CN101791517B - Method for recycling sulfur from acid gases containing hydrogen sulfide - Google Patents
Method for recycling sulfur from acid gases containing hydrogen sulfide Download PDFInfo
- Publication number
- CN101791517B CN101791517B CN2010101416783A CN201010141678A CN101791517B CN 101791517 B CN101791517 B CN 101791517B CN 2010101416783 A CN2010101416783 A CN 2010101416783A CN 201010141678 A CN201010141678 A CN 201010141678A CN 101791517 B CN101791517 B CN 101791517B
- Authority
- CN
- China
- Prior art keywords
- sulfur
- gas
- sulphur
- air
- molten sulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- 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 invention relates to a method for recycling sulfur from acid gases containing hydrogen sulfide, comprising the following steps: (a) air supply; (b) acid gas pretreatment; (c) mixture; (d) primary direct catalytic oxidation; (e) primary sulfur condensation; (f) process gas reheating; (g) secondary direct catalytic oxidation; (h) secondary sulfur condensation; (i) sulfur re-separation; (j) degasification in a liquid sulfur tank; and (k) tail gas burning. When the volume concentration of H2S in the acid gases in the prior art is 1-15%, the recycle rate of sulfur can reach over 99% by the method of the invention, and the emission load of H2S in the acid gases processed by the method of the invention meets the emission requirement of Integrated Emission Standard of Air Pollutants (GB16297-1996).
Description
Technical field
The present invention relates to a kind of sulfur recovery technology, particularly a kind of technology that from the sour gas that contains hydrogen sulfide, reclaims sulphur.
Background technology
According to China's energy resource structure, China is an oil starvation, weak breath, the country of relative rich coal.Verifying in the energy reserve, the 96%th, coal, petroleum resources only account for total amount about 4%.Coal is the main force of China's energy, is that raw material system methyl alcohol and synthetic ammonia project are on the increase at present with the coal, to alleviate the pressure that petroleum resources lacks.According to China " the medium-term and long-term development plan of Coal Chemical Industry industry " (exposure draft), to 2010,2015 and the year two thousand twenty, the annual production of coal system alkene was respectively 1,400,000 tons, 5,000,000 tons and 8,000,000 tons, and 1 ton of alkene can consume 3 tons of methyl alcohol.China has the advantageous resources advantage of low-cost production fuel methanol as coal resources big country.But the environmental regulation of increasingly stringent has proposed emission request to coal gasification system methyl alcohol and synthetic ammonia installation.The Chemical Manufacture that with the coal is raw material has determined that a large amount of sour gas is arranged in the crude synthesis gas, like CO
2, H
2S, COS etc., these sour gas are disadvantageous to synthetic reaction, must before getting into synthesis loop, it be removed.Along with the fast development of Coal Chemical Industry industry, China has dropped into a large amount of research efforts on synthesis gas acid gas removal method and technology.In recent years; The pressing gas metallization processes; Like Texaco's water coal slurry pressure gasification process, Shell fine coal pressing gas metallization processes, supporting employed process for acid gas removal mainly contains polyglycol dimethyl ether process (NHD) technology of Nan Hua company exploitation and the low-temp methanol washing process that Lu Qi, Linde Co develop.Low-temperature rectisol method and the selected solvent of NHD method are to H
2S, CO
2The selectivity absorbability is strong, CO in solvent
2Solubility is big, and required solvent internal circulating load is little, and energy consumption is lower, at sulfide and CO
2The purification process of the coal gas that content is high demonstrates advantage gradually.
But what low-temperature rectisol and NHD gas purification technique adopted all is the method for Physical Absorption, contains a large amount of CO in the regenerated acidic gas behind the solvent flashing
2With a spot of H
2S (mainly is Na with traditional alkalescence
2CO
3) the method large-scale Coal Chemical Industry development need of incompatibility of material+active carrier solution absorption+regeneration, main cause is embodied in: a. product is dark sulphur, purity is low, darker in color, selling price are low; B. operating condition is relatively harsher, and operating cost is high, and labour intensity is big, needs higher cost of investment; C. operating environment is relatively poor, and environmental pollution is serious.
At present, be most widely used technology in refinery gas or the natural gas purification to reclaim sulphur in the sour gas of Crouse (Claus) technology from regeneration gas, be divided into prototype Crouse and various claus process.The prototype claus process that 19th century developed is to be based upon on the basic claus reaction, that is: SO
2+ 2H
2S=3S+2H
2O, i.e. H in the system
2S and SO
2Mol ratio be 2: 1, therefore before the Claus reactor, the Claus incinerator must be arranged, so that can be section H
2S and the O that blasts
2Reaction conversion becomes SO
2, and incinerator will be kept the high temperature more than 1000 ℃, guarantees smooth combustion, its precondition must be the H in the sour gas
2The S volumetric concentration is greater than 25%.For H
2The S volumetric concentration is lower than the processing of 25% gas, and the Claus method just is not suitable for or is uneconomical; Another problem of prototype Claus technology is the restriction that receives chemical balance, and tail gas is difficult to reach the standard of environment protection emission, must set up exhaust treatment system, and the complexity that this has just increased process has reduced the economy of technology.Sulphur output is not only operated inconvenience less than the Cross unit of 10t/d, and do not have economic implications.
In order to solve prototype Claus difficult technique, some claus process have been produced again to handle light concentration gas and the problem that can not reach environmental requirement.Wherein representative is listed below: low temperature selective oxidation process, rope company of Denmark Top that solution absorption-desorb enrichment adds the Clinsulf-DO technology of Crouse's SCOT technology, German Linde Co, the Selectox technology of Ba Ersen company, Dutch Comprimo Corporation's Super claus technology, French Elf Aquitaine company are the WSA technology of product with sulfuric acid.Wherein the Clinsulf-DO technology of Linde Co belongs to direct catalytic oxidation technology.Different with the prototype claus process is: claus reaction belongs to balanced reaction, and its equilibrium constant receives the restriction of reaction temperature, but directly catalytic oxidation is that direct oxidation of hydrogen sulfide is the reaction of elementary sulfur and water, belongs to unidirectional response.Can in the beds of direct oxidation reactor, mend and go into air, on a kind of special catalyst with H
2S is oxidized to elemental sulfur, and this technology has been set up commercial plant, is applied to from the very high regeneration acid gas of carbon dioxide content, reclaim sulphur.The Clinsulf-DO technology all compares harshness, the H in sour gas to operating condition and equipment requirements
2The S volumetric concentration was at 1%～15% o'clock, and the sulfur conversion rate of the Recovered sulphur device of the hydrogen sulfide that the Engineering Projects of domestic introduction such as Huaihe River Group Co.,Ltd remove in the NHD process for purifying gas of 180,000 tons of synthetic ammonia installations of operation in 2000 and the long celebrating gas field first gas production factory first purification plant's sulfur recovery facility is all about 90%.
Summary of the invention
Technical problem to be solved by this invention is: to the H in the sour gas in the prior art
2The S volumetric concentration was used the lower technical problem of Clinsulf-DO technology sulfur conversion rate at 1%～15% o'clock; Provide a kind of sulfur conversion rate the higher method that from the sour gas that contains hydrogen sulfide, reclaims sulphur.
The present invention realizes through following technical scheme: a kind of method that from the sour gas that contains hydrogen sulfide, reclaims sulphur comprises the steps:
(a) air is supplied with: utilize air-blaster to introduce air preheater to air from the external world, be preheating to 240 ℃ through said air preheater and form preheated air;
(b) sour gas preliminary treatment: sour gas is introduced the sour gas separator, isolates the drop that sour gas carries, and the sour gas after separating that comes out from said sour gas separator gets into the sour gas preheater, is heated to 240 ℃ through middle pressure steam;
(c) mix: according to the ratio of the amount of substance of hydrogen sulfide and the amount of substance of oxygen is that 2: 1 ratio is calculated, and respectively the sour gas that is preheating to 240 ℃ in preheated air in the said air preheater and the said sour gas preheater is fed and fully mixes the back in the static mixer and form process gas;
(d) the direct catalytic oxidation of one-level: will be passed into from the process gas of static mixer in the main reactor, and be filled with Ti-base catalyst in the said main reactor, the H in the process gas
2S and airborne O
2Carry out direct catalytic oxidation; Reaction generates elemental sulfur and water, and the pressure of regulating first steamdrum that is connected with main reactor makes said main reactor Outlet Gas Temperature be not less than 290 ℃, avoid elemental sulfur in the condensation of the exit of said main reactor; Stop up the mouth of pipe; The bottom of said main reactor is provided with the coil pipe heat-obtaining, and the temperature of control reaction makes reaction more help the generation of sulphur;
(e) one-level sulphur condensation: the process gas entering one-level sulfur condenser that comes out from said main reactor carries out the product separation, separates the liquid sulfur that obtains and locks the entering molten sulfur pond of struggling against through first molten sulfur;
(f) process gas heats again: the process gas of coming out from said one-level sulfur condenser gets into reheater, and said reheater is gas one a gas heat exchanger, will be heated to 240 ℃ from the process gas that said one-level sulfur condenser comes out;
(g) the direct catalytic oxidation of secondary: the process gas after the reheater heating is sent into auxiliary reactor and is carried out direct catalytic oxidation, is filled with Ti-base catalyst in the said auxiliary reactor, the H in the process gas
2S and airborne O
2Carry out direct catalytic oxidation; Reaction generates elemental sulfur and water; The pressure of regulating second steamdrum be connected with said auxiliary reactor makes said auxiliary reactor Outlet Gas Temperature be not less than 240 ℃, avoid elemental sulfur in the condensation of the exit of said auxiliary reactor, the obstruction mouth of pipe;
(h) secondary sulphur condensation: the process gas entering secondary sulfur condenser that comes out from said auxiliary reactor carries out the product separation, separates the liquid sulfur that obtains and locks the entering molten sulfur pond of struggling against through second molten sulfur;
(i) sulphur separates again: will send into from the process gas that said secondary sulfur condenser comes out and carry out sulphur the sulphur separator and separate, and separate the sulphur that obtains and get into the molten sulfur pond through the 3rd molten sulfur lock bucket;
(j) in said molten sulfur pond, outgas: in said molten sulfur pond, blast air through the air bubbler, molten sulfur fully contacts the H that makes in the molten sulfur with air
2S is oxidized to sulphur, makes remaining H simultaneously
2S separates with molten sulfur, and makes the polysulfide in the molten sulfur resolve into H
2S and sulphur, waste gas is evacuated to incinerator by steam jet ejector;
(k) tail gas calcination: the tail gas that said sulphur separator and said molten sulfur pond are discharged is introduced in the said incinerator and in said incinerator and is imported air, under 700 ℃ of situation with air excess, carries out calcination.
The above-mentioned method that from the sour gas that contains hydrogen sulfide, reclaims sulphur, said Ti-base catalyst comprises TiO
2, binding agent and co-catalyst, specific area is greater than 100m
2/ g, pore volume be more than or equal to 0.2ml/g, average crushing strength greater than 80 newton/, bulk density is 0.95～1.05Kg/L.
The method that from the sour gas that contains hydrogen sulfide, reclaims sulphur of the present invention has following beneficial technical effects: (1) is to H in the prior art
2The S volumetric concentration is at 1%～15% sour gas; The method that from the sour gas that contains hydrogen sulfide, reclaims sulphur of the present invention can make the rate of recovery of sulphur reach more than 99%; Through the sour gas that the method that from the sour gas that contains hydrogen sulfide, reclaims sulphur of the present invention is handled, H
2The discharge capacity of S reaches " discharge standard of air pollutants " emission request (GB16297-1996), and reasonable in design, easy for installation, stable.(2) technological process is simple, and is easy to operate, and the equipment structure is few, and gross investment economizes.(3) public work consumption is little, and operating cost is low.(4) the manufacturing material is durable in use, and regular maintenance is convenient.(5) the by-product sulfur purity is high, and economic benefit is obvious.(6) the recyclable utilization of byproduct steam realizes resource circulation economy, energy-saving and emission-reduction.(7) capital equipment in the technology---the direct catalyst oxidation reactor heat exchange efficiency of two-stage is high.
Description of drawings
Fig. 1 reclaims the molten sulfur pond degasification technique sketch map of the method for sulphur from the sour gas that contains hydrogen sulfide for the present invention;
Fig. 2 reclaims the method flow diagram of sulphur from the sour gas that contains hydrogen sulfide for the present invention.
Wherein: 1-air preheater, 2-boiler feedwater mouth, 3-sour gas separator, 4-sour gas preheater, 5-static mixer; The 6-main reactor, 7-first steamdrum, 8-one-level sulfur condenser, 9-reheater, 10-sulphur separator; The 11-auxiliary reactor, 12-second steamdrum, 13-secondary sulfur condenser, 14-first molten sulfur lock bucket, 15-molten sulfur pond; 16-second molten sulfur lock bucket, 17-the 3rd molten sulfur lock bucket, 18-incinerator, 19-steam jet ejector, the outlet of 20-low-pressure steam; 21-air supply port, 22-nitrogen supply port, 23-sour gas inlet, 24-middle pressure steam supply port, 25-extinguish steam inlet; 26-purging air inlet, 27-sulphur comminutor, 28-liquid sulfur pump, 30-molten sulfur lock bucket.
Embodiment
The method that from the sour gas that contains hydrogen sulfide, reclaims sulphur of present embodiment comprises the steps: the supply of (a) air: utilize air-blaster to introduce air preheater 1 to air from the external world, be preheating to 240 ℃ through said air preheater 1 and form preheated airs; (b) sour gas preliminary treatment: introduce sour gas separator 3 to sour gas; Isolate the drop that sour gas carries; The sour gas after separating that comes out from said sour gas separator 3 gets into sour gas preheater 4, is heated to 240 ℃ through middle pressure steam; (c) mix: according to the ratio of the amount of substance of hydrogen sulfide and the amount of substance of oxygen is that 2: 1 ratio is calculated, and respectively the sour gas that is preheating to 240 ℃ in preheated air in the said air preheater 1 and the said sour gas preheater 4 is fed and fully mixes the back in the static mixer 5 and form process gas; The flow of air is to confirm that according to the desired amount of oxygen of chemical reaction the flow size is regulated control by control valve through DCS by the sour gas body weight sulfide hydrogen amount of the flow of sour gas and assay determination; (d) the direct catalytic oxidation of one-level: will be passed into from the process gas of said static mixer 5 in the main reactor 6, and be filled with Ti-base catalyst in the said main reactor 6, the H in the process gas
2S and airborne O
2Carry out direct catalytic oxidation; Reaction generates elemental sulfur and water, and the pressure of regulating first steamdrum 7 that is connected with main reactor 6 makes said main reactor 6 Outlet Gas Temperatures be not less than 290 ℃, avoid elemental sulfur in the condensation of the exit of said main reactor 6; Stop up the mouth of pipe; The bottom of said main reactor 6 is provided with the coil pipe heat-obtaining, and the temperature of control reaction makes reaction more help the generation of sulphur; Total chemical reaction is that hydrogen sulfide and oxygen react generation sulphur and water in the said main reactor 6, cold water heat exchange in the temperature of the heat raising that reaction produces self and the utilization; Establish beds in the said main reactor 6, top is the high speed reaction zone, and the bottom adds heat production coil pipe.During reaction, reaction heat makes bed temperature rapid rising the in top add fast response, organic sulfur is transformed also can obtain higher reaction rate.Reactor lower part makes it higher conversion ratio through effectively controlling temperature after the cooling, and reactor coil pipe layout is more reasonable, has increased powerful heat exchange efficiency.In order to guarantee security; Take following measure making main reactor: joint for pipe carries out except that each weld bond with argon arc welding welding back 100%X illumination penetrates; Each root pipe is carried out the superpower water pressure test (design operation pressure 3 times), and it is 2 times of operating pressure that integral body is finished the back water pressure test; The temperature that temperature that can be through regulating the coil pipe feedwater and consumption are regulated said main reactor 6 internal upper part heat insulation layers and bottom isothermal layer can move reaction towards the direction that sulphur generates, and has avoided the interior molten sulfurs generation of said main reactor 6 again to greatest extent; (e) one-level sulphur condensation: the process gas entering one-level sulfur condenser 8 that comes out from said main reactor 6 carries out the product separation, separates the liquid sulfur that obtains and locks the 14 entering molten sulfur ponds 15 of struggling against through first molten sulfur; Reaction gas gets into the sulphur in said one-level sulfur condenser 8 refrigerating gases and the condensed gas; The pipe of said one-level sulfur condenser 8 produces low-pressure steam outward; The pressure of steam regulation is regulated the outlet temperature of tube side; Sulphur condensation in the gas is got off, can not be lower than the freezing point of sulphur again and make line clogging; The low-pressure steam that said one-level sulfur condenser 8 produces can be recycled; (f) process gas heats again: the process gas of coming out from said one-level sulfur condenser 8 gets into reheater 9, and said reheater 9 is gas one a gas heat exchanger, will be heated to 240 ℃ from the process gas that said one-level sulfur condenser 8 comes out; (g) the direct catalytic oxidation of secondary: the process gas after reheater 9 heating is sent into auxiliary reactor 11 and is carried out direct catalytic oxidation, is filled with Ti-base catalyst in the said auxiliary reactor 11, the H in the process gas
2S and airborne O
2Carry out direct catalytic oxidation; Reaction generates elemental sulfur and water; The pressure of regulating second steamdrum 12 that is connected with said auxiliary reactor 11 makes said auxiliary reactor 11 Outlet Gas Temperatures be not less than 240 ℃; Avoid elemental sulfur in the condensation of the exit of said auxiliary reactor 11, stop up the mouth of pipe; Total chemical reaction is that hydrogen sulfide and oxygen react generation sulphur and water in the said auxiliary reactor 11, cold water heat exchange in the temperature of the heat raising that reaction produces self and the utilization; Being provided with of said auxiliary reactor 11 one is that working conditions change is played regulating action; The 2nd, share part sulfur recovery function; The 3rd, the flexibility of raising system and the system of assurance sulphur recovery efficiency; Said auxiliary reactor 11 principles, structure, use catalyst and said main reactor 6 are similar, and volume is less than said main reactor 6; (h) secondary sulphur condensation: the process gas entering secondary sulfur condenser 13 that comes out from said auxiliary reactor 11 carries out the product separation, separates the liquid sulfur that obtains and locks the 16 entering molten sulfur ponds 15 of struggling against through second molten sulfur; Reaction gas gets into the sulphur in said secondary sulfur condenser 13 refrigerating gases and the condensed gas; The pipe of said secondary sulfur condenser 13 produces low-pressure steam outward; The pressure of steam regulation is regulated the outlet temperature of tube side; Sulphur condensation in the gas is got off, can not be lower than the freezing point of sulphur again and make line clogging; The low-pressure steam that said secondary sulfur condenser 13 produces can be recycled; (i) sulphur separates again: will send into from the process gas that said secondary sulfur condenser 13 comes out and carry out sulphur the sulphur separator 10 and separate, and separate the sulphur that obtains and get into molten sulfur ponds 15 through the 3rd molten sulfur lock bucket 17; (j) degassing in said molten sulfur pond 15: in said molten sulfur pond 15, blast air through the air bubbler; Molten sulfur fully contacts the H2S that makes in the molten sulfur with air and is oxidized to sulphur; Remaining H2S is separated with molten sulfur; And making the polysulfide in the molten sulfur resolve into H2S and sulphur, waste gas is evacuated to incinerator 18 by steam jet ejector 19; (k) tail gas calcination: the tail gas that said sulphur separator (14) and said molten sulfur pond 15 discharged is introduced in the said incinerator 18 and in said incinerator 18 and is imported air, under 700 ℃ of situation with air excess, carries out calcination; The high-temperature gas that incinerator produces is taken its most of heat away with waste heat boiler earlier, takes after-heat away with steam superheater again, and the flue gas that is cooled to 300 ℃ is discharged into atmosphere through chimney.In the present embodiment, said Ti-base catalyst comprises TiO
2, binding agent and co-catalyst, specific area is greater than 100m
2/ g, pore volume be more than or equal to 0.2mL/g, average crushing strength greater than 80 newton/, bulk density is 0.95～1.05kg/L.H in sour gas
2The S volumetric concentration was greater than 6% o'clock; The adiabatic temperature rise of cooling bed can be above 400 ℃～450 ℃ in the said main reactor 6; In order to prevent corrosion and to keep Crouse's balance, can reduce H through partly being circulated to the exit gas of said one-level sulfur condenser 8 import of said main reactor 6
2The concentration of S inlet is so that the temperature rise of limiting catalyst bed.
The method that from the sour gas that contains hydrogen sulfide, reclaims sulphur of present embodiment adopts concentrates instrument, carries out centralized Control in the DCS control room, to H in the prior art
2The S volumetric concentration can make the rate of recovery of sulphur reach more than 99% at 1%～15% sour gas, through the sour gas that the method that from the sour gas that contains hydrogen sulfide, reclaims sulphur of present embodiment is handled, H
2The discharge capacity of S reaches " discharge standard of air pollutants " emission request (GB16297-1996), and reasonable in design, easy for installation, stable.And technological process is simple, and is easy to operate, and the equipment structure is few, and gross investment economizes; Public work consumes little, and operating cost is low; The manufacturing material is durable in use, and regular maintenance is convenient; The by-product sulfur purity is high, and economic benefit is obvious; The recyclable utilization of byproduct steam realizes resource circulation economy, energy-saving and emission-reduction; Capital equipment in the technology---the direct catalyst oxidation reactor heat exchange efficiency of two-stage is high.
Claims (2)
1. a method that from the sour gas that contains hydrogen sulfide, reclaims sulphur is characterized in that, comprises the steps:
(a) air is supplied with: utilize air-blaster to introduce air preheater (1) to air from the external world, be preheating to 240 ℃ through said air preheater (1) and form preheated air;
(b) sour gas preliminary treatment: introduce sour gas separator (3) to sour gas; Isolate the drop that sour gas carries; The sour gas after separating that comes out from said sour gas separator (3) gets into sour gas preheater (4), is heated to 240 ℃ through middle pressure steam;
(c) mix: according to the ratio of the amount of substance of hydrogen sulfide and the amount of substance of oxygen is that 2: 1 ratio is calculated, and respectively the sour gas that is preheating to 240 ℃ in preheated air in the said air preheater (1) and the said sour gas preheater (4) is fed and fully mixes the back in the static mixer (5) and form process gas;
(d) the direct catalytic oxidation of one-level: will be passed into from the process gas of said static mixer (5) in the main reactor (6), said main reactor is filled with Ti-base catalyst in (6), the H in the process gas
2S and airborne O
2Carry out direct catalytic oxidation; Reaction generates elemental sulfur and water, and the pressure of regulating first steamdrum (7) that is connected with main reactor (6) makes said main reactor (6) Outlet Gas Temperature be not less than 290 ℃, avoids the exit condensation at said main reactor (6) of elemental sulfur; Stop up the mouth of pipe; The bottom of said main reactor (6) is provided with the coil pipe heat-obtaining, and the temperature of control reaction makes reaction more help the generation of sulphur;
(e) one-level sulphur condensation: the process gas entering one-level sulfur condenser (8) that comes out from said main reactor (6) carries out the product separation, separates the liquid sulfur that obtains and locks (14) entering molten sulfur pond (15) of struggling against through first molten sulfur;
(f) process gas heats again: the process gas of coming out from said one-level sulfur condenser (8) gets into reheater (9), and said reheater (9) is a gas-to-gas heat exchanger, will be heated to 240 ℃ from the process gas that said one-level sulfur condenser (8) comes out;
(g) the direct catalytic oxidation of secondary: the process gas after reheater (9) heating is sent into auxiliary reactor (11) and is carried out direct catalytic oxidation, and said auxiliary reactor is filled with Ti-base catalyst in (11), the H in the process gas
2S and airborne O
2Carry out direct catalytic oxidation; Reaction generates elemental sulfur and water; The pressure of regulating second steamdrum (12) that is connected with said auxiliary reactor (11) makes said auxiliary reactor (11) Outlet Gas Temperature be not less than 240 ℃; Avoid the exit condensation at said auxiliary reactor (11) of elemental sulfur, stop up the mouth of pipe;
(h) secondary sulphur condensation: the process gas entering secondary sulfur condenser (13) that comes out from said auxiliary reactor (11) carries out the product separation, separates the liquid sulfur that obtains and locks (16) entering molten sulfur pond (15) of struggling against through second molten sulfur;
(i) sulphur separates again: will send into from the process gas that said secondary sulfur condenser (13) comes out and carry out sulphur the sulphur separator (10) and separate, and separate the sulphur that obtains and get into molten sulfur pond (15) through the 3rd molten sulfur lock bucket (17);
(j) degassing in said molten sulfur pond (15): in said molten sulfur pond (15), blast air through the air bubbler, molten sulfur fully contacts the H that makes in the molten sulfur with air
2S is oxidized to sulphur, makes remaining H simultaneously
2S separates with molten sulfur, and makes the polysulfide in the molten sulfur resolve into H
2S and sulphur, waste gas is evacuated to incinerator (18) by steam jet ejector (19);
(k) tail gas calcination: the tail gas that said sulphur separator (10) and said molten sulfur pond (15) are discharged is introduced in the said incinerator (18) and to said incinerator (18) in, is imported air, under the situation of 700 ℃ and air excess, carries out calcination.
2. the method that from the sour gas that contains hydrogen sulfide, reclaims sulphur according to claim 1 is characterized in that said Ti-base catalyst comprises TiO
2, binding agent and co-catalyst, specific area is greater than 100m
2/ g, pore volume be more than or equal to 0.2mL/g, average crushing strength greater than 80 newton/, bulk density is 0.95～1.05kg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101416783A CN101791517B (en) | 2010-04-08 | 2010-04-08 | Method for recycling sulfur from acid gases containing hydrogen sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101416783A CN101791517B (en) | 2010-04-08 | 2010-04-08 | Method for recycling sulfur from acid gases containing hydrogen sulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101791517A CN101791517A (en) | 2010-08-04 |
| CN101791517B true CN101791517B (en) | 2012-05-23 |
Family
ID=42584562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101416783A Expired - Fee Related CN101791517B (en) | 2010-04-08 | 2010-04-08 | Method for recycling sulfur from acid gases containing hydrogen sulfide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101791517B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9370745B2 (en) | 2013-04-24 | 2016-06-21 | Jiangsu New Century Jiangnan Environmental Protection Co., Ltd | Flue gas-treating method and apparatus for treating acidic tail gas by using ammonia process |
| US10016721B1 (en) | 2017-05-25 | 2018-07-10 | Jiangnan Environmental Protection Group Inc. | Ammonia-based desufurization process and apparatus |
| US10092877B1 (en) | 2017-05-25 | 2018-10-09 | Jiangnan Environmental Protection Group Inc. | Dust removal and desulfurization of FCC exhaust gas |
| US10099170B1 (en) | 2017-06-14 | 2018-10-16 | Jiangnan Environmental Protection Group Inc. | Ammonia-adding system for ammonia-based desulfurization device |
| US10112145B1 (en) | 2017-09-07 | 2018-10-30 | Jiangnan Environmental Protection Group Inc. | Method for controlling aerosol production during absorption in ammonia desulfurization |
| US20190001267A1 (en) | 2017-07-03 | 2019-01-03 | Jiangnan Environmental Protection Group Inc. | Desulfurization absorption tower |
| US10207220B2 (en) | 2017-03-15 | 2019-02-19 | Jiangnan Environmental Protection Group Inc. | Method and apparatus for removing sulfur oxides from gas |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102556977B (en) * | 2010-12-30 | 2013-12-04 | 中国石油天然气股份有限公司 | Inner cooling type direct oxidation recycling method and recycling device of sulfur |
| CN103663386B (en) | 2012-09-19 | 2015-05-20 | 中国石油化工股份有限公司 | Method for reducing SO2 emission concentration of sulfur device |
| CN102849684A (en) * | 2012-09-24 | 2013-01-02 | 邵志辉 | Double-stage isothermal oxidization sulfur-producing device |
| RU2508247C1 (en) * | 2012-11-01 | 2014-02-27 | Андрей Владиславович Курочкин | Method of producing sulphur |
| RU2535041C2 (en) * | 2012-12-25 | 2014-12-10 | Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук | Gas flow desulfurisation procedure |
| CN103007748A (en) * | 2013-01-04 | 2013-04-03 | 济南承乾工程技术有限公司 | System for removing H2S in acid gas |
| CN105314606A (en) * | 2014-06-06 | 2016-02-10 | 中国石油化工股份有限公司 | Liquid sulfur degassing technology |
| CN104083987B (en) * | 2014-06-26 | 2016-08-24 | 安徽淮化股份有限公司 | A kind of NHD solution utilized in purifying ammonia device carries out the method and apparatus of desulfurization carbon process to process gas |
| ES2746552T3 (en) * | 2014-12-24 | 2020-03-06 | Axens | Removal of hydrogen sulfide and recovery of sulfur from a gas stream by direct catalytic oxidation and Claus reaction |
| US10195565B2 (en) | 2014-12-24 | 2019-02-05 | Prosernat | Removal of hydrogen sulfide and sulfur recovery from a gas stream by catalytic direct oxidation and claus reaction |
| CN104555941A (en) * | 2015-01-19 | 2015-04-29 | 西安长庆科技工程有限责任公司 | Natural gas purification plant acid gas sulfur recovery system and method |
| CN104998540B (en) * | 2015-07-09 | 2017-06-16 | 安徽淮化股份有限公司 | A kind of sulfur recovery unit in low pressure, low concentration sulfurous gas |
| CN105521687B (en) * | 2015-11-30 | 2018-08-07 | 华电重工股份有限公司 | A method of utilizing coal tar hydrogenating hydrogen sulfide gas by-product sulphur |
| RU2758897C2 (en) * | 2016-11-10 | 2021-11-02 | Общество с ограниченной ответственностью научно-исследовательский и проектный институт "ПЕГАЗ" | Sulfur production plant |
| CN106629625B (en) * | 2016-12-14 | 2019-04-05 | 山东迅达化工集团有限公司 | Handle the recovery technology of sulfur of low concentration sour gas |
| CN106635184B (en) * | 2016-12-14 | 2020-07-07 | 山东迅达化工集团有限公司 | Process for preparing CO gas |
| CN106698360B (en) * | 2016-12-14 | 2019-04-09 | 山东迅达化工集团有限公司 | The recovery technology of sulfur of low concentration sour gas |
| CN106698361B (en) * | 2016-12-14 | 2019-04-05 | 山东迅达化工集团有限公司 | The recovery technology of sulfur of sour gas |
| CN107376524B (en) * | 2017-06-27 | 2019-10-18 | 苏州克莱尔环保科技有限公司 | Oil plant acid waste gas processing system |
| CN107442159B (en) * | 2017-09-06 | 2020-07-21 | 淄博天净环保技术有限公司 | Catalyst for selectively oxidizing hydrogen sulfide into elemental sulfur, and preparation method and application thereof |
| CN110368816A (en) | 2018-04-13 | 2019-10-25 | 江苏新世纪江南环保股份有限公司 | A kind of method for oxidation and device of ammonia process of desulfurization solution |
| CN110605109B (en) * | 2018-06-14 | 2022-05-10 | 中国石油天然气股份有限公司 | Catalyst for waste gas treatment of liquid sulfur degassing process, preparation method and application process |
| CN110732227B (en) | 2018-07-20 | 2023-02-21 | 江南环保集团股份有限公司 | Method and device for treating acid gas |
| CN111957183A (en) | 2019-12-26 | 2020-11-20 | 江苏新世纪江南环保股份有限公司 | Improved ammonia desulphurization method for controlling aerosol generation in absorption process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103563A (en) * | 1986-04-16 | 1988-01-06 | Veg气体研究所公司 | From sulfurous gas, reclaim the method for sulphur |
| 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 |
| CN1105178A (en) * | 1993-03-16 | 1995-07-12 | 埃尔夫·阿奎坦生产公司 | Method for removing hydrogen sulphide from a gas and recovering in the form of sulphur |
| CN1473066A (en) * | 2000-09-07 | 2004-02-04 | Process and apparatus for recovering sulphur from gas stream containing hydrogen sulphide |
-
2010
- 2010-04-08 CN CN2010101416783A patent/CN101791517B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103563A (en) * | 1986-04-16 | 1988-01-06 | Veg气体研究所公司 | From sulfurous gas, reclaim the method for sulphur |
| CN1105178A (en) * | 1993-03-16 | 1995-07-12 | 埃尔夫·阿奎坦生产公司 | Method for removing hydrogen sulphide from a gas and recovering in the form of sulphur |
| 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 |
| CN1473066A (en) * | 2000-09-07 | 2004-02-04 | Process and apparatus for recovering sulphur from gas stream containing hydrogen sulphide |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9370745B2 (en) | 2013-04-24 | 2016-06-21 | Jiangsu New Century Jiangnan Environmental Protection Co., Ltd | Flue gas-treating method and apparatus for treating acidic tail gas by using ammonia process |
| US10207220B2 (en) | 2017-03-15 | 2019-02-19 | Jiangnan Environmental Protection Group Inc. | Method and apparatus for removing sulfur oxides from gas |
| US10016721B1 (en) | 2017-05-25 | 2018-07-10 | Jiangnan Environmental Protection Group Inc. | Ammonia-based desufurization process and apparatus |
| US10092877B1 (en) | 2017-05-25 | 2018-10-09 | Jiangnan Environmental Protection Group Inc. | Dust removal and desulfurization of FCC exhaust gas |
| US10213739B2 (en) | 2017-05-25 | 2019-02-26 | Jiangnan Environmental Protection Group Inc. | Dust removal and desulfurization of FCC exhaust gas |
| US10099170B1 (en) | 2017-06-14 | 2018-10-16 | Jiangnan Environmental Protection Group Inc. | Ammonia-adding system for ammonia-based desulfurization device |
| US10159929B1 (en) | 2017-06-14 | 2018-12-25 | Jiangnan Environmental Protection Group Inc. | Ammonia-adding system for ammonia-based desulfurization device |
| US20190001267A1 (en) | 2017-07-03 | 2019-01-03 | Jiangnan Environmental Protection Group Inc. | Desulfurization absorption tower |
| US10112145B1 (en) | 2017-09-07 | 2018-10-30 | Jiangnan Environmental Protection Group Inc. | Method for controlling aerosol production during absorption in ammonia desulfurization |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101791517A (en) | 2010-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101791517B (en) | Method for recycling sulfur from acid gases containing hydrogen sulfide | |
| CN113562692B (en) | Method for producing hydrogen by deep peak regulation coupling thermochemical sulfur-iodine open circuit circulation of coal-fired power plant | |
| CN100475313C (en) | Device for the recovery and diffluence of sulfur dioxide and the system and method thereof | |
| CN101519192B (en) | Low temperature Claus sulfur recovery process and device therefor | |
| CN103303872B (en) | System device and method for recycling sulfur dioxide from fume to prepare sulfur | |
| SA516380554B1 (en) | Gasification Based Multi Generation Apparatus | |
| CN102367169B (en) | Method for preparation of sulfuric acid and combined production of fine flour iron through calcination of coal-derived pyrite in presence of oxygen-rich air | |
| CN102531835B (en) | Method for synthesizing methanol through low-carbon technology | |
| CN101693164A (en) | Method for obtaining high-purity sulphur from Claus reactive tail-gases | |
| CN107777663B (en) | A kind of coupling process of lighter hydrocarbons hydrogen manufacturing and hydrogen from methyl alcohol | |
| CN106829875A (en) | A kind of handling process and equipment for carbon disulphide production Process Gas | |
| CN110155953A (en) | A kind of processing low-concentration acid gas carries out the device and technique of sulphur recovery | |
| CN108128757B (en) | A kind of technique of flue gas during smelting sulphur | |
| CN207016486U (en) | A kind of system that sulfuric acid is produced using sour gas | |
| CN102336396B (en) | Continuous heat transfer sulfur dioxide conversion process | |
| CN115959623A (en) | Open system and method for circularly producing hydrogen by using sulfur and iodine | |
| CN201722311U (en) | Device for synthesizing methanol by low-carbon technology | |
| CN101239705A (en) | Method for obtaining high-purity sulfur from gas containing hydrogen sulfide | |
| CN101641284B (en) | Method for producing sulphuric acid and installation for carrying out said method | |
| CN101565172B (en) | Method for recovering sulfur from byproduct of acid gas generated in production of rubber chemicals | |
| CN101792129B (en) | Application of II-stage reactor in sulfur recovery industry | |
| CN105727714B (en) | A kind of process and device for producing NaHS | |
| CN214319665U (en) | Claus tail gas treatment system | |
| CN108217606B (en) | Utilize the cross-flow moving bed device of carbon-based material reduction and desulfurization resolution gas Recovered sulphur | |
| CN216445007U (en) | High-temperature raw gas non-catalytic partial oxidation direct reforming system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for recycling sulfur from acid gases containing hydrogen sulfide Effective date of registration: 20140813 Granted publication date: 20120523 Pledgee: Haidian Beijing science and technology enterprise financing Company limited by guarantee Pledgor: Zhou Qi|Beijing Zhiqingshiguang Environmental Engineering Technology Co Ltd Registration number: 2014990000654 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20170913 Granted publication date: 20120523 Pledgee: Haidian Beijing science and technology enterprise financing Company limited by guarantee Pledgor: Zhou Qi|Beijing Cleartimes Environmental Protection Engineering-Tech Co.,Ltd. Registration number: 2014990000654 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120523 Termination date: 20180408 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |