CN104190424A - Catalyst for preparing methyl ethyl ketone by dehydrogenation of sec-butyl alcohol and preparation method of catalyst - Google Patents
Catalyst for preparing methyl ethyl ketone by dehydrogenation of sec-butyl alcohol and preparation method of catalyst Download PDFInfo
- Publication number
- CN104190424A CN104190424A CN201410430840.1A CN201410430840A CN104190424A CN 104190424 A CN104190424 A CN 104190424A CN 201410430840 A CN201410430840 A CN 201410430840A CN 104190424 A CN104190424 A CN 104190424A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxide
- content
- solution
- dry
- 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.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a catalyst for preparing methyl ethyl ketone by the dehydrogenation of sec-butyl alcohol and a preparation method of the catalyst. The catalyst is prepared by adding 10 to 40 percent of nickel oxide serving as a main active ingredient, 0.5 to 8 percent of manganese oxide, lanthanum oxide, titanium oxide, cerium oxide and the like serving as accessory ingredients, and 0.5 to 6 percent of alkali metal oxide to modify the catalyst, and performing a parallel-flow precipitation and impregnated mixing method. In a preparation process, a precipitating agent is not required to be used, and acidic and alkali waste liquid are not generated, so that the catalyst is environment-friendly. When the catalyst provided by the invention is applied to the dehydrogenation of the sec-butyl alcohol to prepare the methyl ethyl ketone, the activity and the selectivity are relatively high; the problems that a copper-series catalyst is easy to sinter and poor in stability are solved; moreover, the catalytic activity is higher than that of the traditional catalyst, the catalyst provided by the invention is low in content of the active ingredients, low in cost and applicable to industrialized mass production.
Description
Technical field
The present invention relates to catalysis technical field, relate to a kind of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone Catalysts and its preparation method.Specifically a kind of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst taking nickel as main active metal.
Background technology
MEK is a kind of very important organic solvent and industrial chemicals, and purposes is very extensive.Just, due to the premium properties of MEK, caused generally attention in the industry, domestic and international market demand is strengthening.In MEK production process, sec-butyl alcohol dehydrogenizing is a vital step, this step is divided into gas-phase dehydrogenation and two kinds of methods of dehydrogenation in liquid phase, because gas-phase dehydrogenation method conversion per pass is higher than dehydrogenation in liquid phase method, so industrial preparing ethyl methyl ketone generally adopts gas-phase dehydrogenation method.In gas-phase dehydrogenation process, dehydrogenation has occupied abnormal critical role, and the progress of MEK production technology is had to significant impact.
Can be used for Catalysts of Dehydrogenation Secondary Butand has a lot, as Cu-Zn alloy catalyst, ZnO-CaO-K
2o/SiO
2deng.At present industrial widely used be mainly Cu-series catalyst, comprise Cu-Zn/Al
2o
3and Cu/SiO
2deng, show good catalytic performance.But along with improving constantly that commercial Application requires, researcher is devoted to develop more high-performance sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst always.Chinese patent CN102247855B discloses a kind of Cu-Zn/Al
2o
3catalyst, these catalyst improvements are to have added metal component zirconium to reach the object that improves catalyst activity and selectivity, but the evaluating data providing from patent, the performance of this catalyst does not have the raising of highly significant.In Chinese patent CN1415591A, prepare nano metal bulk phase catalyst, this catalyst is owing to not using carrier to have higher ketone product selectivity, but the preparation technology of its nanometer grade gold metal catalyst relates to the high request such as high vacuum, gas starting arc, nm-class catalyst will be preserved under oxygen free condition simultaneously, and these require greatly to have limited applying of it.Chinese patent CN103316677A adopts the mode of the precipitation method to prepare Cu/SiO
2catalyst, this catalyst catalytic performance is better, but its active component content is higher, cost costliness, and SiO
2make carrier, moulding difficulty is large, is unfavorable for industrial applications.The Cu series catalysts that patent CN103170351A also provides a kind of dehydrogenating para-alcohol to prepare ketone, be characterized in adopting sieve and silica-sesquioxide complex carrier and added Metal Palladium to improve the performance of catalyst, obviously cost has been raised in the use of this catalyst preparation process complexity and noble metal.
