CN102764668A - Preparation of phosphomolybdate catalyst loaded on gamma-Al2O3 - Google Patents
Preparation of phosphomolybdate catalyst loaded on gamma-Al2O3 Download PDFInfo
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- CN102764668A CN102764668A CN2011101164645A CN201110116464A CN102764668A CN 102764668 A CN102764668 A CN 102764668A CN 2011101164645 A CN2011101164645 A CN 2011101164645A CN 201110116464 A CN201110116464 A CN 201110116464A CN 102764668 A CN102764668 A CN 102764668A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910003158 γ-Al2O3 Inorganic materials 0.000 title abstract 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 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 claims abstract description 9
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000001103 potassium chloride Substances 0.000 claims abstract description 3
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract 2
- 159000000000 sodium salts Chemical class 0.000 claims abstract 2
- 239000011734 sodium Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 claims 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 claims 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- -1 inorganic acid salts Chemical class 0.000 abstract description 8
- 238000001914 filtration Methods 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical class [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000011964 heteropoly acid Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001802 infusion Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention relates to synthesis of a novel catalyst, especially to a catalyst of various phosphomolybdates, the catalyst being loaded on gamma-Al2O3. The catalyst has a function of improving rare earth, can be used to substantially raise stability and catalytic activity and minimize environmental pollution, and is a novel environmentally friendly catalyst material. The preparation comprises the following concrete steps of: mixing phosphatic with simple inorganic acid salts of molybdate and the like according to a certain ratio for acidification, filtering for liquid separation, extracting an ether acid mixed liquor to prepare phospho molybdic acid, mixing phospho molybdic acid, different salts (such as sodium salt, sylvite, quaternary ammonium salt and the like), a rare earth nitrate solution and the gamma-Al2O3 carrier, filtering, washing and drying to prepare the required catalyst. The catalyst provided by the invention is mainly applied in the catalytic hydrogenation link in the petroleum industry, and can be used to greatly raise oil quality.
Description
Technical field
The present invention relates to a kind of environmentally friendly heteropolyacid salt catalytic hydrogenation material, particularly load on γ-Al
2O
3On the phosphomolybdate Preparation of catalysts, belong to the synthetic field of inorganic material.
Background technology
Phosphomolybdic acid is a kind of heteropoly acid.As solid acid catalyst, its intensity is higher than common inorganic acid far away to heteropoly acid (being called for short HPA), receives the extensive attention of catalytic field in the past over more than 20 year always.Heteropoly acid is the one type of multinuclear complex acid that is passed through the oxygen atom ligand bridging by central atom (hetero atom) and ligand (polyatom).Can be divided into five types of Keggin, Silverton, Daw-son, Waugh, Anderson by its cloudy atomic structure.Heteropoly acid has unique " accurate liquid phase " behavior; It has the same cage structure of zeolite, between the heteropolyacid anions of body in mutually certain gap is arranged, the body that some less polar molecule (like water, alcohol, ammonia, pyridine etc.) can get into heteropoly acid mutually in; Change on the solid heteropoly acid surface; Promptly extend to body mutually in everywhere, thereby in its body, form false liquid phase, so solid heteropoly acid has the characteristics of homogeneous catalytic reaction.This surface type of heteropoly acid and the body existence of (accurate liquid phase) catalytic action mutually do not occur over just on the surface of catalyst its catalytic reaction, and occur in the body phase of whole catalyst, thereby have higher catalytic activity and selectivity.The multi-functional in addition advantages such as (highly acid, strong oxidizing property, inhibition, photoelectrocatalysis) of heteropoly acid.
Because heteropoly acid catalysis reclaims difficulty, and has certain pollution and etching apparatus problem, and the less (＜10m of the specific area of heteropoly acid
2/ g), be unfavorable for giving full play to catalytic activity, its application aspect catalysis is restricted.The heteropoly acid pay(useful) load can be improved its surface area greatly on suitable carriers, can not only improve its catalytic activity and selectivity, and can also make the homogeneous catalytic reaction variation; Product is easily separated; Catalyst is prone to reclaim, and has simplified production technology, thereby has opened up the new world of catalytic field.
