CN110496647A - A kind of synthesis of BV catalysts --- the mesoporous catalyst preparation method of containing transition metal molybdenum ion - Google Patents
A kind of synthesis of BV catalysts --- the mesoporous catalyst preparation method of containing transition metal molybdenum ion Download PDFInfo
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- CN110496647A CN110496647A CN201810498083.XA CN201810498083A CN110496647A CN 110496647 A CN110496647 A CN 110496647A CN 201810498083 A CN201810498083 A CN 201810498083A CN 110496647 A CN110496647 A CN 110496647A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 8
- 239000011733 molybdenum Substances 0.000 title claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000003786 synthesis reaction Methods 0.000 title description 7
- 230000015572 biosynthetic process Effects 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- -1 transition metal molybdenum ion Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 abstract description 16
- 150000002576 ketones Chemical class 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 7
- 239000007800 oxidant agent Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 150000002148 esters Chemical class 0.000 abstract description 5
- 150000002596 lactones Chemical class 0.000 abstract description 5
- 239000002841 Lewis acid Substances 0.000 abstract description 4
- 150000007517 lewis acids Chemical class 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 abstract description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 abstract description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 20
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010813 internal standard method Methods 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—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
- 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
-
- 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
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/04—Seven-membered rings not condensed with other rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of BV catalysts, the i.e. preparation method of the mesoporous catalyst of containing transition metal molybdenum ion.The porous duct that the doping molybdenum ion mesoporous catalyst of this method preparation has biggish specific surface area and freely enters and leaves for macromolecular, with surface hydroxyl abundant and higher hydrothermal stability, therefore it is able to maintain the meso-hole structure of carrier and the Keggin-type structure of silico-tungstic acid；Using Lewis acid, the electropositive of carbonyl carbon on ketone can be enhanced, enhance the electrophilicity of carbonyl carbon, be conducive to oxidant attack carbonyl carbon, can achieve the purpose that activated carbonyl carbon.The catalyst can aoxidize saturated ketone and beta-unsaturated ketone, and the mild dosage of use process simple condition is few.Reaction belongs to heterogeneous reaction, after the reaction was completed easily separates catalyst with product, convenient for recycling.Simultaneously it is also possible that the reaction has the production rate of high selectivity and ester or lactone, and the reaction also complies with the theory of clean manufacturing and Green Chemistry, can also greatly improve the Atom economy of reaction.
Description
Technical field
The present invention relates to a kind of BV catalysts, i.e. the mesoporous catalyst synthesis of containing transition metal ion, the reactions
It is widely used in the medicine such as the synthesis of agriculture chemistry, pharmaceutical intermediate and natural drug, bio-pharmaceutical, organic polymer monomer
And chemical field.
Background technique
It is developed so far, oneself warp of BV oxidation reaction becomes ketone or cyclic ketones is converted into the general designation of ester or lactone, it has also become organises
Learn one of the important reaction of reaction.BV oxidation reaction has functional group conversion and the expansion of ring important in organic synthesis
Meaning can synthesize the heterocycle replaced and function base carbochain by Stereo control well using oxidation reaction, aoxidize resulting product quilt
It is widely used in the synthesis process of natural drug.More importantly can generate a series of valuable by oxidation reaction and be difficult
The ester made from other synthetic methods or lactone can be used as the intermediate of many important organic syntheses.But for tradition
BV oxidation reaction used in oxidant be usually peroxy acid.Since the preparation of these oxidants must use the hydrogen peroxide of high concentration,
And there are many danger in peracid in transport and processing.
