CN102500392A - Catalyst for preparing oxygenated dicarbide by synthesis gas and preparation method of catalyst - Google Patents
Catalyst for preparing oxygenated dicarbide by synthesis gas and preparation method of catalyst Download PDFInfo
- Publication number
- CN102500392A CN102500392A CN2011102868782A CN201110286878A CN102500392A CN 102500392 A CN102500392 A CN 102500392A CN 2011102868782 A CN2011102868782 A CN 2011102868782A CN 201110286878 A CN201110286878 A CN 201110286878A CN 102500392 A CN102500392 A CN 102500392A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxygenatedchemicals
- carbon
- synthesis gas
- sio
- 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
Abstract
The invention discloses catalyst for preparing oxygenated dicarbide by synthesis gas and a preparation method of the catalyst. The catalyst adopts a singly dispersive SiO2 carrier, is prepared by a dipping method, and consists of Rh-Mn-Li-Fe/SiO2, and mass percent of metals to the singly dispersive SiO2 carrier includes that Rh to Mn to Li to Fe to SiO2 is 0.1-5 to 0.02-5 to 0.02-5 to 0.02-10 to 100. The preparation method includes steps of preparing the singly dispersive SiO2 carrier at first, roasting the singly dispersive SiO2 carrier at the temperature ranging from 200 DEG C to 700 DEG C, drying the singly dispersive SiO2 carrier at the temperature ranging from 30 DEG C TO 200 DEG C for 1 hour to 20 hours after being soaked by nitrate or chloride solution containing metals in different components, and accordingly obtaining the catalyst for preparing the oxygenated dicarbide by the synthesis gas. The catalyst has the advantages that carbon monoxide conversion rate is high and the oxygenated dicarbide is fine in selectivity.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method that is used for synthesis gas preparation carbon two oxygenatedchemicals.
Background technology
Carbon two (C such as ethanol, acetaldehyde and acetate
2) oxygenatedchemicals all is important chemical material, and ethanol still is desirable vehicle fuel and gasoline additive.At present, C
2Oxygenatedchemicals is a raw material production with oil or grain all.In recent years, the worsening shortages along with the constantly soaring and staple food supply of crude oil price impels people to seek to substitute C
2The method of oxygenatedchemicals traditional mode of production route.Therefore, carry out from coal, natural gas or living beings etc. through synthesis gas (CO+H
2) system C
2The exploitation of oxygenatedchemicals Study on Technology had both helped to address the above problem, and can make full use of resources such as coal, natural gas and living beings again.In addition, one step of synthesis gas system C
2Oxygenatedchemicals can be simplified existing manufacturing technique to a great extent, has remarkable economic efficiency.Therefore, develop and develop CO hydrogenation system C with prospects for commercial application
2The catalyst of oxygenatedchemicals has important theory and practical significance.Wherein, with SiO
2Be considered to a kind of catalyst that tool exploitation is worth for the Rh of carrier is catalyst based.
Patent CN1074304C has reported a kind of Rh-V-M/SiO of consisting of
2Catalyst, wherein M is one or more the mixing among Ru, Fe, Ir, Mo, Mn, K, Li, Zr or the Cu.Utilize this catalyst under the reaction condition of gentleness, to make CO change into carbon two oxygenatedchemicals efficiently.
Patent CN1177521A has reported a kind of Rh-Ti-Mn-M of consisting of
1-M
2/ SiO
2Catalyst, M wherein
1Be Ru, Fe, Ir or Ni, M
2Be one or more the mixture among K, Li or the Mg.Utilize this catalyst can make CO and H
2Carbon two oxygenatedchemicals such as high conversion, highly selective synthesizing alcohol, acetaldehyde and acetate.
Patent CN1088402C has reported a kind of Rh-a-b-c-d/SiO of consisting of
2Catalyst, wherein a is Ti or V, b is one or more the mixture in the rare earth element, c is a kind of among Ru, Ni, Co or the Pd, d is one or both the mixture in the alkali metal.Utilize this catalyst can high activity and highly selective make carbon two oxygenatedchemicals such as ethanol, acetaldehyde and acetate from the CO hydrogenation.
