CN1056587C - Process for recovering sulfur from gas containing hydrogen sulfide - Google Patents
Process for recovering sulfur from gas containing hydrogen sulfide Download PDFInfo
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- CN1056587C CN1056587C CN96104817A CN96104817A CN1056587C CN 1056587 C CN1056587 C CN 1056587C CN 96104817 A CN96104817 A CN 96104817A CN 96104817 A CN96104817 A CN 96104817A CN 1056587 C CN1056587 C CN 1056587C
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- hydrogen sulfide
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Abstract
The present invention relates to a process for recovering sulfur from gases containing hydrogen sulfide. The gases containing hydrogen sulfide and oxygen are mixed, and then are transported in a reactor filled with active carbon as a catalyst; hydrogen sulfide is catalyzed and oxidated into sulfur vapor and enters a condenser along with reacted gases at a temperature of 160 to 350 DEG C; the sulfur vapor is cooled to be liquid sulfur and then is recovered. The technique of the present invention can both recover hydrogen sulfide low to be a plurality of thousands of ppm, and recover sulfur in acid gases with hydrogen sulfide of high concentration; the present invention has the characteristics of low cost, simple operation process, continuous production and easy control; catalyst deactivation needs no worry; 30% of fresh water can be scarcely influenced. The present invention relates to a technique for recovering sulfur from gases containing hydrogen sulfide with a wide application prospect.
Description
The present invention relates to a kind of from H 2 S-containing gas the technology of recovery sulphur.
In many technological processs such as Sweet natural gas, oil and chemical industry, flow to the user or the gas that is discharged in the atmosphere need be removed sulfide, hydrogen sulfide especially normally is converted into hydrogen sulfide elementary sulfur and is reclaimed.In the prior art, recovery sulphur claus process commonly used from H 2 S-containing gas.It is in the roasting kiln more than 1000 ℃, 1/3rd hydrogen sulfide oxidation generation sulfurous gas is arranged in the sour gas, remaining hydrogen sulfide generates sulphur with the sulfurous gas reaction in thermal response and catalyzed reaction level, simultaneously the sulphur cooling is reclaimed, and its reaction formula is:
The Hou Xiang chief editor, " Chinese oil Refining Technologies " book that Sinopec press publishes has detailed statement to this technology.
Yet claus process commonly used has many shortcomings, is subjected to the control of chemical equilibrium such as its reaction, and sulfur recovery rate still has the tail gas that contains the sulfide about 5% to enter atmosphere about 95%, has not only wasted resource, and has polluted atmosphere; For the low sour gas of hydrogen sulfide content, should not adopt claus process, also uneconomical economically; Reaction produces nearly 30% process water, and feasible recovery to sulphur in its tail gas has brought difficulty; Want strict control H
2S: SO
2=2: 1 is also exceedingly difficult.
In order to reclaim the sulfide in the claus process tail gas, the CN87103687.8 patent disclosure a kind of catalyzer, be some reactive metals such as TiO
2, Fe
2O
3Be applied to Al
2O
3And SiO
2On the carrier, in 200 ℃ of-300 ℃ of scopes, have in the presence of the excess of oxygen, direct oxidation of hydrogen sulfide can be become elementary sulfur, thereby make sulfur recovery rate bring up to 99% from 95% of claus process.This technology has not only improved the sulphur yield, and does not need strict control H
2S: SO
2=2: 1, be subject to people's attention.Yet the price of this catalyzer is more expensive, and can only use under the situation of excess oxygen, and some also requires moisture content to be lower than 5%, thereby extensively promotes some difficulty.
For the low gas of hydrogen sulfide content, use activated-carbon catalyst in recent years, remove hydrogen sulfide and recovery sulphur, be subjected to extensive attention.It is to be lower than under 80 ℃ the situation, adds oxygen and ammonia in gas, makes wherein hydrogen sulfide directly become sulphur and is adsorbed on the gac, treat the gac inactivation after, be increased to again under 350 ℃ and purge out with the sulphur of overheated steam with absorption.Obviously, this technology can only be used in hydrogen sulfide content and be lower than 1% occasion, otherwise, absorption that gac is frequent and desorption, very fast inactivation, and technology is discontinuous, and treatment capacity is low.