As seen from the above analysis, Patents is all using Cu as main active component, and research substantially concentrates on Cu series catalysts is improved.As everyone knows, Cu is at 280 DEG C of easy-sinterings, this inadequate natural endowment causes that the activity of Cu-series catalyst is low, poor stability, improvement potentiality are limited, be difficult to meet the requirement of industrial oxidation regeneration and long-term operation always, and existing patent and research all do not report that the heat endurance of catalyst improves situation, so although these patents obtain some progress aspect selective improving sec-butyl alcohol conversion ratio, MEK, but still can not meet industrial needs.In a word, development of new sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst is still very urgent.
Summary of the invention
In order to solve problems of the prior art, the invention provides a kind of for sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone Catalysts and its preparation method.This catalyst adopts nickel oxide as main active component, has very high catalytic performance and has fundamentally overcome the problem of Cu-series catalyst poor heat stability.
For achieving the above object, the technical scheme that the present invention takes is:
A kind of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst, taking nickel oxide as main active component, manganese oxide, lanthana, titanium oxide, cerium oxide or their mixture etc. are co-catalyst, and aluminium oxide is carrier, adds alkali metal oxide to carry out modification to catalyst simultaneously; Component and the content of catalyst are as follows: the content of nickel oxide is 10%～40%, and preferably 15%～30%, the content of auxiliary agent metal oxides is 0.5%～8%, and preferably 1%～5%, the content of alkali metal oxide is 0.5%～6%, preferably at 1.5%～5%, Al
2o
3content 54%～89%, preferably 60%～82%.Above-mentioned percentage all refers to mass percent.
The preparation method of Catalysts of Dehydrogenation Secondary Butand provided by the invention comprises the following steps:
A) soluble nickel salt and co-catalyst soluble-salt are mixed with to certain concentration solution A with distilled water, and calculate the amount of the solubility meta-aluminate of respective amount according to the mass percent of this catalyst defined, and be mixed with solution B, and require the concentration of B to be more than or equal to the twice of A solution concentration;
B) above-mentioned A, the slow also stream of B two solution are added to plastic in the retort that pure water is housed, regulate the speed that adds of two solution, two materials are added simultaneously, plastic temperature is at 20～70 DEG C and be aided with stirring fully to mix, after adding, regulate the pH value of slurries in retort in 7 left and right with acid or alkali, then continue to stir 0.5～1.5 hour, stop stirring rear ageing 2～5 hours, suction filtration, the filter cake obtaining is dried to 6～12 hours at 40～80 DEG C dry 4～8 hours, 120 DEG C, pulverizes, obtain grained catalyst intermediate;
C) finite concentration alkali metal salt soln is sprayed in the catalyst intermediate that upper step is obtained, room temperature leaves standstill 8～18h, then in 40～80 DEG C of dry 4～8h, 120 DEG C of dry 4～8h;
D) product upper step being obtained, by the mode moulding of extrusion or compressing tablet, after 350～550 DEG C of roasting 3～8h of roasting, finally obtains catalyst finished product.
Above-mentioned related soluble nickel salt can be nitrate, acetate, sulfate, chloride of nickel etc., auxiliary agent is nitrate, the chloride etc. of cerium, manganese, lanthanum, titanium, solubility meta-aluminate refers to the meta-aluminate of potassium or sodium, and alkali metal salt is hydroxide, carbonate, bicarbonate, nitrate of potassium or sodium etc.; The concentration of related nickel salt solution is 0.5～1.2 mol/L, and the concentration of alkali metal salt soln can be calculated by the water absorption rate of alkali metal load capacity and catalyst fines.
The most outstanding technical characterictic of the present invention is to adopt transiting metal nickel as main active metal, and catalytic activity is high, and the use of auxiliary agent has overcome the selective lower problem of nickel-base catalyst MEK; Feature in preparation method is generating compared with the compound jelly of high-ratio surface and pore volume with the strong basicity and the co-precipitation of active component salt that utilize meta-aluminate solution itself, active component is uniformly dispersed, utilization rate is high, also just indirectly reduced the consumption of active metal, avoid a large amount of uses of precipitating reagent simultaneously, effectively reduced cost and environmental protection.