Patent CN1191120C provides a kind of rhodium base catalyst that is used for by synthesis gas preparation carbon two oxygenatedchemicals; It to be to have suitable aperture, to be carrier than the molecular sieve of high silica alumina ratio such as MCM-41 and MCM-22, and what be used for carbon two oxygenatedchemicals syntheticly has a high reaction activity and high.
It is the rhodium base catalyst of carrier that patent CN1390638 provides with the CNT, though this catalyst has preferable performance, and the very expensive and preceding condition that needs through harsh complicacies such as the long-time high-temperature process of red fuming nitric acid (RFNA) of use of CNT price.
In sum, the existing catalyst that is used for synthesis gas preparation carbon two oxygenatedchemicals exists the selectivity of conversion ratio and/or carbon two oxygenatedchemicals of carbon monoxide lower, the shortcoming of Preparation of Catalyst cost height, treatment conditions complicacy etc.
Summary of the invention
The present invention is not high and/or carbon two oxygenatedchemicals selectivity are relatively poor or shortcomings such as Preparation of Catalyst cost height, treatment conditions complicacy in order to solve in the prior art carbon two oxygenatedchemicals synthetic catalyst carbon monoxide conversion ratios, and a kind of possess simultaneously higher carbon monoxide conversion ratio and more excellent carbon two oxygenatedchemicals selectivity and gentle, the with low cost raw catelyst of preparation process condition are provided.
Technical scheme of the present invention
A kind of catalyst that is used for synthesis gas preparation carbon two oxygenatedchemicals, it is with monodispersed SiO
2Be carrier, adopt immersion process for preparing, it consists of Rh-Mn-Li-Fe/SiO
2, wherein each metal is with respect to monodispersed carrier S iO
2Mass percent be Rh:Mn:Li:Fe:SiO
2Be 0.1～5:0.02～5:0.02～5:0.02～10:100.
The described Preparation of catalysts method that is used for synthesis gas preparation carbon two oxygenatedchemicals comprises the steps:
(1), adopt sol-gel process to prepare monodispersed SiO
2
The ethanolic solution of positive tetraethyl orthosilicate is slowly splashed into to the mixed liquor of ammoniacal liquor and absolute ethyl alcohol, and after the magnetic agitation, ageing 10h obtains gel, and centrifugation back is with washing with alcohol three times, products therefrom warp 90
Dry, 120-700
Make monodispersed SiO behind the roasting 1-10h
2
(2), contain the preparation of the mixing salt solution of rhodium, manganese, lithium and iron
The nitrate or the chloride of Rh, Mn, Li, each component metals of Fe are dissolved in the distilled water, and obtaining concentration is the mixing salt solution that contains rhodium, manganese, lithium and iron of 0.001-1mol/L;
(3), in the mixing salt solution that contains rhodium, manganese, lithium and iron of step (2) gained, add the resulting monodispersed SiO of step (1)
2After the carrier 1-10h, in 30-200
oDry 1-20h under the C promptly gets the catalyst that is used for synthesis gas preparation carbon two oxygenatedchemicals.
The described catalyst that is used for synthesis gas preparation carbon two oxygenatedchemicals comprises the steps: in the application that carbon two oxygenatedchemicals prepare process
The catalyst that (1), at first will be used for synthesis gas preparation carbon two oxygenatedchemicals reduces processing; Used reducing gases is the mixture that hydrogen and inert gas are formed in the reduction treatment process; Inert gas is selected from one or more the mixture in nitrogen, helium and the argon gas etc.; The volumn concentration of hydrogen is 0.5～20% in the reducing gases, is preferably 1～10%; Reduction temperature is 200～500
, be preferably 250～450
The air speed of reducing gases is 500～5000h
-1, be preferably 1000～3000h
-1
(2), the catalyst said catalyst that be used for synthesis gas preparation carbon two oxygenatedchemicals of step (1) after reduction is handled is used for fixing the preparation that bed bioreactor carries out carbon two oxygenatedchemicals; Its reaction condition that is suitable for is: the mol ratio of hydrogen and carbon monoxide is 0.5～5:1, is preferably 1～3:1; The volume space velocity of reaction gas is 1000～30000h
-1, be preferably 3000～20000h
-1Reaction temperature is 200～400
, be preferably 220～300
Reaction pressure is 1.0～8.0MPa, is preferably 2.5～6.0MPa.
