CN114573415B - Separation method and device for coupled alkane catalytic dehydrogenation reaction products - Google Patents
Separation method and device for coupled alkane catalytic dehydrogenation reaction products Download PDFInfo
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- CN114573415B CN114573415B CN202011372191.6A CN202011372191A CN114573415B CN 114573415 B CN114573415 B CN 114573415B CN 202011372191 A CN202011372191 A CN 202011372191A CN 114573415 B CN114573415 B CN 114573415B
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- 238000000926 separation method Methods 0.000 title claims abstract description 143
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 45
- 239000007795 chemical reaction product Substances 0.000 title claims abstract description 38
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 22
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 154
- 239000007789 gas Substances 0.000 claims abstract description 102
- 238000005057 refrigeration Methods 0.000 claims abstract description 95
- 239000001294 propane Substances 0.000 claims abstract description 77
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000047 product Substances 0.000 claims abstract description 62
- 239000007788 liquid Substances 0.000 claims abstract description 49
- 238000003303 reheating Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000007791 liquid phase Substances 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000012071 phase Substances 0.000 claims abstract description 27
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 13
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 230000008020 evaporation Effects 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000003507 refrigerant Substances 0.000 claims description 74
- 238000001816 cooling Methods 0.000 claims description 64
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 38
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000011552 falling film Substances 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 9
- 239000012263 liquid product Substances 0.000 claims description 9
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000001273 butane Substances 0.000 claims description 7
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 7
- -1 ethylene, propylene, propane Chemical class 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 21
- 238000005265 energy consumption Methods 0.000 abstract description 14
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004283 Sodium sorbate Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000003211 malignant effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
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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
- F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
- F25J3/0605—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the feed stream
- F25J3/062—Refinery gas, cracking gas, coke oven gas, gaseous mixtures containing aliphatic unsaturated CnHm or gaseous mixtures of undefined nature
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/09—Purification; Separation; Use of additives by fractional condensation
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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
- F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
- F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
- F25J3/0645—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of 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
- F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
- F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
- F25J3/0655—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of hydrogen
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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
- F25J5/00—Arrangements of cold exchangers or cold accumulators in separation or liquefaction plants
-
- 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
- F25J2210/00—Processes characterised by the type or other details of the feed stream
- F25J2210/62—Liquefied natural gas [LNG]; Natural gas liquids [NGL]; Liquefied petroleum gas [LPG]
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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
- F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
- F25J2235/60—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being (a mixture of) hydrocarbons
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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
- F25J2245/00—Processes or apparatus involving steps for recycling of process streams
- F25J2245/02—Recycle of a stream in general, e.g. a by-pass stream
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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
- F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
- F25J2260/02—Integration in an installation for exchanging heat, e.g. for waste heat recovery
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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
- F25J2270/00—Refrigeration techniques used
- F25J2270/12—External refrigeration with liquid vaporising loop
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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
- F25J2270/00—Refrigeration techniques used
- F25J2270/18—External refrigeration with incorporated cascade loop
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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
- 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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2270/00—Refrigeration techniques used
- F25J2270/66—Closed external refrigeration cycle with multi component refrigerant [MCR], e.g. mixture of hydrocarbons
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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
- F25J2270/00—Refrigeration techniques used
- F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
- F25J2270/904—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by liquid or gaseous cryogen in an open loop
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation By Low-Temperature Treatments (AREA)
Abstract
The invention relates to a separation method and a separation device of a coupled alkane catalytic dehydrogenation reaction product, wherein product gas at an outlet of an alkane dehydrogenation reactor is input into a cold box system to obtain a cooled product; inputting the cooled product into N-level serial gas-liquid separation tanks for gas-liquid separation, and then inputting the gas-phase product obtained from the 1 st to N-1 st levels into a cold box system again; collecting the liquid phase products obtained in the stages 1-N, carrying out reheating and sending out the liquid phase products out of the boundary region, and then separating products with different carbon numbers from the liquid phase products through a separating tower; mixing circulating gas obtained from the top of an Nth separation tank with fresh propane according to a preset hydrogen/hydrocarbon ratio through M stages, and providing cold energy for a cold box system through throttle evaporation in the cold box system; introducing tail gas at the top of the deethanizer into a cold box system, and providing cold energy for the cold box system; the cold of the cold box system also comes from the external refrigeration cycle system. The invention can reduce the separation energy consumption, reduce the product loss, and has simple process flow, environmental protection, compact equipment and convenient and quick start/stop.