The present invention compares with known technology, and advantage is:
1, catalyst provided by the invention adopts transiting metal nickel as main active component and is aided with co-catalyst, and catalytic activity is high, and good stability has fundamentally overcome that Cu-series catalyst activity is low, easy-sintering, instability problem;
2, this catalyst activity constituent content is lower, with low cost, and preparation process is without using precipitating reagent, does not produce Acidity of Aikalinity waste liquid, and environmental friendliness is applicable to industrialized mass production;
3, to prepare MEK method reaction temperature lower for sec-butyl alcohol dehydrogenizing provided by the invention, energy-saving and cost-reducing; Simultaneous reactions pressure is normal pressure, mild condition, thus reduce operation and equipment investment expense, improve economic benefit.
Brief description of the drawings
Fig. 1 is the Long-term stability experimental curve diagram of catalyst of the present invention.
Detailed description of the invention
Carry out enumeration technical characterstic of the present invention below in conjunction with specific embodiment, but the present invention is not limited.
embodiment 1
By 58.2gNi (NO
3)
26H
2o adds 312ml distilled water to be made into the 0.6mol/L aqueous solution, separately by 96.1gNaAlO
2add 977ml distilled water to be made into the 1.2mol/L aqueous solution.Two solution are slowly splashed in the retort that 500ml water purification is housed in the mode of parallel-flow precipitation, and regulate the speed that adds of two solution, two materials are added simultaneously, in dropping process, 60 DEG C of constant temperature water baths lasting stirring, after adding, slowly splash into dilute nitric acid solution and make slurry pH value 7, continue again to stir after 1 hour, stop stirring at room temperature ageing 3 hours, filter, filter cake is dried 6 hours at 60 DEG C, 120 DEG C are dried 6 hours, follow 400 DEG C of roastings 4 hours, extruded moulding, obtains catalyst A.This catalyst NiO content is 20%, Al
2o
3content is 80%.
embodiment 2
By 58.2gNi (NO
3)
26H
2o and 7.9gMn (NO
3)
24H
2o adds 312ml distilled water to be made into the 0.6mol/L aqueous solution, separately by 92.5gNaAlO
2add 940ml distilled water to be made into the 1.2mol/L aqueous solution.Two solution are slowly splashed in the retort that 500ml water purification is housed in the mode of parallel-flow precipitation, and regulate the speed that adds of two solution, two materials are added simultaneously, in dropping process, 60 DEG C of constant temperature water baths lasting stirring, after adding, splash into dilute nitric acid solution and make slurry pH value 7, continuing to stir after 1 hour, stop stirring at room temperature constant temperature ageing 3 hours, filter, filter cake is dried 6 hours at 60 DEG C, 120 DEG C are dried 6 hours, follow 400 DEG C of roastings 4 hours, extruded moulding, obtains catalyst B.The content that this catalyst NiO content is 20%, MnO is 3%, Al
2o
3content is 77%.
embodiment 3
By 58.2gNi (NO
3)
26H
2o adds 312ml distilled water to be made into the 0.6mol/L aqueous solution, separately by 92.5gNaAlO
2add 940ml distilled water to be made into the 1.2mol/L aqueous solution.Two solution are slowly splashed in the retort that 500ml water purification is housed in the mode of parallel-flow precipitation, and regulate the speed that adds of two solution, two materials are added simultaneously, and 60 DEG C of constant temperature water baths lasting stirring in dropping process, after adding, splashing into dilute nitric acid solution makes slurry pH value 7, continuing stirring after 1 hour, stop stirring at room temperature constant temperature ageing 3 hours, filter, filter cake is dried 6 hours at 60 DEG C, and 120 DEG C are dried 6 hours.Dried filter cake is pulverized, and the KOH solution of the 0.68mol/L of 70ml is impregnated in above-mentioned material by the mode of spraying, and room temperature leaves standstill 12 hours, dry 4 hours of 60 DEG C of rear elder generations, 120 DEG C dry 4 hours.Follow 400 DEG C of roastings 4 hours, extruded moulding, obtains catalyst C.This catalyst NiO content is 20%, K
2o content is 3%, Al
2o
3content is 77%.
