CN108722139A

CN108722139A - A kind of method and device of processing sour gas

Info

Publication number: CN108722139A
Application number: CN201710240410.7A
Authority: CN
Inventors: 孟凡飞; 彭德强; 王海波; 王璐瑶; 陈新
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2017-04-13
Filing date: 2017-04-13
Publication date: 2018-11-02
Anticipated expiration: 2037-04-13
Also published as: CN108722139B

Abstract

The present invention provides a kind of method and device of processing sour gas, the NaHS products for meeting state quality standard can be produced while realizing sour gas qualified discharge, by production process the being combined into one process of environmental improvement and chemical products.Compared with prior art, the method for the present invention can economical and efficient to containing CO₂The sour gas of gas and hydrogen sulfide gas is pre-processed, and has been carried out reasonable utilization to the energy in technical process, has been greatly reduced energy consumption；Entire processing procedure environmental protection, reliable, nothing " three wastes " generate.

Description

A kind of method and device of processing sour gas

Technical field

The present invention relates to a kind of method and devices of processing sour gas, more particularly to a kind of carbonated and hydrogen sulfide Sour gas purification and pollutant resourcesization recycle.

Background technology

Sour gas is a kind of processing tail gas generated in petroleum refining process, main component H₂S and CO₂.Refining Factory's sour gas mostlys come from the devices such as sewage stripping, desulphurization of recycle hydrogen and dry gas and desulfuration of liquefied gas.Large-scale refinery's acid Property tolerance is larger（Produce sulphur > 5000t/a per year）, generally all establish the Acidic Gas Treating device of production sulphur（Such as Claus techniques With LO-CAT techniques）, to H₂S is recycled.And for medium and small refinery（Produce sulphur < 5000t/a per year）, due to sour gas Measure small, it is higher to establish sulphur unit cost, and most of small refinery is substantially all handled sour gas by the way of burning and exhausting, this Kind method not only causes the waste of resource, and the SO generated that burns₂Huge pressure is brought to environmental protection.Before 2012, 《Discharge standard of air pollutants》（GB16297-1996）Provide SO₂Concentration of emission is not higher than 960 mg/m³, and it is newest 《Petroleum refining industry pollutant emission standard》（GB31570-2015）From 1 day July in 2017 of regulation existing enterprise, newly-built enterprise From 1 day July in 2015, SO in regeneration fume from catalytic cracking or Furnace tail gas₂Emission limit is 100 mg/m³（Especially Regional limit value is only 50 mg/m³）, acid gas recovering device SO₂Emission limit is 400 mg/m³（Especially regional limit value is 100 mg/m³）.As it can be seen that the Acidic Gas Treating mode of small-sized refinery is difficult to meet environmental requirement at present.For environmental protection and ensure resource Make full use of, to the sour gas of small-sized refinery carry out comprehensive treatment and recycle it is imperative.

Sour gas administers the difference that product is made according to recycling at present, can be divided into and produce sulphur, Sulphuric acid and system Asia Sulfate, NaHS etc. change product.

Producing sulfur product, there are mainly two types of mature technologies, and one is two level Claus+ tail gas hydrogenations reduction+solvent absorptions Technology；Another kind is the LO-CAT technologies of gas technology Products Co., Ltd of Merichem companies of U.S. exploitation.Two level Claus+ tail gas hydrogenations reduction+solvent absorption technical matters is ripe, product sulphur stable quality, but due to long flow path, investment it is big, High energy consumption, equipment safety control require height, and Claus techniques can only handle the sour gas of high concentration, therefore, the technology pair Advantage is had no in the improvement of small sour gas.LO-CAT techniques make H using the iron catalyst of multicomponent chelate₂S is converted into member Plain sulphur can be suitble to acid tolerance to fluctuate larger operating mode, H₂The removal efficiency of S is high.This technology not will produce any harmful useless Gas byproduct, environmentally safe catalyst can be constantly regenerating in processing procedure.But since there are operating costs by LO-CAT The drusen for being slightly worse than claus process with high, sulfur purity and color and luster, and being generated in process of production can occur to block existing As catalyst and the problems such as higher patent royalties in addition so that the technology more difficult popularization in the improvement of small sour gas.

Sour gas relieving haperacidity technology can directly utilize sour gas relieving haperacidity, which saves, is at low cost, adaptable, Production process is easy to operate.But sulfuric acid production process is more complex, takes up a large area, and transport, the storage of sulfuric acid acquire a certain degree of difficulty, As its limiting factor.Sour gas production sulfite process flow is simple, different absorbents can be used realizes that product is various Change, but in its production process there are equipment seriously corroded, maintenance cost is higher and product marketing is unsmooth the problems such as, have certain Limitation.

Less novel absorbent method sulfur removal technology technology of investing, production chemical industry production may be used in the comprehensive utilization of sour gas Product akali sulphide（Na₂S/NaHS）.Akali sulphide can be widely applied to the works such as ore dressing, pesticide, dyestuff, tanning production and organic synthesis Industry.In addition to containing H in sour gas₂Outside S gases, also contain a certain amount of CO₂Gas, during producing akali sulphide, CO₂Gas can produce Na with raw material lye₂CO₃/NaHCO₃Impurity causes process pipe in production process to block, production is caused to fill Set can not long period continuous operation, and there are alkaline consumptions it is high, product purity is poor the problems such as.

What NaHS production technologies disclosed in patent CN102765700A and CN102807193A and NaHS continuous absorptions reacted Two-stage absorption, the protection of level-one alkali and primary adsorption process is arranged in process units, and sour gas uses counter-current absorption mode with alkaline agent, most Solution is concentrated by evaporation afterwards and is dehydrated, is cooled and shaped, packaging process, completes the generating process of NaHS, which is only applicable to pure Hydrogen sulfide absorption process, there is no consider CO₂The influence of gas.CN103551018A disclose a kind of purification of sulfur-containing tail gas with Recoverying and utilizing method, using barium sulphide to CO in gas₂It is removed, obtained H₂S gases can produce the NaHS productions of high-quality Product, but generate barium sulfite and barium carbonate sediment, it is difficult to it handles.One-step method prepares NaHS's disclosed in patent CN1109020A Method, using the liquid containing stereoplasm of lime and sodium sulphate to containing CO₂H₂S gases are handled, and have the generation of the precipitations such as calcium carbonate.Specially In preparation NaHS methods described in sharp CN101186280A and CN101337661A, the problem of equally facing Solid state fermentation.Patent CN103754833A disclose it is a kind of using oil refinery dry gas produce NaHS device and method, using high-gravity technology to dry gas into The processing of row selective desulfurization, obtains 99% H₂The NaHS purity of S gas generations is up to 42% or more, but the technology unstripped gas is located in advance Long flow path is managed, process units is complicated, and rich regeneration of absorption solution energy consumption is higher.CN103446849A, CN103466559A and NaHS production technologies described in CN103638802A equally face flow complexity, and amine liquid regeneration energy consumption is higher in sour gas pretreatment The problems such as.

In conclusion the improvement of small-sized sour gas is needed to consider the factors such as safe and environment-friendly, economy, This just needs a kind of flow short, and small investment is easy to operate, and energy consumption and operating cost are low and have the Synthetic of certain economic benefit Reason mode.

Invention content

In view of the deficiencies of the prior art, the present invention provides a kind of method and device of processing sour gas, can realize acid While property gas qualified discharge, the NaHS products for meeting state quality standard are produced, by the life of environmental improvement and chemical products Production process being combined into one process.Compared with prior art, the method for the present invention can economical and efficient to containing CO₂Gas and The sour gas of hydrogen sulfide gas is pre-processed, and has been carried out reasonable utilization to the energy in technical process, has been greatly reduced energy consumption； Entire processing procedure environmental protection, reliable, nothing " three wastes " generate.