Description
Technical Field
The invention relates to the technical field of chemical separation, in particular to a separation method and a separation device for a coupled alkane catalytic dehydrogenation reaction product.
Background
The alkane can be subjected to dehydrogenation reaction in the presence of the catalyst to generate olefin and hydrogen with higher added values. Among the various olefins, propylene is an important petrochemical base stock. The method is mainly used for producing tens of petrochemical products and raw materials such as polypropylene, propylene oxide, acrylic acid, acrylonitrile, alkylate, high-octane gasoline blending materials and the like. In recent years, the demand of propylene in China continues to increase rapidly due to the rapid development of various chemical products downstream of propylene.
Propylene has long been derived mainly from naphtha steam cracking processes and petroleum refining catalytic cracking processes. In recent years, in the background of the growing demand of propylene downstream markets, some new and economical technologies for producing propylene have attracted attention and have been successfully industrialized. Including Methanol To Olefins (MTO), methanol To Propylene (MTP), olefin Cracking (OCP), and propane dehydrogenation to Propylene (PDH). Among the above various processes for producing propylene, propane dehydrogenation, which uses propane for the directional production of propylene, has achieved great success due to its simple process flow and excellent economy. In recent years, more than twenty propane dehydrogenation devices are newly built and put into production in China, and the produced propylene has a scale of more than 1200 ten thousand tons/year. Thus, propane dehydrogenation technology is currently the most competitive propylene production process, and market share is expanding.
The dehydrogenation reaction product of propane is mainly composed of hydrogen and carbon three, and small amounts of methane, carbon two, nitrogen and the like. Methane and part of carbon two come from byproducts of propane dehydrogenation, part of carbon two comes from raw material propane, and nitrogen comes from a regeneration process. The reactor outlet material is cooled, compressed and dried, then enters a separation system, the mixture of propylene and unreacted propane is gradually condensed in a cold box, and propylene and recycled propane are recovered in a downstream rectifying unit and returned to the reactor. Since the propane dehydrogenation reaction product contains a large amount of hydrogen, it is necessary to separate hydrogen from carbon three at cryogenic temperatures. After the hydrogen-rich gas is reheated, the pure hydrogen product is obtained through PSA purification, and the tail gas absorbed by the PSA is used as fuel gas for transmission.
The separation process of the existing industrialized propane dehydrogenation reaction product adopts a low-temperature cryogenic process to realize the separation of light components and carbon three, and the reaction product is cooled to-95 to-125 ℃ step by step in a plate-fin heat exchanger. According to the composition difference of reaction products of different processes, double expansion refrigeration or external single component refrigeration is generally adopted to obtain the cold quantity required by separation, the process is relatively complex, and the recovery rate of the carbon three is limited by the condition of the reaction products or the minimum refrigeration temperature obtained by external refrigeration. The energy consumption and the investment of equipment of the whole separation device are quite high. In addition, the carbon three product obtained by the separation system necessarily contains a certain amount of hydrogen and carbon two, and the separation of polymerization grade propylene and propane can be realized only by sending the light components separated by the deethanizer to the propylene tower. At present, the partial condensation of the gas phase at the top of the deethanizer is realized by independently configuring a set of refrigerating units to provide cold energy with temperature matched with the temperature level at the top of the deethanizer. The whole separation system is complex in unit, and high requirements are placed on stable operation of the device.
Disclosure of Invention
The invention provides a separation method and a separation device for a coupled alkane catalytic dehydrogenation reaction product, which overcome the defects of poor separation effect, high energy consumption, low carbon three recovery rate, complex unit and the like of propane dehydrogenation reaction gas in the prior art.
The aim of the invention can be achieved by the following technical scheme:
the inventor finds that raw material propane of the propane dehydrogenation device is stored in a low-temperature liquid state, and the liquid raw material propane is gasified and enters the reactor according to the characteristics of alkane catalytic dehydrogenation reaction and the feeding requirement, and a large amount of heat is required to be absorbed by the gasification of the raw material, so that the gasification and separation system of the raw material propane can be coupled, the cold energy is provided for the separation system, and the optimization and the matching of energy are realized; in addition, the tail gas at the top of the deethanizer contains a large amount of carbon dioxide, methane and a small amount of hydrogen, the pressure is high (2.25 MPaG-2.85 MPaG can be reached), and the cold energy of minus 100 ℃ to minus 160 ℃ can be generated after precooling, depressurization and throttling, so that the cold energy can be coupled with a separation system, the optimal matching of energy is realized, and the energy consumption of the separation system is saved.
