CN102716739A - Use of catalyst prepared by vacuum method in synthesis of vinyl acetate - Google Patents
Use of catalyst prepared by vacuum method in synthesis of vinyl acetate Download PDFInfo
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- CN102716739A CN102716739A CN2011103839611A CN201110383961A CN102716739A CN 102716739 A CN102716739 A CN 102716739A CN 2011103839611 A CN2011103839611 A CN 2011103839611A CN 201110383961 A CN201110383961 A CN 201110383961A CN 102716739 A CN102716739 A CN 102716739A
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Abstract
The invention provides a use of a catalyst prepared by a vacuum method in synthesis of vinyl acetate. The use is characterized by comprising the following steps of dipping catalyst carriers in solution containing active palladium and gold compounds in vacuum, drying the catalyst carriers dipped with the solution to constant weight to obtain a catalyst precursor, dipping the catalyst precursor in an alkali solution, drying to constant weight, carrying out reduction in a hydrogen protective atmosphere, adding a potassium acetate aqueous solution having a concentration of 10% into the reduced catalyst precursor in vacuum to immerse it, and drying to obtain the catalyst. The catalyst provided by the invention has active metals uniformly distributed on the surface of carriers, and has good catalytic activity and selectivity in a reaction of catalytic synthesis of vinyl acetate from ethylene, acetic acid and oxygen as raw materials.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method, specifically, relate to a kind of method of utilizing the ethylene process of preparing vinyl acetate catalyst, but this catalyst catalyzed ethylene, acetic acid and oxygen obtain vinylacetate through the vapor phase method reaction.
Background technology
With ethene, acetic acid, oxygen is raw material, and the catalytic action through catalyst prepares vinylacetate has become comparatively ripe commercial run.It is raw material that the catalyst that is adopted adopts silica or alundum (Al usually, gets through infusion process supported palladium and gold.It has active preferably, but shortcoming is the accessory substance carbon dioxide that catalytic efficiency is unstable, generation is more.Analyze as follows: the state of metal active constituent and distribution have confidential relation on the performance of catalyst and the carrier; For loaded catalyst; Active component distributes evenly more at carrier surface, and the decentralization of reactive metal is good more, and then activity of such catalysts is high more; Life-span is all long more.Infusion process is that the solution that is dissolved with reactive metal is mixed with porous carrier, makes reactive metal be adsorbed in the surface of carrier, but invades the catalyst that the stain method obtains; Metal is at the skewness of carrier surface; And carrier superficies reactive metal is piled up, and this is mainly from its microcellular structure, when the solution that contains reactive metal contacts with carrier because of the carrier specific area; Because during capillary effect makes that reactive metal solution can not whole micropores of instantaneous entering carrier; But meanwhile, solution metal salt is adsorbed on the superficies of carrier in a large number, when the solution that contains reactive metal has overcome in the micropore that surface tension is penetrated into carrier gradually; Change has taken place in the concentration of the reactive metal in its solution, and promptly the content of reactive metal has been significantly less than initial concentration.This reactive metal not only makes catalytic activity point reduce in the accumulation of carrier outer surface; And be the major reason that causes reactive metal to run off in the catalytic process.Many researchers have done a large amount of useful work in this respect, like US, and 087,622; US 4,048, and 096 makes palladium and golden reactive metal evenly distribute at carrier surface has made useful exploration, and the result proves that this type research is successful to some aspect of performance that improves catalyst.
Summary of the invention
In order to overcome the deficiency of prior art, the object of the invention has been to propose the used Preparation of catalysts method of ethylene process of preparing vinyl acetate, the catalyst of acquisition, and reactive metal is evenly distributed at carrier surface, and has high catalytic activity.
The present invention adopts following technical scheme to realize above purpose of the present invention:
A kind of vacuum method prepares the application of catalyst in synthesizing vinyl acetate, it is characterized in that may further comprise the steps:
S1, catalyst carrier vacuum impregnation reactive metal solution
Get palladium compound, gold compound is dissolved in and is mixed with metallic solution in the polar solvent, and is subsequent use;
Catalyst carrier is vacuumized processing, vacuum is-0.01～-0.09MPa;
Catalyst carrier is immersed in the metallic solution, is dried to constant weight, obtain catalyst precarsor (I);
Described catalyst carrier is silica or alundum (Al;
The load capacity of catalyst carrier is per hundred milliliters of catalyst cupport palladium 1-9g, golden 0.5-4g; Generally speaking, the metallic compound consumption is big more, and the amount that is adsorbed on carrier surface is big more, but carrier loaded amount is greater than per hundred milliliters of palladium catalyst 9g, and golden 4g then because whole micropores of carrier are filled and cause adsorption rate to descend, causes the waste of metallic compound; In like manner, the metallic compound consumption is more little, and the duty factor regular meeting increases, and the amount that all is adsorbed onto carrier surface is more little, and then influences the catalytic efficiency of catalyst.The load capacity of catalyst carrier is preferably per hundred milliliters of catalyst cupport palladium 6.1-8.98g, golden 3.3-3.79g.
The total amount of described metallic solution is the 95-100% of carrier hole capacity;
Described polar solvent is water, ethanol, acetic acid and rare nitric acid;
Described palladium compound is palladium bichloride PdCl
2, palladium Pd (C
2H
3O
2)
2]
3, palladium nitrate Pd (NO
3)
2, palladium sulfate Pd SO
4, tetrachloro closes the sour H of palladium (II)
2PdCl
4, six potassium chloropalladate K
2PdCl
6Any; Said gold compound is chlorauride AuCl
3Tetrachloro alloy acid HAuCl
4Sodium chloraurate NaAuCl
4Potassium chloroaurate KAuCl
4Any.
S2, vacuum impregnation aqueous alkali
The catalyst precarsor (I) that the S1 step is made vacuumizes processing by the S1 step, and catalyst precarsor (I) vacuum suction dipping aqueous slkali left standstill 4-12 hour, was dried to constant weight, obtained catalyst precarsor (II);
Aqueous slkali volume and catalyst precarsor (I) volume ratio is 1-1.2/1;
Wherein the mol ratio of alkali metal amount and porpezite content is 1-10: 1;
Described alkaline solution is selected from any of NaOH, potassium hydroxide, sodium metasilicate, potassium silicate solution;
The reduction of S3, catalyst carrier surface metal
To pass through the catalyst precarsor (I) that step S2 obtains and place quartz ampoule, hydrogen reducing, the reduction after washing is washed, and is dried to constant weight; Described reduction temperature is 400-700, and the recovery time is 2-6 hour;
S4, vacuum impregnation alkali metal acetate solution
The product of S3 step reduction is vacuumized processing by the S1 step, add 10% potassium acetate aqueous solution vacuum impregnation after, obtain catalyst through 1-5 hour drying;
Described liquor kalii acetici volume is the 100-120% of catalyst volume.Liquor kalii acetici plays the effect of solidifying adsorption effect; Traditional method for using is to adopt the solution impregnation that contains the excess potassium acetate; Therefore from the factor of comprehensive solidification effect and economic aspect, selecting the concentration of liquor kalii acetici is 5%-15%, and preferred concentration is 10%; It is not good that concentration is lower than 5% solidification effect, and concentration causes waste greater than 15%.
Catalyst is characterized in that after ethene, acetic acid, oxygen and above-mentioned catalyst mix, under uniform temperature and pressure, making vinylacetate in the application of preparation vinylacetate; Described reaction temperature is 130-170 ℃, is preferably 145 ℃, and pressure is 0.5-1.0MPa, is preferably 0.70MPa.
The present invention accomplishes reactive metal in load, aqueous slkali and the liquor kalii acetici on catalyst carriers such as silica or the alundum (Al surface impregnation process surperficial to catalyst carrier with the solution and the carrier impregnation of active metallic compound under vacuum environment.The catalyst of preparation is compared with conventional method has the advantage that reactive metal is evenly distributed at carrier surface; The state of metal active constituent and distribution have confidential relation on the performance of catalyst and the carrier; For loaded catalyst; Active component distributes evenly more at carrier surface, and the decentralization of reactive metal is good more, and then activity of such catalysts is high more; Life-span is long more.
The specific embodiment
Used metallic compound among the embodiment, carrier are available from Aladdin company; Used chemical reagent, solvent are available from Chemical Reagent Co., Ltd., Sinopharm Group.
