CN103285722A - Highly sulfur-containing pressurized shifted gas wet-process desulphurization technique - Google Patents
Highly sulfur-containing pressurized shifted gas wet-process desulphurization technique Download PDFInfo
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Abstract
The invention provides a highly sulfur-containing pressurized shifted gas wet-process desulphurization technique which comprises the following steps of: enabling shifted gas to enter an inlet separator, enabling the shifted gas water which is separated to enter a pipeline mixer, mixing together with desulphurization solution to remove part of the hydrogen sulfide in the shifted gas, entering into a NO.1 desulphurization tower, contacting with the desulphurization solution to further remove hydrogen sulfide in the shifted gas, enabling the shifted gas to enter into a NO.2 desulphurization tower, contacting with the desulphurization solution again to remove hydrogen sulfide in the shifted gas until the hydrogen sulfide is less than 5mg/Nm<3>, separating foam through an outlet separator to the next procedure; enabling the solution to flow out of the bottom of the desulphurization tower to enter a flash tower, enabling the solution to enter a jet regeneration tank after carbon dioxide is flashed, carrying out solution regeneration through self-absorption air, enabling the regenerated desulphurization solution to enter a solution circulating tank, and pressurizing through a solution circulating pump for circulating desulphurization. According to the highly sulfur-containing pressurized shifted gas wet-process desulphurization technique, the resistance of the system is low, and the towers cannot be plugged; shifted gas with high hydrogen sulfide can be removed, and the desulphurization efficiency is high; the operation is simple, and the desulphurization and regeneration are integrally arranged; the device investment is low and takes up one quarter of a physical absorption method.
Description
Technical field
The present invention relates to sulfur removal technology, be specifically related to a kind of high sulfur-bearing pressurization conversion air humidity method sulfur removal technology.
Background technology
Sulfur removal technology is widely used in synthetic ammonia installation, methanol device, device for producing hydrogen, a major part that belongs to process for purifying, before its technology position is arranged on gasification back decarburization, two kinds of different process before the branch conversion, after the conversion, technology is coal gas desulfurization technology before the conversion, technology is desulfuration of shift gas technology after the conversion, according to the pressure difference, is divided into desulfurization at normal-pressure and pressurization desulfurization.
Remove H
2S is divided into two classes according to the states of matter feature difference of desulfurizing agent, i.e. dry desulfurization and wet desulphurization:
(1) dry desulfurization
Dry desulfurization adopts solid desulfurating agent, and sulfide is adsorbed and reacts at desulfurizing agent, and its sulfur capacity is big, and the desulfurization precision height generally adopts three towers or two tower connection in series-parallel technologies.Its catalysed oxidn that utilizes desulfurizing agent is with the H in the gas
2The S oxidation conversion is elemental sulfur and low amounts of water, and the elemental sulfur of Xing Chenging is deposited in the hole of desulfurizing agent carrier like this, makes the H of gas
2The S component is converted into harmless solid elemental sulfur, is retained in the desulfurizing agent, is mainly used in extremely hanging down the smart desulfurization of sulfurous gas desulfurization or deep desulfuration, the main desulfurization of inapplicable conversion gas.
(2) wet desulphurization
Wet desulphurization is to utilize specific solvent to contact with back flow of gas and remove wherein H
2S, C0
2, solvent absorbs after regenerating again, according to the difference of absorption mechanism, is divided into chemical absorption method, Physical Absorption method, oxidation-reduction method again.
Chemical absorption method is absorbent with the alkaline solution, generate certain compound with acidic components reaction in the gas, absorbed acidic components solution (being called rich solution), under the condition of intensification step-down, make compound decomposition discharge acidic components, most representative method is the MDEA method.
The Physical Absorption method is to utilize the difference of different component solubility in specific physical absorbent in the gas and remove H
2S separates sucking-off H by measures such as step-down flash distillations then from solvent
2S and solvent reclamation is recycled.This method is suitable for higher operating pressure, compares with chemical absorption method, and its calorific requirement is generally lower.But physical solvent will reach high degree of purification difficulty comparatively speaking, and physical solvent process commonly used comprises low-temp methanol method, polyglycol dimethyl ether process.
