CN103316677A - Catalyst for dehydrogenation of sec-butyl alcohol and preparation method thereof - Google Patents
Catalyst for dehydrogenation of sec-butyl alcohol and preparation method thereof Download PDFInfo
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- CN103316677A CN103316677A CN2013102980118A CN201310298011A CN103316677A CN 103316677 A CN103316677 A CN 103316677A CN 2013102980118 A CN2013102980118 A CN 2013102980118A CN 201310298011 A CN201310298011 A CN 201310298011A CN 103316677 A CN103316677 A CN 103316677A
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Abstract
The invention relates to a catalyst for dehydrogenation of sec-butyl alcohol and a preparation method thereof. CuO and SiO2 are used as active components of the catalyst, and the catalyst comprises the following components: by weight, 50-70% of CuO and 30-50% of SiO2. The preparation method of the catalyst comprises the following steps: making soluble copper salt into a solution with a certain concentration by the use of distilled water, calculating corresponding amount of soluble silicate according to prescribed mass percent of the catalyst and making the soluble silicate into a solution which has the same concentration with the copper salt solution; fully mixing the two solutions in a water bath at the constant temperature of 30 DEG C with stirring, and controlling pH value of the solution during precipitation to 3-7 through a buffer solution, wherein the mixing process lasts for 0.5-1h; stopping stirring, aging, washing and filtering, drying and roasting, and moulding to obtain the catalyst finished product. The catalyst requires a simple preparation technology and has good thermal stability. The catalyst is used in the sec-butyl alcohol dehydrogenation technology for preparation of methyl ethyl ketone so as to raise conversion rate of sec-butyl alcohol and selectivity of methyl ethyl ketone.
Description
Technical field
The present invention relates to a kind of catalyst of sec-butyl alcohol dehydrogenizing and prepare the method for this catalyst.
Background technology
The sec-butyl alcohol catalytic dehydrogenation prepares in the technique of MEK, present domestic common employing Cu-Zn-Al catalyst, but along with improving constantly that commercial Application requires, exploitation high-performance Catalysts of Dehydrogenation Secondary Butand receives much concern always.As the method for improving the Cu-Zn-Al catalyst performance all is provided among Chinese patent CN1289752A and the CN1289753A, as by in catalytic component, adding alkali metal oxide or in Organic Ingredients, adding the acid site that organic amine is eliminated the Cu-Zn-Al catalyst, suppress the side reaction generation of dehydration of alcohols and the further condensation of MEK.Although prepared metallic catalyst among the Chinese patent CN1415591A is not in the situation that adopt other carrier to improve the selective of ketone product, but the preparation technology of its nanometer grade gold metal catalyst relates to the high requests such as high vacuum, gas starting arc, nm-class catalyst will be preserved under oxygen free condition simultaneously, has limited the nanometer grade gold metal catalyst in these requirements that prepare and use and has applied.Chinese patent CN101269331A prepares mesopore Cu-Zn-Al catalyst by add organic activating agent in the process of co-precipitation, the method improves catalyst activity by increase aperture, raising surface area, it is existing that to studies show that mesopore material exists hole wall thinner, heat endurance is relatively poor, in use easily therefore avalanche limits its use, and regrettably this patent does not disclose the thermal stability data of relevant mesopore Cu-Zn-Al catalyst.Chinese patent CN102247855A prepares Cu-Zn-Al catalyst basis in coprecipitation and has introduced Zr and alkali metal oxide and solve poor activity, the selective low problem of MEK in addition.
Also carry out at present the Cu-SiO for sec-butyl alcohol dehydrogenizing both at home and abroad
2The research of catalyst, substantially adopting silica gel, Ludox and organic silicone grease is the silicon source, by the methods such as ion-exchange, collosol and gel, ammonia still process method preparations, but these methods limit its large-scale application owing to the defective of technique own.Ion-exchange can only prepare the catalyst of the low copper content of poor activity; The long-time gel process of sol-gel process and the gel that formation is difficult to wash are so that this technique is difficult to industrialization; Hydro-thermal ammonia still process process power consumption in the standby technique of ammonia still process legal system is higher, consuming time longer, and this process is because the existence of ammonia in addition, causes inevitably copper ion and ammonia formation water-soluble copper ammonium complex ion and runs off, and can't obtain the high copper content catalyst.
