CN109529578A - The process unit and process of hydrogen sulfide and sulfur dioxide liquid phase reactor desulfurization - Google Patents

The process unit and process of hydrogen sulfide and sulfur dioxide liquid phase reactor desulfurization Download PDF

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Publication number
CN109529578A
CN109529578A CN201710857845.6A CN201710857845A CN109529578A CN 109529578 A CN109529578 A CN 109529578A CN 201710857845 A CN201710857845 A CN 201710857845A CN 109529578 A CN109529578 A CN 109529578A
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China
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gas
reaction
reactor
hydrogen sulfide
sulfur dioxide
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CN109529578B (en
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李磊
齐慧敏
王海波
金平
方向晨
刘炬
石平利
王昊辰
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • 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
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • 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
    • B01D53/1418—Recovery of products
    • 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
    • B01D53/1468—Removing 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
    • B01D53/14—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
    • B01D53/1481—Removing sulfur dioxide or sulfur trioxide
    • 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
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • 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
    • B01D53/18—Absorbing units; Liquid distributors therefor
    • 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
    • B01D53/523—Mixtures of hydrogen sulfide and sulfur oxides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines

Abstract

The process unit and process of hydrogen sulfide and sulfur dioxide liquid phase reactor desulfurization, including reactor and separator, reactor are from top to bottom followed successively by tail gas absorption area, reaction zone, decanting zone；The decanting zone connects separator, and the other end of separator is connected at the top of the tail gas absorption area of reactor；The reaction zone is provided with flue, is made of gas supervisor and gas service pipe, and each pipeline interconnects in the flue, and supervisor II is closed at both ends.Hydrogen sulfide is carried out using above-mentioned apparatus and sulfur dioxide desulfurization reacts, and reaction solution includes water and at least one organic basic compound that can be dissolved in water, makes pH value >=7.2 of the solution.Apparatus and method of the present invention, the reaction gas into the reactor can be made to be formed with the injection of certain radian, it pushes liquid from stirring, is conducive to that gas is evenly dispersed in reaction solution, significantly increases rate of dissolution and reaction rate of the gas in reaction solution；The response time of hydrogen sulfide and sulfur dioxide reaction, gained sulphur was without purification, purity is high, the simple easy processing of equipment, low investment, safe operation in 15s hereinafter, reaction condition is mild.

Description

The process unit and process of hydrogen sulfide and sulfur dioxide liquid phase reactor desulfurization
Technical field
The present invention relates to a kind of process units for hydrogen sulfide and sulfur dioxide liquid phase reactor desulfurization, and utilize this technique The method that device carries out desulfurization, belongs to industrial production or industrial waste gas purifying field.
Background technique
It due to China's expanding economy, is growing on and on to the demand of crude oil, domestic crude oil has been insufficient for its people Demand, so just continually input is Chinese for imported crude oil.The 1-12 month in 2016 China 381,010,000 tons of imported crude oil, with last year The same period is compared to growth by 13.6%.With the increase year by year of China's imported crude oil amount, specific gravity shared by high-sulphur crude is increasing, Major oil refining enterprise develops a series of high sulfur bauxite technique thus, sour crude in hydrofinishing, be hydrocracked, urge Change to generate in the process such as cracking and largely contains H2S sour gas and contain SO2Flue gas.
For containing SO2The processing of flue gas be divided into dry method, semidry method and three kinds of wet process, mesh wet desulphurization has desulfurization degree It is high, device is reliable for operation, simple operation and other advantages, thus the existing flue gas desulfurization technique in countries in the world is mainly with wet desulphurization It is main.Traditional Wet Flue Gas Desulfurization Technique mainly has limestone-gypsum method, double alkali method desulfurizing, sodium alkali desulfurization, ammonia process of desulfurization method etc..
For containing H2The processing of S sour gas, it is industrial at present it is more commonly used there are two types of recovery technologies, one is uses Fixed bed catalytic oxidation, most common method are claus process；Another kind is U.S. Merichem company gas technology product The LO-CAT technique of company (GTP) exploitation.
Traditional Cross unit is made of a high temperature section and two or three conversion zones.High temperature section includes H2S combustion furnace And waste heat boiler, Claus method are to utilize the H in gas2S makes H in Crouse's combustion furnace2S portion oxidation generates SO2, burning Reaction equation is H2S+1.5O2→SO2+H2O, there are about 1/3 H2S is anti-in combustion furnace with air at a temperature of 1200 DEG C or so SO should be generated2, remaining unreacted H2The same SO of S2Claus reaction is continued to complete by means of catalyst in the lower conversion zone of temperature Generate sulphur.Reaction equation in Claus conversion device is 2H2S+SO2→3S+2H2O。
The reaction process of LO-CAT technique carries out in a kind of weakly alkaline liquid-phase system, will using chelating iron catalyst H2S is converted into elemental sulfur.Its reaction principle are as follows: H2After S gas is dissolved in water, it is ionized into H+And HS-: H2S→H++HS-.In solution Catalyst Fe3+With HS-Redox reaction, HS occurs-It is converted to elemental sulfur, Fe3+Then it is reduced to Fe2+: HS-+2Fe3+→ S+2Fe2++H+.The technique uses the regenerating medium of air (oxygen) as iron catalyst, by Fe2+It is oxidized to Fe3+, make catalyst Activity recovery, process are as follows: 2Fe2++1/2O2+H2O→2Fe3++2OH-.Total chemical equation are as follows: H2S+1/2O2→S+ H2O
LO-CAT technique can only be handled containing H2The sour gas of S, by H2S is converted into elemental sulfur.After claus process and various improvement Claus process to H in unstripped gas2S content requires, H in unstripped gas2S content will at least reach 10% or more, if raw material H in gas2S content is lower, needs to enter Cross unit after concentrate is handled；At method of the claus process using burning Reason contains H2The sour gas of S, thus gas to be processed cannot directly enter Crouse's combustion furnace if having combustibility, it is necessary to The techniques such as amine purification are first passed through by H2S removes out subsequently into claus oven；Claus process need to first make H2S portion oxidation life At SO2Then the two reaction generates sulphur, since claus process desulfuration efficiency is limited, needs more reactor tandems reactions, instead Answer temperature higher；As environment protection emission index is more and more harsher, it is necessary to which mating claus tail-gas clean-up device is wanted with meeting environmental protection It asks.In addition, LO-CAT technique and claus process can only be handled containing H2The sour gas of S is difficult to handle H simultaneously2S gas and SO2 Gas, for the deficiency of two kinds of technique, developing some can be handled simultaneously containing H2S and SO2The technique of gas.
