CN107297216B - Phosphomolybdic acid nano catalyst prepared by hydrothermal method - Google Patents
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- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 27
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 31
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002608 ionic liquid Substances 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 239000003607 modifier Substances 0.000 claims abstract description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 3
- 230000004048 modification Effects 0.000 claims abstract description 3
- 238000012986 modification Methods 0.000 claims abstract description 3
- 239000011148 porous material Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims abstract 4
- 238000003756 stirring Methods 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000012018 catalyst precursor Substances 0.000 claims description 37
- 239000000725 suspension Substances 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 238000005303 weighing Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical class C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 239000010949 copper Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000003825 pressing Methods 0.000 description 7
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- FQERWQCDIIMLHB-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CC[NH+]1CN(C)C=C1 FQERWQCDIIMLHB-UHFFFAOYSA-N 0.000 description 2
- PXAVGTWNUANSAK-UHFFFAOYSA-N 1-hexadecyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[NH+]1CN(C)C=C1 PXAVGTWNUANSAK-UHFFFAOYSA-N 0.000 description 2
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- -1 coatings Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OIWSIWZBQPTDKI-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;hydrobromide Chemical compound [Br-].CCCC[NH+]1CN(C)C=C1 OIWSIWZBQPTDKI-UHFFFAOYSA-N 0.000 description 1
- XIYUIMLQTKODPS-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;acetate Chemical compound CC([O-])=O.CC[N+]=1C=CN(C)C=1 XIYUIMLQTKODPS-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241001023442 Populus suaveolens Species 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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Abstract
The invention relates to a phosphomolybdic acid nano catalyst prepared by a hydrothermal method and used for preparing methacrylic acid by oxidizing methacrolein, belonging to the field of catalyst preparation and application. The mesoporous silicon dioxide material is prepared by taking ionic liquid as a precursor and a modification modifier through hydrothermal treatment and roasting, wherein the mesoporous pore diameter is 4-10 nm, and the specific surface area is 4-800 m2The/g orderly assembled nano catalyst has controllable morphology and structure, high catalytic activity, simple preparation process and no pollution, is used for the oxidation reaction of the MAL, and has high selectivity of the MAA, high conversion rate of the MAL, stable catalyst and long service life.
Description
Technical Field
The invention relates to a phosphomolybdic acid nano catalyst prepared by a hydrothermal method and used for preparing methacrylic acid by oxidizing methacrolein, belonging to the field of catalyst preparation and application.
Background
Methacrylic acid (MAA) is an important raw material for organic synthesis, polymer preparation and synthetic rubber, and can be used for preparing adhesives, coatings, fabric treating agents and the like; in particular, Methyl Methacrylate (MMA), an important derivative product thereof, is widely applied in industry. The traditional MAA and MMA production process adopts a traditional Acetone Cyanohydrin (ACH) method, virulent hydrocyanic acid is used in the production process, more wastewater and solid waste are generated, ethylene, isobutene and the like are used as raw materials to prepare Methacrolein (MAL), then the MAL is catalyzed and oxidized into MAA, and finally the MAA is esterified to obtain MMA, so that the MAA and MMA clean production process is industrially applied in the later period.
The preparation process of the catalytic oxidation of MAL to MAA is often carried outKeggin structure heteropoly acid as catalyst, which has phosphomolybdic acid as main component and added with several counter ions (Cu) in different valence states2+、Fe3+、Cs+Etc.) and a coordinating atom (e.g., vanadium in place of molybdenum). Tianyang reports the preparation method of the catalyst in CN102105223, and mainly reports the influence of the addition sequence of phosphorus element on the selectivity of MAA in the preparation process of the catalyst, the conversion rate of the obtained MAL is more than 70%, and the selectivity of the MAA is more than 80%. However, the catalyst has small specific surface area and low catalytic efficiency. Loading is an important means to improve this problem and to increase catalytic activity. The literature reports (Applied Catalysis A: General 320 (2007) 159-165) that the specific surface area of the molybdophosphovanadate is 4 m of the molybdophosphovanadate supported on the nitrogen-doped mesoporous carbon carrier2The/g is increased to 720 m2The conversion of MAL and the selectivity of MAA are both about 80% per g. However, the loading method is complicated, a toxic solvent hydrofluoric acid is used in the loading process, and the loaded catalyst is easy to inactivate. Therefore, it is necessary to develop a new catalyst to further improve the specific surface area, the catalytic activity, the stability and the service life of the catalyst, and to ensure that the catalyst preparation process is simple and pollution-free as far as possible.
