Method of cleaning gas of sulfurous admixtures

专利摘要:
Method for catalytic desulphuration of an acid gas containing H2S, and optionally a quantity of at the most 3 % by volume of CS2 and/or COS, by contacting said acid gas and oxygen or air with a titanium oxyde based catalyst, at temperatures comprised between 100<o>C and 600<o>C. The catalyst employed comprises in addition to the titanium oxyde, a sulphate of an alkaline earth metal selected among Ca, Sr, Ba and Mg. Application to the desulphuration of acid gases which contain particularly less than 15 % by volume of H2S and therefore may not be processed in the conventional sulphur plants.
公开号:SU1400494A3
申请号:SU833632600
申请日:1983-08-16
公开日:1988-05-30
发明作者:Дюпен Тьерри；Вуарден Робер
申请人:Сосьете Насьональ Елф Акитэн (Продюксьон) (Фирма)；
IPC主号:

专利说明:


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The invention relates to processes for the catalytic purification of sulfur from sulfur impurities.
The purpose of the invention is to increase the degree of purification and increase the selectivity for sulfur.
Example. Catalytic desulfurization of the acid gas having a follow-up volume composition,% 2; 7;
For this purpose, a 1.1 m catalyst is used in a fixed bed catalytic reactor, the reactor is supplied, on the one hand, with a gas supply pipeline, which has a nozzle (perforation) for injection of gas containing free oxygen and on which there is mounted between the nozzle and the reactor inlet an indirect heat exchanger, functioning as a preheater, and, on the other hand, a pipeline to remove the gas, continuing at the outlet of the reactor, and on which is mounted a condenser for cooling sulfur vapor. The passage of gases from the inlet to the outlet of the reactor is carried out through the catalytic layer.
The catalyst used consists of a product formed of titanium oxide and calcium sulphate, it has the following characteristics:
Bulk content
Ti02,%
Bulk content
CaSO; %
Specific surface, m / g Total volume pore, cm / g
Abrasion resistance,%
89.8 10.2 146 0.35 0.4
The catalyst was prepared as follows.
To the suspension of titanium oxide obtained after hydrolysis and filtration in the classical method of treating NL-menitol with €; purnic acid containing sulfate anions in such an amount that the mass ratio of SO: TiO is 0.08, calcium nitrate is added to react all sulfates, and the mass ratio of Ca: Ti02 is then equal to 0.033. The suspension is then dried at ISO - C for 1 hour.
The resulting powder was stirred for 2 hours in the presence of water in mass proportions, corresponding to 64 hours, powder for 36 hours, water. The resulting mixture is then extracted through a 4 mm diameter die plate, and the extruded forms obtained are dried at 110 ° C for 4 hours, then calcined at 400 ° C for 2 hours.
The catalytic desulfurization of said acid gas is carried out as follows.
Acid gas is introduced through a gas supply pipeline with a flow rate of 1,000 Nm3 / h and at a temperature of 40 ° C, air is supplied through the nozzle,
corresponding to a flow rate of 40 Nm. Uch, and this air 0 is injected at room temperature. The mixture of acid gas and air, in which the molar ratio O-iH-S is equal to 0.4, is brought to 200 ° C by passing through a preheater, then injected into the reactor at this temperature. The contact time of this mixture with the catalyst contained in the reactor is 4 seconds, which corresponds to a volume hourly rate of 900 hours. The gaseous effluent leaving the reactor through the pipeline does not contain more free oxygen and has a temperature of 273 ° C. This effluent is cooled to 170 ° C in a condenser to separate the sulfur it contains. The gas leaving the condenser contains H2S as the only sulfur-containing compound at a concentration of 0 vol.%.
Thus, a HfS conversion of 80.5% is obtained with a sulfur selectivity of 100%.
As a comparison, this experiment is repeated under similar conditions, however using a catalyst based on titanium oxide, which does not contain calcium.
five
0
five
carried out the addition of calcium salt to the suspension of titanium oxide. Achieve a conversion of only 35%, with a sulfur selectivity of 95%.

权利要求:
Claims (1)
[1]
Comparative data on the implementation of the method in examples 1-12 are presented in the table. Invention Formula
The method of gas purification from sulfur impurities by their oxidation by oxygen 3U00494
house to elemental sulfur or dioxide earth in the amount of sulfur in the presence of a catalyst 1-40 May. %, and a katana based on titanium oxide at 200-500 ° C is used. The lyser has a specific surface area of 5– in one or several catalytic 300 and a pore volume of 0.05–0.6 cm / g, zones that differ, and the process is carried out at a mole For the purpose of increasing the degree of purification, a catalyst is used, which additionally contains alkali sulfate.
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同族专利:

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公开号 | 公开日

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ES518282A0|1983-09-01|

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NL194033B|2001-01-02|

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SE439118B|1985-06-03|

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WO1983002068A1|1983-06-23|

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JPS58502089A|1983-12-08|

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NL194033C|2001-05-03|

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US4544534A|1985-10-01|

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BE895359A|1983-03-31|

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IT8224820D0|1982-12-17|

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ATA906482A|1987-09-15|

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NO832946L|1983-08-16|

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NO160491B|1989-01-16|

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ES8308223A1|1983-09-01|

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DE3249259C3|2000-04-20|

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DE3249259T1|1983-12-29|

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FR2518424A1|1983-06-24|

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GB2122597A|1984-01-18|

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NL8220457A|1983-11-01|

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GB2122597B|1985-08-07|

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SE8304069D0|1983-07-20|

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GB8321577D0|1983-09-14|

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FR2518424B1|1988-03-11|

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引用文献:

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US5286697A|1989-07-21|1994-02-15|Veg-Gasinstituut N.V.|Catalyst for the selective oxidation of sulphur compounds to elemental sulphur, process for preparing such a catalyst and method for the selective oxidation of sulphur compounds to elemental sulphur|

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RU2677648C1|2017-04-12|2019-01-18|Бейджинг Хуаши Юнайтед Энерджи Технолоджи энд Девелопмент Ко., Лтд.|Renewable highly efficient method of desulfurization using weighed layer|

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RU2687902C1|2017-04-12|2019-05-16|Бейджинг Хуаши Юнайтед Энерджи Технолоджи энд Девелопмент Ко., Лтд.|Desulphurization method using combination of suspension layer and fixed layer|US1900751A|1928-02-27|1933-03-07|Ig Farbenindustrie Ag|Purification of gases|

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FR2518424B1|1981-12-17|1988-03-11|Elf Aquitaine|PROCESS FOR CATALYTIC DESULFURIZATION OF AN ACID GAS CONTAINING H2S, AND POSSIBLY A GLOBAL QUANTITY OF AT LEAST 3% BY VOLUME OF CS2 AND / OR COS|FR2518424B1|1981-12-17|1988-03-11|Elf Aquitaine|PROCESS FOR CATALYTIC DESULFURIZATION OF AN ACID GAS CONTAINING H2S, AND POSSIBLY A GLOBAL QUANTITY OF AT LEAST 3% BY VOLUME OF CS2 AND / OR COS|

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FR2538716B1|1983-01-03|1985-07-05|Elf Aquitaine|PROCESS FOR CATALYTIC DESULFURIZATION OF AN ACID GAS CONTAINING H2S, AND POSSIBLY A GLOBAL QUANTITY OF AT LEAST 3% BY VOLUME OF CS2 AND / OR COS|

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FR2574309B1|1984-12-12|1989-10-06|Elf Aquitaine|PROCESS FOR REMOVAL OF COS AND CS2 COMPOUNDS CONTAINED IN INDUSTRIAL GAS|

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DE4109891A1|1991-03-26|1992-10-01|Metallgesellschaft Ag|PROCEDURE FOR GENERATING ELEMENTARY SWEEP FROM AN H2S CONTAINING GAS|

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DE4206913A1|1992-03-05|1993-09-09|Kronos Titan Gmbh|CATALYST FOR CARBONYL SULFID HYDROLYSIS|

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US5242880A|1992-05-27|1993-09-07|Eastman Kodak Company|Photoactive catalyst of barium phosphate or calcium phosphate supported on anatase titanium dioxide|

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FR2783818B1|1998-09-24|2000-11-10|Elf Exploration Prod|PROCESS FOR OXIDIZING DIRECTLY IN SULFUR, BY CATALYTIC AND VAPOR PHASE, THE LOW-CONTENTED H2S IN GAS|

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FR2830466B1|2001-10-09|2004-02-06|Axens|USE OF A TI02-BASED COMPOSITION AS A CATALYST FOR REALIZING COS AND / OR HCN HYDROLYSIS IN A GASEOUS MIXTURE|

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US20100150805A1|2008-12-17|2010-06-17|Uop Llc|Highly stable and refractory materials used as catalyst supports|

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US8691167B2|2012-07-19|2014-04-08|Tronox Llc|Process for controlling carbonyl sulfide produced during chlorination of ores|

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DE102015005610A1|2015-04-30|2016-11-03|CCP Technology GmbH|Apparatus and method for generating a synthesis gas|

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CN106833783B|2017-01-06|2019-09-20|浙江海洋大学|A kind of deep natural gas desulphurization system and its sulfur method|

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CN108686489B|2017-04-12|2021-01-01|北京华石联合能源科技发展有限公司|Suspension bed wet desulphurization process|

法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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FR8123611A|FR2518424B1|1981-12-17|1981-12-17|PROCESS FOR CATALYTIC DESULFURIZATION OF AN ACID GAS CONTAINING H2S, AND POSSIBLY A GLOBAL QUANTITY OF AT LEAST 3% BY VOLUME OF CS2 AND / OR COS|

---