CN104548906B - Purification method for hydrogen sulfide containing gas - Google Patents
Purification method for hydrogen sulfide containing gas Download PDFInfo
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- CN104548906B CN104548906B CN201310504220.3A CN201310504220A CN104548906B CN 104548906 B CN104548906 B CN 104548906B CN 201310504220 A CN201310504220 A CN 201310504220A CN 104548906 B CN104548906 B CN 104548906B
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Abstract
The invention relates to a purification method for a hydrogen sulfide containing gas. The purification method comprises the following steps: introducing hydrogen sulfide-containing gas into an absorption reactor, contacting and reacting with an absorbent, and then emitting the reacted up-to-standard gas; absorbing the reacted rich absorption liquid into a regenerative reactor, contacting a regenerant for regeneration reaction under the existence of an oxygen-containing gas, to obtain a regenerative absorption liquid and an elemental sulfur mixture, filtering and separating through a powdered sulfur filter, separating elemental sulfur and the regenerative absorption liquid, recycling the regenerative absorption liquid in the absorption reactor, collecting the elemental sulfur and feeding the elemental sulfur into a storage tank. According to the purification method for a hydrogen sulfide containing gas, normal-temperature recycling is carried out, the hidden safety hazards of technology equipment plugging, bed layer combustion, fog and froth entrainment of exhaust gas and the like can also be avoided, secondary pollutants generated during regeneration can be absorbed.
Description
Technical field
The present invention relates to field of environment protection, more particularly to a kind of hydrogen sulfide purification method, specifically oil plant
The method vulcanizing hydrogen purification in discharge waste gas.
Background technology
The tank decks such as the sour water storage tank of oil plant, all kinds of oil product intermediate storage tank volatilize substantial amounts of foul gass, tank deck
High concentration H is contained in gas2S、NH3, organic sulfur compound, oil gas, water vapour and air, in waste gas, the concentration of hydrogen sulfide is up to up to ten thousand
Every cubic metre of milligram.The discharge of tank deck gas produces odor pollution and the wasting of resources.Therefore, all kinds of tank fields are all attached great importance to both at home and abroad
The reduction of discharging of exhaust emission and improvement.
The administering method of hydrogen sulfide contamination thing mainly has ferrum oxide, zinc oxide and activated charcoal solid absorption method, alkanolamine solution
Absorption process, and the wet oxidation process such as Complexing Iron.In oil plant acid water tank field discharge gas, hydrogen sulfide is administered and is inhaled using alkali liquor
Receive administering method more.
Patent CN200910011761.6 and《Petrochemical industry environmental conservation》Magazine the 4th phases of volume 28 in 2005 all describe one
Plant the method that hydrogen sulfide contamination thing adopts alkali liquor absorption to purify.Hydrogen sulfide gas in waste gas are permissible after absorbing in alkali liquor
Reach the purpose of purification, but, after alkali liquor absorption, secondary pollution waste soda residue will be produced, this brings new environment to enterprise again
Administer pressure.
《The design of sulfur phosphorus and split engineering》6th phase in 2004 describes and purifies the discharge of sour water tank using solid absorbent
In hydrogen sulfide gas.The adsorbent that the method adopts is swage adsorbent, and hydrogen sulfide generates sulfuration with swage sorbent reactions
Ferrous product, it is inflammable, may cause the safety problems such as processing meanss combustion explosion.
Patent CN102451612A discloses a kind of method of removing hydrogen sulfide in gas by non-aqueous solvent, and hydrogen sulfide is through inhaling
Sulfur product can be obtained after receipts agent absorption, oxidation.Contain sulfur lytic agent in absorbent, the solution of dissolution of sulphur also need to into
One step crystallisation by cooling isolates sulfur, and the sulfur plug process equipment that the oxidation of the method energy effectively preventing produces and sulfur bubble
Problem, but this technological process is longer, equipment is more.
United States Patent (USP) 4091073, patent 4518576 and patent 4368178 disclose the work removing hydrogen sulfide in the gas flow
Skill, using the solution washing air-flow of metallo-chelate, reaches the purpose of removing hydrogen sulfide, is washed out liquid and aoxidizes in renewing zone
Regeneration chelate.British patent 999800 also discloses that a kind of high price and the polyvalent metal chelates of low price use cooperatively purification sulfur
The method changing hydrogen, hydrogen sulfide is contacted with the chelate of high price ferrum and is converted into elemental sulfur.The ferrum of high price is reduced at a low price simultaneously
Ferrum, in zoneofoxidation, the ferrum of low price will be oxidized to the ferrum of high price, and in this process, the chelate of ferrum will produce insoluble
Iron compound precipitates, and this will block corresponding process equipment.
Existing hydrogen sulfide contamination thing administering method is primarily present secondary pollution problem, technological process complexity, technique
The problems such as equipment blocks.
Content of the invention
It is an object of the invention to provide a kind of purification method of H 2 S-containing gas, H 2 S-containing gas of the present invention
Wet treatment and dry process reasonable combination are got up by administering method, and the method technological process is simple, safe and reliable.
The invention provides a kind of purification method of H 2 S-containing gas, comprise the following steps：
（1）Hydrogen sulfide containing gas enters absorbing reaction device, contacts with absorbent and is reacted, gas row up to standard after reaction
Put；
（2）Step（1）Rich absorbing liquid after absorbing reaction enters regeneration reactor, in the presence of oxygen-containing gas, rich absorption
Liquid is contacted with regenerative agent and carries out regenerative response, obtains absorbing liquid and the elemental sulfur mixture regenerating；
（3）Step（2）The absorbing liquid of middle regeneration and elemental sulfur mixture, after sulphur powder filter filtration separation, elemental sulfur
Realize separating with the absorbing liquid of regeneration, the absorbing liquid of regeneration enters absorbing reaction device and recycles, and elemental sulfur enters after collecting
Storage tank；
Wherein, step（1）Described in absorbent be ethanolamine, diethanolamine, triethanolamine, diisopropanolamine (DIPA), methyl second
Any one in hydramine；Step（2）Described in regenerative agent be iron content, containing zinc oxyhydroxide, be specifically as follows hydroxyl oxidize
Ferrum, zinc oxyhydroxide, preferably FeOOH.
In the inventive method, step（1）Described in absorbent be methyl ethanol amine aqueous solution, solution concentration be 5～25wt%,
Preferably 10～20wt%.
In the inventive method, step（1）Middle absorbent can be adverse current with the flow direction of hydrogen sulfide containing gas, also may be used
To be cocurrent.
In the inventive method, in regeneration reactor, rich absorbing liquid and the flow direction of oxygen-containing gas are reverse flow, rich suction
Receive liquid to flow from top to bottom, the speed of liquid flowing produces the expansion of sulphur powder foam during at least can stoping regenerative response,
The flowing velocity of liquid is 0.5～2.5m/s, preferably 1.5～2.0m/s.
In the inventive method, regenerative agent is honeycomb texture, and the aperture of honeycomb is 5～15mm, preferably 8～12mm.Regeneration is anti-
Answer the regenerative agent in device to load the number of plies and be 2～7 layers, preferably 3～5 layers.
In the inventive method, the operating condition of absorbing reaction device and regeneration reactor is room temperature, atmospheric operation.
In the inventive method, described oxygen-containing gas is air.
In the inventive method, described absorbing reaction device and regeneration reactor can be equipment integrating or split equipment.Inhale
When receiving reactor and regeneration reactor and being integrated equipment, absorbing reaction section upper, regeneration reaction section under, equipment integrating is vertical
Tower structure.When absorbing reaction device and regeneration reactor are split equipment, the upper end of two reactors needs to connect, and communicating pipe is as suction
Receive liquid and gas from circulation road, absorbing liquid and gas are flowed in regeneration reactor by absorbing reaction device.
In the inventive method, absorbing reaction device can be spray-absorption, packing material absorbing, bubble absorption structure, regenerative response
Device is suspended-bed reactor.
In hydrogen sulfide contamination thing purifier of the present invention, described sulphur powder filter is vertical filter, and filtering accuracy is 1
More than millimeter, sulphur powder filter arranges two and two or more, carries out filter handover operation when using.
Compared with prior art, H 2 S-containing gas purification method of the present invention has the following advantages：
1st, in hydrogen sulfide contamination thing purification method of the present invention, hydrogen sulfide is absorbed using Amine Solutions, and absorbent is adopted
With metal oxyhydroxides as regenerative agent.Absorbent is repeatable after regeneration to be utilized.Absorb-add with existing organic amine room temperature
Hot recycling technique is compared, and the inventive method is normal-temperature regeneration, and energy conservation and consumption reduction effects are obvious.