Beneficial effect of the present invention
A kind of catalyst that is used for synthesis gas preparation carbon two oxygenatedchemicals of the present invention is promptly to existing Rh/SiO
2Catalyst based deficiency is to adopt the monodispersed SiO of sol-gel process preparation
2Be carrier, because this monodispersed SiO
2Carrier surface has suitable hydroxyl; Decentralization and suitable R h and the Mn of active component Rh, the interaction between the Fe have been improved; Thereby improved the selectivity of reactive activity and carbon two oxygenatedchemicals simultaneously, overcome the shortcoming of the low and/or carbon two oxygenatedchemicals poor selectivity of synthetic carbon two oxygenatedchemicals catalyst exist in the prior art carbon monoxide conversion ratio.
Description of drawings
Fig. 1 is for being used for the used monodispersed SiO of catalyst of synthesis gas preparation carbon two oxygenatedchemicals in the embodiment of the invention 1
2The SEM figure of carrier.
The specific embodiment
Through embodiment the present invention is described in further detail below, but do not limit the present invention.
The internal diameter of the continuous-flow fixed bed stainless steel reactor that the present invention is used is 6mm, and length is 300mm, adopts electrical heating, and temperature is controlled automatically.
The Agilent 6820 type gas chromatographs that adopt Shanghai Anjelen Sci. & Tech. Inc to produce carry out on-line analysis to product, use thermal conductivity detector (TCD), TDX-01 carbon molecular sieve chromatogram column analysis carbon monoxide and carbon dioxide; Use hydrogen flame ionization detector, the PLOT-Q capillary column is analyzed oxygenatedchemicals and hydro carbons accessory substance.
According to each components contents in the reaction end gas, calculate the selectivity of carbon two oxygenatedchemicals in conversion ratio and the product of carbon monoxide with the molal quantity of carbon atom, computing formula is following:
The conversion ratio of carbon monoxide=[n (CO
2)+n (CHx)+n (RO)]/[n (CO)+n (CO
2)+n (CHx)+n (RO)]
Selectivity=n (R of carbon two oxygenatedchemicals
2O)/[n (CO)+n (CO
2)+n (CHx)+n (RO)]
Wherein, n (CO), n (CO
2), n (CHx) and n (RO) be respectively the CO that CO not reacted in the product and reaction are generated
2, hydro carbons and oxygenatedchemicals molal quantity, n (R
2O) be the molal quantity of carbon two oxygenatedchemicals in the oxygenatedchemicals.
Embodiment 1
A kind of catalyst A that is used for synthesis gas preparation carbon two oxygenatedchemicals, it is with monodispersed SiO
2Be carrier, it consists of Rh-Mn-Li-Fe/SiO
2, wherein each metal is with respect to monodispersed SiO
2The mass percent of carrier is Rh:Mn:Li:Fe:SiO
2Be 1.5:1.5:0.075:0.75:100.
Above-mentioned a kind of preparation method who is used for the catalyst A of synthesis gas preparation carbon two oxygenatedchemicals comprises the steps:
(1), adopt sol-gel process to prepare monodispersed SiO
2Carrier
Under 15 ℃, be that the ethanolic solution (50ml) of 20% positive tetraethyl orthosilicate slowly splashes into to the mixed liquor of 76ml ammoniacal liquor and 210ml absolute ethyl alcohol with volumn concentration; Behind the magnetic agitation 2h; Ageing 10h, gained suspension centrifugation, and with washing with alcohol three times; Products therefrom obtains SiO at 350 ℃ of following roasting 4h again 90 ℃ of dryings
2, its SEM figure is as shown in Figure 1, as can be seen from Figure 1, and prepared SiO
2Be monodispersed SiO
2Carrier;
(2), contain the preparation of the mixing salt solution of rhodium, manganese, lithium and iron
The radium chloride of 0.2 gram, the manganese nitrate of 0.27 gram, the lithium nitrate of 0.04 gram and the iron chloride of 0.01 gram are dissolved in the mixing salt solution that contains rhodium, manganese, lithium and iron that the concentration of processing rhodium, manganese, lithium and iron in 20 milliliters the distilled water is respectively 0.01mol/L, 0.03mol/L, 0.03mol/L and 0.002mol/L;
(3), in the mixing salt solution that contains rhodium, manganese, lithium and iron of step (2) gained, add the resulting monodispersed SiO of step (1)
2Carrier 10 grams are placed 2h through room temperature, and 100 ℃ of following dry 4h promptly obtain catalyst Rh-Mn-Li-Fe/SiO then
2, obtain a kind of catalyst A that is used for synthesis gas preparation carbon two oxygenatedchemicals after compressing tablet, pulverizing and sieve are got 20-40 purpose particle.
The comparative example 1
Adopt and make Rh-Mn-Li-Fe/SiO with embodiment 1 identical method
2Catalyst B, it is with commodity SiO
2Be carrier, wherein each metal is with respect to monodispersed SiO
2The mass percent of carrier is Rh:Mn:Li:Fe:SiO
2Be 1.5:1.5:0.075:0.75:100.
Embodiment 2
Adopt and make catalyst C with embodiment 1 identical method, it is with monodispersed SiO
2Be carrier, it consists of Rh-Mn-Li-Fe/SiO
2, wherein each metal is with respect to monodispersed SiO
2The mass percent of carrier is Rh:Mn:Li:Fe:SiO
2Be 1:1:0.5:1.5:100.
Embodiment 3
Adopt and make catalyst D with embodiment 1 identical method, it is with monodispersed SiO
2Be carrier, it consists of Rh-Mn-Li-Fe/SiO
2, wherein each metal is with respect to monodispersed SiO
2The mass percent of carrier is Rh:Mn:Li:Fe:SiO
2Be 2:1.5:1.5:5:100.
Application implementation example 1
The internal diameter of the continuous-flow fixed bed stainless steel reactor that the present invention is used is 6mm, and length is 300mm, adopts electrical heating, and temperature is controlled automatically.
Each reactor bottom filling 1g size is 20～40 purpose inert material quartz sands, and embodiment 1,2,3 and control Example 1 prepared catalyst A, B, C and D are respectively charged in each reactor, and the loadings of each catalyst is 1g; Each catalyst top filling 1g size again is 20～40 purpose inert material quartz sands, is made for the usefulness of raw material preheating, has loaded the back with reducing gases (10%H
2/ 90%N
2, flow velocity is 30ml/min) and be warming up to 300
Through after the 6h reduction, under the condition of the logical reducing gases of continuation each reaction bed temperature is reduced to 200 again under the condition
, switch unstripped gas then and be warming up to required reaction temperature gradually and react;
The composition of unstripped gas all (percentage by volume) is CO:33%, H
2: 67%;
Reaction condition is pressure: 3MPa, air speed 10000h
-1, system reaches balance behind reaction 3h, then sample analysis.
Adopt that HP6820 type gas chromatograph is online to carry out, use thermal conductivity detector (TCD), carbon molecular sieve chromatogram column analysis carbon monoxide and carbon dioxide; Use hydrogen flame ionization detector, the PLOT-Q capillary column is analyzed oxygenatedchemicals and hydro carbons accessory substance, and the evaluation result of catalyst is seen table 1.
The reactivity worth of table 1, catalyst
| Catalyst | Carbon monoxide conversion ratio (%) | Carbon two oxygenatedchemicals selectivity (%) |
| A | 18.9 | 69.3 |
| B | 10.3 | 45.4 |
| C | 16.9 | 58.1 |
| D | 24.5 | 61.3 |
Visible by table 1 data, adopt of the present invention with monodispersed SiO
2Rh-Mn-Li-Fe/SiO for carrier
2Catalyst is with respect to commodity SiO
2Rh-Mn-Li-Fe/SiO for carrier
2Catalyst is used for the reaction of synthesis gas preparation carbon two oxygenatedchemicals, not only has higher carbon monoxide conversion ratio, has higher carbon two oxygenatedchemicals selectivity simultaneously.
Foregoing is merely the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (10)
1. catalyst that is used for synthesis gas preparation carbon two oxygenatedchemicals, it consists of Rh-Mn-Li-Fe/SiO
2, it is characterized in that the described catalyst that is used for synthesis gas preparation carbon two oxygenatedchemicals is with monodispersed SiO
2Be carrier, adopt immersion process for preparing, wherein each metal is with respect to monodispersed SiO
2The mass percent of carrier is Rh:Mn:Li:Fe:SiO
2Be 0.1～5:0.02～5:0.02～5:0.02～10:100.
2. the catalyst that is used for synthesis gas preparation carbon two oxygenatedchemicals as claimed in claim 1 is characterized in that described each metal is with respect to monodispersed SiO
2The mass percent of carrier is Rh:Mn:Li:Fe:SiO
2Be 1～2:1～1.5:0.075～1.5:0.75～5:100.
3. the catalyst that is used for synthesis gas preparation carbon two oxygenatedchemicals as claimed in claim 2 is characterized in that described each metal is with respect to monodispersed SiO
2The mass percent of carrier is Rh:Mn:Li:Fe:SiO
2Be 1.5:1.5:0.075:0.75:100.
4. the catalyst that is used for synthesis gas preparation carbon two oxygenatedchemicals as claimed in claim 2 is characterized in that described each metal is with respect to monodispersed SiO
2The mass percent of carrier is Rh:Mn:Li:Fe:SiO
2Be 2:1.5:1.5:5:100.
5. like claim 1,2,3 or 4 arbitrary described Preparation of catalysts methods that are used for synthesis gas preparation carbon two oxygenatedchemicals, it is characterized in that comprising the steps:
(1), adopt sol-gel process to prepare monodispersed SiO
2Carrier
The ethanolic solution of positive tetraethyl orthosilicate is slowly splashed into to the mixed liquor of ammoniacal liquor and absolute ethyl alcohol, and after the magnetic agitation, ageing 10h obtains gel, through centrifugation back with washing with alcohol three times, products therefrom warp 90
Dry, 120-700
Make monodispersed SiO behind the roasting 1-10h
2Carrier;
(2), contain the preparation of the mixing salt solution of rhodium, manganese, lithium and iron
Nitrate or the chloride of each component metals Rh, Mn, Li and Fe are dissolved in the distilled water, and obtaining concentration is the mixing salt solution that contains rhodium, manganese, lithium and iron of 0.001-1mol/L;
(3), the monodispersed SiO that adds step (1) gained in the mixing salt solution that contains rhodium, manganese, lithium and iron of step (2) gained
2After the carrier 1-10h, in 30-200
Dry 1-20h promptly gets the catalyst that is used for synthesis gas preparation carbon two oxygenatedchemicals down.
6. the Preparation of catalysts method that is used for synthesis gas preparation carbon two oxygenatedchemicals as claimed in claim 5 is characterized in that:
The described sintering temperature of step (1) be preferably 350
, time 4h;
The described baking temperature of step (3) be preferably 100
, the time is 4h.
Like claim 1,2,3,4 or 5 arbitrary described catalyst that are used for synthesis gas preparation carbon two oxygenatedchemicals in the application that carbon two oxygenatedchemicals prepare process, it is characterized in that comprising the steps:
The catalyst that (1), at first will be used for synthesis gas preparation carbon two oxygenatedchemicals reduces processing; Used reducing gases is the mixture that hydrogen and inert gas are formed in the reduction treatment process; The volumn concentration of hydrogen is 0.5～20% in the reducing gases, and reduction process control temperature is 200～500
, the air speed of reducing gases is 500～5000h
-1
Described inert gas is one or more the mixture in nitrogen, helium or the argon gas;
(2), the catalyst said catalyst that be used for synthesis gas preparation carbon two oxygenatedchemicals of step (1) after reduction is handled is used for fixing the preparation that bed bioreactor carries out carbon two oxygenatedchemicals; Its reaction condition that is suitable for is: the mol ratio of hydrogen and carbon monoxide is 0.5～5:1, and the volume space velocity of reaction gas is 1000～30000h
-1, reaction temperature is 200～400
, reaction pressure is 1.0～8.0MPa.