This patent is with O2For oxidant, avoid preparation, transport with react in numerous danger.The doping transition gold of preparation
Belong to molybdenum ion mesoporous catalyst.It is mesoporous that there is biggish specific surface area and for the porous duct that macromolecular freely enters and leaves, have
Surface hydroxyl abundant and higher hydrothermal stability, therefore it is able to maintain the cellular structure of carrier and the Keggin-type knot of silico-tungstic acid
Structure；Using Lewis acid, the electropositive of carbonyl carbon on ketone can be enhanced, enhance the electrophilicity of carbonyl carbon, be conducive to oxidant attack
Carbonyl carbon can achieve the purpose that activated carbonyl carbon.The catalyst can aoxidize saturated ketone, can also aoxidize beta-unsaturated ketone；It uses
The mild dosage of process simple condition is few.Reaction belongs to heterogeneous reaction, after the reaction was completed easily separates catalyst with product, is convenient for
Recycling.Simultaneously it is also possible that the reaction has the production rate of high selectivity and ester or lactone, and the reaction also accords with
The theory for closing clean manufacturing and Green Chemistry, greatly improves the Atom economy of reaction.
Summary of the invention
The present invention is intended to provide a kind of mesoporous catalyst preparation method of containing transition metal molybdenum ion:
(1), 0.74-2.13wt%g P123 is taken to be dissolved in 20-50mL, 36wt% concentrated hydrochloric acid and 63.98-74.31wt% g
In deionized water.
(2), at 50-70 DEG C 300 revs/min stir one hour or so, be then vigorously stirred and slowly add for 600 revs/min
Enter 5.94-6.4wt%g TEOS, 15min or so is added.
(3), revolving speed slows down to 300 revs/min and is added 0.07-0.21wt% sodium molybdate solid after 5-10min, is added
1.49-2.13wt% ammonium fluoride solid is 8-10 to pH, continues stirring 12 hours.
(4), it is transferred to 100-150 DEG C of crystallization of reaction kettle 24 hours, it is cooling, it filters, washes, it is dry.
(5), last 500-600 DEG C of Muffle furnace roasts 6-8 hours.Finally take out.
The present invention is directed to the mesoporous catalysts of the containing transition metal molybdenum ion of preparation.It is mesoporous that there is biggish specific surface area
And the duct freely entered and left for macromolecular, there is surface hydroxyl abundant and higher hydrothermal stability, therefore be able to maintain load
The structure of body and the Keggin-type structure of silico-tungstic acid；Using Lewis acid, the electropositive of carbonyl carbon on ketone can be enhanced, make carbonyl carbon
Electrophilicity enhancing, be conducive to oxidant attack carbonyl carbon, can achieve the purpose that activated carbonyl carbon.The catalyst can aoxidize
Saturated ketone can also aoxidize beta-unsaturated ketone；The mild dosage of use process simple condition is few.Reaction belongs to heterogeneous reaction, has reacted
Cheng Houyi separates catalyst with product, convenient for recycling.Simultaneously it is also possible that the reaction has high selectivity and ester
Or the production rate of lactone, and the reaction also complies with the theory of clean manufacturing and Green Chemistry, can also greatly improve reaction
Atom economy.
The application method of catalyst in the present invention:
(1), catalyst 20-50mg obtained is taken.
(2), 1-5mmol cyclohexanone, 2-5mmol benzaldehyde, with 1,2- dichloroethanes for solvent are taken.
(3), catalyst acquired by (1) is added in (2).
(4), solution is heated to 40-70 DEG C, 200-600 revs/min of revolving speed, is continually fed into air, be condensed back, constant temperature
Magnetic stirring apparatus reacts 3-6h.
(5), ten minutes cooling, dodecane is added, 3min, is centrifuged by 1000 revs/min.
(6), internal standard method surveys solution gas phase.
The beneficial effects of the present invention are: doping Lewis acid or the mesoporous of transition metal ions can enhance carbonyl carbon on ketone
Electropositive enhances the electrophilicity of carbonyl carbon, is conducive to oxidant attack carbonyl carbon, can achieve the purpose that activated carbonyl carbon.
To be best understood from the present invention, the present invention will be described in further detail with reference to the following examples, but of the invention
Claimed range is not limited to the range of embodiment expression.
Specific embodiment
Embodiment 1:
The preparation of catalyst:
(1), 0.74wt%P123 is taken to be dissolved in the concentrated hydrochloric acid and 63.68wt% deionized water of 20mL, 36wt%.
