CN102319565A - Acid-gas-containing Claus sulfur recovery catalyst and preparation method thereof - Google Patents
Acid-gas-containing Claus sulfur recovery catalyst and preparation method thereof Download PDFInfo
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- CN102319565A CN102319565A CN201110231935A CN201110231935A CN102319565A CN 102319565 A CN102319565 A CN 102319565A CN 201110231935 A CN201110231935 A CN 201110231935A CN 201110231935 A CN201110231935 A CN 201110231935A CN 102319565 A CN102319565 A CN 102319565A
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Abstract
The invention relates to an acid-gas-containing Claus sulfur recovery catalyst and a preparation method thereof. The acid-gas-containing Claus sulfur recovery catalyst is characterized in that active aluminum oxide is used as carriers, ferric oxide is used as active ingredients, the ferric oxide content in the active aluminum oxide carriers is 4 to 5 percent, the alkaline earth metal content is 0.5 to 0.15 percent, and the catalyst is prepared by a twice-dipping method. The catalyst provided by the invention overcomes the defects that the existence form of iron of the traditional ferrous active aluminum oxide catalyst is indefinite or the distribution of Fe2O3 is not uniform, the impurity iron influence is caused in the preparation process, and the like. Simultaneously, the acid-gas-containing Claus sulfur recovery catalyst also has the characteristic of loading a small amount of alkaline earth metal so that the organic sulfur hydrolysis activity is overcome. In addition, compared with ordinary active aluminum oxide catalysts, the acid-gas-containing Claus sulfur recovery catalyst overcomes the defect of catalyst activity loss caused by sulfuric acid salinization poisoning because of the occurrence of trace oxygen and sulfur dioxide and overcomes the defects of small specific area, poor intensity and high performance cost of the pure titanium oxide catalysts. The HQHG-971 sulfur recovery catalyst provided by the invention can be used by full bed layers and can also be filled to a 1/3 position of the upper part of the ordinary aluminum oxide catalysts. The temperature use range is 180 DEG C to 400 DEG C, the hydrolysis rates of COS and CS2 respectively reach 99 percent and 70 percent, and the highest temperature resistance is 700 DEG C.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the catalyst for clause recovering sulfur of acid gas-containing.Be sulphur recovery catalysis and the preparation method that a kind of high-strength and high Crouse's activity and antioxygen can be good.
Background technology
Crouse's recovery technology of sulfur originates from the eighties.After 20th century, realized industrialization the thirties, be widely used in the process of coals such as the production of synthetic ammonia and methanol feedstock gas, refinery gas processing, natural gas purification, oil, natural gas.What in sweetening process, produce contains H
2Reclaim sulphur in the S gas, both can obtain good economic benefit, can solve the pollution problem of industrial waste gas again atmosphere.The claus process characteristics are that flow process is simple, flexible operation, recovery sulphur purity is high, investment cost is low, environment and scale and benefit are remarkable; The purity that claus process reclaims Sulfur can reach 99.8%; Can be used as a kind of sulphur resource of producing sulfuric acid, also can make the industrial chemicals of other departments.In recent years, along with the control increasingly stringent of various countries' environmental pollution, many in the world major companies and scientific research institution have strengthened the exploitation to the sulfur recovery technology, many new technologies, new technology have occurred.According to incompletely statistics, total sulfur recovery facility more than 150 covers in the whole nation in 2011.
The essence of claus reaction process is the partial oxidation reduction reaction, and the main chemical reactions formula of its claus process is:
?H
2S?+3/2O
2?=SO
2?+?H
2O?+Ｑ(1)
2H
2S?+?SO
2=3/XSx?+?2H
2O+Ｑ?(2)
H
2S?+CO
2?=COS+?H
2O+Ｑ?(3)
2H
2S?+CO
2?=CS
2+?H
2O+Ｑ?(4)
Wherein reaction (1) (2) are to carry out at high-temperature area (being higher than 800 ℃) Crouse's combustion furnace, a large amount of side reactions also takes place simultaneously generate COS and CS
2But conversion ratio is no more than 70%; At low-temperature region (being lower than 400 ℃) catalytic reaction (2) taking place, mainly is to carry out catalytic reaction on the beds in converter, and the hydrolysis of organic sulfur takes place simultaneously.General through pyroreaction and two-stage catalytic reaction, H
2The S conversion ratio can reach more than 97%.
