CN105983331B - Industrial sulfur-containing tail gas sulfur removal technology - Google Patents
Industrial sulfur-containing tail gas sulfur removal technology Download PDFInfo
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- CN105983331B CN105983331B CN201510062204.2A CN201510062204A CN105983331B CN 105983331 B CN105983331 B CN 105983331B CN 201510062204 A CN201510062204 A CN 201510062204A CN 105983331 B CN105983331 B CN 105983331B
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Abstract
The invention discloses a kind of industrial sulfur-containing tail gas sulfur removal technologies, after sulfur-containing tail gas is mixed with combustion air, are heated through heater exhaust gas, into selective catalytic reactor, the H in tail gas2S、Sx、COS、SO2Chosen property catalytic oxidation is converted into SO3, containing SO3High-temperature tail gas recycle heat through residual neat recovering system and heater exhaust gas, into downstream sulfuric acid unit or other processing systems, wherein：The inlet temperature of selective catalytic reactor is 200~500 DEG C, and outlet temperature is 300~700 DEG C；The operating pressure of selective catalytic reactor is 0~50Kpa.The present invention is suitable for the sulfur-containing tail gas of the enterprises such as processing petrochemical industry, oil refining and coal chemical industry discharge.
Description
Technical field
The present invention relates to a kind of industrial sulfur-containing tail gas sulfur removal technologies, are a kind of processing of the sulphur-containing exhaust gas of industrial process discharge
Method；More particularly to the selective catalytic oxidation treatment process of sulfur-containing tail gas.
Background technology
The enterprises such as coal chemical industry, petrochemical industry and refinery are in production processed sour crude oil or sulfur-bearing coal,
A large amount of sulphur-containing exhaust gas is generated, if these tail gas are not only not achieved the environmental requirement of country, but will give without processing direct emission
Social environment and the health of the common people damage, and aggravate the meteorological disasters such as acid rain.Therefore, industrial tail gas desulfurization treatment process
The always important topic of the industries such as petrochemical industry concern.
Sulphur-containing exhaust gas generally use sulfur recovery unit in industry is recycled in the form of elemental sulfur, however even across
The processing of recovery unit, in tail gas still remaining H2S、Sx、COS、SO2Etc. a certain amount of sulfur-containing compound, discharge is not achieved will
It asks.
Sulfur-containing tail gas is handled using heating power incineration technology (TO), needs to consume a large amount of fuel, it is less economical, and often can be in height
The by-products such as NOx are generated under the conditions of temperature, cause secondary pollution.The present invention, can will be difficult compared with heating power incineration technology (TO)
Sulfide, foul gas H2All processing is up to standard for the pollutants such as S, and the secondary pollutions such as no NOx generate；Combustion is not consumed simultaneously
Material, byproduct steam amount are more, steam generation is stable, operating cost is very low.Compared to heating power incineration technology (TO), provided in the present invention
Technology every year can the raw benefit for being up to several ten million RMB of fecund, and system is driven safely and fast, and stable, it is very good to have
Economic benefit and social benefit.
Invention content
For the desulfurization process demand of commercial plant sulphur-containing exhaust gas, according to an embodiment of the invention, it is desirable to provide Yi Zhonghan
Sulphur tail gas treatment process only needs single-stage reactor can be by SO2、Sx、COS、H2S is completely converted into SO3, and SO2High conversion rate,
The SO of generation3Product utilizes for downstream sulphuring treatment device, such as relieving haperacidity or sulphur ammonium unit processed.Present invention process simultaneously realize compared with
The advantages such as byproduct steam, relatively low operating cost are stablized in low energy consumption, reach extraordinary economic benefit and environmental benefit.
According to one embodiment, a kind of industrial sulfur-containing tail gas sulfur removal technology provided by the invention, innovative point is：Sulfur-bearing
Tail gas heats after preheating is mixed with combustion air through heater exhaust gas, into selective catalytic reactor, the H in tail gas2S、Sx、
COS、SO2Chosen property catalytic oxidation is converted into SO3, containing SO3High-temperature tail gas through residual neat recovering system and heater exhaust gas
Heat is recycled, into downstream sulfuric acid unit or other processing systems, wherein：
The inlet temperature of selective catalytic reactor is 200~500 DEG C, and outlet temperature is 300~700 DEG C；
The operating pressure of selective catalytic reactor is 0~50Kpa.
According to one embodiment, in aforementioned industrial sulfur-containing tail gas sulfur removal technology of the present invention, selective catalytic reactor can be with
By the H in tail gas2S、Sx、COS、SO2It is converted into SO3.It is selective good with high conversion rate；Resistance to mechanical/sonic impinging ability
It is high, thermal stability is good, pressure drop is small, is readily cleaned, the characteristics of service life is long.
Relative to other tail gas desulfurization techniques, the present invention can be widely used in petrochemical industry, oil refining and coal chemical industry enterprises discharge
Sulfur-containing tail gas, disposably by SO2It is converted into SO3.The present invention, can be by intractable vulcanization compared with heating power incineration technology (TO)
Object, foul gas H2The pollutants such as S all processing it is up to standard, while do not consume fuel, byproduct steam amount are more, steam generation stabilization,
Operating cost is very low.Compared to heating power incineration technology (TO), the technology provided in the present invention every year can the raw up to several million peoples of fecund
The benefit of people's coin, and system is driven safely and fast, it is stable, there is extraordinary economic benefit and social benefit.
Relative to other tail gas desulfurization techniques, the present invention hardly consumes fuel gas, it is only necessary to add fuel in start-up
Gas carries out system the preheating that goes into operation, and during normal operation, fire box temperature can also be maintained by being not required to supplement fuel.It is set in this technological process
Residual neat recovering system, by recycling steam generation by reaction heat.The present invention not only solves the problem of industrial tail gas desulfurization, and
Considerable by-product income is brought to user, has very good economic benefit and social benefit.
Description of the drawings
Fig. 1 is the process flow chart of sulfur-containing tail gas processing of the present invention.
Wherein, 1 is heater exhaust gas；2 be SCO reactors；3 be residual neat recovering system.
Specific embodiment
In the following with reference to the drawings and specific embodiments, the present invention is further explained.These embodiments are interpreted as being only used for
It is bright the present invention rather than limit the scope of the invention.After the content of the invention recorded has been read, art technology
Personnel can make various changes or modifications the present invention, these equivalence changes and modification equally fall into the claims in the present invention and limited
Fixed range.
As shown in Figure 1, the technological process of industrial sulfur-containing tail gas sulfur removal technology is in following embodiment of the present invention：Sulfur-containing tail gas
It is preheated after being mixed with combustion air through heater exhaust gas 1, into selective catalytic oxidation reactor, i.e. SCO reactors 2, tail gas
In H2S、SO2, the chosen property catalytic oxidation of Sx, COS be converted into SO3.More than 2 exit gas of selective catalytic reactor warp
Heat recovery system 3 and heater exhaust gas 1 recycle heat, into downstream sulfuric acid unit or other processing systems.
In the embodiment of the present invention, the group of waste heat boiler, economizer or both may be used in the residual neat recovering system 3
It closes.
In the embodiment of the present invention, the catalyst in SCO reactors 2 is common noble metal catalyst, cheap metal is catalyzed
Agent or metal oxide catalyst.
In the embodiment of the present invention, fixed bed reactors, single-stage reactor can be used in SCO reactors 2.
In the embodiment of the present invention, welded plate type heat exchanger or shell-and-tube heat exchanger or heat pipe may be used in heater exhaust gas 1
Heat exchanger or finned tube exchanger.
The sulphur-containing exhaust gas data discharged in following embodiment of the present invention using certain device, the composition of the tail gas is as follows after measured
Shown in table：
1 sulfur-containing tail gas of table forms
| Ingredient names | Molar flow (kmol/h) | Molar content % |
| CO2 | 170 | 67.03 |
| H2S | 0.1 | 0.039 |
| N2 | 77 | 30.36 |
| O2 | 6 | 2.36 |
| SO2 | 0.5 | 0.20 |
| COS | 50ppm | |
| Sx | 30ppm | |
| Total Total | 253.6 | 100 |
Embodiment 1
As shown in Figure 1, sulfur-containing tail gas enters SCO reactors, at 203 DEG C, outlet temperature controls the control of entrance temperature of charge
At 312 DEG C, operating pressure is controlled in 2.4Kpa.Cleaning of off-gas be sent into follow-up relieving haperacidity/sulphur ammonium processed unit or other.
After measured, other components content is in net tail gas：SO2≤150mg/Nm3；Wherein SO2Conversion ratio >=96%.
Embodiment 2
As shown in Figure 1, sulfur-containing tail gas enters SCO reactors, at 235 DEG C, outlet temperature controls the control of entrance temperature of charge
At 340 DEG C, operating pressure is controlled in 8.5Kpa.Cleaning of off-gas be sent into follow-up relieving haperacidity/sulphur ammonium processed unit or other.
After measured, other components content is in cleaning of off-gas：SO2≤150mg/Nm3；Wherein SO2Conversion ratio >=96%.
Embodiment 3
As shown in Figure 1, sulfur-containing tail gas enters SCO reactors, at 272 DEG C, outlet temperature controls the control of entrance temperature of charge
At 369 DEG C, operating pressure is controlled in 15.8Kpa.Cleaning of off-gas be sent into follow-up relieving haperacidity/sulphur ammonium processed unit or other.
After measured, other components content is in cleaning of off-gas：SO2≤150mg/Nm3；Wherein SO2Conversion ratio >=96%.
Embodiment 4
As shown in Figure 1, sulfur-containing tail gas enters SCO reactors, at 313 DEG C, outlet temperature controls the control of entrance temperature of charge
At 416 DEG C, operating pressure is controlled in 27.0Kpa.Cleaning of off-gas be sent into follow-up relieving haperacidity/sulphur ammonium processed unit or other.
After measured, other components content is in cleaning of off-gas：SO2≤150mg/Nm3；Wherein SO2Conversion ratio >=96%.
Embodiment 5
As shown in Figure 1, sulfur-containing tail gas enters SCO reactors, at 348 DEG C, outlet temperature controls the control of entrance temperature of charge
At 450 DEG C, operating pressure is controlled in 29.1Kpa.Cleaning of off-gas be sent into follow-up relieving haperacidity/sulphur ammonium processed unit or other.
After measured, other components content is in cleaning of off-gas：SO2≤150mg/Nm3；Wherein SO2Conversion ratio >=96%.
Embodiment 6
As shown in Figure 1, sulfur-containing tail gas enters SCO reactors, at 389 DEG C, outlet temperature controls the control of entrance temperature of charge
At 490 DEG C, operating pressure is controlled in 31.3Kpa.Cleaning of off-gas be sent into follow-up relieving haperacidity/sulphur ammonium processed unit or other.
After measured, other components content is in cleaning of off-gas：SO2≤150mg/Nm3；Wherein SO2Conversion ratio >=96%.
Embodiment 7
As shown in Figure 1, sulfur-containing tail gas enters SCO reactors, at 421 DEG C, outlet temperature controls the control of entrance temperature of charge
At 527 DEG C, operating pressure is controlled in 33.4Kpa.Cleaning of off-gas be sent into follow-up relieving haperacidity/sulphur ammonium processed unit or other.
After measured, other components content is in cleaning of off-gas：SO2≤150mg/Nm3；Wherein SO2Conversion ratio >=97%.
Embodiment 8
As shown in Figure 1, sulfur-containing tail gas enters SCO reactors, at 459 DEG C, outlet temperature controls the control of entrance temperature of charge
At 564 DEG C, operating pressure is controlled in 35.5Kpa.Cleaning of off-gas be sent into follow-up relieving haperacidity/sulphur ammonium processed unit or other.
After measured, other components content is in cleaning of off-gas：SO2≤150mg/Nm3；Wherein SO2Conversion ratio >=97%.
Embodiment 9
As shown in Figure 1, sulfur-containing tail gas enters SCO reactors, at 480 DEG C, outlet temperature controls the control of entrance temperature of charge
At 583 DEG C, operating pressure is controlled in 42.0Kpa.Cleaning of off-gas be sent into follow-up relieving haperacidity/sulphur ammonium processed unit or other.
After measured, other components content is in cleaning of off-gas：SO2≤150mg/Nm3；Wherein SO2Conversion ratio >=97%.
Embodiment 10
As shown in Figure 1, sulfur-containing tail gas enters SCO reactors, at 500 DEG C, outlet temperature controls the control of entrance temperature of charge
At 606 DEG C, operating pressure is controlled in 46.7Kpa.Cleaning of off-gas be sent into follow-up relieving haperacidity/sulphur ammonium processed unit or other.
After measured, other components content is in cleaning of off-gas：SO2≤150mg/Nm3；Wherein SO2Conversion ratio >=98%.
Claims (6)
1. a kind of industry sulfur-containing tail gas sulfur removal technology, it is characterised in that：After sulfur-containing tail gas is mixed with combustion air, through tail gas heating
Device heats, into selective catalytic reactor, the H in tail gas2S、Sx、COS、SO2Chosen property catalytic oxidation is converted into
SO3, containing SO3High-temperature tail gas recycle heat through residual neat recovering system and heater exhaust gas, into downstream sulfuric acid unit or its elsewhere
Reason system, wherein：The inlet temperature of selective catalytic reactor is 500 DEG C, and outlet temperature is 606 DEG C；Selective catalysis reacts
The operating pressure of device is 0~50Kpa；H in the sulfur-containing tail gas2The molar content of S is 0.039%.
2. industry sulfur-containing tail gas sulfur removal technology as described in claim 1, it is characterised in that：The residual neat recovering system is remaining
The combination of heat boiler, economizer or both.
3. industry sulfur-containing tail gas sulfur removal technology as described in claim 1, it is characterised in that：Urging in selective catalytic reactor
Agent is noble metal catalyst, cheap metal catalyst or metal oxide catalyst.
4. industry sulfur-containing tail gas sulfur removal technology as described in claim 1, it is characterised in that：Selective catalytic reactor used
For fixed bed reactors.
5. industry sulfur-containing tail gas sulfur removal technology as described in claim 1, it is characterised in that：The heater exhaust gas is welding
Plate heat exchanger or shell-and-tube heat exchanger or heat exchange of heat pipe or finned tube exchanger.
6. industry sulfur-containing tail gas sulfur removal technology as described in claim 1, it is characterised in that：The selective catalytic reactor
For single-stage reactor.
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| CN107055486B (en) * | 2017-04-06 | 2019-03-12 | 赤峰云铜有色金属有限公司 | A kind of flue gas acid preparing process waste heat utilizes method |
| CN107433127B (en) * | 2017-08-01 | 2020-04-21 | 云南省贵金属新材料控股集团有限公司 | Method and device for catalytic oxidation purification and energy utilization of low-calorific-value industrial tail gas |
| CN111097284B (en) * | 2018-10-29 | 2022-03-08 | 中国石油化工股份有限公司 | Method for heating flue gas entering denitration system by using heat of conversion section |
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| CA2690286A1 (en) * | 2009-01-22 | 2010-07-22 | General Electric Company | Systems and methods for treating a stream comprising an undesirable emission gas |
| CN102470315A (en) * | 2009-08-04 | 2012-05-23 | 巴斯夫欧洲公司 | Absorption agent for removing acidic gases from a fluid flow |
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| AU2010233732B2 (en) * | 2009-04-08 | 2013-09-19 | Shell Internationale Research Maatschappij B.V. | Method of treating an acid gas stream and an apparatus therefor |
| US8206669B2 (en) * | 2010-07-27 | 2012-06-26 | Air Products And Chemicals, Inc. | Method and apparatus for treating a sour gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2690286A1 (en) * | 2009-01-22 | 2010-07-22 | General Electric Company | Systems and methods for treating a stream comprising an undesirable emission gas |
| CN102470315A (en) * | 2009-08-04 | 2012-05-23 | 巴斯夫欧洲公司 | Absorption agent for removing acidic gases from a fluid flow |
Non-Patent Citations (1)
| Title |
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| 用硫化氢气体制造硫酸;王爱群等;《硫酸工业》;20010720;第20-24页 * |
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