JGC Corporation discloses a kind of Crouse carried out in the pure water without any additive in CN86101352 Reaction, the H when the pH value of aqueous medium in reactor is lower than 22S and SO2The reaction that liquid phase generates sulphur is the strongest, thus uses Reaction pressure > 5kg/cm2Liquid-phase claus reaction Recovered sulphur is carried out under conditions of (gauge pressure), pH value<2, temperature>120 DEG C.
CN201310546164.X discloses a kind of side for using water mist and water vapour as catalyst treatment hydrogen sulfide gas Method makes H using water mist and water vapour as catalyst2S and SO2It reacts, optimal reaction temperature is 50 ~ 60 DEG C, and sulphur turns Rate can reach 90% or so.
CN201310071884.5 discloses the catalyst system and its technique of a kind of industrial sulphur-containing exhaust gas desulfurization process, this is urged Change system includes polyalcohol, acidic catalyst and water, and reaction process uses low temperature aqueous phase reactions, while not containing H to two stocks2S And SO2Exhaust gas handled, total sulfur removal rate is improved to 99.95%.
CN201610841891.2 discloses a kind of preparation method of sulphur nanoparticulate dispersion, and this method is mainly in solution H is carried out in phase2S and SO2Redox reaction, the mixing of solution Xiang Weishui or Small molecule organic solvents soluble easily in water and water Solution, the Small molecule organic solvents being added are ethyl alcohol, methanol, dimethylformamide etc., in order to which the sulphur made is received Rice grain has better dispersion stabilization；40~80 DEG C of above-mentioned system reaction temperature, is in solution mutually during the reaction Stirring, so that H2S and SO2It sufficiently and is uniformly mixed in solution phase, the small and uniform sulphur nanometer of size can be made Grain dispersion liquid, the sulphur active material as secondary power supply technology (lithium-sulfur cell etc.).
CN201110075021.6 discloses a kind of containing H2The sulfur method of S mixed gas is 0 ~ 80 DEG C in reaction temperature, H will be contained2S and SO2Mixed gas is passed through the spray absorber or Spray column for being marked with tetramethyl guanidine hydroxy-acid salt composite desulfurizing agent Middle circulation, the two is reacted in the liquid phase generates sulphur.
Korean Institute of Science and Technology discloses a kind of while removing H in CN200580018462.52S and SO2Desulfurization Method, aqueous solution of the mixed gas with water or containing the first different-phase catalyst for desulfurization contact, to utilize SO2To aoxidize H2S, The treatment effeciency of tail gas containing 3 ~ 5% sulphur can be up to 99% or more.
Compagnie Francise des Petroles has applied a series of containing H2S and SO2The processing method and equipment of mixed gas, In CN200610058953.9 disclosed method, the temperature that mixed gas is in contact with the solvent containing catalyst system is 20 ~ 160 DEG C, catalyst system at least contains the functional group A being made of carboxylic acid functional at least one and has at least one functional group B Compound, functional group B have at least one nitrogen-atoms and under conditions of implementing the method at least one function Group A carries out acid-base class reaction；CN97120663.5, CN96196144.9 and CN97120546.9 are individually disclosed to containing H2S With SO2The processing method and equipment of mixed gas.
In above-mentioned disclosed patent, H2S and SO2Pressure, temperature and the pH value for reacting required in pure water are very severe It carves, reaction is both needed to that buffer solution or catalyst is added in organic solvent or aqueous solution, to keep organic solvent or aqueous solution is Acidity, acid stronger (pH value is lower) are more conducive to the progress of reaction, and device needs regular replenishment buffer solution or catalysis when running Agent is to keep reacting required acid condition, thus device operating cost increases；It is slow due to containing in resulting liquid phase sulphur iodine solution Solution or catalyst are rushed, the purity of sulfur product is unable to satisfy the market demand, thus needs mating sulphur refining plant to improve sulphur The purity of sulphur product.
