CN1268396A - Preparation method of catalyst for producing vinyl acetate - Google Patents
Preparation method of catalyst for producing vinyl acetate Download PDFInfo
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- CN1268396A CN1268396A CN99113570A CN99113570A CN1268396A CN 1268396 A CN1268396 A CN 1268396A CN 99113570 A CN99113570 A CN 99113570A CN 99113570 A CN99113570 A CN 99113570A CN 1268396 A CN1268396 A CN 1268396A
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- metal silicate
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Abstract
The present invention relates to a prepn. method of catalyst for producing vinyl acetate, it is characterized by that during the step of noble metal precipitation, instead of adding precipitating agent once, it is changed to the method of adding precipitating agent by steps, and the catalyst prepared by the invented method is high in catalytic activity and can be used in industrial production.
Description
The present invention relates to produce the preparation method of vinyl acetate catalyst.
Vinyl acetate is important Organic Chemicals, is widely used in aspects such as making polyvinyl alcohol, vinyl copolymer resins, binding agent, coating, textile processing, paper coating.The main method of producing vinyl acetate in the world today is to be raw material with ethene, oxygen and acetic acid, makes catalyst with palladium-Jin-potassium acetate/silica, and is synthetic by gas phase catalytic reaction.Be to obtain the catalyst of high activity, high selectivity, update at aspects such as the shape of catalyst, preparation technologies.The catalyst that use contains palladium, gold and alkali metal acetate promoter normally loads on the porous carrier, as silica gel or/and on the aluminium oxide.In early days in the document, palladium and gold more or less evenly substep on carrier, as US3725680, US3743607 and GB1333449.Under this distribution situation, the catalyst component of carrier inside is little to the reaction contribution, because reacting gas can not be diffused into carrier inside well, that is to say that the palladium of quite a few, gold do not touch reactant.In order to overcome the above problems, people have designed a kind of new method for preparing catalyst, and purpose is to make the catalyst component point-load on the carrier shell surface.For example the GB1500167 report can be distributed in 90% palladium and gold in the shell of carrier at least, and this outer casing thickness is no more than 30% of radius.A kind of method of controlling the catalyst component load degree of depth by sodium carbonate or naoh treatment porous shell has been described among the GB1283737.Introduced a kind of surface type distribution method for preparing catalyst in the US4048096 document.It is made up of following steps: (1) impregnated in water miscible palladium, gold solution on the carrier; (2) above-mentioned carrier is immersed in the alkali metal silicate solutions 12～24 hours, this moment, the solution pH value was 6.5～9.5; (3) handle with reducing agent, palladium, gold precipitation are reduced to palladium, golden metal; (4) washing; (5) alkali metal carboxylate solution impregnation; (6) the dry finished catalyst that gets.Use the method, catalyst activity in US4048096, to be up to 121 gram vinyl acetate/every gram noble metals hour.In sum, all there is the active relatively low problem of the catalyst that makes in above-mentioned document.
The objective of the invention is provides a kind of new preparation method who produces vinyl acetate catalyst in order to overcome the active relatively low problem of catalyst in the above-mentioned document, and the catalyst that uses this preparation method to make has the high characteristics of catalytic activity.
The objective of the invention is to realize by following technical scheme: a kind of preparation method who produces vinyl acetate catalyst, catalyst is carrier with silica, contains palladium, gold and potassium active constituent, may further comprise the steps successively:
A) aqueous solution that contains palladium, gold compound impregnated on the carrier;
B) at first 50～90% of precipitating reagent alkali metal silicate solutions or the required theoretical amount of alkali metal silicate solution soaked above-mentioned carrier, and then add 10～50% of precipitating reagent alkali metal silicate solutions or the required theoretical amount of alkali metal silicate solution;
C) utilize reduction reaction, palladium and gold precipitation are reduced into Metal Palladium and gold;
D) washing, drying and impregnation alkali metal acetate;
E) the dry finished catalyst that gets.
The precipitating reagent alkali metal silicate solutions that at first adds in the technique scheme or the preferable range of alkali metal silicate solution amount are 70～90% of required theoretical amount.Used alkali metal silicate preferred version is a sodium metasilicate; The reducing agent that reduction reaction is used preferably uses hydrazine hydrate reduction.Add the alkali metal silicate solutions of required theoretical amount 10～50% or alkali metal silicate solution at least with once finishing.
Carrier can be preferably silica gel for silica gel, aluminium oxide or titanium dioxide among the present invention.The bulk density of silica-gel carrier is between 0.39～0.42 grams per milliliter, and pore volume is at 0.8～1.2 milliliter/gram carrier, and specific area is 150～350 meters
2Between/the gram.The shape of carrier can be sphere, also can be abnormity, is preferably Raschig ring shape.The raw material of palladium is selected from the acid of chlorine palladium, and the raw material of gold is selected from gold chloride, and the raw material of potassium is selected from potassium acetate.Palladium content is between 2.5～3.5 gram/every liter of catalyst, and the content of gold is between 1.0～1.7 grams/every liter catalyst, and the ratio of gold/palladium is between 0.2～0.8.The preferable range of palladium content is at 2.7～3.3 gram/every liter of catalyst, and the preferable range of gold content is at 1.2～1.5 gram/every liter of catalyst, and the ratio preferable range of gold/palladium is between 0.3～0.7.Potassium acetate content is in 25～35 gram/every liter of range of catalysts, and preferable range is 28～32 gram/every liter of catalyst.Precipitating reagent among the present invention can add at twice, also can add several times, and the catalytic activity that makes catalyst is in rising trend with the increase of adding number of times.
The present invention adds precipitating reagent step by step, makes palladium, gold can more be evenly distributed in the carrier skin, forms surface type and distributes.At this moment catalyst component by in the carrier to external diffusion, when the precipitating reagent ecto-entad diffused to suitable pH value, catalyst component was deposited on the carrier, formed the palladium-Jin layer of book shell.When reaction, this structure is thinner owing to palladium-Jin layer thickness, thereby can reduce deep reaction, increases the catalytic activity of space-time yield and catalyst.The catalyst that makes with preparation method of the present invention was gas space velocity 1930 hours
-1, ethene: oxygen: acetic acid is 13.29: 1: 3.29 (mol ratio), reaction pressure 0.8MPa, and reaction is investigated under 153 ℃ of conditions of reaction temperature, and its catalytic activity is higher can reach 135.1 gram vinyl acetate/every gram noble metals hour, has obtained effect preferably.
Investigation condition of the present invention is: the use diameter is 25.4 millimeters a reactor evaluations catalyst, and gas space velocity GHSV is 1930 hours
-1, the reaction gas proportioning is an ethene: oxygen: acetic acid (mol ratio)=13.29: 1: 3.29, reaction temperature are 153 ℃, reaction pressure is 0.8MPa.Activity and selectivity computing formula are as follows:
Gram number/the loaded catalyst (liter) of the vinyl acetate of space-time yield (STY)=1 hour production
The present invention is further elaborated below by embodiment.[embodiment 1]
At first in silica white, add releasing agent paraffin and adhesive silicon sol, they are fully mixed, are shaped and make the hollow ring precursor carrier of 5.5 millimeters * 1.8 millimeters * 5.5 millimeters (external diameter * internal diameters * height), then this hollow ring precursor carrier is dried, drying temperature is 25 ℃, and flash-off time is 48 hours.Carry out drying after drying, baking temperature is 100 ℃, and the time is 24 hours, places roasting in the muffle furnace then.Its sintering temperature is 650 ℃, roasting time is 3 hours, put into autoclave after the cooling, the solution that adding acetic acid, ammonium acetate are made into, the solution amount of every liter of hollow ring silica-gel carrier adding is 4 liters, heats up, is pressurized to 1MPa, constant voltage was taken out carrier after 16 hours, be washed till neutrality with distilled water, place then in the muffle furnace in 450 ℃ of roasting temperatures 3 hours, promptly getting specific area after the cooling is 250 meters
2The hollow ring carrier of/gram, the bulk density of carrier is 0.40 grams per milliliter, pore volume is 1.02 a milliliters/gram.
After preparing carriers finished, the preparation catalyst in turn included the following steps:
A) the above-mentioned carrier of 400 grams is added 408 milliliters of chlorine palladium acid (H
2PdCl
4) and gold chloride (HAuCl
4) in the solution, wherein contain palladium 2.69 grams, contain gold 1.22 grams.Gentle agitation to liquid absorbs fully;
B) the above-mentioned wet carrier that has flooded acid of chlorine palladium and gold chloride is soaked in 600 milliliters the solution of sodium metasilicate through (contain 0.0811 mole of sodium metasilicate).Gentle agitation adds 200 milliliters of solution of sodium metasilicate through (containing 0.0143 mole of sodium metasilicate) again after half an hour.Gentle agitation, place half an hour after, solution inclines;
C) add the carrier of hydrazine hydrate solution to the above-mentioned palladium of submergence, golden post precipitation, required hydrazine hydrate molal quantity is 0.92 mole, and gentle agitation was placed 4 hours, and solution inclines;
D) be washed to water after the washing and add liquor argenti nitratis ophthalmicus and do not produce precipitation, after the drying, adds 408 milliliters of liquor kalii aceticis (containing potassium acetate 30 restrains) then;
E) the dry finished catalyst that gets.
Contain palladium 2.66 grams in the finished catalyst, contain gold 1.16 grams, 98.9% palladium has entered catalyst in the initiation material, and 95.1% gold has entered catalyst.
This finished catalyst is investigated under above-mentioned appreciation condition, and its result is: space-time yield is 503 grams per liters hour, and catalytic activity is 131.7 gram vinyl acetate/every gram noble metals hour.[embodiment 2]
In above-mentioned b step, change the amount that adds sodium metasilicate earlier into 600 milliliters (containing 0.0478 mole of sodium metasilicate), the amount that the back adds sodium metasilicate changes 200 milliliters (containing 0.0476 mole of sodium metasilicate) into, and all the other each steps are with embodiment 1.
Contain palladium 2.50 grams in the finished catalyst, contain gold 1.11 grams, 92.9% palladium has entered catalyst in the initiation material, and 91.0% gold has entered in the catalyst.Investigate down with the appreciation condition of embodiment 1, its result is: space-time yield is 478 grams per liters hour, and catalytic activity is 132.4 gram vinyl acetate/every gram noble metals hour.[embodiment 3]
Contain palladium 3.3 grams in the initiation material, gold 1.5 grams add sodium metasilicate amount and hydrazine hydrate amount by the corresponding in proportion increase of theoretical aequum, and all the other are with embodiment 1.
Contain palladium 3.14 grams in the finished catalyst, gold 1.35 grams, 95.2% palladium has entered catalyst in the initiation material, and 90.0% gold has entered in the catalyst.Investigate down with the appreciation condition of embodiment 1, its result is: space-time yield is 550 grams per liters hour, and catalytic activity is 122.5 gram vinyl acetate/every gram noble metals hour.[embodiment 4]
Contain palladium 2.5 grams in the initiation material, gold 1.14 grams add sodium metasilicate amount and hydrazine hydrate amount by the corresponding in proportion minimizing of theoretical aequum, and all the other are with embodiment 1.
Contain palladium 2.49 grams in the finished catalyst, gold 1.1 grams, 99.6% palladium has entered catalyst in the initiation material, and 96.5% gold has entered in the catalyst.Investigate down with the appreciation condition of embodiment 1, its result is: space-time yield is 485 grams per liters hour, and catalytic activity is 135.1 gram vinyl acetate/every gram noble metals hour.[comparative example 1]
Among the embodiment 1 after acid of (a) step dipping chlorine palladium and the gold chloride end, 75 ℃ of oven dry, the solution of sodium metasilicate through of 0.0954 mole of disposable adding in (b) step then, placement is spent the night, and all the other each steps are with embodiment 1.The catalyst that makes like this is protein type distribution (being that the black layer of palladium, gold is in the middle of carrier).Contain palladium 2.66 grams in the finished catalyst, gold 1.21 grams, 98.9% palladium has entered catalyst in the initiation material, and 99.2% gold has entered in the catalyst.Investigate down with the appreciation condition of embodiment 1, its result is: space-time yield is 396 grams per liters hour, and catalytic activity is 102.3 gram vinyl acetate/every gram noble metals hour.
Claims (5)
1, a kind of preparation method who produces vinyl acetate catalyst, catalyst is carrier with silica, contains palladium, gold and potassium active constituent, may further comprise the steps successively:
A) aqueous solution that contains palladium, gold compound impregnated on the carrier;
B) at first 50～90% of precipitating reagent alkali metal silicate solutions or the required theoretical amount of alkali metal silicate solution soaked above-mentioned carrier, and then add 10～50% of precipitating reagent alkali metal silicate solutions or the required theoretical amount of alkali metal silicate solution;
C) utilize reduction reaction, palladium and gold precipitation are reduced into Metal Palladium and gold;
D) washing, drying and impregnation alkali metal acetate;
E) the dry finished catalyst that gets.