(2), it stirs one hour or so for 50 DEG C 300 revs/min, is then vigorously stirred and is slowly added to for 600 revs/min
5.94wt%TEOS, 15min or so are added.
(3), revolving speed slows down to 300 revs/min and is added 0.07wt% sodium molybdate solid after 5min, and 1.49 wt% are added
Ammonium fluoride solid is 8 to pH, is stirred 12 hours.
(4), it is transferred to 100 DEG C of reaction kettle crystallization 24 hours, it is cooling, it filters, washes, it is dry.
(5), last 500 DEG C of Muffle furnaces roast 6 hours.Finally take out.
The use of catalyst:
(1), catalyst 20mg obtained is taken.
(2), 1mmol cyclohexanone, 2mmol benzaldehyde, with 1,2- dichloroethanes for solvent are taken.
(3), catalyst acquired by (1) is added in (2).
(4), solution is heated to 40 DEG C, 500 revs/min of revolving speed, is continually fed into air, be condensed back, constant temperature magnetic force stirs
Mix device reaction 3h.
(5), ten minutes cooling, dodecane is added, 3min, is centrifuged by 1000 revs/min.
(6), internal standard method surveys solution gas phase.
It is 77.4% to the selectivity of cyclohexanone that catalyst, which is finally calculated, and the yield of cyclohexanone is 53.4%.
Embodiment 2:
The preparation of catalyst:
(1), 1.35wt%P123 is taken to be dissolved in the concentrated hydrochloric acid and 72.46wt% deionized water of 22.4mL, 36wt%.
(2), it stirs one hour or so for 60 DEG C 300 revs/min of stirring, is then vigorously stirred and is slowly added to for 600 revs/min
6.08wt%TEOS, 15min are added.
(3), revolving speed slows down to 300 revs/min and is added 0.2wt% sodium molybdate solid after 7min, and 2.03 wt% fluorine are added
Changing ammonium solid to pH is 9, is stirred 12 hours.
(4), it is transferred to 120 DEG C of reaction kettle crystallization 24 hours, it is cooling, it filters, washes, it is dry.
(5), last 550 DEG C of Muffle furnaces roast 6 hours.Finally take out.
The use of catalyst:
(1), catalyst 30mg obtained is taken.
(2), 2mmol cyclohexanone, 4mmol benzaldehyde, with 1,2- dichloroethanes for solvent are taken.
(3), catalyst acquired by (1) is added in (2).
(4), solution is heated to 50 DEG C, 500 revs/min of revolving speed, is continually fed into air, be condensed back, constant temperature magnetic force stirs
Mix device reaction 4h.
(5), ten minutes cooling, dodecane is added, 3min, is centrifuged by 1000 revs/min.
(6), internal standard method surveys solution gas phase.
It is 83.2% to the selectivity of cyclohexanone that catalyst, which is finally calculated, and the yield of cyclohexanone is 60.5%.
Embodiment 3:
The preparation of catalyst:
(1), 2.13wt%P123 is taken to be dissolved in the concentrated hydrochloric acid and 74.31wt% deionized water of 50mL, 36wt%.
(2), at 70 DEG C 300 revs/min stir one hour or so, be then vigorously stirred and be slowly added to for 600 revs/min
6.39wt%TEOS, 15min are added.
(3), revolving speed slows down to 300 revs/min and is added 0.21wt% sodium molybdate solid after 10min, and 2.13 wt% are added
Ammonium fluoride solid is 10 to pH, is stirred 12 hours.
(4), it is transferred to 150 DEG C of reaction kettle crystallization 24 hours, it is cooling, it filters, washes, it is dry.
(5), last 600 DEG C of Muffle furnaces roast 8 hours.Finally take out.
The use of catalyst:
(1), catalysis 50mg obtained is taken.
(2), 5mmol cyclohexanone, 5mmol benzaldehyde, with 1,2- dichloroethanes for solvent are taken.
(3), catalyst acquired by (1) is added in (2).
