CN104511277A - Catalyst for preparing cyclohexanone from cyclohexanol through gas-phase dehydrogenization and preparation method thereof - Google Patents
Catalyst for preparing cyclohexanone from cyclohexanol through gas-phase dehydrogenization and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of preparing catalysts and provides a catalyst for preparing cyclohexanone from cyclohexanol through gas-phase dehydrogenization and a preparation method thereof. The preparation method includes following steps: (1) with a fractional precipitation method, precipitating silica sol with a precipitating agent at a precipitating temperature of 55-70 DEG C to obtain a solution, wherein the precipitating agent is alkaline; (2) performing an ageing step for 20-30 min, adding a copper nitrate solution to the solution to perform precipitation at a precipitating temperature of 60-70 DEG C, and regulating the pH value to 7.2 with an acid or an alkali; (3) performing an ageing step for 20-30 min to obtain a mixture; (4) washing the mixture, performing solid-liquid separation, a drying process and a calcination process, wherein a calcination temperature is 350-450 DEG C; and (5) performing a tablet compressing process to obtain the catalyst. The catalyst is mainly composed of Cu/SiO2. Meanwhile, a modifying aid is introduced to the catalyst. Physical and chemical properties of the catalyst are described as follows: an average specific surface area is 160-280 m<2>/g; an average pore diameter is 2.5-6.0 nm; and an average pore volume is 0.15-0.45 ml/g. The catalyst is high in activity and selectivity and is less in specific gravity.
Description
Technical field
The invention belongs to catalyst technical field, be specifically related to a kind of cyclohexanol gas-phase dehydrogenation preparing cyclohexanone Catalysts and its preparation method.
Background technology
Cyclohexanone is a kind of important Organic Chemicals, it is the main intermediate of producing caprolactam (raw material of nylon-6) and adipic acid (raw material of nylon-66), in addition, cyclohexanone is also widely used in the industrial processes such as organic solvent, synthetic rubber and industrial coating.The production method of cyclohexanone mainly contains phenol hydrogenation method, cyclohexanol dehydrogenation method and cyclohexanol method etc.Because the technique preparing phenol is comparatively complicated, and phenol toxicity is comparatively large, so substantially no longer adopted by phynol method preparing cyclohexanone.Be divided into again oxidizing process and dehydriding by cyclohexanol preparing cyclohexanone, dehydriding is that cyclohexanol dehydrogenation obtains cyclohexanone under catalyst action, and oxidizing process is that cyclohexanol and air are obtained cyclohexanone by catalyst at 250 DEG C ~ 300 DEG C.Dehydriding because of its accessory substance relatively less, simple to operate, yield is high, is widely used in industrial production.
The cyclohexanol dehydrogenation catalyst of industrial early application is red iron oxide, afterwards by zinc system catalyst is replaced, as Ube ZnO-CaCO
3, Romanian Sai Weineishidi Zn-Cr system.Zinc oxide (Scientific Design Co. and BASF), the oxide of zinc calcium and the mixture (Inventa) of carbonate and silica is had to be zinc calcium potassium hopcalite (IFP) etc. of carrier in addition, zinc system catalyst is just succeeded in developing the sixties in 20th century in China, although zinc system catalyst conversion ratio is higher, but reaction temperature is higher (350 ~ 400 DEG C) also, cause selective poor, by-product is more, make the utilization rate of raw material cyclohexanol lower, and the reaction temperature greater catalytic agent life-span is short, substantially replace by other catalyst.
Because zinc cathode catalyst operating temperature is high, product cyclohexanone is selective poor, energy consumption is large, raw material availability is not high, and because accessory substance adds the burden of follow-up flow process more, affect the quality of caprolactam product, so competitively develop low temperature high-selectivity catalyst in the world from 20 century 70s, some adopt the caprolactam production process of low form dehydrogenation to come out one after another simultaneously.Such as patent CN02807661.3 describes a kind of catalyst based on cupric oxide for cyclohexanol dehydrogenation, it comprises very small amount of palladium in addition, and the catalyst based on copper oxide-zinc oxide of platinum or ruthenium or the catalyst based on cupric oxide-silica, compared with traditional catalyst, may be used for producing cyclohexanone under the reaction temperature reduced; CN200810234492.5 describes a kind of catalyst of preparing cyclohexanone by cyclohexanol dehydrogenation, mainly comprise cupric oxide, the zinc oxide of 30%-65%, the aluminium oxide of 1%-10% that content mol ratio is 25%-75%, structural promoter is the mixture of content mol ratio 0.1%-5% scarce metallic compound, and coagent is the alkali metal compound of content mol ratio 0-1.0%; CN200810234493.X describes a kind of preparation method of cyclohexanone catalyst by cyclohexanol dehydrogenation, is prepared by the method for co-precipitation: the nitrate mixed solution of copper, zinc and aluminium and precipitating reagent are carried out precipitation reaction, and precipitating reagent can be K
2cO
3, Na
2cO
3, NH
4hCO
3, (NH4)
2cO
3, one in NaOH, KOH or ammoniacal liquor, controlling precipitation temperature is 20 DEG C-90 DEG C, after precipitate, ageing 25min-35min, add auxiliary agent carry out filtering, wash, dry, calcine and compression molding and obtaining; CN97196061.5 describes a kind of cyclohexanol dehydrogenation Catalysts and its preparation method and application, relate to and a kind ofly make the catalyst that carrier material copper makes active component containing Alpha-alumina, wherein this aluminium oxide BET surface area (as DIN66131 measure) be not less than 30m
2/ g; CN201110210438.9 describes a kind of Catalysts and its preparation method preparing cyclohexanone for cyclohexanol dehydrogenation, and it is with CuO, ZnO and ZrO
2for main active component, with M
oas catalyst modifier, wherein, take percentage by weight as benchmark, each constituent content is: CuO 20 ~ 80%, ZnO 5 ~ 40%, ZrO
21 ~ 40%, M
2o0.5 ~ 10%.The preparation method of this catalyst is: by miscible in deionized water for the slaine of the slaine of copper, the slaine of zinc and zirconium, then, add aqueous slkali and carry out co-precipitation, precipitate complete, be precipitated mixture; By precipitation mixture through washing, after drying, add modifier or modifier raw material mixes, roasting, compression molding; CN201110210414.3 describes a kind of Catalysts and its preparation method preparing cyclohexanone for cyclohexanol dehydrogenation, and it is with CuO, ZnO, ZrO
2and SiO
2for main active component, using MO as catalyst modifier, wherein, take percentage by weight as benchmark, each constituent content is: CuO 20%-80%, ZnO5%-40%, ZrO
21%-40%, SiO
20.1%-10%, M
o0.5%-10%.The preparation method of this catalyst is: by the compound of the slaine of the slaine of copper, zinc, the slaine of zirconium and silicon and modifier raw material miscible in deionized water, then, add aqueous slkali and carry out co-precipitation, precipitate complete, by precipitation mixture through washing, drying, roasting, compression molding; CN201110418867.5 describes a kind of Cu
2o/MgO Catalysts and its preparation method, described catalyst comprises the component of following percentage by weight: nanometer Cu
2o 1% ~ 50%, MgO carrier surplus.The Cu that technical scheme of the present invention provides
2o/MgO catalyst only comprises Cu
2o and MgO carrier, Cu
2o particle is better dispersed on carrier surface, and grain size is nanoscale; CN00133278.3 describes a kind of cyclohexanone by dehydrogenating cyclohexanol Catalysts and its preparation method, it mainly comprises cupric oxide, zinc oxide, the aluminium oxide that content (m/m) is respectively 20%-70%, 28%-70%, 1%-10%, the mixture of content (m/m) 0.1%-5% scarce metallic compound and the alkali metal compound of content 0-1.0%, adopt coprecipitation method to obtain.CN90105453.4 describes a kind of multi component cyclohexanol dehydrogenation catalyst, and its component is CuO, ZnO, MgO, CaO and micro-Na
2o, its percentage by weight is 10%-50%, 10%-40%, 40%-60%, 6%-15%, 5PPM ~ 30PPM.Although the research of associated cryogenic cyclohexanol dehydrogenation catalyst is more, what at present domestic industry device generally used is still CuO/ZnO series catalysts, but this catalyst is with copper silicon series catalysts compared with, there is low, the selective problem such as low of activity.
