CN106931722A - A kind of synthesis gas componentses are separated and retracting device and method - Google Patents

A kind of synthesis gas componentses are separated and retracting device and method Download PDF

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Publication number
CN106931722A
CN106931722A CN201710276715.3A CN201710276715A CN106931722A CN 106931722 A CN106931722 A CN 106931722A CN 201710276715 A CN201710276715 A CN 201710276715A CN 106931722 A CN106931722 A CN 106931722A
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gas
hydrogen
infiltration
membrane
stream
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CN106931722B (en
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廖祖维
胡永欣
包崇龙
黄正梁
孙婧元
杨遥
王靖岱
蒋斌波
阳永荣
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/08—Separating gaseous impurities from gases or gaseous mixtures or from liquefied gases or liquefied gaseous mixtures
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/0605—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the feed stream
    • F25J3/0625—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
    • 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
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/0655—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/067—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of carbon dioxide
    • 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
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D2053/221—Devices
    • B01D2053/223—Devices with hollow tubes
    • B01D2053/224—Devices with hollow tubes with hollow fibres
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/80—Processes or apparatus using other separation and/or other processing means using membrane, i.e. including a permeation step
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/02—Multiple feed streams, e.g. originating from different sources
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/04—Separating impurities in general from the product stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/04—Internal refrigeration with work-producing gas expansion loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/12—External refrigeration with liquid vaporising loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/66—Closed external refrigeration cycle with multi component refrigerant [MCR], e.g. mixture of hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

Separated and the device and method for reclaiming for synthesis gas componentses the invention discloses a kind of.The device includes：Compression mechanism, its infiltration gas for being used to receiving the conveying of UF membrane mechanism, will infiltration atmospheric pressure be compressed to the same grade of unstripped gas, deep cooling mechanism is delivered to after both are mixed；Deep cooling mechanism, it is used to receive the gaseous mixture from the compression mechanism, and separates and recovers carbon dioxide therein, and discharges hydrogen-rich gas；UF membrane mechanism, its be used for receive the hydrogen-rich gas from the deep cooling mechanism, hydrogen in gas and carbon dioxide are further separated, can obtain hydrogen purity it is higher ooze residual air and the more infiltration gas of carbonated.Device of the invention is worked by the cooperation of compression mechanism, deep cooling mechanism and UF membrane mechanism, can not only hydrogen and carbon dioxide in high efficiente callback synthesis gas, and realize and obtain high-recovery simultaneously in the case where low energy consumption is reclaimed.

Description

A kind of synthesis gas componentses are separated and retracting device and method
Technical field
The invention belongs to synthesis gas process field, and in particular to a kind of synthesis gas componentses are separated and the device and side for reclaiming Method.
Background technology
In synthesis gas production with preparation process, due to raw material sources and the difference of processing technology, what reaction was prepared Synthesis gas contains in addition to hydrogen also a large amount of foreign gases (carbon dioxide, hydrogen sulfide, nitrogen etc.).From purifying hydrogen of hydrogen, control Greenhouse gas emission, reduces sour gas and the angle that follow-up equipment corrodes is set out, it is necessary to separated synthesis gas, to prepare Required product, and ensure the safety of lower procedure and product.
Compression condensation method is a kind of traditional gas separating method, using the difference of each component dew point in unstripped gas, is passed through Pressurization and cool down its partial liquefaction, at low temperature rectifying and realize gas and separate.The method has that flow is simple, treating capacity Greatly, the advantages of rate of recovery is high, separates in synthesis gas and has been widely used with recovery.But compression condensation method mainly have with Lower weak point：The startup time is long, very flexible, high energy consumption.In addition it is to avoid gas from blocking pipeline, in addition it is also necessary to which removing is former in advance Carbon dioxide and moisture in material gas.
Selectivity of the pressure swing adsorption method using different component in gaseous mixture in particular adsorbent is different and realization separates mesh 's.It is mainly used in separating synthetic gas at present, and to hydrogen purification.Although pressure swing adsorption method gained hydrogen product purity is high, But its flow is complicated, number of devices is more, and substantial amounts of absorption tower is repeatedly boosted and is depressured, and this needs extra energy consumption with public affairs With engineering, operating cost and investment is caused significantly to be increased.
Domestic and international synthesis gas preparation facilities increased membrane separation device for the separation and recovery of synthesis gas.Patent CN101417799A, washed using low-temp methanol-desulfurization decarbonization purification system pre-processes to synthesis gas, obtain and mainly include CO And H2Purified gas, afterwards using heat exchanger heat up enter the isolated high-purity CO of membrane separator and H2.There is investment in the method High, equipment is complicated, reclaim H2The shortcomings of purity is relatively low.
In patent CN202156925U, pre-separation is carried out to synthesis gas using membrane separation device, then inhale with the use of transformation Adsorption device obtains high-purity hydrogen.Its shortcoming is that impermeable gas are not recycled, and directly reduces returning for the products such as hydrogen Yield, while pressure-swing absorption apparatus voltage raising and reducing repeatedly, energy ezpenditure is higher.
In patent CN101875484A, the synthesis gas more for acid gas-containing removes synthesis using Physical Absorption solvent H in gas2S simultaneously removes CO by chemical absorption solvents from synthesis gas2, obtain purity H higher2, finally by absorbent Treatment obtains high-purity CO2.Disadvantage is that carry out regeneration treatment to absorbent, energy resource consumption is needed than larger for it Lasting supplement is carried out to absorbent, is operated complex.
Although the above method can realize H in synthesis gas2Etc. the separation and recovery of component, but generally existing operation is multiple Miscellaneous, energy consumption is too high, treatment underaction the shortcomings of.Therefore invention one kind efficiently separates synthesis gas, can especially reduce synthesis qi leel The device and method of energy ezpenditure has great economic interests and realistic meaning in recovery.
The content of the invention
An object of the present invention is to provide the device that a kind of synthesis gas componentses are separated and reclaimed.It includes compressor Structure, deep cooling mechanism and UF membrane mechanism.Device of the invention is matched somebody with somebody by the collaboration of compression mechanism, deep cooling mechanism and UF membrane mechanism Work is closed, the hydrogen and carbon dioxide for obtaining high-recovery simultaneously in the case of low energy consumption is realized.
A further object of the present invention is to provide a kind of separation using above-mentioned synthesis gas componentses to separate conjunction with retracting device time Into the method for gas, it includes compression step, cryogenic separation step and UF membrane step.
According to an aspect of the present invention, the device with recovery is separated the invention provides a kind of synthesis gas componentses, it is described Device includes：
Be compressed to for infiltration atmospheric pressure by compression mechanism, its infiltration gas for being used to receive unstripped gas and the conveying of UF membrane mechanism With the same grade of unstripped gas, deep cooling mechanism is cooled down and is delivered to after both are mixed；
Deep cooling mechanism, it is used to receive the gaseous mixture from the compression mechanism, and separates and recovers carbon dioxide therein Gas, and discharge hydrogen-rich gas；
UF membrane mechanism, it is used to receive the hydrogen-rich gas from the deep cooling mechanism, to hydrogen in gas and titanium dioxide Carbon is further separated, and can obtain oozing residual air and infiltration gas, wherein infiltration gas is transfused to compression mechanism and does circular treatment；
Device of the invention is worked by the coordinated of compression mechanism, deep cooling mechanism and the part of UF membrane mechanism three, high Effect has reclaimed hydrogen in synthesis gas.And effectively reclaim the sour gas such as carbon dioxide, hydrogen sulfide present in synthesis gas, it is to avoid It corrodes to follow-up equipment.The wherein rate of recovery of hydrogen about 99%, the rate of recovery of carbon dioxide is more than 90%, vulcanizes hydrogen retrieval Rate about 98%.
A specific embodiment of the invention, the compression mechanism includes：At least one compressor, for receiving film The infiltration gas of separating mechanism conveying, infiltration atmospheric pressure is compressed to and the same grade of unstripped gas；At least one blender, for inciting somebody to action Unstripped gas and infiltration gas mixing, obtain the stream of gases at high pressure first；At least one heat exchanger, for cooling down the first stream.
A specific embodiment of the invention, the entrance of compression mechanism is connected with blender first entrance, compressor Outlet be connected with second entrance of blender, mixer outlet is connected with the entrance of heat exchanger, the outlet of heat exchanger and pressure The outlet of contracting mechanism is connected.
A specific embodiment of the invention, the deep cooling mechanism includes：At least one heat exchanger, for receiving simultaneously First stream of the cooling from compression mechanism, and output temperature is containing gas-liquid mixture the less than the first stream dew-point temperature Two streams；At least one gas-liquid separator, it is used to receive the second stream to carry out gas-liquid separation, and is exported back in liquid-phase outlet The high purity liquid carbon dioxide of receipts, and export the 3rd stream in gaseous phase outlet；At least one expanding machine, film is come from for receiving Separator oozes residual air, freezes and obtain part electric energy using high pressure gas expansion.
A specific embodiment of the invention a, entrance of deep cooling mechanism is connected with the outlet of compression mechanism, pressure The outlet of contracting machine is connected with the entrance of a heat exchanger, and the one outlet of heat exchanger is connected with the entrance of gas-liquid separator, gas-liquid point It is connected with an outlet of deep cooling mechanism from the gaseous phase outlet of device, the liquid-phase outlet of gas-liquid separator exports phase with the one of deep cooling mechanism Even, expander inlet is connected with the one outlet of UF membrane mechanism, an entrance phase of expander outlet and First Heat Exchanger group Even.
A specific embodiment of the invention, First Heat Exchanger is pipe heat exchanger, and its effect is by using just Suitable cold media, such as recirculated cooling water, by compression after the first stream be cooled to alap temperature, to save follow-up machine The energy consumption of structure.
A specific embodiment of the invention, to improve device energy efficiency, it is to avoid cryogenic gas is to subsequent film group The damage of part, the 3rd stream enters First Heat Exchanger group as cold logistics, 25~35 DEG C is warmed up to, while by after the expansion Residual air is oozed to be exchanged heat into First Heat Exchanger group, so as to using gases at high pressure acting cooling obtained by part/whole cold as The low-temperature receiver of First Heat Exchanger group.
A specific embodiment of the invention, deep cooling mechanism is by the first stream from compression mechanism by heat exchanger Group is cooled to -25~-35 DEG C, so as to condense the sour gas such as recovery carbon dioxide.
A specific embodiment of the invention, the UF membrane mechanism includes：At least one membrane separator, it is used for The 3rd stream from the deep cooling mechanism is received, hydrogen in gas and carbon dioxide are further separated, can obtain oozing remaining Gas and infiltration gas.
A specific embodiment of the invention, the entrance of UF membrane mechanism is connected with the first outlet of deep cooling mechanism, Membrane separator entrance is connected with UF membrane mechanism entrance, the first outlet output of UF membrane mechanism ooze residual air and with the deep cooling machine The entrance of expanding machine one in structure is connected, the second outlet output infiltration gas of UF membrane mechanism.
A specific embodiment of the invention, described infiltration gas does circular treatment into the compression mechanism, by This significantly improves the rate of recovery of hydrogen and carbon dioxide.
According to a further aspect of the present invention, separate to come with the device for reclaiming the invention provides a kind of use synthesis gas componentses The method for separating and recovering synthesis gas, it comprises the following steps：
Compression step, receive infiltration gas and unstripped gas, and will infiltration atmospheric pressure be compressed to the same grade of unstripped gas, by two Exported after person's mixing；
Cryogenic separation step, receives gaseous mixture, and separates and recovers carbon dioxide therein, and discharges hydrogen-rich gas；
UF membrane step, receives hydrogen-rich gas, and hydrogen in gas and carbon dioxide are further separated, and residual air is oozed in discharge With infiltration gas, and by infiltration gas make circular treatment.
Compression deep cooling, UF membrane are all common separation means, and the present invention is by the reasonably optimizing to different separation modules With combine, there is provided a kind of synthesis gas componentses separate with the device and method for reclaiming, fully use high pressure feed, it is to avoid repeatedly The energy waste that voltage raising and reducing is caused.And in view of the shortcomings of the prior art, it has advantage following prominent：1st, to gas-liquid separator Gained gas phase stream carries out cold recovery, and oozes residual air swell refrigeration using high pressure, reduces the consumption of expensive low-temperature refrigerant 2nd, UF membrane mechanism gained infiltration gas circular treatment is improve into the rate of recovery 3 of the gases such as hydrogen, carbon dioxide, swollen using turbine Swollen machine produces electric power, and the overall energy consumption 4, plant investment of reduction is few, and high financial profit is environment friendly and pollution-free.
Brief description of the drawings
Technical scheme in order to illustrate more clearly the embodiments of the present invention, below will be to that will make needed for embodiment description Accompanying drawing does simply to be introduced, it is therefore apparent that the accompanying drawing in brief description is only some embodiments of the present invention, for this For the those of ordinary skill of field, on the premise of not paying creative work, can also obtain other according to these accompanying drawings Accompanying drawing.
Fig. 1 represents that a kind of synthesis gas componentses of the invention are separated and the schematic device for reclaiming.
Fig. 2 represents the schematic device of a preferred embodiment of the present invention.
In figure, identical component is indicated by identical reference.Accompanying drawing is not drawn according to actual ratio.
Specific embodiment
With reference to accompanying drawing of the invention, the technical scheme in the embodiment of the present invention understand be fully described by.It is aobvious So, described embodiment is only a part of embodiment of the invention, and is not all whole embodiments.Based in the present invention Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all Belong to the scope of protection of the invention.
As shown in Figure 1, separated the invention provides a kind of synthesis gas componentses includes with the device for reclaiming：
Compression mechanism X, its infiltration gas FP for being used to receive unstripped gas Feed and UF membrane mechanism Z conveyings, by infiltration gas FP Pressure be compressed to the same grade of unstripped gas, deep cooling mechanism is cooled down and is delivered to after both are mixed；
Deep cooling mechanism Y, it is used to receive the gaseous mixture F1 from the compression mechanism, and separates and recovers titanium dioxide therein Carbon gas FL, and discharge hydrogen-rich gas FG；
UF membrane mechanism Z, it is used to receive the hydrogen-rich gas FG from the deep cooling mechanism, to hydrogen in gas and dioxy Change carbon to be further separated, can obtain oozing residual air FR and infiltration gas FP, wherein infiltration gas FP is transfused to compression mechanism X and does at circulation Reason；
In the present embodiment, the molar flow rate of unstripped gas is 30000kmol/h, and pressure is 5MPa, and temperature is 20 DEG C, wherein Each component molar fraction is as follows：Hydrogen 56.4%, carbon dioxide 41.3%, carbon monoxide 1.1%, nitrogen 0.7%, hydrogen sulfide 0.5%.
In the present embodiment, compression mechanism X includes a compressor COM, the infiltration for receiving UF membrane mechanism Z conveyings Gas FP, and its pressure is promoted to 5MPa by 0.61MPa；One blender MIX, for unstripped gas Feed and infiltration gas FP to be mixed Close, obtain the first stream F1, pressure is 5MPa；One heat exchanger HEAT1, for the first stream F1 to be cooled to by 133.5 DEG C 35 DEG C, and export stream stock F2.
In the present embodiment, the entrance T1 of compression mechanism X is connected with blender MIX first entrances T2, and compressor COM's goes out Mouth T7 is connected with second entrance T4 of blender MIX, and mixer outlet T3 is connected with the entrance T8 of heat exchanger HEAT1, heat exchange The outlet T9 of device HEAT1 is connected with the one outlet T10 of compression mechanism X.
In the present embodiment, the heat exchanger HEAT1 is pipe heat exchanger, and its effect is by using cheap refrigerant Be situated between, such as recirculated cooling water, by compression after the first stream F1 be cooled to alap temperature, to save the energy of follow-up mechanism Consumption.
In the present embodiment, the deep cooling mechanism includes Y：One multithread stock heat exchanger MHEX, heat exchange is matched between stream stock Cold is reclaimed, and stream stock F2 is cooled to -15 DEG C；One heat exchanger HEAT2, -30 DEG C are cooled to by stream stock F3；One gas-liquid point From device SEPA, it is used to receive the second stream F4 to carry out gas-liquid separation, and liquid-phase outlet T17 outputs purity up to 96% Liquid CO 2, its ult rec is 90.0%, while discharge also has hydrogen sulfide, its rate of recovery is 98.3%, and Gaseous phase outlet exports the 3rd stream T15；One turbo-expander TURB, residual air FR is oozed for receiving from UF membrane mechanism Z, And its pressure is down to 3.1MPa by 5MPa, temperature is reduced to 2.3 DEG C by 30 DEG C, while the electric power of 4.1MW is produced, after cooling Ooze residual air and be admitted to multithread stock heat exchanger MHEX recovery colds.
In the present embodiment, the entrance T11 of deep cooling mechanism is connected with the outlet T10 of compression mechanism, heat exchanger HEAT1 outlets T9 is connected with an entrance a1 of multithread stock heat exchanger, the one outlet a2 and the entrance of the second heat exchanger of multithread stock heat exchanger T12 is connected, and the second heat exchanger exit T13 is connected with gas-liquid separator entrance T14, the liquid-phase outlet T17 and depth of gas-liquid separator The one outlet T18 of cold structure is connected, and gaseous phase outlet T15 is connected with multithread stock one entrance b1 of heat exchanger, multithread stock heat exchanger One outlet b2 be connected with the one outlet T16 of deep cooling mechanism, the entrance T24 of turbo-expander TURB and deep cooling mechanism An entrance T23, the one outlet T25 of turbo-expander is connected with an entrance c1 of multithread stock heat exchanger MHEX, multithread The one outlet c2 of stock heat exchanger MHEX is connected with the one outlet T26 of deep cooling mechanism.
In a preferred embodiment of the invention, as shown in Figure 2, the first stream F1 will by multithread stock heat exchanger MHEX Stream stock is cooled to -30 DEG C.The outlet T5 of heat exchanger HEAT1 is connected with an entrance a1 of multithread stock heat exchanger MHEX, multithread stock Heat exchanger MHEX one outlets a2 is connected with an entrance T14 of gas-liquid separator SEPA.
In a preferred embodiment of the invention, the multithread stock heat exchanger MHEX introduces low temperature stream stock C-1, and its composition is LPG, effect is for other heat exchange stream stocks provide enough colds.The temperature of low temperature stream stock C1 is -35 DEG C, through multithread stock One entrance f1 of heat exchanger MHEX enters, and is flowed out by the one outlet f2 of MHEX after heat exchange.
In a preferred embodiment of the invention, residual air FR is oozed from membrane separator MEMB, be introduced into multithread stock heat exchange Device MHEX is cooled to -20 DEG C, then by turbo-expander TURB swell refrigerations, its temperature is changed into -56.2 DEG C, less than the second material The dew-point temperature of F3 is flowed, multithread stock heat exchanger MHEX is subsequently entered and is reclaimed cold, final output mixture temperature is 30 DEG C, pressure It is 3.1MPa, wherein hydrogen content can be directly entered pressure-swing absorption apparatus and do further purification processes up to 90.1%.Membrane separator The residual air outlet T21 that oozes of MEMB is connected with an entrance c1 of multithread stock heat exchanger MHEX in deep cooling mechanism Y, multithread stock heat exchanger The entrance T24 of the one outlet c2 and turbo-expander TURB of MHEX is connected, outlet T25 and the multithread stock of turbo-expander TURB One entrance d1 of heat exchanger MHEX is connected, the one outlet of the one outlet d2 and deep cooling mechanism Y of multithread stock heat exchanger MHEX T26 is connected.
In a preferred embodiment of the invention, it is fully to reclaim cold, the condensate liquid from gas-liquid separator SEPA FL, 30 DEG C are warming up into multithread stock heat exchanger MHEX, and are changed into gas from liquid, and pressure is 4.9MPa, and after recovery two Carbonoxide can inject underground, reduce greenhouse gas emission.Gas-liquid separator SEPA one outlets T15 and multithread stock heat exchanger MHEX An entrance e1 be connected, the one outlet e2 of multithread stock heat exchanger MHEX is connected with the outlet T18 of deep cooling mechanism.
In a preferred embodiment of the invention, to oozing methods of the residual air FR using first cooling reflation refrigeration, make its temperature Degree can meet the demand exchanged heat with the second stream F3, reduce the use of expensive cryogenic coolant, effectively reduce flow operations Expense and equipment requirement.
In the present embodiment, the UF membrane mechanism Z includes：One membrane separator MEMB, it is used to receive from described The 3rd stream FG of deep cooling mechanism Y, is further separated to hydrogen in gas and carbon dioxide, can obtain oozing residual air FR and infiltration Gas FP.
In the present embodiment, the entrance T19 of UF membrane mechanism Z is connected with the outlet T16 of deep cooling mechanism, membrane separator MEMB Entrance T20 be connected with the entrance T19 of UF membrane mechanism Z, membrane separator MEMB oozes residual air outlet T21 and expanding machine TURB and enters Mouth T24 is connected, and membrane separator MEMB oozes vent outlet T27 and is connected with an outlet T28 of film separating structure Z, film separating structure Z's Outlet T28 is connected with an entrance T5 of compression mechanism X.
In the present embodiment, membrane separator MEMB uses film type for hollow-fibre membrane, CO2/H2Selectivity be 10, Membrane area is 1620m2。
In the present embodiment, described infiltration gas FP does circular treatment into the compression mechanism X, thus significantly improves The rate of recovery of hydrogen and carbon dioxide.
In a preferred embodiment of the invention, described infiltration gas FP is introduced into swollen by turbine in the deep cooling mechanism Y In the coaxial compressor TURB-COM that swollen machine drives, pressure is increased to 1.03MPa by 0.61MPa.Enter the compression knot afterwards Pressure rise is to 5MPa in the compressor COM of structure X.Membrane separator MEMB to ooze vent outlet T27 coaxial with turbo-expander The entrance T30 of compressor TURB-COM is connected, and compressor enters in the outlet T31 and compression mechanism X of coaxial compressor TURB-COM Mouth T7 is connected.
From the above embodiment of the present invention, apparatus of the present invention are coordinated by cryogenic separation and membrane separator, separate and close Hydrogen and other gases into gas, gas reclaiming rate is improved by setting EGR, and reasonable employment expander refrigeration, reduction is right The dependence of expensive refrigerant, small investment low with energy consumption, the advantages of high financial profit is environment friendly and pollution-free.
Separate with the device for reclaiming to separate and recover the side of synthesis gas using synthesis gas componentses present invention also offers a kind of Method, it comprises the following steps：
Compression step, receive infiltration gas and unstripped gas, and will infiltration atmospheric pressure be compressed to the same grade of unstripped gas, by two Exported after person's mixing, concrete operation step is：(1) be forced into for the infiltration gas FP from membrane separator structure Z by compressor COM 5MPa；(2) the infiltration gas FP after compression and pressure are all 5MPa unstripped gas Feed and mix the first stream F1 of output, pressure by blender Power is 5MPa, 133.5 DEG C of temperature；(3) the first stream F1 is cooled to 35 DEG C by heat exchanger HEAT1.
Cryogenic separation step, receives gaseous mixture, and separates and recovers carbon dioxide therein, and discharges hydrogen-rich gas, Concrete operation step is：(1) using multithread stock heat exchanger MHEX, stream stock F2 temperature is reduced to -30 DEG C, exports the second stream F3 Into gas-liquid separator SPEA；(2) second stream F3 carry out gas-liquid separation in gas-liquid separator SEPA, gaseous phase outlet output the Three stream FG, liquid-phase outlet output liquid carbon dioxide etc.；(3) for recovery cold simultaneously, it is to avoid cryogenic gas is damaged to film unit Evil, the 3rd stream FG carries out re-heat into multithread stock heat exchanger MHEX, and temperature rises to 30 DEG C by -30 DEG C, finally from deep cooling mechanism Y Middle output enters UF membrane mechanism Z；(4) receive and cool down using multithread stock heat exchanger MHEX and ooze remaining from membrane separator MEMB Gas FR, makes its temperature be reduced to -20 DEG C by 30 DEG C, is transported to turbo-expander TURB；(5) residual air FR is oozed in turbine expansion It is depressured in machine TURB and is heated up, pressure is changed into 3.1MPa from 5MPa, and temperature is reduced to -56.2 DEG C by -20 DEG C；(6) after reducing temperature Ooze during residual air FR is transported to multithread stock heat exchanger MHEX and carry out cold recovery, finally in multithread stock heat exchanger MHEX exits Its temperature is 28.1 DEG C, and up to 90.1%, the rate of recovery is 99.6% to hydrogen content, can be used for subsequent technique treatment；(7) returned for abundant Receive cold, the condensate liquid FL from gas-liquid separator SEPA, into multithread stock heat exchanger MHEX temperature by -30 DEG C to 30 DEG C, And gas is changed into from liquid, pressure is 4.9MPa, and the carbon dioxide after recovery can inject underground, reduces greenhouse gas emission.
UF membrane step, receives hydrogen-rich gas, and hydrogen in gas and carbon dioxide are further separated, and residual air is oozed in discharge With infiltration gas, and by infiltration gas make circular treatment；Concrete operation step is：(1) the 3rd stream FG is input into membrane separator MEMB (films Area 1620m2, osmotic lateral pressure 0.61MPa) in, membrane module will dam most of hydrogen, output infiltration gas FP, ooze residual air FR Then it is delivered to the multithread stock heat exchanger MHEX in deep cooling mechanism Y；(2) the infiltration gas FP of output is first through the coaxial pressure of turbo-expander Contracting machine TURB-COM compresses, and pressure rises to 1.02MPa, compression mechanism X is transported to afterwards by 0.61MPa.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to of the invention any Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it is related to And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, conversely, this hair It is bright to can be extended to other all methods and applications with identical function.

Claims (8)

1. a kind of synthesis gas componentses are separated and the device for reclaiming, it is characterised in that including：
Be compressed to for infiltration atmospheric pressure same with unstripped gas by compression mechanism, its infiltration gas for being used to receive the conveying of UF membrane mechanism Grade, is delivered to deep cooling mechanism after both are mixed；
Deep cooling mechanism, it is used to receive the gaseous mixture from the compression mechanism, and separates and recovers carbon dioxide therein, And discharge hydrogen-rich gas；
UF membrane mechanism, it is used to receive the hydrogen-rich gas from the deep cooling mechanism, hydrogen in gas and carbon dioxide is done Further separate, can obtain hydrogen purity it is higher ooze residual air and the more infiltration gas of carbonated.
2. device according to claim 1, it is characterised in that the compression mechanism includes：At least one compressor, is used for The infiltration gas of UF membrane mechanism conveying is received, infiltration atmospheric pressure is compressed to and the same grade of unstripped gas；At least one blender, For unstripped gas and infiltration gas to be mixed, the stream of gases at high pressure first is obtained；At least one heat exchanger, for cooling down gases at high pressure First stream.
3. the device according to any one in claim 1~2, it is characterised in that the deep cooling mechanism includes：At least one Individual heat exchanger, it is used to receive and cool down the first stream from compression mechanism, and output temperature is less than the first stream dew point temperature Second stream containing gas-liquid mixture of degree；At least one gas-liquid separator, it is used to receive the second stream to carry out gas-liquid Separate, and the high-pureness carbon dioxide reclaimed in liquid-phase outlet output, and export the 3rd stream in gaseous phase outlet；At least one is swollen Swollen machine, residual air is oozed for receiving from membrane separator.
4. device according to claim 3, it is characterised in that the first stream from compression mechanism is passed through by deep cooling mechanism Heat exchanger is cooled to -25~-35 DEG C, so that the sour gas of condensation separation and recovery based on carbon dioxide；Expander outlet Pressure is 2.5~3.0MPa, is freezed by high pressure gas expansion and recovery section energy.
5. device according to claim 4, it is characterised in that the heat exchanger is pipe heat exchanger or plate type heat exchanger.
6. device according to claim 3, it is characterised in that the UF membrane mechanism includes：At least one membrane separator, It is used to receive the 3rd stream from the deep cooling mechanism, and hydrogen in gas and carbon dioxide are further separated, and obtains Ooze residual air and infiltration gas.
7. device according to claim 6, it is characterised in that the film type that the membrane separator is used is doughnut Film, CO2/H2Selectivity be 10, membrane area be 1500~2000m2, osmotic lateral pressure is 0.5-1.0MPa.
8. the synthesis gas componentses of any one described device separate the method with reclaiming in a kind of utilization claim 1~7, its bag Include following steps：
Compression step, receive infiltration gas and unstripped gas, and will infiltration atmospheric pressure be compressed to the same grade of unstripped gas, both are mixed Cooled down after conjunction and exported；
Cryogenic separation step, receives described gaseous mixture, and separates and recovers carbon dioxide therein, and discharges hydrogen rich gas Body；
UF membrane step, receives described hydrogen-rich gas, and hydrogen in gas and carbon dioxide are further separated, and discharge is oozed remaining Gas and infiltration gas, and infiltration gas is done into circular treatment.
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