Oxidation-reduction method is to contain the neutrality of oxidant or the H in the weakly alkaline solution absorption air-flow
2S, the carrier of oxygen in the solution is with H
2S is oxidized to elemental sulfur, and solution recycles after with air regenesis.This method combines as a whole desulfurization and sulfur recovery, has advantages such as flow process is simple, investment is lower, and according to the difference of sulphur oxidation catalyst, oxidation-reduction method mainly contains iron-based and two kinds of technologies of vanadium base.
Low sulfur-bearing desulfuration of shift gas technology owing to adopt coal gas desulfurization before conversion, has removed most of H in the gas
2So S is H in the conversion gas
2S content is not high, generally at 100-200mg/Nm
3About, adopt wet desulfurizing process chemiadsorption and redox absorption method, can reach the desulfurization requirement.
High sulfur-bearing desulfuration of shift gas technology appears at the pressing gas metallization processes, and coal gas directly carries out shift conversion step, has not had the preceding desulfurization process of conversion, H in the conversion gas
2S content significantly improves, generally at 1000-2000mg/Nm
3About, mainly adopt Physical Absorption method low-temperature rectisol wet processing, and the low-temp methanol washing process plant investment is big, the investment of more than one hundred million units, apparatus is many, and multistage flash evaporation system, refrigeration system, sulfur recovery system etc. are arranged, complicated operation, operating cost is higher.Because carbon dioxide content height in the pressurization conversion gas, gas flow rate is low under the pressurization operating mode, if adopt conventional wet sulfur removal technology chemiadsorption and redox absorption method, then influence desulfurization regeneration, stifled tower appears easily, can't produce, therefore need a kind of high sulfur-bearing pressurization conversion air humidity method new desulfurization process of development.
Summary of the invention
Technical problem to be solved by this invention is to overcome the above-mentioned defective of existing desulfuration of shift gas technology and a kind of high sulfur-bearing pressurization conversion air humidity method sulfur removal technology is provided, and is specially adapted to high sulfur-bearing pressurization desulfuration of shift gas.
For realizing the object of the invention, this high sulfur-bearing pressurization conversion air humidity method sulfur removal technology may further comprise the steps:
Come 1-5MPa, sulfide hydrogen 500-5000mg/Nm from shift conversion step
3Conversion gas enter the import separator, conversion gas after branch is dried up enters pipe-line mixer, mix to remove with doctor solution and enter the 1# desulfurizing tower in the conversion gas behind the part hydrogen sulfide, contact with doctor solution from top to down, further remove hydrogen sulfide in the conversion gas, conversion gas enters the 2# desulfurizing tower, contacts with from top to down doctor solution again, removes in the conversion gas hydrogen sulfide to little≤5mg/Nm
3, operation after discharge knockout drum separation foam goes; 1# desulfurizing tower and the 2# desulfurizing tower bottom solution that comes out enters flash column, solution advances jet regeneration tank behind the flashed carbon dioxide gas, air self-suction carries out solution regeneration, regeneration back doctor solution advances the solution circulating slot, circulation desulfurization after solution circulation pump pressurization again, regeneration is separated out the elemental sulfur foam and is advanced the sulphur foam tank, goes filter press to reclaim sulphur after the pressurization of sulphur foam pump, and pressing filtering liquid is from flowing back to the solution circulating slot.
Adopt layer 2-4 plastics dumped packing in described 1# desulfurizing tower and the 2# desulfurizing tower, the gas system resistance is less than 0.05MPa, and desulfuration efficiency reaches more than 99%.
Described flash column is a pressure vessel, and solution advances this container flash distillation entirely after all desulfurization, and flashing pressure is controlled to be 0.5-0.6MPa, and the solution after the flashed carbon dioxide all advances jet regeneration tank and carries out solution regeneration.