Summary of the invention
The object of the present invention is to provide a kind of cyclohexanol gas-phase dehydrogenation preparing cyclohexanone Catalysts and its preparation method, be characterized in suitable pore structure, with the addition of modified additive, catalyst is made to have high activity and selective, comparatively low bulk density, greatly reduces the consumption to catalyst in process of cyclohexanone production.
The mass content of catalyst activity component copper of the present invention is 18% ~ 28%, and all the other are silica and modified additive.
The average BET specific surface area of described catalyst characteristics is 180m
2/ g ~ 280m
2/ g, average pore size is 2.5nm ~ 6.0nm, and average pore volume is 0.15ml/g ~ 0.45ml/g.
Catalyst of the present invention is also containing modified additive, and modified additive is one or both the mixture in the compound of metallic element in the Ith A race and the IIth A race in the periodic table of elements.
Preferably, modified additive is one or more in the metallic elements such as K, Mg, Na, Sr, Ba, and mass content 0.01% ~ 2.50%, auxiliary agent is carbonate or hydrous oxide.
The bulk density of catalyst of the present invention is 0.55g/ml ~ 0.85 g/ml, and catalyst reduced about 50% more in the past.Therefore also reduce the catalyst consumption in process of cyclohexanone production, save social resources.
Prepared by the method for infusion process or fractional precipitation that can adopt of catalyst provided by the invention.
Fractional precipitation preparation method, concrete preparation method is that the first step gets a certain amount of precipitating reagent and Ludox precipitates, Cheng Huahou, copper nitrate solution is added in above-mentioned solution with certain speed and precipitates, then pH value is regulated to be 7.2 with acid or alkali, one-tenthization 20 min ~ 30min, washing, Separation of Solid and Liquid, drying, interpolation auxiliary agent, roasting, last compression molding.
Infusion process preparation method, concrete preparation method, for carry out in closed reactor, implements by the following steps.1. prepare cuprammonia: ammoniacal liquor joins in copper nitrate solution, be mixed with the cupric ammine complex solution of clarification, then add ionized water stirring.2. flood: get in the cupric ammine complex solution that 1. silica gel join, vacuumize maintenance under agitation, dipping completes.3. be separated, wash, dry: dipping material is carried out Separation of Solid and Liquid, and solid material to neutrality, then carries out drying through washing, obtains finished catalyst.
Detailed description of the invention
Be described in detail below by embodiment.Enumerate the object of these examples just in order to explain the present invention, instead of limitation of the present invention.
Embodiment 1
Catalyst preparing carries out in closed reactor, implements by the following steps.1. prepare cuprammonia: the ammoniacal liquor getting 100ml 10M joins in the copper nitrate solution of 500ml 0.5M, be mixed with the cupric ammine complex solution of clarification, then add 600 ml ionized waters stirrings.2. flood: (specific area is 163.6m to get 180g commercial silica gel
2/ g, pore volume is 0.55ml/g, and average pore size is 4.8nm) join 1. cupric ammine complex solution, vacuumize maintenance under agitation 3 hours at 70 DEG C, dipping completes.3. be separated, wash, dry: dipping material is carried out Separation of Solid and Liquid, and solid material to neutrality, then carries out drying through washing, obtains finished catalyst.This catalyst copper content is 18.5%, and specific area is 220.5m
2/ g, pore volume is 0.44ml/g, and average pore size is 3.5nm.