As seen from the above analysis, improve coprecipitation in the Patents baseset and prepare problem in the Cu-Zn-Al catalyst, although obtain some progress aspect selective improving sec-butyl alcohol conversion ratio, MEK, but still do not satisfy industrial requirement.Present existing Cu-SiO
2Method for preparing catalyst all because of separately limitation makes such catalyst can't industrial applications.In addition, well-known Cu catalyst causes poor stability because of high temperature sintering, is difficult to satisfy the requirement of oxidation regeneration and industrial long-term operation always, and the heat endurance improvement situation of catalyst is not all reported in existing patent and research.
Summary of the invention
The invention reside in and overcome the problem that exists in the background technology, and a kind of Catalysts and its preparation method for sec-butyl alcohol dehydrogenizing is provided.The catalyst that should be used for sec-butyl alcohol dehydrogenizing can increase substantially the selective of the conversion ratio of sec-butyl alcohol and MEK, in the situation that keep the Cu high degree of dispersion, possessed good heat endurance.
The present invention solves its problem and can reach by following technical solution: a kind of catalyst for sec-butyl alcohol dehydrogenizing, it is with CuO and SiO
2Be active component, its component and proportioning are as follows by mass percentage: CuO50～70%, SiO
230～50%.
A kind of preparation method of the catalyst for sec-butyl alcohol dehydrogenizing may further comprise the steps:
Step a, soluble copper salt is configured to certain concentration solution with distilled water, and calculates the amount of the soluble silicate of respective amount according to the mass percent of this catalyst defined, and it is configured to solution with the copper salt solution equal concentrations; Step b, two solution are fully mixed 30 ℃ of constant temperature water baths and under stirring, and the pH value of solution is controlled at 3～7 when making precipitation by cushioning liquid, mixed process maintains 0.5～1h; Step c, stop to stir and get the catalyst finished product by ageing, distilled water washing, filtration, drying, roasting, compression molding.
The concentration of described soluble copper salt and mensuration dissolubility silicic salting liquid is 0.5～1.0mol/L; The mol ratio of soluble copper salt and soluble silicate is 0.95～2.20; Described soluble copper salt is one or more mixture of nitrate, sulfate, the acetate of copper; Described soluble silicate is sodium metasilicate, potassium silicate or lithium metasilicate; Described ageing condition is: Aging Temperature is 30～70 ℃, and digestion time is 1～3h, and the pH value is 4～6; Described cushioning liquid is acetic acid-sodium acetate, citric acid-sodium citrate or Potassium Hydrogen Phthalate; Described washing and filtering condition is: final mother liquor of precipitation of ammonium electrical conductivity is less than 800 μ s/cm; Baking temperature is 120～150 ℃, and be 2～4h drying time; Described roasting condition is: sintering temperature is 400～600 ℃, and roasting time is 4～6h.
The present invention compares with the above-mentioned background technology can have following beneficial effect: the catalyst preparation process that the present invention is used for sec-butyl alcohol dehydrogenizing is simple, when this catalyst prepares MEK technique for sec-butyl alcohol dehydrogenizing, the conversion ratio and the MEK that have not only improved sec-butyl alcohol are selective, and this catalyst possesses good thermal stability.
Description of drawings:
Accompanying drawing 1 is that prepared catalyst is schemed by the HTEM after 390 ℃ of processing of high temperature among the embodiment 1.
The specific embodiment:
The invention will be further described below in conjunction with specific embodiment:
Embodiment 1:
With 45.38gCu (NO
3)
23H
2O adds 289ml distilled water and is made into the 0.65mol/L aqueous solution, in addition with 37.87gNa
2SiO
3.9H
2O adds 205ml distilled water and is made into the 0.65mol/L aqueous solution.Move to respectively two solution in the separatory funnel, mode with parallel-flow precipitation at the uniform velocity splashes in the 1000ml beaker that 200ml Potassium Hydrogen Phthalate cushioning liquid is housed, 30 ℃ of constant temperature water baths and lasting stirring the in the dropping process, this moment, precipitation solution pH value was controlled at 4～5 by cushioning liquid, and the sedimentation time maintains 0.5h.Titration stops to stir after finishing to continue to stir 5min, mother liquor is constant temperature ageing 2h under 30 ℃ temperature, subsequently it is moved in the Buchner funnel to wash to electrical conductivity through distilled water and be lower than 800 μ s/cm, again after filtration, 120 ℃ of dry 10h, 500 ℃ of roasting 5h, make 20～40 order particles, namely get a kind of catalyst A, it is 60.60%, SiO that this catalyst is measured its CuO content through XRF
2Content is 38.82%.
