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CN108722149A - A kind of processing method and processing device of sour gas - Google Patents

A kind of processing method and processing device of sour gas Download PDF

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Publication number
CN108722149A
CN108722149A CN201710240803.8A CN201710240803A CN108722149A CN 108722149 A CN108722149 A CN 108722149A CN 201710240803 A CN201710240803 A CN 201710240803A CN 108722149 A CN108722149 A CN 108722149A
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CN
China
Prior art keywords
hydrate
liquid
gas
reactor
acidic gas
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CN201710240803.8A
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CN108722149B (en
Inventor
孟凡飞
彭德强
王海波
王璐瑶
陈新
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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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • 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
    • C01B17/22—Alkali metal sulfides or polysulfides
    • C01B17/32—Hydrosulfides of sodium or potassium

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

The invention discloses a kind of processing method and processing device of sour gas, described device includes hydration reactor, hydrate neutralizing device, first order absorption reactor, two level absorbing reaction device and products pot.Additionally provide a kind of method that sour gas is handled using above-mentioned apparatus.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 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 processing method and processing device of sour gas
Technical field
The present invention relates to a kind of processing method and processing devices of 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 processing method and processing device of 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, and the liquid-phase outlet of first order absorption reactor divides two-way, 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, the liquid of two level absorbing reaction device Mutually outlet is connect with the liquid phase entrance of first order absorption reactor, and liquid phase entrance and the alkali liquor inlet pipeline of two level absorbing reaction device connect It connects, 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 NaHS products liquid obtained by the reaction divides two-way, the first via to enter hydrate neutralizing device and used as heat source, Second tunnel enters products pot；
（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.
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 The volume flow ratio of hydrate 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 the obtained NaHS product liquid of first order absorption reactor reaction divide two-way, Enter hydrate neutralizing device all the way to use as heat source, the second tunnel enters products pot, and the first via enters hydrate neutralizing device NaHS product flow quantities account for the 1/3~1/1 of NaHS product liquid total flows, preferably account for the 2/3~1/ of NaHS product liquid total flows 1。
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, 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, preferably 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.
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.
Description of the drawings
Fig. 1 is the processing method and processing device flow diagram of sour gas provided by the invention.
Fig. 2 is that the hydrate in the processing method and processing device of sour gas provided by the invention dissolves device structural schematic diagram.
Specific implementation mode
It elaborates to the processing method and processing device of the 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, and described device includes hydration reactor 4, hydrate neutralizing device 7, one Grade absorbing reaction device 12, two level absorbing reaction device 14 and products pot 22；The gas phase of sour gas feeding line 1 and hydration reactor 4 Entrance connects, and compressor 2 is arranged on sour gas feeding line 1, and the liquid-phase outlet of hydration reactor 4 divides two-way, wherein 6 warp all the way The liquid phase entrance that pipeline dissolves device 7 with hydrate is connect, and another way 27 is connect through pipeline with hydrate working solution suction line 25, The liquid-phase outlet of 7 bottom of hydrate neutralizing device divides two-way, wherein the 8 hydrate working solution through pipeline Yu hydration reactor 4 all the way Suction line 25 connects, and another way 28 is connect through pipeline with hydrate neutralizing device liquid phase entrance, 7 bottom of the hydrate neutralizing device Liquid-phase outlet and hydration reactor 4 hydrate working solution suction line 25 connecting pipeline on be provided with cooler 9.It is described Hydrate neutralizing device lower part of the housing is provided with stripping gas suction line 26.Hydrate dissolves the gaseous phase outlet and level-one at 7 top of device The gas phase entrance of absorbing reaction device 12 connects, the gas phase of the gaseous phase outlet and two level absorbing reaction device 14 of first order absorption reactor 12 Entrance connects, and the gaseous phase outlet of two level absorbing reaction device 14 is connect with clean gas outlet pipeline 15, first order absorption reactor 12 Liquid-phase outlet divides two-way, the first via 20 to be connect with products pot 22, and the second tunnel 19 dissolves heat transmission equipment and production in device 7 through hydrate Product tank 22 connects, and the liquid-phase outlet of two level absorbing reaction device 14 is connect with the liquid phase entrance of first order absorption reactor 12, and two level is inhaled The liquid phase entrance for receiving reactor 14 is connect with alkali liquor inlet pipeline 16, and products pot 22 is exported through pipeline and two level absorbing reaction device 14 Liquid phase entrance connection.