embodiment 4
By 58.2gNi (NO
3)
26H
2o and 6.2g La (NO
3)
36H
2o adds 312ml distilled water to be made into the 0.6mol/L aqueous solution, separately by 92.5gNaAlO
2add 940ml distilled water to be made into the 1.2mol/L aqueous solution.Two solution are slowly splashed in the retort that 500ml water purification is housed in the mode of parallel-flow precipitation, and regulate the speed that adds of two solution, two materials are added simultaneously, 60 DEG C of constant temperature water baths lasting stirring in dropping process, after adding, splash into dilute nitric acid solution and make slurry pH value 7, continuing stirring after 1 hour, stop stirring at room temperature constant temperature ageing 3 hours.Filter, filter cake is dried 6 hours at 60 DEG C, and 120 DEG C are dried 6 hours, follow 400 DEG C of roastings 4 hours, and extruded moulding, obtains catalyst D, and this catalyst NiO content is 20%, La
2o
3content be 3%, Al
2o
3content is 77%.
embodiment 5
By 58.2gNi (NO
3)
26H
2o and 6.2g La (NO
3)
36H
2o adds 312ml distilled water to be made into the 0.6mol/L aqueous solution, separately by 88.9gNaAlO
2add 903ml distilled water to be made into the 1.2mol/L aqueous solution.Two solution are slowly splashed in the retort that 500ml water purification is housed in the mode of parallel-flow precipitation, and regulate the speed that adds of two solution, two materials are added simultaneously, and 60 DEG C of constant temperature water baths lasting stirring in dropping process, after adding, splashing into dilute nitric acid solution makes slurry pH value 7, continuing stirring after 1 hour, stop stirring at room temperature constant temperature ageing 3 hours, filter, filter cake is dried 6 hours at 60 DEG C, and 120 DEG C are dried 6 hours.Dried filter cake is pulverized, and the KOH solution of the 0.68mol/L of 70ml is impregnated in above-mentioned material by the mode of spraying, and room temperature leaves standstill 12 hours, dry 4 hours of 60 DEG C of rear elder generations, 120 DEG C dry 4 hours, then 400 DEG C of roastings 4 hours, extruded moulding, obtains catalyst E.This catalyst NiO content is 20%, La
2o
3content be 3%, K
2o content is 3%, Al
2o
3content is 74%.
reference example
The Cu-Zn-K/Al that reference catalyst is prepared according to Chinese patent CN100360228C
2o
3, catalyst consist of CuO 43%, ZnO 40%, K
2o 3%, Al
2o
312%, remaining is graphite.
In order to verify advantage of the present invention, the sec-butyl alcohol dehydrogenizing performance of five embodiment catalyst of the present invention is evaluated, reference catalyst with under equal conditions carry out contrast test.
Catalyst activity evaluation is to carry out in 100mL fixed-bed micro-reactor.After catalyst filling, first catalyst is activated, the activation condition of catalyst of the present invention is normal pressure, uses 15vol%H
2/ N
2gaseous mixture activates 2 hours at 120 DEG C, rear 380 DEG C of reductase 12s hour; The activation condition of reference catalyst is normal pressure, uses 10vol%H
2/ N
2gaseous mixture was 300 DEG C of activation 4 hours.Then be 8h in 210 DEG C of temperature, liquid hourly space velocity (LHSV)
-1, under the reaction pressure condition that is normal pressure, adopt plunger displacement pump to pump in reactor raw material sec-butyl alcohol and carry out dehydrogenation reaction, product is isolated liquids and gases hydrogen through separator, product liquid flows into and connects sample tank.With gas chromatograph (Varian 3800 capillary chromatographs, fid detector), gas and product liquid are analyzed, result is as following table 1.
Table 1 catalyst of the present invention and reference catalyst activity rating result
Data by table 1 can find out, the catalytic activity of Kaolinite Preparation of Catalyst of the present invention is higher than the Cu-series catalyst of commercial Application, selective suitable with prior art; In order to investigate catalyst stability, be 8h in 210 DEG C of reaction temperatures, liquid hourly space velocity (LHSV) simultaneously
-1condition under, we have done Long-term stability experiment to catalyst E, the results are shown in Figure 1.