Summary of the invention
Hydrogen sulfide and sulfur dioxide severe reaction conditions in the liquid phase in the prior art, generally require catalyst or buffering Side reaction easily occurs in the process for liquid, and obtained sulfur product impurity is more, brings difficulty, in order to solve the above problem, this hair to purification The process unit and process of bright quasi- offer hydrogen sulfide and sulfur dioxide liquid phase reactor desulfurization, the process unit are directed to this hair Bright method synchronous realizes the product sulfur, it can be achieved that hydrogen sulfide and sulfur dioxide being sufficiently mixed in reaction solution and react The separation of sulphur obtains the sulphur of purity is high, and reaction solution is recycled, which can safe and stable, long period fortune Row.
To realize the above-mentioned technical purpose, The technical solution adopted by the invention is as follows:
The technical purpose of first aspect present invention is to provide the process unit of hydrogen sulfide and sulfur dioxide liquid phase reactor desulfurization, including Reactor and separator, the reactor are from top to bottom followed successively by tail gas absorption area, reaction zone and decanting zone；The decanting zone connects Separator is connect, the other end of separator is connected at the top of the tail gas absorption area of reactor；The reaction zone is provided with flue, It is fixed on reactor, the flue is made of gas supervisor and gas service pipe, and the gas supervisor is by supervisor I and supervisor The tee pipe T of II composition, supervisor I are opened on reaction zone wall, extend horizontally to reactor center and be connected to supervisor II, main Pipe II is set to reactor center and perpendicular to supervisor I, and the supervisor II is from top to bottom connected with several groups gas service pipe, and every group Gas service pipe in the horizontal direction to wall stretch and it is symmetrical, each pipeline interconnects in the flue, be responsible for II both ends Closing.
In above-mentioned process unit, further, the gas service pipe is arranged 1 ~ 6 group, is preferably provided with 2 ~ 4 groups.
In above-mentioned process unit, further, every group of gas service pipe is provided with 2 ~ 8 branch pipes, and every branch pipe is circular arc Type pipe.The design of circular arc type pipe is conducive to reaction gas and forms motive force to reaction solution after wherein spraying, and promotes to react molten Liquid rotates in reactor, is formed from mixing effect, can greatly increase dissolution of the gas in reaction solution, and make its dispersion Uniformly, reaction rate is improved.
In above-mentioned process unit, further, the diameter ratio of the tail gas absorption area and reaction zone is 0.1:1 ~ 1: 1, when tail gas absorption area diameter is less than reaction zone, the two is connected by cone-shaped variable diameter.
In above-mentioned process unit, further, tower tray and/or filler are provided in the tail gas absorption area.It is described Tower tray setting is at least one layer of, and the excellent tower tray of the tower tray selection performance of anti-blockage selected from float valve tray, screen hole type tower tray, is led To at least one of screen hole type tower tray, solid tongue tower tray, directional float tray and combined trapezoid spray tray；The filler is filled out selected from Raschig ring Material, Pall ring filler, intalox saddle, berl saddle, becket intalox saddle, ladder ring packing, nanotesla ring filler, corrugated plating are filled out At least one of material and grid packing.
In above-mentioned process unit, further, the decanting zone is cylinder, dish, hemispherical, elliposoidal or falls Cone, preferably hemispherical, elliposoidal or inverted conical shape, most preferably inverted conical shape.
The technical purpose of second aspect of the present invention is to provide anti-using above-mentioned process unit progress hydrogen sulfide and sulfur dioxide liquid phase The process for answering desulfurization is that hydrogen sulfide containing gas and the gas containing sulfur dioxide are passed through reaction zone by flue, reacts Area and decanting zone are provided with reaction solution, and the reaction solution includes water and at least one organic basic chemical combination that can be dissolved in water Object, the organic basic compound make pH value >=7.2 of the solution；Hydrogen sulfide reacts the sulphur generated with sulfur dioxide and is sink to Decanting zone obtains sulphur and reaction solution through solid-liquor separation, reaction solution is back to the top in tail gas absorption area into separator Portion, the reaction end gas counter current contacting with reaction zone, after being absorbed to the complete reaction gas of unreacted, into reaction zone, warp Tail gas discharge after absorption.
In above-mentioned process, the pH value of reaction solution is 7.2 ~ 13.0 preferably in reaction zone；It is furthermore preferred that its pH value It is 8.0 ~ 12.0, most preferably 8.0 ~ 10.0.
In above-mentioned process, as a further preference, the reaction solution in reaction zone presses its total weight, wherein The mass fraction of organic basic compound is 0.1% ~ 30%；Preferably 2% ~ 30%；More preferably 5% ~ 20%.
In above-mentioned process, the solubility >=0.1g/100g water of selected organic basic compound in water, preferably Solubility >=1g/100g water.
In above-mentioned process, it should be noted that the selection of the organic basic compound in solution is relatively broad, former It can be dissolved in water on then, and have certain solubility, the organic basic compound for keeping solution presentation alkaline to can promote this in water and take off The progress of reaction of Salmon-Saxl, those energy and water can achieve better effect with the organic basic compound that arbitrary proportion dissolves each other.
In above-mentioned process, as a further preference, the organic basic compound contains in its structural formula There is the compound of at least one nitrogen-atoms；Contain 1 ~ 3 amino nitrogen compound preferably in its structural formula, more preferably contains 1 A or 2 amino nitrogen compounds.