Compared with prior art, the invention has the advantages that:
1, SR is low, and control is at 0.05MPa, and not stifled tower, pipe-line mixer is set before desulfurizing tower absorbs H
2S arranges a solution flash column behind desulfurizing tower, optimized the desulfurization regeneration operating mode.
2, desulfuration efficiency height adopts pipeline to absorb with packed tower and absorbs combination technique, can take off the high conversion gas of sulfur-bearing, H
2S reaches 500-5000 mg/Nm
3, desulfuration efficiency reaches 99%, and can organic sulfide removal.
3, device is simple to operate, and desulfurization regeneration is integrated, does not need additionally to regenerate source of the gas, does not need low-temperature receiver, and operating cost is lower.
4, plant investment is low, compares with the low-temperature rectisol method, can reduce investment outlay 3/4ths, does not have refrigeration system, does not establish ad hoc sulfur recovery unit, does not need multistage flash evaporation.
Adopt foregoing invention to be applied to high sulfur-bearing pressurization desulfuration of shift gas technology, possess skills, many-sided comprehensive advantages such as economy, fund.
Description of drawings
Fig. 1 is process flow diagram of the present invention.
1: the import separator; 2: pipe-line mixer; The 3:1# desulfurizing tower; The 4:2# desulfurizing tower; 5: discharge knockout drum; 6: flash column; 7: jet regeneration tank; 8: the solution circulating slot; 9: solution circulation pump; 10: the sulphur foam tank; 11: the sulphur foam pump; 12: filter press.
The specific embodiment
The present invention is done to describe in detail with regard to specific embodiment below in conjunction with accompanying drawing.
As shown in Figure 1, come 1.85MPa, 40 ℃, carbon dioxide 40%, hydrogen sulfide 1500mg/Nm from shift conversion step
3Conversion gas enter import separator 1, conversion gas after branch is dried up enters pipe-line mixer 2, mix to remove with doctor solution and enter 1# desulfurizing tower 3 in the conversion gas behind the part hydrogen sulfide, contact with doctor solution from top to down, further remove hydrogen sulfide in the conversion gas, conversion gas enters 2# desulfurizing tower 4, contacts with from top to down doctor solution again, remove hydrogen sulfide in the conversion gas, 1.81MPa, 45 ℃, carbon dioxide 40%, hydrogen sulfide 5mg/Nm
3Conversion gas operation after discharge knockout drum 5 separates foams and goes; 1# desulfurizing tower 3 and the 2# desulfurizing tower 4 bottoms solution that comes out enters flash column 6, the control of flash tank pressure is at 0.5-0.6MPa, solution advances jet regeneration tank 7 behind the flashed carbon dioxide gas, air self-suction carries out solution regeneration, regeneration back doctor solution advances solution circulating slot 8, again through solution circulation pump 9 pressurization back circulation desulfurizations, regenerates and separates out the elemental sulfur foam and advance sulphur foam tank 10, go filter press 12 to reclaim sulphur after 11 pressurizations of sulphur foam pump, pressing filtering liquid is from flowing back to solution circulating slot 8.
Claims (3)
1. one kind high sulfur-bearing pressurization conversion air humidity method sulfur removal technology is characterized in that comprising following flow process: come 1-5MPa, sulfide hydrogen 500-5000mg/Nm from shift conversion step
3Conversion gas enter import separator (1), conversion gas after branch is dried up enters pipe-line mixer (2), mix to remove with doctor solution and enter first desulfurizing tower (3) in the conversion gas behind the part hydrogen sulfide, contact with doctor solution from top to down, further remove hydrogen sulfide in the conversion gas, conversion gas enters second desulfurizing tower (4), contacts with from top to down doctor solution again, removes in the conversion gas hydrogen sulfide to≤5mg/Nm
3, operation after discharge knockout drum (5) separation foam goes; Wherein first desulfurizing tower (3) and second desulfurizing tower (4) the bottom solution that comes out enters flash column (6), solution advances jet regeneration tank (7) behind the flashed carbon dioxide gas, air self-suction carries out solution regeneration, regeneration back doctor solution advances solution circulating slot (8), circulation desulfurization after solution circulation pump (9) pressurization again, regeneration is separated out the elemental sulfur foam and is advanced sulphur foam tank (10), goes filter press (12) to reclaim sulphur after sulphur foam pump (11) pressurization, and pressing filtering liquid is from flowing back to solution circulating slot (8).
