CN104998517A - Method for increasing concentrations of acid gas hydrogen sulfide and carbonyl sulfide in low-temperature methanol washing process - Google Patents
Method for increasing concentrations of acid gas hydrogen sulfide and carbonyl sulfide in low-temperature methanol washing process Download PDFInfo
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- CN104998517A CN104998517A CN201510376268.XA CN201510376268A CN104998517A CN 104998517 A CN104998517 A CN 104998517A CN 201510376268 A CN201510376268 A CN 201510376268A CN 104998517 A CN104998517 A CN 104998517A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
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Abstract
The invention relates to a method for increasing concentrations of acid gas hydrogen sulfide and carbonyl sulfide in a low-temperature methanol washing process. The method comprises the following steps: (1) conducting heat exchange cooling and deamination on transforming gas from carbon monoxide conversion, sending the gas from the bottom of a methanol absorbing tower, and passing the gas a the desulfurization segment and a decarbonization segment; (2) after the decarburization segment and desulfurization segment, sending the methanol solution into an intermediate pressure flash column, conducting vacuum flash to emit carbon monoxide and hydrogen in the methanol solution, and the sending into a re-absorbing tower; (3) removing carbon dioxide in the methanol solution in the re-absorbing tower, and sending the sulfur-rich methanol solution discharged from the bottom of the re-absorbing tower to a thermal regeneration tower by a pump; and (4) removing hydrogen sulfide and carbonyl sulfide in the methanol solution in the thermal regeneration tower. The low-temperature methanol washing process is employed to optimize the operation process, and increase the operating efficiency of a subsequent sulfur recovery section. Meanwhile, the method is simple and feasible in the daily operation and increases the economic efficiency for enterprises.
Description
Technical field
The present invention relates to a kind of method improving sour gas hydrogen sulfide and cos concentration in low-temp methanol washing process, especially wash sour gas concentration of hydrogen sulfide device on the low side for Shandong strange low-temp methanol technique.
Background technology
Low-temp methanol washing process has been widely used in synthesizing methanol, coal liquifaction and other gas purifying technique such as carbonylation synthesis, selexol process and device.Low-temperature rectisol adopts methyl alcohol to make absorbent, absorb the sour gas such as carbon dioxide, hydrogen sulfide and the cos in gaseous mixture, through decompression desorb, air lift separation, heating desorption, methyl alcohol is separated with sour gas again, reaches extraction sour gas, purification gaseous mixture also reclaims the object using methyl alcohol.
In the gas cleaning plant of the strange low-temp methanol washing process in Shandong that current Coal Chemical Engineering Project both at home and abroad runs, the problem that in ubiquity sour gas, hydrogen sulfide and cos concentration are not high, in sour gas, hydrogen sulfide content is about about 20 ~ 35%.Environmental protection treatment is carried out because sour gas is admitted to sulfur recovery system, in the combustion furnace treatment process using direct current method, sour gas concentration just cannot allow furnace temperature reach the minimum temperature 930 DEG C of smooth combustion lower than 45%, the state of arts of combustion furnace just can not be stablized, sulfur recovery rate declines, the serious environmental protection accident very easily causing SO 2 in waste gas to exceed standard.If adopt shunting combustion furnace treatment process to replace direct current method, although not high to sour gas concentration requirement, need to increase expensive ratio shunt regulating equipment, also will increase steam-heating apparatus simultaneously and sour gas be heated to the temperature improving combustion furnace.And the partially acidic gas due to shunting needs to add in stove in the part that furnace body temperature is the highest, very easily occurring that refractory material washes away to come off and the accident causing body of heater to damage, utilizing shunting replacement direct current method also to there is the problems such as fluctuation of service, investment for trnasforming urban land is large, service life of equipment is short by analyzing above.Therefore ensure that the smooth combustion of direct current method combustion furnace is reasonable, the most economic solution by improving sour gas concentration, to the disposal ability improving sulfur recovery unit, reducing sulphur emissions and increasing sulphur output has very important meaning.