The speed of elevated temperature heat reaction (1) (2) reaction is very fast, generally can in 1 s, accomplish.
Low-temperature catalyzed reaction is because this process is exothermic reaction, and theoretically, reaction temperature is low more, and conversion ratio is high more.But, when reaction temperature is lower than the sulphur dew point, has a large amount of molten sulfurs and be deposited on catalyst surface, it is lost activity, the catalytic reaction temperature generally is controlled at 170～350 ℃ for this reason.Along with the raising of system sulphur technical merit, catalytic reaction also can be carried out below the sulphur dew point, like CBA method and MCRC method etc.The sulfur recovery rate of elevated temperature heat reaction and one-level catalytic reaction in order to improve sulfur recovery rate, normal employing increase converter quantity, converter between is provided with condenser separation molten sulfur industry in generally at 75 %～90 %, and reduces measure such as catalytic reaction temperature step by step.
Catalyst for clause recovering sulfur is initial use be the bauxite catalyst, developed activated alumina after the sixties in succession and replaced bauxite.Mainly contain active oxidation Lv Cuiization Ji ﹑ iron content titanium-contained aluminum oxide catalyst and Ti-base catalyst at present.Advantage is separately respectively arranged.Activated alumina catalyst is a kind of well behaved catalyst for recovering sulfur, uses initial activity good, and certain hydrolysis property is also arranged simultaneously.Research and industrial practice show: activated alumina catalyst receives the restriction operation elasticity of operating condition little, and easily sulfation is poisoned and activity reduces very soon.
Ti-base catalyst better performances, but the cost height that involves great expense, intensity is less and abrasion are bigger.The iron content aluminium oxide catalyst is because the difference of the different dipping methods of raw material, intensity, and specific surface, still there be shortcoming and advantage separately in anti-poisoning capability and omitted oxygen and Crouse's activity.
Summary of the invention
The purpose of this invention is to provide a kind of high strength, have the catalyst for recovering sulfur of the active and omitted oxygen of high Crouse.It is high to overcome general iron containing compounds alumina base catalyst sulfate radical content, the preparation method of the iron-based catalyst for recovering sulfur that the while tempreture organic sulphur hydrolysis is effective.
Iron-based catalyst for recovering sulfur of the present invention is a carrier with the activated alumina, is active constituent with the di-iron trioxide, and the ferric oxide content in the active aluminum oxide carrier is 4-5%, and alkaline earth metal content is that 0.5-0.15% is prepared from through twice dipping method.
The predecessor of active component is selected FeSO for use
4.7H
2O is mixed with solution, and as for flooding in the dipping tank, dip time was controlled at two hours with active aluminum oxide carrier, carries out drying after dipping complete back filter is done; Prepare certain density ammoniacal liquor simultaneously, the catalyst of drying was flooded 2 hours in the dipping ammonia solution, carry out drying after draining again; The catalyst normal temperature of oven dry is washed with soft water, wash four times, detect sulfate radical; Until sulfate radical-free is qualified, carries out drying, the finished catalyst that roasting is.
The di-iron trioxide that the present invention adopted is meant FeSO
4.7H
2O.
Of the present invention for guaranteeing the even FeSO of dipping at precursor solution
4.7H
2A spot of dense H during the preparation of O
2SO
4Control PH prevents that about 2.2 the ferrous ion hydrolysis from generating deposition, gives rotation that any hot blast do not stop simultaneously and guarantee that solution evenly and do not have crystal and separate out under the rotation of mixer.Fully guaranteed the variation that brings on the active component predecessor physical chemistry.Its purpose of dipping ammonia solution is that ammonia follows sulfate radical reaction generation sulfate of ammoniac water-soluble, has solved the high problem of catalyst sulfuric acid radical ion content.The washing of catalyst further cements out residual sulphur acid ion in the catalyst pores a spot of other foreign ion of level.Through the skeleton of roasting rear catalyst and structure and because of other ions impaired.