2,, it is characterized in that the precipitating reagent alkali metal silicate solutions that at first adds or the amount of alkali metal silicate solution are 70～90% of required theoretical amount according to the preparation method of the described production vinyl acetate catalyst of claim 1.
3,, it is characterized in that alkali metal silicate is a sodium metasilicate according to the preparation method of the described production vinyl acetate catalyst of claim 1.
4,, it is characterized in that reduction reaction reducing agent hydrazine hydrate reduction according to the preparation method of the described production vinyl acetate catalyst of claim 1.
5,, it is characterized in that adding 10～50% precipitating reagent alkali metal silicate solutions of required theoretical amount or alkali metal silicate solution at least with once finishing according to the preparation method of the described production vinyl acetate catalyst of claim 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113570A CN1090996C (en) | 1999-03-30 | 1999-03-30 | Preparation method of catalyst for producing vinyl acetate |
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|---|---|---|---|
| CN99113570A CN1090996C (en) | 1999-03-30 | 1999-03-30 | Preparation method of catalyst for producing vinyl acetate |
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| CN1268396A true CN1268396A (en) | 2000-10-04 |
| CN1090996C CN1090996C (en) | 2002-09-18 |
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| CN99113570A Expired - Fee Related CN1090996C (en) | 1999-03-30 | 1999-03-30 | Preparation method of catalyst for producing vinyl acetate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7030056B2 (en) | 2002-03-27 | 2006-04-18 | Shell Oil Company | Process for preparing a catalyst, the catalyst and a use of the catalyst |
| US7425647B2 (en) | 2001-03-30 | 2008-09-16 | Shell Oil Company | Process for preparing a group V111-metal containing catalyst, use thereof for preparing an alkenyl carboxylate |
| CN103878023A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthesizing vinyl acetate |
| CN104437648A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Vinyl acetate catalyst, preparation method and vinyl acetate synthesis method |
| CN104549516A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst, preparation method of vinyl acetate catalyst, and vinyl acetate synthesis method |
| CN104549517A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and application thereof |
Family Cites Families (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 |
| US5185308A (en) * | 1991-05-06 | 1993-02-09 | Bp Chemicals Limited | Catalysts and processes for the manufacture of vinyl acetate |
| DE4120492A1 (en) * | 1991-06-21 | 1992-12-24 | Hoechst Ag | METHOD FOR PRODUCING VINYL ACETATE |
| US5314858A (en) * | 1992-10-14 | 1994-05-24 | Hoechst Celanese Corporation | Vinyl acetate catalyst preparation method |
| US5332710A (en) * | 1992-10-14 | 1994-07-26 | Hoechst Celanese Corporation | Vinyl acetate catalyst preparation method |
| ES2249764T3 (en) * | 1994-02-22 | 2006-04-01 | The Standard Oil Company | PREPARATION PROCESS OF A CATALYST TO MANUFACTURE VINYL ACETATE IN A FLUID MILK. |
-
1999
- 1999-03-30 CN CN99113570A patent/CN1090996C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7425647B2 (en) | 2001-03-30 | 2008-09-16 | Shell Oil Company | Process for preparing a group V111-metal containing catalyst, use thereof for preparing an alkenyl carboxylate |
| US7030056B2 (en) | 2002-03-27 | 2006-04-18 | Shell Oil Company | Process for preparing a catalyst, the catalyst and a use of the catalyst |
| CN103878023A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthesizing vinyl acetate |
| 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 |
| CN104437648A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Vinyl acetate catalyst, preparation method and vinyl acetate synthesis method |
| CN104437648B (en) * | 2013-09-24 | 2016-09-07 | 中国石油化工股份有限公司 | Vinyl acetate catalyst, preparation method and vinyl acetate synthesis method |
| CN104549516A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst, preparation method of vinyl acetate catalyst, and vinyl acetate synthesis method |
| CN104549517A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and application thereof |
| CN104549516B (en) * | 2013-10-28 | 2017-02-15 | 中国石油化工股份有限公司 | Vinyl acetate catalyst, preparation method of vinyl acetate catalyst, and vinyl acetate synthesis method |
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| Publication number | Publication date |
|---|---|
| CN1090996C (en) | 2002-09-18 |
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