CN1195717C - Process for separating and recovering ethylene, ethane, propylene and hydrogen from gas mixture containing hydrocarbons - Google Patents
Process for separating and recovering ethylene, ethane, propylene and hydrogen from gas mixture containing hydrocarbons Download PDFInfo
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- CN1195717C CN1195717C CNB001131095A CN00113109A CN1195717C CN 1195717 C CN1195717 C CN 1195717C CN B001131095 A CNB001131095 A CN B001131095A CN 00113109 A CN00113109 A CN 00113109A CN 1195717 C CN1195717 C CN 1195717C
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- fraction
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- propylene
- hydrogen
- ethane
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- 238000000034 method Methods 0.000 title claims abstract description 166
- 239000007789 gas Substances 0.000 title claims abstract description 146
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 104
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 84
- 239000001257 hydrogen Substances 0.000 title claims abstract description 58
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 58
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 57
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 52
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000005977 Ethylene Substances 0.000 title claims abstract description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000000203 mixture Substances 0.000 title claims description 36
- 238000001179 sorption measurement Methods 0.000 claims abstract description 127
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 102
- 238000010521 absorption reaction Methods 0.000 claims abstract description 48
- 238000000926 separation method Methods 0.000 claims abstract description 39
- 238000004821 distillation Methods 0.000 claims abstract description 21
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000007906 compression Methods 0.000 claims description 10
- 238000007781 pre-processing Methods 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 235000011089 carbon dioxide Nutrition 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000005194 fractionation Methods 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 4
- 239000000463 material Substances 0.000 description 20
- 238000001816 cooling Methods 0.000 description 19
- 239000003463 adsorbent Substances 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 14
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 12
- 230000000274 adsorptive effect Effects 0.000 description 12
- 238000007872 degassing Methods 0.000 description 11
- 230000006353 environmental stress Effects 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- 230000003139 buffering effect Effects 0.000 description 9
- 238000009833 condensation Methods 0.000 description 9
- 230000005494 condensation Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000002826 coolant Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000002594 sorbent Substances 0.000 description 7
- 241000282326 Felis catus Species 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000003507 refrigerant Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000004523 catalytic cracking Methods 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 230000002093 peripheral effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000256602 Isoptera Species 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- SZZYLYUVTJLJQM-UHFFFAOYSA-J Cl[Cu](Cl)(Cl)Cl Chemical compound Cl[Cu](Cl)(Cl)Cl SZZYLYUVTJLJQM-UHFFFAOYSA-J 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- 206010016825 Flushing Diseases 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- -1 this Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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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
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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
- F25J3/0228—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
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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
- F25J3/0228—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
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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
- F25J3/0228—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
- F25J3/0242—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 3 carbon atoms or more
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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
- F25J3/0228—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
- F25J3/0247—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 4 carbon atoms or more
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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
- F25J3/0228—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
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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
- 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
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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
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
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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
- F25J2210/00—Processes characterised by the type or other details of the feed stream
- F25J2210/12—Refinery or petrochemical off-gas
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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
- F25J2215/00—Processes characterised by the type or other details of the product stream
- F25J2215/62—Ethane or ethylene
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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
- F25J2215/00—Processes characterised by the type or other details of the product stream
- F25J2215/64—Propane or propylene
Abstract
The present invention relates to a method for separating and recovering ethylene, ethane, propylene and hydrogen from mixed gas which contains hydrocarbon. The method comprises the following steps: an absorption process (A) leads acidic gas in mixed gas (1) which contains hydrocarbon to be eliminated; an adsorption process (C) leads mixed gas (3) which contains hydrocarbon to be divided into a gas distillation fraction (10) which contains rich hydrogen and methane and a gas distillation fraction (4) which contains rich ethylene, ethane and propylene; through a cryogenic separation process (L) of a gas distillation fraction (6) which contains rich ethylene, ethane and propylene, an ethylene distillation fraction (20), an ethane distillation fraction (21), a propylene distillation fraction (22) and a heavy hydrocarbon distillation fraction (17) are respectively obtained; through another adsorption process (J) of the gas distillation fraction (10) which contains the rich hydrogen and the rich methane, a hydrogen distillation fraction (18) and a gas distillation fraction (11) which contains rich methane are obtained.
Description
Affiliated technical field:
The present invention relates to a kind of from the gas mixture that contains hydro carbons the method for separating and reclaiming ethylene, ethane, propylene and hydrogen.
Background technology:
In Crude Oil Processing, most of processing unit (plant)s are a considerable amount of lighter hydrocarbons of by-product all, and thermal cracker, catalytic cracking unit, the rich lighter hydrocarbons that produce of coker all contain a large amount of alkene.