In prior art, conversion gas enters in methanol absorber tower, also needs to carry out pre-wash section before desulfurization section, and not containing pre-wash section in the present invention, in the methanol solution of decarbonization section passes through, press flash column and reabsorber to take off carbon dioxide, and then enter the desulfurization of hot recycling tower.Do not have methanol absorber tower prewashing methyl alcohol directly to enter hot recycling tower, decrease the concentration that hot recycling tower hot recycling section arranges carbon dioxide in sour gas outward, indirectly improve concentration of hydrogen sulfide in sour gas.
The present invention compared with prior art has following beneficial effect:
Carried out the Optimum Operation of low-temp methanol washing process by the present invention, in sour gas, concentration of hydrogen sulfide rises to 44% by 32%, and gas concentration lwevel drops to 56% by 66%, improves postorder sulfur recovery workshop section operational efficiency.The present invention is simultaneously simple in regular job, for enterprise adds economic benefit.
Summary of the invention
The object of the invention is to by Optimum Operation, change the operational efficiency that sour gas flow process improves sulfur recovery unit, the invention provides a kind of method improving sour gas hydrogen sulfide and cos concentration in low-temp methanol washing process.Technical scheme of the present invention is as follows:
Improve a method for sour gas hydrogen sulfide and cos concentration in low-temp methanol washing process, comprise the following steps:
(1) conversion gas obtained from CO Varying Process enters from the bottom of methanol absorber tower after heat exchange cooling, deamination process, pressure in methanol absorber tower is 5.2MPa, conversion gas in methanol absorber tower from bottom to top, enter desulfurization section and decarbonization section, absorbent low-temp methanol liquid enters from the top of methanol absorber tower, successively through decarbonization section and desulfurization section; Preferably, the temperature of low-temp methanol liquid is subzero 55 DEG C to subzero 49 DEG C;
Desulfurization section, removes whole hydrogen sulfide and partial CO 2, and the pressure of desulfurization section is 5.2MPa, and temperature is subzero 49 DEG C, and desulfurization section absorbent low-temp methanol rich solution (namely through the low-temp methanol liquid of desulfurization section) enters the hypomere of middle pressure flash column;
Decarbonization section, carbon dioxide removal, the pressure of decarbonization section is 5.2MPa, temperature is subzero 50 DEG C to subzero 30 DEG C, preferably, temperature is subzero 45 DEG C to subzero 40 DEG C, and decarbonization section absorbent low-temp methanol rich solution (namely through the low-temp methanol liquid of decarbonization section) part enters the epimere of middle pressure flash column; Part enters desulfurization section after cooling;
Conversion gas, after decarbonization section, sends into methanol-fueled CLC workshop section through heat exchanger re-heat to 30 DEG C.Synthesizing section pressure is 5.18MPa, and now, the content of hydrogen sulfide and cos is less than 0.1ppm.
(2) methanol solution enters after middle pressure flash column through decarbonization section and desulfurization section, and vacuum flashing goes out carbon monoxide in methanol solution and hydrogen, then enters reabsorber;
The pressure of middle pressure flash column is 1.6MPa, and temperature is subzero 22 DEG C;
In methanol absorber tower, low-temp methanol meeting absorption portion carbon monoxide and hydrogen, methanol absorber tower to middle pressure flash column is the process of a high pressure to low pressure, and absorb under high pressure, resolve under low pressure, under low pressure carbon monoxide and hydrogen parse, and reclaim.
(3) carbon dioxide in reabsorber in methanol removal liquid, the rich sulphur methanol solution of discharging bottom reabsorber through transport pump to hot recycling tower;
The epimere of reabsorber removes carbon dioxide by vacuum flashing, and epimere temperature is 90 DEG C ~ 95 DEG C, and hypomere is by adding air lift nitrogen, and air lift carbon dioxide, nitrogen is low-pressure nitrogen 0.4MPa, temperature normal temperature.
(4) hydrogen sulfide in hot recycling tower in methanol removal liquid and cos, sour gas with methanol steam is condensed to 73 DEG C-80 DEG C through heat exchanger heat exchange after going out the hot recycling section of hot recycling tower, after enter hot recycling tower backflash and isolate a small amount of methyl alcohol, hot recycling tower backflash top gas phase is sour gas, after heat exchange is to subzero 20 DEG C to subzero 10 DEG C, enter sour gas gas-liquid separator, be separated the methanol condensed liquid obtained and enter hot recycling tower backflash, sour gas then sends into downstream sulfur recovery process after the heating; Be provided with sour gas return duct to reabsorber at the gaseous phase outlet place of sour gas gas-liquid separator, the mode of use partial reflux removes the carbon dioxide in partially acidic gas.Through the inventive method, in the sour gas finally obtained, the volumetric concentration of carbon dioxide is reduced to 56% by 65.682%, and the volumetric concentration of hydrogen sulfide rises to 44% by 32%.