Be not difficult to find out from Fig. 1 curve, in device operation, after more than 10 days, catalyst activity does not significantly decrease and fluctuates less, and having good stability of catalyst is described, can meet industrial requirements.
In a word, catalyst provided by the invention is for sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone, and catalytic activity is high, good stability, and active component content is low, applicable process conditions gentleness, and with low cost, demonstrate huge industrial application value.
Claims (5)
1. a sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst, this catalyst is taking nickel oxide as main active component, manganese oxide, lanthana, titanium oxide, cerium oxide or their mixture etc. are co-catalyst, and aluminium oxide is carrier, adds alkali metal oxide to carry out modification to catalyst simultaneously; Each component and mass percentage content are as follows: the content of nickel oxide is 10%～40%, and preferably 15%～30%, the content of auxiliary agent metal oxides is 0.5%～8%, and preferably 1%～5%, the content of alkali metal oxide is 0.5%～6%, preferably at 1.5%～5%, Al
2o
3content 54%～89%, preferably 60%～82%.
2. the preparation method of catalyst according to claim 1 comprises the following steps:
A) soluble nickel salt and promoter soluble salt are mixed with to certain concentration solution A, and calculate the amount of the meta-aluminate of respective amount according to the mass percent of this catalyst defined, and be mixed with solution B, and require the concentration of B to be more than or equal to the twice of A solution concentration;
B) above-mentioned A, the slow also stream of B two solution are added to plastic in the retort that pure water is housed, by ageing, suction filtration, the dry filter cake obtaining is also pulverized;
C) finite concentration alkali metal salt soln is sprayed on the catalyst fines that upper step is obtained, room temperature leaves standstill certain hour, dry;
D), by shaping of catalyst, roasting, obtains catalyst finished product.
3. in plastic process according to claim 2, require to regulate the speed that adds of two solution, two materials are added simultaneously, plastic temperature is at 20～70 DEG C and be aided with stirring fully to mix, also need the pH value that ensures slurries in end reaction tank in 7 left and right, digestion time 0.5～1.5 hour, drying program is prior to 40～80 DEG C of dry 4～8h, is 120 DEG C of dry 4～8h.
4. after dipping alkali metal according to claim 2, time of repose is 8～18h, and drying program is prior to 40～80 DEG C of dry 4～8h, is 120 DEG C of dry 4～8h.
5. sintering temperature according to claim 2 is 350～550 DEG C, and roasting time is 3～8h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410430840.1A CN104190424B (en) | 2014-08-29 | 2014-08-29 | A kind of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410430840.1A CN104190424B (en) | 2014-08-29 | 2014-08-29 | A kind of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104190424A true CN104190424A (en) | 2014-12-10 |
| CN104190424B CN104190424B (en) | 2016-08-24 |
Family
ID=52075873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410430840.1A Expired - Fee Related CN104190424B (en) | 2014-08-29 | 2014-08-29 | A kind of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104190424B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061140A (en) * | 2015-08-11 | 2015-11-18 | 华东师范大学 | Method for preparing fatty alcohol from fatty acid or fatty acid ester under H-free condition and catalyst applied to method |
| CN105903471A (en) * | 2016-05-06 | 2016-08-31 | 北京石油化工学院 | Catalyst for preparing MEK (Methyl Ethyl Ketone) by carrying out dehydrogenation on 2-butanol and preparation method and application thereof |
| CN105967989A (en) * | 2016-05-06 | 2016-09-28 | 北京石油化工学院 | Method for preparing ethyl methyl ketone from sec-butanol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3884981A (en) * | 1972-12-27 | 1975-05-20 | Union Carbide Corp | Vapor phase hydrogenolysis dehydrogenation process |
| CN101384533A (en) * | 2006-02-14 | 2009-03-11 | 埃克森美孚化学专利公司 | Process for producing phenol and methyl ethyl ketone |
-
2014
- 2014-08-29 CN CN201410430840.1A patent/CN104190424B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3884981A (en) * | 1972-12-27 | 1975-05-20 | Union Carbide Corp | Vapor phase hydrogenolysis dehydrogenation process |
| CN101384533A (en) * | 2006-02-14 | 2009-03-11 | 埃克森美孚化学专利公司 | Process for producing phenol and methyl ethyl ketone |
Non-Patent Citations (1)
| Title |
|---|
| 马隽等: "担载Na对Cu-ZnO/Na-SiO2催化剂结构及催化仲丁醇脱氢反应活性的影响", 《应用化学》, vol. 28, no. 12, 31 December 2011 (2011-12-31) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061140A (en) * | 2015-08-11 | 2015-11-18 | 华东师范大学 | Method for preparing fatty alcohol from fatty acid or fatty acid ester under H-free condition and catalyst applied to method |
| CN105903471A (en) * | 2016-05-06 | 2016-08-31 | 北京石油化工学院 | Catalyst for preparing MEK (Methyl Ethyl Ketone) by carrying out dehydrogenation on 2-butanol and preparation method and application thereof |
| CN105967989A (en) * | 2016-05-06 | 2016-09-28 | 北京石油化工学院 | Method for preparing ethyl methyl ketone from sec-butanol |
| CN105967989B (en) * | 2016-05-06 | 2018-11-02 | 北京石油化工学院 | A kind of sec-butyl alcohol prepares the process of methyl ethyl ketone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104190424B (en) | 2016-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104998659B (en) | It is a kind of to be used to be catalyzed furfural or furfuryl alcohol rearrangement Hydrogenation for the catalyst of cyclopentanol and its preparation method and application method | |
| CN103157471B (en) | Deoxidation catalyst for olefin gas, preparation method and application thereof | |
| CN102302934B (en) | Novel auxiliary-modified catalyst for preparing methanol by catalytic hydrogenation of carbon dioxide and preparation method of catalyst | |
| CN105498756B (en) | The catalyst of hydrogenation of carbon dioxide methanol | |
| CN102211972B (en) | Application of hydrotalcite-based supported catalyst to preparation of isobutene from isobutane by dehydrogenating | |
| CN104148086B (en) | Prepare the catalyst and method of ethanol | |
| CN104043454A (en) | Novel nano composite methanation catalyst and preparation method thereof | |
| CN102218320A (en) | Catalyst for hydrogenation, preparation method and application thereof | |
| CN105363456A (en) | Copper-based catalyst and preparation method and application thereof | |
| TWI746493B (en) | Alkyl aromatic compound dehydrogenation catalyst and its manufacturing method and method of manufacturing alkenyl aromatic compound | |
| CN104785261A (en) | Oxalate hydrogenation catalyst synthesized by mixed silicon source method and preparation method thereof | |
| CN101157041A (en) | A preparation method of nanometer cuprum base methanol synthetic catalyst | |
| CN104624196A (en) | High-specific-surface-area Fischer-Tropsch synthesis catalyst and preparation method and application of high-specific-surface-area Fischer-Tropsch synthesis catalyst | |
| CN101983765B (en) | Catalyst for preparing methyl alcohol by catalytic hydrogenation on assistant modified carbon dioxide and preparation method thereof | |
| CN103230801B (en) | A kind of catalysis CO 2the method of synthesizing methanol modification CuZnZr | |
| CN103521254A (en) | Catalyst for catalyzing isobutane to dehydrogenize to synthesize isobutene as well as preparation method of catalyst | |
| CN103611540A (en) | Catalyst for CO hydrogenation reaction, preparation method and application thereof | |
| CN104190424B (en) | A kind of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst and preparation method thereof | |
| CN104190417B (en) | Preparation method of ruthenium-based bimetallic catalyst for preparing cyclohexene by partial hydrogenation of benzene | |
| CN104525204B (en) | A kind of preparation method of compound methanation catalyst | |
| CN105251505A (en) | Cobalt-based catalyst for producing C2+ oxygen-containing compound and co-producing olefin through synthetic gas, preparation method and applications thereof | |
| CN1139427C (en) | Nano CuZnAl catalyst for synthesizing methanol and dimethylether and its preparing process | |
| CN104028267B (en) | A kind of method for making of benzene selective Hydrogenation cyclohexene noble metal Ru catalyst | |
| CN108579742A (en) | Dehydrogenation and preparation method thereof | |
| CN104437488B (en) | A kind of preparation method of Hexalin gas-phase dehydrogenation preparing cyclohexanone catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160824 Termination date: 20190829 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |