CN1314490C - Catalyzer in use for synthesizing vinyl acetate, and preparation method - Google Patents
Catalyzer in use for synthesizing vinyl acetate, and preparation method Download PDFInfo
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- CN1314490C CN1314490C CNB031165753A CN03116575A CN1314490C CN 1314490 C CN1314490 C CN 1314490C CN B031165753 A CNB031165753 A CN B031165753A CN 03116575 A CN03116575 A CN 03116575A CN 1314490 C CN1314490 C CN 1314490C
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Abstract
The present invention relates to a catalyzer in use for synthesizing vinyl acetate, and a preparation method thereof. A preparation process comprises that a carrier is impregnated in a compound solution containing palladium and gold to make a catalyst precursor, and an alkaline solution is used for infiltrating the catalyst precursor for ageing the catalyst precursor. The compound containing palladium and gold is reduced to metal palladium gold by a reducing agent, and the catalyst precursor is washed by water and dried. The catalyst precursor is calcined in an atmosphere containing gas acetic acid, and the acetic partial pressure occupies 5 to 100% of the total pressure. Other gas is selected from one of reducing gas, oxidizing property gas, inert gas, or a mixture of the reducing gas and the insert gas or a mixture of the oxidizing property gas and the inert gas. The calcined temperature is from 250 to 350 DEG C, and the calcined time is from 1 to 24 hours. The catalyst precursor is infiltrated in the alkali metal acetic acid salt solution, and the catalyst finished product is made after dryness. The present invention has the advantages that the calcined temperature of the catalyst is decreased, so the operational requirements of energy consumption and calcined technology are decreased, and the obtained catalyst also has good properties.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method that contains Metal Palladium and metallic gold, particularly be used for the Preparation of catalysts method that contains Metal Palladium and metallic gold by ethene, acetic acid and oxygen-containing gas gas-phase reaction synthesizing vinyl acetate ester.
Background technology
In the presence of catalyst, be the method for the suitability for industrialized production vinylacetate of comparative maturity by ethene, acetic acid and oxygen-containing gas gas-phase reaction synthesizing vinyl acetate ester.The catalyst that adopts is generally loaded catalyst, and catalyst is with SiO
2, Al
2O
3Or SiO
2With Al
2O
3Mixture is a carrier, and the active component of load is Metal Palladium, metallic gold and alkali metal acetate.Catalyst adopts infusion process to prepare usually, and preparation process mainly comprises: the solution impregnating carrier with the compound that contains palladium and gold is made catalyst precarsor; Soak into catalyst precarsor with alkaline solution and make it ageing, making the water miscible compound precipitation that contains palladium and gold is water-insoluble palladium, gold compound; With reducing agent palladium, gold compound are reduced to Metal Palladium, metallic gold; The washing and drying catalyst precarsor; With alkali metal acetate solution impregnation catalyst precarsor; Make the catalyst finished product after the drying.The catalyst initial activity that this traditional preparation method makes is very high, high initial activity makes the initial reaction stage very exothermic, reactor is limited in the heat-sinking capability of moment, this is easy to cause the beds temperature runaway, so the too high initial activity of catalyst makes the startup procedure of process units be difficult to stablize.
U.S. Pat 5,990,344 propose to make by the way of high-temperature roasting the grain growth of activity of such catalysts component palladium, gold, thereby reduce its initial activity.Roasting process carries out before catalyst precarsor is with the alkali metal acetate solution impregnation, the preferred reducibility gas of calcination atmosphere, but also can carry out in oxidizing gas or inert gas, suitable reducibility gas is hydrogen or carbon monoxide, and suitable oxidizing gas is an oxygen.They can be by inert gas dilution.Use separately or be nitrogen, carbon dioxide and helium with the suitable inert gas that oxidizing gas or reducibility gas use.Sintering temperature is 500～1000 ℃, and roasting time is 1～24 hour.If the use oxidizing gas, then catalyst needs to reduce once more subsequently.Temperature when the shortcoming of this prior preparation method is roasting is higher, and this just needs higher energy consumption, simultaneously roasting apparatus and baking operation is had relatively high expectations.In addition, high-temperature roasting influences the pore structure of catalyst probably, thereby the heat-resisting quantity of catalyst carrier has also been proposed more harsh requirement.