2nd, in hydrogen sulfide contamination thing purification method of the present invention, the regenerative agent of absorbing liquid adopts suspension bed form.With hydroxyl oxygen
Compound desulfurizer slurry doctor treatment is compared, and the inventive method arranges sulphur powder filter in absorbing liquid pump entry, can avoid
The problems such as process equipment blocks.The inventive method, compared with fixed bed desulfurizing agent doctor treatment, can avoid the safety such as bed burning hidden
Suffer from, during absorption and regeneration, do not produce secondary pollution problem simultaneously.
3rd, in hydrogen sulfide contamination thing purification method of the present invention, absorbing liquid liquid regeneration air adverse current in regeneration reactor flows
Dynamic, absorbing liquid circulates between absorbing reaction device and regeneration reactor, and rational circulation flow rate can avoid regenerating
During produce sulphur powder foam it is therefore prevented that there is entrainment in discharge gas.
4th, hydrogen sulfide contamination thing purification method of the present invention and device have that safe and reliable, equipment is simple, investment is low, etc. spy
Point.
Brief description
Fig. 1 is the purification method schematic flow sheet of H 2 S-containing gas of the present invention.
Fig. 2 be H 2 S-containing gas of the present invention purification method in suspension bed regenerative agent structural representation.
Fig. 3 is the purification method second schematic flow sheet of H 2 S-containing gas of the present invention.
Specific embodiment
To further illustrate the concrete condition of the present invention below by specific embodiment, but to be not limited to following embodiments.
Hydrogen sulfide containing gas enters absorbing reaction device through exhaust piping 1 from absorbing reaction device 2 bottom, connects with absorbent 8
Reacted after touch, gas 4 qualified discharge after reaction, rich absorbing liquid enters in regeneration reactor 3, air passes through pipeline 9 through drum
Blower fan 10 enters regeneration reactor bottom, and rich absorbing liquid is contacted with regenerative agent 12 is reacted, and obtains the absorption regenerating after reaction
Liquid and the mixture of elemental sulfur, after filter 6 filtration, the absorbing liquid of regeneration passes through filter to mixture, through absorbent circulation
Pump 7 enters absorbing reaction device and recycles as absorbent, and the sulfur not over filter discharges entrance after collection through pipeline 11
Storage tank.
Embodiment 1
The present embodiment adopts technological process shown in Fig. 3, and in waste gas, hydrogen sulfide content is 8000 ~ 10000mg/m3, tolerance is
500m3/ h, EGT is room temperature, and pressure is pressure-fired, and absorbing reaction device 2 adopts bubble absorption structure, bubbling bed height
2.5m, absorbent is MDEA solution.Regeneration reactor 3 is suspended-bed reactor, and suspension bed height is 3m, and regenerative agent adopts hydroxyl
Base ferrum oxide, is honeycomb texture, and the aperture of honeycomb is 8mm.In regeneration reactor, regenerative agent adopts 3 layers of filling.Regeneration reactor
In 3, the flow direction of liquid and regeneration air is reverse flow, liquid to flows, the flowing velocity of liquid be
1.5m/s.Sulphur powder filter arranges three, handover operation.Waste gas hydrogen sulfide content in the venting of absorption cleaning heel row is less than
100ppm.
Embodiment 2
The present embodiment adopts technological process shown in Fig. 1, and in waste gas, hydrogen sulfide content is 7000 ~ 8000mg/m3, tolerance is
300m3/ h, EGT is room temperature, and pressure is pressure-fired, and absorber portion 2 adopts packing material absorbing structure, using φ 25mm rectangular saddle ring
Filler, packed height 4m, absorbent is MDEA solution.Regenerator section is suspended-bed reactor, and suspension bed height is 3m, and regeneration is anti-
Answer the FeOOH that the desulfurization regeneration agent in section 3 is honeycomb texture, the aperture of honeycomb is 10mm, and regenerative agent adopts 3 layers of filling.
In regeneration reactor 3, the flow direction of liquid and regeneration air is reverse flow, liquid to flows, the flowing of liquid
Speed is 1.5m/s.Sulphur powder filter arranges three, handover operation.Waste gas hydrogen sulfide content in the venting of absorption cleaning heel row
Less than 100ppm.
