CN107128882A - A kind of H2S claus reaction combinations low-temp methanol washs the sulfur recovery technology of tail gas - Google Patents

A kind of H2S claus reaction combinations low-temp methanol washs the sulfur recovery technology of tail gas Download PDF

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Publication number
CN107128882A
CN107128882A CN201710228462.2A CN201710228462A CN107128882A CN 107128882 A CN107128882 A CN 107128882A CN 201710228462 A CN201710228462 A CN 201710228462A CN 107128882 A CN107128882 A CN 107128882A
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methanol
gas
tail gas
gases
claus
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余涛
贺鑫平
周丹黎
于清
郭平利
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Hualu Engineering and Technology Co Ltd
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Hualu Engineering and Technology Co Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8609—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8612—Hydrogen sulfide
    • 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
    • C01B17/0413—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 characterised by the combustion step
    • 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
    • C01B17/0426—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 characterised by the catalytic conversion
    • 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
    • C01B17/16—Hydrogen sulfides
    • 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
    • C01B17/16—Hydrogen sulfides
    • C01B17/161—Preparation from elemental sulfur
    • C01B17/162—Preparation from elemental sulfur from elemental sulfur and hydrogen
    • 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
    • C01B17/16—Hydrogen sulfides
    • C01B17/165—Preparation from sulfides, oxysulfides or polysulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals

Abstract

The invention discloses a kind of H2S claus reaction combinations low-temp methanol washs the sulfur recovery technology of tail gas, contains H2S sour gas passes through H2S gases are washed and preheating unit, after preheating, a certain amount of oxygen are filled into, into H2S gases part is burned and high temperature claus reaction unit is burned, and occurs high temperature claus reaction, and then gas carries out cooling and isolating elemental sulfur, and unreacted gas enters follow-up H2S gases one-level, two grades of claus catalytic reaction unit process generation elemental sulfurs, are reclaimed after elemental sulfur, reacted gas adds a certain amount of H by cooling down2Gas, enters Claus tail-gas hydrogenation reaction member, by SO2Whole hydrogenating reductions are into H2After S, high-temperature gas is cooled to about 40 DEG C and by after tail gas compression to certain pressure by being hydrogenated with tail gas quenching and compression unit, normal temperature methanol liquid is sprayed into reduce the freezing point of gas, then gas enters H by being hydrogenated with after tail gas spray methanol precooling and dewatering unit refrigerated separation moisture therein2S low-temp tail gas methanol washing units, absorb H2The methanol rich solution of S components carries out hot recycling by entering methanol rich solution hot recycling unit after cold recovery and re-heat by low-pressure steam.Whole technical process sulfur recovery rate is about 99.98%.

