CN105692563B - SWSR-7 sulfur recovery technologies and device - Google Patents
SWSR-7 sulfur recovery technologies and device Download PDFInfo
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- CN105692563B CN105692563B CN201610052763.XA CN201610052763A CN105692563B CN 105692563 B CN105692563 B CN 105692563B CN 201610052763 A CN201610052763 A CN 201610052763A CN 105692563 B CN105692563 B CN 105692563B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
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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
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Abstract
The invention belongs to sulphur recovery and tail gas disposal technique fields, and in particular to a kind of SWSR-7 sulfur recovery technologies and device.The technique includes the following steps：1. sulfide hydrogen sour gas generates sulphur and sulphur tail gas processed through burner for producing sulfur, claus reaction system, wherein sulphur recovery is sent into molten sulfur storage facility；2. after sulphur tail gas processed is with or without tail gas hydrogenation reduction or oxidative system, feeding tail gas incineration system being mixed with air and is burned, all sulfur-containing mediums are converted into SO2, formed and contain SO2Flue gas, then recovered thermal energy enter column for smoke purification；3. containing SO2Flue gas contacts in column for smoke purification with absorbent hydrogen peroxide, the SO in flue gas2It is absorbed by absorbent, cyclic absorption agent enters bottom of tower, removes SO2Purifying smoke afterwards is sent into smoke stack emission；4. absorbent prepares and transport system.The technical process is safe and reliable, discharges SO in gas2Content can be reduced to 50mg/Nm3Hereinafter, meeting the requirement of national regulation.
Description
Technical field
The invention belongs to sulphur recovery and tail gas disposal technique fields, and in particular to a kind of SWSR-7 sulfur recovery technologies and dress
It sets.
Background technology
China advocates always energy-saving and emission-reduction work, stringent to control sulfur dioxide in air discharge capacity, before 2012, country's mark
Sulfur dioxide emissioning concentration as defined in standard is not higher than 960mg/Nm3.It is dirty to ferment revision air for national departments concerned at present
Contaminate object comprehensive discharge standard, it is desirable that newly-built sulphur unit sulfur dioxide emissioning concentration is less than 400mg/Nm3(given area discharge is dense
Degree is less than 100mg/Nm3).Sinopec actively implements green low-carbon development strategy, reduction sulphur unit SO 2 from fume
Concentration of emission strives for world-class one of important indicator as oil refining plate, it is desirable that sulfur dioxide emissioning concentration reaches within 2015
Advanced international standard (200mg/Nm3), Some Enterprises reach world lead level (100mg/Nm3)。
Gram that domestic sulphur recovery and tail gas treatment process technology are reacted using high temperature thermal response and two-stage catalysis at present
Louth (Claus) sulfur recovery technology contains a small amount of H in sulphur tail gas processed2S、SO2、COS、SxEtc. harmful substances, directly burn after
The environmental requirement of national regulation is not achieved in discharge.Sulfur recovery tail gas processing method mainly has low temperature Claus process, selective oxidation
Method, reducing absorping method.Hydrogenating reduction absorption technique is by the element S in sulfur recovery tail gas, SO2, COS and CS etc., in very little
Under hydrogen partial pressure and extremely low operating pressure (about 0.01MPa~0.06MPa), with special vent gas treatment Special hydrogenation catalyst,
Restored or be hydrolyzed to H2S, then absorbed with alkanolamine solution, the alkanolamine solution after regeneration recycles.Absorb H2The rich solution of S
Through regeneration treatment, it is rich in H2S gases return to upstream units, through absorbing the total sulfur < 300ppm in treated purified gas.The work
Skill long flow path need to use hydrogen addition technology, and equipment safety control is more demanding, and sulfur recovery effect can not meet environmental requirement into one
Walk the needs improved.
Invention content
To solve the above-mentioned problems in the prior art, the present invention provides a kind of SWSR-7 (SWSR-SunWay
Sulfur recovery) sulfur recovery technology and device, the technique is claus process plus hydrogen or oxidation technology and peroxidating
Hydrogen desulfurization technical optimization combines the sulphur recovery to be formed and vent gas treatment new process, with reduce equipment investment, shorten technological process,
Energy consumption is reduced, is saved and is taken up an area, improves material safety, and the content of sulfur dioxide after processing in flue gas is made to be reduced to 50mg/Nm3
Below.