Embodiment 2
Catalyst preparing carries out in unlimited reactor, implements by the following steps.The magnesium nitrate solution 50ml getting 1.0M copper nitrate solution 1000ml, 1.0M is mixed with mixed solution a, in with the stillpot stirred, the Ludox JN-25 of sodium carbonate liquor and 1048 grams is carried out co-precipitation, control precipitation temperature at 60 DEG C ~ 70 DEG C, precipitation endpoint pH is 7.5, then at 70 DEG C ~ 75 DEG C aging 30min, again solution a is joined in above-mentioned precipitation, through washing, oven dry, pulverizing, 320 DEG C of roastings, add 8.8 grams, potash and 4.0 grams, magnesia, add suitable quantity of water and graphite, last compression molding, obtains available catalyst.
This catalyst copper content is 19.5%, and specific area is 278.4m
2/ g, pore volume is 0.35ml/g, and average pore size is 4.2nm.
Embodiment 3
Catalyst preparing carries out in unlimited reactor, implements by the following steps.The calcium nitrate solution 50ml getting 1.0M copper nitrate solution 1000ml, 1.0M is mixed with mixed solution a, in with the stillpot stirred, the Ludox JN-25 of sodium carbonate liquor and 958 grams is carried out co-precipitation, control precipitation temperature at 60 DEG C ~ 70 DEG C, precipitation endpoint pH is 7.5, then at 70 DEG C ~ 75 DEG C aging 30min, then joins in above-mentioned precipitation by solution a, through washing, oven dry, pulverizing, 320 DEG C of roastings, add suitable quantity of water and graphite, last compression molding, obtain available catalyst.
This catalyst copper content is 20.6%, and specific area is 190.5m
2/ g, pore volume is 0.32ml/g, and average pore size is 3.8nm.
Embodiment 4
Catalyst preparing carries out in unlimited reactor, implements by the following steps.Get 1.0M copper nitrate solution 1000ml solution a, in with the stillpot stirred, the Ludox JN-25 of sodium carbonate liquor and 748 grams is carried out co-precipitation, control precipitation temperature at 60 DEG C ~ 70 DEG C, precipitation endpoint pH is 7.5, then at 70 DEG C ~ 75 DEG C aging 30min, then joins in above-mentioned precipitation by solution a, through washing, oven dry, pulverizing, 320 DEG C of roastings, add 8.8 grams, potash, suitable quantity of water and graphite, last compression molding, obtain available catalyst.
This catalyst copper content is 25.3%, and specific area is 198.5m
2/ g, pore volume is 0.45ml/g, and average pore size is 5.9nm.
Embodiment 5
Catalyst preparing carries out in unlimited reactor, implements by the following steps.Get 1.0M copper nitrate solution 1000ml solution a, in with the stillpot stirred, the Ludox JN-25 of sodium carbonate liquor and 637 grams is carried out co-precipitation, control precipitation temperature at 60 DEG C ~ 70 DEG C, precipitation endpoint pH is 7.5, then at 70 DEG C ~ 75 DEG C aging 30min, then joins in above-mentioned precipitation by solution a, through washing, oven dry, pulverizing, 320 DEG C of roastings, add 13.0 grams, sodium carbonate, suitable quantity of water and graphite, last compression molding, obtain available catalyst.
This catalyst copper content is 27.9%, and specific area is 190.3m
2/ g, pore volume is 0.25ml/g, and average pore size is 4.5nm.
Embodiment 6
Catalyst preparing carries out in unlimited reactor, implements by the following steps.Get 1.0M copper nitrate solution 1000ml solution a, in with the stillpot stirred, the Ludox JN-25 of sodium carbonate liquor and 637 grams is carried out co-precipitation, control precipitation temperature at 60 DEG C ~ 70 DEG C, precipitation endpoint pH is 7.5, then at 70 DEG C ~ 75 DEG C aging 30min, then joins in above-mentioned precipitation by solution a, through washing, oven dry, pulverizing, 360 DEG C of roastings, add 13.0 grams, sodium carbonate and brium carbonate 10 grams, suitable quantity of water and graphite, last compression molding, obtains available catalyst.
This catalyst copper content is 27.9%, and specific area is 180.7m
2/ g, pore volume is 0.23ml/g, and average pore size is 5.0nm.
Comparative example 1
Get 1.0M copper nitrate solution 1200ml solution, 1.0M zinc nitrate solution 2400ml solution and 3.0M aluminum nitrate solution 100ml mix, mixed solution is added drop-wise to while stirring in the sodium carbonate liquor of (10% ~ 15%) under the condition of 30 DEG C ~ 80 DEG C, then at the condition ageing 20min ~ 30min of 30 DEG C ~ 80 DEG C, add auxiliary agent after washing, refilter, dry, granulation, 280 DEG C ~ 400 DEG C roastings 4 ~ 6 hours, last compression molding, obtains available catalyst.
Catalyst sample prepared by the catalyst sample prepare embodiment 1 ~ 6 and comparative example 1, in specification ￠ 32 × 2mm fixed bed reactors, carry out activity rating, be 0.60h in raw material cyclohexanol air speed
-1, control reaction temperature 230 DEG C, catalyst loading amount 50ml condition under carry out activity rating, the results are shown in subordinate list 1.
Subordinate list 1 catalyst activity evaluation result
| Sample | Cyclohexanol conversion ratio % | The selective % of cyclohexanone | Bulk density g/ml |
| Embodiment 1 | 55.68 | 99.61 | 0.55 |
| Embodiment 2 | 60.23 | 99.22 | 0.82 |
| Embodiment 3 | 59.66 | 99.35 | 0.69 |
| Embodiment 4 | 61.33 | 99.62 | 0.73 |
| Embodiment 5 | 60.59 | 99.37 | 0.75 |
| Embodiment 6 | 61.35 | 99.16 | 0.68 |
| Comparative example 1 | 52.30 | 98.65 | 1.48 |
As can be seen from the table, the cyclohexanol conversion ratio of catalyst of the present invention and selective apparently higher than existing levels of catalysts, the bulk density of catalyst is lower simultaneously, effectively reduces the use amount of catalyst, has saved social resources.
Claims (10)
1. a cyclohexanol gas-phase dehydrogenation preparing cyclohexanone catalyst, it is characterized in that the mass content of the active ingredient copper of catalyst is 18% ~ 28%, all the other are silica and modified additive.
2. catalyst as claimed in claim 1, is characterized in that the average BET specific surface area of catalyst is 180m
2/ g ~ 280m
2/ g, average pore size is 2.5nm ~ 6.0nm, and average pore volume is 0.15ml/g ~ 0.45ml/g.
3. catalyst as claimed in claim 1, is characterized in that catalyst contains modified additive, and modified additive is one or more the mixture in the compound of metallic element in the Ith A race and the IIth A race in the periodic table of elements.
4. catalyst as claimed in claim 3, is characterized in that modified additive is one or more in K, Mg, Na, Sr, Ca, Ba metallic element.
5. catalyst as claimed in claim 1, is characterized in that the mass content 0.01% ~ 2.50% of modified additive.
6. the catalyst as described in claim 1,3 or 4, is characterized in that, auxiliary agent is carbonate or hydrous oxide.
7. catalyst as claimed in claim 1, is characterized in that the bulk density of catalyst is 0.55g/ml ~ 0.85 g/ml.
8. the preparation method of catalyst as claimed in claim 1, is characterized in that the method preparation adopting infusion process or fractional precipitation.
9. the preparation method of catalyst as claimed in claim 8, it is characterized in that described fractional precipitation preparation method is that the first step gets precipitating reagent and Ludox precipitates, Cheng Huahou, copper nitrate solution is added in above-mentioned solution and precipitates, then with acid or alkali adjust ph be 7.2, one-tenthization 20 min ~ 30min, washing, Separation of Solid and Liquid, drying, interpolation auxiliary agent, roasting, last compression molding.
10. the preparation method of catalyst as claimed in claim 8, it is characterized in that described infusion process preparation method for carry out in closed reactor, implement by the following steps: 1. prepare cuprammonia: ammoniacal liquor joins in copper nitrate solution, be mixed with the cupric ammine complex solution of clarification, then add ionized water stirring; 2. flood: get in the cupric ammine complex solution that 1. silica gel join, vacuumize maintenance under agitation, dipping completes; 3. be separated, wash, dry: dipping material is carried out Separation of Solid and Liquid, and solid material to neutrality, then carries out drying through washing, obtains finished catalyst.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106890641A (en) * | 2015-12-18 | 2017-06-27 | 中国石油化工股份有限公司 | A kind of preparing cyclohexanone by cyclohexanol dehydrogenation high-selectivity catalyst and preparation method |
| CN107628933A (en) * | 2017-09-28 | 2018-01-26 | 中触媒新材料股份有限公司 | A kind of continuous production technology that the acetone of 1 methoxyl group 2 is synthesized by the propyl alcohol direct dehydrogenation of 1 methoxyl group 2 |
| CN108722498A (en) * | 2017-04-18 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of cyclohexanone catalyst by cyclohexanol dehydrogenation support preparation method and application |
| CN108722420A (en) * | 2017-04-18 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of preparation method of copper silicon systems catalyst |
| CN112742396A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Copper-based silicon-based composite catalyst, preparation method and application thereof |
| CN112742415A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | TiO 22Nanotube composite copper-based silicon-based catalyst, preparation method and application thereof |
| CN113426447A (en) * | 2021-06-22 | 2021-09-24 | 中石化南京化工研究院有限公司 | Method for forming high-strength copper-silicon catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1356170A (en) * | 2000-11-30 | 2002-07-03 | 南化集团研究院 | Catalyst for preparing cyclohexanone by dehydrogenating cyclohexanol and its preparing process |
-
2013
- 2013-10-08 CN CN201310462252.1A patent/CN104511277A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1356170A (en) * | 2000-11-30 | 2002-07-03 | 南化集团研究院 | Catalyst for preparing cyclohexanone by dehydrogenating cyclohexanol and its preparing process |
Non-Patent Citations (2)
| Title |
|---|
| 刘俊等: "Cu/SiO2催化剂的制备及在环己醇脱氢制环己酮反应中的催化性能", 《化学工业与工程技术》, vol. 34, no. 3, 30 June 2013 (2013-06-30), pages 10 - 13 * |
| 殷玉圣: "Cu/SiO2催化剂载体预处理工艺的研究", 《工业催化》, vol. 20, no. 9, 30 September 2012 (2012-09-30), pages 47 - 50 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106890641A (en) * | 2015-12-18 | 2017-06-27 | 中国石油化工股份有限公司 | A kind of preparing cyclohexanone by cyclohexanol dehydrogenation high-selectivity catalyst and preparation method |
| CN108722498A (en) * | 2017-04-18 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of cyclohexanone catalyst by cyclohexanol dehydrogenation support preparation method and application |
| CN108722420A (en) * | 2017-04-18 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of preparation method of copper silicon systems catalyst |
| CN107628933A (en) * | 2017-09-28 | 2018-01-26 | 中触媒新材料股份有限公司 | A kind of continuous production technology that the acetone of 1 methoxyl group 2 is synthesized by the propyl alcohol direct dehydrogenation of 1 methoxyl group 2 |
| CN107628933B (en) * | 2017-09-28 | 2020-08-14 | 中触媒新材料股份有限公司 | Continuous production process for synthesizing 1-methoxy-2-acetone by directly dehydrogenating 1-methoxy-2-propanol |
| CN112742396A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Copper-based silicon-based composite catalyst, preparation method and application thereof |
| CN112742415A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | TiO 22Nanotube composite copper-based silicon-based catalyst, preparation method and application thereof |
| CN113426447A (en) * | 2021-06-22 | 2021-09-24 | 中石化南京化工研究院有限公司 | Method for forming high-strength copper-silicon catalyst |
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