CN1329941A - Regeneration method of carbonyl sulfide hydrolysis catalyst - Google Patents
Regeneration method of carbonyl sulfide hydrolysis catalyst Download PDFInfo
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- CN1329941A CN1329941A CN00111192A CN00111192A CN1329941A CN 1329941 A CN1329941 A CN 1329941A CN 00111192 A CN00111192 A CN 00111192A CN 00111192 A CN00111192 A CN 00111192A CN 1329941 A CN1329941 A CN 1329941A
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- Prior art keywords
- renovation process
- catalyst
- impregnating agent
- compound
- contained
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- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000011069 regeneration method Methods 0.000 title description 5
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 title description 3
- 230000007062 hydrolysis Effects 0.000 title 1
- 238000006460 hydrolysis reaction Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 4
- 238000009418 renovation Methods 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 5
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 5
- 230000002779 inactivation Effects 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000007796 conventional method Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 5
- 229910052782 aluminium Inorganic materials 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- 230000001172 regenerating effect Effects 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000008141 laxative Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001543 purgative effect Effects 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
A process for regenerating the catalyst used to hydrolyze COS includes such steps as calcining deactivated catalyst at a certain temp, washing with deionized water or ammonia water, and immersing in impregnant containing metallic compound at ordinary temp. The regenerated catalyst can be widely used for removing COS in various process gases.
Description
The present invention relates to a kind of renovation process of decaying catalyst, specifically, relate to the renovation process behind a kind of cos (COS) hydrolyst inactivation.
The COS hydrolyst is after moving 1～2 year on the commercial plant, activity obviously descends, but active component content is still very high in the catalyst of inactivation, mechanical strength changes less, thereby is necessary it is regenerated, thereby prolongs its service life, economize on the use of funds, increase the benefit.US4 mentions the renovation process that feeds hot non-absorbent purgative gas in reactor in 098,684, and regeneration temperature is 177～316 ℃; US4, the renovation process that inactivation COS hydrolyst adopts in 835,338 is: the air, hydro carbons gas, the N that feed heating in reactor
2Or other indifferent gas, hot air temperature is 150～300 ℃, duration of ventilation 2h.But about COS hydrolyst renovation process at normal temperatures, still the end is seen practicality and is effectively reported at present.
The purpose of this invention is to provide a kind of inactivation hydrolyst renovation process at normal temperatures.
In order to achieve the above object, can be earlier the decaying catalyst roasting, and then through wash, boil, methods such as dipping, drying make it to regenerate.Concrete grammar is as follows:
(1) at a certain temperature, be generally 350 ℃～650 ℃, preferably under 400 ℃～550 ℃, roasting a period of time, be generally 4～6 hours decaying catalyst;
(2) catalyst after the roasting is washed with deionized water or ammoniacal liquor, and boil 2～3 times;
(3) catalyst after step (2) processing is flooded with the impregnating agent that contains metallic compound, this metallic compound can be one or more alkali-metal compounds, perhaps one or more alkaline earth metal compounds, or the mixture of said two devices; In the ratio of the contained Al of decaying catalyst carrier, the amount of metallic compound is 0.1～7.0% in the impregnating agent, is preferably 2.0～6.0%;
The contained metallic compound of impregnating agent can be hydroxide, carbonate or the nitrate of alkali metal or alkaline-earth metal;
(4) catalyst after step (3) processing is carried out drying with conventional method, can obtain regenerated catalyst.
The renovation process technology that the present invention adopts is simple, and especially flooding operation can carry out at normal temperatures, easy to operate, is easy to industrialization; And alkali metal and alkaline earth metal compounds are cheap and easy to get in the used impregnating agent, and cost is lower; Catalyst activity height after the regeneration, the catalyst of present technique regeneration moves on 10,000 tons of/year methanol units, and the COS conversion ratio reaches more than 94%, has guaranteed the normal operation of methanol unit; Catalyst applied range after the present technique regeneration can be widely used in removing of COS in methyl methanol syngas, propylene, conversion gas, coal gas and other material gas, and hydrolysing activity is suitable with fresh hydrolyst.
For the present invention is described better.We spy enumerates following embodiment.But the present invention is not limited to following embodiment.
Embodiment 1,2,3,4
Decaying catalyst roasting in Muffle furnace earlier, sintering temperature is respectively 350 ℃, and 450 ℃, 550 ℃, 650 ℃, measure activity of such catalysts after the roasting, the time is 5h, the activity of test regenerated catalyst.
Activity of such catalysts can be represented with the COS conversion ratio.
Test reaction carries out in glass reactor, and tube inner diameter is φ 6mm, and it is 20～40 orders that catalyst powder is broken into granularity, gets 0.5ml, and 50 ℃ of reaction temperatures, gas space velocity are 3000h
-1, pressure is normal pressure, unstripped gas is N
2Allocating concentration into is 100mg/m
3COS, measure into implication and the content of COS in working off one's feeling vent one's spleen with chromatograph, both differences are the conversion ratio of COS.Following catalyst activity method of testing herewith.
Active testing the results are shown in Table 1.
Table 1
Embodiment 5
| Embodiment | 1 | ?2 | ????3 | ????4 |
| Sintering temperature ℃ | 350 | ?450 | ????550 | ????650 |
| COS conversion ratio (%) | 15.68 | ?35.72 | ????53.0 | ????21.38 |
Decaying catalyst soaks, boils with deionized water behind 550 ℃ of roasting 5h, washs 3 times, and drainage, oven dry then, recording the COS conversion ratio is 63.98%.
Embodiment 6
Decaying catalyst soaks, boils, washs 3 times with ammoniacal liquor behind 550 ℃ of roasting 5h, drainage, oven dry then, and recording the COS conversion ratio is 64.72%.
Embodiment 7
Decaying catalyst soaks, boils, washs 2～3 times with deionized water behind 550 ℃ of roasting 5h, and with the impregnating agent dipping that contains potash, the K/Al ratio is 4.5wt%, drainage, oven dry then, and recording the COS conversion ratio is 94.72%.
Embodiment 8,9,10,11
K/Al is respectively 0,2%, 4%, 6%, and other condition is identical with embodiment 7, records the table 2 that the results are shown in of COS conversion ratio.
Table 2
Comparative example 1
| Embodiment | ????8 | ????9 | ????10 | ????11 |
| K/Al is than (%) | ????0 | ????2 | ????4 | ????6 |
| Active (COS conversion ratio %) | ????63.92 | ????91.23 | ????93.69 | ????94.02 |
Get fresh COS hydrolyst, detect its activity, recording the COS conversion ratio is 94.92%.Comparative example 2
Decaying catalyst does not process, and detects its activity, and recording the COS conversion ratio is 7.83%.
Claims (13)
1, the renovation process of a kind of cos (hereinafter to be referred as COS) hydrolyst, it comprises:
(a): with catalyst a period of time of roasting at a certain temperature of inactivation;
(b): the catalyst of step (a) gained is washed with ammoniacal liquor or deionized water, and boil 2～3 times;
(c): the catalyst of step (b) gained is flooded with the impregnating agent that contains metallic compound at normal temperatures;
(d): the catalyst after will flooding is drying to obtain regenerated catalyst with conventional method.
2, renovation process as claimed in claim 1 is characterized in that the sintering temperature in the step (a) is 350 ℃～650 ℃.
3, any renovation process as claimed in claim 1 or 2 is characterized in that the sintering temperature in the step (a) is 450 ℃～550 ℃.
4, renovation process as claimed in claim 1 is characterized in that the roasting time in the step (a) is 4～6 hours.
5, renovation process as claimed in claim 1 is characterized in that the contained metallic compound of impregnating agent is one or more alkali-metal compounds in the step (c), or one or more alkaline earth metal compounds, or their mixture.
6, renovation process as claimed in claim 1 is characterized in that in the step (c) in the impregnating agent that the ratio of carrier aluminum is 0.1～7.0wt% in the total amount of contained metallic compound and decaying catalyst.
7, the ratio of carrier aluminum is 2.0～6.0wt% in the renovation process as claimed in claim 6, the total amount that it is characterized in that the contained metallic compound of impregnating agent and decaying catalyst.
8, renovation process according to claim 5 is characterized in that alkali metal compound contained in the impregnating agent is the compound of sodium.
9, renovation process according to claim 5 is characterized in that alkali metal compound contained in the impregnating agent is the compound of potassium.
10, renovation process according to claim 5 is characterized in that alkali metal compound contained in the impregnating agent is the compound of lithium.
11, renovation process according to claim 5 is characterized in that alkaline earth metal compound contained in the impregnating agent is the compound of calcium.
12, renovation process according to claim 5 is characterized in that alkaline earth metal compound contained in the impregnating agent is the compound of magnesium.
13, renovation process as claimed in claim 1 is characterized in that the metallic compound in the step (c) is hydroxide, carbonate or nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001111922A CN1136054C (en) | 2000-06-20 | 2000-06-20 | Regeneration method of carbonyl sulfide hydrolysis catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001111922A CN1136054C (en) | 2000-06-20 | 2000-06-20 | Regeneration method of carbonyl sulfide hydrolysis catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1329941A true CN1329941A (en) | 2002-01-09 |
| CN1136054C CN1136054C (en) | 2004-01-28 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001111922A Expired - Fee Related CN1136054C (en) | 2000-06-20 | 2000-06-20 | Regeneration method of carbonyl sulfide hydrolysis catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1136054C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101961654A (en) * | 2010-09-15 | 2011-02-02 | 昆明理工大学 | Method for regenerating carbonyl sulfide hydrolysis catalyst after inactivation |
| CN101670302B (en) * | 2009-09-27 | 2012-09-05 | 昆明理工大学 | Regeneration method of inactivated carbonyl sulfide hydrolysis catalyst taking activated carbon as carrier |
| JP2015080767A (en) * | 2013-10-23 | 2015-04-27 | 三菱重工業株式会社 | Catalyst regeneration method for cos conversion catalyst |
| CN105228746A (en) * | 2013-12-27 | 2016-01-06 | 三菱重工业株式会社 | The catalyst recovery process of COS reforming catalyst |
| CN111729692A (en) * | 2020-05-19 | 2020-10-02 | 福州大学 | Regeneration method of inactivated COS (COS) hydrolyzing agent |
-
2000
- 2000-06-20 CN CNB001111922A patent/CN1136054C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101670302B (en) * | 2009-09-27 | 2012-09-05 | 昆明理工大学 | Regeneration method of inactivated carbonyl sulfide hydrolysis catalyst taking activated carbon as carrier |
| CN101961654A (en) * | 2010-09-15 | 2011-02-02 | 昆明理工大学 | Method for regenerating carbonyl sulfide hydrolysis catalyst after inactivation |
| CN101961654B (en) * | 2010-09-15 | 2013-04-10 | 昆明理工大学 | Method for regenerating carbonyl sulfide hydrolysis catalyst after inactivation |
| JP2015080767A (en) * | 2013-10-23 | 2015-04-27 | 三菱重工業株式会社 | Catalyst regeneration method for cos conversion catalyst |
| CN105451884A (en) * | 2013-10-23 | 2016-03-30 | 三菱重工业株式会社 | Method for regenerating cos conversion catalyst |
| EP2998024A4 (en) * | 2013-10-23 | 2016-11-30 | Mitsubishi Heavy Ind Ltd | Method for regenerating cos conversion catalyst |
| US9604206B2 (en) | 2013-10-23 | 2017-03-28 | Mitsubishi Heavy Industries, Ltd. | Method for regenerating COS hydrolysis catalyst |
| CN105451884B (en) * | 2013-10-23 | 2017-12-12 | 三菱重工业株式会社 | The catalyst recovery process of COS reforming catalysts |
| CN105228746A (en) * | 2013-12-27 | 2016-01-06 | 三菱重工业株式会社 | The catalyst recovery process of COS reforming catalyst |
| EP2987553A4 (en) * | 2013-12-27 | 2016-07-27 | Mitsubishi Heavy Ind Ltd | Catalyst regeneration method for cos conversion catalyst |
| CN111729692A (en) * | 2020-05-19 | 2020-10-02 | 福州大学 | Regeneration method of inactivated COS (COS) hydrolyzing agent |
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| Publication number | Publication date |
|---|---|
| CN1136054C (en) | 2004-01-28 |
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Owner name: CHINA PETROLEUM & CHEMICAL CORPORATION Free format text: FORMER OWNER: QILU PETROCHEMICAL GROUP CO., CHINA PETROCHEMICAL CORP. Effective date: 20080104 |
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Effective date of registration: 20080104 Address after: Linzi Zibo District, Shandong province Sinopec Qilu Branch of science and technology Patentee after: Sinopec Corp. Address before: 124 letter from Zibo City, Shandong Province Patentee before: Qilu Petrochemical Co., China Petrochemical Group Corp. |
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Granted publication date: 20040128 Termination date: 20130620 |