In above-mentioned process, as a further preference, the organic basic compound is in following compound At least one: azanol, the fatty amines of C1 ~ C10, the alcamines of C1 ~ C10, the alicyclic ring amine of C1 ~ C10, C6 ~ C10 arylamine Class, pyridine, pyridine derivatives, imidazoles, imidazole derivative, pyrazine, Pyrazine derivative, pyrazoles or pyrazole derivatives.
Further, the pyridine derivatives, imidazole derivative, Pyrazine derivative or pyrazole derivatives are pyrrole The derivative that H in pyridine, imidazoles, pyrazine or pyrazoles is replaced by alkyl, amino, alkyl amino, hydroxyl or alkylol.The alkane The alkyl that alkyl in base, alkyl amino and alkylol is C1 ~ C3.
In above-mentioned process, as a further preference, the fatty amines are the fatty amines of C1 ~ C6；It is described The arylamine that alicyclic ring amine that alcamines that alcamines is C1 ~ C6, the alicyclic ring amine are C1 ~ C6, the arylamine class are C6 ~ C8 Class.
In above-mentioned process, as more specific embodiment, the organic basic compound is selected from azanol, front three Amine, ethylenediamine, 1,2- propane diamine, 1,3- propane diamine, ethanol amine, diethanol amine, triethanolamine, diglycolamine, isopropanolamine, N- Methyl diethanolamine, N, N- dimethylethanolamine, N, N- diethyl ethylene diamine, benzene methanamine, O-phthalic amine, m-xylene diamine, P dimethylamine, nafoxidine, 1- methyl -3- pyrrolidinol, hexahydropyridine, morpholine, triethylenediamine, diethylidene three Amine, piperazine, 2- methyl piperazine, pyridine, 2- picoline, 3- picoline, 4- picoline, pyrazine, hydroxypyrazine, amino pyrrole At least one of piperazine, methylpyrazine, imidazoles and pyrazoles.
It will be apparent to a skilled person that in the desulphurization reaction of hydrogen sulfide and sulfur dioxide, in liquid phase environment Under, the raising of pressure and temperature is conducive to the progress of reaction, and in previous research, the condition of desulphurization reaction occurs for the two liquid phase It is more harsh, it generally requires and improves reaction temperature and increase reaction pressure.But in the method for the invention, to hydrogen sulfide and dioxy The temperature and pressure for changing reaction of Salmon-Saxl desulfurization has no particular/special requirement, from the point of view of saving the energy, at this both under normal temperature and pressure The reaction system of invention can be easy to react.The reaction system new as one, the present invention still provide suitable reaction Temperature and pressure: temperature is 0 ~ 90 DEG C, preferably 20 ~ 35 DEG C；Reaction pressure be 0.1 ~ 5MPa, preferably 0.1 ~ 1.5MPa, more Preferably normal pressure.
In above-mentioned process, as a further preference, H in the reaction gas being passed through2S or SO2Volume fraction difference It is 0.1 ~ 100%, preferably 3 ~ 100%, more preferably 10 ~ 100%；In above-mentioned process, the hydrogen sulfide containing gas master To derive from petroleum refining, coal chemical industry, natural gas processing, fine chemistry industry, papermaking, pharmacy, chemical fertilizer, sewage treatment, geothermal power generation Equal industrial tail gas, including but not limited to pure hydrogen sulfide, sour gas, Claus tail gases, natural gas purification tail gas and with The upper gas etc. by concentration.The gas containing sulfur dioxide includes but is not limited to pure sulfur dioxide gas, S-Zorb device Regenerated flue gas, Sulphuric acid tail gas, fire coal boiler fume, coal-fired plant flue gas, catalytic cracking catalyst regenerated flue gas, technique heating Kiln gas, coking flue gas, steel sintering flue gas and flue gas of concentration etc..
Further, in reaction gas hydrogen sulfide and sulfur dioxide theoretical reaction ratio 2:1, it is excellent in this process Choosing is passed through according to 0.1:1 ~ 5:1 ratio, more preferably 1:1 ~ 3:1；Most preferably with the mixing of 2:1 ratio.If being to remove hydrogen sulfide Purpose is then passed through the gas containing sulfur dioxide by the reaction ratio amount of skipping over；If for the purpose of scrubbing CO_2, by reaction ratio The example amount of skipping over is passed through hydrogen sulfide containing gas.
In above-mentioned process, after the hydrogen sulfide containing gas can be pre-mixed with the gas containing sulfur dioxide It is passed through reactor together, or is first passed through one of reaction gas certain time, after certain meltage is reached in reaction solution, It is passed through another gas again.It is wherein preferably first passed through a kind of reaction gas, makes in reactor (pH range after reaction solution pH slant acidity Reach 7.0 or less), then it is passed through another reaction gas, the two can more quickly and effectively react；With this corresponding, preferably exist An online pH detector is provided in reactor.
In above-mentioned process, it should be noted that the drusen that reaction zone generates in reaction process is in itself weight It is deposited under power effect to the decanting zone of reactor bottom, sulphur slurries are continuously or intermittently drawn to point online from decanting zone outlet From device, after solid-liquor separation, sulphur is by repeatedly washing and the dry sulphur that high-purity can be obtained；The reaction solution isolated returns It flow to tail gas absorption area and enters in reactor and recycle, can also supplement fresh reaction solution thereto, be back to tail together The top in aspiration area.