Embodiment 2:
With 37.81gCu (NO
3)
23H
2O adds 240ml distilled water and is made into the 0.65mol/L aqueous solution, in addition with 47.33gNa
2SiO
3.9H
2O adds 257ml distilled water and is made into the 0.65mol/L aqueous solution.Move to respectively two solution in the separatory funnel, mode with parallel-flow precipitation at the uniform velocity splashes in the 1000ml beaker that 200ml Potassium Hydrogen Phthalate cushioning liquid is housed, 30 ℃ of constant temperature water baths and lasting stirring the in the dropping process, this moment, precipitation solution pH value was controlled at 4～5 by cushioning liquid, and the sedimentation time maintains 0.5h.Titration stops to stir after finishing to continue to stir 5min, mother liquor is constant temperature ageing 2h under 30 ℃ temperature, subsequently it is moved in the Buchner funnel to wash to electrical conductivity through distilled water and be lower than 800 μ s/cm, again after filtration, 120 ℃ of dry 10h, 500 ℃ of roasting 5h, make 20～40 order particles, namely get a kind of catalyst B, it is 48.44%, SiO that this catalyst is measured its CuO content through XRF
2Content is 48.88%.
Embodiment 3:
With 52.94gCu (NO
3)
23H
2O adds 337ml distilled water and is made into the 0.65mol/L aqueous solution, in addition with 28.40gNa
2SiO
3.9H
2O adds 154ml distilled water and is made into the 0.65mol/L aqueous solution.Move to respectively two solution in the separatory funnel, mode with parallel-flow precipitation at the uniform velocity splashes in the 1000ml beaker that 200ml Potassium Hydrogen Phthalate cushioning liquid is housed, 30 ℃ of constant temperature water baths and lasting stirring the in the dropping process, this moment, precipitation solution pH value was controlled at 4～5 by cushioning liquid, and the sedimentation time maintains 0.5h.Titration stops to stir after finishing to continue to stir 5min, mother liquor is constant temperature ageing 2h under 30 ℃ temperature, subsequently it is moved in the Buchner funnel to wash to electrical conductivity through distilled water and be lower than 800 μ s/cm, again after filtration, 120 ℃ of dry 10h, 500 ℃ of roasting 5h, make 20～40 order particles, namely get a kind of catalyst C, it is 68.45%, SiO that this catalyst is measured its CuO content through XRF
2Content is 29.37%.
Embodiment 4:
With 54.69g CuSO
45H
2O adds 337ml distilled water and is made into the 0.65mol/L aqueous solution, and other gets 38.5ml density is 1.17ml/g SiO
2Content is 20% Li
2OSiO
2The aqueous solution.Move to respectively two solution in the separatory funnel, mode with parallel-flow precipitation at the uniform velocity splashes in the 1000ml beaker that the 200ml citric acid-sodium citrate buffer is housed, 30 ℃ of constant temperature water baths and lasting stirring the in the dropping process, this moment, precipitation solution pH value was controlled at 3～4 by cushioning liquid, and titration process maintains 1h.Titration stops to stir after finishing to continue to stir 5min, mother liquor is constant temperature ageing 2h under 30 ℃ temperature, subsequently it is moved in the Buchner funnel to wash to electrical conductivity through distilled water and be lower than 800 μ s/cm, again after filtration, 150 ℃ of dry 4h, 600 ℃ of roasting 4h, make 20-40 order particle, namely get a kind of catalyst D, it is 67.05%, SiO that this catalyst is measured its CuO content through XRF
2Content is 28.52%.
Embodiment 5:
With 31.25g Cu (CH
3COO)
2H
2O adds 240ml distilled water and is made into the 0.65mol/L aqueous solution, and other gets 117.3ml density is 1.44ml/g SiO
2Content is 15.5% K
2OSiO
2The aqueous solution.Move to respectively two solution in the separatory funnel, mode with parallel-flow precipitation at the uniform velocity splashes in the 1000ml beaker that the 200ml NaAc_HAc buffer solution is housed, 30 ℃ of constant temperature water baths are accompanied by and continue to stir in the dropping process, this moment, precipitation solution pH value was controlled at 5～6 by cushioning liquid, and titration process maintains 0.65h.Titration stops to stir after finishing to continue to stir 5min, mother liquor is constant temperature ageing 2h under 30 ℃ temperature, subsequently it is moved in the Buchner funnel to wash to electrical conductivity through distilled water and be lower than 800 μ s/cm, again after filtration, 150 ℃ of dry 2h, 600 ℃ of roasting 5h, make 20-40 order particle, namely get a kind of catalyst E, it is 47.95%, SiO that this catalyst is measured its CuO content through XRF
2Content is 49.22%.