The present invention provides a kind of Acidic Gas Treating device, and described device includes hydration reactor, hydrate neutralizing device, level-one Absorbing reaction device, two level absorbing reaction device and products pot；The gas phase entrance of sour gas feeding line and hydration reactor connects, water The liquid-phase outlet for closing reactor is connect with the liquid phase entrance of hydrate neutralizing device, and hydrate dissolves the liquid-phase outlet and water of device bottom The hydrate working solution suction line connection of reactor is closed, hydrate dissolves gaseous phase outlet and first order absorption reactor at the top of device The connection of gas phase entrance, the gaseous phase outlet of first order absorption reactor connect with the gas phase entrance of two level absorbing reaction device, two level suction The gaseous phase outlet for receiving reactor is connect with clean gas outlet pipeline, three tunnels of liquid-phase outlet point of first order absorption reactor, the first via It is connect with products pot, the second tunnel is dissolved the heat transmission equipment in device through hydrate and connect with products pot, and third road and first order absorption are anti- The liquid phase entrance of device is answered to connect, the liquid-phase outlet of two level absorbing reaction device divides two-way, the wherein first via and first order absorption reactor The connection of liquid phase entrance, the second tunnel connect with the liquid phase entrance of two level absorbing reaction device, the liquid phase entrance of two level absorbing reaction device It is connect with alkali liquor inlet pipeline, products pot outlet is connect through pipeline with the liquid phase entrance of two level absorbing reaction device.

In above-mentioned Acidic Gas Treating device, compressor is set on sour gas feeding line, for ensure acid atmospheric pressure with Hydration reactor operating pressure matches.

In above-mentioned Acidic Gas Treating device, the liquid-phase outlet of the hydration reactor divides two-way, wherein all the way with hydrate Dissolve the liquid phase entrance connection of device, the working solution suction line connection of another way and hydration reactor.

In above-mentioned Acidic Gas Treating device, the liquid-phase outlet of hydrate neutralizing device bottom divides two-way, wherein passing through all the way The hydrate working solution suction line of pipeline and hydration reactor connects, and the liquid phase that another way dissolves device through pipeline with hydrate enters Mouth connection.

In above-mentioned Acidic Gas Treating device, the first order absorption reactor and two level absorbing reaction device react for gas-liquid mass transfer Equipment, specially bubbling column reactor, filler tower reactor, impact flow reactor, rotary drill reactor and venturi reactor In one kind, preferably rotary drill reactor.

In above-mentioned Acidic Gas Treating device, the hydration reactor for the benefit of gas-liquid mass transfer and with good heat transfer effect Equipment, form is unlimited, can be in stirring-type, atomizing, bubble type, sieve-board type, material filling type, hypergravity or shock flow type etc. One kind, preferably using liquid phase as the consersion unit of continuous phase.

In above-mentioned Acidic Gas Treating device, the hydration of the liquid-phase outlet and hydration reactor of hydrate neutralizing device bottom It is provided with cooler in object working solution entrance connecting pipeline.

In above-mentioned Acidic Gas Treating device, it is the tower or tank body for being internally provided with heat transmission equipment, shape that hydrate, which dissolves device, Formula is unlimited, and stripping gas suction line is provided on the preferably described hydrate neutralizing device shell.Hydrate dissolves device with first order absorption The NaHS products liquid of reactor output will be enriched in H as heat transmission equipment heat source₂After the hydrate working solution heating of S gases, return Products pot.

In above-mentioned Acidic Gas Treating device, the hydrate neutralizing device is preferably using the hydrate neutralizing having the following structure Device, the hydrate neutralizing device includes upper cover, shell and low head, and air and liquid mixer and gas phase are provided on the upper cover Outlet line is provided with liquid-phase outlet pipeline on the low head, and the enclosure interior is divide into upper part and lower part by partition board, point Not Wei the hydrate bringing-up section on top and the hydrate of lower part dissolve gasification section, being provided with heat exchange in the hydrate bringing-up section sets It is standby, rich hydrate working solution suction line and liquid-phase outlet pipeline are provided on the shell of the hydrate bringing-up section, it is described to change Hot equipment one end is connect with the rich hydrate working solution suction line, and the heat transmission equipment other end extend into hydrate across partition board Dissolve in gasification section, heat transmission equipment is provided in hydrate neutralizing gasification section, is set on the shell of the hydrate neutralizing gasification section It is equipped with gaseous phase outlet pipeline and liquid phase suction line, hydrate dissolves the gas of the gaseous phase outlet pipeline and air and liquid mixer of gasification section Phase entrance connects, liquid phase entrance of the outlet through pipeline and air and liquid mixer of the heat transmission equipment in the hydrate neutralizing gasification section Connection, hydrate dissolve the liquid phase suction line on heat transmission equipment one end in gasification section and the shell of hydrate neutralizing gasification section Connection.

In above-mentioned hydrate neutralizing device, rupture baffle assembly, the rupture are provided in the hydrate neutralizing gasification section Baffle assembly is set to above heat transmission equipment.

In above-mentioned hydrate neutralizing device, stripping gas suction line, vapour are provided on the hydrate neutralizing gasification piece housing It carries gas suction line and is connected with stripping gas distributor, the stripping gas suction line is set to below shell.

In above-mentioned hydrate neutralizing device, the heat transmission equipment is wall-type heat exchange equipment, can be shell-and-tube, board-like, set One kind in tubular type and jacket type etc., preferably pipe shell type heat exchange equipment.

In above-mentioned hydrate neutralizing device, the air and liquid mixer is the air and liquid mixer for having suction capactity to gas, It is preferred that the air and liquid mixer of venturi form.The air and liquid mixer can realize the same of gas-liquid mixed distribution by liquid injection When, the release gas for dissolving gasification section to hydrate aspirates.

In above-mentioned hydrate neutralizing device, hydrate bringing-up section and the volume ratio of hydrate neutralizing gasification section are 1/3~2/1, It is preferred that 1/2~1/1.

In above-mentioned hydrate neutralizing device, in the hydrate bringing-up section, the rich hydrate working solution from hydration reactor Tube side is walked, the NaHS product liquid as heat source carries out external heating, and liquid holdup is the 1/4~3/4 of hydrate bringing-up section volume, excellent Select 1/3~2/3.

In above-mentioned hydrate neutralizing device, heat transmission equipment extend into hydrate neutralizing across partition board in the hydrate bringing-up section One end outlet is connected with liquid distribution trough in gasification section, and liquid distribution trough well known in the art can be used in the liquid distribution trough, Such as nozzle can be realized and be uniformly distributed rich hydrate working solution, ensure that covering domain is that entire hydrate dissolves device section.

In above-mentioned hydrate neutralizing device, filling-material structure, screen net structure or sieve knot may be used in the rupture baffle assembly Any one of structure can realize droplet collision rupture from top to bottom, and gas from bottom to top can be smooth by and to liquid Drop is cut, when rupturing the installation site of component and being set to upper end nozzle operation, the entire neutralizing device section of inlet zone covering Position.The parameters such as the aperture, filling thickness, porosity can be by specifically testing determination to those skilled in the art.

In above-mentioned hydrate neutralizing device, the hydrate is dissolved in gasification section, and NaHS product liquid walks tube side, hydrate work Make liquid to be heated in outside, hydrate working solution liquid holdup is that hydrate dissolves 1/3~2/3, preferably the 1/2 of gasification section total volume ~3/5.

In above-mentioned hydrate neutralizing device, the stripping gas is not work with hydrate in the case where hydrate dissolves device operating condition The arbitrary gas that liquid, sour gas and follow-up NaOH solution react, is specifically as follows low-pressure gas, nitrogen or inert gas One or more of.The volume flow of the stripping gas and the high concentration H released₂The volume flow ratio of S gases is 1/10 ~2/1, preferably 1/5~1/1.

In above-mentioned hydrate neutralizing device, the stripping gas enters neutralizing device bottom, distributor and change by gas distributor Solution device section is uniformly distributed in maximum, makes stripping gas that ability can be used with working solution reverse flow, the distributor in neutralizing device Distributor well known to domain.

In above-mentioned hydrate neutralizing device, hydrate dissolve device bottom liquid by pump be recycled to hydrate bringing-up section with it is defeated Send the liquid measure ratio preferably 1/2~10/1 recycled to hydrate reactor, more preferable 1/1~5/1.

The present invention provides a kind of Acidic Gas Treating method, the treating method comprises following steps：

（1）Raw material sour gas enters hydration reactor, reacts with hydrate working solution, the H in sour gas₂S gases and water The reaction of object working solution is closed, obtains being rich in H₂The hydrate phase of S, sour gas discharge that treated；

（2）Step（1）In obtain be rich in H₂The hydrate of S mutually enters hydrate and dissolves device, and from first order absorption reactor NaHS product liquid exchange heat, be rich in H₂Regeneration hydrate working solution and H are obtained after the hydrate phase decomposition of S₂S gases, obtain Regeneration hydrate working solution return to hydration reactor recycling after cooling, the NaHS product liquid after heat exchange enters product Tank；

（3）Step（2）Obtained H₂S gases enter first order absorption reactor, react generation with from two level absorbing reaction device Liquid contact is reacted, and tri- tunnels NaHS products Ye Fen obtained by the reaction, the first via enters products pot, and the second tunnel enters hydration materialization Heat transmission equipment in solution device is used as heat source, and third road is recycled back to first order absorption reactor；

（4）Through step（3）Gas phase that treated enters two level absorbing reaction device, the NaHS product liquid with lye and from products pot Contact is reacted, the remaining lack of gas qualified discharge obtained after reaction treatment, and reaction obtained by the reaction generates liquid and divides two-way, wherein Enter first order absorption reactor all the way, another way is recycled back to two level absorbing reaction device.

In the method for the present invention, step（1）The pressure of the sour gas and the operating pressure of hydration reactor match, acid Atmospheric pressure is 0.1Mpa~3.0Mpa, preferably 0.3Mpa~1.5Mpa, when sour gas insufficient pressure, can be carried out by compressor Supercharging.

In the method for the present invention, step（1）The hydrate working solution dosage and sour gas volume ratio（Mark condition）For 5~ 100L/m³, preferably 10~50L/m³。

In the method for the present invention, step（1）The hydration reactor for the benefit of gas-liquid mass transfer and with good heat transfer effect Equipment, form is unlimited, can be the one of stirring-type, atomizing, bubble type, sieve-board type, material filling type, hypergravity or shock flow type etc. Kind, preferably using liquid phase as the consersion unit of continuous phase.

In the method for the present invention, in hydration reactor, H is utilized₂S and CO₂Gas forms the difference that balances each other of hydrate, leads to Control formation condition is crossed, realizes the separation of mixed gas.The operating condition of hydration reactor is：Pressure 0.1Mpa~3.0Mpa, It is preferred that 0.3Mpa~1.5Mpa, 0~20 DEG C of temperature, preferably 5~15 DEG C.

In the method for the present invention, step（1）In obtain be rich in H₂The hydrate phase of S divides two-way, the wherein first via to enter water Materialization solution device is closed, the second tunnel returns to hydrate reactor and recycles so that hydrate working solution has preferable gas storage and higher Separating effect ensures that working solution possesses more excellent utilization rate.Wherein, the second tunnel is rich in H₂The hydrate of S is rich in H with the first via₂S's Hydrate volume flow ratio is 1~50, preferably 5~20.

In the method for the present invention, step（2）In obtained regeneration hydrate working solution divide two-way, the wherein first via after cooling It returns to hydration reactor to recycle, the second tunnel backs into hydrate neutralizing device and recycles, wherein the regeneration hydration of the second tunnel Object working solution and the volume flow ratio of first via regeneration hydrate working solution are 1/2~10/1, preferably 1/1~5/1.

In the method for the present invention, step（1）H in the tail gas of the hydration reactor₂S volume fractions are controlled in 1%~20%, CO₂ Volume fraction is higher than 80%, can be incorporated to the refinery gas desulphurization system centralized processing of sour gas upstream.

In the method for the present invention, the operating condition of the hydrate neutralizing device is：Pressure 0.02Mpa~2.0Mpa, preferably 0.05Mpa~1.0Mpa, 10~50 DEG C of temperature, preferably 15~40 DEG C.

In the method for the present invention, step（2）The NaHS productions from first order absorption reactor for dissolving device into hydrate Product liquid temperature is controlled at 70~95 DEG C, and preferably 80~90 DEG C, temperature is reduced to 25~65 DEG C, preferably 35~50 DEG C after heat exchange.

In the method for the present invention, step（2）Temperature is controlled 0 the regeneration hydrate working solution that the decomposition obtains after cooling ~20 DEG C, preferably 5~15 DEG C, regeneration hydrate working solution return to hydration reactor and recycle.

In the method for the present invention, step（2）H in the gas that the hydrate neutralizing device releases₂S volume fractions are higher than 95%, CO₂Volume fraction is less than 5%.

In the method for the present invention, the first order absorption reactor and two level absorbing reaction device are gas-liquid mass transfer consersion unit, excellent Choosing is using gas phase as the consersion unit of continuous phase, specially bubbling column reactor, filler tower reactor, impact flow reactor, rotation One kind in bed reactor and venturi reactor, preferably rotary drill reactor.

In the method for the present invention, the operating condition of the first order absorption reactor and two level absorbing reaction device is：Pressure 0.02Mpa~2.0Mpa, preferably 0.1Mpa~1.0Mpa, 70~95 DEG C of temperature, preferably 80~90 DEG C.

In the method for the present invention, the lye is NaOH solution, and mass concentration is 20%~60%, preferably 32%~48%, Dosage is according to step（3）H in gas phase that treated₂S contents are adjusted, and by adjusting NaOH solution addition, ensure to pass through step （4）H in lack of gas that treated₂S contents are 10 mg/Nm of <³, and control NaOH solution and excessively do not ensure that NaHS products are qualified.

In the method for the present invention, step（3）The products pot is back to the product flow quantity and raw material of two level absorbing reaction device The volume ratio of lye adding amount is 1/2~10/1, preferably 1/1~5/1.

In the method for the present invention, step（3）It is described go out obtained tri- tunnels NaHS products Ye Fen of first order absorption reactor reaction, Enter products pot all the way, the heat transmission equipment that the second tunnel enters in hydrate neutralizing device is used as heat source, and third road is recycled back to one Grade absorbing reaction device.The first via NaHS product liquids product flow is preferably the 0~1/10 of total flow；The second road NaHS Product liquid accumulates 1/10~1/5 that flow is preferred total flow；The preferably total stream of third road NaHS product liquids product flow The 4/5~9/10 of amount.

In the method for the present invention, step（4）Described in secondary absorber reaction obtained by the reaction generate liquid and divide two-way, the first via Into first order absorption reactor, the second tunnel is recycled back to two level absorbing reaction device.The second tunnel absorbing liquid volume flow and first Road absorbing liquid volume flow ratio is 2~20, preferably 4~10.

In the method for the present invention, it is the tower or tank body for being internally provided with heat transmission equipment that hydrate, which dissolves device, and form is unlimited.Water Materialization solution device is closed using the NaHS products liquid of first order absorption reactor output as heat transmission equipment heat source, will be enriched in H₂The water of S gases After closing the heating of object working solution, products pot is returned.

In the method for the present invention, the hydrate neutralizing device is described preferably using the hydrate neutralizing device having the following structure It includes upper cover, shell and low head that hydrate, which dissolves device, and air and liquid mixer and gas phase outlet are provided on the upper cover Line is provided with liquid-phase outlet pipeline on the low head, and the enclosure interior is divide into upper part and lower part by partition board, respectively on The hydrate bringing-up section in portion and the hydrate of lower part dissolve gasification section, are provided with heat transmission equipment in the hydrate bringing-up section, institute It states and is provided with rich hydrate working solution suction line and liquid-phase outlet pipeline, the heat transmission equipment on the shell of hydrate bringing-up section One end is connect with the rich hydrate working solution suction line, and the heat transmission equipment other end extend into hydrate across partition board and dissolves gas Change in section, heat transmission equipment is provided in hydrate neutralizing gasification section, gas is provided on the shell of the hydrate neutralizing gasification section Phase outlet line and liquid phase suction line, hydrate dissolve the gas phase entrance of the gaseous phase outlet pipeline and air and liquid mixer of gasification section Connection, the outlet that the hydrate dissolves the heat transmission equipment in gasification section are connected through the liquid phase entrance of pipeline and air and liquid mixer, The liquid phase suction line that heat transmission equipment one end in hydrate neutralizing gasification section is dissolved with hydrate on the shell of gasification section is connect.

In above-mentioned hydrate neutralizing device, the air and liquid mixer is the air and liquid mixer for having suction capactity to gas, It is preferred that the air and liquid mixer of venturi form.The air and liquid mixer can realize the same of gas-liquid mixed distribution by liquid injection When, the release gas for dissolving gasification section to hydrate aspirates,

In above-mentioned hydrate neutralizing device, hydrate bringing-up section and the volume ratio of hydrate neutralizing gasification section are 1/3~2/1, preferably 1/2~1/1.

In the method for the present invention, the hydrate working solution is the aqueous solution added with auxiliary agent, and the auxiliary agent includes auxiliary agent A, the auxiliary agent A are lauryl sodium sulfate（SDS）, sodium dodecylbenzenesulfonate（SDBS）, linear alkyl sodium sulfonate（LAB- SA）, alkyl polyglycoside（APG）One or more of, mass fraction preferably 0.005%~1.0%, more preferable mass fraction 0.01%~0.5 %.

In the method for the present invention, auxiliary agent B can also be added in the hydrate working solution, the auxiliary agent B is kerosene, diesel oil One or more of with silicone oil, the additive amount of auxiliary agent B is 1/5~2/1, preferably 1/ with the volume ratio of water in hydrate working solution 3~1/1.When adding auxiliary agent B in the hydrate working solution, emulsifier is preferably added, selected emulsifier can be hydrophilic Property emulsifier, formed Water-In-Oil（o/w）Type lotion can also be lipophilic emulsifier, form oil-in-water（w/o）Type breast Liquid, the additive amount of emulsifier are 0.5%~3% with the mole fraction of water in hydrate working solution.

Can also be N- methyl pyrroles including auxiliary agent C, the auxiliary agent C in the hydrate working solution in the method for the present invention One or more of pyrrolidone, propene carbonate, sulfolane, N- N-formyl morpholine Ns, polyethylene glycol, the quality point of the auxiliary agent C Number is 2%~30%, preferably 5%~20 %.

In the method for the present invention, the sour gas can be the sour gas in various sources, be preferably applied to H₂S volume contents are 60%~95%, CO₂Content is 5%~40%, tolerance in 50~1000 Nm³The middle-size and small-size sour gas of/h.

Compared with prior art, the processing method and processing device of sour gas of the present invention has the following advantages that：

（1）In the method for the present invention, using under different condition, H₂S gases and CO₂When gas forms hydrate with water, have larger The characteristic for the difference that balances each other makes H by controlling hydrating condition₂S gases are preferentially produced hydrate with hydrate working solution and enter water Close object phase, CO₂Gas does not generate or generates hydrate less and in gas phase enrichment and be discharged, to realize to H in sour gas₂S gases With CO₂The first step of gas detaches.Whole process operating condition is more mild, and good separating effect, operating flexibility is big, can be economical high Effect to containing CO₂The sour gas of gas is pre-processed, and treated, and sour gas can be divided into high concentration CO₂Gas（Volume fraction > 80%）With high concentration H₂S gases（Volume fraction > 95%）.Rich in H₂The hydrate of S gas molecules decomposes in hydrate neutralizing device And release high-purity H₂S gases；NaHS production units are with high-purity H₂S gases are raw material, pass through the two-stage with raw material lye Counter-current absorption produces NaHS products.

（2）In the method for the present invention, the working solution that the hydrate working solution that uses compounds for various ingredients, by auxiliary agent A, B, Compounding between C three interacts, and can not only reduce gas-liquid interface tension, increases gas solubility in the liquid phase and expansion Dissipate coefficient, it can also be ensured that hydrate has good fluidity, and increases working solution to H₂The solution absorption ability of S, significantly The generation that gas in liquid phase forms hydrate is promoted, hydrate generating rate is effectively improved, increases hydrate gas storage Density, and ensure that the mobility of hydrate phase, improve H₂S and CO₂While the separating effect of gas, the company of device ensure that Continuous even running.

（3）Reasonably optimizing has been carried out to the energy of entire Acidic Gas Treating process and has been made full use of.By NaHS product liquid Surplus heat is sufficiently used for the decomposition of hydrate in hydrate neutralizing device, while being flowed back using the product liquid after heat exchange, realizes The homogenizing of NaHS production unit reaction temperatures field and control, are reasonably utilized maximum system energy, greatly reduce plant energy consumption.

（4）Absorbing liquid systemic circulation is realized by the way that the NaHS solution in products pot is introduced two level absorbing reaction device, is realized Control to the absorbing liquid residence time in reactor, while the circulating and recovering of product liquid can be used as dilution, reduce second order reaction Na in device solution₂S concentration, prevents Na₂S crystallizations are precipitated, and ensure device long-term operation.

（5）The present invention provides a kind of new structural hydrate neutralizing device, and hydrate neutralizing device is divided into two by partition board Section carries out two sections of efficient step heat exchange, the heat of entire technical process has been carried out reasonable utilization, and mixed by the way that gas-liquid is arranged Clutch, by high concentration H₂S gases mix again with NaHS product liquids, it is ensured that contain Na in NaHS products₂S content≤1%, meets 《GB23937-2009》The industrial NaHS products national standard of middle requirement.Meanwhile it ensure that two level absorbing reaction device outlet purification H in gas₂S contents are less than 10mg/Nm³。

（6）The entire processing procedure environmental protection of the present invention, reliable, no waste residue and brine waste etc. " three wastes " generation, realization are acid While gas qualified discharge, the NaHS products for meeting state quality standard are produced, sour gas is turned waste into wealth, product is improved Added value converts environmental improvement to the production process of chemical products.

（7）It is passed through stripping gas by dissolving device bottom in hydrate, realizes multiple action：A. it is risen in hydrate dissolves device It is acted on to stripping, reduces gaseous phase partial pressure, broken for hydrate phase balance and discharge gas bigger power is provided；B. liquid is increased The mixed traverse degree of phase preferably realizes heat exchange and in time by the H of release₂S gases are taken out of, while increasing gas in rupture component pair The wind-force of drop is cut, and preferably by drop tinyization, improves the releasing effect of gas in liquid phase；C. according to neutralizing device H₂S gas The release conditions of body suitably adjust stripping gas, can stablize the air-flow of release gas, improve follow-up NaHS production units unstripped gas Stability, while also enriching the adjustment means of NaHS production unit liquid-gas ratios；D. H in release gas is reduced₂S and CO₂Gas Concentration, especially bigger reduces CO₂Gas concentration greatly reduces and avoids Na₂CO₃/ NaHCO₃Formation to body The influence of system ensures NaHS production units long period, continuous, stable operation.

（8）In the method for the present invention use two-stage gas-liquid counter current absorbing reaction process, and be respectively provided with first-stage reactor and The self-loopa of second reactor reabsorbs process, improves reaction depth, material is made fully to be contacted with sour gas, it is ensured that level-one is anti- Answer the NaHS product designs of device output.According to the difference of raw material concentration of lye, NaHS% can be respectively produced（Mass concentration）≥ 28%, NaHS% >=36% and NaHS% >=42%, meanwhile, it ensure that H in two level absorbing reaction device outlet purified gas₂S contents are less than 10mg/Nm³。

Description of the drawings

Fig. 1 is the method and device flow diagram of processing sour gas provided by the invention.

Fig. 2 is that the hydrate in the method and device of processing sour gas provided by the invention dissolves device structural schematic diagram.

Specific implementation mode

It elaborates to the method and device of the processing sour gas of the present invention below in conjunction with description of the drawings and embodiment, but It is not intended to limit the present invention.

The present invention provides a kind of Acidic Gas Treating device, described device include hydration reactor 4, hydrate neutralizing device 10, First order absorption reactor 17, two level absorbing reaction device 27 and products pot 24；Sour gas feeding line 1 is anti-with hydration through compressor 2 The gas phase entrance of device 4 is answered to connect, the liquid-phase outlet of hydration reactor 4 divides two-way, wherein 9 dissolving device through pipeline and hydrate all the way 10 liquid phase entrance connection, another way 8 are connect through pipeline with hydrate working solution suction line 6, and hydrate dissolves 10 bottom of device Liquid-phase outlet divide two-way, wherein 15 being connect all the way with the hydrate working solution suction line 6 of hydration reactor 4 through pipeline, separately It 14 is connect all the way with hydrate neutralizing device liquid phase entrance through pipeline, the liquid-phase outlet of 10 bottom of the hydrate neutralizing device and hydration It is provided with cooler 12 in the connecting pipeline of the hydrate working solution suction line 6 of reactor 4.The hydrate dissolves device shell Lower part is provided with stripping gas suction line 26.Hydrate dissolves the gas of the gaseous phase outlet and first order absorption reactor 17 at 10 top of device Phase entrance connects, and the gaseous phase outlet of first order absorption reactor 17 is connect with the gas phase entrance of two level absorbing reaction device 27, and two level is inhaled The gaseous phase outlet for receiving reactor 27 is connect with clean gas outlet pipeline 32, three tunnels of liquid-phase outlet point of first order absorption reactor 17, The first via 22 is connect with products pot, and the second tunnel 21 is dissolved the heat transmission equipment in device 10 through hydrate and connect with products pot 24, third Road 20 is connect with the liquid phase entrance of first order absorption reactor 17, and the liquid-phase outlet of two level absorbing reaction device 27 divides two-way, wherein the It 30 is connect all the way with the liquid phase entrance of first order absorption reactor 17, the second tunnel 29 and the liquid phase entrance of two level absorbing reaction device 27 connect It connects, the liquid phase entrance of two level absorbing reaction device 27 is connect with alkali liquor inlet pipeline 31, and products pot 24 is exported through pipeline 25 and two level The liquid phase entrance of absorbing reaction device connects.

As shown in Fig. 2, the present invention also provides a kind of hydrates to dissolve device, the hydrate neutralizing device includes upper cover 50, shell 51 and low head 52 are provided with air and liquid mixer 36 and gas phase outlet line 34, the lower envelope on the upper cover 50 It is provided with liquid-phase outlet pipeline 44 on first 52, is divide into upper part and lower part by partition board 38 inside the shell 51, respectively top Hydrate bringing-up section 46 and the hydrate of lower part dissolve gasification section 49, be provided with heat transmission equipment in the hydrate bringing-up section 46 33, rich hydrate working solution suction line 45 and liquid-phase outlet pipeline 37 are provided on the shell of the hydrate bringing-up section 46, 33 one end of the heat transmission equipment is connect with the rich hydrate working solution suction line 45, and 33 other end of heat transmission equipment passes through partition board 38 extend into 49 in hydrate neutralizing gasification section, and the heat transmission equipment 33 is extend into across partition board 38 in hydrate neutralizing gasification section One end outlet is connected with liquid distribution trough 39, and 49 are provided with heat transmission equipment 47, the hydration materialization in hydrate neutralizing gasification section It solves and is provided with gaseous phase outlet pipeline 35 and liquid phase suction line 41 on the shell of gasification section 49, hydrate dissolves the gas of gasification section 49 Phase outlet line 35 is connect with the gas phase entrance of air and liquid mixer 36, the heat transmission equipment 47 in the hydrate neutralizing gasification section 49 One end is connect through pipeline with the liquid phase entrance of air and liquid mixer 36,47 other end of heat transmission equipment and hydrate neutralizing gasification section 49 Liquid phase entrance 41 on shell connects, and rupture baffle assembly 48, the rupture are provided in the hydrate neutralizing gasification section 49 Baffle assembly is set to above heat transmission equipment.It is provided with stripping gas suction line on hydrate neutralizing 49 shell of gasification section 42, stripping gas suction line is connected with stripping gas distributor 43.

Flow in Acidic Gas Treating method of the present invention is as follows：Sour gas from sour gas feeding line 1 enters compression Machine 2 enters hydration reactor 4 through 2 compressed sour gas 3 of compressor, by controlling the reaction condition of hydration reactor 4, makes H in sour gas₂S gases, which are preferentially reacted with hydrate working solution, is enriched to hydrate phase, and treated, and sour gas 5 is discharged, Rich in H₂The hydrate phase 7 of S gas molecules is divided for two-way, wherein 8 being recycled back to hydration reactor all the way, another way 9 is delivered to water Materialization solution device 10 is closed, is exchanged heat with the products of the NaHS all the way liquid 21 from first order absorption reactor 17, H is rich in₂The hydrate of S Regeneration hydrate working solution 11 and H are obtained after phase decomposition₂S gases 16, obtained regeneration hydrate working solution 11 divide two-way, wherein 15 the recycling of hydration reactor 4 being returned to after the cooling of cooler 12 all the way, 14 self-loopa return water of another way closes materialization solution device 10, NaHS products liquid 23 after heat exchange enters products pot 24；Obtained H₂S gases 16 pass through the stripping from stripping gas suction line 26 Enter first order absorption reactor 17 together after gas stripping, generating liquid 30 with the reaction from two level absorbing reaction device 27 contacts progress Reaction, NaHS products liquid 19 obtained by the reaction divide three tunnels, the first via 22 to enter products pot 24, and the second tunnel 21 enters hydrate and dissolves It uses as heat source in heat transmission equipment in device 10, is connect with products pot 24 after heat exchange, third road 20 is reacted by first order absorption First order absorption reactor is returned in the liquid phase entrance self-loopa of device 17.After the processing of first order absorption reactor 17 obtained gas phase 18 into Enter two level absorbing reaction device 27, is contacted with the lye from alkali liquor inlet pipeline 31 and the NaHS products liquid 25 from products pot 24 It is reacted, the remaining lack of gas obtained after reaction treatment are up to standard to be discharged by clean gas outlet pipeline 32, two level absorbing reaction device 27 obtained reaction responses generate liquid 28 and two-way, the wherein first via 30 are divided to enter first order absorption reactor 17, and the second tunnel 29 passes through Two level absorbing reaction device is returned in the liquid phase entrance self-loopa of two level absorbing reaction device 27.

When using the hydrolysis reactor described in Fig. 2, Acidic Gas Treating method flow of the present invention is as follows：From sour gas into The sour gas of expects pipe line 1 enters compressor 2, enters hydration reactor 4 through 2 compressed sour gas 3 of compressor, by controlling water The reaction condition for closing reactor 4, makes the H in sour gas₂S gases, which are preferentially reacted with hydrate working solution, is enriched to hydrate Phase, treated, and sour gas 5 is discharged, and is rich in H₂The hydrate phase 7 of S gas molecules is divided for two-way, wherein 8 being recycled back to hydration all the way Reactor, another way 9 enter changing in the hydrate bringing-up section 46 of hydrate neutralizing device 10 through rich hydrate working solution pipeline 45 NaHS product liquid in the tube side of hot equipment 33, with 46 shell of hydrate bringing-up section exchanges heat, by being rich in for heat exchange H₂The hydrate of S gas molecules is mutually evenly distributed on through liquid phase distributor 39 in hydrate neutralizing gasification section 49, by hydrate plus Hot arc sprays and lower hydrate work drop hits by rupture baffle assembly 48 and is broken into more tiny droplet/drop, and With gas from bottom to top（Discharge gas and stripping gas）Cutting, the more conducively absorption of heat are realized on rupture baffle assembly 48 simultaneously Discharge and take away gas；Droplet/drop after rupture cutting falls, and further exchanges heat through heat transmission equipment 47, and the heat exchange is set Liquid is that the liquid phase suction line 41 dissolved through hydrate in gasification section 49 enters in 47 tube side of heat transmission equipment in standby 47 tube sides The products of the NaHS all the way liquid 21 of first order absorption reactor 17, the product liquid 23 after heat exchange enter air and liquid mixer through pipeline 53 36 liquid phase entrance enters air and liquid mixer 36, while the stripping gas inlet tube by being arranged on hydrate neutralizing 49 shell of gasification section Line 42 is passed through stripping gas, the H that hydrate phase decomposition is discharged₂S gases dissolve the gaseous phase outlet pipe of gasification section 49 by hydrate Line 35 is passed through in gas phase mixer 36 further to react with the NaHS products liquid 21 by heat exchange, will contain in NaHS products liquid 21 Na₂S further with H₂S gas reactions, Na in the NaHS product liquid ensured₂S contents comply with standard, and the hydrate adds The liquid phase obtained in hot arc 46 is sent through liquid-phase outlet pipeline 37 to products pot 24.This system can be reduced by being passed through stripping gas Balance each other partial pressure, increases H₂The motive force that balances each other that S gas hydrates decompose；Hydrate dissolves the liquid in 49 shell of gasification section By being divided into two-way after liquid-phase outlet pipeline 44, wherein 14 being recycled to hydrate bringing-up section 46 all the way, another way 15 is through cooler The recycling of hydration reactor 4 is delivered to after 12 coolings.Gas in the hydrate bringing-up section 46 is through gaseous phase outlet pipeline 34 Discharge is sent to first order absorption reactor and is handled, with the reaction all the way from two level absorbing reaction device 27 generate liquid 30 contact into Row reaction, NaHS products liquid 19 obtained by the reaction divide three tunnels, the first via 22 to enter products pot 24, and the second tunnel 21 enters hydration materialization It uses, is connect with products pot 24 after heat exchange, third road 20 is anti-by first order absorption as heat source in heat transmission equipment in solution device 10 The liquid phase entrance self-loopa of device 17 is answered to return first order absorption reactor；The gas phase 18 obtained after first order absorption reactor for treatment into Enter two level absorbing reaction device 27, is contacted with the lye from alkali liquor inlet pipeline 31 and the NaHS products liquid 25 from products pot 24 It is reacted, the remaining lack of gas obtained after reaction treatment are up to standard to be discharged by clean gas outlet pipeline 32.

