CN103880661B - A kind of catalysis ethanol direct dehydrogenation is prepared the method for ethyl acetate - Google Patents
A kind of catalysis ethanol direct dehydrogenation is prepared the method for ethyl acetate Download PDFInfo
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- CN103880661B CN103880661B CN201410089186.2A CN201410089186A CN103880661B CN 103880661 B CN103880661 B CN 103880661B CN 201410089186 A CN201410089186 A CN 201410089186A CN 103880661 B CN103880661 B CN 103880661B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
- C07C67/40—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0356—Iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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Abstract
The present invention relates to a kind of catalysis ethanol direct dehydrogenation and prepare the method for ethyl acetate, belong to chemical industry catalysis technical field. The present invention uses Cu-SBA-15 catalyst, catalysis ethanol direct dehydrogenation synthesizing ethyl acetate at 220～300 DEG C of ordinary-pressure gas-phases, and Cu-SBA-15 catalyst is prepared by equi-volume impregnating, and raw material is Cu (NO3)2·3H2O and SBA-15 molecular sieve; With traditional being compared with acid esterification synthesizing ethyl acetate by ethanol, ethanol direct dehydrogenation has that cost is low, equipment corrosion is little and the advantage such as non-toxic, and used catalyst novelty in the present invention, has higher catalytic activity and stability.
Description
Technical field
The present invention relates to ethyl acetate, belong to chemical industry catalysis technical field, refer in particular under ordinary-pressure gas-phase condition, adopt catalyst to carry out ethanol direct dehydrogenation and prepare ethyl acetate.
Technical background
Ethyl acetate is one of most widely used fatty acid ester, has good solubility property, is widely used in acetate fiber, ethyl cellulose, chlorinated rubber, the field of industrial productions such as vinyl; In addition, also can be used as adhesive, medicine and organic acid extractant and fruity perfume base etc.
Ethyl acetate is as the efficient green solvent of one, sustainable growth in commercial Application at home and abroad, and along with the development of global economy, the demand of ethyl acetate is increasing; The synthetic route of ethyl acetate mainly contains the acid catalyzed esterification synthetic method of acetic acid and ethanol; Ethene and acetic acid heteropoly acid catalysis synthetic method; The direct catalytic dehydrogenation method of the aluminium ethylate catalysis synthesis process of acetaldehyde and ethanol; Above-mentioned first three kind ethyl acetate synthetic method belongs to traditional preparation method, there is equipment corrosion, invests the problems such as large and environmental pollution; Compared with traditional preparation method, the direct catalytic dehydrogenation of ethanol prepares that ethyl acetate has that cost is low, equipment corrosion is little and the advantage such as non-toxic, but exists at present the catalytic activity of process system used catalyst not high, the problem that selectivity of product is poor; The Cu-Zn-Al catalyst system and catalyzing that Russian Patent SU 327162 introduces, the conversion ratio of ethanol is no more than 33%; The Cu-Zn-Al-Zr catalyst system and catalyzing that Chinese patent CN1062304 adopts, the conversion ratio of ethanol is only 42%. So prepare ethyl acetate from the direct catalytic dehydrogenation of ethanol, the efficient catalyst of development of new seems particularly important.
Summary of the invention
The present invention is intended to develop the catalyst of a kind of high activity and high selectivity, prepares ethyl acetate for the direct catalytic dehydrogenation of ethanol.
The said ethanol direct dehydrogenation of the present invention is prepared the method for ethyl acetate, and reaction, in fixed bed reactors, is carried out under the condition of ordinary-pressure gas-phase.
The well-regulated pore passage structure of SBA-15 molecular screen material tool and compared with bigger serface, extremely be suitable as catalyst carrier, used catalyst of the present invention is Cu-SBA-15, the wherein loading range of CuO: 5wt%～20wt% in catalyst Precursors, Cu-SBA-15 catalysis ethanol Oxidative Dehydrogenation, for ethyl acetate, comprises the following steps:
(1) first measure the dipping volume of carrier S BA-15, adopt Cu (NO3)2﹒3H2O, as copper source, than composition requirement, takes the Cu (NO of respective amount according to the quality of catalyst3)2﹒3H2O is mixed with the aqueous solution, adds carrier S BA-15 incipient impregnation 8h at normal temperatures, makes CuO content and be respectively the Cu-SBA-15 catalyst of 5%-20%; Sample dried overnight at 120 DEG C after dipping, 550 DEG C of roasting 4h, by sample compressing tablet, are sieved into 40-60 object particle, make catalyst Precursors.