The advantage of catalyst for recovering sulfur of the present invention:
Catalyst of the present invention has overcome the not clear or Fe of traditional iron content activated alumina catalyst iron existence form
2O
3Skewness and preparation process are brought the shortcomings such as influence of foreign ion.Also have the characteristics that load small amount of alkali earth metal has just overcome the active end of tempreture organic sulphur hydrolysis simultaneously.Compare with common activated alumina catalyst in addition, overcome existence generation sulfation poisoning, the shortcoming that causes catalyst activity to scatter and disappear because of the oxygen and the sulfur dioxide of trace.And the little ﹑ of pure zirconia titanium catalyst specific surface spend by force the high shortcoming of poor ﹑ cost performance HQHG-971 catalyst for recovering sulfur of the present invention full bed use, also can fill in 1/3rd of common aluminium oxide catalyst top and use.The temperature scope of application is 180 ℃～400 ℃, COS, CS
2Percent hydrolysis then reaches 99% and 70% respectively, and high-temperature resistant is 700 ℃.
The specific embodiment
Embodiment 1 (Comparative Examples)
Take by weighing FeSO
4.7H
2O13g is dissolved in the 10ml soft water, regulates between the PH 2.0-2.2.With 250 ℃ of oven dry specifications is in the ￠ 4-6mm active aluminum oxide carrier 20g dipping solution, and dip time 2 hours stirred time with glass bar in each one hour, and then 120 ℃ of oven dry 2 hours, 320 ℃ of roastings 4 hours promptly get sample A.
Embodiment 2 (Comparative Examples)
Take by weighing FeSO
4.7H
2O5g and 7g Fe (NO
3)
3.9H
2O is dissolved in the 100ml soft water, regulates between the PH 2.0-2.2.With 250 ℃ of oven dry specifications is in the ￠ 4-6mm active aluminum oxide carrier 20g dipping solution, and dip time 2 hours stirred time with glass bar in each one hour, and then 120 ℃ of oven dry 2 hours, 320 ℃ of roastings 4 hours promptly get sample B.
Embodiment 3
Take by weighing FeSO
4.7H
2O12.5g is dissolved in the 100ml soft water, regulates between the PH 2.0-2.2.With 250 ℃ of oven dry specifications is in the ￠ 4-6mm active aluminum oxide carrier 20g dipping solution, and dip time 2 hours stirred inferior in each one hour with glass bar; 120 ℃ of oven dry 2 hours, compound concentration was 2.5% ammonia spirit then, in the carrier impregnation solution with oven dry; Dip time 2 hours stirred once with glass bar at a distance from 1 hour, then 120 ℃ of oven dry 2 hours; 320 ℃ of roastings 4 hours promptly get sample C.
Embodiment 4
Take by weighing FeSO
4.7H
2O12.5g is dissolved in the 100ml soft water, regulates between the PH 2.0-2.2.With 250 ℃ of oven dry specifications is in the ￠ 4-6mm active aluminum oxide carrier 20g dipping solution, and dip time 2 hours stirred inferior in each one hour with glass bar; 120 ℃ of oven dry 2 hours, compound concentration was 2.5% ammonia spirit then, in the carrier impregnation solution with oven dry; Dip time 2 hours; Stirred once with glass bar at a distance from 1 hour, filter was done 30 minutes, soft water washing four times.Till not having deposition and produce with the barium chloride check aqueous solution.120 ℃ of oven dry 2 hours, 320 ℃ of roastings 4 hours promptly got sample D.
Embodiment 5
Investigate sample A ﹑ B ﹑ C ﹑ D quality index such as following table (1) respectively, its testing result is that sample D each item performance indications are higher than other samples,
The contrast of table 1 sample catalyst each item index
 |
Comparative catalyst A | B | C | D |
| AL 2O 3，% | 85 | 87 | 88 | 89 |
| Fe 2O 3，% | 4.56 | 4.73 | 4.68 | 4.75 |
| Sulfate ion % | ? | ? | ? | ? |
| Pore volume, ml/g | 0.39 | 0.40 | 0.41 | 0.45 |
| Specific surface, m 2/g | 280.32 | 300.32 | 333.87 | 360.58 |
| Compression strength, N/ | 181.2 | 186.3 | 190.2 | 212.3 |
| Bulk density, g/ml | 0.80 | 0.79 | 0.80 | 0.82 |
Embodiment 6
The operating condition of analoging industrial device claus reaction device is investigated Crouse's activity of the Crouse of sample and comparative catalyst under the same conditions respectively, and the result can find out that in table (2) other sample catalysts of catalyst D specific activity are high.