The comparative example 1:
Take by weighing respectively Cu (NO
3)
23H
2O36.46g and Zn (NO
3)
26H
2O21.93g and Al (NO
3)
39H
2O14.72g, miscible in 241.4ml distilled water, with the Na of 2mol/L
2CO
3Solution adopts cocurrent process under 70 ℃ temperature pH value of solution to be transferred to 7 as precipitating reagent.After precipitation was finished, mother liquor was 20 μ s/cm with distilled water washing precipitate several to precipitated liquid electrical conductivity also in 70 ℃ of ageing 4h subsequently after filtration.The filter cake that filtration is obtained changes in the baking oven in 120 ℃ of dry 10h, transfer to again 500 ℃ of lower roasting 5h in the Muffle furnace, catalyst fines after the roasting need pass through compressing tablet, pulverizes, sieve and make 20～40 order particles, namely get a kind of catalyst F, it is 59.64% that this catalyst is measured its CuO content through XRF, ZnO content is 28.77%, Al
2O
3Content is 10.55%.
The comparative example 2:
With 45.38g Cu (NO
3)
23H
2O is configured to the 0.65mol/L aqueous solution with 289ml distilled water, adds subsequently the ammoniacal liquor of 38ml, makes it to become the cuprammonium complex solution, and this moment, pH was about 11.On the other hand, get the 25ml Ludox, Ludox is moved in the separatory funnel, and average rate is added drop-wise in the cuprammonium complex solution for preparing, the dropping process adopts thermostat water bath to make system maintain 30 ℃, and is accompanied by lasting stirring.After titration finishes, stop to stir, 70 ℃ of constant temperature ageing 1h, bath temperature was warming up to 90 ℃ of ammonia still process to pH value of solution and drops to about 6.5 and stop after ageing finished, move in the Buchner funnel through the distilled water washing, filter, 150 ℃ of dry 4h, 500 ℃ of roasting 5h, make 20-40 order particle, namely get a kind of catalyst G, it is 55.46%, SiO that this catalyst is measured its CuO content through XRF
2Content is 43.12%.
The comparative example 3:
With 45.38g Cu (NO
3)
23H
2O is configured to the 0.65mol/L aqueous solution with 289ml distilled water, uses in addition 289ml distilled water with 19.88g Na
2CO
3Also be configured to the 0.65mol/L aqueous solution.With the Na that configures
2CO
3The aqueous solution and Cu (NO
3)
23H
2O solution is respectively charged in the separatory funnel, at the uniform velocity splashes in the beaker that the 25ml Ludox is housed in the mode of parallel-flow precipitation, drips 30 ℃ of process constant temperature water baths and is accompanied by and continues to stir.After titration finishes, stop to stir 30 ℃ of constant temperature ageing 2h, move to subsequently in the Buchner funnel through the distilled water washing, filter, 120 ℃ of dry 8h, 400 ℃ of roasting 6h, make 20-40 order particle, namely get a kind of catalyst H, it is 60.67%, SiO that this catalyst is measured its CuO content through XRF
2Content is 39.12%.
Catalyst activity evaluation method: the catalyst sample among embodiment and the comparative example is estimated its reactivity (stainless steel reaction bore 14mm, long 34mm) with micro fixed-bed reactor; The experiment catalyst consumption is 1.14g, and reaction temperature detects by a thermocouple that is placed in beds, and whole heating furnace is controlled by PID temperature control table.Catalyst need pass through mist (5%H before the reaction
2-95%N
2) at 270 ℃ of lower reduction 4h, reduction phase pressure maintains 0.2MP by counterbalance valve, reduction is finished simultaneously after the catalytic bed temperature drops to reaction temperature from reduction temperature, lays down reactor pressure, throws sec-butyl alcohol into the high pressure liquid phase pump in normal pressure downhill reaction pipe and begins to react.Product is taken out to be measured in the gas-liquid separation pipe after the condensation.Experiment reaction temperature: 240 ℃; Reaction pressure: normal pressure; Reaction velocity (adopting mass space velocity WHSV): 17.5h
-1
Table 1 is that the catalyst sample that embodiment 1～5 and comparative example 1～3 obtain reduces the activity rating contrast table that reacts under 270 ℃ temperature under 240 ℃ temperature.Wherein the catalyst sample that obtains of embodiment 1～5 is respectively catalyst A, B, C, D, E; The catalyst sample that comparative example 1～3 obtains is respectively catalyst F, G, H.