(2) catalyst Precursors is carried out in the gaseous mixture of inert gas and hydrogen to reduction activation pretreatment, under 0.1MPa pressure, with 1.5 DEG C/min temperature programming to 200 DEG C, H in this section of process gaseous mixture2Volume fraction is 10%; Again with 1.0 DEG C/min temperature programming to 280 DEG C, H in this process2Volume fraction is adjusted to 30%, at 280 DEG C of constant temperature reduction 3h, obtains the catalyst after reduction.
(3) ethanolic solution is entered after 180 DEG C of vaporizations to fixed bed reactors (the long 20cm that is mounted with reducing catalyst described in step (2), internal diameter 0.8cm) in carry out vapor catalytic dehydrogenation reaction, wherein loaded catalyst is 3～8g, sample introduction flow velocity 10mL/h, carrier gas N2Flow velocity is 80ml/min, and reaction is carried out under normal pressure, 220～300 DEG C of reaction temperatures, and to continuous sampling 1h under fixed temperature, product is collected in ice-water bath condensation.
Distinguishing feature of the present invention is that adopted Catalysts Cu-SBA-15 preparation technology is simple, has good catalytic activity and stability in course of reaction; For example, use catalyst of the present invention, at liquid phase air speed 0.5h-1, normal pressure, under 280～300 DEG C of reaction conditions, the conversion per pass of ethanol is up to 76%, ethyl acetate selectively reach 70%.
Detailed description of the invention:
Below in conjunction with concrete embodiment, the present invention will be further described:
Embodiment 1
The preparation of catalyst:
Cu-SBA-15(CuO:SBA-15=5:95, W/W) catalyst prepared by equi-volume impregnating: the dipping volume of first measuring carrier MCM-41; According to the composition requirement of catalyst, take the raw material Cu (NO of respective quality3)2·3H2O and SBA-15 carry out incipient impregnation, and the mass content that makes CuO in catalyst sample is 5%, and sample is dried overnight at 120 DEG C, 550 DEG C of roasting 4h, and by sample compressing tablet, catalyst Precursors is made in screening.
The activating pretreatment of catalyst：
Adopt fixed bed reactors (long 20cm, internal diameter 0.8cm), loaded catalyst 5g catalyst, feed ethanol enters stainless steel tube shape reactor (long 20cm, internal diameter 0.8cm) reaction after gasification; Before active testing, catalyst is first used H2-N2(10:90, V/V, 250ml/min) gaseous mixture carries out reduction activation, under 0.1MPa pressure, with 1.5 DEG C/min temperature programming to 200 DEG C; Again with 1.0 DEG C/min temperature programming to 280 DEG C, H in this section of reduction process2Volume fraction is 30%, and at 280 DEG C of constant temperature reduction 3h.
Ethanol gas phase Oxidative Dehydrogenation is for ethyl acetate:
Under normal pressure, ethanolic solution is transported to the speed of 10ml/h in the vaporizer of above-mentioned fixed bed reactors, after 180 DEG C of vaporizations, enters reactor reaction, keep N2Flow velocity is 80ml/min, investigates reaction temperature and is respectively 220,240, and 260,280,300 DEG C, continuous sampling 1h at given temperature, product is collected in water-bath condensation, and gas chromatograph for product (internal standard method) is analyzed, and test result is in table 1.
Table 1Cu-SBA-15(5:95) the selective and feed stock conversion of catalysis ethanol products of dehydrogenation reactions
Embodiment 2
With embodiment 1, be 10:90 but change the mass ratio of CuO and SBA-15 in catalyst, acquired results is in table 2.
Table 2Cu-SBA-15(10:90) the selective and feed stock conversion of catalysis ethanol products of dehydrogenation reactions
Embodiment 3
With embodiment 1, be 20:80 but change the mass ratio of CuO and SBA-15 in catalyst, acquired results is in table 3.
Table 3Cu-SBA-15(20:80) the selective and feed stock conversion of catalysis ethanol products of dehydrogenation reactions
Claims (6)
1. catalysis ethanol direct dehydrogenation is prepared a method for ethyl acetate, and described catalyst is Cu-SBA-15, with SBA-15 moleculeSieve material, as carrier, is characterized in that: by incipient impregnation, CuO is loaded on to SBA-15 molecular sieve material at normal temperaturesOn material, form catalyst Precursors, catalyst Precursors forms catalyst, wherein CuO in catalyst Precursors through reduction activation pretreatment againLoad quality mark be 20wt%, the preparation method of described Catalysts Cu-SBA-15 is as follows:
(1) first measure the dipping volume of carrier S BA-15, adopt Cu (NO3)2﹒3H2O is as copper source, according to the matter of catalystAmount, than composition requirement, takes the Cu (NO of respective amount3)2﹒3H2O is mixed with the aqueous solution, adds carrier S BA-15 at normal temperaturesIncipient impregnation 8h, making CuO content is the Cu-SBA-15 catalyst of 20wt%; After dipping, sample drying spends the night, roastsBurn, by sample compressing tablet, be sieved into particle, make catalyst Precursors;
(2) catalyst Precursors is carried out in the gaseous mixture of inert gas and hydrogen to reduction activation pretreatment, under 0.1MPa pressure,With 1.5 DEG C/min temperature programming to 200 DEG C, H in this section of process gaseous mixture2Volume fraction is 10%; Again with 1.0 DEG C/minTemperature programming to 280 DEG C, H in this process2Volume fraction is adjusted to 30%, at 280 DEG C of constant temperature reduction 3h, obtains after reductionCatalyst.
2. a kind of catalysis ethanol direct dehydrogenation as claimed in claim 1 is prepared the method for ethyl acetate, it is characterized in that: described in soakThe rear sample drying of stain spends the night, roasting refers to: sample dried overnight at 120 DEG C after dipping, 550 DEG C of roasting 4h, described particleFor 40-60 order.
3. a kind of catalysis ethanol direct dehydrogenation as claimed in claim 1 is prepared the method for ethyl acetate, it is characterized in that concrete preparationMethod is as follows: ethanolic solution is entered in the fixed bed reactors that are mounted with described reducing catalyst and carried out after 180 DEG C of vaporizationsVapor catalytic dehydrogenation reaction, wherein loaded catalyst is 3～8g, sample introduction flow velocity 10mL/h, carrier gas N2Flow velocity is 80Ml/min, reaction is carried out under normal pressure, 220～300 DEG C of reaction temperatures, to continuous sampling 1h under fixed temperature, ice-water bath is coldThe solidifying product of collecting.
4. a kind of catalysis ethanol direct dehydrogenation as claimed in claim 3 is prepared the method for ethyl acetate, it is characterized in that: described anti-Answering temperature is 280～300 DEG C.
5. a kind of catalysis ethanol direct dehydrogenation as claimed in claim 3 is prepared the method for ethyl acetate, it is characterized in that: described anti-Answering loaded catalyst is 5g.
6. under a kind of ordinary-pressure gas-phase as claimed in claim 3, catalysis ethanol direct dehydrogenation is prepared the method for ethyl acetate, and its feature existsIn: described fixed bed reactors are stainless steel tubulose reactor, long 20cm, internal diameter 0.8cm.
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| CN106748753B (en) * | 2016-12-28 | 2019-04-12 | 江苏扬农化工集团有限公司 | The method of ethyl alcohol ethyl acetate coproduction arylamine |
| CN108276290B (en) * | 2017-02-07 | 2020-11-27 | 江苏扬农化工集团有限公司 | Method for preparing chloroarylamine and co-producing ethyl acetate by hydrogen transfer method |
| CN110171803B (en) * | 2019-04-29 | 2022-11-01 | 上海电气集团股份有限公司 | Method and system for preparing hydrogen from ethanol |
| CN116196869B (en) * | 2023-01-04 | 2023-10-10 | 泰兴金江化学工业有限公司 | Production equipment and production method of ethyl acetate |
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| CN102553592A (en) * | 2012-03-18 | 2012-07-11 | 吉林大学 | High-dispersion silicon-loaded Cu-based catalyst and preparation method thereof |
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