)/mol.
MoS prepared in example 22/γ-Al2O3The result of the reaction of the catalyst on the synthesis of GVL from ethyl levulinate is ethyl levulinateThe ester conversion was 94.5% and the GVL yield was 79.1%.
Example 19
MoS2/ZrO2The application of the catalyst comprises the following steps:
1) dissolving 0.1mol/L ethyl levulinate and 0.125mol/L dodecane in 20ml isopropanol, then weighing 0.1g of catalyst, fully mixing, adding into a reaction kettle, replacing gas in the kettle with gas for 3 times before the reaction starts, and filling the pressure in the kettle to a target pressure of 1MPa at normal temperature;
2) heating the reaction kettle to 220 ℃, wherein the stirring speed is 1000r/min, and the stirring time is 2 h;
3) after the reaction is finished, the temperature is reduced, the pressure is released, the kettle is opened, solid components in the kettle are filtered, and meanwhile, liquid products are obtained and used for gas chromatography analysis. The conversion of ethyl levulinate was calculated as (initial moles of ethyl levulinate-remaining moles of ethyl levulinate)/(initial moles of ethyl levulinate) x 100%. The yield of the product was calculated as (moles of product/Nc)/(initial moles of ethyl levulinate) x 100%, where Nc is (moles of product formed from 1mol of substrate)/mol.
MoS prepared in example 42/ZrO2The result of the catalyst on the reaction of synthesizing GVL from ethyl levulinate was that the conversion of ethyl levulinate was 84.2% and the yield of GVL was 64.5%.
Example 20
Co-MoS2Use of the/AC catalyst:
1) dissolving 0.1mol/L ethyl levulinate and 0.125mol/L dodecane in 20ml isopropanol, then weighing 0.1g of catalyst, fully mixing, adding into a reaction kettle, replacing gas in the kettle with gas for 3 times before the reaction starts, and filling the pressure in the kettle to a target pressure of 1MPa at normal temperature;
2) heating the reaction kettle to 220 ℃, wherein the stirring speed is 1000r/min, and the stirring time is 2 h;
3) after the reaction is finished, the temperature is reduced, the pressure is released, the kettle is opened, solid components in the kettle are filtered, and meanwhile, liquid products are obtained and used for gas chromatography analysis. The conversion of ethyl levulinate was calculated as (initial moles of ethyl levulinate-remaining moles of ethyl levulinate)/(initial moles of ethyl levulinate) x 100%. The yield of the product was calculated as (moles of product/Nc)/(initial moles of ethyl levulinate) x 100%, where Nc is (moles of product formed from 1mol of substrate)/mol.
Co-MoS prepared in example 42The result of the reaction of the/AC catalyst on the synthesis of GVL from ethyl levulinate was that the conversion of ethyl levulinate was 84.2% and the yield of GVL was 73.4%.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. A supported sulfide catalyst, characterized by: the structural formula of the catalyst is MoS2a/B or A-MoS2The component A is one or more of metal nickel, cobalt and copper; b is a catalyst carrier; the Mo loading is 2-20 wt%, and the A loading in the catalyst is 0-10 wt%.
2. The supported sulfide catalyst of claim 1, wherein: the carrier B of the catalyst is AC, gamma-Al2O3Carbon black, ZrO2、SiO2Molecular sieves, oxides or TiO2And (3) a carrier.
3. The method for preparing the supported sulfide catalyst of claim 1, wherein the precursor of Mo as an active component and the soluble salt of A component are supported on the carrier by an impregnation method, and the method specifically comprises the following steps:
(1) dissolving a precursor of an active component Mo and a soluble salt of a component A in deionized water to form a solution;
(2) after the components are fully dissolved, soaking the carrier in the solution in the step (1) in the same volume;
(3) after the impregnation is finished, putting the black solid in an oven for drying;
(4)the powdery solid taken out is placed in a tube furnace in H2S/H2And carrying out temperature programmed vulcanization in the mixed gas.
