CN105020723A - Low-sulfur-discharge sulfur recovering technique and system based on Claus reaction system - Google Patents
Low-sulfur-discharge sulfur recovering technique and system based on Claus reaction system Download PDFInfo
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- CN105020723A CN105020723A CN201510459789.1A CN201510459789A CN105020723A CN 105020723 A CN105020723 A CN 105020723A CN 201510459789 A CN201510459789 A CN 201510459789A CN 105020723 A CN105020723 A CN 105020723A
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- gas
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- claus reaction
- sulfur
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/30—Technologies for a more efficient combustion or heat usage
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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
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
The invention discloses a low-sulfur-discharge sulfur recovering technique and system based on a Claus reaction system. By the adoption of the low-sulfur-discharge sulfur recovering technique and system based on the Claus reaction system, the problems that according to the Claus reaction system, the tail gas treatment procedure is long, cost is high, and environment pollution is caused are solved. According to the technical scheme, the low-sulfur-discharge sulfur recovering technique comprises the steps that acid raw materials enter the Claus reaction system for a reaction, and tail gas obtained after the reaction is delivered into a incinerator to be incinerated, so that the tail gas is converted into smoke containing SO2; the smoke containing SO2 is delivered into a concentration section on the lower portion of a desulfurizing tower through a smoke inlet and then upwards enters an absorption section in the middle of the desulfurizing tower after waste heat in the smoke containing SO2 is recovered through a heat exchanger; SO2 in the smoke reacts with ammonia water, so that thiamine is formed; liquid obtained after the reaction flows downwards to enter the concentration section and then is discharged through a slurry outlet, and gas obtained after the reaction flows upwards to enter a washing section on the upper portion and then is exhausted through a smoke outlet in the top. According to the low-sulfur-discharge sulfur recovering technique and system based on the Claus reaction system, equipment investment and operation cost are low, and environmental friendliness is achieved; the SO2 content of treated tail gas can be lowered below 100 mg/Nm<3>, and the national standard requirement is met.
Description
Technical field
The present invention relates to chemical technology field, be specifically related to a kind of sulfur recovery unit and technique of low sulphur emissions.
Background technology
Along with the fast development of economy, China is because of the SO of the use discharges such as sulfurous fuels smelting, roasting
2sharply increase, the environmental problem caused thus is more and more outstanding.To this, country puts into effect many policies and regulation control SO
2discharge.Standard-required improves further, never higher than 960mg/Nm
3, to the SO of GB31570 new regulation on the 1st July in 2015
2concentration of emission be less than 400mg/Nm
3(be in particular cases less than 100mg/Nm
3), it serves to show that China petrochemical industry implements the resolution of green low-carbon development strategy.But some chemical plant installations built, particularly coal preparing natural gas project is generally after sulfur recovery unit, SO in final tail gas
2concentration of emission still just meets former standard, reaches 850mg/Nm
3and more than, this is very disadvantageous to environmental protection.
At present, the existing sulfur recovery unit of domestic coal preparing natural gas project mainly adopts Claus+SCOT technique, and this technique comprises sulphur recovery operation, vent gas treatment operation, solvent reclamation operation.Adopt secondary Claus technique, unstripped gas and air (oxygen) are with lower than stoichiometric proportion mixed combustion, and temperature reaches 1200 DEG C,
2H
2S+3O
2＝2SO
2+2H
2O (1)
2H
2S+SO
2＝3S+2H
2O (2)
Separated by molten sulfur through molten sulfur separator afterwards, after tail gas sends into incinerator process, the sulphur steam of organic sulfur wherein and trace is all converted into SO
2.Then the hydrogenation reactor of vent gas treatment operation is mixed into hydrogen, by SO
2and COS is reduced to H
2s, absorbs H wherein by diethanolamine solution
2s, remainder is combusted as SO in tail gas burning furnace
2, after recovery waste heat, gone out by smoke stack emission.In addition, also need again matching dissolvent step for regeneration to regenerate hydramine lean solution for recycling.This technological process is long, and equipment is many, and cost is large, need use hydrogen addition technology, higher to security control requirements, and sulfur recovery effect can not meet the further raising of environmental requirement.Therefore, be badly in need of finding the tail gas SO that a kind of more excellent process reduces sulfur recovery unit
2discharge capacity.
Summary of the invention
The object of the invention is to solve the problems of the technologies described above, the sulfur recovery technology that a kind of technique is simple, floor space is little, low, the environment amenable low sulphur emissions based on Claus reaction system is invested in preparation is provided.
The present invention also provides a kind of sulfur recovery system of the low sulphur emissions based on Claus reaction system of above-mentioned technique, has that system is simple, operating cost and equipment investment is low, vent gas treatment is an effective advantage.
Present invention process is, acid gas enters Claus reaction system and reacts, and the tail gas obtained after reaction is sent into incinerator and burned, and tail gas is converted into containing SO
2flue gas, described containing SO
2flue gas after heat exchanger recovery waste heat, send into desulfurizing tower bottom enriching section by gas approach, lower the temperature with thiamines heat exchange rare in enriching section, then upwards enter the central absorbent section of desulfurizing tower, the SO in flue gas
2react with ammoniacal liquor and generate thiamines, be advanced into enriching section and discharge through slurry outlet, reacted gas is advanced into the washing section on ammonia process desulfuration tower top under reacted liquid, the liquid carried secretly in removing flue gas is also discharged by top exhanst gas outlet after cooling.
Described containing SO
2flue gas mix with high-temperature flue gas after heat exchanger recovery waste heat after send into the bottom enriching section of desulfurizing tower again.
Control containing SO
2flue gas and the mixed gas temperature of high-temperature flue gas be 120-140 DEG C.
The present invention is based on the sulfur recovery system of the low sulphur emissions of Claus reaction system, comprise Claus reaction system, the offgas outlet of described Claus reaction system is connected with the gas approach of desulfurizing tower through incinerator, heat exchanger, described desulfurizing tower top is provided with exhanst gas outlet, bottom is provided with gas approach, bottom is provided with slurry outlet, and tower body is made up of the washing section on top, central absorbent section and bottom enriching section.
The washing section top of described desulfurizing tower is provided with clear water spray head, and bottom is provided with deposed ammonia import.
The pipeline connected between the gas approach of described desulfurizing tower and heat exchanger is also provided with high-temperature flue gas import.
Pipe lining VEGF flake mortar anticorrosive coat between high-temperature flue gas import and the gas approach of desulfurizing tower.
The vent gas treatment flow process of inventor to existing Claus reaction system is analyzed, and finds that the sulfur-containing medium of this tail gas after burning through incinerator in gas phase all can be converted into SO
2, formed containing SO
2flue gas, this part flue gas has following characteristics: 1: temperature is high, 800 DEG C ~ 900 DEG C; 2, SO in flue gas
2content high (5% ~ 30% mass percent); Therefore desulfurization is crucial, for this problem, after inventor's consideration is lowered the temperature for the flue gas heat exchanger recovery waste heat going out incinerator, again high-temperature flue gas is introduced in pipeline and mix, enter the bottom enriching section of desulfurizing tower, the object done like this utilizes the heat energy in flue gas to concentrate the rare thiamines in enriching section, and the flue gas after cooling rises and enters central absorbent section, and deposed ammonia passes into the SO in central absorbent section and flue gas
2reaction generates thiamines, and (reaction equation is xNH
3+ H
2o+SO
2=(NH
4) xH
2-xSO
3), enriching section is advanced under reacted liquid, gas is up washed cooling further by water after discharged by the exhanst gas outlet at desulfurizing tower top, discharge flue-gas temperature and can be down to 48 ~ 50 DEG C, the slurry that bottom desulfurizing tower, slurry outlet is drawn can obtain thiamines byproduct through further processing.
Control containing SO
2flue gas and the mixed gas temperature of high-temperature flue gas be 120-140 DEG C, pressure is 1500Pa, and temperature is too low can produce sour dew condensation phenomenon corrosion pipeline.The too high pipe lining VEGF flake mortar anticorrosive coat that causes of temperature comes off.
High-temperature flue gas described in present invention process can be the boiler smoke of coal chemical engineering equipment, and ammoniacal liquor is the deposed ammonia that can adopt device by-product, achieves the sustainable development strategies turned waste into wealth, decreases waste discharge, save processing cost.
Present invention process comparatively prior art is compared, save hydrogenation reaction and solvent reclamation device, decrease the consumption of electric energy, steam and the solvent brought thus, tail gas burns through incinerator, after heat exchanger cooling, directly introduces ammonia process desulfuration tower, greatly improve the security of production, reduce equipment and energy consumption cost of investment, save floor space, present invention process SO
2the rate of recovery high, discharge gas in SO
2content can be reduced to below 100ppm, compared to former design, SO
2discharge capacity can reduce 301.8t/a ~ 322t/a, while meeting national regulation, limitedly controls atmosphere pollution.
Accompanying drawing explanation
Fig. 1 is schematic flow sheet of the present invention.
In figure: 1-Claus reaction system; 2-incinerator; 3-heat exchanger; The import of 4-high-temperature flue gas, 5-gas approach, 6-exhanst gas outlet, 7-desulfurizing tower, 7.1-washing section, 7.2-absorber portion, 7.3-enriching section, 8-slurry outlet; The import of 9-deposed ammonia, 10-clear water spray head.
Detailed description of the invention
Below in conjunction with accompanying drawing, 1 couple of the present invention is further explained explanation:
As shown in Figure 1, based on the sulfur recovery system of the low sulphur emissions of Claus reaction system, comprise Claus reaction system 1, the offgas outlet of described Claus reaction system 1 is connected with the gas approach 5 of desulfurizing tower 7 through incinerator 2, heat exchanger 3, described desulfurizing tower 7 top is provided with exhanst gas outlet 6, bottom is provided with gas approach 5, bottom is provided with slurry outlet 8, and tower body is made up of concentrated 7.3 sections of the washing section 7.1 on top, central absorbent section 7.2 and bottom.Washing section 7.1 epimere of described desulfurizing tower 7 is provided with clear water spray head 10, and for washing the flue gas from absorber portion 7.2, hypomere is provided with deposed ammonia import 9.The pipeline connected between the gas approach 5 of described desulfurizing tower 7 and heat exchanger 3 is also provided with high-temperature flue gas import 4.Pipe lining VEGF flake mortar anticorrosive coat between the gas approach 5 of high-temperature flue gas import 4 and desulfurizing tower 7.
Technical process:
Acid gas enters Claus reaction system 1 and reacts, the most of H in acid gas
2s is converted into sulphur, the SO simultaneously wherein existed
2, COS and micro-elemental sulfur steam, the tail gas going out Claus reaction system continues to enter in incinerator 2 and burns, and makes sulfur-containing medium all be converted into SO
2, after burning containing SO
2flue gas (be called for short flue gas, 800 DEG C ~ 900 DEG C, SO
2content is by calculating) enter heat exchanger 4 and carry out waste heat recovery and be cooled to 80 DEG C ~ 120 DEG C, then (control flue gas and the mixed gas temperature of high-temperature flue gas is 120-140 DEG C, tolerance is 50349Nm after converging with the high-temperature flue gas (temperature is 120 DEG C ~ 250 DEG C) from coal chemical engineering equipment
3/ h, SO
2content: 0.511% (v) be i.e. 13000mg/Nm
3), enter bottom enriching section 7.3 from the gas approach 5 of ammonia process desulfuration tower 7, the rare thiamines draw heat from heat smoke in enriching section 7.3, concentrate for self, make flue-gas temperature reduce to 55 ~ 60 DEG C; After enriching section, flue gas upwards enters the central absorbent section 7.2 of ammonia process desulfuration tower 7, the SO in flue gas
2react with the deposed ammonia introduced by deposed ammonia import 9 and generate thiamines, flue gas enters the washing section 7.1 on ammonia process desulfuration tower 7 top afterwards, the liquid carried secretly in the clear water washing removing flue gas sprayed by clear water spray head 10 also makes flue-gas temperature be down to 48 ~ 50 DEG C, is finally discharged by the exhanst gas outlet 6 at top.Thiamines slip is then drawn from the slurry outlet 8 of the bottom of ammonia process desulfuration tower 7, sends into follow-up thiamines post-processing unit and obtains thiamines product.
SO in the flue gas of being discharged by exhanst gas outlet 6
2content is reduced to 100mg/Nm
3below, reduce 301.8t/a ~ 322t/a with brake specific emission, meet national regulation requirement, effectively control SO
2to the pollution of air, have important practical significance.
Claims (7)
1. based on a sulfur recovery technology for the low sulphur emissions of Claus reaction system, it is characterized in that, acid gas enters Claus reaction system and reacts, and the tail gas obtained after reaction is sent into incinerator and burned, and tail gas is converted into containing SO
2flue gas, described containing SO
2flue gas after heat exchanger recovery waste heat, send into desulfurizing tower bottom enriching section by gas approach, lower the temperature with thiamines heat exchange rare in enriching section, then upwards enter the central absorbent section of desulfurizing tower, the SO in flue gas
2react with ammoniacal liquor and generate thiamines, be advanced into enriching section and discharge through slurry outlet, reacted gas is advanced into the washing section on ammonia process desulfuration tower top under reacted liquid, the liquid carried secretly in removing flue gas is also discharged by top exhanst gas outlet after cooling.
2., as claimed in claim 1 based on the sulfur recovery unit of the low sulphur emissions of Claus reaction system, it is characterized in that, described containing SO
2flue gas after heat exchanger recovery waste heat, send into the bottom enriching section of desulfurizing tower after mixing with high-temperature flue gas afterwards again.
3. as claimed in claim 1 based on the sulfur recovery unit of the low sulphur emissions of Claus reaction system, it is characterized in that, control containing SO
2flue gas and the mixed gas temperature of high-temperature flue gas be 120-140 DEG C.
4. the sulfur recovery system based on the low sulphur emissions of Claus reaction system, comprise Claus reaction system, it is characterized in that, the offgas outlet of described Claus reaction system is connected with the gas approach of desulfurizing tower through incinerator, heat exchanger, described desulfurizing tower top is provided with exhanst gas outlet, bottom is provided with gas approach, bottom is provided with slurry outlet, and tower body is made up of the washing section on top, central absorbent section and bottom enriching section.
5., as claimed in claim 4 based on the sulfur recovery system of the low sulphur emissions of Claus reaction system, it is characterized in that, the washing section top of described desulfurizing tower is provided with clear water spray head, and bottom is provided with deposed ammonia import.
6. the sulfur recovery system of the low sulphur emissions based on Claus reaction system according to claim 4, is characterized in that: the pipeline connected between the gas approach of described desulfurizing tower and heat exchanger is also provided with high-temperature flue gas import.
7. the sulfur recovery system of the low sulphur emissions based on Claus reaction system according to claim 6, is characterized in that: the pipe lining VEGF flake mortar anticorrosive coat between high-temperature flue gas import and the gas approach of desulfurizing tower.
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| CN201510459789.1A CN105020723A (en) | 2015-07-30 | 2015-07-30 | Low-sulfur-discharge sulfur recovering technique and system based on Claus reaction system |
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|---|---|---|---|
| CN201510459789.1A CN105020723A (en) | 2015-07-30 | 2015-07-30 | Low-sulfur-discharge sulfur recovering technique and system based on Claus reaction system |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110107906A (en) * | 2019-05-31 | 2019-08-09 | 大连科汇工程技术有限公司 | SO is produced in a kind of burning of ammonia process of desulfurization waste liquid fixed bed2Process Gas system and technique |
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| CN103521060A (en) * | 2012-07-04 | 2014-01-22 | 辽宁大唐国际阜新煤制天然气有限责任公司 | Method for desulfurization of sulfur recovery tail gas by using boiler flue gas ammonia method |
| CN203777926U (en) * | 2014-04-18 | 2014-08-20 | 中石化南京工程有限公司 | Ammonia absorption tail gas treatment device of sulfur recovery device |
| CN204853511U (en) * | 2015-07-30 | 2015-12-09 | 中国五环工程有限公司 | Sulphur recovery system that low -sulfur discharged based on claus reaction system |
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2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103521060A (en) * | 2012-07-04 | 2014-01-22 | 辽宁大唐国际阜新煤制天然气有限责任公司 | Method for desulfurization of sulfur recovery tail gas by using boiler flue gas ammonia method |
| CN103301732A (en) * | 2013-06-20 | 2013-09-18 | 义马煤业集团煤生化高科技工程有限公司 | Device and process for recycling and treating hydrogen sulfide-containing chemical acid waste gas |
| CN203777926U (en) * | 2014-04-18 | 2014-08-20 | 中石化南京工程有限公司 | Ammonia absorption tail gas treatment device of sulfur recovery device |
| CN204853511U (en) * | 2015-07-30 | 2015-12-09 | 中国五环工程有限公司 | Sulphur recovery system that low -sulfur discharged based on claus reaction system |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110107906A (en) * | 2019-05-31 | 2019-08-09 | 大连科汇工程技术有限公司 | SO is produced in a kind of burning of ammonia process of desulfurization waste liquid fixed bed2Process Gas system and technique |
| CN110107906B (en) * | 2019-05-31 | 2024-01-05 | 大连科汇工程技术有限公司 | Ammonia desulfurization waste liquid fixed bed incineration firing SO preparation 2 Process gas system and process |
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Application publication date: 20151104 |