CN103880661A - Method of preparing ethyl acetate by catalyzing alcohol to directly dehydrogenize - Google Patents

Method of preparing ethyl acetate by catalyzing alcohol to directly dehydrogenize Download PDF

Info

Publication number
CN103880661A
CN103880661A CN201410089186.2A CN201410089186A CN103880661A CN 103880661 A CN103880661 A CN 103880661A CN 201410089186 A CN201410089186 A CN 201410089186A CN 103880661 A CN103880661 A CN 103880661A
Authority
CN
China
Prior art keywords
ethyl acetate
sba
prepared
catalyzer
catalyst
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
Application number
CN201410089186.2A
Other languages
Chinese (zh)
Other versions
CN103880661B (en
Inventor
高德志
殷恒波
冯永海
朱晓燕
王爱丽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu University
Original Assignee
Jiangsu University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jiangsu University filed Critical Jiangsu University
Priority to CN201410089186.2A priority Critical patent/CN103880661B/en
Publication of CN103880661A publication Critical patent/CN103880661A/en
Application granted granted Critical
Publication of CN103880661B publication Critical patent/CN103880661B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a method of preparing ethyl acetate by catalyzing alcohol to directly dehydrogenize, and belongs to the technical field of chemical catalysis. The method applies a Cu-SBA(soybean agglutinin)-15 catalyst to catalyze alcohol to directly dehydrogenize to synthesize ethyl acetate at 220 DEG C-300 DEG C under gas-phase normal pressure, wherein the Cu-SBA-15 catalyst is prepared by an isovolumetric impregnation method, and materials are Cu(NO3)2.3H2O and SBA-15 molecular sieve. Compared with the conventional method of synthesizing ethyl acetate by alcohol and acetate, the alcohol direct-dehydrogenation method has the advantages of being low in cost, small in equipment corrosion, free of toxicity, and the like; and moreover, the catalyst used in the method disclosed by the invention is novel, and has higher catalytic activity and stability.

