CN102631944A - Synthetic gas-to-oil catalyst using mesoporous molecular sieve SBA-16 as carrier and method for preparing catalyst - Google Patents
Synthetic gas-to-oil catalyst using mesoporous molecular sieve SBA-16 as carrier and method for preparing catalyst Download PDFInfo
- Publication number
- CN102631944A CN102631944A CN2012100887035A CN201210088703A CN102631944A CN 102631944 A CN102631944 A CN 102631944A CN 2012100887035 A CN2012100887035 A CN 2012100887035A CN 201210088703 A CN201210088703 A CN 201210088703A CN 102631944 A CN102631944 A CN 102631944A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- sba
- cobalt
- fischer
- 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.)
- Pending
Links
Images
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing a synthetic gas-to-oil (F-T reaction) cobalt-based catalyst by using mesoporous molecular sieve SBA-16 as a carrier, and application of the catalyst to synthetic gas-to-oil reaction. The highly ordered mesoporous structure of the catalyst is kept, and an original cubic symmetric structure of the carrier SBA-16 is also kept. The catalyst prepared by the method has a high active cobalt capacity, so that high activity of the catalyst is ensured, and the catalyst has the advantages of low CH4 selectivity, high C5+ selectivity and fine reaction stability.
Description
Technical field
The present invention relates to a kind of ICL for Indirect Coal Liquefaction technology, belong to the derived energy chemical field by synthesis gas catalyzed conversion preparing liquid fuel.Mainly be applicable in the fischer-tropsch reaction by synthesis gas (carbon monoxide and hydrogen) catalytic cracking C
5-C
12Liquid hydrocarbon fuels is provided for the synthetic Catalysts and its preparation method of Fischer-Tropsch.
Background technology
Fischer-Tropsch synthetic (Fischer-Tropsch synthesis) is one of ICL for Indirect Coal Liquefaction technology, and it is with synthesis gas (CO and H
2) be raw material, the technical process of synthetic liquid fuel under catalyst and appropriate reaction condition.The synthetic key of Fischer-Tropsch is the use of catalyst, and its catalyst generally includes following component: reactive metal (VIII group 4 transition metal), oxide carrier or structural promoter (SiO
2, Al
2O
3Deng), chemical assistant (alkali metal oxide) and precious metal additive (Ru, Re, Cu etc.).
Metal Ru is a highest active fischer-tropsch synthetic catalyst active component, and its advantage is low reaction temperature and excellent chain growth ability, and certain condition can reach the C more than 90% down
5 +Selectivity, but it costs an arm and a leg and resource scarcity.Ferrum-based catalyst stores abundant and the cheap extensive concern that receives because of it.Ferrum-based catalyst has lot of advantages, obtains low-carbon alkene like highly selective, prepares high-octane gasoline etc.; But ferrum-based catalyst has high activity to water gas shift reaction; Catalyst was prone to carbon distribution and poisoning when reaction temperature was high, and the chain growth ability is relatively poor, was unfavorable for synthetic long-chain product.Characteristics such as metal Co is owing to have high CO hydrogenation activity and high Fischer-Tropsch chain growth ability, and is stable and be difficult for carbon distribution and poisoning in the course of reaction, and oxygenatedchemicals is few in the product, and water gas shift reaction is insensitive, and become the research focus of Fischer-Tropsch synthesis.The activity of cobalt-base catalyst is the metal phase mutually, is made through roasting and reduction by the cobalt source.The active sites of being made up of the metallic cobalt atom has determined activity of such catalysts and selectivity.Cobalt-base catalyst is compared with ferrum-based catalyst, and the water gas reaction activity is lower, and synthetic product is with C
5+ long chain hydrocarbon is main, is the fischer-tropsch catalysts that development potentiality is arranged.
Carrier is very complicated to the influence of Fischer-Tropsch synthesis catalyst activity and selectivity of product, this be since the structure of catalyst and performance all and the strong interaction between the specific surface of catalyst carrier, acidity, pore structure, electronics modification and active component and the carrier etc. closely related.Carrier commonly used had SiO during Fischer-Tropsch was synthetic
2, Al
2O
3, TiO
2, MgO, imvite, diatomite and active carbon etc., in addition people also to be used for Fischer-Tropsch synthetic in the hope of reaching good catalytic effect attempting to study new carrier, like nanoscale composite oxide carrier and molecular sieve etc.Ordered mesoporous material is the novel nano structural material that rises rapidly the nineties in last century.Say from the structure angle; Mesoporous material is the new material with huge surface area and three-dimensional open-framework of a kind of aperture between micropore and macropore; It has the pore passage structure of high-sequential; Pore-size distribution is single, and aperture size excursion broad (2nm～50nm), so mesopore molecular sieve can be used as the optimum carrier that the research aperture influences in the Fischer-Tropsch building-up process cobalt-base catalyst; Mesoporous shape is various, and hole wall composition and character are adjustable, through optimizing the material that synthesis condition can obtain high thermal stability and hydrothermal stability.
