CN108176194A - A kind of processing unit and processing method containing sulphur simple substance and compound tail gas - Google Patents

A kind of processing unit and processing method containing sulphur simple substance and compound tail gas Download PDF

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Publication number
CN108176194A
CN108176194A CN201810039147.XA CN201810039147A CN108176194A CN 108176194 A CN108176194 A CN 108176194A CN 201810039147 A CN201810039147 A CN 201810039147A CN 108176194 A CN108176194 A CN 108176194A
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CN
China
Prior art keywords
gas
tail gas
sulphur
substance
tower
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Pending
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CN201810039147.XA
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Chinese (zh)
Inventor
周明宇
刘棋
杜通林
陈运强
梁宇成
秦兴述
陈彰兵
汤晓勇
蒲远洋
肖秋涛
程林
游龙
杜明志
黄维光
李波
马艳琳
李建
兰林
马先
汤国军
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China Petroleum Engineering and Construction Corp
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China Petroleum Engineering and Construction Corp
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Priority to CN201810039147.XA priority Critical patent/CN108176194A/en
Publication of CN108176194A publication Critical patent/CN108176194A/en
Pending legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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
    • B01D53/1425Regeneration of liquid absorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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
    • B01D53/1456Removing acid components
    • B01D53/1481Removing sulfur dioxide or sulfur trioxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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
    • B01D53/18Absorbing units; Liquid distributors therefor
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23GCREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23GCREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2209/00Specific waste
    • F23G2209/14Gaseous waste or fumes

Abstract

The invention discloses a kind of processing units and processing method containing sulphur simple substance and compound tail gas, processing unit includes sequentially connected incinerator, waste heat boiler, emission flue gas heat-exchange unit, chilling tower, absorption tower, rich or poor absorbent heat exchanger and regenerator, and the hot lean solution outlet of the regeneration tower bottom is connect successively with rich or poor absorbent heat exchanger, lean solution cooler, solution surge tank, absorption tower, gas-liquid separator and emission flue gas heat-exchange unit.The present invention is burned using sulfur-containing tail gas and waste heat recovery, tail gas are cooled down and pre-washed, SO23 formants of absorption and regeneration composition exhaust treatment systems, completely by the sulphur simple substance in tail gas and compound oxidation into SO2, and pass through absorption and regeneration unit removing SO2So that the exhaust emissions after being handled by the system meets harsh environmental requirement, the SO containing high concentration after removing2Gas can return to claus sulphur recovery units and be converted to Sulfur, can also send to sulphuric acid plant and generate sulfuric acid.

Description

A kind of processing unit and processing method containing sulphur simple substance and compound tail gas
Technical field
The present invention relates to a kind of processing units and processing method containing sulphur simple substance and compound tail gas.
Background technology
All sulfur-bearing in most of crude oil, raw natural gas and coal mine, in petroleum refining, natural gas purification process and coal It is required for removing the impurity composition of sulfur-bearing in chemical field.In gas (normally referred to as acid gas) after removing containing it is toxic very Big H2S gases are very big to the existence and environmental hazard of the mankind;Therefore, acid gas could discharge after having to pass through processing.The whole world The most widely used treatment process technology of recent decades is Crouse (Claus) Sulfur recovery process, by the H in acid gas2S is converted It is recycled into elemental sulfur, while achievees the purpose that remove toxic gas in acid gas.
With the continuous development of society, the protective awareness for the natural environment that the mankind depend on to itself for existence is more and more stronger, phase The pollutant emission standard answered is also increasingly stringenter, and China had all put into effect newly in recent years for gas industries, coal chemical technology More stringent environmental protection standard.Such as domestic refinery new standard provides the refinery Sulfur recovery devices SO in general area2It discharges dense It spends for less than 400mg/Nm3, environmentally sensitive area emission limit is 100mg/Nm3.Although domestic coal chemical industry does not temporarily put into effect row Industry standard, but also perform national standard SO2Concentration of emission is less than 960mg/Nm3, environmentally sensitive area execution 100mg/Nm3.My god Industry, which is currently prepared, at right gas purification formulates new environmental protection standard also by SO2Concentration of emission is tentatively scheduled on less than 500mg/Nm3
Meet the requirement of increasingly strict environmental protection standard, conventional Claus and extension class Claus Sulfur recovery process Technology (such as MCRC, CBA, CPS, Clinsulf, super Claus) all cannot meet the needs, only the technique of magnetic tape trailer gas disposal Technology could meet environment protection emission requirement.
For the existing sulfur-containing tail gas treatment process technology in the current whole world, mainly have Reducing and absorption class technology, Flue gas desulfurization technique, liquid phase oxidation law technology.
Reducing absorping method technology is mainly characterized by sulfur-containing tail gas through hydrotreating, by the various forms in tail gas Sulfur-containing compound be converted into H2S carries out desulfurization, then the H by concentrate with alcohol amine solvent after cooling2S returns to the processing of upstream acid gas Device recycles elementary sulfur, and most representative technique has the SCOT techniques of Dutch Shell Co. Ltd's exploitation.Such technique can relatively often Rule or low-temperature Claus sulfur recovery technology further improve the Sulfur rate of recovery, but can not meet SO2Concentration of emission be less than 400mg/Nm3;Such technological process is long, if the reduction of tail gas hydrogenation section is not thorough, sulfur dioxide penetrates that easily cause upstream device tight Heavy corrosion.
Flue gas desulfurization technique is mainly characterized by using alkaline solution, such as soda, calcium hydroxide, ammonia etc. by acid-base neutralization SO in chemical reaction removing tail gas2Deng other acid sulphides, representative is Dual alkali, ammonia-fertilizer method.Such technique Due to being chemical reaction, rate is fast, removal efficiency is high, SO2Concentration of emission is even smaller than 50mg/Nm3, disclosure satisfy that more tight Severe environment protection emission index.Nevertheless, since such technique is acid-base neutralization reaction, final SO2Salts substances can be converted into In the presence of, therefore such technique is in removing SO2While can generate the byproducts such as gypsum or even waste water can be generated and bring secondary pollution The problem of object processing.
Liquid phase oxidation law technology is mainly characterized by sulfur-containing tail gas through hydrotreating, by containing for the various forms in tail gas Convert sulfur compounds are H2S recycles proprietary complexing ferrous solution in the liquid phase by H2S is direct oxidation into elemental sulfur, final sulphur list Matter output in the form of aqueous Sulfur filter cake.Primarily directed to containing H at the beginning of the process exploitation2The process gas desulfurization process of S, needle To contain SO2Based on vent gas treatment, the technique need increase hydrogenating reduction processing.Sulfur-containing tail gas passes through after the process Emission in almost without SO2, only H of the content no more than 10ppm2S.Although such technique can also meet more harsh Environmental emission standard, but product Sulfur purity is not high, it is difficult to handle;Simultaneously device in normal course of operation easily by Sulfur Particle blocks, and influences the smooth long term running of exhaust gas processing device.
Invention content
The shortcomings that in order to overcome the prior art, the present invention provides a kind of processing units containing sulphur simple substance and compound tail gas And processing method, it is burned using sulfur-containing tail gas and waste heat recovery, tail gas is cooled down and pre-washed, SO23 formants of absorption and regeneration Exhaust treatment system is formed, completely by the sulphur simple substance in tail gas and compound oxidation into SO2, and pass through absorption-regeneration unit and take off Except SO2So that the exhaust emissions after being handled by the system meets harsh environmental requirement (by technological parameter special setting Minimum SO2Concentration of emission may be less than 100mg/Nm3), the SO containing high concentration after removing2Gas can return to Crouse sulphur and return Receiving apparatus is converted to Sulfur, can also send to sulphuric acid plant and generate sulfuric acid.
The technical solution adopted in the present invention is:A kind of processing unit containing sulphur simple substance and compound tail gas, including successively The incinerator of connection, waste heat boiler, emission-flue gas heat-exchange unit, chilling tower, absorption tower, rich or poor absorbent heat exchanger and again Raw tower, the hot lean solution outlet of the regeneration tower bottom successively with rich or poor absorbent heat exchanger, lean solution cooler, solution surge tank, Absorption tower, gas-liquid separator are connected with emission-flue gas heat-exchange unit.
The present invention also provides a kind of processing methods containing sulphur simple substance and compound tail gas, include the following steps:
Step 1: it is 760~850 DEG C to enter incinerator to be converted into temperature by burning containing sulphur simple substance and compound tail gas Containing SO2It is cooled to 300 DEG C in advance into waste heat boiler after tail gas, subsequently into emission-flue gas heat-exchange unit with coming from gas-liquid separation Enter in chilling tower after 35~70 DEG C of the emission heat exchange cooling of device after being finally cooled to 30~65 DEG C and enter absorption tower;
Step 2: contain SO in absorption tower2Tail gas passes through lean solution absorbing and removing SO2Enter gas-liquid separator separates afterwards and fall folder After being heated to 130 DEG C or more into emission-flue gas heat-exchange unit after the absorbent of band air is discharged into through exhaust emissions chimney;
Step 3: lean solution absorbs SO in absorption tower2After become rich solution from absorb the bottom of the tower into rich or poor absorbent exchange heat Enter regenerator after device preheating and carry out solvent reclamation;
Enter Step 4: the hot lean solution after having regenerated enters from regeneration tower bottom after the precooling of rich or poor absorbent heat exchanger Lean solution cooler is finally cooled down, and then enters in absorption tower the SO absorbed in tail gas through solution surge tank2, start next The cycle that lean solution absorption-rich solution regeneration-lean solution absorbs.
Compared with prior art, the positive effect of the present invention is:
(1) present invention is to SO2Gas has higher reaction speed and preferable assimilation effect, can further reduce discharge SO in tail gas2Concentration, pass through the minimum SO of technical arrangement plan2Concentration of emission may be less than 100mg/Nm3, meet more harsh Environmental requirement.
(2) present invention absorbs SO using with superelevation selection2Lyosoption, can be grasped under higher gas liquid ratio Make, effectively reduce the solution internal circulating load of device, reduce the size of capital equipment.
(3) present invention is except the SO of production high concentration2Outside gas, reluctant solid product is not generated, is had higher Environment friendly and operability.
(4) present invention is using the sulfur-containing tail gas burning specially designed and waste heat recovery unit, and is integrated at entire tail gas It manages in technological process, high temperature oxygen can melt H in all tail gas completely2S utmostly reduces absorption-regeneration unit SO2It absorbs The degradation and loss of agent.
(5) emission-flue gas heat-exchange unit is provided in flow of the present invention, by the exhaust gas reheater of absorption tower top discharge extremely 130 DEG C or more, ensure that higher exhaust temperature causes the moisture content in emission not condense;Further it is lowered into chilling simultaneously The gas temperature of tower reduces the operational load of chilling tower.
(6) setting absorbs tower top catchment gauze and the dual separation of external gas-liquid separator, maximum journey in flow of the present invention Degree isolates the SO carried secretly in overhead gas2Absorbent reduces the loss of absorbent, reduces the operating cost of device.
Description of the drawings
Examples of the present invention will be described by way of reference to the accompanying drawings, wherein:
Fig. 1 is the process flow chart of the present invention.
Specific embodiment
A kind of processing unit containing sulphur simple substance and compound tail gas, as shown in Figure 1, including:Sulfur-containing tail gas incinerator 1 gives up Heat boiler 2, emission-flue gas heat-exchange unit 3, chilling tower 4, absorption tower 5, rich or poor absorbent heat exchanger 6, regenerator 7, hot lean solution Circulating pump 8, lean solution cooler 9, solution surge tank 10, lean solution circulating pump 11, gas-liquid separator 12 and solution in-line purification system 13 etc., wherein:
The sulfur-containing tail gas incinerator 1 is connect by flange with waste heat boiler 2;The outlet of the waste heat boiler 2 passes through pipe Line is connect with the tube-side inlet of emission-flue gas heat-exchange unit 3, and the tube side outlet of the emission-flue gas heat-exchange unit 3 passes through Pipeline is connect with 4 lower inlet of chilling tower, and 4 top exit of chilling tower is connect by pipeline with 5 lower inlet of absorption tower, institute The outlet at bottom for stating absorption tower 5 is connect by pipeline with the tube-side inlet of rich or poor absorbent heat exchanger 6, and the rich or poor absorbent changes The tube side outlet of hot device 6 is connect by pipeline with 7 centre inlet of regenerator, and the hot lean solution outlet of 7 bottom of regenerator passes through Pipeline is connect with the import of hot lean solution circulating pump 8, and the outlet of the hot lean solution circulating pump 8 is exchanged heat by pipeline and rich or poor absorbent The shell side import connection of device 6, the shell-side outlet of the rich or poor absorbent heat exchanger 6 pass through pipeline and the import of lean solution cooler 9 Connection, the outlet of the lean solution cooler 9 are connect by pipeline with the upper inlet of solution surge tank 10, the solution surge tank 10 outlet at bottom is connect by pipeline with the import of lean solution circulating pump 11, the outlet of the lean solution circulating pump 11 by pipeline with The top lean solution import connection on absorption tower 5, the top exit on the absorption tower 5 are connect by pipeline with gas-liquid separator 12, institute The liquid-phase outlet for stating gas-liquid separator 12 accesses the upper inlet on absorption tower 5, the gas of the gas-liquid separator 12 by circulating pump Mutually outlet is connect by pipeline with the shell side import of emission-flue gas heat-exchange unit 3, the emission-flue gas heat-exchange unit 3 Shell-side outlet is connected to exhaust emissions chimney by pipeline;The solution surge tank 10 passes through pipeline and solution in-line purification system 13 Connection.
The invention also discloses a kind of processing methods containing sulphur simple substance and compound tail gas, include the following steps:
Step 1: upstream sulfur-containing tail gas by pipeline 1. into sulfur-containing tail gas incinerator 1 be warming up to 760~850 DEG C it is laggard Enter waste heat boiler 2, high-temperature gas is cooled to 300 DEG C in advance;
Step 2: the gas after the outlet of waste heat boiler 2 precooling enters back into 3 tube side of emission-flue gas heat-exchange unit, changing In hot device with about 35~70 DEG C of the mutual heat exchange amount of emission from gas-liquid separator 12;
It carries out finally being cooled to 30~65 DEG C Step 3: the gas after cooling enters in chilling tower 4, enters absorb later SO is carried out in tower 52The absorption of gas;
Step 4: the enrichment SO after absorbing2Lyosoption (i.e. rich solution) come out from 5 bottom of absorption tower, be introduced into poor Regenerator 7, which is entered back into, after the preheating of rich absorbent heat exchanger 6 carries out solvent reclamation;
Step 5: the hot lean solution after having regenerated comes out from 7 bottom of regenerator, after being pressurized into hot lean solution circulating pump 8, into Enter rich or poor absorbent heat exchanger 6 and carry out heat exchange with the rich solution come out from absorption tower 5;
Step 6: the lean solution after rich absorbent heat exchanger 6 tentatively precooling enter lean solution cooler 9 carry out it is final cold But, later into solution surge tank 10;
Step 7: the lean solution in solution surge tank 10 is sent into absorption tower 5 after being pressurized by lean solution circulating pump 11 carries out tail gas Middle SO2Absorption, so far complete the cycle that a lean solution absorption-rich solution regeneration-lean solution absorbs;
Step 8: by 5 lean solution absorbing and removing SO of absorption tower2Tail gas later enters gas-liquid separator 12 and carries out gas-liquid point From separating and enter absorption tower 5 by circulating pump after the absorbent carried secretly in gas phase;
Step 9: the tail gas for going out gas-liquid separator 12 enters back into emission-flue gas heat-exchange unit 3, gone out from waste heat boiler 2 The high-temperature gas that mouth comes is heated to 130 DEG C or more, and exhaust emissions chimney is 3. emitted into finally by pipeline, is discharged into air;
Step 10: the height for going out 7 top of regenerator contains SO2Gas after supercooling, gas-liquid separation, gas phase passes through pipeline 2. can send to claus sulphur recovery units to generate Sulfur or send to sulphuric acid plant and produce sulfuric acid, liquid phase is again introduced by circulating pump Regenerator 7.
The present invention operation principle be:Sulphur simple substance and non-SO will be contained2The compound of form carries out high temperature by incinerator 1 and burns Oxidation conversion is burnt, H in gas can be made after oxidation2S contents are reduced to the level of below 5ppm, greatly reduce in follow-up process by In H2The degrading solvent that S is brought with lyosoption generation irreversible reaction is lost, while ensure that solvent to SO2Moderately good Absorbing and removing effect.
Waste heat be classified effectively using heat recovery boiler 2 and emission-flue gas heat-exchange unit 3 after high temperature incineration Ground utilize, can byproduct steam for the present apparatus solvent reclamation process use and preheat emission simultaneously, prevent emission The too low acid corrosion problem for leading to moisture content condensation problem therein, being effectively reduced emission pipeline and chimney of temperature.
SO is completely converted by way of high-temperature oxydation2Afterwards, it selects to absorb SO using superelevation2Lyosoption, carry out SO2The selection of gas component absorbs, and due to the characteristic of lyosoption, almost only absorbs the SO in mixed gas2Component, thus it is molten Agent regenerates SO in the gas come2Concentration may be up to more than 90%, have good utility value.In addition, according in sulfur-containing tail gas SO2Concentration and exhaust emissions requirement it is different, absorption process can be in wider gas-liquid ratio ranges (1000~5000) and solution matter It is operated under amount concentration (5~30wt%), enhances the operability of device.
After being handled by the exhaust gas processing device, SO in emission can be effectively reduced2Concentration, by adjusting The parameters such as absorption tower inlet temperature of stabilizer, gas liquid ratio, solution concentration may be such that the emission SO after being handled by the present apparatus2Concentration Less than 100mg/Nm3

Claims (9)

1. a kind of processing unit containing sulphur simple substance and compound tail gas, it is characterised in that:Including sequentially connected incinerator, waste heat Boiler, emission-flue gas heat-exchange unit, chilling tower, absorption tower, rich or poor absorbent heat exchanger and regenerator, the regenerator bottom Portion hot lean solution outlet successively with rich or poor absorbent heat exchanger, lean solution cooler, solution surge tank, absorption tower, gas-liquid separator It is connected with emission-flue gas heat-exchange unit.
2. a kind of processing unit containing sulphur simple substance and compound tail gas according to claim 1, it is characterised in that:It is described again The hot lean solution outlet of raw tower bottom accesses rich or poor absorbent heat exchanger by hot lean solution circulating pump.
3. a kind of processing unit containing sulphur simple substance and compound tail gas according to claim 1, it is characterised in that:The gas The liquid-phase outlet of liquid/gas separator accesses absorption tower by circulating pump.
4. a kind of processing unit containing sulphur simple substance and compound tail gas according to claim 1, it is characterised in that:It is described molten The outlet at bottom of liquid surge tank accesses absorption tower by lean solution circulating pump.
5. a kind of processing unit containing sulphur simple substance and compound tail gas according to claim 1, it is characterised in that:It is described again The top exit of raw tower is connect successively with cooler, gas-liquid separator.
6. a kind of processing unit containing sulphur simple substance and compound tail gas according to claim 5, it is characterised in that:It is described again The gaseous phase outlet access claus sulphur recovery units or sulphuric acid plant, liquid phase of the gas-liquid separator of the top exit connection of raw tower go out Mouth accesses regenerator by circulating pump.
7. a kind of processing method containing sulphur simple substance and compound tail gas, it is characterised in that:Include the following steps:
Step 1: enter incinerator containing sulphur simple substance and compound tail gas is converted into temperature as 760 ~ 850 DEG C containing SO by burning2 It is cooled to 300 DEG C in advance into waste heat boiler after tail gas, subsequently into emission-flue gas heat-exchange unit and 35 from gas-liquid separator Enter in chilling tower after ~ 70 DEG C of emission heat exchange cooling after being finally cooled to 30 ~ 65 DEG C and enter absorption tower;
Step 2: contain SO in absorption tower2Tail gas passes through lean solution absorbing and removing SO2Fall entrainment into gas-liquid separator separates afterwards After being heated to 130 DEG C or more into emission-flue gas heat-exchange unit after absorbent air is discharged into through exhaust emissions chimney;
Step 3: lean solution absorbs SO in absorption tower2After become rich solution from absorb the bottom of the tower into rich or poor absorbent heat exchanger preheat Enter regenerator later and carry out solvent reclamation;
Step 4: the hot lean solution after having regenerated, which enters from regeneration tower bottom after the precooling of rich or poor absorbent heat exchanger, enters lean solution Cooler is finally cooled down, and then enters in absorption tower the SO absorbed in tail gas through solution surge tank2, start next lean solution The cycle that absorption-rich solution regeneration-lean solution absorbs.
8. a kind of processing method containing sulphur simple substance and compound tail gas according to claim 7, it is characterised in that:In gas-liquid The absorbent being separated in separator enters absorption tower through circulating pump.
9. a kind of processing method containing sulphur simple substance and compound tail gas according to claim 7, it is characterised in that:Solvent is again What life generated in the process contains SO2Gas at the top of the regenerator out after supercooling, gas-liquid separation, gas phase is sent to Crouse Sulfur recovery unit, which generates Sulfur or send to sulphuric acid plant, produces sulfuric acid, and liquid phase is again introduced into regenerator by circulating pump.
CN201810039147.XA 2018-01-16 2018-01-16 A kind of processing unit and processing method containing sulphur simple substance and compound tail gas Pending CN108176194A (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN109351126A (en) * 2018-11-16 2019-02-19 中石化炼化工程(集团)股份有限公司 Sulphur-containing exhaust gas processing method

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