Table 1 embodiment 1～5 and comparative example's 1～3 catalyst activity are estimated contrast table
| Catalyst | Sec-butyl alcohol conversion ratio/% | MEK is selective/% |
| A | 86.6 | 96.3 |
| B | 80.8 | 97.5 |
| C | 88.1 | 97.1 |
| D | 90.4 | 95.6 |
| E | 87.1 | 98.5 |
| F | 75.7 | 90.8 |
| G | 84.2 | 92.4 |
| H | 84.8 | 93.1 |
For showing the Cu-SiO among the present invention
2Cu-Zn-Al and the Cu-SiO of catalyst and traditional co-precipitation method preparation
2The difference of catalyst on heat endurance reduced catalyst A, F, G and H in addition under 390 ℃ high temperature, the activity rating contrast of reacting under 240 ℃ temperature is to observe catalyst by the heat endurance after the high-temperature process.
Table 2 embodiment 1 catalyst and comparative example's 1～3 catalyst activity rating contrast table after high-temperature process
| Catalyst | Sec-butyl alcohol conversion ratio/% | MEK is selective/% |
| A | 86.1 | 95.6 |
| F | 68.9 | 93.9 |
| G | 80.2 | 90.7 |
| H | 77.3 | 91.2 |
By the data in the table 1 as seen, Cu-SiO of the present invention
2Cu-Zn-Al and the Cu-SiO of catalyst and traditional co-precipitation method preparation
2Catalyst relatively not only have high sec-butyl alcohol dehydrogenizing activity, and MEK is selectively all apparently higher than other method.
By the data in the table 2 as seen, adopt Cu-SiO of the present invention
2After 390 ℃ of processing of catalyst process high temperature, its sec-butyl alcohol conversion ratio and MEK selectively only slightly have decline, have good heat endurance.And the Cu-Zn-Al catalyst and the Cu-SiO that adopt traditional co-precipitation method to prepare
2After 390 ℃ of reduction of catalyst process high temperature, obvious decline has appearred in its catalyst activity.
Accompanying drawing 1 is prepared Cu-SiO among the embodiment 1
2By the high-resolution TEM result after 390 ℃ of processing of high temperature.Can find out from the picture of TEM, although the activated centre Cu particle (dark part) of this catalyst is by height Uniform Dispersion still after 390 ℃ of processing of high temperature, and obvious poly-and sintering does not further show Cu-SiO of the present invention from microstructure analysis
2Has good heat endurance.
Above experimental result explanation, the Cu-SiO of the present invention's development
2Cu-Zn-Al catalyst and the Cu-SiO of catalyst and traditional co-precipitation method preparation
2Catalyst is compared, and not only has higher sec-butyl alcohol conversion ratio and a MEK selective in sec-butyl alcohol dehydrogenizing reaction, also possesses good heat endurance simultaneously.
Embodiment of the invention institute with medicament is all commercially available.
The above only is preferred embodiment of the present invention, and is in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. catalyst that is used for sec-butyl alcohol dehydrogenizing, it is characterized in that: it is with CuO and SiO
2Be active component, its component and proportioning are as follows by mass percentage: CuO 50 ~ 70%, SiO
230 ~ 50%.
2. the preparation method of the catalyst for sec-butyl alcohol dehydrogenizing according to claim 1 is characterized in that: may further comprise the steps:
Step a, soluble copper salt is configured to certain concentration solution with distilled water, and calculates the amount of the soluble silicate of respective amount according to the mass percent of this catalyst defined, and it is configured to solution with the copper salt solution equal concentrations;
Step b, two solution are fully mixed 30 ℃ of constant temperature water baths and under stirring, and the pH value of solution is controlled at 3 ~ 7 when making precipitation by cushioning liquid, mixed process maintains 0.5 ~ 1h;
Step c, stop to stir and get the catalyst finished product by ageing, distilled water washing, filtration, drying, roasting, compression molding.