The activity contrast of table 2 different catalysts sample
| Catalyst sample | A | B | C | D |
| η O2 ,/% | <99 | >;99 | >;99 | >;99 |
| η H2O+SO2,/% | 76.2 | 77.0 | 77.5 | 79 |
Claims (3)
1. one kind high chlorosity type high-strength alumina antichlor; It is characterized in that with the activated alumina being carrier; With the di-iron trioxide is active constituent, and the ferric oxide content in the active aluminum oxide carrier is 4-5%, and alkaline earth metal content is that 0.5-0.15% is prepared from through twice dipping method.
2. the method for one kind high chlorosity type high-strength alumina of claim 1 antichlor is characterized in that the predecessor of active component is selected FeSO for use
4.7H
2O is mixed with solution, and as for flooding in the dipping tank, dip time was controlled at two hours with active aluminum oxide carrier, carries out drying after dipping complete back filter is done; Prepare certain density ammoniacal liquor simultaneously, the catalyst of drying was flooded 2 hours in the dipping ammonia solution, carry out drying after draining again; The catalyst normal temperature of oven dry is washed with soft water, wash four times, detect sulfate radical; Until sulfate radical-free is qualified, carries out drying, the finished catalyst that roasting is.
3. according to the method for one kind high chlorosity type high-strength alumina of claim 2 antichlor, it is characterized in that FeSO at precursor solution
4.7H
2A spot of dense H during the preparation of O
2SO
4Control PH prevents that about 2.2 the ferrous ion hydrolysis from generating deposition; Give rotation that any hot blast do not stop simultaneously and guarantee that solution evenly and do not have crystal and separate out under the rotation of mixer; Fully guaranteed the variation that brings on the active component predecessor physical chemistry; Its purpose of dipping ammonia solution is that ammonia follows sulfate radical reaction generation sulfate of ammoniac water-soluble; Solved the high problem of catalyst sulfuric acid radical ion content, the washing of catalyst further cements out residual sulphur acid ion in the catalyst pores a spot of other foreign ion of level.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112844362A (en) * | 2021-01-27 | 2021-05-28 | 陕西师范大学 | Method for improving activity of metal oxide catalyst in oxidation and oxidative dehydrogenation reaction |
| CN113731457A (en) * | 2021-09-28 | 2021-12-03 | 四川天人能源科技有限公司 | Organic sulfur hydrolysis catalyst and preparation method thereof |
| CN113941330A (en) * | 2020-07-15 | 2022-01-18 | 中国石油天然气股份有限公司 | Sulfur recovery catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1336252A (en) * | 2000-08-09 | 2002-02-20 | 中国石化集团齐鲁石油化工公司 | Double-function sulfur recovery catalyst and its prepn |
| CN1383913A (en) * | 2001-04-27 | 2002-12-11 | 中国石化集团齐鲁石油化工公司 | Double-function sulphur recovering catalyst and its prepn |
-
2011
- 2011-08-15 CN CN201110231935A patent/CN102319565A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1336252A (en) * | 2000-08-09 | 2002-02-20 | 中国石化集团齐鲁石油化工公司 | Double-function sulfur recovery catalyst and its prepn |
| CN1383913A (en) * | 2001-04-27 | 2002-12-11 | 中国石化集团齐鲁石油化工公司 | Double-function sulphur recovering catalyst and its prepn |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113941330A (en) * | 2020-07-15 | 2022-01-18 | 中国石油天然气股份有限公司 | Sulfur recovery catalyst and preparation method thereof |
| CN112844362A (en) * | 2021-01-27 | 2021-05-28 | 陕西师范大学 | Method for improving activity of metal oxide catalyst in oxidation and oxidative dehydrogenation reaction |
| CN112844362B (en) * | 2021-01-27 | 2023-07-21 | 陕西师范大学 | Method for improving activity of metal oxide catalyst in oxidation and oxidative dehydrogenation reactions |
| CN113731457A (en) * | 2021-09-28 | 2021-12-03 | 四川天人能源科技有限公司 | Organic sulfur hydrolysis catalyst and preparation method thereof |
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Application publication date: 20120118 |