Summary of the invention
The invention provides a kind of Preparation of catalysts method that is used for by ethene, acetic acid and oxygen-containing gas gas-phase reaction synthesizing vinyl acetate ester, its technical problem to be solved is the condition by the roasting of improvement catalyst, thereby significantly reduces the sintering temperature of catalyst.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of Preparation of catalysts method that is used for by ethene, acetic acid and oxygen-containing gas gas-phase reaction synthesizing vinyl acetate ester, catalyst is with SiO
2, Al
2O
3Or SiO
2With Al
2O
3Mixture is a carrier, and the active component of load is Metal Palladium, metallic gold and alkali metal acetate, and the content of palladium is that the content of 1～12g/l, gold is that the content of 0.5～10g/l, alkali metal acetate is 10～80g/l in the catalyst.The preparation method may further comprise the steps successively: carrier dipping in the water miscible solution that contains palladium compound and gold-containing compound is made catalyst precarsor; Catalyst precarsor contacts ageing with alkaline solution; Catalyst precarsor in containing the liquid phase material of reducing agent, flood make in the catalyst precarsor contain palladium compound and gold-containing compound is converted into Metal Palladium and gold; In addition roasting after the catalyst precarsor washing; With alkali metal acetate solution impregnation catalyst precarsor; Make finished catalyst after the drying.The roasting of catalyst precarsor is carried out in the atmosphere that contains gas acetic acid, wherein the branch of acetic acid covers 5～100% of gross pressure, when containing other gas in the atmosphere, other gas is selected from a kind of in the mixture of the mixture of reducibility gas, oxidizing gas, inert gas, reducibility gas and inert gas or oxidizing gas and inert gas, sintering temperature is 250～350 ℃, and roasting time is 1～24 hour.
The sintering temperature of above-mentioned catalyst precarsor is preferably 250～300 ℃; Roasting time is preferably 5～10 hours.Above-mentioned reducibility gas is preferably hydrogen or carbon monoxide; Oxidizing gas is preferably oxygen or air; Inert gas is preferably nitrogen, carbon dioxide or helium.
Cover 5～20% of gross pressure and the calcination atmosphere that it is considered herein that catalyst precarsor is preferably the branch of acetic acid, other gas is air.
For method for preparing catalyst provided by the invention, its key problem in technology is that the roasting of catalyst precarsor is to contain gas acetic acid or all be to carry out in the atmosphere of gas acetic acid, other step is same as the prior art, and this is known by those of ordinary skill in the art.Concrete process can be:
1) carrier dipping in the water miscible solution that contains palladium compound and gold-containing compound is made catalyst precarsor.
The compound of palladium can be that palladium, palladium sulfate, palladium nitrate, palladium bichloride, the acid of Halogen palladium are as H
2PdCl
4Or Halogen palladate such as Na
2PdCl
4Or K
2PdCl
4, the compound of gold can be selected chlorauride, acetic acid gold, HAuCl for use
4, NaAuCl
4Or KAuCl
4, solvent can be water, carboxylic acid, alcohol, benzene etc., preferred solvent is water and acetic acid.The dipping liquid measure is 95～100% of a carrier hygroscopicity value, the required amount that contains palladium compound and gold-containing compound of preparation maceration extract, target content according to palladium or gold in the content of palladium in the corresponding compounds wherein or gold and the catalyst determines that both equate usually.
2) catalyst precarsor contacts ageing with alkaline solution.
Handle catalyst precarsor with the aqueous solution that contains alkali compounds, alkali compounds can be NaOH, potassium hydroxide or sodium metasilicate, preferred sodium metasilicate.The ageing liquid measure is 5～15% of a carrier hygroscopicity value, and the consumption of alkali compounds is that palladium, gold compound are converted into palladium, the required reaction equivalent of golden hydroxide 1.1～1.8 times fully.Ageing is at room temperature carried out usually, and digestion time is no less than 24 hours.
3) catalyst precarsor floods the palladium that makes in the catalyst precarsor in containing the liquid phase material of reducing agent, golden hydroxide is converted into Metal Palladium and gold.
Reduce and at room temperature carry out in the liquid phase, reducing agent is a hydrazine hydrate, and the consumption of hydrazine hydrate is to make palladium, golden hydroxide be converted into palladium, the required reaction equivalent of metal 5～20 times fully.
4) washing of catalyst precarsor and drying.
Use the deionized water rinsing catalyst precarsor, to there not being Cl
-Till (checking) with silver nitrate.Carry out drying then, baking temperature is no more than 120 ℃.
5) catalyst precarsor is with foregoing condition roasting.
6) with alkali metal acetate solution impregnation catalyst precarsor.
Alkali metal acetate solution is generally the aqueous solution of potassium acetate, and soaking into liquid measure is 90～100% of carrier hygroscopicity value, and the amount of the potassium acetate that the preparation infiltrate is required is determined according to the target content of potassium acetate in the catalyst.
The inventor finds through experiment back, and when catalyst precarsor was containing in the atmosphere of acetic acid roasting, (250～350 ℃) just can make activity of such catalysts component palladium, golden grain growth under lower sintering temperature.Perhaps, this is in the process of roasting, and palladium, gold form the compound of acetic acid, and the compound of the palladium of this transitional form, gold and acetic acid can move under lower temperature, thereby impels grain growth.Compared with prior art, advantage of the present invention is to reduce the sintering temperature of catalyst, thereby the operation requirement that cuts down the consumption of energy and reduce roasting technique has good reactivity worth equally and the present invention prepares the catalyst of gained.
Below will the invention will be further described by specific embodiment.
The specific embodiment
[embodiment 1～4]
(4～6mm) 1.1 liters of particle diameters are with containing 4.21 gram H to get the preparing spherical SiO 2 carrier
2PdCl
4With 2.04 gram HAuCl
4450 milliliters of dippings of mixed solution, under the room temperature dipping 1 hour, make catalyst precarsor.
27.5g nine hydrated sodium silicates are made into the 100ml aqueous solution are added in the above-mentioned catalyst precarsor, shake several, left standstill then 24 hours to avoid caking.
With concentration is that the hydrazine hydrate 30ml impregnated catalyst precursor of 85wt% reduces, and dip time is 5 hours.
Spend deionised water catalyst precarsor to water outlet and do not contain chlorion (checking) with silver nitrate, dry down in 60 ℃ then.
Catalyst precarsor is containing acetic acid or all is being roasting under the atmosphere of acetic acid, and the concrete roasting condition of each embodiment sees Table 1.
With the catalyst precarsor behind the 450ml aqueous solution impregnation-calcination that contains the 45g potassium acetate, flood after 5 hours in 60 ℃ of dry down catalyst finished products that get.
The composition of catalyst: palladium content 3.83g/l, gold content 1.85g/l, potassium acetate content 30g/l
[comparative example 1,2]
The roasting of catalyst precarsor is carried out in the atmosphere that does not contain acetic acid, and all the other are with embodiment 1～4, and concrete roasting condition sees Table 1.
[evaluation of catalyst]
The 900ml catalyst of in 900 milliliters of fixed bed reactors, packing into, with ethene pressure testing leak test, confirm not have leak after, the ethene flow is not transferred to 64.4mol/h, heat up simultaneously.When temperature in the beds reaches 120 ℃, drop into acetic acid, the acetic acid flow is 9.30mol/h.After half an hour, progressively drop into oxygen, throw sufficient oxygen amount after 2 hours, flow reaches 3.87mol/h, and the control raw material ratio is: ethene/acetic acid/oxygen=83.0/12.0/5.0 (mol ratio).
Control bed hot(test)-spot temperature is 142 ℃ in the course of reaction, reactor inlet pressure 0.8MPa.Ethene, acetic acid and oxygen are chargings after mixing in preheater.Regulate the acetic acid pump to control its flow, ethene and oxygen flow all adopt the control of mass velocity controller, reaction gas discharges after condenser condenses, product vinyl acetate in the analytical reactions liquid and unreacted acetic acid amount, and side reaction product carbon dioxide in the tail gas, uncooled vinyl acetate and unreacted oxygen.
The evaluation result of each embodiment and comparative example catalyst sees Table 2, and activity of such catalysts and selectivity definition are:
Table 1.
| Sintering temperature (℃) | Roasting time (hour) | Calcination atmosphere is formed | Acetic acid dividing potential drop (%) | |
| Embodiment 1 | 300 | 5 | Air/acetic acid | 20 |
| Embodiment 2 | 250 | 24 | Nitrogen/acetic acid | 5 |
| Embodiment 3 | 350 | 5 | Acetic acid | 100 |
| Embodiment 4 | 300 | 1 | Hydrogen/acetic acid | 33 |
| Comparative example 1 | 500 | 5 | Hydrogen | 0 |
| Comparative example 2 | 700 | 5 | Hydrogen | 0 |
Table 2.
| Catalyst | Grain size * (nm) | Active | Selectivity (%) |
| Embodiment 1 | 6.0 | 336 | 94.6 |
| Embodiment 2 | 5.5 | 354 | 94.5 |
| Embodiment 3 | 6.1 | 332 | 94.4 |
| Embodiment 4 | 6.1 | 334 | 94.5 |
| Embodiment 5 | 5.6 | 356 | 94.5 |
| Embodiment 6 | 6.0 | 334 | 94.6 |
* catalyst crystal grain is measured with X-ray diffractometer.
Claims (7)
1, a kind of Preparation of catalysts method that is used for by ethene, acetic acid and oxygen-containing gas gas-phase reaction synthesizing vinyl acetate ester, catalyst is with SiO
2, Al
2O
3Or SiO
2With Al
2O
3Mixture is a carrier, the active component of load is Metal Palladium, metallic gold and alkali metal acetate, the content of palladium is that the content of 1～12g/l, gold is that the content of 0.5～10g/l, alkali metal acetate is 10～80g/l in the catalyst, and the preparation method may further comprise the steps successively: carrier dipping in the water miscible solution that contains palladium compound and gold-containing compound is made catalyst precarsor; Catalyst precarsor contacts ageing with alkaline solution; Catalyst precarsor in containing the liquid phase material of reducing agent, flood make in the catalyst precarsor contain palladium compound and gold-containing compound is converted into Metal Palladium and gold; In addition roasting after the catalyst precarsor washing; With alkali metal acetate solution impregnation catalyst precarsor; Make finished catalyst after the drying, the roasting that it is characterized in that described catalyst precarsor is carried out in the atmosphere that contains gas acetic acid, wherein the branch of acetic acid covers 5～100% of gross pressure, when containing other gas in the atmosphere, other gas is selected from a kind of in the mixture of the mixture of reducibility gas, oxidizing gas, inert gas, reducibility gas and inert gas or oxidizing gas and inert gas, sintering temperature is 250～350 ℃, and roasting time is 1～24 hour.
2, Preparation of catalysts method according to claim 1, the sintering temperature that it is characterized in that described catalyst precarsor is 250～300 ℃.
3, Preparation of catalysts method according to claim 1, the roasting time that it is characterized in that described catalyst precarsor is 5～10 hours.
4, Preparation of catalysts method according to claim 1 is characterized in that described reducibility gas is hydrogen or carbon monoxide.
5, Preparation of catalysts method according to claim 1 is characterized in that described oxidizing gas is oxygen or air.
6, Preparation of catalysts method according to claim 1 is characterized in that described inert gas is nitrogen, carbon dioxide or helium.
7, Preparation of catalysts method according to claim 1 is characterized in that the roasting of described catalyst precarsor is carried out in the atmosphere that contains gas acetic acid, wherein the branch of acetic acid covers 5～20% of gross pressure, and other gas is air.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031165753A CN1314490C (en) | 2003-04-23 | 2003-04-23 | Catalyzer in use for synthesizing vinyl acetate, and preparation method |
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|---|---|---|---|
| CNB031165753A CN1314490C (en) | 2003-04-23 | 2003-04-23 | Catalyzer in use for synthesizing vinyl acetate, and preparation method |
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|---|---|
| CN1539552A CN1539552A (en) | 2004-10-27 |
| CN1314490C true CN1314490C (en) | 2007-05-09 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103028438A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Catalyst for preparing saturated acetic ester |
| CN103120958B (en) * | 2011-11-18 | 2015-02-11 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
| CN103878023B (en) * | 2012-12-19 | 2016-05-18 | 中国石油化工股份有限公司 | The preparation method of catalyzer for synthesizing vinyl acetate |
| CN114425454B (en) * | 2020-10-14 | 2024-02-02 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and vinyl acetate synthesis method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4048096A (en) * | 1976-04-12 | 1977-09-13 | E. I. Du Pont De Nemours And Company | Surface impregnated catalyst |
| US5194417A (en) * | 1991-12-05 | 1993-03-16 | Quantum Chemical Corporation | Pretreatment of palladium-gold catalysts useful in vinyl acetate synthesis |
| CN1184808A (en) * | 1996-11-04 | 1998-06-17 | 英国石油化学品有限公司 | Process for production of vinyl acetate |
| CN1235561A (en) * | 1996-10-31 | 1999-11-17 | 米兰纽姆石化公司 | Improved process for production of supported palladium-gold catalysts |
| 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 |
| CN1340378A (en) * | 2000-08-30 | 2002-03-20 | 上海石油化工股份有限公司 | High-activity catalyst for preparing vinyl acetate by ethylene method |
-
2003
- 2003-04-23 CN CNB031165753A patent/CN1314490C/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4048096A (en) * | 1976-04-12 | 1977-09-13 | E. I. Du Pont De Nemours And Company | Surface impregnated catalyst |
| US5194417A (en) * | 1991-12-05 | 1993-03-16 | Quantum Chemical Corporation | Pretreatment of palladium-gold catalysts useful in vinyl acetate synthesis |
| CN1235561A (en) * | 1996-10-31 | 1999-11-17 | 米兰纽姆石化公司 | Improved process for production of supported palladium-gold catalysts |
| CN1184808A (en) * | 1996-11-04 | 1998-06-17 | 英国石油化学品有限公司 | Process for production of vinyl acetate |
| 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 |
| CN1340378A (en) * | 2000-08-30 | 2002-03-20 | 上海石油化工股份有限公司 | High-activity catalyst for preparing vinyl acetate by ethylene method |
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