CN105618062A - Sec-butyl acetate hydrogenation catalyst, preparation method and application thereof - Google Patents
Sec-butyl acetate hydrogenation catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a supported metal catalyst, and especially relates to a sec-butyl acetate hydrogenation catalyst, a preparation method and an application thereof. The sec-butyl acetate hydrogenation catalyst comprises an active component and a carrier, and the active ingredient comprises Cu and Zr. The catalyst has the advantages of low-temperature hydrogenation high activity under high velocity and high selectivity of products, under optimization condition, a conversion rate of sec-butyl acetate can reach 100%, and selectivity of ethanol and sec-butyl alcohol can reach more than 99%.
Description
Technical field
The present invention relates to a kind of load type metal catalyst, particularly relate to a kind of sec-butyl acetate hydrogenation catalyst and its preparation method and application.
Background technology
Along with sec-butyl acetate popularization commercially and application and production-scale continuous expansion, sec-butyl acetate is increasingly becoming a kind of large chemical products, and its market price is also relatively cheap, and the exploitation of product is to cause extensive concern downstream.
As one of sec-butyl acetate downstream product, sec-butyl alcohol purposes is wider. Sec-butyl alcohol is industrially used as solvent, it is also possible to as the cosolvent of methanol, as the component improving octane number, it is also possible to as plasticizer, dressing agent, herbicide etc., but topmost purposes is used to produce butanone. Owing to the apparent consumption of butanone is huge, result in the market demand of its raw materials for production sec-butyl alcohol also very big. The traditional sulfur process preparing sec-butyl alcohol is to adopt liquid sulfur acid as catalyst, is first esterified by n-butene, and the butyl ester of generation is hydrolyzed prepared sec-butyl alcohol again. But method ubiquity reaction conversion ratio is low, energy consumption is high and to shortcomings such as environment close friends not, therefore urgently new process route synthesizes sec-butyl alcohol for this.
As another important downstream product of sec-butyl acetate hydrogenation, ethanol has purposes quite widely. Except as variable concentrations disinfectant, manufacture beverage and essence except, ethanol or a kind of important basic organic chemical industry raw material, be used for preparing the industrial chemicals such as acetaldehyde, ether, ethyl acetate, ethamine, be also the raw material producing the products such as dyestuff, coating and detergent. In recent years, ethanol can also call in gasoline, as vehicle fuel. The addition of certain proportion ethanol in gasoline, it is possible to improve performance and the quality of oil product, reduces the discharge of the major pollutants such as carbon monoxide, Hydrocarbon. Therefore, the sustainable growth of ethanol demand is also led to. The industrial making method of ethanol mainly has fermentation method and ethylene hydration method. Fermentation method is a kind of important method of ethanol production, but in order to ensure grain security, China to Ethanol Production by Fermentation with caution relatively always. And the ethylene that ethylene hydration rule produces with petroleum cracking is for raw material, it is necessary to consume substantial amounts of ethylene. Due to the resources characteristic of the few oil of the many coals of China, ethylene hydration ethanol route has been also affected by restriction. Therefore, for features such as the current coal acetic acid production capacity of China are sufficient, it is possible to the new technology route of the synthesizing alcohol that development is raw material with acetic acid, it is possible to give full play to the resources advantage of China.
Therefore, the downstream product developing sec-butyl acetate has very important strategic importance. It is possible not only to extend the industrial chain of sec-butyl acetate, it is also possible to alleviate the problems such as acetic acid industry production capacity surplus. At present, sec-butyl acetate Hydrogenation it is specifically designed to also rare for catalyst and the hydrogenation technique report of sec-butyl alcohol.