Meanwhile, the method of refrigerating by adopting the mixed refrigerant can effectively reduce the temperature of cryogenic separation and improve the recovery rate of the carbon three products. The three cold quantities are skillfully and effectively coupled into the separation system, the original trend and the original connection form of the materials are changed and adjusted, the three cold quantities are coupled with the pre-cooling refrigeration cycle and the mixed refrigerant cryogenic refrigeration cycle according to the temperature grade, the cold quantities required by separation are provided for the separation system together, the generated reaction gas does not need throttling expansion refrigeration, and the temperature grade between-160 ℃ and-40 ℃ is finally realized only by adjusting reasonable refrigerant proportion and operation parameters. The purpose of fully recycling the carbon three products is achieved under the condition of reducing the equipment investment in advance.
The separation method of the coupled alkane catalytic dehydrogenation reaction product comprises the following steps:
inputting reaction product gas at the outlet of the alkane catalytic dehydrogenation reactor into a cold box system to obtain a cooled product;
and inputting the cooled product into N-stage serial gas-liquid separation tanks for gas-liquid separation, and then:
re-inputting the gas-phase product obtained in the 1 st to N-1 st stage into a cold box system, and finally cooling to-95 ℃ to-160 ℃, preferably-115 ℃ to-145 ℃, more preferably-120 ℃ to-138 ℃;
collecting the liquid phase products obtained in the stages 1-N, then reheating and sending out of a cold box system, and then separating products with different carbon numbers from the liquid phase products through a separation tower;
mixing circulating gas obtained from the top of an N-th-stage gas-liquid separation tank with fresh propane according to a preset hydrogen/hydrocarbon ratio through M stages, and performing throttle evaporation in a cold box system to provide cold energy for the cold box system, and delivering the cold box system after reheating, wherein M is less than or equal to N;
the dry gas obtained from the top of the N-th-stage gas-liquid separation tank is reheated in the cold box system and then sent out of the cold box system;
introducing tail gas at the top of the deethanizer into a cold box system, cooling to the temperature of N-stage separation through a multi-stage cold box, reducing pressure and throttling to 125 kPaG-400 kPaG, preferably 200 kPaG-375 kPaG, returning to the cold box, reheating to 15-45 ℃, and delivering out of the cold box system;
the cold volume of the cold box system is also from an external refrigeration cycle system.
Further, the series stages of the heat exchangers of the cold box system are equal to the N-stage separation tank stages and are matched step by step, the cold box system comprises a pre-cooling section by one or more stages, and the rest of the cold box system comprises a deep cooling section.
Further, 60% -100% of the fresh propane flow is distributed to the pre-cooling section, the rest is distributed to the deep cooling section, and the distribution flow and the fresh propane temperature level are matched according to negative correlation.
Further, part of cold energy of the cold box system is from cold energy generated after the fresh propane and the circulating gas are mixed in multiple stages, throttled, gasified and evaporated, and the tail gas at the top of the deethanizer is cooled and throttled; the inventor finds that 60% -100% of fresh propane flow needs to be distributed to the pre-cooling section in order to achieve the optimal energy coupling effect after a large number of researches, and the principle that the distribution is gradually reduced along with the rising of the temperature level is satisfied. The tail gas at the top of the deethanizer is subjected to multistage precooling to the temperature of N-stage separation by a cold box system, throttled and returned to the cold box and reheated to a boundary area at 15-45 ℃.
Further, the liquid phase products of the gas-liquid separation tanks at each level are returned to the cold box system for reheating and summarized and then enter the liquid product tank, and then are pumped into the cold box system for reheating again and enter the deethanizer to realize the separation of hydrogen, carbon one, carbon two and carbon three.
Further, the external refrigeration cycle system includes: a precooling refrigeration cycle system for providing cold energy to the precooling section and a cryogenic refrigeration cycle system for providing cold energy to the cryogenic section.
Further, the N is greater than 2, preferably 3 to 5, more preferably 3 to 4.