4. The method according to claim 3, wherein the precursor of Mo, the active component, is ammonium molybdate, and the soluble salt of A, the component, is nitrate or carbonate.
5. The method according to claim 3, wherein the dipping temperature in step (1) is room temperature and the time is 12-50h.
6. The method according to claim 3, wherein the drying temperature in step (3) is 60-200 ℃ and the drying time is 1-24 hours.
7. The method according to claim 3, wherein the step (4) is carried out in step (4H)2S/H2The flow rate of the mixed gas is 20-100mL/min, wherein H2The volume fraction of S is 2-100%, and the vulcanization procedure is as follows: raising the temperature from room temperature to 800 ℃ at the speed of 2-20 ℃/min, maintaining for 2-5h, and cooling to room temperature under inert atmosphere.
8. A process for the synthesis of gamma valerolactone using the catalyst of claim 1; the method is characterized in that the reaction of gamma-valerolactone is carried out in an intermittent high-pressure reaction kettle, a reaction internal standard substance is a thermostable organic substance n-dodecane, and a reaction solvent dissolves a substrate and a reaction product; the method comprises the following specific steps:
1) fully mixing a reaction substrate, a catalyst, an internal standard substance and a reaction solvent, adding the mixture into a reaction kettle, replacing gas in the kettle for 3-5 times before the reaction starts, and filling the pressure in the kettle to the target pressure of 0-5 MPa at normal temperature;
2) heating the reaction kettle to 100-300 ℃, wherein the stirring speed is 100-1500r/min, and the stirring time is 0-5 h;
3) after the reaction is finished, reducing the temperature, releasing the pressure, opening the kettle, and filtering the solid catalyst component to obtain a liquid product.
9. The method of claim 8, wherein: the reaction substrate comprises levulinic acid, methyl levulinate, ethyl levulinate or butyl levulinate; the reaction solvent is water, 1, 4-dioxane, methanol, ethanol, isopropanol, n-butanol or sec-butanol.
10. The negative method of claim 8, wherein: the concentration of the reaction substrate in the reaction solvent is 0.1-0.5 mol/L; the mass ratio of the reaction substrate to the catalyst is 1-10: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911223596.0A CN111036239B (en) | 2019-12-03 | 2019-12-03 | Supported sulfide catalyst, preparation method thereof and method for synthesizing gamma-valerolactone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911223596.0A CN111036239B (en) | 2019-12-03 | 2019-12-03 | Supported sulfide catalyst, preparation method thereof and method for synthesizing gamma-valerolactone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111036239A true CN111036239A (en) | 2020-04-21 |
| CN111036239B CN111036239B (en) | 2023-02-03 |
Family
ID=70233524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911223596.0A Active CN111036239B (en) | 2019-12-03 | 2019-12-03 | Supported sulfide catalyst, preparation method thereof and method for synthesizing gamma-valerolactone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111036239B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117899895A (en) * | 2024-03-01 | 2024-04-19 | 福州大学 | Multi-metal composite catalyst for hydrodeoxygenation of biomass oil |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193736A (en) * | 2013-03-30 | 2013-07-10 | 浙江工业大学 | Method for synthesizing gamma-valerolactone based on catalytic hydrogenation |
| CN106111163A (en) * | 2016-06-17 | 2016-11-16 | 天津大学 | A kind of molybdenum sulfide catalyst of support type high dispersive and preparation method thereof |
| CN106179421A (en) * | 2016-07-19 | 2016-12-07 | 天津大学 | The preparation of sulfide catalyst and the application in lignin conversion thereof |
| CN110479279A (en) * | 2019-07-03 | 2019-11-22 | 天津大学 | For synthesizing the preparation method and application of the catalyst of gamma-valerolactone |
-
2019
- 2019-12-03 CN CN201911223596.0A patent/CN111036239B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193736A (en) * | 2013-03-30 | 2013-07-10 | 浙江工业大学 | Method for synthesizing gamma-valerolactone based on catalytic hydrogenation |
| CN106111163A (en) * | 2016-06-17 | 2016-11-16 | 天津大学 | A kind of molybdenum sulfide catalyst of support type high dispersive and preparation method thereof |
| CN106179421A (en) * | 2016-07-19 | 2016-12-07 | 天津大学 | The preparation of sulfide catalyst and the application in lignin conversion thereof |
| CN110479279A (en) * | 2019-07-03 | 2019-11-22 | 天津大学 | For synthesizing the preparation method and application of the catalyst of gamma-valerolactone |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117899895A (en) * | 2024-03-01 | 2024-04-19 | 福州大学 | Multi-metal composite catalyst for hydrodeoxygenation of biomass oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111036239B (en) | 2023-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN118287085B (en) | Non-noble metal catalyst Cu-ZnO/TiO2Preparation method and application thereof in catalyzing N-methylaniline N-methylation in heterogeneous system | |
| AU2021100679A4 (en) | A method of preparing carbon supported transition metal catalysts for hydrogenation from bio-oil | |
| CN111087370A (en) | A method for preparing furfuryl alcohol by non-precious metal supported nitrogen-doped carbon catalyzed transfer hydrogenation of furfural | |
| CN104152171B (en) | A kind of Catalytic lignin derives the method that aryl oxide prepares alkane liquid fuel | |
| CN108997274A (en) | A kind of method that liquid phase hydrogen migration catalysis furfural hydrogenation prepares 2- methylfuran | |
| CN106582666B (en) | Gamma-valerolactone hydrogenation catalyst, preparation method and the method for being used to prepare 1,4- pentanediol and 2- methyltetrahydrofuran | |
| CN113546664A (en) | A kind of cobalt-nitrogen co-doped fish scale biochar catalyst and its preparation method and application | |
| CN111036239A (en) | Supported sulfide catalyst and preparation method and method for synthesizing γ-valerolactone | |
| CN111085212B (en) | Method for preparing 2-methylfuran by catalyzing hydrogenation of D-xylose | |
| CN104588033A (en) | Slurry bed Fischer-Tropsch synthesis catalyst, and preparation method and application thereof | |
| CN111057030B (en) | Preparation method and application of hydrotalcite-based sulfide catalyst for synthesizing gamma-valerolactone | |
| CN110354857A (en) | A kind of preparation method and applications of Ni-based heterogeneous catalyst are in catalysis aldehyde compound hydrogenation deoxidation reaction | |
| CN107286006B (en) | A kind of method for preparing vanilla ethyl ketone and acetosyringone by catalyzing alcoholysis of lignin | |
| CN115709073B (en) | Preparation method of tin-based catalyst and its application in catalyzing the preparation of methyl lactate from biomass sugar | |
| CN113979837B (en) | Application of cobalt-based catalyst in hydrogenolysis reaction of biomass and derivative thereof | |
| CN113649017A (en) | Preparation method and application of vegetable oil hydrodeoxygenation water-resistant core-shell type catalyst | |
| CN104588022A (en) | High-activity Fischer-Tropsch synthesis catalyst, and preparation method and application thereof | |
| CN112569945A (en) | Metal-loaded dolomite catalyst for preparing ethanol by glycerol dehydration and preparation thereof | |
| CN117463318A (en) | A kind of catalyst for catalytic hydrogenation to prepare gamma-valerolactone and its application | |
| CN107652252B (en) | A kind of method for preparing gamma-valerolactone | |
| CN114410336B (en) | A method for directly preparing long-chain alkanes based on biomass levulinic acid | |
| CN117843694A (en) | A hydroxyphenanthroline binuclear cobalt complex and its preparation method and application | |
| CN111389395B (en) | Ruthenium iridium catalyst, preparation method thereof and application of ruthenium iridium catalyst in hydrogenolysis reaction of 5-hydroxymethylfurfural | |
| CN111116525B (en) | 2, 5-dimethylfuran and method for preparing 2, 5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural | |
| CN114289045A (en) | Hydrogenation catalyst and application thereof in preparation of cyclopentanone or furfuryl alcohol by catalyzing hydrogenation of furfural |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |