CN103657734B - The renovation process of vinyl acetate commercial plant decaying catalyst - Google Patents
The renovation process of vinyl acetate commercial plant decaying catalyst Download PDFInfo
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- CN103657734B CN103657734B CN201210324513.9A CN201210324513A CN103657734B CN 103657734 B CN103657734 B CN 103657734B CN 201210324513 A CN201210324513 A CN 201210324513A CN 103657734 B CN103657734 B CN 103657734B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention relates to the renovation process of vinyl acetate commercial plant decaying catalyst, mainly solve the problem that the space time yield of existing renovation process gained regeneration vinyl acetate catalyst is low.The invention provides the renovation process of vinyl acetate commercial plant decaying catalyst, the carrier of described decaying catalyst is SiO
2, Al
2o
3or its mixture, described carrier loadedly have Metal Palladium, metallic gold, alkali metal acetate and acetic acid, comprises the following steps: aqueous solution a) in order to water or reducing agent is that wash liquid washs described decaying catalyst; B) at oxygenous atmosphere and 150 ~ 650 DEG C of process 2 ~ 10hr, with volume percentage oxygenous 5 ~ 100% in wherein said oxygenous atmosphere; C) reduce with reducing agent; D) flood alkali metal acetate solution, drying obtains the technical scheme of regenerated catalyst, preferably resolves this problem, can be used in the regeneration production of vinyl acetate commercial plant decaying catalyst.
Description
Technical field
The present invention relates to the renovation process of vinyl acetate commercial plant decaying catalyst.
Background technology
Vinyl acetate is important industrial chemicals, is widely used in aspects such as manufacturing polyvinyl alcohol, vinyl copolymer resin, binding agent, coating, textile processing, paper coating.The main method of the world today producing vinyl acetate is with ethene, oxygen and acetic acid for raw material, makes catalyst with palladium-Jin-potassium acetate/silica, is synthesized by gas phase catalytic reaction.But it is well-known, in commercial Application process, due to reasons such as noble metal grain growths, catalysqt deactivation is common phenomenon, in general, the catalyst of vinyl acetate commercial plant inactivation mainly comprises the impurity such as catalyst carrier, porpezite isoreactivity component and acetic acid, because the noble metals such as porpezite do not run off in a large number, enable decaying catalyst by regeneration activity recovery, therefore the regeneration techniques of catalyst becomes study hotspot.Chinese patent application (application number 99803776.1) provides and a kind ofly adopts water vapour and use the catalyst exposure after a period of time, and make the method that catalyst activity recovers, the method exists the low problem of regenerated catalyst space time yield.
Summary of the invention
Technical problem to be solved by this invention is the problem that in prior art, regenerated catalyst space time yield is low, a kind of renovation process of vinyl acetate commercial plant decaying catalyst is provided, uses the regeneration vinyl acetate catalyst of this renovation process gained to have the high feature of space time yield.
For solving the problems of the technologies described above, technical scheme of the present invention is as follows: the renovation process of vinyl acetate commercial plant decaying catalyst, and the carrier of described decaying catalyst is SiO
2, Al
2o
3or its mixture, described carrier loadedly have Metal Palladium, metallic gold, alkali metal acetate and acetic acid, wherein in decaying catalyst, the content of palladium is 0.9 ~ 11g/L, the content of gold is 0.08 ~ 8g/L, the content of alkali metal acetate is 7 ~ 80g/L, content 2.0 ~ the 10g/L of acetic acid, the porpezite crystal grain of described decaying catalyst is 8 ~ 10nm, comprises the following steps:
A) aqueous solution in order to water or reducing agent is that wash liquid washs described decaying catalyst;
B) at oxygenous atmosphere and 150 ~ 650 DEG C of process 2 ~ 10hr, with volume percentage oxygenous 5 ~ 100% in wherein said oxygenous atmosphere;
C) reduce with reducing agent;
D) flood alkali metal acetate solution, drying obtains regenerated catalyst, and wherein in regenerated catalyst, alkali metal acetate content is 10 ~ 90g/L.
In technique scheme step a) described in wash liquid can be preferably the aqueous solution of hydrazine hydrate, the now concentration of hydrazine hydrate more preferably 100 ~ 900g/L; Step a) described in wash liquid can preferably from the aqueous solution of following reducing agent: formic acid, sodium formate or formaldehyde, now step a) washs the temperature more preferably 40 ~ 100 DEG C of described decaying catalyst with described wash liquid, and wherein the concentration of the aqueous solution of reducing agent is further preferably 10 ~ 600g/L; In technique scheme, step is a) that the temperature that wash liquid washs described decaying catalyst is preferably 40 ~ 100 DEG C in order to water; Step a) described in the weight ratio of decaying catalyst and described wash liquid be preferably 1:2 ~ 20; Step c) described in reducing agent can be selected from as hydrazine hydrate, formic acid, sodium formate, formaldehyde; When reducing agent in described step c) is hydrazine hydrate, reduction temperature is preferably greater than zero degree ~ 40 DEG C, wherein the concentration of hydrazine hydrate more preferably 100 ~ 900g/L; When reducing agent in described step c) is formic acid, sodium formate and formaldehyde, reduction temperature is preferably 40 ~ 100 DEG C, the concentration more preferably 10 ~ 600g/L of reducing agent; Step c) described in reducing agent can preferred hydrogen, reduction temperature preferably 100 ~ 400 DEG C, hydrogen can adopt pure hydrogen, uses, such as, adopt the nitrogen hydrogen mixture with volume percentage hydrogen 5-25% after reacting the preferred hydrogen nitrogen of milder or inert gas dilution.
In technique scheme, the concentration of hydrazine hydrate is to contain N in often liter of hydrazine hydrate solution
2h
4h
2the grams meter of O.
Through commercial Application, because of noble metal grain growth, activity reduces even after inactivation catalyst, the inventive method is adopted to regenerate, noble metal crystal grain disperseed again thus improves the space time yield of regenerated catalyst, and overcoming the cracked defect of regenerated catalyst due to the washing step that have employed step a) before carrying out redox process.Experimental result shows, reaction pressure is 0.7MPa, reaction temperature 140 DEG C, when reacting gas comprises the oxygen of the ethene of 41% mol ratio, the nitrogen of 43% mol ratio, the acetic acid of 10% mol ratio and 6% mol ratio, the space time yield of regenerated catalyst of the present invention brings up to 560g/Lhr by the 320g/Lhr of prior art catalyst, achieves good technique effect.
Detailed description of the invention
[embodiment 1]
(1) catalyst regeneration
Step (a): the catalyst 600g getting inactivation in commercial plant, wherein catalyst carrier is the preparing spherical SiO 2 of 4 ~ 6mm, in catalyst, the content of palladium is 2.8g/L, the content of gold is 0.6g/L, potassium acetate content is 18g/L, acetic acid content is 2.0g/L, and porpezite size of microcrystal is 9.5nm, by this catalyst at 70 DEG C 7000g pure water (namely step a) in the weight ratio of decaying catalyst and wash liquid be 1:11.7) process;
Step (b): 300 DEG C of process 6hr in the oxygen-nitrogen mixed-gas atmosphere containing 20% oxygen with volume basis;
Step (c): with hydrogen content with temperature in the hydrogen nitrogen mixture atmosphere of volume percentage 10% be 260 DEG C reduction 3hr.
Step (d): dipping liquor kalii acetici, supplements potassium acetate content to 30g/L.
For the ease of comparing, the regeneration condition of catalyst is listed in table 1.
(2) catalyst characterization
Use X-ray diffractometer carrys out the porpezite size of microcrystal in analysis and characterization regenerated catalyst, uses inductively coupled plasma spectrum generator (ICP) to measure the content of each element in catalyst before and after regeneration.The data obtained lists in table 2.
(3) evaluating catalyst
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 400g;
Reaction raw materials composition (in mole hundred parts of ratios): the ethene of 41%, the nitrogen of 43%, the acetic acid of 10% and the oxygen of 6%;
Reaction raw materials Feed space velocities: 2000hr
-1;
Reaction pressure: 0.7MPa;
Reaction temperature: 140 DEG C;
Reaction time: 500hr;
With the content of each component in gas chromatography analytical reactions product, then calculate the space time yield of catalyst, gained test data lists in table 2.
[embodiment 2] to [embodiment 11]
Except step a) in weight ratio, the step b of the physical property of decaying catalyst, wash temperature, the kind of wash liquid, the concentration of reducing agent wash liquid, decaying catalyst and wash liquid) in oxygen content, the temperature and time of oxygen treatments applied, the kind of reducing agent in step c), the concentration of reducing agent, the amount of supplementing potassium acetate in step d) change except, other steps are all identical with embodiment 1.For the ease of comparing, the physical data of catalyst before and after the regeneration condition of catalyst, regeneration and regenerated catalyst space time yield are listed in table 1 and table 2.
[comparative example 1]
The vinyl acetate catalyst of inactivation in commercial plant is evaluated without the appreciation condition that any process is as identical in embodiment 1.For the ease of comparing, the physical data of regeneration procatalyst and regeneration procatalyst space time yield are listed in table 2.
[comparative example 2]
With reference to adopting the disclosed technology of Chinese patent application (application number 99803776.1).The oxygen mixed gas process 4h of the vinyl acetate catalyst of inactivation in commercial plant to be used in temperature be 150 DEG C of pressure to be the steam of 13.8kPa and pressure be 13.8kPa, and assay step is all identical in embodiment 1, for the ease of comparing, the physical data of catalyst before and after regeneration and regenerated catalyst space time yield are listed in table 2.
[comparative example 3]
By the vinyl acetate catalyst of inactivation in commercial plant without wash liquid process directly with volume basis containing the oxygen-nitrogen mixed-gas atmosphere of 20% oxygen in 300 DEG C of process 6hr, obtain the catalyst fines that average grain diameter in irregular shape is 0.5 ~ 1.5mm, particle thin like this will cause beds pressure drop too high, therefore regenerate nonsensical, stop regeneration also not carry out catalyst performance evaluation.
table 1. catalyst regeneration conditions
table 2 catalyst physical property and evaluating data
Claims (7)
1. the renovation process of vinyl acetate commercial plant decaying catalyst, the carrier of described decaying catalyst is SiO
2, Al
2o
3or its mixture, described carrier loadedly have Metal Palladium, metallic gold, alkali metal acetate and acetic acid, wherein in decaying catalyst, the content of palladium is 0.9 ~ 11g/L, the content of gold is 0.08 ~ 8g/L, the content of alkali metal acetate is 7 ~ 80g/L, content 2.0 ~ the 10g/L of acetic acid, the porpezite crystal grain of described decaying catalyst is 8 ~ 10nm, comprises the following steps:
A) aqueous solution in order to water or reducing agent is that wash liquid washs described decaying catalyst;
B) at oxygenous atmosphere and 150 ~ 650 DEG C of process 2 ~ 10hr, with volume percentage oxygenous 5 ~ 100% in wherein said oxygenous atmosphere;
C) reduce with reducing agent;
D) flood alkali metal acetate solution, drying obtains regenerated catalyst, and wherein in regenerated catalyst, alkali metal acetate content is 10 ~ 90g/L;
Step a) described in reducing agent be selected from hydrazine hydrate, formic acid or formaldehyde.
2. the renovation process of vinyl acetate commercial plant decaying catalyst according to claim 1, is characterized in that the concentration of hydrazine hydrate in the aqueous solution of hydrazine hydrate described in step a) is 100 ~ 900g/L.
3. the renovation process of vinyl acetate commercial plant decaying catalyst according to claim 1, is characterized in that step is a) 40 ~ 100 DEG C by the temperature that described wash liquid washs described decaying catalyst.
4. the renovation process of vinyl acetate commercial plant decaying catalyst according to claim 1, is characterized in that step be a) temperature that wash liquid washs described decaying catalyst in order to water is 40 ~ 100 DEG C.
5. the renovation process of vinyl acetate commercial plant decaying catalyst according to claim 1, is characterized in that the weight ratio of decaying catalyst described in step a) and described wash liquid is 1:2 ~ 20.
6. the renovation process of vinyl acetate commercial plant decaying catalyst according to claim 1, is characterized in that step c) described in reducing agent be hydrazine hydrate, formic acid, sodium formate, formaldehyde.
7. the renovation process of vinyl acetate commercial plant decaying catalyst according to claim 1, is characterized in that step c) described in reducing agent be hydrogen, reduction temperature 100 ~ 400 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210324513.9A CN103657734B (en) | 2012-09-05 | 2012-09-05 | The renovation process of vinyl acetate commercial plant decaying catalyst |
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| CN201210324513.9A CN103657734B (en) | 2012-09-05 | 2012-09-05 | The renovation process of vinyl acetate commercial plant decaying catalyst |
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| CN103657734A CN103657734A (en) | 2014-03-26 |
| CN103657734B true CN103657734B (en) | 2015-12-09 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3650983A (en) * | 1969-12-23 | 1972-03-21 | Nat Distillers Chem Corp | Alkaline wash reactivation of palladium catalysts used in vinyl acetate synthesis |
| CN1089885A (en) * | 1992-10-14 | 1994-07-27 | 赫希斯特人造丝公司 | Vinyl acetate catalyst preparation method |
| CN1114917A (en) * | 1994-07-13 | 1996-01-17 | 中国石油化工总公司 | Catalyzer and carrier for synthetic unsaturated acid ester |
| WO1999039824A1 (en) * | 1998-02-05 | 1999-08-12 | Engelhard Corporation | Suppression of aging for pd-au vinyl acetate monomer catalyst |
| CN1921938A (en) * | 2004-02-24 | 2007-02-28 | 利安德化学技术有限公司 | Catalyst regeneration process |
-
2012
- 2012-09-05 CN CN201210324513.9A patent/CN103657734B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3650983A (en) * | 1969-12-23 | 1972-03-21 | Nat Distillers Chem Corp | Alkaline wash reactivation of palladium catalysts used in vinyl acetate synthesis |
| CN1089885A (en) * | 1992-10-14 | 1994-07-27 | 赫希斯特人造丝公司 | Vinyl acetate catalyst preparation method |
| CN1114917A (en) * | 1994-07-13 | 1996-01-17 | 中国石油化工总公司 | Catalyzer and carrier for synthetic unsaturated acid ester |
| WO1999039824A1 (en) * | 1998-02-05 | 1999-08-12 | Engelhard Corporation | Suppression of aging for pd-au vinyl acetate monomer catalyst |
| CN1921938A (en) * | 2004-02-24 | 2007-02-28 | 利安德化学技术有限公司 | Catalyst regeneration process |
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