Accompanying drawing explanation
Fig. 1 is the process chart that the present invention improves sour gas hydrogen sulfide and cos concentration in low-temp methanol washing process.
Symbol description:
1. methanol absorber tower, 2. in press flash column, 3. reabsorber, 4. hot recycling tower, 5. sour gas gas-liquid separator, 6. hot recycling tower backflash, 7. sour gas return duct.
Detailed description of the invention
Further describe the present invention below in conjunction with specific embodiment, advantage and disadvantage of the present invention will be more clear along with description.But embodiment is only exemplary, does not form any restriction to scope of the present invention.It will be understood by those skilled in the art that and can modify to the details of technical solution of the present invention and form or replace down without departing from the spirit and scope of the present invention, but these amendments and replacement all fall within the scope of protection of the present invention.
Embodiment 1 one kinds improves the method for sour gas hydrogen sulfide and cos concentration in low-temp methanol washing process, comprises the following steps:
(1) conversion gas obtained from CO Varying Process enters from the bottom of methanol absorber tower 1 after heat exchange cooling, deamination process, pressure in methanol absorber tower 1 is 5.2MPa, conversion gas in methanol absorber tower 1 from bottom to top, enter desulfurization section and decarbonization section, absorbent low-temp methanol liquid enters from the top of methanol absorber tower 1, successively through decarbonization section and desulfurization section, the temperature of low-temp methanol liquid is subzero 55 DEG C to subzero 49 DEG C;
Desulfurization section, removes whole hydrogen sulfide and partial CO 2, and the pressure of desulfurization section is 5.2MPa, and temperature is subzero 49 DEG C, and desulfurization section absorbent low-temp methanol rich solution (namely through the low-temp methanol liquid of desulfurization section) enters the hypomere of middle pressure flash column 2;
Decarbonization section, carbon dioxide removal, the pressure of decarbonization section is 5.2MPa, and temperature is subzero 45 DEG C to subzero 40 DEG C, and decarbonization section absorbent low-temp methanol rich solution (namely through the low-temp methanol liquid of decarbonization section) part enters the epimere of middle pressure flash column 2; Part enters desulfurization section after cooling;
Conversion gas, after decarbonization section, sends into methanol-fueled CLC workshop section through heat exchanger re-heat to 30 DEG C.Synthesizing section pressure is 5.18MPa, and now, the content of hydrogen sulfide and cos is less than 0.1ppm.
(2) methanol solution enters after middle pressure flash column 2 through decarbonization section and desulfurization section, and vacuum flashing goes out carbon monoxide in methanol solution and hydrogen, then enters reabsorber 3;
The pressure of middle pressure flash column 2 is 1.6MPa, and temperature is subzero 22 DEG C;
In methanol absorber tower 1, low-temp methanol meeting absorption portion carbon monoxide and hydrogen, methanol absorber tower 1 to middle pressure flash column 2 is high pressure processes to low pressure, and absorb under high pressure, resolve under low pressure, under low pressure carbon monoxide and hydrogen parse, and reclaim.
(3) carbon dioxide in reabsorber 3 in methanol removal liquid, bottom reabsorber 3 discharge rich sulphur methanol solution through transport pump to hot recycling tower 4;
The epimere of reabsorber to remove carbon dioxide by vacuum flashing, and epimere temperature is 90 DEG C ~ 95 DEG C, and hypomere is by adding air lift nitrogen, and air lift carbon dioxide, nitrogen is low-pressure nitrogen 0.4MPa, temperature normal temperature.