Description

A kind of catalysis ethanol direct dehydrogenation is prepared the method for ethyl acetate
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 catalyzer 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 cellulose acetate, ethyl cellulose, chlorinated rubber, the field of industrial productions such as ethenoid resin; In addition, also can be used as sizing agent, medicine and organic acid extraction agent and fruity perfume base etc.
Ethyl acetate is as the efficient green solvent of one, sustainable growth in industrial 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 synthesis method of acetic acid and ethanol; Ethene and acetic acid heteropoly acid catalysis synthesis method; The direct catalytic dehydrogenation method of the aluminum ethylate catalysis synthesis process of acetaldehyde and ethanol; Above-mentioned first three kind ethyl acetate synthesis 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 nontoxicity, 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 that russian patent SU 327162 introduces, the transformation efficiency of ethanol is no more than 33%; The Cu-Zn-Al-Zr catalyst system that Chinese patent CN1062304 adopts, the transformation efficiency of ethanol is only 42%.So prepare ethyl acetate from the direct catalytic dehydrogenation of ethanol, the efficient catalyzer of development of new seems particularly important.
Summary of the invention
The present invention is intended to develop the catalyzer of a kind of high reactivity and highly selective, 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 reactor, 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 support of the catalyst, used catalyst of the present invention is Cu-SBA-15, the wherein load 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 (NO 3) 2﹒ 3H 2o, as copper source, than composition requirement, takes the Cu (NO of respective amount according to the quality of catalyzer 3) 2﹒ 3H 2o is mixed with the aqueous solution, adds carrier S BA-15 incipient impregnation 8 h at normal temperatures, makes CuO content and be respectively the Cu-SBA-15 catalyzer of 5%-20%; Sample dried overnight at 120 ℃ after dipping, 550 ℃ of roasting 4 h, by sample compressing tablet, are sieved into 40-60 object particle, make catalyst Precursors.
(2) catalyst Precursors is carried out in the gas mixture of rare gas element and hydrogen to reduction activation pre-treatment, under 0.1 MPa pressure, with 1.5 ℃/min temperature programming to 200 ℃, H in this section of process gas mixture 2volume fraction is 10%; Again with 1.0 ℃/min temperature programming to 280 ℃, H in this process 2volume fraction is adjusted to 30%, reduces 3 h at 280 ℃ of constant temperature, obtains the catalyzer after reduction.
(3) ethanolic soln is entered after 180 ℃ of vaporizations to fixed-bed reactor (long 20 cm that are mounted with reducing catalyst described in step (2), internal diameter 0.8cm) in carry out vapor catalytic dehydrogenation reaction, wherein loaded catalyst is 3～8 g, sample introduction flow velocity 10 mL/h, carrier gas N 2flow velocity is 80 ml/min, and reaction is carried out under normal pressure, 220～300 ℃ of temperature of reaction, and to 1 h of serial sampling 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 reaction process; For example, use catalyzer of the present invention, at liquid phase air speed 0.5 h -1, normal pressure, under 280～300 ℃ of reaction conditionss, the per pass conversion of ethanol is up to 76%, and the selectivity of ethyl acetate reaches 70%.
embodiment:
Below in conjunction with concrete embodiment, the present invention will be further described:
embodiment 1
the preparation of catalyzer:
Cu-SBA-15(CuO:SBA-15=5:95, W/W) catalyzer prepared by equi-volume impregnating: the dipping volume of first measuring carrier MCM-41; According to the composition requirement of catalyzer, take the raw material Cu (NO of respective quality 3) 23H 2o 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 ℃, 550 ℃ of roasting 4h, and by sample compressing tablet, catalyst Precursors is made in screening.
the activating pretreatment of catalyzer:
Adopt fixed-bed reactor (long 20 cm, internal diameter 0.8cm), loaded catalyst 5 g catalyzer, feed ethanol enters stainless steel tube shape reactor (long 20 cm, internal diameter 0.8cm) reaction after gasification; Before active testing, catalyzer is first used H 2-N 2(10:90, V/V, 250 ml/min) gas mixture carries out reduction activation, under 0.1 MPa pressure, with 1.5 ℃/min temperature programming to 200 ℃; Again with 1.0 ℃/min temperature programming to 280 ℃, H in this section of reduction process 2volume fraction is 30%, and reduces 3 h at 280 ℃ of constant temperature.
ethanol gas phase Oxidative Dehydrogenation is for ethyl acetate:
Under normal pressure, ethanolic soln is transported to the speed of 10 ml/h in the vaporizing chamber of above-mentioned fixed-bed reactor, after 180 ℃ of vaporizations, enters reactor reaction, keep N 2flow velocity is 80 ml/min, investigates temperature of reaction and is respectively 220,240, and 260,280,300 ℃, serial sampling 1 h at given temperature, product is collected in water-bath condensation, and gas chromatograph for product (marker method) is analyzed, and test result is in table 1.
Table 1 Cu-SBA-15(5:95) catalysis ethanol products of dehydrogenation reactions selectivity and feed stock conversion
Figure 615582DEST_PATH_IMAGE002
embodiment 2
With embodiment 1, be 10:90 but change the mass ratio of CuO and SBA-15 in catalyzer, acquired results is in table 2.
Table 2 Cu-SBA-15(10:90) catalysis ethanol products of dehydrogenation reactions selectivity and feed stock conversion
Figure 532722DEST_PATH_IMAGE004
embodiment 3
With embodiment 1, be 20:80 but change the mass ratio of CuO and SBA-15 in catalyzer, acquired results is in table 3.
Table 3 Cu-SBA-15(20:80) catalysis ethanol products of dehydrogenation reactions selectivity and feed stock conversion
Figure 843618DEST_PATH_IMAGE006

Claims (8)