Embodiment 1

Certain sour gas amount Q=280Nm³/ h, pressure 0.6Mpa, wherein H₂S volume fractions are 78%, CO₂Volume fraction is 21%, remaining as substances such as hydro carbons.Sour gas is handled using processing method and processing device shown in Fig. 1.Wherein, hydrate Dissolve device using the conventional tank structure for being internally provided with heat transmission equipment, and stripping is provided on hydrate neutralizing device shell Gas suction line.

Operating condition and treatment effect in processing procedure is as follows：Hydrate working solution by water, account for aqueous solution mass fraction 0.03% SDS, the polyethylene glycol for accounting for aqueous solution mass fraction 8%, be 1/2 with water volume ratio diesel oil, with water molar ratio be 0.8% sapn（Fatty acid esters of sorbitan）Emulsifier forms.Sour gas introduces hydration after compressor is pressurized to 1.2Mpa Reactor, reacts in hydration reactor with hydrate working solution, and reaction condition is：8 DEG C of pressure 1.2Mpa, temperature, work It is 6m to make liquid dosage³/h.In hydration reactor, H₂S gases preferentially generate hydrate with working solution and are enriched to hydrate Phase, CO₂And inert gas is discharged in gas phase enrichment and as tail gas, the CO in tail gas₂A concentration of 88%.Rich in H₂S gas molecules Hydrate be mutually delivered to hydrate neutralizing device, hydrate neutralizing device operating condition be：Pressure 0.3Mpa, 23 DEG C of temperature, bottom Portion's stripping gas uses nitrogen, flow 60Nm³/h.In hydrate neutralizing device, hydrate is mutually broken and decomposes and release height Concentration H₂S gases enter NaHS production units, wherein CO together with nitrogen₂Concentration < 3%, the hydrate working solution warp after decomposition Heat exchanger is cooled to 8 DEG C of return hydration reactors and recycles.Hydrate dissolves the high concentration H discharged in device₂S gases lead to successively First order absorption reactor and two level absorbing reaction device are crossed, counter current contacting is carried out with 45% NaOH lye and is reacted.Wherein, level-one The operating condition of absorbing reaction device is：Pressure 0.3Mpa, 86 DEG C of temperature；The operating condition of two level absorbing reaction device is：Pressure 0.2Mpa, 90 DEG C of temperature.Go out 86 DEG C of the NaHS liquid-phase products temperature of first-stage reactor, tri- tunnels product Ye Fen, the first via accounts for total stream The 1/10 of amount enters products pot, and the second tunnel accounts for the heat transmission equipment that the 1/10 of total flow enters in hydrate neutralizing device to be made as heat source With surplus products liquid is that third road is recycled back to first order absorption reactor.Go out two level and inhales the reaction generation liquid point that reaction receipts device obtains Two-way, the first via account for the 1/5 of total flow and enter first order absorption reactor, and residue generates liquid and is recycled back to two level absorption as the second tunnel Reactor.Whole process in the present embodiment can produce the NaHS products that mass concentration is higher than 42%, and Na₂S contents are less than 1w% meets《GB23937-2009》The industrial NaHS fluid products national standard of middle requirement；Meanwhile sour gas is through two stage treatment H in lack of gas afterwards₂S contents are less than 10mg/Nm³。

Embodiment 2

It is same as Example 1, the difference is that, using the neutralizing device structure described in Fig. 2, the hydrate of hydrate neutralizing device adds Hot arc and the volume ratio of hydrate neutralizing gasification section are 1/1, and liquid holdup is the 1/2 of this segment body product in hydrate bringing-up section, hydration Materialization solution gasification section liquid holdup is the 1/2 of this section of total volume, and hydrate dissolves the rupture baffle assembly in device using average Kong Zhi Diameter is the mesh structure of 5mm.

Dissolve device due to providing preferred hydrate using the present invention, two sections of efficient step heat exchange is carried out, by entire technique mistake The heat of journey has carried out reasonable utilization, working solution can be made to decompose under hydrate neutralizing operating condition same as Example 1 （Regeneration）More completely, when reaching 1 same effect of embodiment, hydrate working solution dosage can be reduced to 4.6m³/ h, reduces again Raw 20% or more energy consumption of absorbing liquid cooling；And preferred hydrate neutralizing device upper cover provided by the invention is provided with air and liquid mixer, By high concentration H₂S gases and NaHS product liquids Forced Mixing again contain Na in NaHS products₂S contents can be reduced to 0.5 w% with Under, it can be directly as the raw material of NaHS solid high-class products.

Embodiment 3

It is same as Example 2, the difference is that, the hydrate working solution of use by water, account for aqueous solution mass fraction 0.03% The diesel oil that SDS is 1/2 with water volume ratio and the sapn emulsifier that water molar ratio is 0.8% form.

Under hydrate reactor operating condition same as Example 2, CO in hydration reactor treated tail gas₂It is dense Degree is 70% or so；Rich hydrate working solution is after hydrate neutralizing device processing, CO in gas₂Concentration > 4%, increases CO₂It is formed Na₂CO₃/ NaHCO₃Continuous, stable operation the influence to NaHS production units of equal substances, increases the behaviour of device long-term operation Make difficulty.

Claims

1. a kind of Acidic Gas Treating device, described device include hydration reactor, hydrate neutralizing device, first order absorption reactor, Two level absorbing reaction device and products pot；The gas phase entrance of sour gas feeding line and hydration reactor connects, hydration reactor The liquid phase entrance that liquid-phase outlet and hydrate dissolve device connect, the liquid-phase outlet of hydrate neutralizing device bottom and hydration reactor Hydrate working solution suction line connects, and hydrate dissolves the gas phase entrance of the gaseous phase outlet and first order absorption reactor at the top of device Connection, the gaseous phase outlet of first order absorption reactor are connect with the gas phase entrance of two level absorbing reaction device, two level absorbing reaction device Gaseous phase outlet is connect with clean gas outlet pipeline, and three tunnels of liquid-phase outlet point of first order absorption reactor, the first via connects with products pot It connects, the second tunnel is dissolved the heat transmission equipment in device through hydrate and connect with products pot, the liquid phase on third road and first order absorption reactor Entrance connects, and the liquid-phase outlet of two level absorbing reaction device divides two-way, wherein the liquid phase entrance of the first via and first order absorption reactor Connection, the second tunnel are connect with the liquid phase entrance of two level absorbing reaction device, the liquid phase entrance and alkali liquor inlet of two level absorbing reaction device Pipeline connects, and products pot outlet is connect through pipeline with the liquid phase entrance of two level absorbing reaction device.

2. Acidic Gas Treating device described in accordance with the claim 1, wherein compressor is arranged on sour gas feeding line, is used for Ensure that acid atmospheric pressure matches with hydration reactor operating pressure.

3. Acidic Gas Treating device described in accordance with the claim 1, wherein the liquid-phase outlet of the hydration reactor divides two-way, The liquid phase entrance for wherein dissolving device with hydrate all the way is connect, the working solution suction line connection of another way and hydration reactor.