(4) hydrogen sulfide in hot recycling tower 4 in methanol removal liquid and cos, 73 DEG C ~ 80 DEG C are condensed to through heat exchanger heat exchange after sour gas with methanol steam goes out the hot recycling section of hot recycling tower 4, after enter hot recycling tower backflash 6 and isolate a small amount of methyl alcohol, hot recycling tower backflash 6 top gas phase is sour gas, after heat exchange is to subzero 20 DEG C to subzero 10 DEG C, enter sour gas gas-liquid separator 5, be separated the methanol condensed liquid obtained and enter hot recycling tower backflash 6, sour gas then sends into downstream sulfur recovery process after the heating; Be provided with sour gas return duct 7 to reabsorber at the gaseous phase outlet place of sour gas gas-liquid separator 5, the mode of use partial reflux removes the carbon dioxide in partially acidic gas.
Process chart of the present invention as shown in Figure 1.
Embodiment 2 one kinds improves the method for sour gas hydrogen sulfide and cos concentration in low-temp methanol washing process, comprises the following steps:
(1) conversion gas obtained from CO Varying Process enters from the bottom of methanol absorber tower 1 after heat exchange cooling, deamination process, pressure in methanol absorber tower 1 is 5.2MPa, conversion gas in methanol absorber tower 1 from bottom to top, enter desulfurization section and decarbonization section, absorbent low-temp methanol liquid enters from the top of methanol absorber tower 1, successively through decarbonization section and desulfurization section, the temperature of low-temp methanol liquid is subzero 55 DEG C to subzero 49 DEG C;
Desulfurization section, removes whole hydrogen sulfide and partial CO 2, and the pressure of desulfurization section is 5.2MPa, and temperature is subzero 49 DEG C, and desulfurization section absorbent low-temp methanol rich solution (namely through the low-temp methanol liquid of desulfurization section) enters the hypomere of middle pressure flash column 2;
Decarbonization section, carbon dioxide removal, the pressure of decarbonization section is 5.2MPa, and temperature is subzero 40 DEG C to subzero 30 DEG C, and decarbonization section absorbent low-temp methanol rich solution (namely through the low-temp methanol liquid of decarbonization section) part enters the epimere of middle pressure flash column 2; Part enters desulfurization section after cooling;
Conversion gas, after decarbonization section, sends into methanol-fueled CLC workshop section through heat exchanger re-heat to 30 DEG C.Synthesizing section pressure is 5.18MPa, and now, the content of hydrogen sulfide and cos is less than 0.1ppm.
(2) methanol solution enters after middle pressure flash column 2 through decarbonization section and desulfurization section, and vacuum flashing goes out carbon monoxide in methanol solution and hydrogen, then enters reabsorber 3;
The pressure of middle pressure flash column 2 is 1.6MPa, and temperature is subzero 22 DEG C;
In methanol absorber tower 1, low-temp methanol meeting absorption portion carbon monoxide and hydrogen, methanol absorber tower 1 to middle pressure flash column 2 is high pressure processes to low pressure, and absorb under high pressure, resolve under low pressure, under low pressure carbon monoxide and hydrogen parse, and reclaim.
(3) carbon dioxide in reabsorber 3 in methanol removal liquid, bottom reabsorber 3 discharge rich sulphur methanol solution through transport pump to hot recycling tower 4;
The epimere of reabsorber removes carbon dioxide by vacuum flashing, and epimere temperature is 90 DEG C ~ 95 DEG C, and hypomere is by adding air lift nitrogen, and air lift carbon dioxide, nitrogen is low-pressure nitrogen 0.4MPa, temperature normal temperature.
(4) hydrogen sulfide in hot recycling tower 4 in methanol removal liquid and cos, 73 DEG C ~ 80 DEG C are condensed to through heat exchanger heat exchange after sour gas with methanol steam goes out the hot recycling section of hot recycling tower 4, after enter hot recycling tower backflash 6 and isolate a small amount of methyl alcohol, hot recycling tower backflash 6 top gas phase is sour gas, after heat exchange is to subzero 20 DEG C to subzero 10 DEG C, enter sour gas gas-liquid separator 5, be separated the methanol condensed liquid obtained and enter hot recycling tower backflash 6, sour gas then sends into downstream sulfur recovery process after the heating; Be provided with sour gas return duct 7 to reabsorber 3 at the gaseous phase outlet place of sour gas gas-liquid separator 5, the mode of use partial reflux removes the carbon dioxide in partially acidic gas.
Process chart of the present invention as shown in Figure 1.
