CN103878023B - The preparation method of catalyzer for synthesizing vinyl acetate - Google Patents
The preparation method of catalyzer for synthesizing vinyl acetate Download PDFInfo
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Abstract
The present invention relates to the preparation method of vinyl acetate catalyst, mainly solve the problem of the load factor low noble metal loss of preparing vinyl acetate catalyst gold in present technology, by adopting complexing agent nitrogenous in maceration extract, described nitrogenous complexing agent is the technical scheme of ethylenediamine or thiocarbamide or both mixtures, solve preferably this technical problem, can be used in the industrial production of vinyl acetate catalyst.
Description
Technical field
The present invention relates to the preparation method of vinyl acetate catalyst.
Background technology
Vinyl acetate is important industrial chemicals, be widely used in manufacture polyvinyl alcohol, vinyl copolymer resins, binding agent,The aspects such as coating, textile processing, paper coating. The main method of producing vinyl acetate in the world today is with ethene, oxygenWith acetic acid be raw material, make catalyst with palladium-Jin-potassium acetate/silica, synthesize by gas phase catalytic reaction.
US Patent No. P3275680(title is: ProductionofOrganicAcetateinPresenceOfaNobleMetalCatalystandOxygen) provide one to prepare load to have major catalyst noble metal, help catalysisThe preparation method of the catalyst of agent metal and alkali metal or alkaline earth metal compound. Its concrete manufacture process is as follows: will configureNoble metal and the mixed liquor of co-catalyst add, dry, then by alkaline matter for processing such as sodium metasilicate by original water solublePalladium and golden salt change into palladium and the gold of the insoluble hydroxide state of water, then in reducing gases, reduce palladium and the gold of hydroxide stateCatalyst, is reduced into palladium and the Au catalyst of metallic state, and washing is dry, soaks potassium acetate, obtains described catalysis after dryAgent. 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, expensiveThe problem of metal loss, provides a kind of preparation method of catalyzer for synthesizing vinyl acetate, and using this preparation method to have can carryThe load factor of Gao Jin, the feature of the loss of minimizing noble metal.
In order to solve the problems of the technologies described above, technical scheme of the present invention is as follows: the preparation side of catalyzer for synthesizing vinyl acetateMethod, with SiO2、Al2O3Or its mixture is carrier, load active component comprises Metal Palladium, metallic gold and alkali metal acetate, urgesIn agent, 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, shouldMethod comprises the following steps:
(a) in the solution that dissolves gold-containing compound, add nitrogenous complexing agent to mix, add carrier impregnation, makeCatalyst 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 DEG C, 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; Described excellent containing palladium compoundElect the acid of chlorine palladium or chloropalladate as; The weight ratio of described gold-containing compound and nitrogenous complexing agent is preferably 1:0.5 ~ 10; DescribedWhen nitrogenous complexing agent is the mixture of ethylenediamine and thiocarbamide, the weight ratio of ethylenediamine and thiocarbamide is preferably 1:0.1 ~ 5; Described alkaliSolution is preferably alkali-metal silicate or hydroxide; Described reducing agent is preferably hydrogen or hydrazine hydrate; Described alkali metal vinegarHydrochlorate 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, makes with thisThe load factor of the catalyst gold of Preparation Method gained brings up to 95% by 87% of prior art, is 0.7MPa in reaction pressure, reaction140 DEG C of temperature, reacting gas comprises the acetic acid of nitrogen, 10% mol ratio of ethene, 43% mol ratio of 41% mol ratio and 6% moleWhen the oxygen of ratio, the space time yield that the present invention prepares vinyl acetate catalyst is improved by the 560g/Lhr of prior art catalystTo 580g/Lhr, obtain good technique effect.
Detailed description of the invention
[embodiment 1]
(1) catalyst preparation
Step (a): get and contain HAuCl4Solution 1200ml, wherein gold content be 0.625g/L, in above-mentioned solutionAdd 6.54g ethylenediamine (weight ratio of gold chloride and ethylenediamine is 1:5), mix, then flood 1100ml diameter and be 4 ~The preparing spherical SiO 2 carrier of 6mm obtains catalyst precarsor I;
Step (b): get and contain H2PdCl4Aqueous 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 100ml aqueous solution and are added in catalyst precarsor II, mix allEven, leave standstill 24hr, then, at 80 DEG C of dry 8hr, make catalyst precarsor III;
Step (d): catalyst precarsor III is reduced in hydrogen atmosphere, and hydrogen flow rate is 0.2ml/min, and pressure is0.5MPa, reduction temperature is 200 DEG C, obtains catalyst precarsor IV;
Step (e): calcined catalyst future IV obtains catalyst precarsor V at 300 DEG C;
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. InstituteObtain data and list 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 DEG C;
Reaction time: 500hr;
With the content of each component in gc analysis product, then calculate the space time yield of catalyst, gainedTest data is listed in table 2.
[embodiment 2] to [embodiment 8]
Except gold-containing compound kind, containing kind, the gold-containing compound of the kind of palladium compound, nitrogenous complexing agent with containKind and the reduction temperature of the composition of the weight ratio of the complexing agent of nitrogen, nitrogenous complexing agent, sintering temperature, reducing agent changeOutward, other steps are all identical with embodiment 1. For the ease of relatively, the preparation condition of catalyst is listed in to table 1, by catalystThe space time yield data of physical property and catalyst are listed in table 2.
[comparative example 1]
Get and contain HAuCl4And H2PdCl4Aqueous solution 1200ml be maceration extract, wherein in solution, palladium content is 2.75g/L,Gold content is 0.625g/L, and the preparing spherical SiO 2 carrier that dipping 1100ml diameter is 4 ~ 6mm obtains catalyst precarsor; Will27.5g nine hydrated sodium silicates are made into the 100ml aqueous solution and are added in above-mentioned catalyst precarsor, mix, and leave standstill 24hr, thenAt 80 DEG C of dry 8hr. Dried product is reduced in hydrogen atmosphere, and hydrogen flow rate is 0.2ml/min, and pressure is0.5MPa, reduction temperature is 200 DEG C, it is 50g/L that dipping liquor kalii acetici makes the content of potassium acetate, the dry catalyst one-tenth that makesProduct. The method of evaluating performance of catalyst physical property sign and catalyst is with embodiment 1. For ease of the bar of preparing of catalyst more justPart is listed in table 1, and 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 comparing, willThe preparation condition of catalyst is listed in table 1, and 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 Na6P6O18) replace ethylenediamine be outside complexing agent, other stepsAll identical with embodiment 1. For the ease of relatively, the preparation condition of catalyst is listed in to table 1, by the physical property of catalyst and catalystSpace time yield data list in table 2.
[comparative example 4]
Except using the anhydrous EDTA-2Na of 6.54g to replace ethylenediamine for complexing agent, other steps all with embodiment 1 phaseWith. For the ease of relatively, the preparation condition of catalyst is listed in to table 1, by the space time yield number of the physical property of catalyst and catalystAccording to listing in table 2.
Table 1. catalyst preparation condition
| The kind of porpezite compound | Palladium in maceration extractContent, g/L | In maceration extract goldContent, g/L | Nitrogenous complexing agent kindClass | Gold-containing compound and nitrogenousThe weight ratio of complexing agent | Nitrogenous complexing agentWeight ratio | Reducing agent kind | Reduction temperature, DEG C | Sintering temperature, DEG C | |
| 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 3 --> |
| 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 SiO2、Al2O3Or its mixture is carrier, load active component bagDraw together Metal Palladium, metallic gold and alkali metal acetate, in catalyst, the content of palladium is that the content of 1～12g/L, gold is 0.1～10g/The content of 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 catalysisAgent precursor 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 DEG C, 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 complexing agent is the mixture of ethylenediamine and thiocarbamide.
2. the preparation method for the synthesis of vinyl acetate catalyst according to claim 1, is characterized in that described containing goldCompound 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 described containing goldThe weight ratio of 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, it is characterized in that ethylenediamine withThe weight ratio of 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 alkali is moltenLiquid 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 reductionAgent 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 alkaliMetal acetate salt is potassium acetate.
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| 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 |
| 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 |
| 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 |
| 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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| 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 |
| 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 |
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| 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 |
| 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 |
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