CN103878023A - Preparation method of catalyst for synthesizing vinyl acetate - Google Patents
Preparation method of catalyst for synthesizing vinyl acetate Download PDFInfo
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- CN103878023A CN103878023A CN201210553951.2A CN201210553951A CN103878023A CN 103878023 A CN103878023 A CN 103878023A CN 201210553951 A CN201210553951 A CN 201210553951A CN 103878023 A CN103878023 A CN 103878023A
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Abstract
The invention relates to a preparation method of a catalyst for synthesizing vinyl acetate, and mainly overcomes the problems of low load rate and loss of noble metals in preparation of a catalyst for preparing vinyl acetate in the prior art. By adopting a technical solution that employs a nitrogen-containing complexing agent in an impregnation solution, wherein the nitrogen-containing complexing agent is ethanediamine or thiourea or a mixture of the above two, the technical problems are overcome relatively well. The preparation method can be used for industrial production of the catalyst for synthesizing vinyl acetate.
Description
Technical field
The present invention relates to the preparation method of vinyl acetate catalyst.
Background technology
Vinyl acetate is important industrial chemicals, is widely used in aspects such as manufacturing polyvinyl alcohol, vinyl copolymer resins, binding agent, coating, textile processing, paper coating.The main method of producing vinyl acetate in the world today is take ethene, oxygen and acetic acid as raw material, makes catalyst with palladium-Jin-potassium acetate/silica, synthesizes by gas phase catalytic reaction.
U.S. Pat P 3275680(title is: Production of Organic Acetate in Presence of a Noble Metal Catalyst and Oxygen) 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 palladium of original water soluble and golden salt are changed into palladium and the gold of the insoluble hydroxide state of water, then in reducing gases, reduce palladium and the Au catalyst of hydroxide state, be reduced into palladium and the Au catalyst of metallic state, washing, dry, soak potassium acetate, after being dried, obtain described catalyst.It is low that this preparation method has golden load factor, the noble metal serious shortcoming that runs off.
Summary of the invention
Technical problem to be solved by this invention is that in present technology, to prepare the load factor of vinyl acetate catalyst gold low, the problem that noble metal runs off, a kind of preparation method of catalyzer for synthesizing vinyl acetate is provided, use this preparation method to have and can improve golden load factor, reduce the feature of the loss of noble metal.
In order to solve the problems of the technologies described above, technical scheme of the present invention is as follows: the preparation method of catalyzer for synthesizing vinyl acetate, and with SiO
2, Al
2o
3or its mixture is carrier, load active component comprises Metal Palladium, metallic gold and alkali metal acetate, in catalyst, the content of palladium is that the content of 1 ~ 12g/L, gold is that the content of 0.1 ~ 10g/L, alkali metal acetate is 10 ~ 100g/L, and the method comprises the following steps:
(a) in the solution that dissolves gold-containing compound, add nitrogenous complexing agent to mix, add carrier impregnation, make catalyst precarsor I;
(b) catalyst precarsor I dipping is dissolved with in the solution containing palladium compound, makes catalyst precarsor II;
(c) process catalyst precarsor II with aqueous slkali and obtain catalyst precarsor III;
(d) obtain catalyst precarsor IV with reducing agent reducing catalyst precursor II I;
(e) at 200 ~ 500 ℃, calcined catalyst precursor I V makes catalyst precarsor V;
(f) with alkali metal acetate solution impregnation catalyst precarsor V, after being dried, make described catalyst;
Wherein said nitrogenous complexing agent is preferably ethylenediamine or thiocarbamide or both mixtures.
In technique scheme, described gold-containing compound is preferably gold chloride or chloroaurate; The described palladium compound that contains is preferably the acid of chlorine palladium or chloropalladate; The weight ratio of described gold-containing compound and nitrogenous complexing agent is preferably 1:0.5 ~ 10; When described nitrogenous complexing agent is the mixture of ethylenediamine and thiocarbamide, the weight ratio of ethylenediamine and thiocarbamide is preferably 1:0.1 ~ 5; Described aqueous slkali is preferably alkali-metal silicate or hydroxide; Described reducing agent is preferably hydrogen or hydrazine hydrate; Described alkali metal acetate is preferably potassium acetate.