Say that in principle any solid matter can be as the carrier of heteropoly acid.Mainly contained active carbon, SiO by broad research and used carrier at present
2, Al
2O
3, MCM-41 molecular sieve, TiO
2, large pore material such as diatomite (DE), bentonite and ion exchange resin.The preparation method of carried heteropoly acid mainly contains infusion process, absorption method, sol-gel process and hydro-thermal dispersion method etc.And γ-Al
2O
3(γ-aluminum oxide) has the big and big characteristic of porosity of specific area as one type of porous aluminium oxide solid, and strong adsorption capacity and catalytic activity are arranged, and is the fine selection of carrier.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of environmentally friendly phosphomolybdate catalyst material of high catalytic performance.Adopt simple immersion process for preparing to go out to load on γ-Al
2O
3On, and handle through certain rare earth, have highly active, the phosphomolybdate catalyst.
Concrete concrete grammar is following: under normal pressure and water-bath heating, stir the Na of certain proportioning
2MoO
4Solution and Na
2HPO
4Solution, be heated to 90 ℃ after, regulate between the pH scope 1～3 through dripping HCl solution, filter while hot after the backflow.To filtrate then through two hypo acid ether mixed liquors, extraction, separatory, and it is dry to put into drier.The phosphomolybdic acid that makes is made multiple phosphomolybdate through metathesis reaction.With phosphomolybdate and a certain amount of γ-Al
2O
3Carrier adds the rare earth salpeter solution, and constant temperature stirs under the uniform temperature, and is behind filtration and the recrystallization that sample is dry down at 60 ℃ after leaving standstill.
The specific embodiment
Instance 1
In there-necked flask, add 50ml Na
2MoO
4(0.12mmol) solution stirs adding 25mlNa down
2HPO
4(0.01mmol) solution, water-bath are heated to 90 ℃.Hydrochloric acid 25ml with constant pressure funnel dropping 4mol/L regulates pH to 1～3, and the 1～4h that refluxes stops to filter while hot after the heating, and filtrating is cooled to room temperature, moves into separatory funnel, adds the 30ml absolute ether, dropwise adds 15mlv (H
2O): v (concentrated sulfuric acid)=1: 1, fully vibration, standing demix, layer oily matter is the heteropoly acid etherate, utilizes moving air to dry up ether, and product is dissolved in the distilled water, puts into vacuum desiccator, separates out the buff crystal, in 80 ℃ of drying for standby.Utilize ion exchange, with the K of the phosphomolybdic acid that makes with certain metering
2CO
3The reaction, phosphomolybdic acid sylvite, through with rare earth nitrate solution and γ-Al
2O
3The carrier hybrid infusion, washing and filtering is also dry.
Instance 2
In there-necked flask, add 50ml Na
2MoO
4(0.12mmol) solution stirs adding 25ml Na down
2HPO
4(0.011mmol) solution, water-bath are heated to 90 ℃.Hydrochloric acid 25ml with constant pressure funnel dropping 4mol/L regulates pH to 1～3, and the 1～4h that refluxes stops to filter while hot after the heating, and filtrating is cooled to room temperature, moves into separatory funnel, adds the 30ml absolute ether, dropwise adds 15mlv (H
2O): v (concentrated sulfuric acid)=1: 1, fully vibration, standing demix, layer oily matter is the heteropoly acid etherate, utilizes moving air to dry up ether, and product is dissolved in the distilled water, puts into vacuum desiccator, separates out the buff crystal, in 80 ℃ of drying for standby.Utilize ion exchange, with the Na of the phosphomolybdic acid that makes with certain metering
2CO
3The reaction, the phosphomolybdic acid sodium salt, through with rare earth nitrate solution and γ-Al
2O
3The carrier hybrid infusion, washing and filtering is also dry.