The present invention is intended to overcome the deficiencies in the prior art, provides a kind of and can handle the high gas of hydrogen sulfide content, also can handle the low gas of hydrogen sulfide content, and the technology of direct recovery sulphur.
The object of the present invention is achieved like this: will contain the gas of hydrogen sulfide and oxygen mix and enter the reactor that gac is a catalyzer is housed, in temperature is under 160-350 ℃, hydrogen sulfide becomes sulfur vapor through catalyzed oxidation, enter condenser with reacted gas, make sulfur vapor be cooled to molten sulfur and reclaimed.See Fig. 1.After the air mixed from the H 2 S-containing gas of pipeline (1-1) and pipeline (1-2), enter catalyst oxidation reactor (1-4) through pipeline (1-3).In reactor (1-4), it is catalyzer that gac is housed.Hydrogen sulfide is under 160-350 ℃ in temperature, particularly under 200 ℃-350 ℃, becomes sulfur vapor through catalyzed oxidation; Reacted gas enters condenser (1-6) by pipeline (1-5); Feed water coolant by pipeline (1-8) in the condenser (1-6), make sulfur vapor be cooled to molten sulfur and reclaimed from pipeline (1-10); After being come out by pipeline (1-7), cooled gas enters the next stage catalyst oxidation reactor with the air mixed of pipeline (2) again.Because the reaction of hydrogen sulfide and oxygen reaction generting element sulphur is a strong exothermal reaction, when concentration of hydrogen sulfide is higher than 1.5% in the gas in entering reactor (4), catalyst oxidation reactor (4) should be installed spiral coil cooling tube, the cooling water inflow that adjusting is entered by pipeline (11), make temperature out be unlikely to too high, incorporate total vapor line into by the low-pressure steam of pipeline (12) and (9) output.
The progression of sulfur recovery unit is by the content decision of hydrogen sulfide in the gas.When hydrogen sulfide content is lower than 3%, adopt usually 1 grade just passable; When hydrogen sulfide content is 3%-10%, can adopt 2 grades; During hydrogen sulfide content 10%-20%, can adopt 3 utmost points; Hydrogen sulfide content is higher than at 20% o'clock, needs to adopt 4 grades or 5 grades.Some is different for the processing condition of previous stages and final stage: the temperature in of final stage is 160-200 ℃, and temperature out is lower than 300 ℃, O
2/ H
2The S mol ratio is controlled at 0.5-0.8, air speed 1000-2000H
-1, the temperature in of previous stages is 160-200 ℃, temperature out is lower than 350 ℃, O
2/ H
2S mol ratio 0.1-0.5, air speed is 2000-3000H
-1The molten sulfur cooling temperature of condensers at different levels is controlled at 160-170 ℃.If contain enough oxygen in the air-flow, just do not add air in addition.
The catalyst oxidation reactor (4) of processing Claus tail gases or the last step of multistage sulfur recovery unit can be as shown in Figure 2.4 reversing valves are set, by following circulation back blowing process operation; At first open valve 1 (13) and valve 2 (14), shut-off valve 3 (15) and valve 4 (16), the gas of score behind sulphur is from bottom to top by catalytic chlorination reactor (4), when the outlet concentration of hydrogen sulfide obviously improves, open valve 3 (15) and valve 4 (16), shut-off valve 1 (13) and valve 2 (14), allow process gas blowback from top to bottom, this moment, catalyzer top sulfur-bearing was low, temperature is low, thereby can deposit macroelement sulphur, a large amount of reaction heat will make the elementary sulfur gasification that is deposited on the catalyzer lower section take reactor (4) out of, also absorb big calorimetric simultaneously, make temperature be unlikely to rapid increase.So circulation blowback operation, reactor (4) has also saved the preheating of process gas without spiral coil cooling tube; Because the medial temperature of reaction reduces, the generation of sulfurous gas has also reduced again.
Adopt recovery sulphur technology of the present invention, the both recyclable hydrogen sulfide that is low to moderate several thousand ppm, the also sulphur in the sour gas of recyclable high-concentration hydrogen sulfide, operating process is simple, produce continuously, control easily is if oxygen is excessive or not enough, mishandles such as temperature surpasses can not make catalyst deactivation, do not worry generating vitriol or sulfide to make catalyst deactivation yet; 30% process water is not influence almost, and cost is low, is a kind of application prospect technology of recovery sulphur from H 2 S-containing gas widely.
The drawing of accompanying drawing is described as follows:
Fig. 1 is a recovery sulphur process flow sheet of the present invention;
Fig. 2 is the circulation back blowing process schema of recovery sulphur.
By the following examples technology of the present invention is done further statement.
In internal diameter is 7 millimeters Glass tubing, the 1 milliliter of gac of packing into, two is blocked with glass wool.The JH gac that adopts Yuxin Activated Carbon Plant, Henan Prov. to produce through grinding, sifts out the catalyzer of 5-60 order part as present embodiment.The catalytic oxidation Glass tubing is packed into and is heated in the tube furnace strict controlled temperature.Process gas is formulated with carbonic acid gas, nitrogen and hydrogen sulfide, through with the oxygen mix that adds after, enter in the catalyzed oxidation Glass tubing, measure the hydrogen sulfide amount that enters the Glass tubing front and back, can calculate the transformation efficiency of hydrogen sulfide.And the selectivity definition is for changing into the percentage composition of sulphur from hydrogen sulfide.Experimental result is listed in the table 1.(table 1 is seen the literary composition back)
From the data of table 1 as can be seen, process gas by catalyst oxidation reactor once, the yield of elementary sulfur can reach more than 80%, and adopt the circulation blowback also can suitably to improve, therefore, when technology of the present invention was used to handle the tail gas of conventional claus process, the sulphur yield can reach 99%.It can also be seen that when technology of the present invention is used for reclaiming the sulphur of the acid gas of high density, adopt 4 grades of recovery sulphur devices, first three level is at O
2/ H
2Operate under the condition of S mol ratio 0.2, the sulphur yield can reach about 94%.
Behind the reactor of 2 grades of claus process, add 1 grade of recovery sulphur device of the present invention, be used to handle the tail gas of conventional claus process.Process gas to prime does not require H
2S/SO
2=2: 1, only require the superfluous 0.8-3% of hydrogen sulfide, this part hydrogen sulfide is oxidized to elementary sulfur more than 80% in catalyst oxidation reactor of the present invention, the sulphur yield that makes whole device brings up to 99% by original 95%, the sulfurous gas of discharging significantly reduces, the adjusting proportional range of air and acid gas increases, more convenient operation.
Table 1
| ??H 2S content (volume %) | ??H 2O content % | Temperature of reaction ℃ | Air speed H -1 | ???O 2/H 2The S mol ratio | H 2S transformation efficiency % | Selectivity % | Sulphur yield % |
| ?????5.7 | ????4 | ????300 | ???3000 | ????0.20 | ????35 | ???98 | ????34 |
| ?????5.7 | ????4 | ????250 | ???3000 | ????0.40 | ???58.5 | ???97 | ????57 |
| ?????5.7 | ????4 | ????250 | ???3000 | ????0.65 | ????91 | ???88 | ????80 |
| ?????5.7 | ????4 | ????200 | ???1000 | ????0.80 | ????85 | ???90 | ???76.5 |
| ?????5.7 | ????4 | ????250 | ???1000 | ????0.58 | ???90.2 | ???94 | ???84.5 |
| ??????1 | ????4 | ????250 | ???1000 | ????0.7 | ???93.1 | ???87 | ????81 |
| ??????1 | ????28 | ????250 | ???1000 | ????0.7 | ???89.6 | ???87 | ????78 |
Claims (3)
1. the technology of a recovery sulphur from H 2 S-containing gas, after comprising the gas and oxygen mix that will contain hydrogen sulfide, enter and be equipped with in the catalyst oxidation reactor that gac is a catalyzer, it is characterized in that with oxygen mix after the gas that contains hydrogen sulfide enter this catalyst oxidation reactor after, in temperature is under 200-350 ℃, hydrogen sulfide becomes sulfur vapor through catalyzed oxidation and enters condenser with reacted gas, makes sulfur vapor be cooled to molten sulfur and is reclaimed.