Chinese patent CN 101411988 discloses and a kind ofly has been doped in the cobalt-based Fischer-Tropsch catalyst preparation method that the mesoporous silicon based molecular sieve of M41S type is a carrier with Ce; With sodium metasilicate and cerous nitrate solution; Join with the cetylpyridinium chloride is in the aqueous solution of template; Through agitation and filtration, after washing, oven dry, the roasting, prepare mesoporous silicon based molecular sieve; Through the infusion process load active component, the silica-based molecular sieve with regular meso-hole structure that after roasting, obtains the Ce doping is the Co based Fischer-Tropsch synthesis catalyst of carrier; It is low that this catalyst has a methane selectively, gasoline and the high characteristics of diesel component selectivity.But the addition manner of this auxiliary agent finally is doped in the active component with the form of oxide, and the randomness that adjuvant component distributes in carrier is very strong, and skewness is prone to clustering phenomena.
Chinese patent CN1401736 discloses a kind of preparation method of high-efficiency cobalt-based catalyst for Fischer-Tropsch synthesis of heavy hydrocarbon; With the zirconium oxychloride aqueous solution is raw material, and ammoniacal liquor is precipitating reagent, at a certain temperature reaction; After filtration, washing, roasting; Obtain Zirconia carrier, adopt equi-volume impregnating that the nitrate solution of active component cobalt and auxiliary agent La, Ce is impregnated on the Zirconia carrier, after aging, drying, roasting, obtain the supported cobalt Zr catalyst.Catalyst has higher activity and C
5 +Selectivity.With the carrier granular size Control of precipitation method preparations difficulty relatively, size is uneven, and aperture, pore volume are less; When adopting infusion process load active component and auxiliary agent, both disperse inhomogeneous at carrier surface, reunite during roasting easily in easy blocking carrier duct; Above-mentioned two factors all will be to activity of such catalysts and C
5 +Selectivity has a negative impact.
For Co based Fischer-Tropsch synthesis catalyst, high cobalt load capacity is necessary often, because the deactivation rate that high cobalt load capacity helps to improve the catalytic activity of catalyst and reduces catalyst.The cobalt-base catalyst that adopts with bubbling paste state bed reactor on the current industrial is an example, and its catalyst consists of the metallic cobalt of load 33g on every 100g carrier.Disperse so high cobalt active component, selecting a kind of material of high-specific surface area is considerable as catalyst carrier.
Mesopore molecular sieve SBA-16 has the super large cage shape cubic symmetry structure of unified size, thicker hole wall, high specific area and heat endurance in the SBA series; Especially the connectedness of its 3 D pore canal more helps the diffusion of material transmission and reaction molecular, so SBA-16 has good prospects for application in catalysis, absorption, separation and biomolecule aspect fixing.
Summary of the invention
The objective of the invention is for a kind of synthetic Co/SBA-16 catalyst of Fischer-Tropsch that is used for is provided; Be primarily aimed at the cobalt load capacity problem of Co based Fischer-Tropsch synthesis catalyst; Do presoma with cobalt nitrate; With novel mesopore molecular sieve SBA-16 is carrier, and a kind of Catalysts and its preparation method with well dispersed property is provided.This catalyst has low CH under the condition of low cobalt load capacity
4Selectivity and higher C
5+ selectivity.
The present invention mainly comprises steps such as load and the catalyst reaction evaluation of preparing carriers and active component.Below be operating procedure of the present invention and schematic illustration:
(1) preparation of mesopore molecular sieve SBA-16 carrier
Get a certain amount of template; Add deionized water and stirring to dissolving fully; Add hydrochloric acid and ethyl orthosilicate, under uniform temperature and pressure, carry out hydro-thermal reaction, in 120 ℃ of dryings; 550 ℃ of roasting temperatures were cooled to room temperature after 6 hours in air atmosphere then, promptly got carrier mesopore molecular sieve SBA-16.