4. Acidic Gas Treating device described in accordance with the claim 1, wherein the liquid-phase outlet point of hydrate neutralizing device bottom Two-way, wherein being connected all the way through the hydrate working solution suction line of pipeline and hydration reactor, another way is through pipeline and hydration The liquid phase entrance of materialization solution device connects.

5. Acidic Gas Treating device described in accordance with the claim 1, wherein the first order absorption reactor and two level absorbing reaction Device is gas-liquid mass transfer consersion unit, specially bubbling column reactor, filler tower reactor, impact flow reactor, rotating bed reaction One kind in device and venturi reactor, preferably rotary drill reactor.

6. Acidic Gas Treating device described in accordance with the claim 1, wherein the liquid-phase outlet of hydrate neutralizing device bottom with It is provided with cooler in the hydrate working solution entrance connecting pipeline of hydration reactor.

7. Acidic Gas Treating device described in accordance with the claim 1, wherein hydrate neutralizing device is to be internally provided with heat transmission equipment Tower or tank body.

8. Acidic Gas Treating device according to claim 7, wherein be provided with stripping on the hydrate neutralizing device shell Gas suction line.

9. Acidic Gas Treating device described in accordance with the claim 1, wherein the hydrate neutralizing device includes upper cover, shell And low head, air and liquid mixer and gas phase outlet line are provided on the upper cover, and being provided with liquid phase on the low head goes out Mouth pipeline, the enclosure interior are divide into upper part and lower part by partition board, respectively the hydrate bringing-up section on top and the water of lower part Materialization solution gasification section is closed, heat transmission equipment is provided in the hydrate bringing-up section, is arranged on the shell of the hydrate bringing-up section There are rich hydrate working solution suction line and liquid-phase outlet pipeline, described heat transmission equipment one end to enter with the rich hydrate working solution Mouth pipeline connection, the heat transmission equipment other end are extend into across partition board in hydrate neutralizing gasification section, and hydrate is dissolved in gasification section It is provided with heat transmission equipment, gaseous phase outlet pipeline and liquid phase suction line are provided on the shell of the hydrate neutralizing gasification section, The gas phase entrance for the gaseous phase outlet pipeline and air and liquid mixer that hydrate dissolves gasification section connects, and the hydrate dissolves gasification section In heat transmission equipment outlet through the liquid phase entrance of pipeline and air and liquid mixer connect, hydrate neutralizing gasification section in heat exchange set The liquid phase suction line that standby one end is dissolved with hydrate on the shell of gasification section is connect.

10. Acidic Gas Treating device according to claim 9, wherein be provided with brokenly in the hydrate neutralizing gasification section Baffle assembly is split, the rupture baffle assembly is set to above heat transmission equipment.

11. Acidic Gas Treating device according to claim 9, wherein be arranged on the hydrate neutralizing gasification piece housing There are stripping gas suction line, stripping gas suction line to be connected with stripping gas distributor, the stripping gas suction line is set to shell Below body.

12. Acidic Gas Treating device according to claim 9, wherein the heat transmission equipment is wall-type heat exchange equipment, is One kind in shell-and-tube, board-like, bushing type and jacket type etc., preferably pipe shell type heat exchange equipment.

13. Acidic Gas Treating device according to claim 9, wherein the air and liquid mixer is to have to take out to gas The air and liquid mixer of energy-absorbing power, the preferably air and liquid mixer of venturi form.

14. Acidic Gas Treating device according to claim 11, wherein hydrate bringing-up section dissolves gasification section with hydrate Volume ratio be 1/3~2/1, preferably 1/2~1/1.

15. Acidic Gas Treating device according to claim 9, wherein in the hydrate bringing-up section, come from hydration reaction The rich hydrate working solution of device walks tube side, and the NaHS product liquid as heat source carries out external heating, and liquid holdup heats for hydrate 1/4~3/4, preferably the 1/3~2/3 of segment body product.

16. Acidic Gas Treating device according to claim 9, wherein heat transmission equipment passes through in the hydrate bringing-up section Partition board extend into one end outlet in hydrate neutralizing gasification section and is connected with liquid distribution trough.

17. Acidic Gas Treating device according to claim 9, wherein the rupture baffle assembly is using filling-material structure, silk Any one of web frame or mesh structure.

18. Acidic Gas Treating device according to claim 9, wherein in the hydrate neutralizing gasification section, NaHS productions Product liquid walks tube side, and hydrate working solution is heated in outside, and hydrate working solution liquid holdup is that hydrate dissolves gasification section totality Long-pending 1/3~2/3, preferably 1/2~3/5.

19. Acidic Gas Treating device according to claim 11, wherein the stripping gas is to dissolve device operation in hydrate Under the conditions of the arbitrary gas that does not react with hydrate working solution, sour gas and follow-up NaOH solution, specially low pressure gas One or more of gas, nitrogen or inert gas.

20. Acidic Gas Treating device according to claim 11, wherein the volume flow of the stripping gas and release High concentration H₂The volume flow ratio of S gases is 1/10~2/1, preferably 1/5~1/1.

21. a kind of Acidic Gas Treating method, the treating method comprises following steps：

（1）Raw material sour gas enters hydration reactor, reacts with hydrate working solution, the H in sour gas₂S gases and hydration Object working solution reacts, and obtains being rich in H₂The hydrate phase of S, sour gas discharge that treated；

（2）Step（1）In obtain be rich in H₂The hydrate of S mutually enters hydrate and dissolves device, and from first order absorption reactor NaHS product liquid exchanges heat, and is rich in H₂Regeneration hydrate working solution and H are obtained after the hydrate phase decomposition of S₂S gases, obtain Regeneration hydrate working solution returns to hydration reactor recycling after cooling, and the NaHS product liquid after heat exchange enters products pot；

（3）Step（2）Obtained H₂S gases enter first order absorption reactor, and liquid is generated with reacting from two level absorbing reaction device Contact is reacted, tri- tunnels NaHS products Ye Fen obtained by the reaction, and the first via enters products pot, and the second tunnel enters hydrate neutralizing Heat transmission equipment in device is used as heat source, and third road is recycled back to first order absorption reactor；

22. according to the Acidic Gas Treating method described in claim 21, wherein step（1）The pressure of the sour gas and hydration The operating pressure of reactor matches, and acid atmospheric pressure is 0.1Mpa~3.0Mpa, preferably 0.3Mpa~1.5Mpa, sour gas When insufficient pressure, it is pressurized by compressor.

23. according to the Acidic Gas Treating method described in claim 21, wherein step（1）The hydrate working solution dosage with Sour gas volume ratio is 5~100L/m³, preferably 10~50L/m³。

24. according to the Acidic Gas Treating method described in claim 21, wherein the operating condition of hydration reactor is：Pressure 0.1Mpa~3.0Mpa, preferably 0.3Mpa~1.5Mpa, 0~20 DEG C of temperature, preferably 5~15 DEG C.

25. according to the Acidic Gas Treating method described in claim 21, wherein step（1）In obtain be rich in H₂The hydrate of S Phase divides two-way, the wherein first via to enter hydrate neutralizing device, and the second tunnel returns to hydrate reactor and recycles, wherein second Road is rich in H₂The hydrate of S is rich in H with the first via₂The hydrate volume flow ratio of S is 1~50, preferably 5~20.

26. according to the Acidic Gas Treating method described in claim 21, wherein step（2）In obtain regeneration hydrate work Liquid divides two-way, the wherein first via to return to hydration reactor recycling after cooling, and the second tunnel backs into hydrate neutralizing device It recycles, wherein it is 1/2 that the second tunnel, which regenerates hydrate working solution and the volume flow ratio of first via regeneration hydrate working solution, ~10/1, preferably 1/1~5/1.

27. according to the Acidic Gas Treating method described in claim 21, wherein step（1）In the tail gas of the hydration reactor H₂S volume fractions are controlled in 1%~20%, CO₂Volume fraction is higher than 80%.

28. according to the Acidic Gas Treating method described in claim 21, wherein the operating condition of hydrate neutralizing device is： Pressure 0.02Mpa~2.0Mpa, preferably 0.05Mpa~1.0Mpa, 10~50 DEG C of temperature, preferably 15~40 DEG C.