8. the catalyst that is used for synthesis gas preparation carbon two oxygenatedchemicals as claimed in claim 7 contains oxidation at carbon two
Compound prepares the application in the process, it is characterized in that the volumn concentration of hydrogen in the reducing gases in the step (1) is preferably 1～10%; Reduction temperature is preferably 250～450
The air speed of reducing gases is preferably 1000～3000h
-1
9. the application that the catalyst that is used for synthesis gas preparation carbon two oxygenatedchemicals as claimed in claim 8 prepares process at carbon two oxygenatedchemicals; It is characterized in that the mol ratio that reaction condition in the step (2) is preferably hydrogen and carbon monoxide is 1～3:1, the volume space velocity of reaction gas is 3000～20000h
-1, reaction temperature is 220～350
, reaction pressure is 2.5～6.0MPa.
10. the catalyst that is used for synthesis gas preparation carbon two oxygenatedchemicals as claimed in claim 9 is characterized in that in the application that carbon two oxygenatedchemicals prepare process:
The volumn concentration of hydrogen is preferably 10% in the reducing gases in the step (1); Reduction temperature be preferably 300
;
The mol ratio that reaction condition in the step (2) is preferably hydrogen and carbon monoxide is 2:1, and the volume space velocity of reaction gas is 10000h
-1, reaction temperature is 300
, reaction pressure is 3.0MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102868782A CN102500392A (en) | 2011-09-26 | 2011-09-26 | Catalyst for preparing oxygenated dicarbide by synthesis gas and preparation method of catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102868782A CN102500392A (en) | 2011-09-26 | 2011-09-26 | Catalyst for preparing oxygenated dicarbide by synthesis gas and preparation method of catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102500392A true CN102500392A (en) | 2012-06-20 |
Family
ID=46212559
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102868782A Pending CN102500392A (en) | 2011-09-26 | 2011-09-26 | Catalyst for preparing oxygenated dicarbide by synthesis gas and preparation method of catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102500392A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106140125A (en) * | 2015-04-24 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of support type catalyst for preparing cis-anhydride by n-butane oxidation and preparation method thereof |
| CN106492862A (en) * | 2015-09-08 | 2017-03-15 | 中国石油化工股份有限公司 | A kind of for preparing catalyst of cis-butenedioic anhydride and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4014913A (en) * | 1975-06-26 | 1977-03-29 | Union Carbide Corporation | Process for producing oxygenated two carbon compounds |
| CN1179993A (en) * | 1996-10-16 | 1998-04-29 | 厦门大学 | Rhodium base catalyst for preparation of low carbon alcohol by synthetic gas and its preparing method |
| CN102029173A (en) * | 2009-09-25 | 2011-04-27 | 中国科学院化学研究所 | Rhodium-based catalyst used in process of preparing low carbon mixed alcohols from synthesis gas |
-
2011
- 2011-09-26 CN CN2011102868782A patent/CN102500392A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4014913A (en) * | 1975-06-26 | 1977-03-29 | Union Carbide Corporation | Process for producing oxygenated two carbon compounds |
| CN1179993A (en) * | 1996-10-16 | 1998-04-29 | 厦门大学 | Rhodium base catalyst for preparation of low carbon alcohol by synthetic gas and its preparing method |
| CN102029173A (en) * | 2009-09-25 | 2011-04-27 | 中国科学院化学研究所 | Rhodium-based catalyst used in process of preparing low carbon mixed alcohols from synthesis gas |
Non-Patent Citations (1)
| Title |
|---|
| 聂鲁美 等: "单分散二氧化硅微球的制备及反应机理", 《陶瓷学报》, vol. 31, no. 1, 31 March 2010 (2010-03-31), pages 75 - 78 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106140125A (en) * | 2015-04-24 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of support type catalyst for preparing cis-anhydride by n-butane oxidation and preparation method thereof |