Catalytic cracking is under the effect of catalyzer, and cracking decompression diesel oil, atmospheric residue, vacuum residuum to be producing the processing means of gasoline and solar oil, when the course of processing is produced vapour, diesel oil, and a large amount of olefin gas of by-product.Under certain condition, in the olefin gas of by-product, carbon four following gas generating amounts can reach more than 30%.Thermally splitting is the important means that the heavy oil lighting of lightweight oil is produced in decompression diesel oil, depressed heavy oil cracking, when the mixed phase cracking, and 1m
3Crude oil manufacture gas scale of construction 18-80m
3, when cracking in vapour phase, 1m
3The crude oil manufacture gas scale of construction is at 170m
3More than, along with the raising of cracking temperature, the content of ethene also can increase.Coking is to make mink cell focus add thermally splitting, and generates the processing means of lightweight oil and coke with condensation reaction, in the course of processing also by-product contain the gas of a large amount of alkene.
At present, the 50-60% of U.S.'s propone output comes catalytic cracking, and the cracker of Europe and Japan is based on the fraction oil breaking, and refinery's working depth is lower, but catalytic cracking production propylene still accounts for 25% of propone output.Also contain a large amount of ethene in the catalysis drying gas, reclaim the ethene in the catalysis drying gas, also cause in recent years widely and note.
" ethene engineering " P22-23 introduced Japanese kobe steel once the ethene that adopts the Activated Carbon Adsorption Separation method to reclaim in the low-concentration ethane gas was carried out research, ethene purity that its pilot plant obtains and ethylene recovery rate are 85-90%, since less economical, be difficult to realize industrialization." petrochemical complex handbook (2) P127 has introduced U.S. TENNECO chemical company based on the aluminum tetrachloride copper absorption techniques (COSORB method) that the said firm reclaims carbon monoxide, has developed the ESEP method that is reclaimed ethene by waste gas.This genealogy of law is by the CuAICl that is dissolved in aromatic solvent
4Complex compound absorbs ethene from gaseous mixture, because network and agent are very responsive to impurity component such as water, sulfide, they need be made deep removal, and pre-treatment is complicated, and complexing agent is relatively poor to the selectivity between the alkene simultaneously, is difficult to obtain highly purified ethene.
" petrochemical complex handbook (2) P127-128 has introduced separation by deep refrigeration and reclaimed ethene from refinery gas, this method have very big shortcoming be in the refinery gas except alkene, also contain a large amount of hydrogen and methane, directly from refinery gas, reclaim the energy consumption of ethylene unit and invest all bigger with separation by deep refrigeration, and be difficult to obtain highly purified hydrogen, so never be applied and promote.
Summary of the invention:
The object of the invention provide a kind of economy, energy-conservation from the gas mixture that contains hydro carbons the method for separating and reclaiming ethylene, ethane, propylene, hydrogen, adopt present method on basis than lower power intake, when obtaining the high purity fraction, obtain high extraction.
By the present invention, above-mentioned purpose realizes in the following manner, and the gas mixture that contains hydro carbons is by means of absorption process, preferably will contain acid gas removal in the gas mixture of hydro carbons by means of MODEL OF CHEMICAL ABSORPTION PROCESS.By means of adsorption process, preferably by means of pressure-swing adsorption process, the mixed gas separation that will contain hydro carbons becomes one gas fraction that is enriched with hydrogen, methane and one is enriched with the gas fraction of ethene, ethane, propylene.With being enriched with the gas fraction of ethene, ethane, propylene, by means of the low temperature separation process process, obtain ethylene fraction, ethane fraction respectively, propylene fraction and than the heavy hydrocarbons fraction.By means of another adsorption process, pressure-swing adsorption process preferably obtains the hydrogen fraction and is enriched with the gas fraction of methane with the gas fraction that is enriched with hydrogen and methane.
Can from the gas mixture that contains hydro carbons, obtain ethene, propylene and the highly purified hydrogen of polymerization-grade by means of the inventive method.
At least the ethene that contains 99.0mol% in the ethylene fraction of the present invention is preferably the ethene of the ethene, particularly 99.95mol% of 99.9mol%.
At least the propylene that contains 99.00mol% in the propylene fraction of the present invention is preferably the propylene of the propylene, particularly 99.9mol% of 99.6mol%.
At least the hydrogen that contains 98.0mol% in the hydrogen fraction of the present invention is preferably the hydrogen of the hydrogen, particularly 99.9995mol% of 99.9mol%.
Though the United Technologies of employing adsorption process, especially pressure-swing adsorption process and low temperature separation process process, than independent employing both one of monotechnics complicated, these shortcomings are compensated by the advantage that the inventive method can reach more.