3. the preparation method of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst according to claim 2, it is characterized in that: the concentration of described soluble copper salt and mensuration dissolubility silicic salting liquid is 0.5 ~ 1.0mol/L; The mol ratio of soluble copper salt and soluble silicate is 0.95 ~ 2.20.
4. according to claim 2 or the preparation method of 3 described sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst, it is characterized in that: described soluble silicate is sodium metasilicate, potassium silicate or lithium metasilicate.
5. it is characterized in that according to claim 2 or the preparation method of 3 described sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst: described soluble copper salt is one or more mixture of nitrate, sulfate, the acetate of copper.
6. the preparation method of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst according to claim 2, it is characterized in that: described cushioning liquid is acetic acid-sodium acetate, citric acid-sodium citrate or Potassium Hydrogen Phthalate.
7. the preparation method of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst according to claim 2, it is characterized in that: described ageing condition is: Aging Temperature is 30 ~ 70 ℃, and digestion time is 1 ~ 3h, and the pH value is 4 ~ 6.
8. the preparation method of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst according to claim 2, it is characterized in that: described drying condition is: baking temperature is 120 ~ 150 ℃, be 2 ~ 4h drying time.
9. the preparation method of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst according to claim 2, it is characterized in that: described roasting condition is: sintering temperature is 400 ~ 600 ℃, roasting time is 4 ~ 6h.
10. the preparation method of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst according to claim 2, it is characterized in that: described washing and filtering condition is: final mother liquor of precipitation of ammonium electrical conductivity is less than 800 μ s/cm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103599786A (en) * | 2013-11-18 | 2014-02-26 | 大庆中蓝石化有限公司 | Catalyst for preparing methyl ethyl ketone through dehydrogenation of sec-butyl alcohol and preparation method thereof |
| CN103739469A (en) * | 2013-12-24 | 2014-04-23 | 山东滨州裕华化工厂有限公司 | Process for preparing MEK (Methyl Ethyl Ketone) by utilizing C4 fraction in etherified liquefied petroleum gas |
| CN114192156A (en) * | 2021-12-09 | 2022-03-18 | 沈阳化工大学 | Preparation method of sec-butyl alcohol dehydrogenation methyl ethyl ketone catalyst |
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| CN1687045A (en) * | 2005-04-14 | 2005-10-26 | 复旦大学 | Catalysis method for synthesizing gamma butyrolactone |
| CN101947455A (en) * | 2010-09-10 | 2011-01-19 | 南京化工职业技术学院 | Gamma-butyrolactone catalyst prepared by hydrogenation of maleic anhydride and dehydrogenation coupling of 1,4-butanediol, preparation method and application thereof |
| CN102886263A (en) * | 2012-10-16 | 2013-01-23 | 中科合成油淮南催化剂有限公司 | Catalyst for preparing gamma-butyrolactone through dehydrogenation and preparation method of catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1687045A (en) * | 2005-04-14 | 2005-10-26 | 复旦大学 | Catalysis method for synthesizing gamma butyrolactone |
| CN101947455A (en) * | 2010-09-10 | 2011-01-19 | 南京化工职业技术学院 | Gamma-butyrolactone catalyst prepared by hydrogenation of maleic anhydride and dehydrogenation coupling of 1,4-butanediol, preparation method and application thereof |
| CN102886263A (en) * | 2012-10-16 | 2013-01-23 | 中科合成油淮南催化剂有限公司 | Catalyst for preparing gamma-butyrolactone through dehydrogenation and preparation method of catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103599786A (en) * | 2013-11-18 | 2014-02-26 | 大庆中蓝石化有限公司 | Catalyst for preparing methyl ethyl ketone through dehydrogenation of sec-butyl alcohol and preparation method thereof |
| CN103739469A (en) * | 2013-12-24 | 2014-04-23 | 山东滨州裕华化工厂有限公司 | Process for preparing MEK (Methyl Ethyl Ketone) by utilizing C4 fraction in etherified liquefied petroleum gas |
| CN114192156A (en) * | 2021-12-09 | 2022-03-18 | 沈阳化工大学 | Preparation method of sec-butyl alcohol dehydrogenation methyl ethyl ketone catalyst |
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