Further, the refrigerant in the precooling refrigeration cycle system is one or a combination of more of ammonia, ethane, ethylene, propylene, propane, butane and pentane;
the refrigerant in the cryogenic refrigeration cycle system is a combination of a plurality of nitrogen, methane, ethane, ethylene, propane, propylene and butane.
Further, the circulating gas flow is proportionally matched with a preset hydrogen/hydrocarbon ratio;
when the preset hydrogen/hydrocarbon ratio is zero, the circulating gas flow is set to zero, and the fresh propane is throttled and evaporated only in the corresponding stage number of the pre-cooling section.
And further, cooling the tail gas at the top of the deethanizer to the temperature of the N-stage separation by a cold box system, throttling and returning the tail gas to the cold box system, and delivering the tail gas out of the cold box system after reheating.
The invention relates to a separation device of a coupled alkane catalytic dehydrogenation reaction product, which comprises a cold box system, a precooling refrigeration cycle system and a cryogenic refrigeration cycle system, wherein the separation device specifically comprises the following components:
the cold box system is respectively connected with an alkane catalytic dehydrogenation reactor outlet and a separation tower top tail gas outlet and is connected with a fresh propane storage tank, and the cold box system comprises a pre-cooling section and a deep cooling section;
the precooling refrigeration cycle system is in heat exchange connection with the precooling section and provides cold energy for the precooling cooling separation process of the reaction product gas at the outlet of the alkane catalytic dehydrogenation reactor;
the cryogenic refrigeration circulating system is connected with the cryogenic section in a heat exchange mode, and provides cooling capacity for the cryogenic cooling separation process of the reaction product gas at the outlet of the alkane catalytic dehydrogenation reactor;
the N-stage separation tank is connected with the cold box system and is matched step by step, the gas phase at the top of the N-stage separation tank is divided into two material flows of dry gas and circulating gas, the circulating gas and fresh propane are mixed according to a preset hydrogen/hydrocarbon ratio through M stages and are input into the cold box system, wherein M is less than or equal to N, and the outlets of liquid-phase products obtained from the separation tanks 1-N are sequentially connected with the liquid-product tank and the separation tower, so that separation of products with different carbon numbers is realized.
Further, a falling film condenser is arranged on the top of the liquid product tank;
the separation tower is a deethanizer;
the cold box system comprises a multi-stage plate-fin heat exchanger.
Further, the precooling refrigeration cycle system is also respectively connected with a condenser of the deethanizer, a falling film condenser and a cryogenic refrigeration cycle system in a heat exchange mode.
For convenience of explanation, the propane dehydrogenation reaction products are taken as examples, but most of alkane dehydrogenation reaction products are actually used in the separation method and device of the alkane catalytic dehydrogenation reaction products.
Compared with the prior art, the invention has the following technical advantages:
1) Saving the energy consumption of separation: the process flow of the invention achieves the aim of saving separation energy consumption by adopting the following points: 1. the product of the propane dehydrogenation reactor is gradually condensed in a cold box system and then is subjected to multiple extraction, the product enters a separation tank, a liquid-phase product is separated, and a gas phase returns to the cold box to be further condensed and then enters a next-stage separation tank. The design can play a role in reducing separation energy consumption, and reduce energy required by an external refrigeration cycle system; 2. the reaction raw material propane is mixed with circulating gas (hydrogen-rich gas) at a plurality of positions and then throttled and gasified to generate cold energy, the cold energy of the raw material is brought into a cold box system, and the cold energy required to be provided by an external refrigeration circulating system is reduced; 3. introducing tail gas of the deethanizer into a cold box system, generating low temperature through cooling and throttling, providing cold energy for a separation system, and saving the energy consumption of separation; 4. the mixed refrigerant is adopted for refrigeration, the temperature difference is ensured to be smaller in the whole heat transfer process, the accurate matching of the condensation demand refrigeration capacity of the reaction product and the refrigeration generation refrigeration capacity can be realized, the goals of 'refrigeration capacity matching and equivalent temperature level' are realized, and the irreversibility of the heat transfer process are reducedAnd loss, and finally, the aim of reducing the separation energy consumption is fulfilled.