| CN106140125B (en) * | 2015-04-24 | 2019-03-26 | 中国石油化工股份有限公司 | A kind of support type catalyst for preparing cis-anhydride by n-butane oxidation and preparation method thereof |
| CN106492862A (en) * | 2015-09-08 | 2017-03-15 | 中国石油化工股份有限公司 | A kind of for preparing catalyst of cis-butenedioic anhydride and preparation method thereof |
| CN106492862B (en) * | 2015-09-08 | 2019-04-16 | 中国石油化工股份有限公司 | A kind of catalyst and preparation method thereof being used to prepare cis-butenedioic anhydride |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10287233B2 (en) | Methyl acetate preparation method | |
| CN103896769B (en) | A kind of method of preparing methyl acetate by carbonylating dimethyl ether | |
| CN103894208A (en) | Low noble metal mercury-free catalyst for acetylene hydrochlorination reaction, preparation method and application thereof | |
| CN103831111B (en) | A kind of Catalysts and its preparation method for CO low-temperature catalytic oxidation | |
| CN104275180B (en) | A kind of high selectivity coalbed methane containing oxygen catalytic deoxidation catalyst and preparation method thereof | |
| CN102407112A (en) | Catalyst for preparing C2-oxygenates through hydrogenation of carbon monoxide as well as preparation method and application thereof | |
| CN101851160A (en) | Preparation method of oxalate by CO gas phase coupling synthesis using regular catalyst | |
| CN102658165A (en) | Catalyst for preparing ethanol by acetic acid gas phase hydrogenation and preparation method thereof | |
| CN103785391B (en) | A kind of high activity fischer-tropsch synthetic catalyst and its preparation method and application | |
| CN103691442A (en) | Catalyst for synthesis of isobutanol from synthesis gas and preparation method of catalyst | |
| CN103691450B (en) | A kind of Catalysts and its preparation method of acetic acid hydrogenation ethanol | |
| CN108371952A (en) | A kind of method that coordination-infusion process prepares methane-CO 2 reformation nickel-base catalyst | |
| CN106365994B (en) | A kind of production method of lower aliphatic carboxylic acid's Arrcostab | |
| CN104353465B (en) | A kind of catalyst used by formaldehyde through catalytic oxidation and preparation method thereof | |
| CN102500392A (en) | Catalyst for preparing oxygenated dicarbide by synthesis gas and preparation method of catalyst | |
| CN106732539A (en) | Compound non-noble metal oxide catalyst for catalysis burning toluene and its preparation method and application | |
| CN102319566B (en) | Copper-cobalt-silicon catalyst used in preparation of lower alcohol from synthetic gas and preparation method thereof | |
| CN104368360A (en) | Catalyst for selectively hydrogenating crotonaldehyde gas phase to synthesize crotonyl alcohol and preparation method | |
| CN105944733B (en) | A kind of rare earth modified multi-stage porous loading type nickel-based catalyst, preparation method and application | |
| CN102407126A (en) | Catalyst used for preparing synthetic natural gas by using coal derived synthesis gas and preparation method thereof | |
| CN113546622B (en) | Catalyst for catalytic oxidation of toluene at low temperature and high activity, and preparation method and application thereof | |
| CN104588022A (en) | High-activity Fischer-Tropsch synthesis catalyst, and preparation method and application thereof | |
| CN106881084B (en) | One kind is for reverse water-gas-shift reaction noble metal catalyst and its preparation and application | |
| CN105709777B (en) | The method of catalyst of acetic acid hydrogenation ethyl alcohol and preparation method thereof and acetic acid hydrogenation ethyl alcohol | |
| CN105709729B (en) | The method of catalyst of acetic acid hydrogenation ethyl alcohol and preparation method thereof and acetic acid hydrogenation ethyl alcohol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120620 |