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CN106256813A - A kind of separation and recovery method of Fischer-Tropsch process exhaust - Google Patents

A kind of separation and recovery method of Fischer-Tropsch process exhaust Download PDF

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Publication number
CN106256813A
CN106256813A CN201510333938.XA CN201510333938A CN106256813A CN 106256813 A CN106256813 A CN 106256813A CN 201510333938 A CN201510333938 A CN 201510333938A CN 106256813 A CN106256813 A CN 106256813A
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China
Prior art keywords
gas
separation
methane
ethylene
liquid
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CN201510333938.XA
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CN106256813B (en
Inventor
赵百仁
王振维
赵明瑞
王鑫泉
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Sinopec Engineering Inc
Sinopec Engineering Group Co Ltd
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Sinopec Engineering Inc
Sinopec Engineering Group Co Ltd
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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
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0219—Refinery gas, cracking gas, coke oven gas, gaseous mixtures containing aliphatic unsaturated CnHm or gaseous mixtures of undefined nature
    • 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
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0233—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 1 carbon atom or more
    • 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
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0238—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 2 carbon atoms or more
    • 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
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0252—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream 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
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/74—Refluxing the column with at least a part of the partially condensed overhead gas
    • 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
    • F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
    • F25J2205/04—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation 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
    • F25J2210/12—Refinery or petrochemical off-gas
    • 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
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/04—Recovery of liquid products
    • 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
    • F25J2270/08—Internal refrigeration by flash gas recovery 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
    • F25J2270/60—Closed external refrigeration cycle with single component refrigerant [SCR], e.g. C1-, C2- or C3-hydrocarbons

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses the separation and recovery method of a kind of Fischer-Tropsch process exhaust, Fischer-Tropsch process exhaust is first carried out thick gas-liquid separation by the method, then in domethanizing column, carry out demethanation process with thick gas-liquid separation together with the product liquid obtained after being lowered the temperature successively by the gaseous product that thick gas-liquid separation obtains, after the separation product obtained carries out a series of subsequent treatment, thick hydrogen production, liquefied natural gas and other hydrocarbon products are obtained.The method flow of the present invention is simple and direct, uses number of devices few, invests and take up an area saving, and product recovery rate is high, and comprehensive energy consumption is relatively low.

Description

A kind of separation and recovery method of Fischer-Tropsch process exhaust
Technical field
The present invention relates to the separation and recovery method of a kind of Fischer-Tropsch process exhaust.
Background technology
The coal resources of China are the abundantest, and Coal Chemical Industry is an emerging strategy field of China, and development is just Ground zero, in the ascendant.In the indirect liquefaction technique of coal liquifaction, a set of 1,000,000 tons/year of Low Temperature Fischer Tropsch The synthesis tail gas that synthesizer produces is more than 40 ton hour, and a set of 1,000,000 tons/year of high temperature FT synthesis Device produce synthesis tail gas especially more than 100 ton hour, wherein H2、CH4、C2H4And C3H6Deng Hydrocarbon component content is considerable, effectively recycles, and economic worth is notable.
FT synthesis tail gas is except containing a small amount of oxygen-containing organic compound and a certain amount of CO2Outward, possibly together with The H of the highest molar concentration2、N2, CO, Ar and CH4Etc. low boiling component, C2 ' s and C2 ' s+ hydrocarbon Class only accounts for 10～13% (weight accounts for 30～50%) of total gas volume.FT synthesis tail gas segregation apparatus Process target, it is simply that these objectionable impurities will be removed, reclaim useful constituent therein, make ethylene and propylene Reach polymer grade, methane reaches LNG (i.e. liquefied natural gas) standard, thick hydrogen send PSA to refine, and Isolate other hydrocarbon products as much as possible.
Owing to Coal Chemical Industry is a new industry, FT synthesis tail gas compared with various light hydrocarbon gas (as Ethylene cracking gas, MTO technology gas, dehydrogenating propane reaction gas, oil refinery dry gas, natural gas With coke-stove gas etc.), component and content all differ greatly, and product separation requirement is also the most comprehensive, Can directly use so there is presently no a kind of ready-made process for separating and recovering technology.
Summary of the invention
It is an object of the invention to provide the separation and recovery method of a kind of Fischer-Tropsch process exhaust, the letter of the method flow process Victory, uses number of devices few, invests and take up an area saving, and product recovery rate is high, and comprehensive energy consumption is relatively low.