2) Reducing the loss of carbon three in the hydrogen-rich gas: during the separation of the propane dehydrogenation reaction product, the final cryogenic temperature of the reaction product has a positive correlation with the loss of carbon three. The invention adopts the mixed refrigerant as the refrigerant of the cryogenic refrigeration cycle system, can reach the expected cryogenic temperature through the selection and the optimization of the composition of the components of the refrigerant formula, and can break through the limit of the lowest refrigeration temperature of ethylene refrigeration and generate the refrigeration capacity of the temperature below-100 ℃ compared with the existing refrigeration cycle adopting the ethylene single refrigerant, thereby achieving the purpose of reducing the loss rate of the three-carbon products. Compared with the existing refrigeration process adopting double expansion, the method can break through the refrigeration temperature of the expander to generate lower temperature than that of the expander process, and the purpose of reducing the loss rate of the three-carbon products is achieved.
3) The equipment and the flow are more compact, and the investment is reduced: compared with the existing flow, the method has the advantages that the refrigeration capacity of the condenser at the top of the deethanizer is integrated into the precooling refrigeration cycle system, a refrigerating unit can be prevented from being independently arranged, the flow is more simplified and compact, the equipment investment of the whole propane dehydrogenation device is reduced, and the economical efficiency is improved. In addition, if the pre-cooling and the deep cooling of the technical scheme adopt the mixed refrigerant refrigeration cycle system to provide cold energy for the separation system, the power consumption of the two compressors can be equivalent by adjusting the respective refrigerant formulas of the two refrigeration cycle systems, and the power devices with the same specification can be adopted, so that the complete difficulty and the running operation cost of the compressor unit are reduced, and the overall economy and the operability of the device are improved.
4) The cold box system operates more steadily: the raw propane is subjected to multistage distribution in the cold box system according to a certain temperature grade matching principle, so that the complete gasification of the propane in the cold box system is ensured, and the cold energy is provided; avoiding the malignant circulation of the un-gasified propane accumulated in the runner to submerge the runner, resulting in reduced heat exchange area and reduced gasification rate, and finally resulting in shutdown of the separation system.
5) The process is more environment-friendly: the refrigeration capacity of the raw material propane and the tail gas at the top of the deethanizer is coupled in the traditional refrigeration cycle system, so that the refrigeration capacity required to be provided by the external refrigeration cycle system is reduced, and the quantity of the refrigerant is reduced; when the device is parked, the discharge amount of the torch is reduced, the generated greenhouse gas amount is reduced, and the discharge time is shorter, so that the process is more environment-friendly. Meanwhile, the design load of a torch system can be reduced due to the reduction of the discharge quantity, and equipment investment and occupied area are reduced.
6) The driving is more concise, stable and rapid: because the pre-cooling and cryogenic double-circulation refrigerating system is adopted to provide cold energy for the separating device, the pre-cooling circulating system is started preferentially when the vehicle starts, the pre-cooling cold energy is provided for the cold box system, and the cryogenic circulating system is started after the pre-cooling and cryogenic double-circulation refrigerating system is stabilized, and the cryogenic cold energy is provided for the cold box system. The process is safe and simple and is easy to operate. The driving process is more stable and convenient, the driving efficiency is high, the driving time is shortened, and the overall operability of the device is improved.
Drawings
FIG. 1 is a schematic and schematic illustration of the process flow of the present invention;
FIG. 2 is a schematic flow chart of embodiment 1 of the present invention;
FIG. 3 is a schematic flow chart of embodiment 2 of the present invention;
FIG. 4 is a schematic flow chart of embodiment 3 of the present invention;
FIG. 5 is a schematic flow chart of embodiment 4 of the present invention;
FIG. 6 is a schematic flow chart of embodiment 5 of the present invention;
FIG. 7 is a schematic flow chart of comparative example 1.
The content represented by each reference numeral is specifically:
plate-fin heat exchanger: EX-101, EX-102, EX-103, EX-104; gas-liquid separation tanks V-101, V-102, V-103, V-104 and V-201; carbon three product tank V-105; falling film condenser E-201; deethanizer overhead condenser E-301; carbon three product pump P-101A/B.
