CN102463129A - Catalyst for carbonyl sulfide hydrolysis - Google Patents
Catalyst for carbonyl sulfide hydrolysis Download PDFInfo
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- CN102463129A CN102463129A CN2010105519327A CN201010551932A CN102463129A CN 102463129 A CN102463129 A CN 102463129A CN 2010105519327 A CN2010105519327 A CN 2010105519327A CN 201010551932 A CN201010551932 A CN 201010551932A CN 102463129 A CN102463129 A CN 102463129A
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- Prior art keywords
- catalyst
- carbonyl sulfide
- sulfide hydrolysis
- cos
- percent
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Abstract
The invention relates to a catalyst for carbonyl sulfide hydrolysis, which mainly solves the problems that the catalyst in the prior art has a narrow reaction temperature interval, and the application material gas air speed is low. The catalyst for the carbonyl sulfide hydrolysis adopts the technical scheme that the catalyst comprises the following ingredients in percentage by weight: (1) 1 to 5 percent of materials selected from alkali carbonate, alkaline earth metal oxide or mixtures of the alkali carbonate and the alkaline earth metal oxide; (2) 15 to 25 percent of rare earth oxide; and (3) 70 to 82 percent of Al2O3. The technical problems are perfectly solved, and the catalyst can be used in industrial production of carbonyl-sulfide-containing compound removal in petroleum gas, natural gas and refinery gas.
Description
Technical field
The present invention relates to a kind of catalyst that is used for carbonyl sulfide hydrolysis.
Background technology
It is in the chemical process of raw material that cos (COS) extensively is present in coal, oil, natural gas, and its existence is contaminated environment not only, and can cause catalyst poisoning in the subsequent production process, and product quality descends, equipment corrosion.Hydrolysis is to remove the most practical method of organic sulfur such as COS, and its process equation formula is: COS+H
2O → H
2S+CO
2, organic sulfur is converted into easy-to-handle H
2S is converted into S at last and reclaims.
Japan Patent JP2,002,224,572 disclose the method for a kind of cos catalyst and hydrolyzing carbonyl sulfur, and this catalyst loads on γ-Al with sodium carbonate or potash
2O
3On, the COS hydrolysising reacting temperature is 200 ℃.
U.S. Pat P4,5111,668 disclose a kind of with TiO
2Be carrier, contain a kind of alkali metal, alkaline-earth metal COS hydrolyst at least, but this catalyst in use handles unstripped gas COS content and be merely 73ppm, and reaction temperature is higher, is 200～400 ℃ as active component.
Chinese patent CN1069673 discloses a kind of normal tempreture organic sulphur hydrolysis catalyst, and it is at spherical gamma-Al
2O
3Last load 2～5%K
2CO
3, the weak point of this catalyst is that unstripped gas COS content and air speed are all lower, is respectively 1～5mg/m
3With 2,000hr
-1
Chinese patent CN1134312 discloses a kind of by 4～20wt%TiO
2And γ-Al
2O
3The organic sulfur hydrolyst of forming, the weak point of this catalyst is that air speed is merely 1,800hr
-1
Chinese patent CN1304781 discloses a kind of 83～97% γ-Al that consists of
2O
3, 2～25%K
2The COS hydrolyst of O, 0.12BaO, less than 150 ℃, COS content is less than 800mg/m in temperature
3, air speed 6,000～9,000hr
-1Carry out desulfurization under the condition, the COS hydrolysis conversion is greater than 95%.
The weak point of the catalyst of above-mentioned prior art is: the reaction temperature interval of COS hydrolysis is narrower, and the unstripped gas air speed that is suitable for is low.
Summary of the invention
Technical problem to be solved by this invention is that the catalyst reaction temperatures interval that exists in the prior art is narrow, and the technical problem that applicable raw materials gas air speed is low provides a kind of new catalyst that is used for carbonyl sulfide hydrolysis.This catalyst is used for the carbonyl sulfide hydrolysis reaction, has the characteristics that reaction temperature is wide, adapt to higher unstripped gas air speed concurrently.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of catalyst that is used for carbonyl sulfide hydrolysis comprises following component by weight percentage:
(a) be selected from alkali carbonate, alkaline earth oxide or its mixture 1～5%;
(b) rare earth oxide 15～25%;
(c)Al
2O
370～82％。
In the technique scheme, said rare earth oxide preferred version is selected from La
2O
3, Nd
2O
3, Sm
2O
3, Eu
2O
3Or Gd
2O
3In at least a; Said alkali carbonate preferred version is selected from Na
2CO
3Or K
2CO
3Said alkaline earth oxide preferred version is selected from least a among MgO, CaO or the BaO; Said Al
2O
3Preferred version is γ-Al
2O
3
Key problem in technology of the present invention is that the rare earth oxide that contains in the catalytic component and the interaction of aluminium oxide have improved activity of such catalysts, thereby has increased temperature applicable range and improved air speed.Experimental result shows that the temperature range that catalyst of the present invention is suitable for is 50～300 ℃, the empty scooter 20 of unstripped gas, 000hr
-1, obtained better technical effect.
Preparation of catalysts method of the present invention is following:
(1) chooses pulverous γ-Al
2O
3With Powdered rare earth oxide under 60～100 ℃ condition, preferred 85～95 ℃, hydrothermal treatment consists 2～8 hours, preferred 4～6 hours, process colloidal, left standstill 8～15 hours.
(2) mixture with step (1) gained was descending dry 16～24 hours at 100～130 ℃, the sample compressing tablet, fragmentation, the screening that obtain, and it is subsequent use to get its 40～60 order sample.
(3) be alkali carbonate Na with active component
2CO
3, K
2CO
3With at least a being distributed in the pure water of alkaline earth oxide MgO, CaO, BaO institute constitute, it is subsequent use to be configured to 10% dispersion liquid.
(4) sample with step (2) is impregnated in the dispersion liquid of step (3), floods 8～10 hours, descends dry 16～24 hours at 100～130 ℃ then, is required catalyst.
Through embodiment the present invention is done further elaboration below.
The specific embodiment
[embodiment 1]
Preparation of Catalyst: take by weighing the pulverous γ-Al of 75g respectively
2O
3With the Powdered La of 20g
2O
3, adding the 800ml deionized water, hydrothermal treatment consists is 4 hours under 85 ℃ of conditions, leaves standstill 10 hours; 110 ℃ of dryings 18 hours, get 40～60 purpose samples after compressing tablet, fragmentation, the screening then as required carrier; Take by weighing 20gNa
2CO
3Dissolve in the 180g pure water, be configured to 10% solution, the 50g solution impregnation was required catalyst in 10 hours 110 ℃ of dryings then to the 95g carrier.For ease of relatively the composition of catalyst being listed in table 1.
Evaluating catalyst: be reflected in Ф 10 * 300 fixed bed quartz tube reactors and carry out, temperature is 50 ℃, COS content 100ppm, mol ratio H
2O: COS is 10, air speed 5,000hr
-1Evaluation result shows that the COS conversion ratio of catalyst of the present invention is greater than 90%.For ease of relatively the appreciation condition and the evaluation result of catalyst being listed in table 2
[embodiment 2～11]
Catalyst preparation process embodiment 1, and the concrete composition of catalyst is seen table 1, and the appreciation condition and the evaluation result of catalyst are seen table 2.The result shows that catalyst of the present invention goes for the air speed 5000～20 of 50～300 ℃ of temperature ranges and unstripped gas, 000hr
-1Scope.
[embodiment 12]
Get the 1 prepared catalyst by embodiment, at 50～300 ℃, air speed is 10,000hr
-1, COS content is under the 100ppm condition, the COS conversion ratio is as shown in table 3.The result shows that further catalyst of the present invention can adapt to very wide temperature range.
The composition of table 1 catalyst of the present invention
Table 2 catalyst activity appreciation condition and COS conversion ratio
| Temperature (℃) | Air speed (h -1) | COS concentration (ppm) | COS conversion ratio (%) | |
| Embodiment 1 | 50 | 5,000 | 100 | 91.5 |
| Embodiment 2 | 80 | 10,000 | 100 | 95.0 |
| Embodiment 3 | 100 | 10,000 | 150 | 96.8 |
| Embodiment 4 | 120 | 15,000 | 150 | 99.0 |
| Embodiment 5 | 150 | 15,000 | 150 | 99.1 |
| Embodiment 6 | 200 | 10,000 | 200 | 99.4 |
| Embodiment 7 | 250 | 15,000 | 250 | 99.2 |
| Embodiment 8 | 200 | 15,000 | 250 | 99.9 |
| Embodiment 9 | 300 | 20,000 | 300 | 99.5 |
| Embodiment 10 | 200 | 15,000 | 250 | 99.7 |
| Embodiment 11 | 150 | 10.000 | 200 | 99.6 |
Table 3 temperature is to the influence of Catalyst for CO S hydrolysing activity
| Temperature, ℃ | 50 | 100150200 | 250 | 300 |
| COS conversion ratio % | 91.5 | 99.299.699.9 | 99.9 | 99.7 |
Claims (5)
1. catalyst that is used for carbonyl sulfide hydrolysis comprises following component by weight percentage:
(a) be selected from alkali carbonate, alkaline earth oxide or its mixture 1～5%;
(b) rare earth oxide 15～25%;
(c)Al
2O
370～82％。
2. according to the said catalyst that is used for carbonyl sulfide hydrolysis of claim 1, it is characterized in that said rare earth oxide is selected from La
2O
3, Nd
2O
3, Sm
2O
3, Eu
2O
3Or Gd
2O
3In at least a.
3. according to the said catalyst that is used for carbonyl sulfide hydrolysis of claim 2, it is characterized in that said alkali carbonate is Na
2CO
3Or K
2CO
3
4. according to the said catalyst that is used for carbonyl sulfide hydrolysis of claim 3, it is characterized in that said alkaline earth oxide is selected from least a among MgO, CaO or the BaO.
5. according to the said catalyst that is used for carbonyl sulfide hydrolysis of claim 1, it is characterized in that said Al
2O
3Be γ-Al
2O
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105519327A CN102463129B (en) | 2010-11-17 | 2010-11-17 | Catalyst for carbonyl sulfide hydrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105519327A CN102463129B (en) | 2010-11-17 | 2010-11-17 | Catalyst for carbonyl sulfide hydrolysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102463129A true CN102463129A (en) | 2012-05-23 |
| CN102463129B CN102463129B (en) | 2013-12-04 |
Family
ID=46067424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105519327A Active CN102463129B (en) | 2010-11-17 | 2010-11-17 | Catalyst for carbonyl sulfide hydrolysis |
Country Status (1)
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|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1593751A (en) * | 2004-06-25 | 2005-03-16 | 同济大学 | Rare earth hydroxide catalyst for moderate/low temperature carbonyl sulfur hydrolysis and preparation method thereof |
| CN101121123A (en) * | 2007-07-25 | 2008-02-13 | 太原理工大学 | Medium temperature carbon bisulfide hydrolytic catalyst and preparation method and application thereof |
| US20080242749A1 (en) * | 2004-07-22 | 2008-10-02 | Rudolf Robert Gouman | Process For the Removal of Cos From a Synthesis Gas Stream Comprising H2S and Cos |
-
2010
- 2010-11-17 CN CN2010105519327A patent/CN102463129B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1593751A (en) * | 2004-06-25 | 2005-03-16 | 同济大学 | Rare earth hydroxide catalyst for moderate/low temperature carbonyl sulfur hydrolysis and preparation method thereof |
| US20080242749A1 (en) * | 2004-07-22 | 2008-10-02 | Rudolf Robert Gouman | Process For the Removal of Cos From a Synthesis Gas Stream Comprising H2S and Cos |
| CN101121123A (en) * | 2007-07-25 | 2008-02-13 | 太原理工大学 | Medium temperature carbon bisulfide hydrolytic catalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《石油与天然气化工》 20071231 柯明等 "常温羰基硫水解催化剂的研究进展" 第1，271－274页 1-5 第36卷, 第4期 * |
| 柯明等: ""常温羰基硫水解催化剂的研究进展"", 《石油与天然气化工》, vol. 36, no. 4, 31 December 2007 (2007-12-31) * |
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| Publication number | Publication date |
|---|---|
| CN102463129B (en) | 2013-12-04 |
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