Cryogenic separation device according to the monotechnics of introducing among " ethene engineering " P337-356, remove hydrogen and methane in the gas mixture that contains hydro carbons, be to contain the link that investment is maximum, energy consumption is maximum in the mixed gas separation device of hydro carbons, need carry out removing of hydrogen and methane under the cold condition between-90-140 ℃, its freezing power consumption accounts for more than 50% of freezing power consumption of full device.In order to improve the service temperature of cryogenic separation device, cryogenic separation device generally all requires to carry out sepn process under higher pressure, contain the hydrogen of the 40-60% in the gas mixture of hydro carbons and methane (in some cases, also has other light component, as nitrogen in the catalysis drying gas etc.) also along with being compressed to higher pressure, and in some occasion, compressed hydrogen and methane are unwanted, and this has just caused the waste of the energy.
Mentioned, contain in the gas mixture of hydro carbons and contain a large amount of hydrogen and methane, by adsorption process, pressure-swing adsorption process preferably, the mixed gas separation that will contain hydro carbons becomes one gas fraction that is enriched with hydrogen, methane and one is enriched with the gas fraction of ethene, ethane, propylene.Like this, enter the gas flow of the low temperature separation process process of United Technologies, compare with the direct gas flow of the low temperature separation process process by monotechnics, the former has only the latter's 30-40% (according to the difference of the gas ingredients in the gas mixture that contains hydro carbons, the difference of hydrogen, methane content particularly, and have any different).Say roughly, the 30-40% of the low temperature separation process process that the investment of the low temperature separation process process of United Technologies and energy consumption account for monotechnics, the adsorption process of United Technologies, though especially the investment of pressure-swing adsorption process can be too not low, the energy consumption of pressure-swing adsorption process is but quite low.Therefore, be significant by United Technologies separating and reclaiming ethylene, ethane, propylene and hydrogen from the gas mixture that contains hydro carbons.
Accompanying drawing and description of drawings:
Fig. 1 process flow diagram of the present invention
Embodiment:
] by diagram the present invention and further arrangement thereof are done more detailed the explanation.Following explanation is set forth according to Figure of description.
The gas mixture (1) that contains hydro carbons transfers to absorptive unit (A) through piping, the sour gas that contains in the gas mixture of hydro carbons all can have very big harm to cryogenic separation device and ethene and acryloyl derivative processing unit (plant), and by means of absorptive unit (A) sour gas being removed from the gas mixture that contains hydro carbons is needs.The undesirable component of low temperature separation process process (L) such as carbonic acid gas, sulfide etc. separate by absorption process (A).Absorption process (A) can be carried out before at adsorption process (C), also can carry out afterwards at adsorption process (C), preferably carries out before in adsorption process (C).
Absorption process according to chemistry and the work of physical absorption principle is known, chemistry and/or physical absorbent, and preferably amine such as thanomin are delivered in the absorption process (A) as washings.Most of acidic components that will contain in the absorption tower in the gas mixture of hydro carbons sponges, particularly to the absorption of carbonic acid gas and sulfide.The absorption agent that the bottom, absorption tower has absorbed sour gas heats up through a series of heat exchange, is heated regeneration in stripping tower.Sour gas desorbs from absorption agent, through heat exchange cooling, condensation, sour gas (14) discharger.Phlegma turns back to stripping tower, and the absorption agent of stripping tower middle part and/or bottom is through after a series of heat exchange and lowering the temperature, and absorption process is carried out at the top and/or the middle part that reenter the absorption tower.Absorption liquid after the regeneration can be that one top from the absorption tower enters, and also can be divided into several strands of different heights from the absorption tower and enter.The absorption liquid of bottom, absorption tower can be that one top from regenerator column enters, and also can be divided into several strands of different heights from regenerator column and enter.
Still contain a spot of sour gas in the gas mixture that contains hydro carbons after the hydramine method is handled, use alkali lye again, preferably sodium hydroxide thoroughly removes the sour gas in the gas mixture that contains hydro carbons, to satisfy the requirement of low temperature separation process process (L).The alkali liquid washing process can be one section alkali cleaning, and in order to improve the alkali lye utilization ratio, alkaline cleaning procedure also can adopt the multistage alkali cleaning.The professional understands certainly, under the situation seldom of the content of acid gas in containing the gas mixture of hydro carbons, can be directly removes sour gas in the gas mixture that contains hydro carbons by the alkali liquid washing method.
The gas mixture that contains hydro carbons (2) that removes sour gas transfers to preprocessing process (B) through piping, to relate to adsorption bed in the adsorption process (C) (especially pressure-swing adsorption process) that causes the back impaired or stain if contain heavy hydrocarbons component presumable in the gas mixture of hydro carbons, and removing the undesirable component of adsorption process (C) by means of preprocessing process (B) also needs.
Under the situation of envrionment temperature, the behavior on sorbent material is to be easy to absorption, the characteristic that is difficult to desorb based on high boiling component.The principle of work of alternating temperature adsorption cleaning gas is to adsorb the component that these have strong adsorptive power at ambient temperature, under the situation of heating, reduce the adsorptive power of these components, cause these components to desorb from sorbent material, like this, sorbent material can recycle.
The adsorption tower of preprocessing process (B) can have the combination more than 2 or 2 according to the flow that contains the gas mixture of hydro carbons, and every adsorption tower is in step such as once need to experience absorption, step-down, heating in the circulation, cool off, boost.The professional understands certainly, in the once circulation of adsorption tower, may also include other steps, as isolation step etc.
Adsorption step is that the gas mixture that contains hydro carbons enters adsorption tower under the top pressure of this process, remove wherein may relate to the component that adsorption bed in the adsorption process (C) (especially pressure-swing adsorption process) that causes the back is impaired or stain, contain the gas mixture of hydro carbons can be from the top of adsorption tower or bottom or middle part enter adsorption tower.
Depressurization step is to reduce the pressure of adsorption tower to the adsorptive pressure that is lower than this process, preferably be reduced to environmental stress or be lower than environmental stress, it can be that the pressure that the process between the adsorption tower causes reduces, also can be that the pressure that the process between adsorption tower and the intermediate buffering jar causes reduces, can also be that the pressure that the process between adsorption tower and outside atmosphere or the peripheral equipment (as vacuum pump) causes reduces.
Heating steps is by hot gas flow adsorption tower to be heated up, hot gas flow can be the device gas inside, also can be the gas that provides of outside or steam etc., preferably pass through the gas that is enriched with methane (12) of adsorption process (J) discharge of heating, to of the gradually rising of the deleterious component of adsorption process (C) possibility along with adsorbent temperature, desorb stripping gas (15) discharger gradually from sorbent material.
Cooling step is by normal temperature or low-temperature airflow adsorption tower to be lowered the temperature, normal temperature or low-temperature airflow can be the gas in the device, also can be the gas that the outside provides, adsorption process (J) gas that is enriched with methane (12) of discharging preferably, sorbent material is lowered to envrionment temperature or is lower than envrionment temperature, has recovered the adsorptive power to harmful component again.
The step of boosting is to improve the adsorptive pressure of the pressure of adsorption tower to this process of approaching, it can be that the pressure that the process between the adsorption tower causes raises, also can be that the pressure that causes of the process between adsorption tower and the intermediate buffering jar raises, can also be the pressure that improves adsorption tower by the gas mixture that importing contains hydro carbons.
The gas mixture that contains hydro carbons (3) after the purification transfers to adsorption process (C) through piping, by means of pressure-swing adsorption process, the mixed gas separation that will contain hydro carbons becomes one gas fraction (10) that is enriched with hydrogen, methane and one gas fraction (4) that is enriched with ethene, ethane, propylene.
Adsorption process (C), especially pressure-swing adsorption process, undesirable component such as heavy hydrocarbons etc. separate by preprocessing process (B).Preprocessing process (B) can be absorption method or absorption process or cold method, preferably alternating temperature absorption method.
The adsorption tower of adsorption process (C) can have the combination more than 2 or 2 according to the flow that contains the gas mixture of hydro carbons, and every adsorption tower is in step such as once need experience absorption, forward step-down, cleaning, reverse step-down in the circulation, boost.The professional understands certainly, in the once circulation of adsorption tower, may also include other steps, as isolation step etc.
Adsorption step is that the gas mixture that contains hydro carbons enters adsorption tower from feed end under the top pressure of this process, and the hydrogen and the methane gas component that are difficult for absorption are passed through whole adsorption tower, and discharge from adsorption tower.Easily gaseous fractions such as the ethene of absorption, ethane, propylene are rested in the adsorption tower.Contain the gas mixture of hydro carbons can be from the top of adsorption tower or bottom or middle part enter adsorption tower.
Forward depressurization step is to reduce adsorptive pressure and the minimal pressure intermediary some pressure of the pressure of adsorption tower to this process, preferably is reduced to a little more than environmental stress, and the gas flow direction was consistent when the gas flow direction was with adsorption process in the step-down process.By forward step-down process, improved the separating effect that is difficult between adsorbent component and the easy adsorbent component, the easy adsorbent component in the adsorption tower is further concentrated.Forward step-down process can be that the pressure that the process between the adsorption tower causes reduces, also can be that the pressure that the process between adsorption tower and the intermediate buffering jar causes reduces, can also be that the pressure that the process between adsorption tower and outside atmosphere or the peripheral equipment (as vacuum pump) causes reduces.
Cleaning step is by the easy adsorbent component after concentrating adsorption tower to be cleaned, the easy adsorbent component of part desorb is imported finishes the adsorption tower of Gu to depressurization step, the direction that purge gas flows during with adsorption process the gas flow direction consistent.By cleaning step, the adsorbent component that is difficult in the adsorption tower is driven out of, and easily adsorbent component concentration further improves.
Reverse depressurization step is to reduce the minimal pressure of the pressure of adsorption tower to this process, preferably be reduced to be lower than environmental stress, in the step-down process when gas flow direction and adsorption process the gas flow direction opposite.By reverse step-down process, the easy adsorbent component in the adsorption tower desorbs from sorbent material, separates the easy adsorbent component (4) of sucking-off and transports to compression process (D).Reverse step-down process can be that the pressure that the process between adsorption tower and the intermediate buffering jar causes reduces, and also can be that the pressure that the process between adsorption tower and outside atmosphere or the peripheral equipment (as vacuum pump) causes reduces.
The step of boosting is to improve the adsorptive pressure of the pressure of adsorption tower to this process of approaching, it can be that the pressure that the process between the adsorption tower causes raises, also can be that the pressure that causes of the process between adsorption tower and the intermediate buffering jar raises, can also be to contain the gas mixture of hydro carbons and/or be difficult for adsorbent component and/or the device gas inside improves the pressure of adsorption tower by importing.
The gas fraction (4) that is enriched with ethene, ethane, propylene transfers to compression process (D) through piping, and the gas fraction after the compression transfers to drying process (E).Compression can be finished by one or more levels, the sum of series resulting pressure of compression is mainly adopted definite by low temperature separation process process (L), the pressure of gas fraction (5) can be 0.2-10.0MPa after the supercharging, wherein: be preferably 0.4-3.0MPa, especially preferably 1.0-2.5MPa.
The gas fraction (5) that is enriched with ethene, ethane, propylene after the supercharging transfers to drying process (E) through piping, and dried gas fraction transfers to low temperature separation process process (L).By means of drying process (E) moisture content in the gas fraction (5) that is enriched with ethene, ethane, propylene after the supercharging is thoroughly removed, it is essential removing the undesirable component of low temperature separation process process (L).Drying process (E) can be carried out before at adsorption process (C), also can carry out afterwards at compression process (D), preferably carries out afterwards in compression process (D).
The step of drying process (E) and preprocessing process (B) are basic identical, and what only remove at drying unit is moisture content, can draw the step of drying unit (E) with reference to the process of preprocessing process (B).
The dried gas fraction (6) that is enriched with ethene, ethane, propylene transfers to the degas module (F) of low temperature separation process process through piping.
Dried gas fraction (6) transfers to low temperature separation process process (L).The gas fraction (6) that is enriched with ethene, ethane, propylene that enters low temperature separation process system (L) is cooled by heat exchange unit (K) and each fraction countercurrent flow of supporting by the arm out low temperature separation process system (L), the ethylene fraction of discharge system (20), ethane fraction (21), propylene fraction (22), than heavy hydrocarbons fraction (17) and a spot of hydrogen, methane fraction (19) through heat exchange, its cold is reclaimed.
The cooled fraction (6) that is enriched with ethene, ethane, propylene directly enters degas module (F), to be enriched with by degas module (F) that undesirable component (19) falls as a spot of hydrogen, methane separation in the fraction (6) of ethene, ethane, propylene, remaining component (7) is sent to ethylene distillation unit (G).
The cooled fraction that is enriched with ethene, ethane, propylene is divided into 2 stocks and does not enter from the different heights of degassing tower, the material that is condensed into liquid phase at first step heat transfer process enters from the middle and upper part of degassing tower, is entered by the top of the gas-liquid mixed phase material of partial condensation from degassing tower connecing what heat transfer process of adopting down.The gas of degassing cat head cools off and partial condensation through coolant flow, and non-condensable gas (19) is discharged behind the recovery cold through the ice chest heat exchange, and phlegma is as the backflow of degassing tower.Coolant flow can be the inner material that needs heating of device, also can be ethene or the propylene or the methane refrigerant of circularly cooling, also can be the combination between the ethene, propylene, methane refrigerant of circularly cooling.The degassing tower bottom is provided with reboiler, termite stream can be that device inside needs the refrigerative material, also can be ethene or propylene or the methane material that needs the refrigerative circularly cooling, also can be the combination between the ethene that needs the refrigerative circularly cooling, propylene, the methane material.
The professional understands certainly, under the less situation of hydrogen in the fraction that is enriched with ethene, ethane, propylene (6) and methane content, perhaps under to the not high situation of the ethene purity requirement in the ethylene fraction, can directly extract ethylene fraction, and not need degas module (F) by ethylene distillation unit (G).
The fraction that is enriched with ethene, ethane, propylene (7) of degassing tower bottom enters ethylene distillation unit (G) through piping, and the fraction (7) that will be enriched with ethene, ethane, propylene by ethylene distillation unit (G) is separated into one ethylene fraction (20) and one is enriched with the fraction (8) of ethane, propylene.
The fraction that is enriched with ethene, ethane, propylene enters from the middle part of ethylene rectification tower.After the gas process overhead condenser partial condensation that the ethylene distillation cat head takes out, noncondensable gas is discharged behind the recovery cold through the ice chest heat exchange, and phlegma is as the backflow of ethylene rectification tower.Ethylene fraction (20) takes out from the side line position near the top.Ethylene distillation cat head coolant flow can be the inner material that needs heating of device, also can be ethene or the propylene or the methane refrigerant of circularly cooling, also can be the combination between ethene, propylene and the methane refrigerant of circularly cooling.Ethylene rectification tower middle part and/or bottom are provided with reboiler, termite stream can be that device inside needs the refrigerative material, also can be ethene or propylene or the methane material that needs the refrigerative circularly cooling, also can be ethene, the propylene that needs the refrigerative circularly cooling, the combination between the methane material.
The professional understands certainly, in degassing tower bottom still liquid (7) under dissolved hydrogen, the methane content situation seldom, perhaps under to the undemanding situation of other component content requirement in the ethylene fraction, can take out the ethylene gas fraction from the ethylene distillation top of tower, rather than above-mentioned from side line taking-up Ethylene Liquid fraction.In this case, after the gas process overhead condenser partial condensation that the ethylene distillation cat head takes out, uncooled ethene cut (20) is discharged behind the recovery cold through the ice chest heat exchange, and phlegma is as the backflow of ethylene rectification tower.
The fraction that is enriched with ethane, propylene (8) of ethylene distillation tower bottom enters deethanizing unit (H) through piping, and the fraction (8) that will be enriched with ethane, propylene by deethanizing unit (H) is separated into one ethane fraction (21) and one is enriched with the fraction (9) of propylene.
The fraction that is enriched with ethane, propylene enters from the middle part of deethanizing column.After the ethane fraction process overhead condenser partial condensation that the deethanizing cat head takes out, uncooled ethane fraction (21) is discharged behind the recovery cold through the ice chest heat exchange, and phlegma is as the backflow of deethanizing column.Deethanizing cat head coolant flow can be the inner material that needs heating of device, also can be ethene or the propylene or the methane refrigerant of circularly cooling, also can be the combination between ethene, propylene and the methane refrigerant of circularly cooling.Deethanizing column middle part and/or bottom are provided with reboiler, termite stream can be that device inside needs the refrigerative material, also can be ethene or propylene or the methane material that needs the refrigerative circularly cooling, also can be the combination between the ethene that needs the refrigerative circularly cooling, propylene, the methane material, can also be water or water vapor material.
The fraction that is enriched with propylene (9) of deethanizing column bottom enters propylene rectification cell (I) through piping, heats up in a steamer fraction (9) that unit (I) will be enriched with propylene and is separated into one propylene fraction (22) and one and is enriched with fraction (17) than heavy hydrocarbons by propylene is poor.
The fraction that is enriched with propylene enters from the middle part of propylene rectification tower.After the gas process overhead condenser partial condensation that take out on the propylene rectification tower top, uncooled propylene fraction (22) is discharged behind the recovery cold through the ice chest heat exchange, and phlegma is as the backflow of propylene rectification tower.Propylene rectification tower top coolant flow can be the inner material that needs heating of device, also can be ethene or the propylene or the water coolant of circularly cooling, also can be the combination between ethene, propylene and the water coolant of circularly cooling.Propylene rectification tower middle part and/or bottom are provided with reboiler, termite stream can be that device inside needs the refrigerative material, also can be ethene or propylene or the methane material that needs the refrigerative circularly cooling, also can be the combination between the ethene that needs the refrigerative circularly cooling, propylene, the methane material, can also be water or water vapor material.
The gas fraction (10) that is enriched with hydrogen and methane transfers to adsorption process (J) through piping, by means of pressure-swing adsorption process, the gas fraction (10) that is enriched with hydrogen, methane is separated into one hydrogen fraction (18) and one is enriched with the gas fraction (11) of methane.
The adsorption tower of absorbing unit (J) can have the combination more than 2 or 2, and every adsorption tower is in step such as once need experience absorption, forward step-down, reverse step-down in the circulation, boost.The professional understands certainly, in the once circulation of adsorption tower, may also include other steps, as steps such as isolation and flushings.
Adsorption step is that the fraction that is enriched with hydrogen, methane enters adsorption tower from feed end under the top pressure of this process, and the hydrogen component that is difficult for absorption passes through whole adsorption tower, and discharges from adsorption tower.Easily the gas compositions such as methane of absorption are rested in the adsorption tower.Be enriched with the gas fraction of hydrogen, methane can be from the top of adsorption tower or bottom or middle part enter adsorption tower.
Forward depressurization step is to reduce adsorptive pressure and the minimal pressure intermediary some pressure of the pressure of adsorption tower to this process, preferably is reduced to a little more than environmental stress, and the gas flow direction was consistent when the gas flow direction was with adsorption process in the step-down process.By turning round and look at, particularly between the adsorption tower and/or the pressure equilibrium between adsorption tower and the intermediate buffering jar, improved the rate of recovery of hydrogen component to the step-down process.Forward step-down process can be that the pressure that the process between the adsorption tower causes reduces, also can be that the pressure that the process between adsorption tower and the intermediate buffering jar causes reduces, can also be that the pressure that the process between adsorption tower and outside atmosphere or the peripheral equipment (as vacuum pump) causes reduces.