2. by the described recovery sulphur technology of claim 1, it is characterized in that H 2 S-containing gas is a successive by catalyzer.
3. by the described recovery sulphur technology of claim 1, it is characterized in that operating by the circulation back blowing process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96104817A CN1056587C (en) | 1996-04-30 | 1996-04-30 | Process for recovering sulfur from gas containing hydrogen sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96104817A CN1056587C (en) | 1996-04-30 | 1996-04-30 | Process for recovering sulfur from gas containing hydrogen sulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1163858A CN1163858A (en) | 1997-11-05 |
| CN1056587C true CN1056587C (en) | 2000-09-20 |
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ID=5118558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96104817A Expired - Fee Related CN1056587C (en) | 1996-04-30 | 1996-04-30 | Process for recovering sulfur from gas containing hydrogen sulfide |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100450917C (en) * | 2006-02-28 | 2009-01-14 | 中国石油大学(北京) | Method for recovering sulfur and making hydrogen from hydrogen sulfide |
| CN101870883B (en) * | 2009-04-24 | 2013-07-31 | 中国石油天然气股份有限公司 | Method for producing sulfur through separation, vulcanization and hydrogen oxidation of circling foam |
| US8663596B2 (en) * | 2010-01-25 | 2014-03-04 | Fluor Enterprises, Inc. | Reactor, a structure packing, and a method for improving oxidation of hydrogen sulfide or polysulfides in liquid sulfur |
| CN102249197A (en) * | 2010-05-17 | 2011-11-23 | 淄博高汇化工有限公司 | Method for converting hydrogen sulfide gas in production of thiofide MTB |
| CN102849684A (en) * | 2012-09-24 | 2013-01-02 | 邵志辉 | Double-stage isothermal oxidization sulfur-producing device |
| CN105712300B (en) * | 2014-12-04 | 2017-12-22 | 中国石油化工股份有限公司 | The technique that a kind of hydrogen sulfide is converted into sulphur |
| CN105126848B (en) * | 2015-08-21 | 2017-05-24 | 山东迅达化工集团有限公司 | Catalyst having macro-porous structure and used for production of sulfur through selective oxidation of H2S, and preparation method thereof |
| CN107158880B (en) * | 2017-06-27 | 2020-06-23 | 苏州克莱尔环保科技有限公司 | Device for treating purge gas of oil refinery by using active carbon |
| CN107720705B (en) * | 2017-11-08 | 2024-02-13 | 中国石油化工集团公司 | Device and method for producing hydrogen by coupling ammonia decomposition in Claus sulfur production |
| CN112999842B (en) * | 2019-12-20 | 2023-06-30 | 陕西青朗万城环保科技有限公司 | Microwave-induced active carbon adsorption steam desorption hydrogen sulfide removal device |
| CN115072670B (en) * | 2022-05-19 | 2023-06-13 | 西南石油大学 | Reaction device for preparing elemental sulfur and hydrogen by decomposing hydrogen sulfide with molten salt |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5256384A (en) * | 1991-03-26 | 1993-10-26 | Metallgesellschaft Aktiengesellschaft | Activated carbon process for removing hydrogen sulfide from gases |
-
1996
- 1996-04-30 CN CN96104817A patent/CN1056587C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5256384A (en) * | 1991-03-26 | 1993-10-26 | Metallgesellschaft Aktiengesellschaft | Activated carbon process for removing hydrogen sulfide from gases |
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|---|---|
| CN1163858A (en) | 1997-11-05 |
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