CN103121955A - Method for preparing allyl acetate - Google Patents
Method for preparing allyl acetate Download PDFInfo
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- CN103121955A CN103121955A CN2011103695812A CN201110369581A CN103121955A CN 103121955 A CN103121955 A CN 103121955A CN 2011103695812 A CN2011103695812 A CN 2011103695812A CN 201110369581 A CN201110369581 A CN 201110369581A CN 103121955 A CN103121955 A CN 103121955A
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- allyl acetate
- palladium
- copper
- catalyzer
- crystal grain
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Abstract
The invention relates to a method for preparing allyl acetate, and the method is mainly used for solving the problems of space time yield and low selectivity of the prior art. The method for preparing allyl acetate is adopted, reaction raw materials which consist of propylene, acetic acid, oxygen and water are contacted with a catalyst so as to obtain a reaction product containing allyl acetate, wherein the catalyst takes SiO2, Al2O3 or a mixture thereof as a carrier, and load active components comprise metal palladium, metal copper and alkali metal acetate; and the catalyst comprises 1-12g/L of palladium, 0.1-10g/L of copper and 10-100g/L of alkali metal acetate, wherein the average crystal grain diameters of palladium and copper are between 4 and 10nm, and crystal grains with the average crystal grain diameters within a scope of plus or minus 20% account for 60-80% of the whole crystal grains. The method can be utilized for better solving the problems and used for allyl acetate industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of allyl acetate.
Background technology
Allyl acetate is important industrial chemicals, and is of many uses.The main method of producing allyl acetate in the world today is take propylene, oxygen and acetic acid as raw material, synthesizes by gas phase catalytic reaction.For obtaining the catalyzer of high space time yield, highly selective, constantly improve at the aspects such as active ingredient composition, preparation technology and even shape of catalyzer always.
European patent (EP0361484A2) provides a kind of preparation method that load has the catalyzer of Primary Catalysts precious metal, promoter metal and basic metal or alkaline earth metal compound for preparing.Its concrete manufacturing processed is as follows: (1) adds the precious metal that configures and the mixed solution of promotor in the steeping vat of rotation, passes into hot-air dry; (2) get a certain amount of solution with alkaline matters such as water glass and make an addition in dried catalyzer, the salt of the palladium of original water soluble and copper is changed into palladium and the copper of the insoluble hydroxide attitude of water; (3) palladium and the copper catalyst of reduction hydroxide attitude in reducing gas namely are reduced into palladium and the copper catalyst of metallic state; (4) be washed till without chlorion drying; (5) soak Potassium ethanoate, namely get described catalyzer after drying.The space time yield of the catalyzer that the method obtains and selectivity are all lower.
Summary of the invention
Technical problem to be solved by this invention is space time yield and the low problem of selectivity that exists in prior art, and a kind of preparation method of new allyl acetate is provided, and this preparation method has space time yield and the high characteristics of selectivity.
For solving the problems of the technologies described above, technical scheme of the present invention is as follows: a kind of preparation method of allyl acetate, reaction raw materials with propylene, acetic acid, oxygen, water composition, contact catalyst obtains containing the reaction product of allyl acetate under 130～200 ℃ of temperature of reaction and 0.5～0.9MPa reaction pressure, the mol ratio of various reaction raw materials is oxygen: propylene: nitrogen: acetic acid=1: 5～7: 4～8: 1～2, described catalyzer is with SiO
2, Al
2O
3Or its mixture is carrier, load active component comprises palladium metal, metallic copper and alkali metal acetate, in catalyzer, the content of palladium is that the content of 1～12g/L, copper is that the content of 0.1～10g/L, alkali metal acetate is 10～100g/L, the crystal grain median size that it is characterized in that described palladium copper is 4～10nm, and the number of the crystal grain in median size ± 20% scope accounts for whole crystal grain 60～80%.
In technique scheme, the crystal grain median size of described palladium copper is preferably 5～7nm; The number of the crystal grain in median size ± 20% scope preferably accounts for whole crystal grain 75～80%; Described alkali metal acetate is preferably Potassium ethanoate; Described temperature of reaction is preferably 140～160 ℃; Described reaction pressure is preferably 0.6～0.8MPa.
Compared with prior art, the method load active component of liquid carbon dioxide dipping has been adopted in catalyzer preparation of the present invention, the characteristics that the size of microcrystal of palladium copper in the catalyzer for preparing is evenly distributed, thus space time yield and the selectivity of catalyzer can be improved.Experimental result shows, reaction pressure is 0.7MPa, 140 ℃ of temperature of reaction, when reactant gases comprises the oxygen of the acetic acid of nitrogen, 10% mol ratio of propylene, 43% mol ratio of 41% mol ratio and 6% mol ratio, the space time yield of catalyzer of the present invention is brought up to 415g/Lhr by the 375g/Lhr of prior art catalyzer, selectivity has also improved 3.6%, has obtained technique effect preferably.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
(1) catalyzer preparation
Step (a): getting the liquid carbon dioxide solution 1200ml that contains hexafluoroacetylacetone palladium (II) and hexafluoroacetylacetone copper (II) is steeping fluid, the palladium content 2.75g/L of this steeping fluid, copper content 0.625g/L, dipping 1100ml diameter is that the preparing spherical SiO 2 carrier of 4～6mm obtains catalyst precursor I under the dipping temperature of the impregnation pressure of 69MPa and 28 ℃;
Step (b): then decompression, the liquid carbon dioxide with in the speed evaporation catalyst precursor I of 0.3ml (liquid carbon dioxide)/min until liquid carbon dioxide evaporates, obtains catalyst precursor II;
Step (c): catalyst precursor II is reduced in hydrogen atmosphere, and hydrogen flow rate is 0.2ml/min, and reduction temperature is 75 ℃, obtains catalyst precursor III;
Step (d): the liquor kalii acetici 450ml that is 0.1g/ml with concentration infiltrates catalyst precursor III 5hr, then the dry catalyzer finished product that gets under 60 ℃.
The main preparation condition of catalyzer is listed in table 1.
(2) physical property characterizes
Use inductively coupled plasma spectrum generator (ICP) to measure palladium copper metal content in finished catalyst, adopt electronic transmission Electronic Speculum (TEM) that the size of microcrystal of palladium is measured and counted.The physical property of catalyzer is listed in table 2.
(3) catalyst performance evaluation
Use the fixed-bed reactor evaluation, actual conditions is:
Catalyst loading volume: 700ml;
Reaction raw materials forms (with molar ratio computing): oxygen: propylene: nitrogen: acetic acid=1: 6.8: 7.2: 1.7;
Unstripped gas air speed: 2000hr
-1
Reaction pressure: 0.7MPa;
Temperature of reaction: 140 ℃;
Reaction times: 500hr.
With the content of each component in the gc analysis reaction product, then calculate space time yield and the selectivity of catalyzer.
Table 3 has been listed the appreciation condition of catalyzer, space time yield and selective data.
[embodiment 2]
Except other step increasing calcination steps between step (c) and step (d) all identical with embodiment 1.Wherein calcination steps is: catalyst precursor III roasting under nitrogen/acetic acid atmosphere, and wherein acetic acid divides and covers 5% of total pressure, and maturing temperature is 250 ℃, and roasting time is 24hr.List in table 1 for ease of the preparation condition of catalyzer more just, the physical data of catalyzer is listed in table 2, the appreciation condition of catalyzer, space time yield and selective data are listed in table 3.
[embodiment 3～14]
Concentration, impregnation pressure, dipping temperature, reducing gas, reduction temperature, reaction raw materials mol ratio, unstripped gas air speed, reaction pressure and the temperature of reaction of the kind of the concentration of palladium copper, palladium copper compound, liquor kalii acetici, other operation steps is all identical with embodiment 2 in changing the liquid carbon dioxide steeping fluid.List in table 1 for ease of the preparation condition of catalyzer more just, the physical data of catalyzer is listed in table 2, the appreciation condition of catalyzer, space time yield and selective data are listed in table 3.
[comparative example 1]
Get and contain H
2PdCl
4And CuCl
2Aqueous solution 1000ml be steeping fluid, wherein in solution, palladium content is 2.75g/L, copper content is 0.625g/L, dipping 1100ml diameter is that the preparing spherical SiO 2 carrier of 4～6mm obtains catalyst precursor; 27.5g nine hydrated sodium silicates are made into the 100ml aqueous solution are added in above-mentioned catalyst precursor, shake several to avoid caking, standing 24hr is then successively at 80 ℃ of dry 8hr.
Infiltrate dried product with the concentration hydrazine hydrate 30ml that is 85wt% and reduce, the recovery time is 5hr, and being then 0.1g/ml with concentration, the 450ml liquor kalii acetici mixes, standing 5hr, dry under 60 ℃ must the catalyzer finished product.The method of evaluating performance of catalyzer physical property sign and catalyzer is with embodiment 2.List in table 1 for ease of the preparation condition of catalyzer more just, the physical data of catalyzer is listed in table 2, the appreciation condition of catalyzer, space time yield and selective data are listed in table 3.
[comparative example 2]
Get and contain H
2PdCl
4And CuCl
2Aqueous solution 1000ml be steeping fluid, wherein in solution, palladium content is 2.75g/L, copper content is 0.625g/L, dipping 1100ml diameter is that the preparing spherical SiO 2 carrier of 4～6mm obtains catalyst precursor; 27.5g nine hydrated sodium silicates are made into the 100ml aqueous solution are added in above-mentioned catalyst precursor, shake several to avoid caking, standing 24hr is then successively at 80 ℃ of dry 8hr.Dried product is reduced in hydrogen atmosphere, and hydrogen flow rate is 0.2ml/min, and reduction temperature is 75 ℃, is down to room temperature, and the 450ml liquor kalii acetici that is 0.1g/ml with concentration mixes, standing 5hr, the dry catalyzer finished product that gets under 60 ℃.The method of evaluating performance of catalyzer physical property sign and catalyzer is with embodiment 2.List in table 1 for ease of the preparation condition of catalyzer more just, the physical data of catalyzer is listed in table 2, the appreciation condition of catalyzer, space time yield and selective data are listed in table 3.
Table 1 catalyzer preparation condition
Table 2 catalyzer physical data
Table 3 evaluating catalyst data
Claims (6)
1. the preparation method of an allyl acetate, with the reaction raw materials that propylene, acetic acid, oxygen, water form, be 1600～3000hr in 130～200 ℃ of temperature of reaction, unstripped gas air speed
-1Obtain containing the reaction product of allyl acetate with contact catalyst under 0.5～0.9MPa reaction pressure, the mol ratio of described reaction raw materials is oxygen: propylene: nitrogen: acetic acid=1: 5～7: 4～8: 1～2, described catalyzer is with SiO
2, Al
2O
3Or its mixture is carrier, load active component comprises palladium metal, metallic copper and alkali metal acetate, in catalyzer, the content of palladium is that the content of 1～12g/L, copper is that the content of 0.1～10g/L, alkali metal acetate is 10～100g/L, the crystal grain median size that it is characterized in that described palladium copper is 4～10nm, and the number of the crystal grain in median size ± 20% scope accounts for whole crystal grain 60～80%.
2. the preparation method of allyl acetate according to claim 1, the crystal grain median size that it is characterized in that the palladium copper of described catalyzer is 5～7nm.
3. the preparation method of allyl acetate according to claim 1 is characterized in that the number of the crystal grain in the palladium copper median size ± 20% scope at described catalyzer accounts for whole crystal grain 75～80%.
4. the preparation method of allyl acetate according to claim 1, is characterized in that described alkali metal acetate is Potassium ethanoate.
5. the preparation method of allyl acetate according to claim 1, is characterized in that described temperature of reaction is 140～160 ℃.
6. the preparation method of allyl acetate according to claim 1, is characterized in that described reaction pressure is 0.6～0.8MPa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103695812A CN103121955A (en) | 2011-11-18 | 2011-11-18 | Method for preparing allyl acetate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103695812A CN103121955A (en) | 2011-11-18 | 2011-11-18 | Method for preparing allyl acetate |
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|---|---|
| CN103121955A true CN103121955A (en) | 2013-05-29 |
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|---|---|---|---|
| CN2011103695812A Pending CN103121955A (en) | 2011-11-18 | 2011-11-18 | Method for preparing allyl acetate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437670A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Preparation method of propenyl ethanoate catalyst and synthesis method of propenyl ethanoate |
| CN106413268A (en) * | 2015-07-27 | 2017-02-15 | Ｊｘ金属株式会社 | Carrier-attached copper foil, laminate, method for manufacturing printed-wiring board and method for manufacturing electronic device |
| CN106582825A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for preparation of allyl acetate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3903139A (en) * | 1971-12-07 | 1975-09-02 | Hoechst Ag | Process for the manufacture of allyl acetate |
| US5011980A (en) * | 1988-09-29 | 1991-04-30 | Showa Denko K.K. | Process for preparation of allyl acetate |
| CN1759089A (en) * | 2003-03-07 | 2006-04-12 | 昭和电工株式会社 | Processes for the production of alkenyl esters of lower carboxylic acids and process for the production of alkenyl alcohols |
-
2011
- 2011-11-18 CN CN2011103695812A patent/CN103121955A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3903139A (en) * | 1971-12-07 | 1975-09-02 | Hoechst Ag | Process for the manufacture of allyl acetate |
| US5011980A (en) * | 1988-09-29 | 1991-04-30 | Showa Denko K.K. | Process for preparation of allyl acetate |
| CN1759089A (en) * | 2003-03-07 | 2006-04-12 | 昭和电工株式会社 | Processes for the production of alkenyl esters of lower carboxylic acids and process for the production of alkenyl alcohols |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437670A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Preparation method of propenyl ethanoate catalyst and synthesis method of propenyl ethanoate |
| CN104437670B (en) * | 2013-09-24 | 2017-01-11 | 中国石油化工股份有限公司 | Preparation method of propenyl ethanoate catalyst and synthesis method of propenyl ethanoate |
| CN106413268A (en) * | 2015-07-27 | 2017-02-15 | Ｊｘ金属株式会社 | Carrier-attached copper foil, laminate, method for manufacturing printed-wiring board and method for manufacturing electronic device |
| CN106413268B (en) * | 2015-07-27 | 2019-02-01 | Ｊｘ金属株式会社 | The manufacturing method of Copper foil with carrier, laminate, the manufacturing method of printing distributing board and electronic equipment |
| CN106582825A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for preparation of allyl acetate |
| CN106582825B (en) * | 2015-10-19 | 2019-05-14 | 中国石油化工股份有限公司 | It is used to prepare the catalyst of allyl acetate |
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Application publication date: 20130529 |