CN103878022A - Preparation method of catalyst for synthesizing allyl acetate - Google Patents
Preparation method of catalyst for synthesizing allyl acetate Download PDFInfo
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- CN103878022A CN103878022A CN201210553909.0A CN201210553909A CN103878022A CN 103878022 A CN103878022 A CN 103878022A CN 201210553909 A CN201210553909 A CN 201210553909A CN 103878022 A CN103878022 A CN 103878022A
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Abstract
The invention relates to a preparation method of a catalyst for synthesizing allyl acetate, and mainly overcoming the problems of low space time yield and selectivity of a conventional catalyst for allyl acetate. The preparation method of the catalyst for synthesizing allyl acetate comprises the following steps of (a) impregnating a carrier in a solution dissolving a palladium-containing compound and a copper-containing compound to obtain a catalyst precursor I; (b) treating the catalyst precursor I with an alkali solution to obtain a catalyst precursor II; (c) impregnating the catalyst precursor I in a solution containing a stabilizer to obtain a catalyst precursor III, wherein the stabilizer is polyvinyl pyrrolidone or polyacrylic acid alkali metal salt or a mixture of the above two; (d) reducing the catalyst precursor III by using a reducing agent to obtain a catalyst precursor IV; and (e) impregnating the catalyst precursor IV with an alkali metal acetate solution, drying to obtain a finished product of the catalyst. By adopting the above technical solution, the problems are overcome relatively well; and the preparation method can be used for industrial production of allyl acetate.
Description
Technical field
The present invention relates to the preparation method of acetic acid synthesized allyl ester catalyst.
Background technology
Allyl acetate is important industrial chemicals, 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 catalyst of high space time yield, high selectivity, constantly improve at aspects such as active component composition, preparation technology and even the shapes of catalyst always.
European patent EP 0361484A2(title is: Process for preparation allyl acetate) provide a kind of and prepare load and have the preparation method of the catalyst of major catalyst noble metal, promoter metal and alkali metal or alkaline earth metal compound.Its concrete manufacture process is as follows: the mixed liquor of the noble metal configuring and co-catalyst is added, dry, then by alkaline matter for processing such as sodium metasilicate, the salt of the palladium of original water soluble and copper is changed into palladium and the copper of the insoluble hydroxide state of water, then in reducing gases, reduce palladium and the copper catalyst of hydroxide state, be reduced into palladium and the copper catalyst of metallic state, washing, dry, soak potassium acetate, after being dried, obtain described catalyst.The space time yield of the catalyst that the method obtains and selectively all lower.
Summary of the invention
Technical problem to be solved by this invention is acetic acid synthesized allyl ester catalyst space time yield and selective lower problem in prior art, a kind of preparation method of allyl acetate catalyst is provided, and the catalyst that the method makes has space time yield and selective high feature.
For solving the problems of the technologies described above, technical scheme of the present invention is as follows: for the synthesis of the preparation method of allyl acetate catalyst, with SiO
2, Al
2o
3or its mixture is carrier, load active component comprises Metal Palladium, metallic copper and alkali metal acetate, in catalyst, 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, and the method comprises the following steps:
(a) carrier in being dissolved with containing palladium compound and copper-containing compound solution, dipping is obtained to catalyst precarsor I;
(b) process catalyst precarsor I with aqueous slkali and obtain catalyst precarsor II;
(c) catalyst precarsor II is flooded in the solution that contains stabilizing agent and obtains catalyst precarsor III, described stabilizing agent is PVP or polyacrylic acid alkali metal salt or both mixtures;
(d) obtain catalyst precarsor IV with reducing agent reducing catalyst precursor II I;
(e) with alkali metal acetate solution impregnation catalyst precarsor IV, after being dried, make finished catalyst.
Described in technique scheme, be preferably the acid of chlorine palladium or chloropalladate containing palladium compound, copper-containing compound is preferably copper chloride or Schweinfurt green; Described aqueous slkali is preferably alkali-metal silicate or hydroxide solution; The weight average molecular weight of described stabilizing agent polyvinylpyrrolidone is preferably 320000 ~ 400000, and the weight average molecular weight of polyacrylic acid alkali metal salt is preferably 1800 ~ 2400; Described stabilizing agent polyacrylic acid alkali metal salt is preferably Sodium Polyacrylate or polyacrylic acid potassium; Stabilizing agent in maceration extract content be preferably 1 ~ 200g/L; Described stabilizing agent is preferably the mixture of PVP and polyacrylic acid alkali metal salt, and the weight ratio of PVP and polyacrylic acid alkali metal salt is preferably 1:0.05 ~ 50; Described reducing agent is preferably hydrazine hydrate and hydrogen; Described alkali metal acetate is preferably potassium acetate.
Compared with prior art, the preparation of catalyst of the present invention has added stabilizing agent before reduction, can make palladium copper grain shape in catalyst stablize, good dispersion, thus the space time yield that can improve catalyst is with selective.Experimental result shows, reaction pressure is 0.7MPa, 140 ℃ of reaction temperatures, when reacting gas comprises the nitrogen, the acetic acid of 10% mol ratio of propylene, 43% mol ratio of 41% mol ratio and the oxygen of 6% mol ratio, the space time yield of the prepared allyl acetate catalyst of the present invention is brought up to 430g/Lhr by the 380g/Lhr of prior art catalyst, selectively also improve 4.5%, obtained good technique effect.
The specific embodiment
[embodiment 1]
(1) catalyst preparation
Step (a): getting the aqueous solution 1200ml that contains the acid of chlorine palladium and copper chloride is maceration extract, wherein in solution, in solution, palladium content is 2.75g/L, copper content is 0.625 g/L, and the preparing spherical SiO 2 carrier that dipping 1100ml diameter is 4 ~ 6mm obtains catalyst precarsor I;
Step (b): 27.5g nine hydrated sodium silicates are made into the 100 ml aqueous solution and are added in catalyst precarsor I, mix, leave standstill 24hr, then, at 80 ℃ of dry 8hr, make catalyst precarsor II;
Step (c): get the aqueous solution 100ml that contains PVP (weight average molecular weight is 360000), wherein the content of PVP is 100g/L, and impregnated catalyst precursor II makes catalyst precarsor III;
Step (d): catalyst precarsor III is reduced in hydrogen atmosphere, and hydrogen flow rate is 0.2 ml/min, and pressure is 0.5Mpa, and reduction temperature is 200 ℃, obtains catalyst precarsor IV;
Step (e): the dipping potassium acetate aqueous solution, making potassium acetate content is 50g/L, the dry finished catalyst that makes.
For the ease of relatively, the preparation condition of catalyst is listed in to table 1.
(2) catalyst characterization
Carry out the porpezite size of microcrystal in analysis and characterization catalyst with X-ray diffractometer, use inductively coupled plasma spectrum generator (ICP) to measure the content of each element in catalyst.The data obtained is listed in table 2.
(3) evaluating catalyst
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 400ml;
Reaction raw materials composition (in mole hundred parts of ratios): 41% propylene, 43% nitrogen, 10% acetic acid and 6% oxygen;
Raw material volume space velocity: 2000hr
-1;
Reaction pressure: 0.7MPa;
Reaction temperature: 140 ℃;
Reaction time: 500hr;
With the content of each component in gc analysis product, then calculate the space time yield of catalyst, gained test data is listed in table 2.
[embodiment 2] to [embodiment 11]
Changing except the kind containing palladium compound and copper-containing compound, containing the kind of the weight ratio of the weight average molecular weight of the concentration of the kind of the content of palladium compound and copper-containing compound, stabilizing agent, stabilizing agent, stabilizing agent, stabilizing agent, reducing agent and reduction temperature, other steps are all identical with embodiment 1.For the ease of relatively, the preparation condition of catalyst is listed in to table 1, the space time yield of the physical property of catalyst and catalyst and selective data are listed in to table 2.
[comparative example 1]
Get and contain H
2pdCl
4and CuCl
2aqueous solution 1000ml be maceration extract, wherein in solution, palladium content is 2.75g/L, copper content is 0.625 g/L, the preparing spherical SiO 2 carrier that dipping 1100ml diameter is 4 ~ 6mm obtains catalyst precarsor; 27.5g nine hydrated sodium silicates are made into the 100 ml aqueous solution and are added in above-mentioned catalyst precarsor, mix, leave standstill 24hr, then at 80 ℃ of dry 8hr.Dried product is reduced in hydrogen atmosphere, and hydrogen flow rate is 0.2 ml/min, and pressure is 0.5Mpa, and reduction temperature is 200 ℃, and it is 50g/L that dipping liquor kalii acetici makes the content of potassium acetate, the dry catalyst finished product that makes.The method of evaluating performance of catalyst physical property sign and catalyst is with embodiment 1.List in table 1 for ease of the preparation condition of catalyst more just, the space time yield of the physical property of catalyst and catalyst and selective data are listed in to table 2.
[comparative example 2]
Except using ammonium polyacrylate as stabilizing agent, other steps are all identical in embodiment 1.List in table 1 for ease of the preparation condition of catalyst more just, the space time yield of the physical property of catalyst and catalyst and selective data are listed in to table 2.
table 1 catalyst preparation condition
| ? | The kind of palladium copper compound | The content of palladium in maceration extract, g/L | The content of copper in maceration extract, g/L | The kind of stabilizing agent | The weight average molecular weight of stabilizing agent | The content of stabilizing agent, g/L | The weight ratio of stabilizing agent | The kind of reducing agent | Reduction temperature, ℃ |
| Embodiment 1 | Chlorine palladium acid/copper chloride | 2.75 | 0.625 | PVP | 360000 | 100 | - | Hydrogen | 200 |
| Embodiment 2 | Chlorine palladium acid/copper chloride | 2.75 | 0.625 | PVP | 320000 | 1.0 | - | Hydrogen | 200 |
| Embodiment 3 | Chlorine palladium acid/copper chloride | 2.75 | 0.625 | PVP | 400000 | 200 | - | Hydrogen | 200 |
| Embodiment 4 | Chlorine palladium acid/copper chloride | 2.75 | 0.625 | Sodium Polyacrylate | 1800 | 1.0 | - | Hydrogen | 200 |
| Embodiment 5 | Chlorine palladium acid/copper chloride | 2.75 | 0.625 | Sodium Polyacrylate | 2100 | 100 | - | Hydrogen | 200 |
| Embodiment 6 | Chlorine palladium acid/copper chloride | 2.75 | 0.625 | Polyacrylic acid potassium | 2400 | 200 | - | Hydrogen | 200 |
| Embodiment 7 | Chlorine palladium acid/copper chloride | 2.75 | 0.625 | PVP/Sodium Polyacrylate | 360000/2100 | 100 | 0.05 | Hydrogen | 200 |
| Embodiment 8 | Chlorine palladium acid/copper chloride | 2.75 | 0.625 | PVP/Sodium Polyacrylate | 360000/2100 | 100 | 50 | Hydrogen | 200 |
| Embodiment 9 | Chlorine palladium acid/copper chloride | 2.75 | 0.625 | PVP/Sodium Polyacrylate | 360000/2100 | 100 | 25 | Hydrogen | 200 |
| Embodiment 10 | Chlorine palladium acid/copper chloride | 4.58 | 1.04 | PVP/polyacrylic acid potassium | 320000/1800 | 1.0 | 25 | Hydrazine hydrate | 40 |
| Embodiment 11 | Chlorine palladium acid sodium/Schweinfurt green | 11.3 | 9.17 | PVP/polyacrylic acid potassium | 400000/2400 | 200 | 25 | Hydrogen | 200 |
| Comparative example 1 | Chlorine palladium acid/copper chloride | 2.75 | 0.625 | - | ? | - | - | Hydrogen | 200 |
| Comparative example 2 | Chlorine palladium acid/copper chloride | 2.75 | 0.625 | Ammonium polyacrylate | 2100 | 100 | - | Hydrogen | 200 |
table 2 catalyst physical property and evaluating data
Claims (9)
1. for the synthesis of the preparation method of allyl acetate catalyst, with SiO
2, Al
2o
3or its mixture is carrier, load active component comprises Metal Palladium, metallic copper and alkali metal acetate, in catalyst, 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 method is characterized in that and comprises the following steps:
(a) carrier in being dissolved with containing palladium compound and copper-containing compound solution, dipping is obtained to catalyst precarsor I;
(b) process catalyst precarsor I with aqueous slkali and obtain catalyst precarsor II;
(c) catalyst precarsor II is flooded in the solution that contains stabilizing agent and obtains catalyst precarsor III, described stabilizing agent is PVP or polyacrylic acid alkali metal salt or both mixtures;
(d) obtain catalyst precarsor IV with reducing agent reducing catalyst precursor II I;
(e) with alkali metal acetate solution impregnation catalyst precarsor IV, after being dried, make finished catalyst.