The purpose of the present invention can be reached by following measure：
A kind of SWSR-7 sulfur recovery technologies comprising following steps：
1. sulfide hydrogen sour gas generates sulphur and sulphur tail gas processed, wherein sulphur through burner for producing sulfur, claus reaction system
Molten sulfur storage facility is sent into sulphur recycling；
2. after sulphur tail gas processed is with or without tail gas hydrogenation reduction or oxidative system, being mixed with air and being sent into tail gas burning
System is burned, and all sulfur-containing mediums are converted into SO2, formed and contain SO2Flue gas, then recovered thermal energy enter gas cleaning
Tower；
3. containing SO2Flue gas contacts in column for smoke purification with absorbent hydrogen peroxide, the SO in flue gas2It is absorbed by absorbent,
Cyclic absorption agent enters bottom of tower, removes SO2Purifying smoke afterwards is sent into smoke stack emission；
4. absorbent prepares and transport system：
A) water is supplemented：The regulating valve on condensate make-up piping is controlled by liquid level gauge, keeps the liquid level of absorption tower bottoming cycle liquid,
With the liquid evaporated during Balance Absorption and drain is lost；
B) hydrogen peroxide supplements：Bottom of tower recycles and analyzer is housed on pump conduit, and chimney is equipped with SO2Analyzer, by dividing
Analyse the concentration and SO of diluted acid in tower2Discharge value, the amount of hydrogen peroxide into column for smoke purification is adjusted with metering pump, to keep de-
The concentration of dilute sulfuric acid in sulphur tower, meets the requirement of sulfur dioxide absorption；
C) absorbent recycles：Cyclic absorption agent is stored in purification tower bottom, and purifying column urgency is sent to respectively by bottom of tower circulating pump
Absorption nozzle in the middle part of cold-zone cooling nozzles and purifying column；
D) absorption tower drain：Relief liquor is pumped into diluted acid tank by bottom of tower cycle, is periodically discharged, with control loop absorbing liquid
The content of middle diluted acid ensures the efficiency of desulfurization.
Wherein, using the strong oxidizing property of hydrogen peroxide by SO2Be oxidized to sulfuric acid, by the concentration of diluted acid in the solution of bottom of tower and
The discharge capacity of chimney sulfur dioxide controls the addition of hydrogen peroxide.Water-gas ratio needed for sulfur dioxide absorption and nozzle quantity
Selection be to determine according to the temperature of the entrance concentration of sulfur dioxide, the demand of discharge and saturated gas.
Its chemical equation is：
The first step, gas-liquid mass transfer and hydro-combination process are dissolved in water, and and water when SO2 molecules are contacted with water that is, in flue gas
Molecule is combined into sulfurous acid：
SO2+H2O→H2SO3
Second step, oxidative absorption：
H2SO3+H2O2→H2SO4+H2O
Net reaction is：
H2O2+SO2→H2SO4
When during sulphur processed without tail gas hydrogenation or oxidation reaction, sulfur recovery rate is 95%~98%；And pass through tail
After gas hydrogenating reduction or oxidative system, sulfur recovery rate can reduce tail gas and burn and fume desulfurizing tower up to 99%~99.7%
Load reduces the consumption of device fuel gas and chemicals.
Oxygen-excess combustion technique is used in the tail gas incineration system.
Step 3. in industrial hydrogen peroxide is diluted with water 0.1-5wt.% by being pumped in dilution trap, then added by metering pump
Force feed is toward purifying column bottom of tower.
Step 3. in contain SO2Flue gas enters horizontally into the chilling area of purifying column, and hydrogen peroxide circulation fluid is sprayed by nozzle
The high density cascade vertical with flue gas approach axis is formed, the two comes into full contact with, substantially reduces flue-gas temperature and be allowed to be saturated to
50~80 DEG C；Then, flue gas rises to uptake zone, and 4 layers of nozzle is arranged in uptake zone, and circulating cleaning solution is pumped into nozzle by cycle
It is sprayed, spray liquid and flue gas are sufficiently mixed, and the sulfur dioxide and other sour gas in flue gas are by oxidative absorption；Most
Afterwards, flue gas ascends into gas-liquid separation zone, and separation water falls into tower reactor from gas-liquid separation zone bottom, and dewatered purifying smoke is through upper
Portion's chimney is discharged into air.
The operation temperature of the column for smoke purification is 40~80 DEG C.
Gained retrieval of sulfuric acid in step d) is utilized or is back to burner for producing sulfur heat resolve.
A kind of SWSR-7 sulfur recovery units for realizing the technique comprising sequentially connected burner for producing sulfur, Crouse
Reaction system, tail gas incineration system, column for smoke purification, absorbent prepares and transport system, wherein can be in claus reaction system
Tail gas hydrogenation reduction or oxidative system are connected between tail gas incineration system.
