CN101239705A - Method for obtaining high-purity sulfur from gas containing hydrogen sulfide - Google Patents
Method for obtaining high-purity sulfur from gas containing hydrogen sulfide Download PDFInfo
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- CN101239705A CN101239705A CNA200810101611XA CN200810101611A CN101239705A CN 101239705 A CN101239705 A CN 101239705A CN A200810101611X A CNA200810101611X A CN A200810101611XA CN 200810101611 A CN200810101611 A CN 200810101611A CN 101239705 A CN101239705 A CN 101239705A
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- sulphur
- high purity
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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
Abstract
The present invention provides a method for acquiring high purity sulphur from gas containing H2S, gas containing H2S enters acid furface by removing water, the gas out of furnace enters in high pressure boiler to produce steam and cool at the same time, entering in gas-to-gas heat exchanger, waste heat boiler cooling, entering the first level condenser to 150 Celsius; gas outlet form the first level condenser ascending to 200 Celsius via gas-to-gas heat exchanger enters the first stage reactor, separating liquid sulfur by cooling in the second stage reactor after being reacted; the gas after being separated enters in acid gas preheater to heat wind pipe catalytic oxidation reactor by steam; the gas then enters in sulfur condenser to cool gas and condense sulfur in gas, then enters in sulfur separator; the separated gas then is drained via washing tower; the method checks content of H2S and SO2 in the first stage reactor, controlling air inlet content in acid gas furnace, the content ratio of H2S and SO2 in the first stage reactor is 2:1-7:1; the method has lower cost, and equipment, high purity sulfur in the environment protection condition.
Description
Technical field
The present invention relates to environmental technology field, particularly a kind of method that from H 2 S-containing gas, obtains high purity sulphur.
Background technology
In China's energy proven reserve, 96% be coal, hydrocarbon resources only accounts for about 4% of total amount.Therefore coal is the main force of China's energy, thus be that raw material system methyl alcohol and synthetic ammonia and coal system oil and alkene are on the increase in recent years with the coal, to alleviate the pressure of hydrocarbon resources.
A new generation's Coal Chemical Industry is based on C-1 chemistry, synthetic various oil fuel and Chemicals.In the Coal Chemical Industry reaction process, owing to contain impurity such as sulphur in the coal, these impurity are present in the coal gas, and coal gas is further used toxic effect, must remove; Simultaneously, the recovery of elemental sulfur has higher economic value.The complicacy of sulphur composition and be subjected to Coal Chemical Industry technology, influence that temperature is different in the coal, sulphur is transformed into that the form of sulphur is very complicated in the gas in the coal, mainly is inorganic sulfur (H
2S) and the organosulfur of various forms, this recovery that removes with sulphur to sulphur brings difficulty.
Since used low-temp methanol technology from conversion gas with H
2The acid qi exhaustion of sulfur-bearings such as S is got off, and carry dense, born again sour gas sulfur-bearing and can reach 25%, in addition higher.Because tolerance is bigger, use separately my company's (bright suitable sulfur recovery technology) former declare around the tubular type catalyst oxidation reactor, though solved claus reaction can not reach emission standard in environmental protection problem, but source of the gas for high density, need build two cover sulfur recovery units, and recirculation blower need be set the concentration that tail gas boosts sour gas is reduced to H
2Below the S5%.So not only increase process cost, also increased equipment, increased facility investment.
Summary of the invention
Main purpose of the present invention is to address the above problem, and a kind of method that obtains high purity sulphur from H 2 S-containing gas is provided, and this method can meet under the environmental protection requirement under the situation that does not increase process cost and facility investment, obtains high purity sulphur.
In order to achieve the above object, technical scheme provided by the invention is: a kind of method that obtains high purity sulphur from H 2 S-containing gas, enter the sour gas roasting kiln after the steps include: hydrogen sulfide containing gas removed liquid water through the sour gas water distributing can, after the advanced high-duty boiler generation of high-temperature gas after coming out of the stove steam is lowered the temperature simultaneously, air inlet gas interchanger, waste heat boiler cooling, enter first-stage condenser and be cooled to about 150 ℃, isolate molten sulfur; Temperature raising enters first stage reactor to about 200-220 ℃ and carries out catalytic oxidation the gas that comes out from first-stage condenser through gas-gas heat exchanger, and reaction is after secondary condenser cooling and separates molten sulfur down; Gas after the separation enters the sour gas preheater and is heated to 200-220 ℃ with middle pressure steam and advances around the tubular type catalyst oxidation reactor; Reacted gas enters the sulphur in sulfur condenser cooling gas and the condensed gas, enters the sulphur separator again; The gas of isolating liquid sulfur enters washing tower behind spray cooling; Emptying then; Should from H 2 S-containing gas, obtain the method for high purity sulphur after first stage reactor carries out catalytic oxidation, detect the content of hydrogen sulfide and sulfurous gas, the air inlet amount of control sour gas roasting kiln makes first stage reactor carry out the content of catalytic oxidation postcure hydrogen and sulfurous gas than between 2: 1 to 7: 1;
The concentration of the gas of hydrogen sulfide added fuel combustion less than 25% o'clock after entering the sour gas roasting kiln;
Emptying after the gaseous combustion of coming out from washing tower.
The present invention obtains the principle of work and the beneficial effect of the method for high purity sulphur from H 2 S-containing gas: H 2 S-containing gas enters the sour gas roasting kiln after removing liquid water through the sour gas water distributing can, with the air mixed burning of allocating into by a certain percentage, the main reaction that takes place in the air input of control air, stove is following oxidizing reaction:
H
2S+3/2O
2→SO
2+H
2O+Q1
H
2S+1/2SO
2→H
2O+3/4S
2+Q2
After steam about the advanced high-duty boiler product of the high-temperature gas after coming out of the stove 4.0MPa was lowered the temperature simultaneously, air inlet gas interchanger, waste heat boiler cooling entered first-stage condenser and are cooled to 150 ℃, isolate molten sulfur at this.Temperature raising enters first stage reactor to 200-220 ℃ and carries out the low-temperature Claus conversion reaction gas that comes out from first-stage condenser through gas-gas heat exchanger, obtains high Crouse's transformation efficiency.
Reacted gas enters the secondary condenser recovery sulphur, sloughing gas behind the sulphur enters the sour gas preheater and is heated to 200-220 ℃ with middle pressure steam (40Bar) and enters around the tubular type catalyst oxidation reactor (at this moment, the concentration of sulfide hydrogen and sulfurous gas should be below 5%), reactor charge catalyzer (titanium dioxide), total chemical reaction is that hydrogen sulfide and sulfurous gas reaction generate sulphur and water in reactor, specific to thermal insulation layer, its reaction is:
H
2S+O
2→S+H
2O
H
2S+SO
2→H
2O+S
2
H
2S+O
2→SO
2+H
2O
Because H
2S: SO
2Ratio between 2: 1 to 7: 1, under catalyst action, H
2S+SO
2→ H
2O+S
2Reaction moment finish, obtain elemental sulfur.
Reaction in isothermal layer is:
H
2S+O
2→S+H
2O
H
2S+SO
2→H
2O+S
2
Like this, utilize first stage reactor to carry out the SO that claus reaction contains
2, increased the chance that elemental sulfur produces.
Go into the heat that produces around the reaction of tubular type catalyst oxidation reactor and improve the temperature of self, water-vapour pipe was cold in reactor adopted, be connected with drum, regulate drum pressure and come the interior temperature of controlling reactor, reaction gas enters the sulphur in sulfur condenser cooling gas and the condensed gas, the pipe of sulfur condenser produces low-pressure steam outward, the pressure of steam regulation is regulated the temperature out of tube side, sulphur condensation in the gas is got off, can not be lower than the zero pour of sulphur again and make line clogging, enter the sulphur separator again, the gas of isolating liquid sulfur enters washing tower behind spray cooling, residual sulphur compound is carried out once more washing, and making drops a hint reaches environmental requirement, goes emptying house steward emptying.
Carrying out the claus reaction control reaction temperature at first stage reactor is 200-220 ℃, and this conversion zone is carried out at a lower temperature, makes that the transformation efficiency of sulphur is higher.
If the concentration of the gas of source of the gas hydrogen sulfide added fuel combustion less than 25% o'clock after entering the sour gas roasting kiln, be that refuel makes this method wider general because concentration can not be kept reaction less than 25% o'clock institute's thermal discharge.
The content of the hydrogen sulfide of the gas that comes out from washing tower is lower than 1000ppm, has reached national environmental requirement, but may be bigger for the total emission volumn of atm number, and burning back emptying at this moment guarantees that total emission volumn is little.
Embodiment:
Embodiment 1: the hydrogen sulfide catalyst oxidation reactor with 200,000 tons of methanol project of adapted annual production is an example, and the concentration of hydrogen sulfide is 26%:
A kind of method that from H 2 S-containing gas, obtains high purity sulphur, enter the sour gas roasting kiln after the steps include: hydrogen sulfide containing gas removed liquid water through the sour gas water distributing can, after the advanced high-duty boiler generation of high-temperature gas after coming out of the stove 4.0MPa steam is lowered the temperature simultaneously, air inlet gas interchanger, waste heat boiler cooling, enter first-stage condenser and be cooled to 150 ℃, isolate molten sulfur; The gas that comes out from first-stage condenser ℃ enters first stage reactor through gas-gas heat exchanger temperature raising to 200 and carries out claus reaction, and reaction is after secondary condenser cooling and separates molten sulfur down; Gas after the separation enters the sour gas preheater and is heated to 220 ℃ with middle pressure steam and advances around the tubular type catalyst oxidation reactor; Reacted gas enters the sulphur in sulfur condenser cooling gas and the condensed gas, enters the sulphur separator again; The gas of isolating liquid sulfur enters washing tower behind spray cooling; Emptying then; Should from H 2 S-containing gas, obtain the method for high purity sulphur after first stage reactor carries out claus reaction, detect the content of hydrogen sulfide and sulfurous gas, the air inlet amount of control sour gas roasting kiln makes first stage reactor carry out the content ratio of catalytic oxidation postcure hydrogen and sulfurous gas at 2: 1;
Should obtain the principle of work and the beneficial effect of the method for high purity sulphur from H 2 S-containing gas: H 2 S-containing gas enters the sour gas roasting kiln after removing liquid water through the sour gas water distributing can, with the air mixed burning of allocating into by a certain percentage, the reaction that takes place in the air input of control air, stove is following oxidizing reaction:
H
2S+3/2O
2→SO
2+H
2O+Q1
H
2S+1/2SO
2→H
2O+3/4S
2+Q2
After steam about the advanced high-duty boiler product of the high-temperature gas after coming out of the stove 4.0MPa was lowered the temperature simultaneously, air inlet gas interchanger, waste heat boiler cooling entered first-stage condenser and are cooled to 150 ℃, isolate molten sulfur at this.The gas that comes out from first-stage condenser ℃ enters first stage reactor through gas-gas heat exchanger temperature raising to 200 and carries out claus reaction.
Reacted gas enters the secondary condenser recovery sulphur, sloughing gas behind the sulphur enters the sour gas preheater and is heated to 220 ℃ with middle pressure steam (40Bar) and enters around the tubular type catalyst oxidation reactor, reactor charge catalyzer (titanium dioxide), total chemical reaction is that hydrogen sulfide and sulfurous gas reaction generate sulphur and water in reactor, specific to thermal insulation layer, its reaction is:
H
2S+O
2→S+H
2O
H
2S+SO
2→H
2O+S
2
H
2S+O
2→SO
2+H
2O
Because H
2S: SO
2Ratio between 2: 1 to 7: 1, under catalyst action, H
2S+SO
2→ H
2O+S
2Reaction moment finish, obtain elemental sulfur.
Reaction in isothermal layer is:
H
2S+O
2→S+H
2O
H
2S+SO
2→H
2O+S
2
Like this, utilize first stage reactor to carry out the SO that claus reaction contains
2, increased the chance that elemental sulfur produces.
Go into the heat that produces around the reaction of tubular type catalyst oxidation reactor and improve the temperature of self, water-vapour pipe was cold in reactor adopted, be connected with drum, regulate drum pressure and come the interior temperature of controlling reactor, reaction gas enters the sulphur in sulfur condenser cooling gas and the condensed gas, the pipe of sulfur condenser produces low-pressure steam outward, the pressure of steam regulation is regulated the temperature out of tube side, sulphur condensation in the gas is got off, can not be lower than the zero pour of sulphur again and make line clogging, enter the sulphur separator again, the gas of isolating liquid sulfur enters washing tower behind spray cooling, residual sulphur compound is carried out once more washing, and making drops a hint reaches environmental requirement, goes emptying house steward emptying.
Embodiment 2: the hydrogen sulfide catalyst oxidation reactor with the methanol project of 200,000 tons of adapted annual production is an example, and the concentration of hydrogen sulfide is about 20%:
Difference from Example 1 is: the gas after the separation enters the sour gas preheater and is heated to 220 ℃ with middle pressure steam and advances around the tubular type catalyst oxidation reactor; Carrying out the catalytic oxidation control reaction temperature at first stage reactor is 220 ℃, and this conversion zone is carried out at a lower temperature, makes that the transformation efficiency of sulphur is higher; Because of the concentration of the gas of source of the gas hydrogen sulfide less than 25% o'clock, after entering the sour gas roasting kiln, add fuel combustion, make this method wider general.
Embodiment 3: the hydrogen sulfide catalyst oxidation reactor with the methanol project of 200,000 tons of adapted annual production is an example, and the concentration of hydrogen sulfide is about 30%:
Difference from Example 1 is: the gas after the separation enters the sour gas preheater and is heated to 200 ℃ with middle pressure steam and advances around the tubular type catalyst oxidation reactor; Carrying out the claus reaction control reaction temperature at first stage reactor is 200 ℃, and this conversion zone is carried out at a lower temperature, makes that the transformation efficiency of sulphur is higher; Emptying after the gaseous combustion of coming out from washing tower, the content of the hydrogen sulfide of this section gas is lower than 1000ppm, has reached national environmental requirement, but may be bigger for the total emission volumn of atm number, and this is burning back emptying, guarantees that total emission volumn is little.
The utility model catalyst oxidation reactor is applicable to gases such as handling different concns hydrogen sulfide in sum; The rate of recovery height of sulphur, the purity height of byproduct; Under the situation that does not increase process cost and facility investment, can meet under the environmental protection requirement, obtain high purity sulphur.
Though the present invention utilizes the foregoing description to carry out at length setting forth, and is not to limit the present invention, any those skilled in the art should do various changes and modification, without departing from the spirit and scope of the present invention, should be considered as protection scope of the present invention.
Claims (3)
1, a kind of method that from H 2 S-containing gas, obtains high purity sulphur, enter the sour gas roasting kiln after the steps include: hydrogen sulfide containing gas removed liquid water through the sour gas water distributing can, after the advanced high-duty boiler generation of high-temperature gas after coming out of the stove steam is lowered the temperature simultaneously, air inlet gas interchanger, waste heat boiler cooling, enter first-stage condenser and be cooled to about 150 ℃, isolate molten sulfur; Temperature raising enters first stage reactor to about 200-220 ℃ and carries out catalytic oxidation the gas that comes out from first-stage condenser through gas-gas heat exchanger, and reaction is after secondary condenser cooling and separates molten sulfur down; Gas after the separation enters the sour gas preheater and is heated to 200-220 ℃ with middle pressure steam and advances around the tubular type catalyst oxidation reactor; Reacted gas enters the sulphur in sulfur condenser cooling gas and the condensed gas, enters the sulphur separator again; The gas of isolating liquid sulfur enters washing tower behind spray cooling; Emptying then; It is characterized in that: should from H 2 S-containing gas, obtain the method for high purity sulphur after first stage reactor carries out catalytic oxidation, detect the content of hydrogen sulfide and sulfurous gas, the air inlet amount of control sour gas roasting kiln makes first stage reactor carry out the content of catalytic oxidation postcure hydrogen and sulfurous gas than between 2: 1 to 7: 1.
2, the method that obtains high purity sulphur from H 2 S-containing gas according to claim 1, it is characterized in that: the concentration of the gas of described hydrogen sulfide added fuel combustion less than 25% o'clock after entering the sour gas roasting kiln.
3, the method that obtains high purity sulphur from H 2 S-containing gas according to claim 3 is characterized in that: emptying after the described gaseous combustion of coming out from washing tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810101611XA CN101239705A (en) | 2008-03-10 | 2008-03-10 | Method for obtaining high-purity sulfur from gas containing hydrogen sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810101611XA CN101239705A (en) | 2008-03-10 | 2008-03-10 | Method for obtaining high-purity sulfur from gas containing hydrogen sulfide |
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|---|---|
| CN101239705A true CN101239705A (en) | 2008-08-13 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792129A (en) * | 2010-04-08 | 2010-08-04 | 周琪 | Application of II-stage reactor in sulfur recovery industry |
| CN102381686A (en) * | 2011-07-29 | 2012-03-21 | 山东三维石化工程股份有限公司 | Treatment process of high-ammonia and low-sulfur gas |
| CN103663386A (en) * | 2012-09-19 | 2014-03-26 | 中国石油化工股份有限公司 | Method for reducing SO2 emission concentration of sulfur device |
| US9556030B2 (en) | 2013-11-08 | 2017-01-31 | Saudi Arabian Oil Company | Sulfur recovery unit |
| CN108128921A (en) * | 2017-12-23 | 2018-06-08 | 江苏恒新能源科技有限公司 | A kind of sewage disposal containing sodium thiocarbonate and resource recovery device and its method |
| CN113654034A (en) * | 2021-07-20 | 2021-11-16 | 山东联盟化工股份有限公司 | Comprehensive recycling technology for low-grade steam containing acidic non-condensable gas |
-
2008
- 2008-03-10 CN CNA200810101611XA patent/CN101239705A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792129A (en) * | 2010-04-08 | 2010-08-04 | 周琪 | Application of II-stage reactor in sulfur recovery industry |
| CN102381686A (en) * | 2011-07-29 | 2012-03-21 | 山东三维石化工程股份有限公司 | Treatment process of high-ammonia and low-sulfur gas |
| CN103663386A (en) * | 2012-09-19 | 2014-03-26 | 中国石油化工股份有限公司 | Method for reducing SO2 emission concentration of sulfur device |
| US9556030B2 (en) | 2013-11-08 | 2017-01-31 | Saudi Arabian Oil Company | Sulfur recovery unit |
| CN108128921A (en) * | 2017-12-23 | 2018-06-08 | 江苏恒新能源科技有限公司 | A kind of sewage disposal containing sodium thiocarbonate and resource recovery device and its method |
| CN113654034A (en) * | 2021-07-20 | 2021-11-16 | 山东联盟化工股份有限公司 | Comprehensive recycling technology for low-grade steam containing acidic non-condensable gas |
| CN113654034B (en) * | 2021-07-20 | 2023-08-29 | 山东联盟化工股份有限公司 | Comprehensive recycling method for low-grade steam containing acidic noncondensable gas |
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Open date: 20080813 |