2. according to claim 1 for the synthesis of the preparation method of allyl acetate catalyst, it is characterized in that described is the acid of chlorine palladium or chloropalladate containing palladium compound, and copper-containing compound is copper chloride or Schweinfurt green.
3. according to claim 1 for the synthesis of the preparation method of allyl acetate catalyst, it is characterized in that described aqueous slkali is alkali-metal silicate or hydroxide solution.
4. according to claim 1 for the synthesis of the preparation method of allyl acetate catalyst, the weight average molecular weight that it is characterized in that described stabilizing agent polyvinylpyrrolidone is 320000 ~ 400000, and the weight average molecular weight of polyacrylic acid alkali metal salt is 1800 ~ 2400.
5. according to claim 1 for the synthesis of the preparation method of allyl acetate catalyst, it is characterized in that described polyacrylic acid alkali metal salt is polyacrylic acid potassium or Sodium Polyacrylate.
6. according to claim 1 for the synthesis of the preparation method of allyl acetate catalyst, it is characterized in that the content of described stabilizing agent in maceration extract is 1 ~ 200g/L.
7. according to claim 1 for the synthesis of the preparation method of allyl acetate catalyst, it is characterized in that described stabilizing agent is for both mixtures, the weight ratio of PVP and polyacrylic acid alkali metal salt is 1:0.05 ~ 50.
8. according to claim 1 for the synthesis of the preparation method of allyl acetate catalyst, it is characterized in that described reducing agent is hydrazine hydrate or hydrogen.
9. according to claim 1 for the synthesis of the preparation method of allyl acetate catalyst, it is characterized in that described alkali metal acetate is potassium acetate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112517065A (en) * | 2019-09-18 | 2021-03-19 | 中国石油化工股份有限公司 | Preparation method of catalyst for ethylene vapor phase method vinyl acetate process |
| CN112517063A (en) * | 2019-09-18 | 2021-03-19 | 中国石油化工股份有限公司 | Preparation method of vinyl acetate catalyst |
| CN114478253A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Synthesis method of methyl methacrylate and obtained methyl methacrylate |
| CN116550383A (en) * | 2023-07-12 | 2023-08-08 | 中国天辰工程有限公司 | Preparation method of unsaturated acetate and catalyst thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0291045A (en) * | 1988-09-29 | 1990-03-30 | Showa Denko Kk | Production 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 |
| CN101157029A (en) * | 2007-11-12 | 2008-04-09 | 中国海洋石油总公司 | A dicyclopentadiene hydrogenation special-purpose catalyzer and its preparing method |
| CN101850265A (en) * | 2010-06-11 | 2010-10-06 | 中国海洋石油总公司 | Method for preparing catalyst by hydrofining lubricating oil and application of catalyst |
-
2012
- 2012-12-19 CN CN201210553909.0A patent/CN103878022B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0291045A (en) * | 1988-09-29 | 1990-03-30 | Showa Denko Kk | Production 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 |
| CN101157029A (en) * | 2007-11-12 | 2008-04-09 | 中国海洋石油总公司 | A dicyclopentadiene hydrogenation special-purpose catalyzer and its preparing method |
| CN101850265A (en) * | 2010-06-11 | 2010-10-06 | 中国海洋石油总公司 | Method for preparing catalyst by hydrofining lubricating oil and application of catalyst |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112517065A (en) * | 2019-09-18 | 2021-03-19 | 中国石油化工股份有限公司 | Preparation method of catalyst for ethylene vapor phase method vinyl acetate process |
| CN112517063A (en) * | 2019-09-18 | 2021-03-19 | 中国石油化工股份有限公司 | Preparation method of vinyl acetate catalyst |
| CN112517065B (en) * | 2019-09-18 | 2023-05-02 | 中国石油化工股份有限公司 | Preparation method of catalyst for vinyl acetate process by ethylene gas phase method |
| CN112517063B (en) * | 2019-09-18 | 2023-08-04 | 中国石油化工股份有限公司 | Preparation method of vinyl acetate catalyst |
| CN114478253A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Synthesis method of methyl methacrylate and obtained methyl methacrylate |
| CN116550383A (en) * | 2023-07-12 | 2023-08-08 | 中国天辰工程有限公司 | Preparation method of unsaturated acetate and catalyst thereof |
| CN116550383B (en) * | 2023-07-12 | 2023-10-31 | 中国天辰工程有限公司 | Preparation method of unsaturated acetate and catalyst thereof |
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