Column for smoke purification includes mainly flue gas chilling area, uptake zone, gas-liquid separator and chimney.
Compared with prior art, the present invention has the following advantages：
(1) Crouse's recovery technology of sulfur, sulphur Process Gas processed are added into oxidation process and hydrogen peroxide flue gas desulfurization for the first time
Technology is combined, and use is during sulphur recovery and vent gas treatment, while improving device sulfur recovery rate as far as possible,
Content of sulfur dioxide in discharge gas is set to be preferably minimized, the effect reached is far superior to the effect that can be played when the two respectively works
Fruit.
(2) equipment investment is low, and material is safe, and technological process is short, and low energy consumption, takes up an area and saves, and technical process is safe and reliable,
There is no dangerous larger techniques and equipment.
(3) desulfurizing agent is hydrogen peroxide, and China's abundance, price is relatively low, and operating cost is low.
(4) sulphur process output processed meets the sulfur product in GB/T2449 more than Grade A, and device desulfuration efficiency is high, ensures
Sulfur recovery facility discharges SO in gas2Concentration < 50mg/Nm3, meet the requirement of national regulation.
(5) steam, fuel gas consumption are saved, operating cost is low, and load performance is strong, can meet sulfur recovery facility not
With the lasting safe operation under operating mode, can be opened in device, the downtime ensures flue gas qualified discharge.
(6) diluted acid that flue gas desulfurization generates is recycled or is back to burner for producing sulfur heat resolve, and device is except de-
Outside cleaning of off-gas and dead catalyst after sulphur, no extra waste residue, waste water, exhaust gas generate, and do not generate secondary pollution.
Description of the drawings
Fig. 1 is SWSR-7 sulfur recovery technologies flow diagram of the present invention.
Specific implementation mode
The present invention will be further described with reference to the accompanying drawings and embodiments.
Embodiment 1
A kind of SWSR-7 sulfur recovery technologies comprising following steps：
1. sulfide hydrogen sour gas generates sulphur and sulphur tail gas processed, wherein sulphur through burner for producing sulfur, claus reaction system
Molten sulfur storage facility is sent into sulphur recycling；
2. sulphur tail gas processed mixes feeding tail gas incineration system with air and burned, all sulfur-containing mediums are converted into SO2,
It is formed and contains SO2The content of flue gas, 180 DEG C of flue-gas temperature, sulfur dioxide is about 12000mg/Nm3, then recovered thermal energy enter cigarette
Gas purifying column；
3. containing SO2Flue gas contacts in column for smoke purification with absorbent 3wt.% hydrogenperoxide steam generators, the SO in flue gas2Quilt
Absorbent absorbs, and cyclic absorption agent enters bottom of tower, removes SO2Purifying smoke afterwards is sent into smoke stack emission；
4. absorbent prepares and transport system：
A) water is supplemented：The regulating valve on condensate make-up piping is controlled by liquid level gauge, keeps the liquid level of absorption tower bottoming cycle liquid；
B) hydrogen peroxide supplements：Bottom of tower recycles and analyzer is housed on pump conduit, and chimney is equipped with SO2Analyzer, by dividing
Analyse the concentration and SO of diluted acid in tower2Discharge value, with metering pump adjust into column for smoke purification amount of hydrogen peroxide；
C) absorbent recycles：Cyclic absorption agent is stored in purification tower bottom, and purifying column urgency is sent to respectively by bottom of tower circulating pump
Absorption nozzle in the middle part of cold-zone cooling nozzles and purifying column；
D) absorption tower drain：Relief liquor is pumped into diluted acid tank by bottom of tower cycle, is periodically discharged.
The content of sulfur dioxide is 41mg/Nm in detection discharge gas3。
A kind of SWSR-7 sulfur recovery units for realizing the method comprising sequentially connected burner for producing sulfur, Crouse
Reaction system, tail gas incineration system, column for smoke purification, absorbent prepares and transport system, wherein can be in claus reaction system
Tail gas hydrogenation or oxidative system are connected between tail gas incineration system.Column for smoke purification mainly include flue gas chilling area, uptake zone,
Gas-liquid separator and chimney.
Embodiment 2
A kind of SWSR-7 sulfur recovery technologies comprising following steps：
1. sulfide hydrogen sour gas generates sulphur and sulphur tail gas processed, wherein sulphur through burner for producing sulfur, claus reaction system
Molten sulfur storage facility is sent into sulphur recycling；
2. sulphur tail gas processed after tail gas hydrogenation also original system, mixes feeding tail gas incineration system with air and is burned,
All sulfur-containing mediums are converted into SO2, formed and contain SO2The content of flue gas, 270 DEG C of flue-gas temperature, sulfur dioxide is 600mg/Nm3,
Then recovered thermal energy enters column for smoke purification；
3. containing SO2Flue gas contacts in column for smoke purification with absorbent 2.5wt.% hydrogenperoxide steam generators, the SO in flue gas2
It is absorbed by absorbent, cyclic absorption agent enters bottom of tower, removes SO2Purifying smoke afterwards is sent into smoke stack emission；
4. absorbent prepares and transport system：
A) water is supplemented：The regulating valve on condensate make-up piping is controlled by liquid level gauge, keeps the liquid level of absorption tower bottoming cycle liquid；
B) hydrogen peroxide supplements：Bottom of tower recycles and analyzer is housed on pump conduit, and chimney is equipped with SO2Analyzer, by dividing
Analyse the concentration and SO of diluted acid in tower2Discharge value, with metering pump adjust into column for smoke purification amount of hydrogen peroxide；
C) absorbent recycles：Cyclic absorption agent is stored in purification tower bottom, and purifying column urgency is sent to respectively by bottom of tower circulating pump
Absorption nozzle in the middle part of cold-zone cooling nozzles and purifying column；
D) absorption tower drain：Relief liquor is pumped into diluted acid tank by bottom of tower cycle, is periodically discharged.
The content of sulfur dioxide is 32mg/Nm in detection discharge gas3。
Used device is same as Example 1, and so it will not be repeated.
Embodiment 3
A kind of SWSR-7 sulfur recovery technologies comprising following steps：
1. sulfide hydrogen sour gas generates sulphur and sulphur tail gas processed, wherein sulphur through burner for producing sulfur, claus reaction system
Molten sulfur storage facility is sent into sulphur recycling；
2. sulphur tail gas processed after oxidative system, mixes feeding tail gas incineration system with air and is burned, all sulfur-bearings
Medium is converted into SO2, formed and contain SO2The content of flue gas, 270 DEG C of flue-gas temperature, sulfur dioxide is 410mg/Nm3, then pass through back
It receives thermal energy and enters column for smoke purification；
3. containing SO2Flue gas contacts in column for smoke purification with absorbent 2.5wt.% hydrogenperoxide steam generators, the SO in flue gas2
It is absorbed by absorbent, cyclic absorption agent enters bottom of tower, removes SO2Purifying smoke afterwards is sent into smoke stack emission；
4. absorbent prepares and transport system：
A) water is supplemented：The regulating valve on condensate make-up piping is controlled by liquid level gauge, keeps the liquid level of absorption tower bottoming cycle liquid；
B) hydrogen peroxide supplements：Bottom of tower recycles and analyzer is housed on pump conduit, and chimney is equipped with SO2Analyzer, by dividing
Analyse the concentration and SO of diluted acid in tower2Discharge value, with metering pump adjust into column for smoke purification amount of hydrogen peroxide；
C) absorbent recycles：Cyclic absorption agent is stored in purification tower bottom, and purifying column urgency is sent to respectively by bottom of tower circulating pump
Absorption nozzle in the middle part of cold-zone cooling nozzles and purifying column；
D) absorption tower drain：Relief liquor is pumped into diluted acid tank by bottom of tower cycle, is periodically discharged.
The content of sulfur dioxide is 27mg/Nm in detection discharge gas3。
Used device is same as Example 1, and so it will not be repeated.
Claims (6)
1. a kind of SWSR-7 sulfur recovery technologies, which is characterized in that include the following steps：
1. sulfide hydrogen sour gas generates sulphur and sulphur tail gas processed through burner for producing sulfur, claus reaction system, wherein sulphur returns
Sending and receiving enter molten sulfur storage facility；
After 2. sulphur tail gas processed is with or without tail gas hydrogenation reduction or oxidative system, is mixed with air and be sent into tail gas incineration system
It is burned, all sulfur-containing mediums are converted into SO2, formed and contain SO2Flue gas, then recovered thermal energy enter column for smoke purification；
3. containing SO2Flue gas contacts in column for smoke purification with absorbent hydrogen peroxide, the SO in flue gas2It is absorbed, recycles by absorbent
Absorbent enters bottom of tower, removes SO2Purifying smoke afterwards is sent into smoke stack emission；
Step 3. in contain SO2Flue gas enters horizontally into the chilling area of purifying column, hydrogen peroxide circulation fluid sprayed by nozzle formed with
The vertical high density cascade of flue gas approach axis, the two come into full contact with；Then, flue gas rises to uptake zone, uptake zone setting spray
4 layers of mouth, circulating cleaning solution are pumped into nozzle by cycle and are sprayed, and spray liquid and flue gas are sufficiently mixed, the dioxy in flue gas
Change sulphur and other sour gas by oxidative absorption；Finally, flue gas ascends into gas-liquid separation zone, detaches water from gas-liquid separation zone
Bottom falls into tower reactor, and dewatered purifying smoke is discharged into air through top chimney；
4. absorbent prepares and transport system：
A) water is supplemented：The regulating valve on condensate make-up piping is controlled by liquid level gauge, keeps the liquid level of absorption tower bottoming cycle liquid；
B) hydrogen peroxide supplements：Bottom of tower recycles and analyzer is housed on pump conduit, and chimney is equipped with SO2Analyzer, by analyzing in tower
The concentration and SO of diluted acid2Discharge value, with metering pump adjust into column for smoke purification amount of hydrogen peroxide；
C) absorbent recycles：Cyclic absorption agent is stored in purification tower bottom, and purifying column chilling area is sent to respectively by bottom of tower circulating pump
Absorption nozzle in the middle part of cooling nozzles and purifying column；
D) absorption tower drain：Relief liquor is pumped into diluted acid tank by bottom of tower cycle, and periodically discharge gained retrieval of sulfuric acid is utilized or returned
It is back to burner for producing sulfur heat resolve.
2. SWSR-7 sulfur recovery technologies according to claim 1, which is characterized in that used in the tail gas incineration system
Oxygen burning process.
3. SWSR-7 sulfur recovery technologies according to claim 1, which is characterized in that step 3. in by industrial hydrogen peroxide by pumping
It send to being diluted with water 0.1-5wt.% in dilution trap, then purifying column bottom of tower is sent to by metering pump pressurization.
4. SWSR-7 sulfur recovery technologies according to claim 1, which is characterized in that the operation temperature of the column for smoke purification
It is 40~80 DEG C.
5. a kind of SWSR-7 sulfur recovery units for realizing technique described in claim 1-4 any one, which is characterized in that including according to
The burner for producing sulfur of secondary connection, claus reaction system, tail gas incineration system, column for smoke purification, absorbent prepares and delivery system
System, wherein tail gas hydrogenation reduction or oxidative system are connected between claus reaction system and tail gas incineration system.
6. SWSR-7 sulfur recovery units according to claim 5, which is characterized in that column for smoke purification includes mainly that flue gas is anxious
Cold-zone, uptake zone, gas-liquid separator and chimney.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107585744A (en) * | 2017-10-04 | 2018-01-16 | 山东胜星化工有限公司 | A kind of sulfuric acid concentration adjusting means |
| CN107890763A (en) * | 2017-11-30 | 2018-04-10 | 成武县晨晖环保科技有限公司 | A kind of chlorinated exhaust absorption process for producing trichloro-acetic chloride |
| CN107899403A (en) * | 2017-11-30 | 2018-04-13 | 成武县晨晖环保科技有限公司 | Chloroethene acylating acid method produces the tail gas sulphur dioxide sulfur method of chloracetyl chloride |
| CN110182764B (en) * | 2019-05-13 | 2021-03-23 | 中国神华煤制油化工有限公司 | Sulfur recovery device and sulfur recovery method |
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| CN104961103A (en) * | 2015-07-10 | 2015-10-07 | 山东三维石化工程股份有限公司 | Sulfur recovery process and apparatus |
| CN105016309A (en) * | 2015-07-09 | 2015-11-04 | 山东三维石化工程股份有限公司 | SWSR-2 sulfur recovery device and process |
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| CN102078760A (en) * | 2010-12-05 | 2011-06-01 | 姜玉贵 | Method for desulfurizing and denitrifying flue gas |
| CN103303872A (en) * | 2013-07-04 | 2013-09-18 | 陕西智惠环保科技有限公司 | System device and method for recycling sulfur dioxide from fume to prepare sulfur |
| CN103482583A (en) * | 2013-09-10 | 2014-01-01 | 山东三维石化工程股份有限公司青岛分公司 | SWSR (SunWay Sulfur recovery)-1 device and technique |
| CN104555940A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Sulfur recovery process for reducing SO2 emission |
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