Claims (8)
1. improve a method for sour gas hydrogen sulfide and cos concentration in low-temp methanol washing process, it is characterized in that, said method comprising the steps of:
(1) conversion gas obtained from CO Varying Process enters from the bottom of methanol absorber tower after heat exchange cooling, deamination process, pressure in methanol absorber tower is 5.2MPa, conversion gas in methanol absorber tower from bottom to top, enter desulfurization section and decarbonization section, absorbent low-temp methanol liquid enters from the top of methanol absorber tower, successively through decarbonization section and desulfurization section;
(2) methanol solution enters after middle pressure flash column through decarbonization section and desulfurization section, and vacuum flashing goes out carbon monoxide in methanol solution and hydrogen, then enters reabsorber;
(3) carbon dioxide in reabsorber in methanol removal liquid, the rich sulphur methanol solution of discharging bottom reabsorber through transport pump to hot recycling tower;
(4) hydrogen sulfide in hot recycling tower in methanol removal liquid and cos, 73 DEG C ~ 80 DEG C are condensed to through heat exchanger heat exchange after sour gas with methanol steam goes out the hot recycling section of hot recycling tower, after enter hot recycling tower backflash and isolate a small amount of methyl alcohol, hot recycling tower backflash top gas phase is sour gas, after heat exchange is to subzero 20 DEG C to subzero 10 DEG C, enter sour gas gas-liquid separator, be separated the methanol condensed liquid obtained and enter hot recycling tower backflash, sour gas then sends into downstream sulfur recovery process after the heating.
2. method according to claim 1, is characterized in that, in described step (1), the temperature of low-temp methanol liquid is subzero 55 DEG C to subzero 49 DEG C.
3. method according to claim 1, is characterized in that, desulfurization section in described step (1), remove whole hydrogen sulfide and partial CO 2, the pressure of desulfurization section is 5.2MPa, and temperature is subzero 49 DEG C, and desulfurization section absorbent low-temp methanol rich solution enters the hypomere of middle pressure flash column.
4. method according to claim 1, is characterized in that, decarbonization section in described step (1), carbon dioxide removal, the pressure of decarbonization section is 5.2MPa, and temperature is subzero 50 DEG C to subzero 30 DEG C, and decarbonization section absorbent low-temp methanol rich solution part enters the epimere of middle pressure flash column; Part enters desulfurization section after cooling.
5. method according to claim 1, is characterized in that, in described step (1), the temperature of decarbonization section is subzero 45 DEG C to subzero 40 DEG C.
6. method according to claim 1, is characterized in that, in described step (2), the pressure of pressure flash column is 1.6MPa, and temperature is subzero 22 DEG C.
7. method according to claim 1, is characterized in that, in described step (3), the epimere of reabsorber removes carbon dioxide by vacuum flashing, epimere temperature is 90 DEG C ~ 95 DEG C, hypomere by adding air lift nitrogen, air lift carbon dioxide, nitrogen is low-pressure nitrogen 0.4MPa, temperature normal temperature.
8. method according to claim 1, is characterized in that, is provided with sour gas return duct to reabsorber in described step (4) at the gaseous phase outlet place of sour gas gas-liquid separator.
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| CN201510376268.XA CN104998517A (en) | 2015-07-01 | 2015-07-01 | Method for increasing concentrations of acid gas hydrogen sulfide and carbonyl sulfide in low-temperature methanol washing process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106823691A (en) * | 2017-02-21 | 2017-06-13 | 西南化工研究设计院有限公司 | A kind of method of hydrogen sulfide gas concentrate |
| CN107473938A (en) * | 2017-09-19 | 2017-12-15 | 中建安装工程有限公司 | Utilize the device and method of sulfide in dividing plate extractive distillation column methanol removal |
| CN107754558A (en) * | 2016-08-19 | 2018-03-06 | 中国石油化工股份有限公司 | A kind of NHD desulfurization concentrating method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107754558A (en) * | 2016-08-19 | 2018-03-06 | 中国石油化工股份有限公司 | A kind of NHD desulfurization concentrating method |
| CN107754558B (en) * | 2016-08-19 | 2020-10-20 | 中国石油化工股份有限公司 | Desulfurization and concentration method of polyethylene glycol dimethyl ether |
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