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, It will be enriched in H again2The hydrate phase of S gas molecules, wherein 27 being recycled back to hydration reactor all the way, another way 6 is delivered to hydrate Dissolve device 7, exchange heat with the NaHS products liquid 19 from first order absorption reactor 12, is rich in H2After the hydrate phase decomposition of S Obtain regeneration hydrate working solution and H2S gases 11, obtained regeneration hydrate working solution divide two-way, wherein all the way 8 through cooling Device 9 returns to hydration reactor 4 after cooling down and recycles, and 28 self-loopa return water of another way closes materialization solution device, the NaHS productions after heat exchange Product liquid 19 enters products pot；Obtained H2S gases 11 by from the stripping gas of stripping gas suction line 26 stripping after together into Enter first order absorption reactor 12, generates liquid 17 with the reaction from two level absorbing reaction device 14 and contact and reacted, is obtained by the reaction NaHS products liquid 18 divide two-way, the first via 19 enters hydrate neutralizing device and is used as heat source, and the second tunnel 20 is into products pot； The gas phase 13 that is obtained after first order absorption reactor for treatment enters two level absorbing reaction device 14, and from alkali liquor inlet pipeline 16 Lye and the contact of NaHS products liquid 23 from products pot 22 reacted, the remaining lack of gas obtained after reaction treatment are up to standard logical Cross the discharge of clean gas outlet pipeline 15.
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 of S gas molecules mutually 27 returns to hydration reactor recycling all the way, Another way 6 enters the heat transmission equipment 33 in the hydrate bringing-up section 46 of hydrate neutralizing device 7 through rich hydrate working solution pipeline 45 Tube side, exchange heat with the NaHS product liquid in 46 shell of hydrate bringing-up section, by heat exchange be rich in H2S gases point The hydrate of son is mutually evenly distributed on through liquid phase distributor 39 in hydrate neutralizing gasification section 49, sprayed by hydrate bringing-up section and Under hydrate work drop be broken into more tiny droplet/drop by the rupture shock of baffle assembly 48, and with from bottom to top Gas（Discharge gas and stripping gas）The realization cutting on rupture baffle assembly 48, the more conducively absorption of heat are simultaneously discharged and are taken away Gas；Droplet/drop after rupture cutting falls, and further exchanges heat through heat transmission equipment 47, in 47 tube side of the heat transmission equipment Liquid is anti-into the first order absorption in 47 tube side of heat transmission equipment through the liquid phase suction line 41 in hydrate neutralizing gasification section 49 The products of the NaHS all the way liquid 19 for answering device 12, the liquid phase that the product liquid 19 after heat exchange enters air and liquid mixer 36 through pipeline 53 enter Mouth enters air and liquid mixer 36, while the stripping gas suction line 42 by being arranged on hydrate neutralizing 49 shell of gasification section is passed through vapour Gas is carried, the H that hydrate phase decomposition is discharged2The gaseous phase outlet pipeline 35 that S gases dissolve gasification section 49 by hydrate is passed through gas It mixes in device 36 and is further reacted with the NaHS products liquid 19 by heat exchange, the Na that will contain in NaHS products liquid 192S is into one Step and H2S gas reactions, Na in the NaHS product liquid ensured2S contents comply with standard, in the hydrate bringing-up section 46 To liquid phase sent to products pot through liquid-phase outlet pipeline 37.The partial pressure that balances each other of this system can be reduced by being passed through stripping gas, Increase H2The motive force that balances each other that S gas hydrates decompose；Liquid in hydrate neutralizing 49 shell of gasification section is gone out by liquid phase It is divided into two-way after mouth 44, wherein 28 being recycled to hydrate bringing-up section 46 all the way, another way 8 is delivered to water after the cooling of cooler 9 Reactor 4 is closed to recycle.Gas in the hydrate bringing-up section 46 is sent through the discharge of gaseous phase outlet pipeline 34 to first order absorption Reactor is handled, and is generated liquid 17 with the reaction from two level absorbing reaction device 14 and is contacted and is reacted, obtained by the reaction NaHS products liquid 18 divides two-way, the first via 19 to enter hydrate neutralizing device and used as heat source, and the second tunnel 20 enters products pot；Through It crosses the gas phase 13 that is obtained after first order absorption reactor for treatment and enters two level absorbing reaction device 14, and from alkali liquor inlet pipeline 16 Lye and from products pot 22 NaHS products liquid 23 contact reacted, the remaining lack of gas obtained after reaction treatment are up to standard to be passed through Clean gas outlet pipeline 15 discharges.