Reverse depressurization step is to reduce the minimal pressure of the pressure of adsorption tower to this process, preferably be reduced to be lower than environmental stress, in the step-down process when gas flow direction and adsorption process the gas flow direction opposite.By reverse step-down process, the easy adsorbent component in the adsorption tower is separated sucking-off from sorbent material and is adopted, and separates the easy adsorbent component (11) of sucking-off and transports to preprocessing process (B) and drying process (E).Reverse step-down process can be that the pressure that the process between adsorption tower and the intermediate buffering jar causes reduces, and also can be that the pressure that the process between adsorption tower and outside atmosphere or the peripheral equipment (as vacuum pump) causes reduces.
The step of boosting is to improve the adsorptive pressure of the pressure of adsorption tower to this process of approaching, it can be that the pressure that the process between the adsorption tower causes raises, also can be that the pressure that causes of the process between adsorption tower and the intermediate buffering jar raises, can also be to be enriched with the pressure that the gas fraction of hydrogen, methane and/or hydrogen fraction and/or unit gas inside improve adsorption tower by importing.
The following description is as embodiments of the invention, and this example is separation and Extraction ethene, ethane, propylene and a hydrogen from catalysis drying gas.
The catalysis drying gas that refinery catalytic cracking unit produces, entering this device pressure is 0.6MPa, and temperature is 40 ℃, and its typical case forms as table 1:
The typical case of table 1 catalysis drying gas forms
| Component | H 2 | CO 2 | N 2 | O 2 | CH 4 | C2H 4 | C2H 6 |
| Mol％ | 33.75 | 2 | 15 | 1 | 24 | 15 | 5 |
| Component | C 2H 6 | C 3H 8 | C 4H 8 | C 4H 10 | C 5 + | H 2O | Add up to |
| Mol％ | 3 | 1 | 0.1 | 0.05 | 0.05 | 0.05 | 100 |
According to method of the present invention, catalysis drying gas at first enters absorptive unit.With the Monoethanolamine MEA BASF counter current contact, carbon dioxide content is 30ppm in the gas of Monoethanolamine MEA BASF absorption tower outlet in the absorption tower, and through after the sodium hydroxide washing, the total amount of sour gas is lower than 1ppm to catalysis drying gas in the soda-wash tower exit gas again.
The catalysis drying gas that has removed sour gas enters pretreatment unit, every pretreater needs experience absorption in a circulation, steps such as step-down (be specially reverse putting and be pressed onto environmental stress), heat, cool off, boost (be specially catalysis drying gas reflux boost near adsorptive pressure).Wherein pretreater is in the adsorption step of the carbon five above components that remove in the catalysis drying gas, and another pretreater is in other steps, and heating air flow and cooling draught are from the unitary gas fraction that is enriched with methane of transformation absorption purified hydrogen.Carbon five above components in the catalysis drying gas of pretreater outlet are lower than 1ppm.
Catalysis drying gas after the purification enters the transformation adsorption separation unit, the transformation adsorption separation unit mainly is made up of 7 adsorption towers, every adsorption tower needs experience absorption in a circulation, forward step-down (is specially the once all pressure drops between the adsorption tower, the equal pressure drop of secondary), clean, reverse step-down (is specially reverse putting and is pressed onto environmental stress, be evacuated down to and be lower than environmental stress), boost and (be specially the equal voltage rise of secondary between the adsorption tower, once all voltage rises, be difficult for adsorbent component reflux boost near adsorptive pressure) etc. step, the wherein equal voltage rise of secondary and once all between the voltage rise isolation step is arranged.
Through adsorption separation unit, catalysis drying gas is divided into light fraction and heavy fraction, and light fraction wherein is enriched with components such as hydrogen, nitrogen, oxygen and methane, and heavy fraction is enriched with components such as ethene, ethane, propylene, propane, butylene and butane.
Heavy fraction enters drying unit through after being compressed to 2.0MPa, and the process and the pretreatment unit of drying unit are similar, and the water-content in the heavy fraction of drying tower outlet is lower than 1ppm.
Heavy fraction behind the drying and dehydrating through with the fraction heat exchange that goes out the low temperature separation process process after, the heavy fraction of partial condensation enters from the middle part and the top of degassing tower, overhead gas cools off and partial condensation through coolant flow, hydrogen and methane gas fraction are through the ice chest heat exchange, discharge after reclaiming cold, phlegma is as the backflow of degassing tower.