(2) with SBA-16 be the catalyst based preparation of load C o of carrier
Adopt infusion process, the aqueous solution that will contain the solubility cobalt salt is impregnated on the carrier, and then 120 ℃ of dryings, 350 ℃ of following roastings are cooled to room temperature, obtain the F-T synthetic catalyst.
The present invention also provides the application of said catalyst in the reaction of F-T artificial oil.
Adopt technique scheme, technique effect of the present invention has:
(1) synthetic SBA-16 carrier has the pore passage structure of narrower pore-size distribution, rule, bigger specific area and advantage such as hydrothermal stability preferably.
(2) because the connectedness of carrier S BA-16 3 D pore canal more helps the diffusion of material transmission and reaction molecular, thereby improved the activity and the selectivity of product, made that with SBA-16 to be that the load C o of carrier is catalyst based have higher CO conversion rate, low CH
4Selectivity and higher C
5 +Selectivity.
(3) compare with other mesopore molecular sieve, SBA-16 has thicker hole wall and higher hydrothermal stability, and this makes with SBA-16, and to be that the load C o of carrier is catalyst based have a higher stability.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) photo of carrier S BA-16;
Fig. 2 is for being X-ray diffraction (XRD) collection of illustrative plates of the cobalt-base catalyst of carrier with SBA-16;
Fig. 3 is for being transmission electron microscope (TEM) photo of the cobalt-base catalyst of carrier with SBA-16.
The specific embodiment
Below being embodiment provided by the present invention, only is to further specify application of the present invention, rather than limits.
Embodiment 1
A kind of be used for Fischer-Tropsch synthetic be the preparation method of the load cobalt-base catalyst of carrier with SBA-16, its step comprises:
(1) mesopore molecular sieve SBA-16's is synthetic: under 35 ℃ of constant temperatures, get the EO of M=5800 respectively
20PO
70EO
20Be the EO of P123 0.8g and M=12600
106PO
70EO
106Be that F127 2.36g joins in the 250mL conical flask, make solvent with the 134mL deionized water, magnetic agitation is to dissolving fully; The concentrated hydrochloric acid that in above-mentioned conical flask, adds 22mL 37wt%; 35 ℃ are continued down to stir, and after solution mixed, the positive tetraethyl orthosilicate of impouring 13mL was TEOS; Continue to stir 1h, the mol ratio of each material is P123: F127: TEOS: HCl: H in the mixed solution at this moment
2O=0.0016: 0.0037: 1.0: 4.4: 144; And be in the Teflon bottle with the stainless steel cauldron that solution moves to the band polytetrafluoroethylsubstrate substrate, earlier under 35 ℃, leave standstill 24h, under 100 ℃, leave standstill 24h again; Cooling off the back suction filtration and being washed with distilled water to neutrality is that PH approximates 7; Suction filtration gained solid 120 ℃ of dryings, is removed template in 550 ℃ of following roasting 6h, promptly get mesopore molecular sieve SBA-16 white powder.Fig. 1 is transmission electron microscope (TEM) photo of carrier S BA-16.
(2) with SBA-16 the load 20%Co Preparation of catalysts of carrier: get the prepared SBA-16 carrier of 1g above-mentioned steps, drip distilled water, write down its water absorption, promptly soak the needed minimum amount of carrier to just wetting.Proportionate relationship according to water absorption that records and carrier quality; Load capacity according to cobalt is 20wt%; Dissolve the cobalt nitrate of amount of calculation fully with the distilled water of certain volume, the SBA-16 carrier is dipped in the maceration extract, sealing; Leave standstill after 12 hours 120 ℃ of oven dry down, again through 350 ℃ of calcinings can make in 4 hours be used for Fischer-Tropsch synthetic be the load cobalt-base catalyst of carrier with SBA-16.Fig. 2 is for being X-ray diffraction (XRD) collection of illustrative plates of the load cobalt-base catalyst of carrier with SBA-16; Fig. 3 is for being transmission electron microscope (TEM) photo of the load cobalt-base catalyst of carrier with SBA-16.