1. a catalysis ethanol direct dehydrogenation is prepared the method for ethyl acetate, it is characterized in that: described catalyzer is Cu-SBA-15, using SBA-15 molecular screen material as carrier, CuO loads on SBA-15 molecular screen material and forms catalyst Precursors, catalyst Precursors forms catalyzer, wherein the load quality scope of CuO: 5wt%～20wt% in catalyst Precursors through reduction activation pre-treatment again.
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 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 (NO 3) 2﹒ 3H 2o, as copper source, than composition requirement, takes the Cu (NO of respective amount according to the quality of catalyzer 3) 2﹒ 3H 2o is mixed with the aqueous solution, adds carrier S BA-15 incipient impregnation 8 h at normal temperatures, makes CuO content and be respectively the Cu-SBA-15 catalyzer of 5wt%-20wt%; The rear sample drying of dipping spends the night, roasting, by sample compressing tablet, is sieved into particle, makes catalyst Precursors;
(2) catalyst Precursors is carried out in the gas mixture of rare gas element and hydrogen to reduction activation pre-treatment, under 0.1 MPa pressure, with 1.5 ℃/min temperature programming to 200 ℃, H in this section of process gas mixture 2volume fraction is 10%; Again with 1.0 ℃/min temperature programming to 280 ℃, H in this process 2volume fraction is adjusted to 30%, reduces 3 h at 280 ℃ of constant temperature, obtains the catalyzer after reduction.
3. a kind of catalysis ethanol direct dehydrogenation as claimed in claim 2 is prepared the method for ethyl acetate, it is characterized in that: after described dipping, sample drying spends the night, roasting refers to: sample dried overnight at 120 ℃ after dipping, 550 ℃ of roasting 4 h, described particle is 40-60 order.
4. 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 preparation method is as follows: ethanolic soln is entered after 180 ℃ of vaporizations and in the fixed-bed reactor that are mounted with described reducing catalyst, carry out vapor catalytic dehydrogenation reaction, wherein loaded catalyst is 3～8 g, sample introduction flow velocity 10 mL/h, carrier gas N 2flow velocity is 80 ml/min, and reaction is carried out under normal pressure, 220～300 ℃ of temperature of reaction, and to 1 h of serial sampling under fixed temperature, product is collected in ice-water bath condensation.
5. a kind of catalysis ethanol direct dehydrogenation as claimed in claim 4 is prepared the method for ethyl acetate, it is characterized in that: described temperature of reaction is 280～300 ℃.
6. a kind of catalysis ethanol direct dehydrogenation as claimed in claim 4 is prepared the method for ethyl acetate, it is characterized in that: described catalysts loadings is 5 g.
7. under a kind of ordinary-pressure gas-phase as claimed in claim 4, catalysis ethanol direct dehydrogenation is prepared the method for ethyl acetate, it is characterized in that: described fixed-bed reactor are stainless steel tubulose reactor, long 20 cm, internal diameter 0.8cm.
8. a kind of catalysis ethanol direct dehydrogenation as claimed in claim 1 is prepared the method for ethyl acetate, it is characterized in that: in catalyst Precursors, the load quality of CuO is 20wt%.
CN201410089186.2A 2014-03-12 2014-03-12 A kind of catalysis ethanol direct dehydrogenation is prepared the method for ethyl acetate Expired - Fee Related CN103880661B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410089186.2A CN103880661B (en) 2014-03-12 2014-03-12 A kind of catalysis ethanol direct dehydrogenation is prepared the method for ethyl acetate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410089186.2A CN103880661B (en) 2014-03-12 2014-03-12 A kind of catalysis ethanol direct dehydrogenation is prepared the method for ethyl acetate

Publications (2)

Publication Number Publication Date
CN103880661A true CN103880661A (en) 2014-06-25
CN103880661B CN103880661B (en) 2016-05-25

Family

ID=50949831

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410089186.2A Expired - Fee Related CN103880661B (en) 2014-03-12 2014-03-12 A kind of catalysis ethanol direct dehydrogenation is prepared the method for ethyl acetate

Country Status (1)

Country Link
CN (1) CN103880661B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106748753A (en) * 2016-12-28 2017-05-31 江苏扬农化工集团有限公司 The method of ethanol ethyl acetate coproduction arylamine
CN108276290A (en) * 2017-02-07 2018-07-13 江苏扬农化工集团有限公司 A kind of method that hydrogen migration method prepares chloro arylamine coproduction ethyl acetate
CN110171803A (en) * 2019-04-29 2019-08-27 上海电气集团股份有限公司 A kind of ethanol hydrogen production method and system
CN116196869A (en) * 2023-01-04 2023-06-02 泰兴金江化学工业有限公司 Production equipment and production method of ethyl acetate

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102553592A (en) * 2012-03-18 2012-07-11 吉林大学 High-dispersion silicon-loaded Cu-based catalyst and preparation method thereof
US20120178962A1 (en) * 2009-10-20 2012-07-12 Greenyug, Llc Ethyl Acetate Production

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120178962A1 (en) * 2009-10-20 2012-07-12 Greenyug, Llc Ethyl Acetate Production
CN102553592A (en) * 2012-03-18 2012-07-11 吉林大学 High-dispersion silicon-loaded Cu-based catalyst and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106748753A (en) * 2016-12-28 2017-05-31 江苏扬农化工集团有限公司 The method of ethanol ethyl acetate coproduction arylamine
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
CN108276290A (en) * 2017-02-07 2018-07-13 江苏扬农化工集团有限公司 A kind of method that hydrogen migration method prepares chloro arylamine coproduction ethyl acetate
CN110171803A (en) * 2019-04-29 2019-08-27 上海电气集团股份有限公司 A kind of ethanol hydrogen production method and system
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
CN116196869A (en) * 2023-01-04 2023-06-02 泰兴金江化学工业有限公司 Production equipment and production method of ethyl acetate
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

Also Published As

Publication number Publication date
CN103880661B (en) 2016-05-25

Similar Documents

Publication Publication Date Title
CN102716744B (en) Preparation method for synthesizing copper-based catalyst by sol-gel ammonia still process
CN103172516B (en) Method for producing methyl methoxyacetate by methylal vapor-phase carbonylation by using supported heteropoly acid catalyst
CN103769094B (en) A kind of egg-shell catalyst for selective hydrogenation, preparation method and application
CN103008001B (en) Fischer-Tropsch synthesis catalyst comprising composite molecular sieve, and preparation method and application thereof
CN108620127B (en) Catalyst for preparing 1, 5-pentanediol through hydrogenolysis of tetrahydrofurfuryl alcohol, preparation method and application thereof
CN103007982B (en) Fischer-Tropsch synthesis catalyst comprising zeolite molecular sieve, and preparation method and application thereof
KR101855876B1 (en) Method for producing ethanol and coproducing methanol
CN103880661B (en) A kind of catalysis ethanol direct dehydrogenation is prepared the method for ethyl acetate
CN111514925B (en) Catalyst for co-production of methyl acetate and acetone from dimethyl ether, preparation method and application thereof
Silbaugh et al. Selective oxidation of ethanol over Ag, Cu and Au nanoparticles supported on Li2O/γ-Al2O3
CN106866360A (en) A kind of method that 5 hydroxymethyl furfural catalyzed conversion prepares 1,6-HD
CN103894228A (en) Catalyst used for producing methyl methoxyacetate, and preparation method thereof
JP2010180156A (en) Process for producing lower saturated aldehyde from 1,2-diol
CN105312044B (en) C6~C10 dehydration of alcohols prepares the catalyst of corresponding carbon number
CN105859555A (en) Method for preparing methyl formate from methyl alcohol through dehydrogenation conducted at normal pressure
CN106673977B (en) A kind of ethyl alcohol direct dehydrogenation prepares the catalyst of acetaldehyde, preparation method and applications
CN102173977B (en) Cu/Al2O3 catalyst and preparation method thereof as well as method for catalyzing hydrolysis of glycerol
CN102153446B (en) Cu/MgO catalyst, preparation method thereof and method for catalyzing glycerin hydrogenolysis
CN101530805B (en) Catalyst for preparing tert-olefins by cracking tert-alkyl ethers, preparation method and application thereof
CN103008000B (en) Fischer-Tropsch synthesis catalyst comprising non-zeolite molecular sieve, and preparation method and application thereof
CN103880660B (en) Under a kind of ordinary-pressure gas-phase, catalysis ethanol direct dehydrogenation is prepared the method for ethyl acetate
CN109622031A (en) The preparation method of 2- hydroxyphosphonoacetic acid zirconium and its application in furfuryl alcohol synthesis
CN104672058A (en) Method of preparing 1, 3-propanediol by virtue of hydrogenation of glycerol
CN103880662A (en) Preparation method for preparing ethyl acetate by directly dehydrogenizing ethanol
CN106281526A (en) A kind of two-step method prepares the method for liquefied petroleum gas

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: 20160525

Termination date: 20170312

CF01 Termination of patent right due to non-payment of annual fee