2. a kind of high sulfur-bearing pressurization conversion air humidity method sulfur removal technology according to claim 1, it is characterized in that: adopt layer 2-4 plastics dumped packing in described first desulfurizing tower (3) and second desulfurizing tower (4), its gas system resistance is less than 0.05MPa, and desulfuration efficiency reaches more than 99%.
3. a kind of high sulfur-bearing pressurization conversion air humidity method sulfur removal technology according to claim 1, it is characterized in that: described flash column (6) is a pressure vessel, solution advances this container flash distillation entirely after all desulfurization, flashing pressure is controlled to be 0.5-0.6MPa, and the solution after the flashed carbon dioxide all advances jet regeneration tank (7) and carries out solution regeneration.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104174273A (en) * | 2014-08-12 | 2014-12-03 | 天津大学 | Direct solar driven carbon dioxide flash evaporation and desorption integrated system and method |
| CN106335876A (en) * | 2016-08-22 | 2017-01-18 | 中国神华能源股份有限公司 | Purification device for sulfur-containing conversion gases |
| CN111905549A (en) * | 2019-05-08 | 2020-11-10 | 北京化工大学 | Absorb H2S desulfurization solution, desulfurization system and desulfurization method |
| CN114292672A (en) * | 2021-12-27 | 2022-04-08 | 湖南金牛化工有限公司 | Variable-pressure wet desulphurization process for high-sulfur-content gas |
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| CN1456639A (en) * | 2003-05-09 | 2003-11-19 | 湖北宜化化工股份有限公司 | Multistage desulfurizing method for synthetic ammonia system |
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| CN102872713A (en) * | 2012-10-25 | 2013-01-16 | 北京三聚环保新材料股份有限公司 | Desulfurization and regeneration device for removing hydrogen sulfide by utilizing gas transmission pipeline |
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2013
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| CN1088131A (en) * | 1993-09-12 | 1994-06-22 | 浙江大学 | Remove high-concentration hydrogen sulfide and dithiocarbonic anhydride waste gas and reclaim the method and system of sulphur |
| CN1456639A (en) * | 2003-05-09 | 2003-11-19 | 湖北宜化化工股份有限公司 | Multistage desulfurizing method for synthetic ammonia system |
| CN101402884A (en) * | 2008-11-16 | 2009-04-08 | 李大路 | Process and apparatus for removing and recovering sulphur in coke oven gas |
| CN102872713A (en) * | 2012-10-25 | 2013-01-16 | 北京三聚环保新材料股份有限公司 | Desulfurization and regeneration device for removing hydrogen sulfide by utilizing gas transmission pipeline |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104174273A (en) * | 2014-08-12 | 2014-12-03 | 天津大学 | Direct solar driven carbon dioxide flash evaporation and desorption integrated system and method |
| CN104174273B (en) * | 2014-08-12 | 2016-09-07 | 天津大学 | A kind of solar energy directly drives the integrated system and method that carbon dioxide flash distillation desorbs |
| CN106335876A (en) * | 2016-08-22 | 2017-01-18 | 中国神华能源股份有限公司 | Purification device for sulfur-containing conversion gases |
| CN111905549A (en) * | 2019-05-08 | 2020-11-10 | 北京化工大学 | Absorb H2S desulfurization solution, desulfurization system and desulfurization method |
| CN111905549B (en) * | 2019-05-08 | 2022-06-17 | 北京化工大学 | Absorb H2S desulfurization solution, desulfurization system and desulfurization method |
| CN114292672A (en) * | 2021-12-27 | 2022-04-08 | 湖南金牛化工有限公司 | Variable-pressure wet desulphurization process for high-sulfur-content gas |
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