Embodiment 2
A kind of be used for Fischer-Tropsch synthetic be the preparation method of the load cobalt-base catalyst of carrier with SBA-16, its step comprises:
(1) mesopore molecular sieve SBA-16's is synthetic: under 35 ℃ of constant temperatures, get the EO of M=5800 respectively
20PO
70EO
20Be the EO of P123 0.8g and M=12600
106PO
70EO
106Be that F127 2.36g joins in the 250mL conical flask, make solvent with the 134mL deionized water, magnetic agitation is to dissolving fully; The concentrated hydrochloric acid that in above-mentioned conical flask, adds 22mL 37wt%; 35 ℃ are continued down to stir, and after solution mixed, the positive tetraethyl orthosilicate of impouring 13mL was TEOS; Continue to stir 1h, the mol ratio of each material is P123: F127: TEOS: HCl: H in the mixed solution at this moment
2O=0.0016: 0.0037: 1.0: 4.4: 144; And be in the Teflon bottle with the stainless steel cauldron that solution moves to the band polytetrafluoroethylsubstrate substrate, earlier under 35 ℃, leave standstill 24h, under 100 ℃, leave standstill 24h again; Cooling off the back suction filtration and being washed with distilled water to neutrality is that PH approximates 7; Suction filtration gained solid 120 ℃ of dryings, is removed template in 550 ℃ of following roasting 6h, promptly get mesopore molecular sieve SBA-16 white powder.
(2) with SBA-16 the catalyst based preparation of load 15%Co of carrier: get the prepared SBA-16 carrier of 1g above-mentioned steps, drip distilled water, write down its water absorption, promptly soak the needed minimum amount of carrier to just wetting.Proportionate relationship according to water absorption that records and carrier quality; Load capacity according to cobalt is 15wt%; Dissolve the cobalt nitrate of amount of calculation fully with the distilled water of certain volume, the SBA-16 carrier is dipped in the maceration extract, sealing; Leave standstill after 12 hours 120 ℃ of oven dry down, again through 350 ℃ of calcinings can make in 4 hours be used for Fischer-Tropsch synthetic be the load cobalt-base catalyst of carrier with SBA-16.
Embodiment 3
A kind of be used for Fischer-Tropsch synthetic be the preparation method of the load cobalt-base catalyst of carrier with SBA-16, its step comprises:
(1) mesopore molecular sieve SBA-16's is synthetic: under 35 ℃ of constant temperatures, get the EO of M=5800 respectively
20PO
70EO
20Be the EO of P123 0.8g and M=12600
106PO
70EO
106Be that F127 2.36g joins in the 250mL conical flask, make solvent with the 134mL deionized water, magnetic agitation is to dissolving fully; The concentrated hydrochloric acid that in above-mentioned conical flask, adds 22mL 37wt%; 35 ℃ are continued down to stir, and after solution mixed, the positive tetraethyl orthosilicate of impouring 13mL was TEOS; Continue to stir 1h, the mol ratio of each material is P123: F127: TEOS: HCl: H in the mixed solution at this moment
2O=0.0016: 0.0037: 1.0: 4.4: 144; And be in the Teflon bottle with the stainless steel cauldron that solution moves to the band polytetrafluoroethylsubstrate substrate, earlier under 35 ℃, leave standstill 24h, under 100 ℃, leave standstill 24h again; Cooling off the back suction filtration and being washed with distilled water to neutrality is that PH approximates 7; Suction filtration gained solid 120 ℃ of dryings, is removed template in 550 ℃ of following roasting 6h, promptly get mesopore molecular sieve SBA-16 white powder.
(2) with SBA-16 the catalyst based preparation of load 10%Co of carrier: get the prepared SBA-16 carrier of 1g above-mentioned steps, drip distilled water, write down its water absorption, promptly soak the needed minimum amount of carrier to just wetting.Proportionate relationship according to water absorption that records and carrier quality; Load capacity according to cobalt is 10wt%; Dissolve the cobalt nitrate of amount of calculation fully with the distilled water of certain volume, the SBA-16 carrier is dipped in the maceration extract, sealing; Leave standstill after 12 hours 120 ℃ of oven dry down, again through 350 ℃ of calcinings can make in 4 hours be used for Fischer-Tropsch synthetic be the load cobalt-base catalyst of carrier with SBA-16.