Compared with prior art, the present invention has the advantage that
(1) process unit of the invention is used, the flue design of reactor can be such that the reaction gas into the reactor is formed There is the injection of certain radian, the liquid in driving a reaction area forms rotation clockwise or counterclockwise, realizes from stirring, has It is evenly dispersed in reaction solution conducive to gas, significantly increase rate of dissolution and reaction speed of the gas in reaction solution Rate.
(2) the sulphur slurries rotation in reactor lower part decanting zone is driven when liquid in rotation in reactor, prevents sulphur Fouling is deposited on wall, is avoided drusen cohesion agglomeration obstruction pipeline, is guaranteed equipment safety, stabilization, long-term operation.
(3) process of hydrogen sulfide of the invention and sulfur dioxide reaction desulfuration, using containing organic basic compound Water is reaction solution, realizes H2S and SO2Desulphurization reaction under aqueous environment, and can realize under normal temperature and pressure conditions, two Person greatly shortens in the reaction time, illustrates that the rate of dissolution of the two in water tends to be close, to be easier to react.And it is another Aspect, with H2S and SO2Dissolution, the acid of reaction solution increase (pH value reduction) therewith, neutralized organic basic compound Addition bring alkalinity, acidic environment is also beneficial to the progress of reaction, thus the two reaction generates the rate of sulphur and substantially mentions It is high.
(4) process unit and method of the invention, H are utilized2S and SO2Can react desulfurization at normal temperatures and pressures, instead Answer the response time lower than 15 seconds, required reaction condition is mild, the simple easy processing of equipment, low investment, safe operation.
(5) in technique of the invention, the reaction solution used absorbs H2S and SO2It is not necessarily to buffer solution or catalyst afterwards It reacts and generates sulphur, reduce the operating cost of device, sulphur is free of buffer solution or catalyst in resulting slurries, holds It is easily separated, the expense of sulphur purification is also reduced, the purity of sulfur product is improved.
(6) in technique of the invention, the reaction solution of reaction zone can recycle after isolation, can absorbing reaction tail gas In hydrogen sulfide and sulfur dioxide make tail gas qualified discharge, and the hydrogen sulfide in reaction end gas can be recycled and sulfur dioxide is further Reaction, increases the yield of sulphur and the processing capacity to exhaust gas.
(7) claus process after traditional and improvement is to H in unstripped gas2S content requires, and needs to reach 10% or more, It is lower for concentration to carry out entering Cross unit after concentrate processing；And reaction system of the invention is suitable for arbitrary proportion H2S and SO2Reaction, can cope with containing H2The sour gas of S and contain SO2Flue gas flow and the operating condition that changes greatly of composition.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the process unit schematic diagram of embodiment 1；
Fig. 2 is the top view of reaction zone flue in Fig. 1；
Wherein, 100. reactor, 200. separators, 101. tail gas absorption areas, 102. reaction zones, 103. decanting zones, 104. gases Pipe, 1041. gases supervisor, 1041-1. are responsible for I, 1041-2. supervisor II, 1042. gas service pipes, 105.pH on-line computing model.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with Any mode limits the present invention.
Embodiment 1
The process unit of hydrogen sulfide and sulfur dioxide liquid phase reactor desulfurization, as shown in Figure 1, including reactor 100 and separator 200, the reactor 100 is from top to bottom followed successively by tail gas absorption area 101, reaction zone 102, decanting zone 103；Tail gas absorption area 101 with the diameter ratio of reaction zone 102 be 1:2, and the two is connected by cone-shaped variable diameter.Tail gas absorption area 101 is provided with valve tower Disk；It is provided with flue 104 on the reaction zone 102, is fixed on reactor 100, the flue 104 is responsible for by gas 1041 and gas service pipe 1042 form, gas supervisor 1041 is by I 1041-1 of supervisor and is responsible for the fourth that II 1041-2 forms Font pipe, I 1041-1 of supervisor are opened on the wall of reaction zone 102, extend horizontally to 100 center of reactor and be connected to supervisor II 1041-2, supervisor II 1041-2 be set to reactor 100 be centrally and perpendicular to supervisor I 1041-1, II 1041-2 of the supervisor by Up to 4 groups of gas service pipes 1042 of lower connection, every group of gas service pipe 1042 is provided with 4 arc-shaped branch pipes, in the horizontal direction to Wall stretching, extension is simultaneously symmetrical, as shown in Figure 2；Each pipeline interconnects in the flue 104, is responsible for II 1041-2, two end seal It closes；PH on-line computing model 105 is additionally provided in the wall of reaction zone 102, the decanting zone 103 is inverted conical shape, and bottom goes out Mouth connection separator 200, the other end of separator 200 are connected to 101 top of tail gas absorption area of reactor.
Embodiment 2
The process for carrying out hydrogen sulfide and sulfur dioxide reaction desulfuration using process unit shown in FIG. 1 is as follows:
First by pure SO2Gas is passed into the reaction zone 102 of reactor 100 via flue 104, and gas is successively by supervisor I 1041-1 and II 1041-2 of supervisor are sprayed by gas service pipe 1042 to the reaction solution of reaction zone, and reaction solution is organic basic The aqueous solution of compound drives reaction solution rotation, realizes liquid in reactor and is conducive to SO from the effect of stirring2Gas It is evenly dispersed in reaction solution, and significantly increase SO2Rate of dissolution of the gas in reaction solution, when pH is supervised online When survey instrument 105 is shown as 6.5, start to be passed through pure H into reaction zone 1022S gas, the liquid in reaction zone 102 quickly become Huang Color, it is seen that the two immediate response generates sulphur；Sulphur enters decanting zone 103 under the effect of gravity, in company with part reaction solution from The outflow of 103 bottom of decanting zone, squeezes into separator 200 by pump, sulphur and reaction solution is separated, to isolated reaction solution It is sent after pump pressurization after the fresh reaction solution of middle supplement to 101 top of tail gas absorption area, first reacts tail in reaction zone 102 The SO that the circulation of vital energy in the wrong direction is not reacted completely on a small quantity into contact removing tail gas2And H2S enters back into reaction zone 102 and is recycled, through inhaling Tail gas emptying after receipts.
Organic basic compound aqueous solution used in above-mentioned technique is benzene methanamine solution, mass fraction 30%, SO2 Gas flow is 300mL/min, H2S gas flow is 600mL/min.It is passed through H2The reaction response time of two gases is 5s after S, Reaction temperature and pressure in reactor 100 are normal temperature and pressure.
It is to be installed set even running 2h after, the sulphur separating obtained to separator 200 is repeatedly washed, dry weighing, root According to MaterialBalance Computation, H2The conversion ratio of S is 94.8%.
Embodiment 3
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
In addition to organic basic compound aqueous solution is 20% benzene methanamine solution, other conditions are the same as embodiment 2.
It is passed through H2The reaction response time of two gases is 5s after S, according to MaterialBalance Computation, H2The conversion ratio of S is 94.9%.
Embodiment 4
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the isopropanolamine solution that organic basic compound aqueous solution is 20%, SO2Gas flow is 400mL/min, H2S gas Flow be 800mL/min outside, other conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 98.5%.
Embodiment 5
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
In addition to organic basic compound aqueous solution is 15% trimethylamine solution, other conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 97.3%.
Embodiment 6
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
The diglycolamine that organic basic compound aqueous solution used is 15%, H is first passed through into reactor2S gas, flow are 300mL/min when pH on-line computing model 105 is shown as 6.8, then is passed through SO thereto2Gas, flow 150mL/min, His condition is the same as embodiment 2.
According to MaterialBalance Computation, SO2Conversion ratio be 98.8%.
Embodiment 7
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
The pyridine that organic basic compound aqueous solution used is 5%, H is first passed through into reactor2S gas, flow 500mL/ Min when pH on-line computing model 105 is shown as 6.8, then is passed through SO thereto2Gas, flow 250mL/min, other conditions With embodiment 2.
According to MaterialBalance Computation, SO2Conversion ratio be 97.0%.
Embodiment 8
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the nafoxidine solution that organic basic compound aqueous solution is 2%, SO2Gas flow is 250mL/min, H2S gas Flow is outside 500mL/min, and other conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 92.8%.
Embodiment 9
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
1- methyl -3- the pyrrolidinol that organic basic compound aqueous solution used is 0.5%, H is first passed through into reactor2S gas Body, flow 300mL/min when pH on-line computing model 105 is shown as 6.8, then are passed through SO thereto2Gas, flow are 150mL/min, other conditions are the same as embodiment 2.
According to MaterialBalance Computation, SO2Conversion ratio be 78.8%.
Embodiment 10
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except 1, the 3- propane diamine solution that organic basic compound aqueous solution is 20%, SO2Gas flow is 500mL/min, H2S gas The flow of body is outside 1000mL/min, and other conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 99.2%.
Embodiment 11
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
The ethylenediamine solution that used organic basic compound aqueous solution is 10%, SO2Total gas flow rate is 300mL/min, H2The total flow of S gas is 600mL/min；Other operating conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 96.6%.
Embodiment 12
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Terephthaldehyde's amine aqueous solution that used organic basic compound aqueous solution is 1%, SO2Total gas flow rate is 150mL/ Min, H2The total flow of S gas is 300mL/min；Other operating conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 74.2%.
Embodiment 13
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the triethylenediamine solution that organic basic compound aqueous solution is 20%, SO2Total gas flow rate is 500mL/min, H2The total flow of S gas is outside 1000mL/min, and other conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 99.5%.
Embodiment 14
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the piperazine solution that organic basic compound aqueous solution is 10%, SO2Gas flow is 350mL/min, H2The stream of S gas Amount is outside 700mL/min, and other conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 98.5%.
Embodiment 15
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the pyrazine solution that organic basic compound aqueous solution is 3%, SO2Gas flow is 500mL/min, H2The flow of S gas Outside for 1000mL/min, other conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 96.9%.
Embodiment 16
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the hydroxypyrazine solution that organic basic compound aqueous solution is 5%, SO2Gas flow is 200mL/min, H2S gas Flow is outside 400mL/min, and other conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 96.7%.
Embodiment 17
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the morpholine solution that organic basic compound aqueous solution is 25%, SO2Gas flow is 1000mL/min, H2The stream of S gas Amount is outside 2000mL/min, and other conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 99.7%.
Embodiment 18
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the imidazole solution that organic basic compound aqueous solution is 10%, SO2Gas flow is 500mL/min, H2The stream of S gas Amount is outside 1000mL/min, and other conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 98.8%.
Embodiment 19
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the imidazole solution that organic basic compound aqueous solution is 6%, SO2Gas flow is 500mL/min, H2The flow of S gas Outside for 1000mL/min, other conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 96.5%.
Embodiment 20
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the diethylenetriamines solution that organic basic compound aqueous solution is 5%, SO2Gas flow is 400mL/min, H2S gas The flow of body is outside 800mL/min, and other conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 97.1%.
Embodiment 21
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the N methyldiethanol amine solution that organic basic compound aqueous solution is 10%, SO2Gas flow is 200mL/min, H2The flow of S gas is outside 400mL/min, and other conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 99.7%.
Embodiment 22
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the N methyldiethanol amine solution that organic basic compound aqueous solution is 15%, SO2Gas uses S-Zorb regenerated flue gas (SO2Volume fraction is 4.5%) flow 500mL/min, H2S gas uses certain petroleum chemical enterprise's sour gas (dry gas, liquefied gas etc. The rich solution of desulfurizer regenerates generated sour gas, wherein H2S volume content be 55%), flow be 80mL/min outside, other Condition is the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 96.8%.
Embodiment 23
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the N that organic basic compound aqueous solution is 8%, N- dimethylethanolaminesolution solution, SO2Gas is using catalytic cracked regenerated Flue gas (SO2Volume fraction is 1.45%) flow 1000mL/min, H2S gas uses certain petroleum chemical enterprise's sour gas (submarine discharge Sour gas, wherein H2S volume content is that 60%), flow is outside 50mL/min, and other conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 94.0%.
Embodiment 24
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the triethanolamine solution that organic basic compound aqueous solution is 20%, SO2Gas uses pure SO2, flow 300mL/ Min, H2S gas is using certain petroleum chemical enterprise's sour gas (sour gas after concentrate, wherein H295%) S volume content is that flow is 630mL/min, other conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 99.2%.
Embodiment 25
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the triethanolamine solution that organic basic compound aqueous solution is 12%, SO2Gas uses S-Zorb regenerated flue gas (SO2Body Fraction is 4.5%) flow 1000mL/min, H2S gas uses certain petroleum chemical enterprise's sour gas (desulfurization such as dry gas, liquefied gas The rich solution of device regenerates generated sour gas, wherein H2S volume content is that 55%), flow is other conditions outside 160mL/min With embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 97.2%.
Embodiment 26
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the triethanolamine solution that organic basic compound aqueous solution is 6%, SO2Gas uses S-Zorb regenerated flue gas (SO2Body Fraction is 4.5%) flow 1000mL/min, H2S gas uses certain petroleum chemical enterprise's sour gas (desulfurization such as dry gas, liquefied gas The rich solution of device regenerates generated sour gas, wherein H2S volume content is that 55%), flow is other conditions outside 160mL/min With embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 95.1%.
Embodiment 27
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the 4- picoline solution that organic basic compound aqueous solution is 12%, SO2Gas uses fire coal boiler fume (SO2Body Product content is 0.5%) flow 5000mL/min, H2S gas using certain petroleum chemical enterprise's sour gas (sour gas after concentrate, Wherein H2S volume content is that 95%), flow is outside 50mL/min, and other conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 94.2%.
Embodiment 28
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the mixing amine aqueous solution that organic basic compound aqueous solution is 5% 2- picoline and 5% 1,2- propane diamine, SO2Gas Body uses fire coal boiler fume (SO2Volume content is 0.5%) flow 3000mL/min, H2S gas is using certain petroleum chemical enterprise acid Property gas (sour gas after concentrate, wherein H2S volume content is that 95%), flow is the same embodiment of other conditions outside 30mL/min 2。
According to MaterialBalance Computation, H2The conversion ratio of S is 92.7%.
Embodiment 29
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except the mixing amine aqueous solution that organic basic compound aqueous solution is 1% methylpyrazine and 9% N methyldiethanol amine, SO2 Gas uses regeneration fume from catalytic cracking (SO2Volume fraction is 1.45%) flow 2000mL/min, H2S gas uses certain stone Change enterprise's sour gas (submarine discharge sour gas, wherein H2S volume content is that 60%), flow is outside 95mL/min, and other conditions are same Embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 96.0%.
Embodiment 30
The process of hydrogen sulfide and sulfur dioxide reaction desulfuration is carried out using device shown in FIG. 1:
Except organic basic compound aqueous solution be 5% diethylenetriamines, 5% ethanol amine and 5% N, N- diethyl ethylene diamine Mixing amine aqueous solution, SO2Gas uses regeneration fume from catalytic cracking (SO2Volume fraction is 1.45%) flow 2000mL/min, H2S gas is using certain petroleum chemical enterprise's sour gas (submarine discharge sour gas, wherein H2S volume content is 60%) flow 95mL/ Outside min, other conditions are the same as embodiment 2.
According to MaterialBalance Computation, H2The conversion ratio of S is 97.8%.

Claims (19)

1. the process unit of hydrogen sulfide and sulfur dioxide liquid phase reactor desulfurization, including reactor and separator, the reactor by Tail gas absorption area, reaction zone and decanting zone are followed successively by under；The decanting zone connects separator, the other end connection of separator To the tail gas absorption area of reactor；The reaction zone is provided with flue, is fixed on reactor, the flue by Gas supervisor and gas service pipe composition, the gas supervisor is the tee pipe T being made of supervisor I and supervisor II, and supervisor I is open In on reaction zone wall, extending horizontally to reactor center and be connected to supervisor II, supervisor II is set to reactor center and vertical In supervisor I, the supervisor II is from top to bottom connected with several groups gas service pipe, and every group of gas service pipe is stretched to wall in the horizontal direction It opens up and symmetrical, each pipeline interconnects in the flue, and supervisor II is closed at both ends.
2. process unit according to claim 1, which is characterized in that the gas service pipe is arranged 1 ~ 6 group, it is preferably provided with 2 ~ 4 groups.
3. process unit according to claim 1, which is characterized in that every group of gas service pipe is provided with 2 ~ 8 branch pipes, and every Branch pipe is circular arc type pipe.
4. process unit according to claim 1, which is characterized in that the diameter ratio in the tail gas absorption area and reaction zone For 0.1:1 ~ 1:1, when tail gas absorption area diameter is less than reaction zone, the two is connected by cone-shaped variable diameter.
5. process unit according to claim 1, which is characterized in that be provided in the tail gas absorption area tower tray and/ Or filler.
6. process unit according to claim 1, which is characterized in that the decanting zone is cylindrical, dish, hemisphere Shape, elliposoidal or inverted conical shape, preferably hemispherical, elliposoidal or inverted conical shape.
7. carrying out hydrogen sulfide and sulfur dioxide liquid phase reactor desulfurization using process unit described in claim 1 ~ 6 any one Process is that hydrogen sulfide containing gas and the gas containing sulfur dioxide are passed through reaction zone, reaction zone and sedimentation by flue Area is provided with reaction solution, and the reaction solution includes water and at least one organic basic compound that can be dissolved in water, described to have Machine alkali compounds makes pH value >=7.2 of the solution；Hydrogen sulfide reacts the sulphur generated with sulfur dioxide and is sink to decanting zone, into Enter separator, obtains sulphur and reaction solution through solid-liquor separation, reaction solution is back to the top in tail gas absorption area, with reaction zone Reaction end gas counter current contacting, the tail gas after being absorbed to the complete reaction gas of unreacted, into reaction zone, after absorbing Discharge.
8. process according to claim 7, which is characterized in that in reaction zone the pH value of reaction solution be 7.2 ~ 13.0, preferably 8.0 ~ 12.0.
9. process according to claim 7, which is characterized in that the reaction solution in reaction zone presses its total weight, Wherein the mass fraction of organic basic compound is 0.1% ~ 30%；Preferably 2% ~ 30%.
10. process according to claim 7, which is characterized in that selected organic basic compound in water molten Xie Du >=0.1g/100g water, preferably solubility >=1g/100g water.
11. process according to claim 7, which is characterized in that the organic basic compound is selected from its structural formula In the compound containing at least one nitrogen-atoms.
12. process according to claim 11, which is characterized in that the organic basic compound is selected from its structural formula In contain 1 ~ 3 amino nitrogen compound, preferably contain 1 or 2 amino nitrogen compounds.
13. process according to claim 11, which is characterized in that the organic basic compound is selected from following chemical combination At least one of object: azanol, the fatty amines of C1 ~ C10, the alcamines of C1 ~ C10, the alicyclic ring amine of C1 ~ C10, C6 ~ C10 Arylamine class, pyridine, pyridine derivatives, imidazoles, imidazole derivative, pyrazine, Pyrazine derivative, pyrazoles or pyrazoles are derivative Object.
14. process according to claim 13, which is characterized in that the pyridine derivatives, imidazole derivative, Pyrazine derivative or pyrazole derivatives are the H in pyridine, imidazoles, pyrazine or pyrazoles by alkyl, amino, alkyl amino, hydroxyl The derivative that base or alkylol replace.
15. process according to claim 13, which is characterized in that the fatty amines are the fatty amines of C1 ~ C6； The virtue that alicyclic ring amine that alcamines that the alcamines is C1 ~ C6, the alicyclic ring amine are C1 ~ C6, the arylamine class are C6 ~ C8 Amine.
16. process according to claim 13, which is characterized in that the organic basic compound is selected from azanol, three Methylamine, ethylenediamine, 1,2- propane diamine, 1,3- propane diamine, ethanol amine, diethanol amine, triethanolamine, diglycolamine, isopropanolamine, N methyldiethanol amine, N, N- dimethylethanolamine, N, N- diethyl ethylene diamine, benzene methanamine, O-phthalic amine, isophthalic diformazan Amine, p dimethylamine, nafoxidine, 1- methyl -3- pyrrolidinol, hexahydropyridine, morpholine, triethylenediamine, diethylidene Triamine, piperazine, 2- methyl piperazine, pyridine, 2- picoline, 3- picoline, 4- picoline, pyrazine, hydroxypyrazine, amino At least one of pyrazine, methylpyrazine, imidazoles and pyrazoles.
17. process according to claim 7, which is characterized in that H in the reaction gas being passed through2S or SO2Volume fraction Respectively 0.1 ~ 100%.
18. process according to claim 7, which is characterized in that the ratio of hydrogen sulfide and sulfur dioxide in reaction gas For 0.1:1 ~ 5:1.
19. process according to claim 7, which is characterized in that hydrogen sulfide containing gas and the gas containing sulfur dioxide Body is passed through simultaneously, or is first passed through a kind of reaction gas and is made in reactor after reaction solution pH < 7.0, then is passed through another reaction gas.
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