CN103880662A - Preparation method for preparing ethyl acetate by directly dehydrogenizing ethanol - Google Patents
Preparation method for preparing ethyl acetate by directly dehydrogenizing ethanol Download PDFInfo
- Publication number
- CN103880662A CN103880662A CN201410089202.8A CN201410089202A CN103880662A CN 103880662 A CN103880662 A CN 103880662A CN 201410089202 A CN201410089202 A CN 201410089202A CN 103880662 A CN103880662 A CN 103880662A
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- Prior art keywords
- ethyl acetate
- preparation
- ethanol
- prepared
- catalyzer
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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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing ethyl acetate by directly dehydrogenizing ethanol, belonging to the technical field of chemical catalysis. In the method, ethyl acetate is prepared by directly dehydrogenizing ethanol in the presence of Cu/Ca10(PO4)6(OH)2 serving as a catalyst under a gas-phase normal-pressure condition. Compared with the conventional way of synthesizing ethyl acetate by esterfying ethanol and acetic acid, the method of direct dehydrogenization of ethanol has the advantages of low cost, low equipment corrosion, nontoxicity and the like. Moreover, the catalyst used in the method is novel, and high selectivity and high yield are achieved.
Description
Technical field
The present invention relates to a kind of method of preparing ethyl acetate, belong to chemical industry catalysis technical field, refer in particular under ordinary-pressure gas-phase condition, adopt Cu/Ca
10(PO
4)
6(OH)
2catalyzer carries out ethanol direct dehydrogenation and prepares 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 method of ethyl acetate is prepared in the direct catalytic dehydrogenation of the said ethanol of the present invention, and reaction, in fixed-bed reactor, is carried out under the condition of ordinary-pressure gas-phase.
Used catalyst of the present invention is Cu/Ca
10(PO
4)
6(OH)
2, the wherein load range of CuO: 5wt%～20wt% in catalyst Precursors, Cu/Ca
10(PO
4)
6(OH)
2catalysis ethanol Oxidative Dehydrogenation, for ethyl acetate, comprises the following steps:
(1) first measure support C a
10(PO
4)
6(OH)
2dipping volume; 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 support C a
10(PO
4)
6(OH)
2incipient impregnation 8 h at normal temperatures, make CuO content and are respectively the Cu/Ca of 5wt%-20wt%
10(PO
4)
6(OH)
2catalyzer; 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) by catalyst Precursors in the hydrogen of hydrogen or inert gas dilution, 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 in the fixed-bed reactor that are mounted with reducing catalyst described in step (2) and carries out vapor catalytic dehydrogenation reaction after 180 ℃ of vaporizations, 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 adopted Catalysts Cu/Ca
10(PO
4)
6(OH)
2preparation 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 83%.
embodiment:
Below in conjunction with concrete embodiment, the present invention will be further described:
embodiment 1
the preparation of catalyzer:
Cu/Ca
10(PO
4)
6(OH)
2(CuO:Ca
10(PO
4)
6(OH)
2=5:95, W/W) catalyzer prepared by equi-volume impregnating: first measure support C a
10(PO
4)
6(OH)
2dipping volume, according to the composition requirement of catalyzer, take the raw material Cu (NO of respective quality
3)
23H
2o and Ca
10(PO
4)
6(OH)
2carry out incipient impregnation, 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, loaded catalyst 5 g catalyzer, feed ethanol enters stainless steel tube shape reactor (long 20 cm, internal diameter 0.8cm) reaction after gasification, and 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 ℃, takes notice of 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, and the method can be reduced to zerovalent copper by the cupric in catalyzer more thoroughly.
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/ Ca
10(PO
4)
6(OH)
2(5:95) catalysis ethanol products of dehydrogenation reactions selectivity and feed stock conversion
embodiment 2
With embodiment 1, but change CuO and Ca in catalyzer
10(PO
4)
6(OH)
2mass ratio be 10:90, acquired results is in table 2.
Table 2 Cu/ Ca
10(PO
4)
6(OH)
2(10:90) catalysis ethanol products of dehydrogenation reactions selectivity and feed stock conversion
embodiment 3
With embodiment 1, but change CuO and Ca in catalyzer
10(PO
4)
6(OH)
2mass ratio be 20:80, acquired results is in table 3.
Table 3 Cu/ Ca
10(PO
4)
6(OH)
2(20:80) catalysis ethanol products of dehydrogenation reactions selectivity and feed stock conversion
Claims (8)
1. ethanol direct dehydrogenation is prepared a preparation method for ethyl acetate, it is characterized in that: described catalyzer is Cu/Ca
10(PO
4)
6(OH)
2, with Ca
10(PO
4)
6(OH)
2as carrier, CuO loads on Ca
10(PO
4)
6(OH)
2upper formation 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 ethanol direct dehydrogenation as claimed in claim 1 is prepared the preparation method of ethyl acetate, it is characterized in that described Catalysts Cu/Ca
10(PO
4)
6(OH)
2preparation method as follows:
(1) first measure support C a
10(PO
4)
6(OH)
2dipping volume; 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 support C a
10(PO
4)
6(OH)
2incipient impregnation 8 h at normal temperatures, make CuO content and are respectively the Cu/Ca of 5wt%-20wt%
10(PO
4)
6(OH)
2catalyzer; The rear sample drying of dipping spends the night, roasting, by sample compressing tablet, is sieved into particle, makes catalyst Precursors;
(2) by catalyst Precursors in the hydrogen of hydrogen or inert gas dilution, 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 ethanol direct dehydrogenation as claimed in claim 2 is prepared the preparation method of 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 ethanol direct dehydrogenation as claimed in claim 1 is prepared the preparation method of 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 ethanol direct dehydrogenation as claimed in claim 4 is prepared the preparation method of ethyl acetate, it is characterized in that: described temperature of reaction is 280～300 ℃.
6. a kind of ethanol direct dehydrogenation as claimed in claim 4 is prepared the preparation method of ethyl acetate, it is characterized in that: described catalysts loadings is 5 g.
7. a kind of ethanol direct dehydrogenation as claimed in claim 4 is prepared the preparation method of 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 ethanol direct dehydrogenation as claimed in claim 1 is prepared the preparation method of ethyl acetate, it is characterized in that: in catalyst Precursors, the load quality of CuO is 20wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410089202.8A CN103880662B (en) | 2014-03-12 | 2014-03-12 | A kind of ethanol direct dehydrogenation prepares the preparation method of ethyl acetate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410089202.8A CN103880662B (en) | 2014-03-12 | 2014-03-12 | A kind of ethanol direct dehydrogenation prepares the preparation method of ethyl acetate |
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|---|---|
| CN103880662A true CN103880662A (en) | 2014-06-25 |
| CN103880662B CN103880662B (en) | 2016-08-24 |
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|---|---|---|---|
| CN201410089202.8A Expired - Fee Related CN103880662B (en) | 2014-03-12 | 2014-03-12 | A kind of ethanol direct dehydrogenation prepares the preparation method of ethyl acetate |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1781899A (en) * | 2004-11-30 | 2006-06-07 | 中国科学院兰州化学物理研究所 | Process for preparing ethyl acetate from ethanol |
| CN101559370A (en) * | 2009-05-27 | 2009-10-21 | 天津大学 | Cu-Cr series ethyl acetate catalyst added with modified additive and manufacturing method thereof |
| WO2013116492A1 (en) * | 2012-02-01 | 2013-08-08 | Greenyug, Llc | Ethyl acetate production |
-
2014
- 2014-03-12 CN CN201410089202.8A patent/CN103880662B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1781899A (en) * | 2004-11-30 | 2006-06-07 | 中国科学院兰州化学物理研究所 | Process for preparing ethyl acetate from ethanol |
| CN101559370A (en) * | 2009-05-27 | 2009-10-21 | 天津大学 | Cu-Cr series ethyl acetate catalyst added with modified additive and manufacturing method thereof |
| WO2013116492A1 (en) * | 2012-02-01 | 2013-08-08 | Greenyug, Llc | Ethyl acetate production |
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| Publication number | Publication date |
|---|---|
| CN103880662B (en) | 2016-08-24 |
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