With method for preparing is that the catalyst of the different cobalt load capacity of carrier carries out F-T synthetic reaction catalytic performance test with SBA-16 in the stainless steel fixed bed reactors.The reduction of catalyst is 400 ℃ of temperature of control, air speed 1000h in hydrogen atmosphere
-1With reduction under the condition of pressure 0.1MPa 10 hours.After treating that system temperature drops to 200 ℃, switch to synthesis gas, be warming up to 220 ℃ then, boost to 2.0MPa, control synthesis gas CO/H
2=2: 1, air speed 1000h
-1React.Reaction behind the stable equilibrium, H in the tail gas
2, CO, CH
4And CO
2By the GC-8A gas chromatograph of the Shimadzu company that carbon molecular sieve post TDX-01 is housed, the on-line analysis of TCD detector; C in the tail gas
2-C
4By the fixedly GC-8A gas chromatograph of the Shimadzu company of phase chromatographic column of Propack-Q, fid detector on-line analysis are housed.Obtain forming of gas phase by above-mentioned two kinds of analysis results.Each species uses the GC-2014 gas chromatograph of Shimadzu company to analyze the OV-101 capillary column in the liquid product.
To above be that the catalyst of the different cobalt load capacity of carrier carries out Fischer-Tropsch synthesis catalytic performance evaluation result with SBA-16:
The test result of embodiment 1:
With SBA-16 is the load 20%Co Catalyst for CO conversion ratio 91.1% of carrier, CH
4Selectivity 2.9%, C
2～C
4Selectivity 5.4%, C
5 +Selectivity 91.5%.
The test result of embodiment 2:
With SBA-16 is the load 15%Co Catalyst for CO conversion ratio 86.1% of carrier, CH
4Selectivity 3.4%, C
2～C
4Selectivity 6.1%, C
5 +Selectivity 90.4%.
The test result of embodiment 3:
With SBA-16 is the load 10%Co Catalyst for CO conversion ratio 66.6% of carrier, CH
4Selectivity 6.6%, C
2～C
4Selectivity 12.3%, C
5 +Selectivity 81.1%.
Can know that by above-mentioned test embodiment 1 makes is that the load 20%Co catalyst of carrier is a preferred forms with SBA-16, this catalyst reaction good stability, long catalytic life is good fischer-tropsch synthetic catalyst.
What should explain at last is; Above embodiment is only unrestricted in order to technical scheme of the present invention to be described; Although with reference to preferred embodiment the present invention is specified, those of ordinary skill in the art should be appreciated that and can make amendment or be equal to replacement technical scheme of the present invention; And not breaking away from the spirit and the scope of technical scheme of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (5)
- One kind to be used for Fischer-Tropsch synthetic, by the method for synthesis gas (carbon monoxide and hydrogen) catalytic cracking liquid fuel, it is characterized in that the composition and the preparation method of catalyst.
- 2. the synthetic catalyst of Fischer-Tropsch that is used for according to claim 1, the carrier that it is characterized in that catalyst is mesopore molecular sieve SBA-16.
- 3. the synthetic catalyst of Fischer-Tropsch that is used for according to claim 1 is characterized in that the activity of such catalysts component is a metallic cobalt.
- 4. the synthetic catalyst of Fischer-Tropsch that is used for according to claim 3, the mass fraction that it is characterized in that active component cobalt in the catalyst is 10～30%.
- 5. the synthetic catalyst of Fischer-Tropsch that is used for according to claim 1 is characterized in that the Preparation of catalysts method:(1) mesopore molecular sieve SBA-16's is synthetic: under 35 ℃ of constant temperatures, get the EO of M=5800 respectively 20PO 70EO 20Be the EO of P123 0.8g and M=12600 106PO 70EO 106Be that F127 2.36g joins in the 250mL conical flask, make solvent with the 134mL deionized water, magnetic agitation is to dissolving fully; The concentrated hydrochloric acid that in above-mentioned conical flask, adds 22mL 37wt%; 35 ℃ are continued down to stir, and after solution mixed, the positive tetraethyl orthosilicate of impouring 13mL was TEOS; Continue to stir 1h, the mol ratio of each material is P123: F127: TEOS: HCl: H in the mixed solution at this moment 2O=0.0016: 0.0037: 1.0: 4.4: 144, and be in the Teflon bottle with the stainless steel cauldron that solution moves to the band polytetrafluoroethylsubstrate substrate, earlier under 35 ℃, leave standstill 24h; Under 100 ℃, leave standstill 24h again; Cooling back suction filtration, and to be washed with distilled water to neutrality be that PH approximates 7, with suction filtration gained solid 120 ℃ of dryings; Remove template in 550 ℃ of following roasting 6h, promptly get mesopore molecular sieve SBA-16 white powder.