To achieve these goals, the present invention provides the separation and recovery method of a kind of Fischer-Tropsch process exhaust, should Method includes: a, will be containing nitrogen, argon, carbon monoxide, carbon dioxide, hydrogen, methane, second The Fischer-Tropsch process exhaust of alkane, ethylene, propane, propylene, butane, butylene and gasoline component takes off successively After carbon dioxide treatment, compression process, cooling process, gas-liquid separation and dried, obtain 14～17 DEG C Gas phase Fischer-Tropsch process exhaust with 3.6～3.9 MPas and liquid phase Fischer-Tropsch process exhaust；B, by step a The gas phase Fischer-Tropsch process exhaust of gained uses two-stage nitration propylene refrigerant to carry out first order propylene condensation, obtains -15～the first order propylene condensed product of-19 DEG C and 3.69～3.89 MPas；By cold for described first order propylene Solidifying product uses one section of propylene refrigerant to carry out second level propylene condensation, obtains-30～-34 DEG C and 3.68～3.88 MPa second level propylene condensed product；C, the second level propylene condensed product of gained in step b is adopted Carry out the first ethylene Quench with two-stage nitration ethylene cryogen, obtain-50～-60 DEG C and 3.66～3.86 through gas-liquid separation MPa the first ethylene shock gas and the first ethylene Quench liquid；Described first ethylene shock gas is adopted Carry out the second ethylene Quench with one section of ethylene cryogen, obtain-96～-98 DEG C and 3.6～3.8 through gas-liquid separation MPa the second ethylene shock gas and the second ethylene Quench liquid；By described second ethylene shock gas by Off-gas expander provide cold condense further, through gas-liquid separation obtain-160 DEG C～-165 DEG C and The first time methane of 3.58～3.78 MPas/hydrogen separation gas separates liquid with methane/hydrogen for the first time；By institute State for the first time methane/hydrogen separation liquid and be warmed up to-101 DEG C～-102 DEG C and 3.09～3.29 MPas, as the One demethanation feeds；D, by the liquid phase Fischer-Tropsch process exhaust cooling decompression of gained in step a to-53～ After-57 DEG C and 3.2～3.4 MPas, obtain liquid phase Fischer-Tropsch process exhaust before demethanation processes；E, by step First burst of demethanation charging of gained, the second ethylene Quench liquid and the first ethylene Quench liquid and step in c Before in rapid d, gained demethanation processes, liquid phase Fischer-Tropsch process exhaust is-100～-105 DEG C and 3.00～3.20 million Carry out demethanation process under handkerchief, obtain-102～-105 DEG C and 3.00～3.20 MPas and ethylene contents little Demethanation gas and the demethanation liquid of 50～55 DEG C and 3.07～3.27 MPas in 0.2mol%；f、 The demethanation gas of gained in step e is separated gas mix with the first time methane/hydrogen of gained in step c Close, enter after off-gas expander swell refrigeration together, carry out second time methane/hydrogen and separate, obtain-175～ -180 DEG C of expansions with 0.25～0.33 MPa separate hydrogen and expand separation of methane；G, by institute in step f Must expand separation hydrogen successively with the second ethylene shock gas of gained in step c and the first ethylene Quench gas Gained second level propylene condensed product and institute in first order propylene condensed product, step a in body, step b State gas phase Fischer-Tropsch process exhaust and 38～40 DEG C of propylene refrigerant liquid carry out heat exchange after obtain the thick hydrogen of room temperature and produce Product.
Preferably, wherein, carbon dioxide removal described in step a process successively include washing or amine is washed, with And alkali cleaning.
Preferably, the method also includes: α, by more than half expansion separation of methane of gained in step f Carry out heat exchange with described second ethylene shock gas, obtain first burst of heat exchange and expand separation of methane gas；Will The gained demi-inflation separation of methane overhead condensation heat exchange that demethanation processes in step e in step f, Obtain second burst of heat exchange and expand separation of methane gas；By the expansion separation first of gained remainder in step f After alkane is vaporized hyperthermic treatment, obtains the 3rd burst of heat exchange and expand separation of methane gas；β, by step α Described in first burst of heat exchange expands separation of methane gas, second burst of heat exchange expands separation of methane gas and the 3rd Stock heat exchange expands separation of methane gas and merges into total heat exchange expansion of-100～-104 DEG C and 0.26-0.28 MPa After separation of methane gas, further heat up and process to room temperature, then at the most most three second compression After reason and cooling process, the expansion obtaining the 38-40 DEG C of compression cooling process with 5.0-6.5 MPa separates first Alkane gas；γ, by described in step β compress cooling process expansion separation of methane gas carry out desuperheating, Again, after liquefying and crossing cold treatment, expenditure and pressure obtains-162～the liquefaction sky of-163 DEG C and 15～20 kPas So gas product；δ, the flashed vapour of liquefied natural gas product described in step γ is carried out two-stage hyperthermic treatment After, after alternately 2～3 times boostings and cooling, as fuel gas.
Preferably, the method also includes: one section of ethylene cryogen used by described step c and two-stage nitration ethylene cold Agent, with step γ are compressed the ethylene cold used that again liquefies expanding separation of methane gas after cooling processes Agent, from same ethylene refrigeration machine.
Preferably, the method also includes: by the vapour expanding separation of methane of remainder described in step α Change the first order hyperthermic treatment of the flashed vapour of liquefied natural gas product described in hyperthermic treatment and step δ to be produced Raw cold for compress described in step γ that cooling processes expand separation of methane gas cross cold treatment.
Preferably, the method also includes: total heat exchange described in step β is expanded entering of separation of methane gas The second level hyperthermic treatment institute of the flashed vapour of liquefied natural gas product described in one step hyperthermic treatment and step δ The cold produced is for compressing described in step γ at the desuperheating expanding separation of methane gas that cooling processes Reason.
Preferably, the method also includes: total heat exchange described in step β expands the compression of separation of methane gas Process power demand all to be provided by the off-gas expander in step f.
Preferably, the method also includes: by gained demethanation liquid in step e-12～-16 DEG C and 2.1～ Carry out deethanization process under 2.3 MPas, obtain the deethanization gas containing ethylene and ethane and containing propane, The deethanization liquid of propylene, butane, butylene and gasoline component；Described deethanization gas is carried out ethylene essence Evaporate, obtain ethylene and ethane；Described deethanization liquid is carried out at 13～17 DEG C and 0.65～0.85 MPa Depropanization processes, and obtains the depropanization gas containing propane and propylene and containing butane, butylene and gasoline group The depropanization liquid divided；Described depropanization gas is carried out propylene rectification, obtains propylene and propane；By institute State depropanization liquid and carry out debutanization process at 46～50 DEG C and 0.35～0.45 MPa, obtain the mixed of liquid Close carbon four product and the gasoline component of liquid.
The method of the present invention can be to H2、N2, CO, Ar and CH4The highest Deng amount of components having low boiling points FT synthesis tail gas is successfully separated, and removes objectionable impurities, has reclaimed hydrocarbon component to greatest extent, Ethylene and propylene reaches polymer grade, methane reaches liquefied natural gas (i.e. LNG) standard can be made.Thick hydrogen In H2Yield >=99.9%；Yield of ethene >=99.1%；The yield of other heavy hydrocarbon is almost 100%.Adopt Methane recompression machine, energy efficient is driven with off-gas expander.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.? In accompanying drawing:
Fig. 1 is the schematic diagram that the present invention includes the used device of detailed description of the invention that demethanation processes；
Fig. 2 is the specific embodiment party that the present invention includes that Fischer-Tropsch process exhaust pretreatment separates with demethanation liquid The schematic diagram of the used device of formula.
Description of reference numerals
1 6# hydrogen recuperator 2 5# hydrogen recuperator 3 4# hydrogen recuperator
4 3# hydrogen recuperator 5 2# hydrogen recuperator 6 1# hydrogen recuperators
7 Fischer-Tropsch tail gas 1# condenser 8 Fischer-Tropsch tail gas 2# condenser 9 Fischer-Tropsch tail gas 1# ethylene condenser
10 Fischer-Tropsch tail gas 2# ethylene condenser 11 Fischer-Tropsch tail gas undercooling devices
12 domethanizing columns first feed knockout drum 13 domethanizing column second and feed knockout drum
14 domethanizing columns the 3rd feed knockout drum 15 demethanizer reboiler 16 domethanizing column
17 domethanizing column condenser 18 demethanizer reflux tank 19 decompressor head tanks
20 off-gas expander 21 liquid phase choke valve 22 hydrogen/methane separation tank 23 gas phase Fischer-Tropsch process exhaust
24 liquid phase Fischer-Tropsch process exhaust 25 thick hydrogen production 26 propylene refrigerant 27 demethanation liquid
28 one section 30 of natural gas condenser 29 methane recompression machine methane recompression machine two-stage nitration
31 three section 32 of methane recompression machine methane recompression machine the first aftercoolers
33 methane recompression machine the second aftercooler 34 methane recompression machine the 3rd aftercoolers
35 low temperature methane JT valve 36 natural gas storage tank 37 gas product 38 natural gas 1# heat exchangers
39 one section of 41 BOG compressor two-stage nitration of natural gas 2# heat exchanger 40 BOG compressor
42 BOG compressor the first aftercooler 43 BOG compressor the second aftercooler 44 fuel gas
45 Fischer-Tropsch process exhaust 46 water scrubber 47 Fischer-Tropsch tail gas heater 48 caustic wash towers
49 alkali cleaning tower top cooler 50 Fischer-Tropsch tail gas increase machine suction tank 51 Fischer-Tropsch tail gas and increase machine
52 Fischer-Tropsch tail gas dryer feed chiller 53 dryer feed knockout drums
54 Fischer-Tropsch tail gas gas phase exsiccator 55 Fischer-Tropsch tail gas liquid phase exsiccator 56 dethanizers
57 ethylene rectifying column 58 deethanization tower reactor cooler 59 depropanizing tower 60 propylene rectification towers
61 debutanizing tower 62 ethylene 63 ethane 64 propylene 65 propane
66 mixing carbon four product 67 gasoline components
Detailed description of the invention
Below in conjunction with accompanying drawing, the detailed description of the invention of the present invention is described in detail.It should be appreciated that Detailed description of the invention described herein is merely to illustrate and explains the present invention, is not limited to this Bright.
The present invention provides the separation and recovery method of a kind of Fischer-Tropsch process exhaust, and the method includes: a, will contain Have nitrogen, argon, carbon monoxide, carbon dioxide, hydrogen, methane, ethane, ethylene, propane, third The Fischer-Tropsch process exhaust of alkene, butane, butylene and gasoline component carries out carbon dioxide removal process, compression successively After process, cooling process, gas-liquid separation and dried, obtain 14～17 DEG C and 3.6～3.9 MPas Gas phase Fischer-Tropsch process exhaust and liquid phase Fischer-Tropsch process exhaust；B, by step a gained gas phase Fischer-Tropsch close Become tail gas to use two-stage nitration propylene refrigerant to carry out first order propylene condensation, obtain-15～-19 DEG C and 3.69～3.89 MPa first order propylene condensed product；Described first order propylene condensed product is used one section of propylene refrigerant Carry out second level propylene condensation, obtain the second level propylene condensation of-30～-34 DEG C and 3.68～3.88 MPas Product；C, the second level propylene condensed product of gained in step b use two-stage nitration ethylene cryogen carry out the One ethylene Quench, obtains the first ethylene Quench of-50～-60 DEG C and 3.66～3.86 MPas through gas-liquid separation Gas and the first ethylene Quench liquid；One section of ethylene cryogen is used to carry out described first ethylene shock gas Second ethylene Quench, obtains the second ethylene Quench gas of-96～-98 DEG C and 3.6～3.8 MPas through gas-liquid separation Body and the second ethylene Quench liquid；Cold is provided to enter by off-gas expander described second ethylene shock gas Row condensation further, obtains the first time first of-160 DEG C～-165 DEG C and 3.58～3.78 MPas through gas-liquid separation Alkane/hydrogen separation gas separates liquid with methane/hydrogen for the first time；By described first time methane/hydrogen separation liquid liter Temperature to-101 DEG C～-102 DEG C and 3.09～3.29 MPas, as first burst of demethanation charging；D, by step In a the liquid phase Fischer-Tropsch process exhaust cooling decompression of gained to-53～-57 DEG C and 3.2～3.4 MPas after, must Liquid phase Fischer-Tropsch process exhaust before processing to demethanation；E, by first burst of demethanation of gained in step c charging, Liquid phase before gained demethanation processes in second ethylene Quench liquid and the first ethylene Quench liquid and step d Fischer-Tropsch process exhaust carries out demethanation process under-100～-105 DEG C and 3.00～3.20 MPas, obtains -102～demethanation gas less than 0.2mol% of-105 DEG C and 3.00～3.20 MPas and ethylene contents and The demethanation liquid of 50～55 DEG C and 3.07～3.27 MPas；F, by the demethanation gas of gained in step e Separate gas mixing with the first time methane/hydrogen of gained in step c, enter off-gas expander together and expand system After cold, carry out second time methane/hydrogen and separate, obtain-175～-180 DEG C and the expansion of 0.25～0.33 MPa Separate hydrogen and expand separation of methane；G, by step f gained expand separate hydrogen successively with step c In middle gained the second ethylene shock gas and the first ethylene shock gas, step b, gained second level propylene is cold Solidifying product and gas phase Fischer-Tropsch process exhaust described in first order propylene condensed product, step a and 38～40 DEG C of propylene refrigerant liquid obtain the thick hydrogen production of room temperature after carrying out heat exchange.
According to the present invention, in step a, gas-liquid separation processes is first time simple separation, the most described gas phase Fischer-Tropsch process exhaust is similar with the substance classes contained by liquid phase Fischer-Tropsch process exhaust, but the content of material Difference, gas phase Fischer-Tropsch process exhaust contains more light component, and liquid phase Fischer-Tropsch process exhaust contains more restructuring Point.First ethylene shock gas described in step c be mainly composed of nitrogen, argon, carbon monoxide, Hydrogen, methane, ethylene, ethane and propylene etc., and the first ethylene Quench liquid contains carbon three and above Heavy constituent is more；Described second ethylene shock gas be mainly composed of nitrogen, argon, carbon monoxide, Hydrogen, methane, ethylene and ethane etc., described second ethylene Quench liquid then contains carbon two and above weight Component is more；Described first time methane/hydrogen separation gas be mainly composed of hydrogen, nitrogen, carbon monoxide, Argon and methane etc., for the first time methane/hydrogen separation liquid be mainly composed of methane, ethylene and ethane etc.. In demethanation gas described in step e, ethylene contents is less than 0.2mol% and rich in methane, described demethanation Liquid be mainly composed of carbon two and above component.The main one-tenth separating hydrogen is expanded described in step f It is divided into hydrogen, nitrogen, carbon monoxide, argon and a small amount of methane, described expansion separation of methane main Composition is methane.
According to the present invention, carbon dioxide removal described in step a processes and dried is all art technology Known to personnel, the process of described carbon dioxide removal can include washing successively or amine is washed and alkali cleaning, Described dried can use the desiccant such as 3A molecular sieve to be dried process.
According to a kind of detailed description of the invention of the present invention, this separation and recovery method can also include: α, general In step f, more than half expansion separation of methane and described second ethylene shock gas of gained carries out heat exchange, Obtain first burst of heat exchange and expand separation of methane gas；Gained demi-inflation separation of methane in step f is used for The overhead condensation heat exchange that in step e, demethanation processes, obtains second burst of heat exchange and expands separation of methane gas； After the expansion separation of methane of gained remainder is vaporized hyperthermic treatment in step f, obtain the 3rd strand Heat exchange expands separation of methane gas；β, described in step α first burst of heat exchange is expanded separation of methane gas, Second strand of heat exchange expansion separation of methane gas and the 3rd burst of heat exchange expand separation of methane gas and merge into -100～after total heat exchange of-104 DEG C and 0.26-0.28 MPa expand separation of methane gases, rise further Temperature processes to room temperature, more most three second compression process and after cooling process, obtain 38-40 DEG C The expansion separation of methane gas that compression cooling with 5.0-6.5 MPa processes；γ, will described in step β press After the expansion separation of methane gas that contracting cooling processes carries out desuperheating, again liquefies and crosses cold treatment, throttle Decompression obtains-162～-163 DEG C and the liquefied natural gas product of 15～20 kPas；δ, by institute in step γ State after the flashed vapour of liquefied natural gas product carries out two-stage hyperthermic treatment, alternately 2～3 times boostings and cold But after, as fuel gas.Wherein, the process of desuperheating described in step γ can take heat exchange mode, Again liquefaction can use the condensing modes such as ethylene refrigeration, crosses cold treatment and can also use the mode of heat exchange； Flashed vapour described in step δ is well-known to those skilled in the art, refers to when the pressure of high-pressure liquid material When power declines, the boiling point of this liquid can reduce, even below the temperature of this liquid, thus sends out The gas that raw instantaneous portion vaporizes and produces, becomes flashed vapour.
According to a kind of detailed description of the invention of the present invention, the present invention can arrange an ethylene refrigeration machine system Using two sections of ethylene cryogens to carry out two-stage ethylene Quench, the temperature of first order ethylene Quench can be -50～-62 DEG C, the temperature of second level ethylene Quench can be-95～-98 DEG C, and therefore, the method is all right It is cold including: one section of ethylene cryogen used by described step c and two-stage nitration ethylene cryogen, with step γ compress But the ethylene cryogen again liquefying used of separation of methane gas is expanded after processing, from same ethylene system Cold.It addition, the present invention can use three sections of propylene refrigerants to carry out three grades of propylene refrigerations, first order propylene The temperature of condensation can less than-30 DEG C, the temperature of second level propylene condensation can between-20～-15 DEG C, Third level propylene refrigeration, can be more than 10 DEG C.Described propylene refrigeration or ethylene refrigeration refer to use propylene Or ethylene is compressed as cold-producing medium, the refrigerating method of the revaporization that liquefies refrigeration.
According to a kind of detailed description of the invention of the present invention, the method can also include: described in step α Liquefied natural gas product described in the vaporization hyperthermic treatment expanding separation of methane of remainder and step δ Cold produced by the first order hyperthermic treatment of flashed vapour is for compressing the swollen of cooling process described in step γ The cold treatment excessively of swollen separation of methane gas.Described cold refers to the concept relative with heat, moves away heat And produce.
According to a kind of detailed description of the invention of the present invention, the method can also include: described in step β Total heat exchange expands further heating up of separation of methane gas and processes and liquefied natural gas product described in step δ Flashed vapour second level hyperthermic treatment produced by cold compress what cooling processed described in step γ The desuperheating expanding separation of methane gas processes.
According to a kind of detailed description of the invention of the present invention, the method can also include: total described in step β Heat exchange expands the compression process power demand of separation of methane gas and is all carried by the off-gas expander in step f Supply.Described off-gas expander refers to that utilizing the industrial tail gas of high pressure outwards to export mechanical power when expanding blood pressure lowering makes The principle that gas temperature reduces is to obtain the machinery of more multi-energy, it is possible to obtain lower than direct expenditure and pressure Temperature.
According to a kind of detailed description of the invention of the present invention, the method can also include: by gained in step e Demethanation liquid carries out deethanization process under-12～-16 DEG C and 2.1～2.3 MPas, obtains containing ethylene With the deethanization gas of ethane and containing propane, propylene, butane, butylene and the deethanization liquid of gasoline component Body；Described deethanization gas is carried out ethylene distillation, obtains ethylene and ethane；By described deethanization liquid Carry out depropanization process at 13～17 DEG C and 0.65～0.85 MPa, obtain de-third containing propane and propylene Alkane gas and containing butane, butylene and the depropanization liquid of gasoline component；Described depropanization gas is carried out Propylene rectification, obtains propylene and propane；By described depropanization liquid at 46～50 DEG C and 0.35～0.45 million Handkerchief carries out debutanization process, obtains mixing carbon four product and the gasoline component of liquid of liquid.
At ambient pressure Fischer-Tropsch process exhaust contained by the boiling point of Common materials it is provided below: nitrogen, -195.8℃；Argon ,-185.7 DEG C；Carbon monoxide ,-191.4 DEG C；Methane ,-164.5 DEG C；Hydrogen ,-252.8 DEG C； Ethane ,-88.6 DEG C；Ethylene ,-109.4 DEG C；Propane ,-42.1 DEG C；Normal butane ,-0.5 DEG C；Butylene ,-6.9 DEG C； Iso-butane ,-12 DEG C.But the pressure used due to the inventive method is higher than normal pressure, so, relatively At a temperature of height, the relatively heavy substance contained by Fischer-Tropsch process exhaust just can liquefy, thus can reach the mesh of separation 's.
The present invention will be illustrated by embodiment below, but the most therefore the method for the present invention will be subject to To any restriction.
As in figure 2 it is shown, will containing nitrogen, argon, carbon monoxide, carbon dioxide, hydrogen, methane, The Fischer-Tropsch process exhaust of ethane, ethylene, propane, propylene, butane, butylene and gasoline component sequentially passes through The water scrubber 46 of Fischer-Tropsch process exhaust pretreatment unit, Fischer-Tropsch tail gas heater 47, caustic wash tower 48, alkali Wash top cooler 49, Fischer-Tropsch tail gas increases machine 51, demethanizer reboiler 15 and Fischer-Tropsch tail gas exsiccator Enter dry after charging chiller 52 carries out carbon dioxide removal process, compression process, cooling process successively Carrying out gas-liquid separation process in dry device charging knockout drum 53, the tail gas being separated into gas phase and liquid phase enters expense After torr tail gas gas phase exsiccator 54 and Fischer-Tropsch tail gas liquid phase exsiccator 55 are dried process, obtain The gas phase Fischer-Tropsch process exhaust of 15 DEG C and 3.81 MPas and liquid phase Fischer-Tropsch process exhaust.
As it is shown in figure 1, gas phase Fischer-Tropsch process exhaust to be sequentially passed through 5# hydrogen recuperator 2 and Fischer-Tropsch tail gas 1# condenser 7 carries out first order propylene condensation, obtains the first order propylene condensation of-17 DEG C and 3.79 MPas Product；First order propylene condensed product is sequentially passed through 4# hydrogen recuperator 3 and the condensation of Fischer-Tropsch tail gas 2# Device 8 carries out second level propylene condensation, obtains the second level propylene condensed product of-32 DEG C and 3.78 MPas； By second level propylene condensed product according to by 3# hydrogen recuperator 4 and Fischer-Tropsch tail gas 1# ethylene condenser 9 Send into domethanizing column first after carrying out the first ethylene Quench to feed knockout drum 12 and carry out gas-liquid separation, obtain The first ethylene shock gas of-55 DEG C and 3.74 MPas and the first ethylene Quench liquid；By described first second Alkene shock gas sequentially passes through 2# hydrogen recuperator 5 and Fischer-Tropsch tail gas 2# ethylene condenser 10 carries out second Send into domethanizing column second after ethylene Quench to feed knockout drum 13 and carry out gas-liquid separation, obtain-98 DEG C and 3.7 MPa the second ethylene shock gas and the second ethylene Quench liquid；By above-mentioned second ethylene shock gas warp Send into domethanizing column the 3rd charging knockout drum 14 after crossing 1# hydrogen recuperator 6 and carry out gas-liquid separation, obtain -160 DEG C of the first methane/hydrogen with 3.68 MPas separate gas and the first methane/hydrogen separation liquid；By first Methane/hydrogen separation liquid is warmed up to-101.5 DEG C and 3.19 MPas through 1# hydrogen recuperator 6, as One demethanation feeds.Wherein said hydrogen recuperator is plate-fin.
By liquid phase Fischer-Tropsch process exhaust after Fischer-Tropsch tail gas undercooling device 11 carries out cooling decompression, Liquid phase Fischer-Tropsch process exhaust before processing to the demethanations of-54 DEG C and 3.3 MPas.By above-mentioned first burst of demethanation Charging, the second ethylene Quench liquid, the first ethylene Quench liquid and demethanation process front liquid phase F-T synthesis Tail gas is sequentially sent to the first feed distributing plate of domethanizing column 16, the second feed distributing plate, the 3rd charging Distribution grid and the 4th feed distributing plate carry out demethanation process under-101 DEG C and 3.10 MPas (tower tops), Obtain demethanation top gaseous phase and the demethanation liquid of 52 DEG C and 3.13 MPas, by demethanation top gaseous phase After domethanizing column condenser 17 condense, send into demethanizer reflux tank 18 carry out gas-liquid separation, Obtain-103 DEG C and 3.1 MPas and demethanation gas that ethylene contents is 0.10mol%.Wherein, demethanation Tower is single column high pressure demethanizer, and tower is pressed between 3.00～3.16MPaG, and its tower reactor is mainly by FT Tail gas increases machine outlet gas phase provides the most boiling hot amount；Overhead reflux ratio is the least, but needs by off-gas expander System provides the cold of less than-106 DEG C, effectively to control ethylene loss.
Demethanation gas is separated gas with the first methane/hydrogen from domethanizing column the 3rd charging knockout drum 14 Sending into decompressor head tank 19 together after body mixing, the product liquid obtained is saved by liquid phase choke valve 21 Send into hydrogen/methane separation tank 22 together with the gaseous product after feeding off-gas expander 20 refrigeration after stream to carry out Gas-liquid separation, obtains-177 DEG C of expansions with 0.29 MPa and separates hydrogen and expand separation of methane；By piptonychia The liquid that alkane tower return tank 18 obtains refluxes back in domethanizing column 16.Wherein, the first of separation of methane is expanded Alkane concentration is 93.3mol% (generally individually should be greater than 92mol%).Expansion separation hydrogen is sequentially passed through 1# Hydrogen recuperator 6,2# hydrogen recuperator 5,3# hydrogen recuperator 4,4# hydrogen recuperator 3,5# hydrogen Recuperator 2 and 6# hydrogen recuperator 1 successively with the second ethylene shock gas, the first ethylene shock gas, Second level propylene condensed product, first order propylene condensed product, gas phase Fischer-Tropsch process exhaust and 39 DEG C Propylene refrigerant liquid (being used for absorbing cold) carries out heat exchange, obtains the thick hydrogen production of room temperature.
Expansion separation of methane by 52% is sent into 1# hydrogen recuperator 6 and is carried out with the second ethylene shock gas Heat exchange, obtains first burst of heat exchange and expands separation of methane gas；Expansion separation of methane by 22% sends into piptonychia Alkane tower condenser 17 and the overhead condensation heat exchange of domethanizing column, obtain second burst of heat exchange and expand separation of methane Gas；The expansion separation of methane of residue 26% is sent into natural gas 1# heat exchanger 38 and carries out heat exchange, obtain 3rd burst of heat exchange expands separation of methane gas.Natural gas is sent into after being converged by three strands of expansion separation of methane gases 2# heat exchanger 39 further heats up to room temperature, then be sequentially sent to methane recompression one section 29 of machine, After methane recompression machine the first aftercooler 32, methane recompression machine two-stage nitration 30, methane recompression machine second Cooler 33, methane three section 31 of machine of recompression and methane recompression machine the 3rd aftercooler 34 are alternately pressed Contracting and cooling process, and obtain the expansion separation of methane gas that the compression cooling of 39 DEG C and 5.7 MPas processes； The expansion separation of methane gas that compression cooling processes is passed sequentially through natural gas 2# heat exchanger 39, natural gas Condenser 28 and natural gas 1# heat exchanger 38 carry out desuperheating, again liquefy and after cooling processes, then send Enter low temperature methane JT valve 35 and carry out expenditure and pressure, obtain the liquefied natural gas of-163 DEG C and 20 kPas (i.e. LNG) product, deposits in the natural gas storage tank 36 that atmospheric low-temperature list contains pattern；Natural gas is stored up Flashed vapour produced by tank 36 (i.e. bubble point gas BOG) is sequentially sent to natural gas 1# heat exchanger 38 and sky After so gas 2# heat exchanger 39 heats up, then it is sequentially sent to BOG compressor one section 40, BOG compressor the One aftercooler 42, BOG compressor two-stage nitration 41 and BOG compressor the second aftercooler 43 alternately rise After pressure and cooling, as fuel gas.Wherein, the driver of methane recompression machine is off-gas expander, BOG The driver of compressor is motor；The condensation of gas phase Fischer-Tropsch tail gas the coldest level, domethanizing column condensation and LNG Supercool required cold, is all provided by off-gas expander.
As in figure 2 it is shown, demethanation liquid feeding dethanizer 56 is carried out under-14 DEG C and 2.23 MPas Deethanization process, obtain the deethanization gas containing ethylene and ethane and containing propane, propylene, butane, The deethanization liquid of butylene and gasoline component；Deethanization gas feeding ethylene rectifying column 57 is carried out ethylene Rectification, obtains ethylene and ethane；Described deethanization liquid is lowered the temperature through deethanization tower reactor cooler 58 Rear feeding depropanizing tower 59 carries out depropanization process at 15 DEG C and 0.76 MPa, obtains containing propane and third The depropanization gas of alkene and containing butane, butylene and the depropanization liquid of gasoline component；By depropanization gas Send into propylene rectification tower 60 and carry out propylene rectification, obtain propylene and propane；Depropanization liquid is sent into de- Butane tower 61 carries out debutanization process at 48 DEG C and 0.42 MPa, obtain liquid mixing carbon four product and The gasoline component of liquid.
H in thick hydrogen in this embodiment2Yield >=99.9%；Yield of ethene >=99.1%；Other ethylene with The yield of upper heavy hydrocarbon is almost 100%；Ethylene is with propylene reaches polymer grade, methane reaches liquefied natural gas (i.e. LNG) standard.Methane recompression machine, energy efficient is driven with off-gas expander.As processed one Overlap the tail gas of 1,000,000 tons/year of high temperature FT synthesis, about 57000 degree can be economized on electricity every day.

Claims (8)

1. a separation and recovery method for Fischer-Tropsch process exhaust, the method includes:
A, will be containing nitrogen, argon, carbon monoxide, carbon dioxide, hydrogen, methane, ethane, second The Fischer-Tropsch process exhaust of alkene, propane, propylene, butane, butylene and gasoline component carries out de-titanium dioxide successively After carbon process, compression process, cooling process, gas-liquid separation and dried, obtain 14～17 DEG C and 3.6～ The gas phase Fischer-Tropsch process exhaust of 3.9 MPas and liquid phase Fischer-Tropsch process exhaust；
B, by step a gained gas phase Fischer-Tropsch process exhaust use two-stage nitration propylene refrigerant carry out the first order Propylene condenses, and obtains the first order propylene condensed product of-15～-19 DEG C and 3.69～3.89 MPas；By institute State first order propylene condensed product use one section of propylene refrigerant carry out second level propylene condensation, obtain-30～ The second level propylene condensed product of-34 DEG C and 3.68～3.88 MPas；
C, two-stage nitration ethylene cryogen is used to carry out first the second level propylene condensed product of gained in step b Ethylene Quench, obtains the first ethylene Quench gas of-50～-60 DEG C and 3.66～3.86 MPas through gas-liquid separation Body and the first ethylene Quench liquid；Described first ethylene shock gas use one section of ethylene cryogen carry out the Divinyl Quench, obtains the second ethylene shock gas of-96～-98 DEG C and 3.6～3.8 MPas through gas-liquid separation With the second ethylene Quench liquid；Cold is provided to carry out by off-gas expander described second ethylene shock gas Condensation, obtains the first time methane of-160 DEG C～-165 DEG C and 3.58～3.78 MPas through gas-liquid separation further / hydrogen separation gas separates liquid with methane/hydrogen for the first time；Described first time methane/hydrogen separation liquid is heated up To-101 DEG C～-102 DEG C and 3.09～3.29 MPas, as first burst of demethanation charging；
D, by the liquid phase Fischer-Tropsch process exhaust cooling decompression of gained in step a to-53～-57 DEG C and 3.2～ After 3.4 MPas, obtain liquid phase Fischer-Tropsch process exhaust before demethanation processes；
E, by first burst of demethanation of gained in step c charging, the second ethylene Quench liquid and the first ethylene Before in Quench liquid and step d, gained demethanation processes, liquid phase Fischer-Tropsch process exhaust is-100～-105 DEG C Carry out demethanation process under 3.00～3.20 MPas, obtain-102～-105 DEG C and 3.00～3.20 MPas And ethylene contents is less than the demethanation gas of 0.2mol% and 50～55 DEG C and 3.07～3.27 MPas de- Methane liquid；
F, the demethanation gas of gained in step e is separated with the first time methane/hydrogen of gained in step c Gas mixes, and after entering off-gas expander swell refrigeration together, carries out second time methane/hydrogen and separates, obtain -175～-180 DEG C of expansions with 0.25～0.33 MPa separate hydrogen and expand separation of methane；
G, by step f gained expand separate hydrogen successively with the second ethylene Quench gas of gained in step c In body and the first ethylene shock gas, step b, gained second level propylene condensed product is cold with first order propylene Described in solidifying product, step a, gas phase Fischer-Tropsch process exhaust and 38～40 DEG C of propylene refrigerant liquid change The thick hydrogen production of room temperature is obtained after heat.
Method the most according to claim 1, wherein, carbon dioxide removal described in step a processes successively Including washing or amine is washed and alkali cleaning.
Method the most according to claim 1, the method also includes:
α, by more than half expansion separation of methane and described second ethylene shock gas of gained in step f Carry out heat exchange, obtain first burst of heat exchange and expand separation of methane gas；Gained demi-inflation in step f is divided From the methane overhead condensation heat exchange that demethanation processes in step e, obtain second burst of heat exchange and expand separation Methane gas；After in step f, the expansion separation of methane of gained remainder is vaporized hyperthermic treatment, Obtain the 3rd burst of heat exchange and expand separation of methane gas；
β, described in step α first burst of heat exchange is expanded separation of methane gas, second burst of heat exchange expands point Expand separation of methane gas from methane gas and the 3rd burst of heat exchange and merge into-100～-104 DEG C and 0.26-0.28 MPa total heat exchange expand after separation of methane gas, further heat up process to room temperature, then replace into Most three second compression of row process and after cooling process, obtain the compression cooling of 38-40 DEG C and 5.0-6.5 MPa The expansion separation of methane gas processed；
γ, by described in step β compress cooling process expansion separation of methane gas carry out desuperheating, weight New liquefaction and after crossing cold treatment, expenditure and pressure obtain-162～the liquefaction of-163 DEG C and 15～20 kPas natural Gas product；
δ, the flashed vapour of liquefied natural gas product described in step γ is carried out two-stage hyperthermic treatment after, hand over After carrying out 2～3 boostings and cooling, as fuel gas.
Method the most according to claim 3, the method also includes: one section of second used by described step c Alkene cryogen and two-stage nitration ethylene cryogen, with step γ compress the weight expanding separation of methane gas after cooling processes Ethylene cryogen used by new liquefaction, from same ethylene refrigeration machine.
Method the most according to claim 3, the method also includes: by remainder described in step α The vaporization hyperthermic treatment expanding separation of methane and step δ described in the flashed vapour of liquefied natural gas product Cold produced by first order hyperthermic treatment is for compressing the expansion separation first that cooling processes described in step γ The cold treatment excessively of alkane gas.
Method the most according to claim 3, the method also includes: by swollen for heat exchange total described in step β Further heating up of swollen separation of methane gas processes and the flashed vapour of liquefied natural gas product described in step δ Second level hyperthermic treatment produced by cold compress the expansion that cooling processes described in step γ and separate The desuperheating of methane gas processes.
Method the most according to claim 3, the method also includes: total heat exchange described in step β expands The compression of separation of methane gas processes power demand and is all provided by the off-gas expander in step f.
Method the most according to claim 1, the method also includes:
Gained demethanation liquid in step e is carried out deethanization under-12～-16 DEG C and 2.1～2.3 MPas Process, obtain the deethanization gas containing ethylene and ethane and containing propane, propylene, butane, butylene and The deethanization liquid of gasoline component；
Described deethanization gas is carried out ethylene distillation, obtains ethylene and ethane；By described deethanization liquid Carry out depropanization process at 13～17 DEG C and 0.65～0.85 MPa, obtain de-third containing propane and propylene Alkane gas and containing butane, butylene and the depropanization liquid of gasoline component；
Described depropanization gas is carried out propylene rectification, obtains propylene and propane；By described depropanization liquid Carry out debutanization process at 46～50 DEG C and 0.35～0.45 MPa, obtain liquid mixing carbon four product and The gasoline component of liquid.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106938170A (en) * 2017-03-31 2017-07-11 武汉金中石化工程有限公司 A kind of processing unit and processing method of cobalt-based fixed bed F- T synthesis off-gas
CN108276236A (en) * 2017-01-06 2018-07-13 中国石化工程建设有限公司 A kind of Fischer-Tropsch process exhaust cryogenic separation recovery method of volume increase alkene
CN108676579A (en) * 2018-05-09 2018-10-19 天津市天地创智科技发展有限公司 A kind of dry gas sequence piece-rate system and separation method based on argon circularly cooling
CN109111336A (en) * 2018-09-28 2019-01-01 北京恒泰洁能科技有限公司 A kind of expense drags synthesis tail gas deep cooling recyclable device and technique
CN109321268A (en) * 2018-11-15 2019-02-12 中国科学院山西煤炭化学研究所 A method and device for preparing gasoline and aromatic hydrocarbons from Fischer-Tropsch synthesis tail gas
CN109704899A (en) * 2017-10-26 2019-05-03 中国石油化工股份有限公司 The method that synthesis gas prepares alkene
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101434507A (en) * 2008-11-19 2009-05-20 上海惠生化工工程有限公司 Separation method for fischer-tropsch synthesis tail gas
CN101475427A (en) * 2008-12-29 2009-07-08 陕西金巢投资有限公司 Novel generation fischer-tropsch synthesis process
CN101559320A (en) * 2009-04-15 2009-10-21 上海惠生化工工程有限公司 Separation method of Fischer-Tropsch synthesis gas by combining rectification and solvent absorption
CN102212381A (en) * 2010-04-12 2011-10-12 中科合成油技术有限公司 Equipment system for Fischer-Tropsch synthetic reaction and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101434507A (en) * 2008-11-19 2009-05-20 上海惠生化工工程有限公司 Separation method for fischer-tropsch synthesis tail gas
CN101475427A (en) * 2008-12-29 2009-07-08 陕西金巢投资有限公司 Novel generation fischer-tropsch synthesis process
CN101559320A (en) * 2009-04-15 2009-10-21 上海惠生化工工程有限公司 Separation method of Fischer-Tropsch synthesis gas by combining rectification and solvent absorption
CN102212381A (en) * 2010-04-12 2011-10-12 中科合成油技术有限公司 Equipment system for Fischer-Tropsch synthetic reaction and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
吕建宁等: "一种费托合成尾气的分离方法", 《化工进展》 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109952363A (en) * 2016-11-17 2019-06-28 南非沙索有限公司 Receipts hydro carbons is flowed back to from gas
CN108276236A (en) * 2017-01-06 2018-07-13 中国石化工程建设有限公司 A kind of Fischer-Tropsch process exhaust cryogenic separation recovery method of volume increase alkene
CN106938170A (en) * 2017-03-31 2017-07-11 武汉金中石化工程有限公司 A kind of processing unit and processing method of cobalt-based fixed bed F- T synthesis off-gas
CN106938170B (en) * 2017-03-31 2023-02-28 武汉金中石化工程有限公司 Treatment device and treatment method for Fischer-Tropsch synthesis purge gas of cobalt-based fixed bed
CN109704899B (en) * 2017-10-26 2022-07-08 中国石油化工股份有限公司 Method for preparing olefin from synthesis gas
CN109704899A (en) * 2017-10-26 2019-05-03 中国石油化工股份有限公司 The method that synthesis gas prepares alkene
CN108676579A (en) * 2018-05-09 2018-10-19 天津市天地创智科技发展有限公司 A kind of dry gas sequence piece-rate system and separation method based on argon circularly cooling
CN108676579B (en) * 2018-05-09 2023-04-25 天津市天地创智科技发展有限公司 Dry gas sequential separation system and separation method based on argon circulation refrigeration
CN109111336A (en) * 2018-09-28 2019-01-01 北京恒泰洁能科技有限公司 A kind of expense drags synthesis tail gas deep cooling recyclable device and technique
CN109111336B (en) * 2018-09-28 2024-04-05 北京恒泰洁能科技有限公司 Deep cooling recovery device and process for waste towed synthetic tail gas
CN111116299A (en) * 2018-10-30 2020-05-08 中国石油化工股份有限公司 Method and device for product separation and byproduct utilization of olefin prepared from synthesis gas
CN109321268A (en) * 2018-11-15 2019-02-12 中国科学院山西煤炭化学研究所 A method and device for preparing gasoline and aromatic hydrocarbons from Fischer-Tropsch synthesis tail gas
CN111394120B (en) * 2019-09-18 2022-02-22 中国石化工程建设有限公司 Light hydrocarbon recovery method and device
CN111394120A (en) * 2019-09-18 2020-07-10 中国石化工程建设有限公司 Light hydrocarbon recovery method and device

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