Instance 3
In there-necked flask, add 50ml Na
2MoO
4(0.12mmol) solution stirs adding 25ml Na down
2HPO
4(0.011mmol) solution, water-bath are heated to 90 ℃.Hydrochloric acid 25ml with constant pressure funnel dropping 4mol/L regulates pH to 1～3, and the 1～4h that refluxes stops to filter while hot after the heating, and filtrating is cooled to room temperature, moves into separatory funnel, adds the 30ml absolute ether, dropwise adds 15mlv (H
2O): v (concentrated sulfuric acid)=1: 1, fully vibration, standing demix, layer oily matter is the heteropoly acid etherate, utilizes moving air to dry up ether, and product is dissolved in the distilled water, puts into vacuum desiccator, separates out the buff crystal, in 80 ℃ of drying for standby.Utilize ion exchange, make four kinds of phosphomolybdic acid quaternary ammonium salts with tetramethyl ammonium chloride, DTAC, hexadecyltrimethylammonium chloride, OTAC through metathesis reaction respectively, through with rare earth nitrate solution and γ-Al
2O
3The carrier hybrid infusion, washing and filtering is also dry.
Instance 4
In there-necked flask, add 50ml Na
2MoO
4(0.12mmol) solution stirs adding 25ml Na down
2HPO
4(0.011mmol) solution, water-bath are heated to 90 ℃.Hydrochloric acid 25ml with constant pressure funnel dropping 4mol/L regulates pH to 1～3, and the 1～4h that refluxes stops to filter while hot after the heating, and filtrating is cooled to room temperature, moves into separatory funnel, adds the 30ml absolute ether, dropwise adds 15mlv (H
2O): v (concentrated sulfuric acid)=1: 1, fully vibration, standing demix, layer oily matter is the heteropoly acid etherate, utilizes moving air to dry up ether, and product is dissolved in the distilled water, puts into vacuum desiccator, separates out the buff crystal, in 80 ℃ of drying for standby.With phosphomolybdic acid through with rare earth nitrate solution and γ-Al
2O
3The carrier hybrid infusion, washing and filtering is also dry.
Claims (10)
1. that novel phosphomolybdate Preparation of catalysts, characteristics are that carrier selects for use is γ-Al
2O
3, and utilized rare earth modifiedly, improved the stability of catalyst, heat endurance and catalytic reaction activity etc.
2. said according to claim 1, its characteristics are that the carrier of selecting for use is the high γ-Al of specific area
2O
3, it is big to have a hole, characteristics such as strong adsorption capacity and catalytic activity.
3. said according to claim 1, its characteristics are to have dripped nitrate of rare earth element solution in carrier and the phosphomolybdate catalyst solution dipping process; Through regulating pH to 5～6; Filter recrystallization, the phosphomolybdate catalyst of the rare earth element that obtained mixing.
4. said according to claim 2, need prepare and have higher specific surface area (800～1300m
2/ g), the γ-Al of higher heat endurance (800 ℃ down stable) and certain hydrothermal stability
2O
3
5. said according to claim 3, preparation phosphomolybdate catalyst need be with phosphorus molybdenum acid solution and sodium salt, sylvite, and quaternary ammonium salts etc. make through ion exchange, need certain stoichiometric proportion, according to the equation proportioning.
6. said according to claim 5, the preparation phosphomolybdic acid need mix acidifying according to proportioning with simple inorganic acid, leaves standstill separatory after the stirring, behind the extraction lower floor solution, and vacuum drying.
7. said according to claim 6, inorganic acid need adopt Na
2MoO
4With Na
2HPO
4Solution.
8. said according to claim 6, need hydrochloric acid solution acidifying with 4mol/L.
9. said according to claim 6, utilize ether, the sour ether mixed liquor extraction of sulfuric acid, be specially add the 30mL absolute ether after, dropwise add 15ml v (H
2O): v (concentrated sulfuric acid)=1: 1, fully vibration, standing demix.
10. said according to claim 3, the nitrate solution of rare earth, employing be cerous nitrate, lanthanum nitrate and praseodymium nitrate solution (mass fraction of rare earth nitrades is 0.02%).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101164645A CN102764668A (en) | 2011-05-06 | 2011-05-06 | Preparation of phosphomolybdate catalyst loaded on gamma-Al2O3 |
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|---|---|---|---|
| CN2011101164645A CN102764668A (en) | 2011-05-06 | 2011-05-06 | Preparation of phosphomolybdate catalyst loaded on gamma-Al2O3 |
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|---|---|
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ID=47092374
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084232A (en) * | 2014-06-18 | 2014-10-08 | 浙江工业大学 | Preparation method for catalyst used for deoxidation of biological fatty alcohol |
| CN108126751A (en) * | 2017-12-27 | 2018-06-08 | 中海油天津化工研究设计院有限公司 | Molecular sieve supported heteropoly acid alkylating and desulfurizing catalyst of multi-stage porous and preparation method thereof |
| CN108772100A (en) * | 2018-05-22 | 2018-11-09 | 广东工业大学 | A kind of heteropolyacid salt solid catalyst and its preparation method and application |
| WO2019109213A1 (en) * | 2017-12-04 | 2019-06-13 | 天津大学 | Al2o3 particles synergistically modified by rare-earth metal and phosphorus, and preparation method therefor |
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|---|---|---|---|---|
| CN1668770A (en) * | 2002-07-08 | 2005-09-14 | 英格哈得公司 | removal of metal compounds |
| CN1792446A (en) * | 2005-12-21 | 2006-06-28 | 中国科学院山西煤炭化学研究所 | Catalyst, Preparation Method and Application of Synthesis of Methylal by Oxidation of Dimethyl Ether |
| CN101152630A (en) * | 2006-07-24 | 2008-04-02 | Ifp公司 | Process for the preparation of at least one cobalt and/or nickel salt of at least one heteropolyanion |
-
2011
- 2011-05-06 CN CN2011101164645A patent/CN102764668A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1668770A (en) * | 2002-07-08 | 2005-09-14 | 英格哈得公司 | removal of metal compounds |
| CN1792446A (en) * | 2005-12-21 | 2006-06-28 | 中国科学院山西煤炭化学研究所 | Catalyst, Preparation Method and Application of Synthesis of Methylal by Oxidation of Dimethyl Ether |
| CN101152630A (en) * | 2006-07-24 | 2008-04-02 | Ifp公司 | Process for the preparation of at least one cobalt and/or nickel salt of at least one heteropolyanion |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084232A (en) * | 2014-06-18 | 2014-10-08 | 浙江工业大学 | Preparation method for catalyst used for deoxidation of biological fatty alcohol |
| CN104084232B (en) * | 2014-06-18 | 2016-03-02 | 浙江工业大学 | A kind of preparation method of catalyst of biological fatty alcohol deoxidation |
| WO2019109213A1 (en) * | 2017-12-04 | 2019-06-13 | 天津大学 | Al2o3 particles synergistically modified by rare-earth metal and phosphorus, and preparation method therefor |
| CN108126751A (en) * | 2017-12-27 | 2018-06-08 | 中海油天津化工研究设计院有限公司 | Molecular sieve supported heteropoly acid alkylating and desulfurizing catalyst of multi-stage porous and preparation method thereof |
| CN108126751B (en) * | 2017-12-27 | 2020-11-24 | 中海油天津化工研究设计院有限公司 | Multi-stage pore molecular sieve supported heteropoly acid alkylation desulfurization catalyst and preparation method thereof |
| CN108772100A (en) * | 2018-05-22 | 2018-11-09 | 广东工业大学 | A kind of heteropolyacid salt solid catalyst and its preparation method and application |
| CN108772100B (en) * | 2018-05-22 | 2021-04-16 | 广东工业大学 | A kind of heteropolyacid salt solid catalyst and its preparation method and application |
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