Degassing tower bottoms enters ethylene rectification tower, and from the side line extraction ethylene fraction of ethylene column, the ethylene content in the ethylene fraction is 99.95%, and total extraction yield of ethene is 98%.
The ethylene distillation tower bottoms enters propylene rectification tower through behind the deethanizing, takes out the propylene fraction from the top of propylene rectification tower, and the propylene content in the propylene fraction is 99.6%, and total extraction yield of propylene is 95%.
Light fraction enters transformation absorption purified hydrogen unit, every adsorption tower in a circulation, need experience absorption, forward step-down (being specially once all pressure drops, the equal pressure drop of secondary between the adsorption tower), reverse step-down (be specially reverse put be pressed onto environmental stress, be evacuated down to be lower than environmental stress), the steps such as (the equal voltage rise of secondary, once all voltage rises, the hydrogen fraction that are specially between the adsorption tower reflux and boost near adsorptive pressure) of boosting.Take out the hydrogen fraction from the top of adsorption tower, the hydrogen richness in the hydrogen fraction is 99.99%, and total extraction yield of hydrogen is 95%.
Claims (10)
1, the method for separating and reclaiming ethylene, ethane, propylene and hydrogen from the gas mixture that contains hydro carbons, it is characterized in that, nationality helps the United Technologies of absorption extraction, fractionation by adsorption and low temperature separation process, and Separation and Recovery contains ethene, ethane, propylene and the hydrogen in the gas mixture of hydro carbons; By absorption process (A), will contain the acid gas removal in the gas mixture (1) of hydro carbons; By adsorption process (C), promptly be to be separated into one gas fraction (10) that is enriched with hydrogen, methane and one gas fraction (4) that is enriched with ethene, ethane, propylene by adsorbing the gas mixture (3) that will contain hydro carbons; The gas fraction (6) that is enriched with ethene, ethane, propylene by low temperature separation process process (L), is obtained ethylene fraction (20), ethane fraction (21), propylene fraction (22) respectively and than heavy hydrocarbons fraction (17); The gas fraction (10) that is enriched with hydrogen and methane by another adsorption process (J), is obtained hydrogen fraction (18) and is enriched with the gas fraction (11) of methane.
2, according to the method for claim l, it is characterized in that: the ethene that contains 99.0mol% in the ethylene fraction at least.
3, according to the method for claim 1, it is characterized in that: the propylene that contains 99.00mol% in the propylene fraction at least.
4, according to the method for claim 1, it is characterized in that: the hydrogen that contains 98.0mol% in the hydrogen fraction at least.
5, according to the method for claim 1, it is characterized in that: undesirable carbonic acid gas, sulfide separate by absorption process (A) in the low temperature separation process process (L); Absorption process (A) is carried out before in adsorption process (C), or carries out afterwards in adsorption process (C).
6, according to the method for claim 1 or 5, it is characterized in that: absorption process (A) adopts chemistry and/or physical absorption, and wherein chemistry and/or physical absorbent are amine and/or bases, deliver in the absorption process (A) as washings.
7, according to the method for claim 1, it is characterized in that: the gas fraction (4) that will be enriched with ethene, ethane, propylene transfers to compression process (D) by pipeline, gas fraction after the compression transfers to drying process (E), and the pressure of gas fraction (5) is 0.2-10.0Mpa after the supercharging.
8, according to the method for claim 1, it is characterized in that: undesirable component water separates by drying process (E) in the low temperature separation process process (L); Drying process (E) is carried out before in adsorption process (C), or carries out afterwards in compression process (D).
9, according to the method for claim 1, it is characterized in that: adsorption process (C) does not wish that the component heavy hydrocarbons that has separates by preprocessing process (B), and preprocessing process (B) is the alternating temperature absorption method.
10, according to the method for claim 1, it is characterized in that: will be enriched with in the gas fraction (6) of ethene, ethane, propylene undesirable component hydrogen, methane separation by degas module (F) and fall, remaining component (7) is sent to ethylene distillation unit (G).
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| CN101353286B (en) * | 2007-07-25 | 2011-12-07 | 惠生工程（中国）有限公司 | Non-copious cooling lower carbon number hydrocarbons separation method containing light gas |
| CN101445419B (en) * | 2007-11-27 | 2012-10-31 | 惠生工程（中国）有限公司 | Method for separating lower hydrocarbon containing light gas by combining distillation and solvent absorption |
| CN101633595B (en) * | 2008-07-24 | 2012-10-24 | 中国石油化工股份有限公司 | Method for reclaiming ethylene in catalytic dry gas |
| CN101823933A (en) * | 2010-05-12 | 2010-09-08 | 天津市泰亨气体有限公司 | Technology for producing high-purity ethane by large-scale chromatography |
| CN101811922A (en) * | 2010-05-12 | 2010-08-25 | 天津市泰源工业气体有限公司 | Technology for producing high-purity propane through large-scale chromatography |
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2000
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