29. according to the Acidic Gas Treating method described in claim 21, wherein step（2）It is described to dissolve device into hydrate NaHS product liquid temperature from first order absorption reactor is controlled at 70~95 DEG C, preferably 80~90 DEG C, and temperature drops after heat exchange It is 25~65 DEG C, preferably 35~50 DEG C.

30. according to the Acidic Gas Treating method described in claim 21, wherein step（2）It is described to decompose obtained regeneration hydration Temperature control is at 0~20 DEG C after cooling for object working solution, preferably 5~15 DEG C, and regeneration hydrate working solution returns to hydration reactor It recycles.

31. according to the Acidic Gas Treating method described in claim 21, wherein step（2）The hydrate neutralizing device releases Gas in H₂S volume fractions are higher than 95%, CO₂Volume fraction is less than 5%.

32. according to the Acidic Gas Treating method described in claim 21, wherein the first order absorption reactor and two level absorb instead It is gas-liquid mass transfer consersion unit to answer device, preferably using gas phase as the consersion unit of continuous phase, specially bubbling column reactor, packed tower One kind in reactor, impact flow reactor, rotary drill reactor and venturi reactor, preferably rotary drill reactor.

33. according to the Acidic Gas Treating method described in claim 21, wherein the first order absorption reactor and two level absorb instead The operating condition of device is answered to be：Pressure 0.02Mpa~2.0Mpa, preferably 0.1Mpa~1.0Mpa, 70~95 DEG C of temperature, preferably 80~ 90℃。

34. according to the Acidic Gas Treating method described in claim 21, wherein the lye is NaOH solution, and mass concentration is 20%~60%, preferably 32%~48%.

35. according to the Acidic Gas Treating method described in claim 21, wherein step（3）The products pot is back to two level suction The volume ratio of the product flow quantity and raw material lye adding amount of receiving reactor is 1/2~10/1, preferably 1/1~5/1.

36. according to the Acidic Gas Treating method described in claim 21, wherein step（3）It is described go out first order absorption reactor it is anti- Tri- tunnels NaHS products Ye Fen that should be obtained, the first via enter products pot, and the second tunnel enters the heat transmission equipment in hydrate neutralizing device It is used as heat source, third road is recycled back to first order absorption reactor, and the first via NaHS product liquids product flow is total flow 0~1/10；The second road NaHS product liquids product flow is the 1/10~1/5 of total flow；The third road NaHS products Liquid volume flow is the 4/5~9/10 of total flow.

37. according to the Acidic Gas Treating method described in claim 21, wherein step（4）Described in secondary absorber react To reaction generate liquid divide two-way, the first via to enter first order absorption reactor, the second tunnel is recycled back to two level absorbing reaction device, described Second tunnel absorbing liquid volume flow is 2~20, preferably 4~10 with first via absorbing liquid volume flow ratio.

38. according to the Acidic Gas Treating method described in claim 21, wherein hydrate neutralizing device is to be internally provided with heat exchange to set Standby tower or tank body.

39. according to the Acidic Gas Treating method described in claim 21 or 38, wherein the hydrate neutralizing device includes upper envelope Head, shell and low head are provided with air and liquid mixer and gas phase outlet line on the upper cover, are provided on the low head Liquid-phase outlet pipeline, the enclosure interior are divide into upper part and lower part by partition board, and respectively the hydrate bringing-up section on top is under The hydrate in portion dissolves gasification section, and heat transmission equipment, the shell of the hydrate bringing-up section are provided in the hydrate bringing-up section On be provided with rich hydrate working solution suction line and liquid-phase outlet pipeline, described heat transmission equipment one end and the rich hydrate work Make the connection of liquid suction line, the heat transmission equipment other end is extend into across partition board in hydrate neutralizing gasification section, and hydrate dissolves gas Change and be provided with heat transmission equipment in section, gaseous phase outlet pipeline and liquid phase entrance are provided on the shell of the hydrate neutralizing gasification section The gas phase entrance of pipeline, the gaseous phase outlet pipeline and air and liquid mixer that hydrate dissolves gasification section connects, the hydrate neutralizing The outlet of heat transmission equipment in gasification section is connected through the liquid phase entrance of pipeline and air and liquid mixer, and hydrate is dissolved in gasification section The liquid phase suction line that heat transmission equipment one end is dissolved with hydrate on the shell of gasification section is connect.

40. according to the Acidic Gas Treating method described in claim 39, wherein be provided with brokenly in the hydrate neutralizing gasification section Baffle assembly is split, the rupture baffle assembly is set to above heat transmission equipment.

41. according to the Acidic Gas Treating method described in claim 39, wherein be arranged on the hydrate neutralizing gasification piece housing There are stripping gas suction line, stripping gas suction line to be connected with stripping gas distributor, the stripping gas suction line is set to shell Below body.

42. according to the Acidic Gas Treating method described in claim 39, wherein the heat transmission equipment is wall-type heat exchange equipment, For one kind in shell-and-tube, board-like, bushing type and jacket type etc., preferably pipe shell type heat exchange equipment.

43. according to the Acidic Gas Treating method described in claim 39, wherein the air and liquid mixer is to have to take out to gas The air and liquid mixer of energy-absorbing power, the preferably air and liquid mixer of venturi form.

44. according to the Acidic Gas Treating method described in claim 39, wherein hydrate bringing-up section dissolves gasification section with hydrate Volume ratio be 1/3~2/1, preferably 1/2~1/1.

45. according to the Acidic Gas Treating method described in claim 39, wherein anti-from hydration in the hydrate bringing-up section The rich hydrate working solution of device is answered to walk tube side, the NaHS product liquid as heat source carries out external heating, and liquid holdup adds for hydrate The 1/4~3/4 of hot arc volume, preferably 1/3~2/3.

46. according to the Acidic Gas Treating method described in claim 39, wherein the rupture baffle assembly using filling-material structure, Any one of screen net structure or mesh structure.

47. according to the Acidic Gas Treating method described in claim 39, wherein in the hydrate neutralizing gasification section, NaHS Product liquid walks tube side, and hydrate working solution is heated in outside, and hydrate working solution liquid holdup is that hydrate neutralizing gasification section is total The 1/3~2/3 of volume, preferably 1/2~3/5.

48. according to the Acidic Gas Treating method described in claim 39, wherein the stripping gas is to dissolve device operation in hydrate Under the conditions of the arbitrary gas that does not react with hydrate working solution, sour gas and follow-up NaOH solution, specially low pressure gas One or more of gas, nitrogen or inert gas.

49. according to the Acidic Gas Treating method described in claim 39, wherein the volume flow of the stripping gas and release High concentration H₂The volume flow ratio of S gases is 1/10~2/1, preferably 1/5~1/1.

50. according to the Acidic Gas Treating method described in claim 21, wherein the hydrate working solution is added with auxiliary agent Aqueous solution, the auxiliary agent includes auxiliary agent A, the auxiliary agent A be lauryl sodium sulfate, sodium dodecylbenzenesulfonate, linear alkane One or more of base sodium sulfonate, alkyl polyglycoside, mass fraction 0.005%~1.0%, preferably 0.01%~0.5 %.

51. according to the Acidic Gas Treating method described in claim 50, wherein also add auxiliary agent in the hydrate working solution B, the auxiliary agent B are one or more of kerosene, diesel oil and silicone oil, the additive amount of auxiliary agent B and water in hydrate working solution Volume ratio is 1/5~2/1, preferably 1/3~1/1.

52. according to the Acidic Gas Treating method described in claim 51, wherein when adding auxiliary agent in the hydrate working solution When B, add emulsifier, selected emulsifier is hydrophilic emulsifier or lipophilic emulsifier, the additive amount of emulsifier with The mole fraction of water is 0.5%~3% in hydrate working solution.

53. according to the Acidic Gas Treating method described in claim 50, wherein further include auxiliary agent in the hydrate working solution C, the auxiliary agent C are N-Methyl pyrrolidone, propene carbonate, sulfolane, N- N-formyl morpholine Ns, one kind in polyethylene glycol or several Kind, the mass fraction of the auxiliary agent C is 2%~30%, preferably 5%~20 %.