Description

A kind of H2S claus reaction combinations low-temp methanol washs the sulfur recovery technology of tail gas
Technical field
The present invention relates to reclaim sour gas in hydrogen sulfide, cos chemical technology field, specially a kind of H2S gases gram The process unit and technology of the sulfur recovery of Louth reaction bonded low-temp methanol carrying out washing treatment tail gas.
Background technology
China's coal chemical industry was quickly grown in recent years, while a large amount of sulfur acids produced in coal chemical industry production process Property waste gas, equipment corrosion, environmental pollution can be caused, and then endanger national health.China is announced《Odorant pollutant discharge mark It is accurate》It is required that H2S total emission volumns are less than 2.3kg/h,《Petro chemical industry pollutant emission standard》It is required that SO2Special emission limit For 50mg/m3, for problem of environmental pollutions such as recently prominent hazes, future may propose tightened up environmental protection requirement And discharge standard, reflect the resolution that Environmental is administered.
And existing refinery, coal chemical engineering equipment sulfur recovery generally using Crouse (Claus) and improve Crouse (Claus) Method, i.e., the rich hydrogen sulfide gas discharged using upstream device is reclaimed conversion by Crouse (Claus) method and prepares solid sulfur.Stream Journey is simple, small investment, and Recovered sulphur purity is high, but the general principle of Claus method and improvement Crouse (Claus) method belongs to Balanced reaction, the waste gas after processing can not meet existing discharge standard.
Recently the A claus reaction combination tail gas by ammonia method treatment technologies of CN 105020723 proposed, the i.e. wet ammonia process of ammoniacal liquor take off Except the sulfur dioxide in Claus tail gases, ammonium sulfate further then is oxidized to down in Oxygen Condition, is analysed by crystallizing evaporator Go out finished product.If ammonia process reclaims producing ammonium sulfate byproduct product, long flow path is crystallized, equipment is more, investment is high, in addition ammonium sulfate product yield Few, quality is unstable, and economic benefit is not obvious.If not reclaiming ammonium sulfate, sulfur recovery unit will continuously discharge substantial amounts of sulfur-bearing Sour ammonium, ammonium sulfite, bisulfite waste liquor of ammonium, form more serious pollution source.
The content of the invention
The problem of for presently, there are, it is an object of the invention to provide a kind of H2S gas claus reaction combination low temperature first The sulfur recovery technology of alcohol carrying out washing treatment tail gas, is specially by H2S gases claus reaction washs tail gas and methanol with low-temp methanol Regenerate the method being combined so that sulfur recovery tail gas sulfur-containing compound (H2S) concentration is down to 10PPm (mol%) below, SO2Content Below 5PPm is down to, tail gas is up to standard can directly to discharge air.
The technical scheme is that：A kind of H2The sulfur recovery of S claus reaction combination low-temp methanol carrying out washing treatment tail gas Technique,
Specifically include following 10 reactions steps：
(1)H2S gases are washed and preheated
The H out-of-bounds come2S gases (20~40 DEG C, 0.12~0.3MPaG) and the H of circulation2After the mixing of S tail gas, pass through desalination Water washing removes the CH contained in gas3The components such as OH, are then preheating to 180~240 DEG C by middle pressure steam and enter H2S high temperature Incinerator.The washings that acid gas washing is produced contain micro H2S and CH3OH components, are sent to follow-up first after being pressurizeed by pump Alcohol/water separation column is handled.
(2)H2Burn and high temperature claus reaction S gases part
H2S+1.5O2=SO2+H2O 2H2S+SO2=3S+2H2O
H after preheating2S gases fill into a certain amount of oxygen and enter high-temperature incinerator, incineration temperature control 1050 DEG C with On so that 1/3 H2S components burn generation SO2, while at high temperature, the SO of generation2With H2It is anti-that S components carry out high temperature Crouse Elemental sulfur should be generated.During sulphur production rate account for feed total sulfur 50%.
(3)H2S gases one-level, two grades of claus catalytic reactions
2H2S+SO2=3S+2H2O
H2S gases are urged by one-level (300~350 DEG C of reaction temperature), two grades of (210~250 DEG C of reaction temperature) Crouses Change reaction and further improve sulfur recovery rate.During sulphur production rate account for feed total sulfur 50%.
(4) Claus tail-gas hydrogenation reacts
H2SO in S gases2Component whole catalytic hydrogenating reduction is H2S, while H2COS and CS in S gases2It is hydrolyzed to H2S。 In this catalytic hydrogenation, all sulfide in Claus tail gases are converted into H2S components.The reaction temperature is about 200~ 255 DEG C, specific course of reaction is as follows：
SO2+3H2=H2S+2H2O
S+H2=H2S
COS+H2O=H2S+CO2
CS2+2H2O=2H2S+CO2
To ensure SO2Conversion ratio is, it is necessary to fill into certain H2Gas, and maintain H2Concentration is between 3~4mol%.
(5) hydrogenation tail gas quenching and compression
Tail gas after hydrogenation is cooled down into quenching column by water Quench, while the water vapour in gas is condensed Into liquid.Exhaust temperature is about 40~50 DEG C after Quench, and pressure is 0.03~0.05MpaG, is then compressed by tail-gas compressor To~0.5MPaG.A small amount of condensate liquid that Quench is produced, which is sent to, out-of-bounds to be handled.
(6) the spray methanol precooling of hydrogenation tail gas and dehydration
Tail gas (0.5MpaG ,~40 DEG C) after compression, sprays into normal temperature methanol solvate, to reduce the freezing point of gas.Then Tail gas is cooled to about -25 DEG C by propylene cooler and enters gas separator, isolates methanol aqueous solution so that tail gas reclaimed water is steamed Vapour content is less than 20PPm, and tail gas enters Methanol Wash Column, and methanol aqueous solution sends into follow-up methanol-water separating.
(7)H2S low-temp tail gas methanol is washed
The operating pressure of Methanol Wash Column is about 0.45MpaG, and the pure methanol solvate of low temperature (about -35 DEG C) is washed from methanol Top of tower enters, with the sulfur recovery tail gas that is entered by bottom of towe on tower tray counter current contacting, low-temp methanol absorbed in tail gas all H2S components and part CO2Component, the methanol rich solution (about -23 DEG C) that bottom of towe is produced after re-heat into methanol hot recycling tower by entering Row methanol solvate regenerates.The exhaust temperature of Methanol Wash Column tower top is about -27 DEG C, H2S contents are less than 10PPm, are returned by cold High point emptying is carried out after receipts.
(8) methanol solution hot recycling
Absorb H2S and CO2Methanol rich solution (about -23 DEG C) first by the re-heat of poor methanol cooler to 30 DEG C, then Exchanged heat by hot recycling tower feed exchanger to 75 DEG C and enter hot recycling tower, hot recycling tower operating pressure is 0.2MpaG, and bottom of towe is adopted With 0.5MpaG low-pressure steam as reboiler thermal source, hot recycling tower bottom of towe obtains H2S is less than 1PPm poor methanol liquid.Heat The gas (about 85 DEG C) of regenerator overhead extraction is cooled to 42 DEG C by water cooler and enters gas-liquid separator, the gas isolated Body (contains H2S, CO2Etc. component) return in the feed gas of sulfur recovery unit, the condensate liquid isolated returns to hot recycling tower It is used as overhead reflux liquid.
(9) poor methanol cooling and pressurized circulation
It is poor that the poor methanol liquid (about 97 DEG C) that hot recycling tower bottom of towe is obtained is cooled to 44 DEG C of entrance by feed exchanger Methanol storage tank, is then pressurized to 1.5MpaG by pump, pass sequentially through poor methanol cooler, poor methanol propylene cooler be cooled to- 35 DEG C are recycled into sulfur recovery tail gas Methanol Wash Column.
(10) methanol/water separation and recovery methanol
The methanol aqueous solution (about -25 DEG C) that tail gas precooling is produced is hydrogenated with, by entering methanol/water knockout tower after preheating Carry out Methanol Recovery.While H2What S feed gas water scrubber was produced also delivers to methanol/water knockout tower progress methanol time containing methanol-water Receive.Bottom of towe uses 0.5MpaG low-pressure steam as reboiler thermal source, the sub-fraction poor methanol liquid come from hot recycling tower bottom of towe Body is used as overhead reflux liquid.The methanol steam feeding hot recycling tower that methanol/water separation column overhead is produced carries out Methanol Recovery, first The waste water (methanol content is less than 100PPm) of alcohol/water separation column bottom of towe extraction is out-of-bounds returned by being sent out after cooling for other devices With.
According to the concrete scheme of the present invention, from H2Burn and high temperature claus reaction and H S gases part2S gases One-level, the molten sulfur of two grades of claus catalytic reactions out-of-bounds, are packed through granulation and filled in the storage of molten sulfur pond, the submitting of finished product molten sulfur after cooling down Put the hydrogen sulfide containing very small amount in production Grade A sulphur, molten sulfur pond, the gas of nitrogen gas and water is extracted out through steam jet ejector and send torch Device is vented after burning.