Experimental result shows, in maceration extract, the content of palladium is 2.75g/L, when the content of gold is 0.625g/L, bring up to 95% by 87% of prior art by the load factor of the catalyst gold of this preparation method's gained, be 0.7MPa in reaction pressure, 140 ℃ of reaction temperatures, when reacting gas comprises the nitrogen, the acetic acid of 10% mol ratio of ethene, 43% mol ratio of 41% mol ratio and the oxygen of 6% mol ratio, the present invention prepares the space time yield of vinyl acetate catalyst and brings up to 580g/Lhr by the 560g/Lhr of prior art catalyst, has obtained good technique effect.
The specific embodiment
[embodiment 1]
(1) catalyst preparation
Step (a): get and contain HAuCl
4solution 1200ml, wherein the content of gold is 0.625g/L, in above-mentioned solution, add 6.54g ethylenediamine (weight ratio of gold chloride and ethylenediamine is 1:5), mix, the preparing spherical SiO 2 carrier that then floods 1100ml diameter and be 4 ~ 6mm obtains catalyst precarsor I;
Step (b): get and contain H
2pdCl
4aqueous solution 1200ml be maceration extract, wherein in solution, palladium content is 2.75g/L, impregnated catalyst precursor I makes catalyst precarsor II;
Step (c): 27.5g nine hydrated sodium silicates are made into the 100 ml aqueous solution and are added in catalyst precarsor II, mix, leave standstill 24hr, then, at 80 ℃ of dry 8hr, make 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): calcined catalyst future IV obtains catalyst precarsor V at 300 ℃;
Step (f): 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
Use inductively coupled plasma spectrum generator (ICP) to measure the content of each element in the catalyst of regeneration front and back.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% ethene, 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 8]
Except the kind of the composition of the weight ratio of gold-containing compound kind, kind containing the kind of palladium compound, nitrogenous complexing agent, gold-containing compound and nitrogenous complexing agent, nitrogenous complexing agent, sintering temperature, reducing agent and reduction temperature change, 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 data of the physical property of catalyst and catalyst are listed in to table 2.
[comparative example 1]
Get and contain HAuCl
4and H
2pdCl
4aqueous solution 1200ml be maceration extract, wherein in solution, palladium content is 2.75g/L, gold 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 data of the physical property of catalyst and catalyst are listed in to table 2.
[comparative example 2]
In omitting embodiment 1, step (e), 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 data of the physical property of catalyst and catalyst are listed in to table 2.
[comparative example 3]
Except using 6.54g calgon, (molecular formula is Na
6p
6o
18) replace ethylenediamine be outside complexing agent, 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 data of the physical property of catalyst and catalyst are listed in to table 2.
[comparative example 4]
Except using the anhydrous EDTA-2Na of 6.54g to replace ethylenediamine for complexing agent, 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 data of the physical property of catalyst and catalyst are listed in to table 2.
table 1. catalyst preparation condition
| ? | The kind of porpezite compound | The content of palladium in maceration extract, g/L | The content of gold in maceration extract, g/L | Nitrogenous complexing agent kind | The weight ratio of gold-containing compound and nitrogenous complexing agent | The weight ratio of nitrogenous complexing agent | Reducing agent kind | Reduction temperature, ℃ | Sintering temperature, ℃ |
| Embodiment 1 | Chlorine palladium acid/gold chloride | 2.75 | 0.625 | Ethylenediamine | 1：5 | - | Hydrogen | 200 | 300 |
| Embodiment 2 | Chlorine palladium acid/gold chloride | 2.75 | 0.625 | Thiocarbamide | 1：5 | - | Hydrogen | 200 | 300 |
| Embodiment 3 | Chlorine palladium acid/gold chloride | 2.75 | 0.625 | Ethylenediamine/thiocarbamide | 1：0.5 | 1：0.1 | Hydrogen | 200 | 200 |
| Embodiment 4 | Chlorine palladium acid/gold chloride | 2.75 | 0.625 | Ethylenediamine/thiocarbamide | 1：5 | 1：2.5 | Hydrogen | 200 | 300 |
| Embodiment 5 | Chlorine palladium acid/gold chloride | 2.75 | 0.625 | Ethylenediamine/thiocarbamide | 1：10 | 1：5 | Hydrogen | 200 | 500 |
| Embodiment 6 | Chlorine palladium acid/gold chloride | 4.58 | 1.04 | Ethylenediamine/thiocarbamide | 1：5 | 1：2.5 | Hydrogen | 200 | 300 |
| Embodiment 7 | Chlorine palladium acid/gold chloride | 11.3 | 9.17 | Ethylenediamine/thiocarbamide | 1：5 | 1：2.5 | Hydrogen | 200 | 300 |
| Embodiment 8 | Chlorine palladium acid sodium/sodium chloraurate | 2.75 | 0.625 | Ethylenediamine/thiocarbamide | 1：10 | 1：5 | Hydrazine hydrate | 40 | 300 |
| Comparative example 1 | Chlorine palladium acid/gold chloride | 2.75 | 0.625 | - | - | - | Hydrogen | 200 | 300 |
| Comparative example 2 | Chlorine palladium acid/gold chloride | 2.75 | 0.625 | Ethylenediamine | 1：5 | - | Hydrogen | 200 | - |
| Comparative example 3 | Chlorine palladium acid/gold chloride | 2.75 | 0.625 | Calgon | 1：5 | - | Hydrogen | 200 | 300 |
| Comparative example 4 | Chlorine palladium acid/gold chloride | 2.75 | 0.625 | Calgon | 1：5 | - | Hydrogen | 200 | 300 |
table 2 catalyst physical property and evaluating data
| ? | Palladium content, g/L | Potassium acetate content, g/L | The load factor of gold, % | Space time yield, g/Lhr |
| Embodiment 1 | 3.0 | 50 | 91.6 | 568 |
| Embodiment 2 | 3.0 | 50 | 91.4 | 567 |
| Embodiment 3 | 3.0 | 50 | 93.6 | 570 |
| Embodiment 4 | 3.0 | 50 | 95.0 | 580 |
| Embodiment 5 | 3.0 | 50 | 94.2 | 574 |
| Embodiment 6 | 1.0 | 10 | 94.5 | 576 |
| Embodiment 7 | 12 | 100 | 94.7 | 578 |
| Embodiment 8 | 3.0 | 50 | 94.8 | 578 |
| Comparative example 1 | 3.0 | 50 | 87.0 | 560 |
| Comparative example 2 | 3.0 | 50 | 94.6 | 530 |
| Comparative example 3 | 3.0 | 50 | 87.3 | 522 |
| Comparative example 4 | 3.0 | 50 | 87.5 | 510 |
Claims (7)
1. the preparation method of catalyzer for synthesizing vinyl acetate, with SiO
2, Al
2o
3or its mixture is carrier, load active component comprises Metal Palladium, metallic gold and alkali metal acetate, in catalyst, the content of palladium is that the content of 1 ~ 12g/L, gold 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) in the solution that dissolves gold-containing compound, add nitrogenous complexing agent to mix, add carrier impregnation, make catalyst precarsor I;
(b) catalyst precarsor I dipping is dissolved with in the solution containing palladium compound, makes catalyst precarsor II;
(c) process catalyst precarsor II with aqueous slkali and obtain catalyst precarsor III;
(d) obtain catalyst precarsor IV with reducing agent reducing catalyst precursor II I;
(e) at 200 ~ 500 ℃, calcined catalyst precursor I V makes catalyst precarsor V;
(f) with alkali metal acetate solution impregnation catalyst precarsor V, after being dried, make described catalyst;
Wherein said nitrogenous complexing agent is ethylenediamine or thiocarbamide or both mixtures.
2. the preparation method for the synthesis of vinyl acetate catalyst according to claim 1, is characterized in that described gold-containing compound is gold chloride or chloroaurate, is the acid of chlorine palladium or chloropalladate containing palladium compound.
3. the preparation method for the synthesis of vinyl acetate catalyst according to claim 1, is characterized in that the weight ratio of described gold-containing compound and nitrogenous complexing agent is 1:0.5 ~ 10.
4. the preparation method for the synthesis of vinyl acetate catalyst according to claim 1, while it is characterized in that described nitrogenous complexing agent is ethylenediamine and thiocarbamide mixture, the weight ratio of ethylenediamine and thiocarbamide is 1:0.1 ~ 5.