Claims (11)
1. a kind of purification method of H 2 S-containing gas is it is characterised in that comprise the following steps：
（1）Hydrogen sulfide containing gas enters absorbing reaction device, contacts with absorbent and is reacted, gas qualified discharge after reaction；
（2）Step（1）Rich absorbing liquid after absorbing reaction enters regeneration reactor, in the presence of oxygen-containing gas, rich absorbing liquid with
Regenerative agent contact carries out regenerative response, obtains absorbing liquid and the elemental sulfur mixture regenerating；
（3）Step（2）The absorbing liquid of middle regeneration and elemental sulfur mixture, after sulphur powder filter filtration separation, elemental sulfur and again
Raw absorbing liquid is realized separating, and the absorbing liquid of regeneration enters absorbing reaction device and recycles, and elemental sulfur enters storage tank after collecting；
Wherein, step（1）Described in absorbent be ethanolamine, diethanolamine, triethanolamine, diisopropanolamine (DIPA), methylethanolamine
In any one；Step（2）Described in regenerative agent be FeOOH or zinc oxyhydroxide, described regenerative agent be honeycomb texture,
The aperture of honeycomb is 5～15mm.
2. in accordance with the method for claim 1 it is characterised in that：Step（1）Described in absorbent be methyl ethanol amine aqueous solution,
Solution concentration is 5～25wt%.
3. in accordance with the method for claim 1 it is characterised in that：The flowing of rich absorbing liquid and oxygen-containing gas in regeneration reactor
Direction is reverse flow, and rich absorbing liquid flows from top to bottom, and rich absorbing liquid flowing velocity at least can stop regenerative response process
The expansion of the sulphur powder foam of middle generation.
4. according to the method described in claim 1 or 3 it is characterised in that：In regeneration reactor, the flowing velocity of rich absorbing liquid is
0.5～2.5m/s.
5. in accordance with the method for claim 1 it is characterised in that：The regenerative agent filling number of plies in regeneration reactor is 2～7
Layer.
6. in accordance with the method for claim 1 it is characterised in that：The regenerative agent filling number of plies in regeneration reactor is 3～5
Layer.
7. in accordance with the method for claim 1 it is characterised in that：Described oxygen-containing gas is air.
8. in accordance with the method for claim 1 it is characterised in that：Described absorbing reaction device and regeneration reactor are integrated and set
Standby or split equipment.
9. in accordance with the method for claim 8 it is characterised in that：When absorbing reaction device and regeneration reactor are integrated equipment,
Absorbing reaction section upper, regeneration reaction section under, equipment integrating is vertical tower structure.
10. in accordance with the method for claim 8 it is characterised in that：When absorbing reaction device and regeneration reactor are split equipment,
The upper end of two reactors needs to connect, and communicating pipe, absorbing liquid and gas were anti-by absorbing as absorbing liquid and gas from circulation road
Device is answered to flow in regeneration reactor.
11. in accordance with the method for claim 1 it is characterised in that：Regeneration reactor is suspended-bed reactor.
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| CN106047424B (en) * | 2016-06-30 | 2021-12-10 | 华东理工大学 | Coke oven gas hydrogen sulfide gas recovery method and device |
| CN108970380B (en) * | 2018-09-07 | 2023-07-21 | 宜宾丝丽雅股份有限公司 | Method and device for removing hydrogen sulfide in waste gas by continuous oxidation |
| CN113893677B (en) * | 2021-09-29 | 2022-10-18 | 河南嘉颖生物科技有限公司 | Method and device for refining and purifying ethyl chloride byproduct hydrochloric acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101766946A (en) * | 2008-12-30 | 2010-07-07 | 北京三聚环保新材料股份有限公司 | Technology for removing hydrogen sulfide in gas at room temperature |
| CN102451612A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工集团公司 | Method for removing hydrogen sulfide in gas by non-aqueous solvent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101766946A (en) * | 2008-12-30 | 2010-07-07 | 北京三聚环保新材料股份有限公司 | Technology for removing hydrogen sulfide in gas at room temperature |
| CN102451612A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工集团公司 | Method for removing hydrogen sulfide in gas by non-aqueous solvent |
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