Embodiment 1
Certain sour gas amount Q=400Nm3/ h, pressure 0.7Mpa, wherein H2S volume fractions are 84%, CO2Volume fraction is 15%, 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 12%, 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 8m 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 83%.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 90Nm3/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.86 DEG C of NaHS liquid-phase products temperature for going out first-stage reactor fully enters hydrate neutralizing device as heat Source, 48 DEG C of greenhouse cooling enters products pot after heat exchange.Products pot is back to production of the two level absorbing reaction device as systemic circulation Product flow quantity is 3.2m3/h.Whole process in the present embodiment can produce the NaHS products that mass concentration is higher than 42%, and Na2S Content is less than 1w%, meets《GB23937-2009》The industrial NaHS fluid products national standard of middle requirement；Meanwhile sour gas passes through H in lack of gas after two stage treatment2S 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 6.5m3/ h, reduces again Raw absorbing liquid cooling energy consumption 20% or so；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 wt% Hereinafter, 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 75% or so；Rich hydrate working solution is after hydrate neutralizing device processing, CO in gas2A concentration of 5% or so, increase CO2 Form Na2CO3/ NaHCO3Continuous, stable operation the influence to NaHS production units of equal substances, increases device long-term operation Operation difficulty.

Claims (53)

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 the liquid-phase outlet of first order absorption reactor divides two-way, the first via to connect 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 outlet and one of two level absorbing reaction device The liquid phase entrance connection of grade absorbing reaction device, the liquid phase entrance of two level absorbing reaction device are connect with alkali liquor inlet pipeline, 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 set on the sour gas feeding line, For ensureing that acid atmospheric pressure matches with hydration reactor operating pressure.
3. 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.
4. Acidic Gas Treating device described in accordance with the claim 3, wherein the first order absorption reactor and two level absorbing reaction Device is one in bubbling column reactor, filler tower reactor, impact flow reactor, rotary drill reactor and venturi reactor Kind, preferably rotary drill reactor.
5. 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.
6. Acidic Gas Treating device described in accordance with the claim 1, wherein the hydrate neutralizing device is to be internally provided with heat exchange The tower or tank body of equipment.
7. Acidic Gas Treating device according to claim 6, wherein be provided with stripping on the hydrate neutralizing device shell Gas suction line.
8. according to the Acidic Gas Treating device described in claim 1 or 6, wherein the hydrate neutralizing device includes upper cover, shell Body and low head are provided with air and liquid mixer and gas phase outlet line on the upper cover, liquid phase are provided on the low head Outlet line, the enclosure interior are divide into upper part and lower part by partition board, respectively the hydrate bringing-up section on top and lower part Hydrate dissolves gasification section, is provided with heat transmission equipment in the hydrate bringing-up section, is set on the shell of the hydrate bringing-up section It is equipped with rich hydrate working solution suction line and liquid-phase outlet pipeline, described heat transmission equipment one end and the rich hydrate working solution Suction line connects, and the heat transmission equipment other end is extend into across partition board in hydrate neutralizing gasification section, and hydrate dissolves gasification section It is inside provided with heat transmission equipment, gaseous phase outlet pipeline and liquid phase inlet tube are provided on the shell of the hydrate neutralizing gasification section The gas phase entrance of line, the gaseous phase outlet pipeline and air and liquid mixer that hydrate dissolves gasification section connects, and the hydrate dissolves gas The outlet for changing the heat transmission equipment in section is connected through the liquid phase entrance of pipeline and air and liquid mixer, changing in hydrate neutralizing gasification section The liquid phase suction line that hot equipment one end is dissolved with hydrate on the shell of gasification section is connect.
9. Acidic Gas Treating device according to claim 8, wherein be provided with rupture in the hydrate neutralizing gasification section Baffle assembly, the rupture baffle assembly are set to above heat transmission equipment.
10. Acidic Gas Treating device according to claim 8, 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.
11. Acidic Gas Treating device described in accordance with the claim 1, wherein the heat transmission equipment is wall-type heat exchange equipment, tool Body is one kind in shell-and-tube, board-like, bushing type and jacket type, preferably pipe shell type heat exchange equipment.
12. Acidic Gas Treating device according to claim 8, wherein the air and liquid mixer is to have suction to gas The air and liquid mixer of ability, the preferably air and liquid mixer of venturi form.
13. Acidic Gas Treating device according to claim 8, wherein the hydrate bringing-up section dissolves gas with hydrate The volume ratio for changing section is 1/3~2/1, preferably 1/2~1/1.
14. Acidic Gas Treating device according to claim 8, 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.
15. Acidic Gas Treating device according to claim 8, wherein described to state heat transmission equipment in hydrate bringing-up section and wear Cross partition board extend into hydrate neutralizing gasification section in one end outlet be connected with liquid distribution trough.
16. Acidic Gas Treating device according to claim 8, wherein the rupture baffle assembly is using filling-material structure, silk Any one of web frame or mesh structure.
17. Acidic Gas Treating device according to claim 8, wherein the installation site of the rupture component is set to When holding nozzle operation, the position in the entire neutralizing device section of inlet zone covering.
18. Acidic Gas Treating device according to claim 8, 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 10, 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 19, wherein the volume flow of the stripping gas and release High concentration H2The volume flow ratio of S gases is 1/10~2/1.