5. the preparation method for the synthesis of vinyl acetate catalyst according to claim 1, is characterized in that described aqueous slkali is preferably alkali-metal silicate or hydroxide.
6. the preparation method for the synthesis of vinyl acetate catalyst according to claim 1, is characterized in that described reducing agent is hydrogen or hydrazine hydrate.
7. the preparation method for the synthesis of vinyl acetate catalyst according to claim 1, is characterized in that described alkali metal acetate is potassium acetate.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106423269A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Unsaturated acetic ester catalyst and preparing method thereof |
| CN106423284A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparing method thereof |
| CN107282136A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The preparation method and vinyl acetate synthesis method of vinyl acetate catalyst |
| CN107866277A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | The preparation method of vinyl acetate catalyst |
| CN111135840A (en) * | 2018-11-06 | 2020-05-12 | 中国科学院大连化学物理研究所 | Preparation method of supported monatomic dispersed noble metal catalyst |
| CN114177939A (en) * | 2020-09-14 | 2022-03-15 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by acetylene method |
| CN115845845A (en) * | 2022-11-21 | 2023-03-28 | 北京沐秀新能源科技有限公司 | Catalyst for flameless combustion of low-quality oilfield associated gas and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1268396A (en) * | 1999-03-30 | 2000-10-04 | 中国石油化工集团公司 | Preparation method of catalyst for producing vinyl acetate |
| CN1539552A (en) * | 2003-04-23 | 2004-10-27 | 中国石化上海石油化工股份有限公司 | Catalyzer in use for synthesizing vinyl acetate, and preparation method |
| JP2010275160A (en) * | 2009-05-29 | 2010-12-09 | Bridgestone Corp | Intermediate film for heat ray shielding laminated glass and heat ray shielding laminated glass |
| CN102247864A (en) * | 2011-05-26 | 2011-11-23 | 中国海洋石油总公司 | Preparation method of catalyst for hydrogenation desulfurization and denitrification of light-weight oil |
-
2012
- 2012-12-19 CN CN201210553951.2A patent/CN103878023B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1268396A (en) * | 1999-03-30 | 2000-10-04 | 中国石油化工集团公司 | Preparation method of catalyst for producing vinyl acetate |
| CN1539552A (en) * | 2003-04-23 | 2004-10-27 | 中国石化上海石油化工股份有限公司 | Catalyzer in use for synthesizing vinyl acetate, and preparation method |
| JP2010275160A (en) * | 2009-05-29 | 2010-12-09 | Bridgestone Corp | Intermediate film for heat ray shielding laminated glass and heat ray shielding laminated glass |
| CN102247864A (en) * | 2011-05-26 | 2011-11-23 | 中国海洋石油总公司 | Preparation method of catalyst for hydrogenation desulfurization and denitrification of light-weight oil |
Cited By (12)
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|---|---|---|---|---|
| CN106423269A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Unsaturated acetic ester catalyst and preparing method thereof |
| CN106423284A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparing method thereof |
| CN106423284B (en) * | 2015-08-12 | 2019-01-25 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
| CN106423269B (en) * | 2015-08-12 | 2019-06-11 | 中国石油化工股份有限公司 | Unsaturated acetic acid ester catalyst and preparation method thereof |
| CN107282136A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The preparation method and vinyl acetate synthesis method of vinyl acetate catalyst |
| CN107866277A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | The preparation method of vinyl acetate catalyst |
| CN107866277B (en) * | 2016-09-26 | 2020-06-09 | 中国石油化工股份有限公司 | Preparation method of vinyl acetate catalyst |
| CN111135840A (en) * | 2018-11-06 | 2020-05-12 | 中国科学院大连化学物理研究所 | Preparation method of supported monatomic dispersed noble metal catalyst |
| CN111135840B (en) * | 2018-11-06 | 2021-11-23 | 中国科学院大连化学物理研究所 | Preparation method of supported monatomic dispersed noble metal catalyst |
| CN114177939A (en) * | 2020-09-14 | 2022-03-15 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by acetylene method |
| CN114177939B (en) * | 2020-09-14 | 2023-08-08 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by acetylene method |
| CN115845845A (en) * | 2022-11-21 | 2023-03-28 | 北京沐秀新能源科技有限公司 | Catalyst for flameless combustion of low-quality oilfield associated gas and preparation method and application thereof |
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