(4), solution is heated to 70 DEG C, 1000 revs/min of revolving speed, is continually fed into air, be condensed back, constant temperature magnetic force stirs
Mix device reaction 6h.
(5), ten minutes cooling, dodecane is added, 3min, is centrifuged by 1000 revs/min.
(6), internal standard method surveys solution gas phase.
It is 78.9% to the selectivity of cyclohexanone that catalyst, which is finally calculated, and the yield of cyclohexanone is 51.8%.
Claims (1)
1. a kind of mesoporous catalyst of containing transition metal molybdenum ion, which is prepared by following steps and is completed:
(1), 0.74-2.13wt%P123 is taken to be dissolved in 20-50mL, 36wt% concentrated hydrochloric acid and 63.98-74.31wt% deionized water
In.
(2), at 50-70 DEG C 300 revs/min stir one hour or so, be then vigorously stirred and be slowly added to for 600 revs/min
5.94-6.39wt%TEOS, 15min or so are added.
(3), revolving speed slows down to 300 revs/min and is added 0.07-0.21wt% sodium molybdate solid after 5-10min, and 1.49- is added
2.13wt% ammonium fluoride solid is 8-10 to pH, continues stirring 12 hours.
(4), it is transferred to 100-150 DEG C of crystallization of reaction kettle 24 hours, it is cooling, it filters, washes, it is dry.
(5), last 500-600 DEG C of Muffle furnace roasts 6-8 hours.Finally take out.
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| CN201810498083.XA CN110496647A (en) | 2018-05-18 | 2018-05-18 | A kind of synthesis of BV catalysts --- the mesoporous catalyst preparation method of containing transition metal molybdenum ion |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724365A (en) * | 2005-06-15 | 2006-01-25 | 浙江大学 | Process for synthesizing mesic porous molecular sieve SBA-15 |
| CN102500407A (en) * | 2011-10-09 | 2012-06-20 | 南京大学 | Preparation method of bimetal-doped mesoporous material SBA-15 catalyst and bimetal-doped SBA-15 catalyst |
| ES2389799A1 (en) * | 2011-02-10 | 2012-10-31 | Urbaser, S.A. | Procedure in two stages for the obtaining of gasoline type fuels from plastic residues. (Machine-translation by Google Translate, not legally binding) |
| CN103464192A (en) * | 2013-09-26 | 2013-12-25 | 中国石油大学(北京) | Mesoporous nickel-molybdenum oxide catalyst, and preparation method and application thereof |
| CN106927476A (en) * | 2015-12-30 | 2017-07-07 | 中国石油天然气股份有限公司 | The preparation method of Mo-SBA-15 molecular sieves and hydrogenation catalyst |
-
2018
- 2018-05-18 CN CN201810498083.XA patent/CN110496647A/en active Pending
Patent Citations (5)
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| CN1724365A (en) * | 2005-06-15 | 2006-01-25 | 浙江大学 | Process for synthesizing mesic porous molecular sieve SBA-15 |
| ES2389799A1 (en) * | 2011-02-10 | 2012-10-31 | Urbaser, S.A. | Procedure in two stages for the obtaining of gasoline type fuels from plastic residues. (Machine-translation by Google Translate, not legally binding) |
| CN102500407A (en) * | 2011-10-09 | 2012-06-20 | 南京大学 | Preparation method of bimetal-doped mesoporous material SBA-15 catalyst and bimetal-doped SBA-15 catalyst |
| CN103464192A (en) * | 2013-09-26 | 2013-12-25 | 中国石油大学(北京) | Mesoporous nickel-molybdenum oxide catalyst, and preparation method and application thereof |
| CN106927476A (en) * | 2015-12-30 | 2017-07-07 | 中国石油天然气股份有限公司 | The preparation method of Mo-SBA-15 molecular sieves and hydrogenation catalyst |
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| Title |
|---|
| 张健等: ""双金属Mo-Ti-SBA-15 的制备及催化环己烯环氧化性能"", 《精细化工》 * |
| 杨传武: ""硅基复合金属氧化物的合成及BAEYER-VILLIGER催化性能的研究"", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
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