(2) with SBA-16 the catalyst based preparation of load C o of carrier: get the prepared SBA-16 carrier of 1g above-mentioned steps, drip distilled water, write down its water absorption, promptly soak the needed minimum amount of carrier to just wetting.Proportionate relationship according to water absorption that records and carrier quality; Load capacity according to cobalt is 10-30wt%; Dissolve the cobalt nitrate of amount of calculation fully with the distilled water of certain volume, the SBA-16 carrier is dipped in the maceration extract, sealing; Leave standstill after 12 hours 120 ℃ of oven dry down, again through 350 ℃ of calcinings can make in 4 hours be used for Fischer-Tropsch synthetic be the load cobalt-base catalyst of carrier with SBA-16.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100887035A CN102631944A (en) | 2012-03-30 | 2012-03-30 | Synthetic gas-to-oil catalyst using mesoporous molecular sieve SBA-16 as carrier and method for preparing catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100887035A CN102631944A (en) | 2012-03-30 | 2012-03-30 | Synthetic gas-to-oil catalyst using mesoporous molecular sieve SBA-16 as carrier and method for preparing catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102631944A true CN102631944A (en) | 2012-08-15 |
Family
ID=46616627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100887035A Pending CN102631944A (en) | 2012-03-30 | 2012-03-30 | Synthetic gas-to-oil catalyst using mesoporous molecular sieve SBA-16 as carrier and method for preparing catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102631944A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015090127A1 (en) | 2013-12-18 | 2015-06-25 | 武汉凯迪工程技术研究总院有限公司 | Metal-matrix integrated membrane catalyst for fischer-tropsch synthesis, and preparation method thereof |
| CN105032470A (en) * | 2015-07-16 | 2015-11-11 | 湖北荟煌科技有限公司 | Catalyst for methane production from coke oven gas and preparation method thereof |
| WO2016202076A1 (en) * | 2015-06-16 | 2016-12-22 | 武汉凯迪工程技术研究总院有限公司 | Support for selective synthesis of high-quality kerosene fraction from synthesis gas, catalyst thereof, and preparation method therefor |
| CN108325496A (en) * | 2018-02-07 | 2018-07-27 | 苏州科技大学 | A method of grinding auxiliary permeates synthesizing efficient catalytic degradation methylene blue metal mesopore silicon oxide certainly |
| CN113150397A (en) * | 2021-04-20 | 2021-07-23 | 山东理工大学 | Preparation method of potato starch sustained-release antibacterial film |
| CN113842941A (en) * | 2021-09-23 | 2021-12-28 | 湖南昕逸辰科技有限公司 | Catalyst for cracking fluororesin and preparation method and application thereof |
| CN114284512A (en) * | 2021-12-29 | 2022-04-05 | 吉林大学 | Preparation method of carbon molecular sieve-cobalt monoatomic catalyst for zinc-air battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102078818A (en) * | 2010-12-27 | 2011-06-01 | 中南民族大学 | Catalyst using SBA-16 molecular sieve as carrier, and preparation method and application thereof |
-
2012
- 2012-03-30 CN CN2012100887035A patent/CN102631944A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102078818A (en) * | 2010-12-27 | 2011-06-01 | 中南民族大学 | Catalyst using SBA-16 molecular sieve as carrier, and preparation method and application thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015090127A1 (en) | 2013-12-18 | 2015-06-25 | 武汉凯迪工程技术研究总院有限公司 | Metal-matrix integrated membrane catalyst for fischer-tropsch synthesis, and preparation method thereof |
| WO2016202076A1 (en) * | 2015-06-16 | 2016-12-22 | 武汉凯迪工程技术研究总院有限公司 | Support for selective synthesis of high-quality kerosene fraction from synthesis gas, catalyst thereof, and preparation method therefor |
| RU2654205C1 (en) * | 2015-06-16 | 2018-05-17 | Ухань Кайди Инджиниринг Текнолоджи Рисерч Инститьют Ко., Лтд. | Substrate for a method for selectively synthesizing a high-quality kerosene fraction from synthesis gas, catalyst for this method and method of their manufacturing |