The present invention is provided with Claus tail-gas hydrogenation reaction member after two grades of claus reactions.It is catalyzed using hydrogenation reaction Agent, while controlling the density of hydrogen in sour gas, H is converted into by the sulfide of all oxidation state in Claus tail gases2S groups Point, efficiently solve SO2、COS、CS2The problem of sulfides exhaust emission air.
The present invention is provided with hydrogenation tail gas quenching and compression, hydrogenation tail gas spray after Claus tail-gas hydrogenation reaction member Methanol precooling and dehydration, H2S low-temp tail gas methanol is washed and methanol rich solution hot recycling unit.So that vent gas treatment and solution circulation As a complete technique so that device safe operation is flexible, according to H in hydrogenation tail gas2S contents, adjust poor methanol flow, The quantity of steam of hot recycling tower is adjusted simultaneously.The other device has also reclaimed H simultaneously2S charge raw material air waters wash the acid water of generation Middle H2S and methanol component, further increase the sulfur recovery rate of device.
A kind of H of the present invention2The technique of S claus reaction combination low-temp methanol carrying out washing treatment sulfur recovery tail gas, emission Middle H2S contents are less than 10PPm, without SO2, COS sulfides, total sulfur recovery be higher than 99.98%.The same of sulphur is reclaimed realizing When, the low-pressure steam of the useless pot of high temperature Crouse and sulfur condenser by-product can be used for the heating of system pipe network, be integrated heat Utilize.With good economic benefit, and environmental protection and safety coefficient are high.
Brief description of the drawings
Fig. 1 is the process schematic representation of the present invention.
Drawing reference numeral explanation：H2S gases are washed and preheating unit (1), H2Burn and high temperature claus reaction S gases part Unit (2), H2S gases one-level, two grades of claus catalytic reaction units (3), Claus tail-gas hydrogenation reaction member (4), hydrogenation Tail gas quenching and compression unit (5), the spray methanol precooling of hydrogenation tail gas and dewatering unit (6), H2The washing of S low-temp tail gas methanol is single First (7), methanol rich solution hot recycling unit (8), poor methanol cooling and pressurized circulation unit (9), methanol/water separation and recovery methanol list First (10) and molten sulfur pond (11).
Embodiment
Referring to accompanying drawing 1, enter device H2S gas feed rates are 4745Nm3/ h, wherein H2S contents are 55.86vt%, temperature 30 DEG C, pressure 0.25MPaG.The gas and circulation H2The mixing of S tail gas is by de- H2S gases are washed and preheating unit (1) preheats it Afterwards, a certain amount of oxygen-enriched air is filled into, into H2S gases part is burned and high temperature claus reaction unit (2) is burned, and Generation high temperature claus reaction, then gas progress cools and isolates elemental sulfur, and unreacted gas enters follow-up H2S gases One-level, two grades of claus catalytic reaction unit (3) reaction generation elemental sulfurs, are reclaimed after elemental sulfur, reacted gas by cooling down Body adds a certain amount of H2Gas, then into Claus tail-gas hydrogenation reaction member (4), the technique for going out hydrogenation reactor Gas is cooled to penetrating normal temperature methanol liquid after 40 DEG C and pressurization by being hydrogenated with tail gas quenching and compression unit (5), and then gas leads to The spray methanol precooling of hydrogenation tail gas and dewatering unit (6) refrigerated separation moisture therein are crossed, H is entered afterwards2S low-temp tail gas first Alcohol washing unit (7), whole H are absorbed by low temperature poor methanol solvent (about -35 DEG C)2S and part CO2Component.Tail gas methanol It is 5458Nm to wash column overhead exhaust flow3/ h, wherein H2S content ＜ 10ppm, 30 DEG C of temperature can direct high point discharge up to standard. The methanol rich solution of bottom of towe is entered by entering methanol rich solution hot recycling unit (8) after cold recovery and re-heat by low-pressure steam Row poor methanol hot recycling.Poor methanol (the H that methanol hot recycling tower tower reactor is produced2S is less than 1PPm) cooled down and pressurizeed by poor methanol Enter H after cycling element (9) supercharging2S low-temp tail gas methanol washing units (7) are recycled.What Mathanol regenerating top of tower was produced Containing H2S gases are separated after moisture therein by partial condensation, H2S gas circulations enter H2Recycled in S unstrpped gases.

Claims (2)

1. a kind of H2S claus reaction combinations low-temp methanol washs the sulfur recovery technology of tail gas, it is characterised in that out-of-bounds comes contains There is H2S sour gas passes through H2S gases are washed and preheating unit (1), after preheating, a certain amount of oxygen are filled into, into H2S Gas part is burned and high temperature claus reaction unit (2) is burned, and occurs high temperature claus reaction, and then gas carries out cold But elemental sulfur is isolated, unreacted gas enters follow-up H2S gases one-level, two grades of claus catalytic reaction units (3) are anti- Elemental sulfur should be generated, is reclaimed by cooling down after elemental sulfur, reacted gas adds a certain amount of H2Gas, enters Crouse Tail gas hydrogenation reaction member (4), by SO2Whole hydrogenating reductions are into H2After S, high-temperature gas is by being hydrogenated with tail gas quenching and compression Unit (5) is cooled to about 40 DEG C and by after tail gas compression to certain pressure, sprays into normal temperature methanol liquid to reduce the solidifying of gas Solid point, then gas is by being hydrogenated with after tail gas spray methanol precooling and dehydration (6) unit refrigerated separation moisture therein, entrance To H2S low-temp tail gas methanol washing units (7), pass through the whole H of low-temp methanol solvent absorption2S and part CO2Component, now tail H in gas2S contents are less than 10PPm, are directly discharged to air.Absorb H2The methanol rich solution of S components passes through cold recovery and re-heat Enter methanol rich solution hot recycling unit (8) afterwards, hot recycling, the poor first that Mathanol regenerating tower tower reactor is produced are carried out by low-pressure steam Alcohol after poor methanol cooling and the supercharging of pressurized circulation unit by entering H2S low-temp tail gas methanol washing units (7) are recycled, first What is produced at the top of alcohol regenerator contains H2S gases are separated after moisture therein by partial condensation, H2S gas circulations enter H2S raw materials Recycled in gas, whole technical process sulfur recovery rate is about 99.98%.
2. H as claimed in claim 12S claus reaction combinations low-temp methanol washs the sulfur recovery technology of tail gas, and its feature exists In specifically including following 10 reactions steps：
(1)H2S gases are washed and preheated
The H out-of-bounds come2S gases and the H of circulation2After the mixing of S tail gas, the CH contained in gas is removed by desalination water washing3OH etc. Component, is then preheating to 180~240 DEG C by middle pressure steam and enters H2S high-temperature incinerators, the washings that acid gas washing is produced Contain micro H2S and CH3OH components, are sent to follow-up methanol/water knockout tower and are handled after being pressurizeed by pump；
(2), H2Burn and high temperature claus reaction S gases part
H after preheating2S gases fill into a certain amount of oxygen and enter high-temperature incinerator, and incineration temperature is controlled more than 1050 DEG C, made 1/3 H2S components burn generation SO2, while at high temperature, the SO of generation2With H2S components carry out high temperature claus reaction life Into elemental sulfur, during the production rate of sulphur account for feeding the 50% of total sulfur；
(3)H2S gases one-level, two grades of claus catalytic reactions
H2S gases further improve sulfur recovery rate by one-level, two grades of claus catalytic reactions, during sulphur production rate Account for feeding the 50% of total sulfur, wherein one-level claus catalytic reaction temperature is 300~350 DEG C；Two grades of claus catalytic reactions Temperature is 210~250 DEG C；
(4) Claus tail-gas hydrogenation reacts
H2SO in S gases2Component whole catalytic hydrogenating reduction is H2S, while H2COS and CS in S gases2It is hydrolyzed to H2S, this is urged Change in hydrogenation process, all sulfide in Claus tail gases are converted into H2S components, the reaction temperature is about 200~255 DEG C, to ensure SO2Conversion ratio is, it is necessary to fill into certain H2Gas, and maintain H2Concentration is in the range of 3~4mol%；
(5) hydrogenation tail gas quenching and compression
Tail gas after hydrogenation is cooled down into quenching column by water Quench, while the water vapour in gas is condensed into liquid Exhaust temperature is about 40~50 DEG C after body, Quench, and pressure is 0.03~0.05MpaG, be then compressed to by tail-gas compressor~ 0.5MpaG, a small amount of condensate liquid that Quench is produced, which is sent to, out-of-bounds to be handled；
(6) the spray methanol precooling of hydrogenation tail gas and dehydration
Tail gas after compression, sprays into normal temperature methanol solvate, to reduce the freezing point of gas, then tail gas is cold by propylene cooler But about -25 DEG C are arrived and enters gas separator, methanol aqueous solution is isolated so that vapour content is less than 20PPm, tail gas in tail gas Into Methanol Wash Column, methanol aqueous solution sends into follow-up methanol-water separating；
(7)H2S low-temp tail gas methanol is washed
The operating pressure of Methanol Wash Column is about 0.45MpaG, and the pure methanol solvate of low temperature enters at the top of Methanol Wash Column, with by The sulfur recovery tail gas that bottom of towe enters counter current contacting on tower tray, low-temp methanol absorbs whole H in tail gas2S components and part CO2 Component, the methanol rich solution that bottom of towe is produced carries out methanol solvate regeneration, Methanol Wash Column by entering methanol hot recycling tower after re-heat The exhaust temperature of tower top is about -27 DEG C, H2S contents are less than 10PPm, by carrying out high point emptying after cold recovery；
(8) methanol rich solution hot recycling
Absorb H2S and CO2Methanol rich solution first by the re-heat of poor methanol cooler to 30 DEG C, then entered by hot recycling tower Material heat exchanger, which exchanges heat to 75 DEG C, enters hot recycling tower, and hot recycling tower operating pressure is 0.2MpaG, and bottom of towe is low using 0.5MpaG's Press steam as reboiler thermal source, hot recycling tower bottom of towe obtains H2S is less than 1PPm poor methanol liquid, the extraction of hot recycling column overhead Gas be cooled to 42 DEG C by water cooler and enter gas-liquid separator, the gas isolated returns to the charging of sulfur recovery unit In gas, the condensate liquid isolated returns to hot recycling tower as overhead reflux liquid；
(9) poor methanol cooling and pressurized circulation
The poor methanol liquid that hot recycling tower bottom of towe is obtained is cooled to 44 DEG C by feed exchanger and enters poor methanol storage tank, Ran Houtong Cross pump and be pressurized to 1.5MpaG, pass sequentially through poor methanol cooler, poor methanol propylene cooler and be cooled to -35 DEG C and be recycled into sulphur Reclaim tail gas Methanol Wash Column；
(10) methanol/water separation and recovery methanol
The methanol aqueous solution that tail gas precooling is produced is hydrogenated with, Methanol Recovery is carried out by entering methanol/water knockout tower after preheating, together When H2What S feed gas water scrubber was produced also delivers to methanol/water knockout tower progress Methanol Recovery containing methanol-water, and bottom of towe is used 0.5MpaG low-pressure steam is as reboiler thermal source, and the sub-fraction poor methanol liquid come from hot recycling tower bottom of towe is used as tower top Phegma.The methanol steam feeding hot recycling tower that methanol/water separation column overhead is produced carries out Methanol Recovery, methanol/water knockout tower The waste water of bottom of towe extraction out-of-bounds supplies other device reuses by being sent out after cooling.
CN201710228462.2A 2017-04-10 2017-04-10 A kind of H2S claus reaction combinations low-temp methanol washs the sulfur recovery technology of tail gas Pending CN107128882A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4795620A (en) * 1983-09-20 1989-01-03 Linde Akitengesellschaft Claus residual gas cleanup using tetraethylene glycol dimethyl ethers as SO2 scrubbing agent
CN101418246A (en) * 2008-12-05 2009-04-29 华陆工程科技有限责任公司 Low temperature methanol washing integrated Claus sulfur recovery system and process
CN102631827A (en) * 2012-04-11 2012-08-15 山东三维石化工程股份有限公司 Zero-emission sulfur recovery technology combined with low-temperature methanol washing acid gas treatment
CN203781843U (en) * 2014-04-02 2014-08-20 戴玉玲 System for treating Claus sulfur recovery tail gas by low-temperature methanol washing hydrogen sulfide concentrating tower
CN106115632A (en) * 2016-06-28 2016-11-16 山东三维石化工程股份有限公司 Improve device and the recovery method thereof of sulfur recovery rate
CN106512650A (en) * 2016-11-23 2017-03-22 北京丰汉工程技术有限公司 Method and system for treating Claus process tail gas

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4795620A (en) * 1983-09-20 1989-01-03 Linde Akitengesellschaft Claus residual gas cleanup using tetraethylene glycol dimethyl ethers as SO2 scrubbing agent
CN101418246A (en) * 2008-12-05 2009-04-29 华陆工程科技有限责任公司 Low temperature methanol washing integrated Claus sulfur recovery system and process
CN102631827A (en) * 2012-04-11 2012-08-15 山东三维石化工程股份有限公司 Zero-emission sulfur recovery technology combined with low-temperature methanol washing acid gas treatment
CN203781843U (en) * 2014-04-02 2014-08-20 戴玉玲 System for treating Claus sulfur recovery tail gas by low-temperature methanol washing hydrogen sulfide concentrating tower
CN106115632A (en) * 2016-06-28 2016-11-16 山东三维石化工程股份有限公司 Improve device and the recovery method thereof of sulfur recovery rate
CN106512650A (en) * 2016-11-23 2017-03-22 北京丰汉工程技术有限公司 Method and system for treating Claus process tail gas

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
张国民等: ""低温甲醇洗工艺的研究进展与应用"", 《化学工程师》 *
张德义: "《含硫含酸原油加工技术》", 31 January 2013 *

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