Disclosure of Invention
The invention provides a nano catalyst with excellent catalytic performance, ordered structure, large specific surface area and high stability and a preparation method thereof. In the invention, ionic liquid is introduced as a precursor, phosphomolybdic acid is modified and modified, and a hydrothermal method is adopted to prepare the nano catalyst which is used for preparing methacrylic acid by oxidizing methacrolein. Compared with the prior art, the prepared catalyst has the advantages of regular and ordered appearance, excellent catalytic performance, good thermal stability and long service life.
1. The invention relates to a phosphomolybdic acid nano catalyst prepared by a hydrothermal method and used for preparing methacrylic acid by oxidizing methacrolein, which is characterized in that a catalyst precursor expression is XxYySsH4-x-y-sPMo12-mVmOnTaking ionic liquid as a precursor as a modifying modifier, and preparing the mesoporous silica gel by hydrothermal treatment and roasting, wherein the mesoporous silica gel has the pore diameter of 4-10 nm and the specific surface area of 4~800 m2The ordered assembled phosphomolybdic acid nanometer catalyst is prepared. Wherein X is one or two of Cs, Cu, Fe and Zn, Y is one or more of Na, Mn, La, Ce, Cd, Co, Bi, Sb and Rh, S is one of ionic liquid of cation end nitrogen-containing elements, X is the atomic number of the element X in a molecule and is 0-2, Y is the atomic number of the element Y in the molecule and is 0-2, and S is the adding amount of the ionic liquid S in the molecule and is 0<s is less than or equal to 4, m is the number of V atoms replacing Mo atoms in the Keggin structure of the catalyst and is 0<m is less than or equal to 3, and n is the number of oxygen atoms required by the valence.
2. The preparation of the catalyst related by the invention comprises the following steps:
(a) weighing a certain amount of ionic liquid, dissolving the ionic liquid in deionized water at a certain temperature, and stirring for a certain time to obtain a clear solution A;
(b) weighing a certain amount of phosphomolybdic acid, dissolving in deionized water at a certain temperature, and stirring for a certain time to obtain a clear solution B;
(c) weighing a certain amount of compounds containing X and Y, respectively dissolving the compounds in deionized water at a certain temperature, and stirring for a certain time to form solutions C and D;
(d) dropwise adding the solution C and the solution D into the solution B, and stirring and reacting for a period of time at a certain temperature to form a solution or suspension E;
(e) dropwise adding the solution A into the solution or the suspension E at a certain temperature under the condition of stirring for reacting for a period of time to form a suspension F;
(f) transferring the suspension F into a hydrothermal reaction kettle, further reacting for a period of time at a certain temperature, and then carrying out solid-liquid separation, solid concentration and drying to obtain a catalyst precursor;
(g) and (f) roasting the precursor in the step f for a period of time in flowing air or oxygen-rich atmosphere at a certain temperature to obtain a final catalyst product.
Wherein the ionic liquid in the step (a) is an ionic liquid of a cation-terminated nitrogen-containing element, wherein the cation is one of imidazoles, pyridines and pyrrolidinium salts, and the anion is BF4 -、PF6 -、Cl-、Br-、CH3COO-、NO3 -One of (1); the temperature in the step (a) is 25-80 ℃, and the stirring time is 0.5-2 h; the temperature in the working procedures (b) and (c) is 40-80 ℃, and the stirring time is 0.5-1 h; the temperature in the working procedure (d) is 20-100 ℃; the reaction time is 0.5-2 h, the temperature in the working procedure (e) is 20-100 ℃, and the reaction time is 0.5-72 h; in the step (f), the hydrothermal reaction temperature is 80-200 ℃, and the reaction time is 10-72 h; in the step (g), the roasting condition is that the temperature is 250-380 ℃ and the time is 6-72 h.
The catalyst is used for catalytically oxidizing MAL into MAA, the evaluation device is a fixed bed reactor, and the MAA as a main product is generated by the reaction of molecular oxygen in the air and gas-phase MAL.
The conversion rate of the methacrolein MAL is calculated as follows:
the selectivity of methacrylic acid was calculated as follows:
compared with the prior art, the invention has the following advantages: the ionic liquid is used as a precursor and a modification modifier, the environment is friendly, the phosphomolybdic acid catalyst prepared by hydrothermal method is self-assembled into a regular and ordered layered structure after roasting treatment, and the specific surface area is wide in controllable range (4-800 m)2The catalyst has the advantages of controllable morphology and structure, high catalytic activity, simple preparation process and no pollution, and is used in the oxidation reaction of the MAL, the selectivity of the MAA is high, the conversion rate is high, the catalyst is stable, and the service life is long.
Drawings
FIG. 1 is an SEM photograph of a catalyst prepared in example 1.
Detailed Description
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
example 1
Weighing 2.9Dissolving 4g of 1-ethyl-3-methylimidazole chloride ion liquid in 100 mL of deionized water at 25 ℃, and stirring continuously to obtain a clear solution A; weighing 35.64g of phosphomolybdic acid, dissolving in 400 mL of deionized water at 40 ℃ and stirring to obtain an orange solution B; then dropwise adding the solution A into the orange solution B under the stirring state to react for 1h to obtain a suspension, transferring the suspension into a hydrothermal reaction kettle to react for 48 h at the temperature of 150 ℃, and then centrifugally separating, washing and drying to obtain a catalyst precursor with the composition Expression of (EMIM)1H3PMo11VO40. And crushing and pressing the dried catalyst precursor, placing the crushed catalyst precursor in a tubular furnace for roasting in the air atmosphere, firstly heating to 200 ℃, roasting for 4 hours, then heating to 350 ℃, and roasting for 6 hours. Finally obtaining the catalyst with activity.
0.8 mL of the catalyst particles were charged to a fixed bed reactor made of a stainless steel tube having a diameter of 6 mm and a length of 400 mm. Reaction at 310 ℃ under normal pressure, methacrolein: oxygen: nitrogen gas: the water molar ratio was 1:2.5:15:4 and the contact time was 3 s. After the reaction is carried out for 24 hours, sampling and analysis are started, a liquid sample is detected by gas chromatography FID, a gas sample is detected by gas chromatography TCD, the conversion rate of the MAL is 48.6%, and the selectivity of the MAA is 99.4%. After continuous operation for 400 h, the conversion of MAL is still maintained at 45.2%, and the selectivity of MAA is 95.5%.
Comparative example 1
Weighing 2.94 g of 1-ethyl-3-methylimidazole chloride ionic liquid, dissolving in 100 mL of deionized water at 25 ℃, and stirring continuously to obtain a clear solution A; weighing 35.64g of phosphomolybdic acid, dissolving in 400 mL of deionized water at 40 ℃ and stirring to obtain an orange solution B; weighing 4g of cesium nitrate, dissolving the cesium nitrate in 50 mL of deionized water at 40 ℃, dropwise adding the cesium nitrate into the B under a stirring state, and reacting for 2 hours to obtain a suspension C; then dropwise adding the solution A into the suspension C under the stirring state to react for 1h to obtain a suspension, transferring the suspension into a hydrothermal reaction kettle to react for 48 h at the temperature of 150 ℃ to obtain a suspension D, and performing centrifugal separation, water washing and drying to obtain a catalyst precursor, wherein the composition expression of the catalyst precursor is as follows: (EMIM)1CsH2PMo11VO40. The catalyst was worked up and evaluated as in example 1. Conversion of MAL was 83.6% and selectivity of MAA was 84.5%.
Example 2
Weighing 2.19g of 1-butyl-3-methylimidazole bromide ionic liquid, dissolving in 50 mL of deionized water at 25 ℃, and stirring continuously to obtain a clear solution A; weighing 12.87g of phosphomolybdic acid, dissolving in 200 mL of deionized water at 40 ℃ under stirring to obtain an orange solution B; weighing 2g of cesium nitrate, dissolving the cesium nitrate in 25 mL of deionized water at 40 ℃, dropwise adding the cesium nitrate into the B under a stirring state, and reacting for 2 hours to obtain a suspension C; then dropwise adding the solution A into the suspension C under the stirring state, reacting for 1h, transferring into a hydrothermal reaction kettle, placing in a 180 ℃ oven, reacting for 72 h to obtain a suspension D, centrifugally separating, washing with water, and drying to obtain a catalyst precursor, wherein the composition expression of the catalyst precursor is as follows: (BMIM)1CsH2PMo11VO40. And crushing and pressing the dried catalyst precursor, placing the crushed catalyst precursor in a tubular furnace for roasting in an oxygen-rich atmosphere, firstly heating to 200 ℃, roasting for 4 hours, then heating to 380 ℃, and roasting for 6 hours. Finally obtaining the catalyst with activity.
The catalyst was evaluated as in example 1. Finally obtaining the catalyst with activity. Conversion of MAL was 93.6% and selectivity of MAA was 87.8%.
Example 3
Weighing 3.5 g of 1-ethyl-3-methylimidazolium acetate ionic liquid, dissolving in 50 mL of deionized water at 25 ℃, and stirring continuously to obtain a clear solution A; weighing 35.64g of phosphomolybdic acid, dissolving in 400 mL of deionized water at 40 ℃ and stirring to obtain an orange solution B; weighing 1g of copper nitrate, dissolving in 50 mL of deionized water at 40 ℃, dropwise adding into the solution B under a stirring state, and reacting for 2 hours to obtain a solution C; then dropwise adding the solution A into the solution C under the stirring state to obtain a suspension D, reacting for 2 hours, transferring the suspension D into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a 120 ℃ oven for reacting for 24 hours, and performing centrifugal separation, water washing and drying to obtain a catalyst precursor, wherein the composition expression of the catalyst precursor is as follows: (EMIM)1Cu0.2H2.8PMo11VO40. The catalyst was worked up and evaluated as in example 1. Conversion of MAL was 94.8% and selectivity of MAA was 93.5%.
Example 4
Weighing 4.2g of 1-butyl-3-methylimidazolium tetrafluoroboric acidDissolving salt ionic liquid in 50 mL of deionized water at 50 ℃, and stirring continuously to obtain a clear solution A; weighing 35.64g of phosphomolybdic acid, dissolving in 400 mL of deionized water at 40 ℃ and stirring to obtain an orange solution B; weighing 1g of copper nitrate and 3 g of ferrous nitrate, dissolving in 50 mL of deionized water at 40 ℃, dropwise adding into the solution B under a stirring state, and reacting for 2 hours to obtain a solution C; dropwise adding the solution A into the solution C under the stirring state to obtain a suspension D, reacting for 3 hours, transferring the suspension D into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a 200 ℃ oven, reacting for 48 hours to obtain the suspension D, and performing centrifugal separation, water washing and drying to obtain a catalyst precursor, wherein the composition expression of the catalyst precursor is as follows: (BMIM)1Cu0.2Fe0.1H2.7PMo11VO40. And crushing and pressing the dried catalyst precursor, placing the crushed catalyst precursor in a tubular furnace for roasting in an oxygen-rich atmosphere, firstly heating to 150 ℃, roasting for 4 hours, then heating to 360 ℃, and roasting for 6 hours. Finally obtaining the catalyst with activity.
The catalyst was evaluated as in example 1. Conversion of MAL was 98.8% and selectivity of MAA was 82.5%.
Example 5
Weighing 6.6 g of 1-hexadecyl-3-methylimidazole chloride ionic liquid, dissolving in 50 mL of deionized water at 80 ℃, and stirring continuously to obtain a clear solution A; weighing 35.64g of phosphomolybdic acid, dissolving in 400 mL of deionized water at 40 ℃ and stirring to obtain an orange solution B; weighing 1g of copper nitrate and 3 g of ferrous nitrate, dissolving in 50 mL of deionized water at 40 ℃, dropwise adding into the solution B under a stirring state, and reacting for 2 hours to obtain a solution C; dropwise adding the solution A into the solution C under the stirring state to obtain a suspension D, reacting for 4 hours, transferring the suspension D into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a 180 ℃ oven, reacting for 72 hours to obtain the suspension D, and performing centrifugal separation, water washing and drying to obtain a catalyst precursor, wherein the composition expression of the catalyst precursor is as follows: (C)16MIM)1Cu0.2Fe0.1H2.7PMo11VO40. And crushing and pressing the dried catalyst precursor, placing the crushed catalyst precursor in a tubular furnace for roasting in an oxygen-rich atmosphere, firstly heating to 150 ℃, roasting for 8 hours, then heating to 380 ℃, and roasting for 12 hours. Finally obtaining the catalyst with activity.
The catalyst was evaluated as in example 1. Conversion of MAL was 97.8% and selectivity of MAA was 92.5%.
Example 6
Weighing 6.6 g of 1-hexadecyl-3-methylimidazole chloride ionic liquid, dissolving in 50 mL of deionized water at 100 ℃, and stirring continuously to obtain a clear solution A; weighing 35.64g of phosphomolybdic acid, dissolving in 400 mL of deionized water at 40 ℃ and stirring to obtain an orange solution B; weighing 1g of copper nitrate and 3 g of ferrous nitrate, dissolving in 50 mL of deionized water at 40 ℃, dropwise adding into the solution B under a stirring state, and reacting for 2 hours to obtain a solution C; dropwise adding the solution A into the solution C under the stirring state to obtain a suspension D, reacting for 6 hours, transferring the suspension D into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a 180 ℃ oven, reacting for 48 hours to obtain the suspension D, and performing centrifugal separation, water washing and drying to obtain a catalyst precursor, wherein the composition expression of the catalyst precursor is as follows: (C)16MIM)1Cu0.2Fe0.1H2.7PMo11VO40. And crushing and pressing the dried catalyst precursor, placing the crushed catalyst precursor in a tubular furnace for roasting in an oxygen-rich atmosphere, firstly heating to 150 ℃, roasting for 4 hours, then heating to 500 ℃, and roasting for 12 hours. Finally obtaining the catalyst with activity.
The catalyst was evaluated as in example 1. Conversion of MAL was 35.8% and selectivity of MAA was 86.5%.
Example 7
Weighing 4.46 g of 1-butyl-1-methylpyrrolidine bromide ionic liquid, dissolving in 50 mL of deionized water at 80 ℃, and stirring continuously to obtain a clear solution A; 53.46 g of phosphomolybdic acid is weighed and dissolved in 600 mL of deionized water at 40 ℃ under the condition of stirring to obtain an orange solution B; weighing 5.85 g of cesium nitrate and 1.5 g of ferrous nitrate, dissolving in 100 mL of deionized water at 40 ℃, dropwise adding into the solution B under a stirring state, and reacting for 2 hours to obtain a solution C; dropwise adding the solution A into the solution C under the stirring state to obtain a suspension D, reacting for 4 hours, transferring the suspension D into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a 180 ℃ oven, reacting for 48 hours to obtain the suspension D, and performing centrifugal separation, water washing and drying to obtain a catalyst precursor, wherein the composition expression of the catalyst precursor is as follows: ([ BMPyrr)])2Cs1Fe0.1H0.9PMo11VO40. Crushing and pressing the dried catalyst precursor, and placing the crushed catalyst precursor in a moldRoasting in a tubular furnace in an oxygen-rich atmosphere, heating to 150 ℃, roasting for 4 hours, heating to 350 ℃, and roasting for 24 hours. Finally obtaining the catalyst with activity.
The catalyst was evaluated as in example 1. Conversion of MAL was 85.8% and selectivity of MAA was 88.5%.
Example 8
Weighing 5.62g of 1-butylpyridine hexafluorophosphate ionic liquid, dissolving in 100 mL of deionized water at 80 ℃, and stirring continuously to obtain a clear solution A; weighing 35.64g of phosphomolybdic acid, dissolving in 400 mL of deionized water at 40 ℃ and stirring to obtain an orange solution B; 1.87 g of copper nitrate and 2.91g of cobalt nitrate are weighed and dissolved in 100 mL of deionized water at 40 ℃, and dropwise added into the solution B under the stirring state to react for 2 hours to obtain a solution C; then dropwise adding the solution A into the solution C under the stirring state to obtain a suspension D, reacting for 4 hours, transferring the suspension D into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a 120 ℃ oven for reacting for 48 hours, and performing centrifugal separation, water washing and drying to obtain a catalyst precursor, wherein the composition expression of the catalyst precursor is as follows: (BPyrd)2Cu0.1Co0.1H1.8PMo11VO40. And crushing and pressing the dried catalyst precursor, placing the crushed catalyst precursor into a tubular furnace, roasting the crushed catalyst precursor in an oxygen-rich atmosphere, firstly heating to 150 ℃, roasting for 4 hours, then heating to 350 ℃, and roasting for 48 hours. Finally obtaining the catalyst with activity.
The catalyst was evaluated as in example 1. Conversion of MAL was 93.8% and selectivity of MAA was 80.5%.
Table 1: in the examples, the conversion of MAL and the selectivity of MAA
| Examples | Catalyst precursor expression | Conversion of MAL | MAA Selectivity |
| Example 1 | (EMIM)1H3PMo11VO40 | 48.6% | 99.4% |
| Comparative example 1 | (EMIM)1CsH2PMo11VO40 | 83.6% | 84.5% |
| Example 2 | (BMIM)1CsH2PMo11VO40 | 93.6% | 87.8% |
| Example 3 | (EMIM)1Cu0.2H2.8PMo11VO40 | 94.8% | 93.5% |
| Example 4 | (BMIM)1Cu0.2Fe0.1H2.7PMo11VO40 | 98.8% | 82.5% |
| Example 5 | (C16MIM)1Cu0.2Fe0.1H2.7PMo11VO40 | 97.8% | 92.5% |
| Example 6 | (C16MIM)1Cu0.2Fe0.1H2.7PMo11VO40 | 35.8% | 86.5% |
| Example 7 | ([BMPyrr])2Cs1Fe0.1H0.9PMo11VO40 | 85.8% | 88.5% |
| Example 8 | (BPyrd)2Cu0.1Co0.1H1.8PMo11VO40 | 93.8% | 80.5% |
Claims (9)
1. A phosphomolybdic acid nano catalyst prepared by a hydrothermal method and used for preparing methacrylic acid by oxidizing methacrolein is characterized in that a catalyst precursor expression is XxYySsH4-x-y-sPMo12-mVmOnTaking ionic liquid as a precursor as a modification modifier, and preparing the mesoporous silica gel by hydrothermal treatment and roasting, wherein the mesoporous silica gel has the pore diameter of 4-10 nm and the specific surface area of 4-800 m2The ordered assembled phosphomolybdic acid nano catalyst comprises a material I, a material II and a material II, wherein X is one or two of Cs, Cu, Fe and Zn, Y is one or more of Na, Mn, La, Ce, Cd, Co, Bi, Sb and Rh, S is one of ionic liquid of cation end nitrogen-containing elements, X is the atomic number of the element X in a molecule and is 0-2, Y is the atomic number of the element Y in the molecule and is 0-2, and S is the adding amount of the ionic liquid S in the molecule and is 0<s is less than or equal to 4, m is the number of V atoms replacing Mo atoms in the Keggin structure of the catalyst and is 0<m is less than or equal to 3, and n is the number of oxygen atoms required by the valence.
2. The method for preparing a catalyst according to claim 1, wherein the preparation of the catalyst mainly comprises the following steps:
(a) weighing a certain amount of ionic liquid, dissolving the ionic liquid in deionized water at a certain temperature, and stirring for a certain time to obtain a clear solution A;
(b) weighing a certain amount of phosphomolybdic acid, dissolving in deionized water at a certain temperature, and stirring for a certain time to obtain a clear solution B;
(c) weighing a certain amount of compounds containing X and Y, respectively dissolving the compounds in deionized water at a certain temperature, and stirring for a certain time to form solutions C and D;
(d) dropwise adding the solution C and the solution D into the solution B, and stirring and reacting for a period of time at a certain temperature to form a solution or suspension E;
(e) dropwise adding the solution A into the solution or the suspension E at a certain temperature under the condition of stirring for reacting for a period of time to form a suspension F;
(f) transferring the suspension F into a hydrothermal reaction kettle, further reacting for a period of time at a certain temperature, and then carrying out solid-liquid separation, solid concentration and drying to obtain a catalyst precursor;
(g) and (f) roasting the precursor in the step f for a period of time in flowing air or oxygen-rich atmosphere at a certain temperature to obtain a final catalyst product.
3. The method according to claim 2, wherein the ionic liquid in the step (a) is an ionic liquid containing a nitrogen element at the cation end, wherein the cation is one of imidazoles, pyridines and pyrrolidinium salts, and the anion is BF4 -、PF6 -、Cl-、Br-、CH3COO-、NO3 -One kind of (1).
4. The method of claim 2, wherein the temperature in the step (a) is 25 to 80 ℃ and the stirring time is 0.5 to 2 hours.
5. The method for preparing the catalyst according to claim 2, wherein the temperature in the steps (b) and (c) is 40 to 80 ℃ and the stirring time is 0.5 to 1 hour.
6. The method of claim 2, wherein the temperature in the step (d) is 20 to 100 ℃ and the reaction time is 0.5 to 2 hours.
7. The method of claim 2, wherein the temperature in the step (e) is 20 to 100 ℃ and the reaction time is 0.5 to 72 hours.
8. The method for preparing the catalyst according to claim 2, wherein the hydrothermal reaction temperature in the step (f) is 80 to 200 ℃ and the reaction time is 10 to 72 hours.
9. The method for preparing the catalyst according to claim 2, wherein the calcination in the step (g) is carried out at a temperature of 250 to 380 ℃ for 6 to 72 hours.
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