Ethyl acetate preparation of ethanol through hydrogenation is widely studied, and close with sec-butyl acetate hydrogenation reaction character have certain reference value. Chinese Patent Application No. is the patent of invention of 201410239745, disclose a kind of catalyst for acetic acid hydrogenation acetic acid ethyl reaction, including a kind of active component being selected from Cu, Co, Ni, one or both auxiliary agents in Fe, Mn, Ge, Sn, V, Zn, W, Mo, Cd and SiO2 carrier, for the conversion ratio of acetic acid hydrogenation acetic acid ethyl reaction up to 100%, the selectivity of product-ethyl acetate reaches as high as 81%; But we test and find that catalyst prepared by this formula is relatively low for the conversion ratio of sec-butyl acetate hydrogenation reaction. Chinese Patent Application No. is the patent of invention of 201010584928, discloses one and divides for activity knob with Cu, with SiO2For the copper-based catalysts of carrier, for ethyl acetate preparation of ethanol through hydrogenation, acetate hydrogenation is made to generate ethanol under the reaction temperature of 180��300 DEG C and the reaction pressure of 1.0��5.0MPa. Catalyst has the high response rate and high ethanol selectivity, but result shows that this formulated catalyst is relatively low for the conversion ratio of sec-butyl acetate hydrogenation reaction.
Because above-mentioned defect, the design people, actively in addition research and innovation, to founding a kind of hydrogenation catalyst so that it is for sec-butyl acetate hydrogenation reaction, and meet the requirement of commercial Application.
Summary of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide high activity when a kind of low temperature, high-speed, high selective sec-butyl acetate hydrogenation catalyst and its preparation method and application.
The present invention provides a kind of sec-butyl acetate hydrogenation catalyst, and including active component and carrier, described active component includes Cu and Zr.
Concrete, in described active component, the mass ratio of Cu and Zr is 10: 1��30: 1.
Concrete, described active constituent loading is to the silica supports modified containing calcium oxide.
Concrete, described active component is the soluble metallic salt of Cu and Zr.
The preparation method that the present invention also provides for a kind of sec-butyl acetate hydrogenation catalyst, concrete steps include: 1) under deposition condition, the soluble metallic salt of active component is dissolved in water, after being subsequently adding precipitant and carrier, raises temperature, after back flow reaction a period of time, generate precipitation;
2) by step 1) in precipitation through filtering, washing, after dry and roasting, obtain described sec-butyl acetate hydrogenation catalyst.
Concrete, described precipitant is alkali-metal hydroxide, alkali-metal carbonate or carbamide.
Concrete, described step 2) in dry condition be 60-150 DEG C, the time is 2-24h, and the condition of roasting is that temperature is 200-600 DEG C, and the time is 2-12h.
The present invention also provides for the application in sec-butyl acetate preparation of ethanol through hydrogenation and sec-butyl alcohol are reacted of a kind of sec-butyl acetate hydrogenation catalyst, first sec-butyl acetate hydrogenation catalyst is reduced in a hydrogen atmosphere, reduction temperature is 150-400 DEG C, and reduction pressure is normal pressure, and the recovery time is 2-12h; Then reactant sec-butyl acetate is introduced, carry out hydrogenation reaction at catalyst surface.
Further, the reaction temperature of described hydrogenation reaction is 150-250 DEG C, and reaction pressure is 2-6MPa, and hydrogen and sec-butyl acetate mol ratio are 5-300, and ester air speed is 0.5-1.5h-1��
Further, the reaction temperature of described hydrogenation reaction is 190-250 DEG C, and reaction pressure is 4-6MPa, and hydrogen and sec-butyl acetate mol ratio are 15-30, and ester air speed is 0.5-1.0h-1��
By such scheme, the present invention at least has the advantage that the catalyst of the present invention has the advantage such as low temperature hydrogenation high activity when high-speed, product height selectivity, under optimal conditions, sec-butyl acetate conversion ratio reaches 100%, and the selectivity of ethanol and sec-butyl alcohol is all more than 99%.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention, and can be practiced according to the content of description, below with presently preferred embodiments of the present invention and coordinate detailed description as after.
Detailed description of the invention
Below in conjunction with embodiment, the specific embodiment of the present invention is described in further detail. Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.
Embodiment 1
1) catalyst is prepared:
By 7.06 grams of Zr (NO3)4��5H2O, 103.83 grams of Cu (NO3)2��2.5H2O deionized water is made into metal mixed solution 1,112.8 grams of carbamide are under agitation joined in metal mixed solution 1, then (wherein silica content is 30wt.%, and is dissolved into the Ca (CH of 5.0wt% in Ludox in advance to drip Ludox 233.3 grams again3COO)2, amount to 4.0wt%CaO/SiO2), be warming up to 95 DEG C, be stirred continuously condition under carry out condensing reflux and allow each component co-precipitation, control endpoint pH is 7-8, and metal ion is solids 1 by co-precipitation; Dry after overnight at 60 DEG C after finally solids 1 being filtered, washs and within 2 hours, namely obtain catalyst A in 600 DEG C of roastings, urge part agent and composition thereof in Table 1.
2) catalyst reduction and sec-butyl acetate hydrogenation:
Take in 2 grams of catalyst A fixing bed stainless steel reactor loading diameter to be 8mm, length be 30cm, reactor upper and lower two ends filling quartz sand, middle loading catalyst, to ensure that catalyst is in the flat-temperature zone of reactor (if no special instructions, following example all use this reactor, type of feed is also consistent), first this reactor carries out catalyst reduction, then carries out sec-butyl acetate hydrogenation reaction;
Wherein, catalyst reduction condition includes: temperature is 400 DEG C, and pressure is 0.5MPa, and reducing atmosphere is pure hydrogen, and the recovery time is 4h; Sec-butyl acetate hydroconversion condition includes: temperature is 150-250 DEG C, and pressure is 5MPa, and hydrogen ester mol ratio is 300: 1, and ester liquid hourly space velocity (LHSV) is 1.5h-1, and reaction result is in Table 1.
Embodiment 2
1) catalyst is prepared:
By 4.71 grams of Zr (NO3)4��5H2O, 110 grams of Cu (NO3)2��2.5H2O deionized water is made into metal mixed solution 1, is under agitation joined by NaOH in metal mixed solution 2, then drips containing 4.0wt%Ca (CH again3COO)2Ludox 230 grams, be stirred continuously under condition to allow each component co-precipitation, control endpoint pH is 7-8, and metal ion is solids 2 by co-precipitation; Dry after overnight at 100 DEG C after finally solids 2 being filtered, washs and within 5 hours, namely obtain catalyst B, catalyst and composition thereof in Table 1 in 400 DEG C of roastings.
2) catalyst reduction and sec-butyl acetate hydrogenation:
Take 2 grams of catalyst B and first carry out catalyst reduction in the reactor, then carry out sec-butyl acetate hydrogenation reaction;
Wherein, catalyst reduction condition includes: temperature is 250 DEG C, and pressure is 0.5MPa, and reducing atmosphere is pure hydrogen, and the recovery time is 8h; Sec-butyl acetate hydroconversion condition includes: temperature is 170-230 DEG C, and pressure is 4MPa, and hydrogen ester mol ratio is 200: 1, and ester liquid hourly space velocity (LHSV) is 0.5h-1, and reaction result is in Table 1.
Embodiment 3
1) catalyst is prepared:
By 14.1 grams of Zr (NO3)4��5H2O, 110 grams of Cu (NO3)2��2.5H2O deionized water is made into metal mixed solution 1, by Na2CO3Under agitation join in metal mixed solution 3, then drip containing 3.0wt%Ca (CH again3COO)2Ludox 223.3 grams, be warming up to 50 DEG C, be stirred continuously condition under allow each component co-precipitation, control endpoint pH is 7-8, and metal ion is solids 3 by co-precipitation; Dry after overnight at 150 DEG C after finally solids 3 being filtered, washs and within 12 hours, namely obtain catalyst C, catalyst and composition thereof in Table 1 in 200 DEG C of roastings.
2) catalyst reduction and sec-butyl acetate hydrogenation:
Take 2 grams of catalyst C and first carry out catalyst reduction in the reactor, then carry out sec-butyl acetate hydrogenation reaction;
Wherein, catalyst reduction condition includes: temperature is 150 DEG C, and pressure is 0.5MPa, and reducing atmosphere is pure hydrogen, and the recovery time is 12h; Sec-butyl acetate hydroconversion condition includes: temperature is 170-250 DEG C, and pressure is 2MPa, and hydrogen ester mol ratio is 100: 1, and ester liquid hourly space velocity (LHSV) is 1h-1, and reaction result is in Table 1.
Comparative example
In order to compare sec-butyl acetate hydrogenation catalyst provided by the invention and hydrogenation catalyst of the prior art, catalytic efficiency in sec-butyl acetate hydrogenation reaction, the present invention provides this comparative example, the hydrogenation catalyst mentioned in the patent of invention adopting Chinese Patent Application No. to be 201410239745, its active component adopts Cu and Fe.
1) catalyst is prepared:
16.3 grams of Fe (NO3) 3 6H2O, 110 grams of Cu (NO3) 2 2.5H2O deionized waters are made into metal mixed solution 1, by Na2CO3Under agitation join in metal mixed solution 4, then drip containing 3.0wt%Ca (CH again3COO)2Ludox 223.3 grams, be warming up to 50 DEG C, be stirred continuously condition under allow each component co-precipitation, control endpoint pH is 7-8, and metal ion is solids 4 by co-precipitation; Dry after overnight at 150 DEG C after finally solids 4 being filtered, washs and within 12 hours, namely obtain catalyst D, catalyst and composition thereof in Table 1 in 200 DEG C of roastings.
2) catalyst reduction and sec-butyl acetate hydrogenation:
Take 2 grams of catalyst D and first carry out catalyst reduction in the reactor, then carry out sec-butyl acetate hydrogenation reaction;
Wherein, catalyst reduction condition includes: temperature is 150 DEG C, and pressure is 0.5MPa, and reducing atmosphere is pure hydrogen, and the recovery time is 12h; Sec-butyl acetate hydroconversion condition includes: temperature is 170-250 DEG C, and pressure is 2MPa, and hydrogen ester mol ratio is 100: 1, and ester liquid hourly space velocity (LHSV) is 1h-1, and reaction result is in Table 1.
The contrast of catalytic efficiency in sec-butyl acetate hydrogenation reaction of each catalyst of table 1
The above is only the preferred embodiment of the present invention; it is not limited to the present invention; should be understood that; for those skilled in the art; under the premise without departing from the technology of the present invention principle; can also making some improvement and modification, these improve and modification also should be regarded as protection scope of the present invention.
Claims (10)
1. a sec-butyl acetate hydrogenation catalyst, it is characterised in that: including active component and carrier, described active component includes Cu and Zr.
2. sec-butyl acetate hydrogenation catalyst according to claim 1, it is characterised in that: in described active component, the mass ratio of Cu and Zr is 10: 1��30: 1.
3. sec-butyl acetate hydrogenation catalyst according to claim 1, it is characterised in that: described active constituent loading is to the silica supports modified containing calcium oxide.
4. sec-butyl acetate hydrogenation catalyst according to claim 1, it is characterised in that: described active component is the soluble metallic salt of Cu and Zr.
5. the preparation method of the sec-butyl acetate hydrogenation catalyst according to any one of Claims 1-4, it is characterised in that: concrete steps include:
1) under deposition condition, the soluble metallic salt of active component is dissolved in water, after being subsequently adding precipitant and carrier, raise temperature, after back flow reaction a period of time, generate precipitation;
2) by step 1) in precipitation through filtering, washing, after dry and roasting, obtain described sec-butyl acetate hydrogenation catalyst.
6. preparation method according to claim 5, it is characterised in that: described precipitant is alkali-metal hydroxide, alkali-metal carbonate or carbamide.