Embodiment 1:
Vacuum method prepares the application of catalyst in synthesizing vinyl acetate, may further comprise the steps:
(1), get silica supports 100ml, place two-mouth bottle; Take by weighing the PdCl that contains Pd 3.73g
2With the HAuCl that contains Au 1.98g
4Be dissolved in the 75ml ethanol separatory funnel of packing into; Separatory funnel is installed in the vertical mouthful of two-mouth bottle, with vavuum pump two-mouth bottle is evacuated to negative 0.07MPa after, close vacuum system; Open the separatory funnel valve, make metallic solution rapidly with after carrier contacts, under less than 100 ℃ of conditions; Be dried to constant weight, process catalyst precarsor (I).
(2), take by weighing 5.0g NaOH and be dissolved in and process 5% sodium hydroxide solution in the 100ml water, by above-mentioned steps (1) vacuum pumping, after catalyst precarsor (I) vacuum impregnation, left standstill 4 hours, be dried to constant weight at 100 ℃;
(3), will place quartz ampoule through the catalyst precarsor (I) that step (2) is handled, under hydrogen shield, 400 ℃ of reduction 6 hours, the samples with water washing is taken out in the cooling back, and is dry under less than 150 ℃ of conditions, obtains the metal catalysts precursors through reduction;
(4), take by weighing the 10g potassium acetate and be mixed with the 100ml aqueous solution, adopt the metal catalysts precursors of abovementioned steps (1) vacuum mode impregnation steps (3) through reduction, the dipping back is dried to constant weight under less than 100 ℃ of conditions, obtain catalyst.
Catalyst the preparation vinylacetate application:
The above-mentioned catalyst of 10ml of in tubular fixed-bed reactor, packing into; After the ethene flow transferred to 7mol/h, reaction temperature is risen to 130 ℃, add acetic acid with the 1.2mol/h flow with compression pump; Reaction temperature is controlled at 145 ℃, and reactor inlet pressure is 0.70MPa.Aerating oxygen gradually, oxygen flow is controlled at 0.4mol/h after 40 minutes, uses the cooling device collecting reaction product, ethylene selectivity 94.4%, active 286g vinyl acetate/liters per hour.
Embodiment 2:
Vacuum method prepares the application of catalyst in synthesizing vinyl acetate, may further comprise the steps:
(1), get alumina carrier 100ml and place two-mouth bottle, take by weighing the K that contains Pd 4.2g
2PdCl
6Compound and the 2.3g KAuCl that contains Au
4Compound is dissolved in the 75ml water, the separatory funnel of packing into; Separatory funnel is installed in the vertical mouthful of two-mouth bottle, with vavuum pump two-mouth bottle is evacuated to negative 0.04MPa after, close vacuum system; Open the separatory funnel valve, make metallic solution rapidly with after carrier contacts, under less than 100 ℃ of conditions; Be dried to constant weight, process catalyst precarsor (I).
(2), take by weighing 7.0g potassium hydroxide and process the 110ml aqueous solution, by above-mentioned steps (1) vacuum pumping, after the catalyst precarsor vacuum impregnation, left standstill 8 hours, under 100 ℃ of conditions, be dried to constant weight;
(3), will pass through the catalyst precarsor (I) that step (2) handles and place quartz ampoule, under hydrogen shield, 700 ℃ of reduction 5 hours, the samples with water washing is taken out in the cooling back, and is dry under less than 150 ℃ of conditions;
(4), take by weighing the 10g potassium acetate and be mixed with the 100ml aqueous solution, the metal catalysts precursors that adopts the vacuum mode impregnation steps (3) of abovementioned steps (1) to obtain through reduction, the dipping back is dried to constant weight under less than 100 ℃ of conditions, obtain catalyst.
Catalyst the preparation vinylacetate application:
The above-mentioned catalyst of 10ml of in tubular fixed-bed reactor, packing into, the ethene flow transferred to 7mol/h after, reaction temperature is risen to 130 ℃, add acetic acid with compression pump with the 1.2mol/h flow; Reaction temperature is controlled at 145 ℃, and reactor inlet pressure is 0.70MPa.Aerating oxygen gradually, oxygen flow is controlled at 0.4mol/h after 40 minutes, uses the cooling device collecting reaction product, ethylene selectivity 94.7%, active 313g vinyl acetate/liters per hour.
Embodiment 3:
Vacuum method prepares the application of catalyst in synthesizing vinyl acetate, may further comprise the steps:
(1), get alumina carrier 100ml and place two-mouth bottle, take by weighing and contain Pd 6.10gPdSO
4Compound with contain the AuCl of Au 3.3g
3Compound is dissolved in the 75ml water, the separatory funnel of packing into; Separatory funnel is installed in the vertical mouthful of two-mouth bottle, with vavuum pump two-mouth bottle is evacuated to negative 0.09MPa after, close vacuum system; Open the separatory funnel valve, make metallic solution rapidly with after carrier contacts, under less than 100 ℃ of conditions; Be dried to constant weight, process catalyst precarsor (I).
(2), take by weighing the 10.0g sodium metasilicate and process the 100ml aqueous solution, by above-mentioned steps (1) vacuum pumping, after catalyst precarsor (I) vacuum impregnation, left standstill 12 hours, under 100 ℃ of conditions, be dried to constant weight.
(3), will pass through the catalyst precarsor (I) that step (2) handles and place quartz ampoule, under hydrogen shield, 600 ℃ of reduction 4.6 hours, the samples with water washing is taken out in the cooling back, and is dry under less than 150 ℃ of conditions.
(4), take by weighing the 12g potassium acetate and be mixed with the 120ml aqueous solution, adopt the metal catalysts precursors of the vacuum mode impregnation steps (3) of abovementioned steps (1) through reduction, the dipping back is dried to constant weight under less than 100 ℃ of conditions, obtain catalyst.
Catalyst the preparation vinylacetate application:
The above-mentioned catalyst of 10ml of in tubular fixed-bed reactor, packing into, the ethene flow transferred to 7mo l/h after, reaction temperature is risen to 130 ℃, add acetic acid with compression pump with the 1.2mol/h flow; Reaction temperature is controlled at 145 ℃, and reactor inlet pressure is 0.70MPa.Aerating oxygen gradually, oxygen flow is controlled at 0.4mol/h after 40 minutes, uses the cooling device collecting reaction product, ethylene selectivity 95.1%, active 436g vinyl acetate/liters per hour.
The preparation parameter and the serviceability data of embodiment 4-8 catalyst system therefor are listed in the table 1
Table 1 Preparation of catalysts parameter and catalytic performance data
Except the listed content of table 1, other technological parameters are all identical with embodiment 1.
The above-mentioned specific embodiment does not limit technical scheme of the present invention in any form, and the technical scheme that mode obtained that every employing is equal to replacement or equivalent transformation all drops on protection scope of the present invention.
Claims (9)
1. vacuum method prepares the application of catalyst in synthesizing vinyl acetate, it is characterized in that may further comprise the steps:
S1, catalyst carrier vacuum impregnation reactive metal solution
Get palladium compound, gold compound is dissolved in and is mixed with metallic solution in the polar solvent, and is subsequent use;
Catalyst carrier is vacuumized processing, vacuum is-0.01～-0.09MPa;
Catalyst carrier is immersed in the metallic solution under vacuum condition, is dried to constant weight, process metallic catalyst precarsor (I);
S2, catalyst precarsor (I) vacuum impregnation aqueous alkali
Catalyst precarsor (I) is vacuumized processing by the S1 step, aqueous alkali and catalyst precarsor (I) vacuum suction dipping, leave standstill 4-12 hour after, be dried to constant weight, obtain catalyst precarsor (II);
The reduction of S3, catalyst precarsor (I) surface metal
The catalyst precarsor (I) that will pass through step S2 processing places quartz ampoule, reduction under hydrogen shield, and the reduction after washing is washed, and is dried to constant weight;
The vacuum method dipping of S4, alkali metal acetate
The product of S3 step reduction is vacuumized processing by the S1 step, add 10% potassium acetate aqueous solution vacuum impregnation after, obtain catalyst through 1-5 hour drying.
2. vacuum method according to claim 1 prepares the application of catalyst in synthesizing vinyl acetate, it is characterized in that the described catalyst carrier of step S1 is silica or alundum (Al; The volume of described metallic solution is the 95-100% of carrier hole capacity; Described polar solvent is the arbitrary of water, ethanol, acetic acid or rare nitric acid; Carrier loaded amount is per hundred milliliters of catalyst cupport palladium 1-9g, golden 0.5-4g.
3. vacuum method according to claim 1 prepares the application of catalyst in synthesizing vinyl acetate, it is characterized in that the described palladium compound of step S1 is PdCl
2, Pd (C
2H
3O
2)
2]
3, Pd (NO
3)
2, PdSO
4, H
2PdCl
4, K
2PdCl
6Any; Said gold compound is AuCl
3, HAuCl
4, NaAuCl
4, KAuCl
4Any.
4. vacuum method according to claim 1 prepares the application of catalyst in synthesizing vinyl acetate, it is characterized in that the mol ratio of described alkali metal amount of step S2 and porpezite content is 1-10:1; Described alkaline solution is to be selected from any of NaOH, potassium hydroxide, sodium metasilicate, potassium silicate solution, and alkali metal soln volume and catalyst precarsor (I) volume ratio is 1-1.2:1; The ratio of fixative and palladium, golden total amount is 1:1-1.5mol.
5. vacuum method according to claim 1 prepares the application of catalyst in synthesizing vinyl acetate, it is characterized in that the described hydrogen reducing temperature of step S3 is 400-700 ℃, and the recovery time is 2-6 hour.
6. vacuum method according to claim 1 prepares the application of catalyst in synthesizing vinyl acetate, it is characterized in that step S4 liquor kalii acetici volume is the 100-120% of catalyst precarsor (II) volume.
7. vacuum method according to claim 1 prepares the application of catalyst in synthesizing vinyl acetate, and the load capacity that it is characterized in that catalyst carrier is per hundred milliliters of catalyst cupport palladium 6.1-8.98g, golden 3.3-3.79g.
8. the application of catalyst according to claim 1 in ethylene process of preparing vinyl acetate is characterized in that in the described course of reaction, and the control bed temperature is 130-170 ℃, and reactor inlet pressure is 0.5-1.0MPa.
9. the application of catalyst according to claim 1 in ethylene process of preparing vinyl acetate is characterized in that in the described course of reaction, and the control bed temperature is 145 ℃, and reactor inlet pressure is 0.70MPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104645931A (en) * | 2013-11-22 | 2015-05-27 | 北京有色金属研究总院 | Preparation method of highly homogeneous Pd-loaded diatomite composite material |
| CN114425445A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
| CN114433248A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst and preparation method thereof |
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| CN1297789A (en) * | 1999-12-02 | 2001-06-06 | 上海石油化工股份有限公司 | Catalyst for ethylene process of preparing vinyl acetate |
| CN101007275A (en) * | 2007-01-25 | 2007-08-01 | 南京工业大学 | Catalyst for p-nitrophenol hydrogenation and preparation method thereof |
| CN101402038A (en) * | 2008-11-14 | 2009-04-08 | 江苏索普（集团）有限公司 | Catalyst for ethylene process of preparing vinyl acetate and method for producing the same |
-
2011
- 2011-11-28 CN CN2011103839611A patent/CN102716739A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1297789A (en) * | 1999-12-02 | 2001-06-06 | 上海石油化工股份有限公司 | Catalyst for ethylene process of preparing vinyl acetate |
| CN101007275A (en) * | 2007-01-25 | 2007-08-01 | 南京工业大学 | Catalyst for p-nitrophenol hydrogenation and preparation method thereof |
| CN101402038A (en) * | 2008-11-14 | 2009-04-08 | 江苏索普（集团）有限公司 | Catalyst for ethylene process of preparing vinyl acetate and method for producing the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104645931A (en) * | 2013-11-22 | 2015-05-27 | 北京有色金属研究总院 | Preparation method of highly homogeneous Pd-loaded diatomite composite material |
| CN114425445A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
| CN114425445B (en) * | 2020-10-14 | 2023-09-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
| CN114433248A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst and preparation method thereof |
| CN114433248B (en) * | 2020-10-20 | 2023-10-27 | 中国石油化工股份有限公司 | Catalyst and preparation method thereof |
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Application publication date: 20121010 |