| JP2018524156A (en) * | 2015-06-16 | 2018-08-30 | 武▲漢凱▼迪工程技▲術▼研究▲総▼院有限公司 | Support for selective synthesis of high-quality kerosene fraction from synthesis gas, its catalyst, and its preparation method |
| CN105032470A (en) * | 2015-07-16 | 2015-11-11 | 湖北荟煌科技有限公司 | Catalyst for methane production from coke oven gas and preparation method thereof |
| CN108325496A (en) * | 2018-02-07 | 2018-07-27 | 苏州科技大学 | A method of grinding auxiliary permeates synthesizing efficient catalytic degradation methylene blue metal mesopore silicon oxide certainly |
| CN113150397A (en) * | 2021-04-20 | 2021-07-23 | 山东理工大学 | Preparation method of potato starch sustained-release antibacterial film |
| CN113842941A (en) * | 2021-09-23 | 2021-12-28 | 湖南昕逸辰科技有限公司 | Catalyst for cracking fluororesin and preparation method and application thereof |
| CN113842941B (en) * | 2021-09-23 | 2024-04-02 | 长沙松润新材料有限公司 | Catalyst for cracking fluorine resin, preparation method and application thereof |
| CN114284512A (en) * | 2021-12-29 | 2022-04-05 | 吉林大学 | Preparation method of carbon molecular sieve-cobalt monoatomic catalyst for zinc-air battery |
| CN114284512B (en) * | 2021-12-29 | 2023-09-19 | 吉林大学 | Preparation method of carbon molecular sieve-cobalt monoatomic catalyst for zinc-air battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108262055B (en) | Catalyst for preparing hydrocarbons by one-step hydrogenation of carbon dioxide and preparation method thereof | |
| CN102631944A (en) | Synthetic gas-to-oil catalyst using mesoporous molecular sieve SBA-16 as carrier and method for preparing catalyst | |
| CN102416328B (en) | Catalyst for preparing synthesis gases through methane carbon dioxide reforming (DMR) and preparation method thereof | |
| CN105728020B (en) | A kind of hud typed iron-carbonide catalyst preparation method | |
| EP2783750A1 (en) | Fischer-tropsch synthesis cobalt nano-catalyst based on porous material confinement, and preparation method therefor | |
| Ye et al. | Enhancing hydrogen production from the pyrolysis-gasification of biomass by size-confined Ni catalysts on acidic MCM-41 supports | |
| CN104437504B (en) | A kind of CO2The catalyst of Efficient Conversion producing light olefins | |
| CN102614934A (en) | Alumina carrier with composite pore structure and preparation method thereof | |
| Wang et al. | Experimental study and life cycle assessment of CO2 methanation over biochar supported catalysts | |
| CN111229215A (en) | Metal high-dispersion supported catalyst based on carbon quantum dot induction and preparation method and application thereof | |
| CN112169815B (en) | Application of iron-based catalyst in synthesis of low-carbon olefin by carbon dioxide hydrogenation | |
| CN105665003A (en) | Hierarchical pore molecular sieve catalyst and preparation method thereof | |
| CN105597772A (en) | Cobalt-based catalyst having core-shell structure, and preparation method thereof | |
| KR101236636B1 (en) | Ni-M-Al2O3 xerogel catalyst, preparation method thereof, and method for preparing methane using said catalyst | |
| CN102441386A (en) | Novel Fischer Tropsch synthesis method | |
| Wang et al. | Anchoring Co on CeO2 nanoflower as an efficient catalyst for hydrogenolysis of 5-hydroxymethylfurfural | |
| CN106268856A (en) | Rhodium base catalyst of one-step method from syngas ethanol and its preparation method and application | |
| Chen et al. | Impact of preparation method on nickel speciation and methane dry reforming performance of Ni/SiO2 catalysts | |
| CN102294249A (en) | Hydrotalcite type catalyst used for carrying out reforming reaction on natural gas and low carbon hydrocarbon (C1-C4) and preparation method thereof | |
| Lin et al. | La2O3-promoted Ni/H-ZSM-5 catalyzed aqueous-phase guaiacol hydrodeoxygenation to cyclohexanol | |
| CN102500386A (en) | Preparation method for cerium nickel composite oxide catalytic material | |
| CN110329992B (en) | Catalyst for preparing hydrogen by reforming methanol with low temperature water vapor and preparation method thereof | |
| CN108126701B (en) | A kind of syngas catalytic conversion catalyst and preparation method thereof | |
| CN103230797A (en) | Cobalt-loaded-on-alkali activated montmorillonoid catalyst and preparation method and application thereof | |
| CN114768804B (en) | Solid solution photo-thermal catalysis CO 2 Application of conversion reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120815 |