7. preparation method according to claim 5, it is characterised in that: described step 2) in dry condition be 60-150 DEG C, the time is 2-24h, and the condition of roasting is that temperature is 200-600 DEG C, and the time is 2-12h.
8. the sec-butyl acetate hydrogenation catalyst according to any one of the Claims 1-4 application in sec-butyl acetate preparation of ethanol through hydrogenation and sec-butyl alcohol are reacted, it is characterized in that: first sec-butyl acetate hydrogenation catalyst is reduced in a hydrogen atmosphere, reduction temperature is 150-400 DEG C, reduction pressure is normal pressure, and the recovery time is 2-12h; Then reactant sec-butyl acetate is introduced, carry out hydrogenation reaction at catalyst surface.
9. application according to claim 8, it is characterised in that: the reaction temperature of described hydrogenation reaction is 150-250 DEG C, and reaction pressure is 2-6MPa, and hydrogen and sec-butyl acetate mol ratio are 5-300, and ester air speed is 0.5-1.5h-1��
10. application according to claim 8, it is characterised in that: the reaction temperature of described hydrogenation reaction is 190-250 DEG C, and reaction pressure is 4-6MPa, and hydrogen and sec-butyl acetate mol ratio are 15-30, and ester air speed is 0.5-1.0h-1��
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569618A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | The method of catalyst for acetate low temperature hydrogenation and preparation method thereof and acetic acid ester through hydrogenation alcohol |
| CN111036218A (en) * | 2019-12-19 | 2020-04-21 | 山东京博石油化工有限公司 | Catalyst for sec-butyl acetate hydrogenation reaction and preparation method and application thereof |
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| CN101934228A (en) * | 2010-09-30 | 2011-01-05 | 江苏丹化煤制化学品工程技术有限公司 | Catalyst for preparing alcohol by acetic ester hydrogenation as well as preparation method and application thereof |
| CN103170352A (en) * | 2013-03-28 | 2013-06-26 | 湖南长岭石化科技开发有限公司 | Sec-butyl acetate hydrogenation catalyst and preparation method and application thereof |
| CN103172492A (en) * | 2011-12-23 | 2013-06-26 | 北京石油化工学院 | Preparation method of sec-butyl alcohol |
| US20130211150A1 (en) * | 2012-02-10 | 2013-08-15 | Celanese International Corporation | Chemisorption of Ethyl Acetate During Hydrogenation of Acetic Acid to Ethanol |
| CN103566933A (en) * | 2012-08-08 | 2014-02-12 | 中国石油化工股份有限公司 | Catalyst for preparing alcohol by acetate hydrogenation as well as preparation method thereof |
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- 2014-11-26 CN CN201410692710.5A patent/CN105618062A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101934228A (en) * | 2010-09-30 | 2011-01-05 | 江苏丹化煤制化学品工程技术有限公司 | Catalyst for preparing alcohol by acetic ester hydrogenation as well as preparation method and application thereof |
| CN103172492A (en) * | 2011-12-23 | 2013-06-26 | 北京石油化工学院 | Preparation method of sec-butyl alcohol |
| US20130211150A1 (en) * | 2012-02-10 | 2013-08-15 | Celanese International Corporation | Chemisorption of Ethyl Acetate During Hydrogenation of Acetic Acid to Ethanol |
| CN103566933A (en) * | 2012-08-08 | 2014-02-12 | 中国石油化工股份有限公司 | Catalyst for preparing alcohol by acetate hydrogenation as well as preparation method thereof |
| CN103170352A (en) * | 2013-03-28 | 2013-06-26 | 湖南长岭石化科技开发有限公司 | Sec-butyl acetate hydrogenation catalyst and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569618A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | The method of catalyst for acetate low temperature hydrogenation and preparation method thereof and acetic acid ester through hydrogenation alcohol |
| CN111036218A (en) * | 2019-12-19 | 2020-04-21 | 山东京博石油化工有限公司 | Catalyst for sec-butyl acetate hydrogenation reaction and preparation method and application thereof |
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Application publication date: 20160601 |