21. Acidic Gas Treating device according to claim 20, wherein the volume flow of the stripping gas and release High concentration H2The volume flow ratio of S gases is 1/5~1/1.
22. 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, and NaHS products liquid obtained by the reaction divides two-way, the first via to enter hydrate neutralizing device and used as heat source, the Two tunnels enter products pot；
（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.
23. according to the Acidic Gas Treating method described in claim 22, wherein the step（1）The hydrate working solution is used Amount is 5~100L/m with sour gas volume ratio3, preferably 10~50L/m3。
24. according to the Acidic Gas Treating method described in claim 22, 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.
25. according to the Acidic Gas Treating method described in claim 22, 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.
26. according to the Acidic Gas Treating method described in claim 22, 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%.
27. according to the Acidic Gas Treating method described in claim 22, 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.
28. according to the Acidic Gas Treating method described in claim 22, 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.
29. according to the Acidic Gas Treating method described in claim 22, 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.
30. according to the Acidic Gas Treating method described in claim 22, wherein step（2）The hydrate neutralizing device releases Gas in H2S volume fractions are higher than 95%, CO2Volume fraction is less than 5%.
31. according to the Acidic Gas Treating method described in claim 22, 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.
32. according to the Acidic Gas Treating method described in claim 22, 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℃。
33. according to the Acidic Gas Treating method described in claim 22, wherein the lye is NaOH solution, and mass concentration is 20%~60%, preferably 32%~48%.
34. according to the Acidic Gas Treating method described in claim 22, wherein the lye dosage is according to step（3）After processing Gas phase in H2S contents are adjusted, and by adjusting NaOH solution addition, ensure to pass through step（4）H in lack of gas that treated2S contains Amount is 10 mg/Nm of <3, and control NaOH solution and excessively do not ensure that NaHS products are qualified.
35. according to the Acidic Gas Treating method described in claim 22, 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 22, wherein step（3）It is described go out first order absorption reactor it is anti- The NaHS product liquid that should be obtained divides two-way, the first via to enter hydrate neutralizing device and used as heat source, and the second tunnel enters products pot, The NaHS product flow quantities that the first via enters hydrate neutralizing device account for the 1/3~1 of NaHS product liquid total flows, preferably account for The 2/3~1 of NaHS product liquid total flows.
37. according to the Acidic Gas Treating method described in claim 22, wherein hydrate neutralizing device is to be internally provided with heat exchange to set Standby tower or tank body, hydrate dissolve device using the NaHS products liquid of first order absorption reactor output as heat transmission equipment heat source, It will be enriched in H2After the hydrate working solution heating of S gases, products pot is returned.
38. according to the Acidic Gas Treating method described in claim 22 or 37, 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.
39. according to the Acidic Gas Treating method described in claim 38, 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.
40. according to the Acidic Gas Treating method described in claim 38, 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.
41. according to the Acidic Gas Treating method described in claim 22, wherein the heat transmission equipment is wall-type heat exchange equipment, One kind specially in shell-and-tube, board-like, bushing type and jacket type etc., preferably pipe shell type heat exchange equipment.
42. according to the Acidic Gas Treating method described in claim 38, 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.
43. according to the Acidic Gas Treating method described in claim 38, wherein hydrate bringing-up section dissolves gasification section with hydrate Volume ratio be 1/3~2/1, preferably 1/2~1/1.
44. according to the Acidic Gas Treating method described in claim 38, 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.
45. according to the Acidic Gas Treating method described in claim 38, wherein the rupture baffle assembly using filling-material structure, Any one of screen net structure or mesh structure.
46. according to the Acidic Gas Treating method described in claim 38, 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.
47. according to the Acidic Gas Treating method described in claim 40, 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.
48. according to the Acidic Gas Treating method described in claim 47, 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.
49. according to the Acidic Gas Treating method described in claim 38, wherein hydrate neutralizing device bottom liquid is followed by pump Ring to hydrate bringing-up section and be delivered to hydrate reactor recycling liquid measure ratio preferably 1/2~10/1, more preferable 1/1~ 5/1。
50. according to the Acidic Gas Treating method described in claim 22, 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 are 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, emulsifier is added, selected emulsifier is hydrophilic emulsifier or lipophilic emulsifier, the additive amount and water of emulsifier The mole fraction for closing water in object working solution is 0.5%~3%.
53. according to the Acidic Gas Treating method described in any claim in claim 50-52, wherein the hydrate Working solution includes auxiliary agent C, and the auxiliary agent C is N-Methyl pyrrolidone, propene carbonate, sulfolane, N- N-formyl morpholine Ns, poly- second The mass fraction of one or more of glycol, the auxiliary agent C is 2%~30%, preferably 5%~20 %.
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