Detailed Description
The method and the device for separating the coupled propane dehydrogenation reaction product provided in the embodiment can be realized by adopting the following technical scheme:
the reaction product gas at the outlet of the propane dehydrogenation reactor enters a separation system after being pretreated by cooling, compressing, purifying, filtering and the like, is pumped out to enter a gas-liquid separation tank for gas-liquid separation after being cooled in a cold box system of the separation system, and the gas phase continuously enters the cold box system for cooling to the next stage of gas-liquid separation until reaching the expected cooling temperature and meeting the recovery rate requirement of the carbon three products. The top gas phase (hydrogen-rich gas) of the final-stage separation tank is divided into two material flows of dry gas and circulating gas, the circulating gas is required to be mixed with fresh propane according to a certain hydrogen/hydrocarbon ratio through M stages (M is less than or equal to N), and the mixture is subjected to throttle evaporation in a cold box system to provide cooling capacity, and the cooled mixture is sent out of a separation system boundary zone after reheating and enters a reactor; the dry gas is sent out of the boundary region after reheating. If the preset hydrogen/hydrocarbon ratio is zero, no recycle gas is required and the fresh propane only needs to be throttled and vaporized in the pre-cooling section. The tail gas at the top of the deethanizer is cooled to the temperature of the N-stage separation by a heat exchanger in a multi-stage cold box system, throttled and returned to the cold box system, and sent out of the separation system boundary region after reheating. The tank bottom liquid of each level of gas-liquid separation tank returns to the cold box system for reheating by utilizing the pressure of the tank bottom liquid and enters the liquid product tank after summarized, and then enters the deethanizer for realizing the separation of hydrogen/carbon one/carbon two and carbon three after being pumped into the cold box system for reheating. The tail gas from the top of the deethanizer enters a cold box system, is throttled and depressurized after being cooled in multiple stages, returns to the cold box system for reheating to provide cold, and is sent out of the boundary region. After the flash gas generated by the liquid product tank is condensed by adopting the falling film heat exchanger, the gas phase enters a reheating outlet area of the cold box system, and the condensed liquid phase (mainly carbon three) flows back to the liquid product tank due to self gravity.
The cold box system (plate-fin heat exchanger) is one of the key equipment of the separation system, comprises a heat exchange core body, matched pipelines, meters and other components, mainly meets the heat exchange requirement of multiple streams, and has the advantages of compact structure and high heat exchange efficiency. Part of the cold energy of the separation system is derived from the throttling evaporation of a mixture of fresh propane raw material feed and hydrogen-rich gas in the cold box system, and the other part of the cold energy is provided by an external refrigeration cycle system, and in addition, the tail gas at the top of the deethanizer is introduced into the cold box system, and low temperature is generated through cooling and throttling, so that the cold energy is provided for the separation system. In order to simplify the flow and reduce the investment and energy consumption, the external refrigeration cycle system consists of two independent refrigeration cycle systems, namely a precooling system and a cryogenic system, and the external refrigeration cycle system basically comprises the following components: a refrigeration cycle compressor, a matched suction tank, a pipeline, a pipe fitting, a control instrument, a heat exchanger and the like. The precooling refrigeration cycle system can adopt a single component as a refrigerant, and can also adopt a mixed refrigerant consisting of two or more components of ammonia, ethane, ethylene, propane, propylene, butane and pentane. The cryogenic refrigeration cycle system adopts a multi-component mixture as a mixed refrigerant, and the formula of the mixed refrigerant can be as follows: nitrogen, methane, ethane, ethylene, propane, propylene, butane, and combinations of two or more thereof. The precooling refrigeration cycle system mainly bears the cold energy supplement from the raw material inlet temperature to minus 15 ℃ to minus 65 ℃, and part of cold energy is also used for condensing mixed refrigerant of the cryogenic cycle system and providing cold energy for a deethanizer top condenser and a falling film condenser on the top of a liquid product tank; the cryogenic refrigeration cycle system mainly bears the refrigeration quantity supplement from the refrigeration temperature of the precooling end to minus 95 ℃ to minus 160 ℃, and can also be the refrigeration quantity supplement from the raw material inlet temperature to minus 95 ℃ to minus 160 ℃. The refrigerant of the refrigeration cycle system is gasified back to the compressor of each refrigeration cycle system after reheating and absorbing the heat released by the cooling of the reaction product in the cold box system, and then compressed and cooled and throttled to form low-temperature refrigerant to enter the cold box system to provide cold energy, thus completing the refrigeration cycle.
The invention will now be described in detail with reference to the drawings and specific examples.
Example 1
As shown in figure 2, the reaction product gas at the outlet of the propane dehydrogenation reactor is subjected to pretreatment such as cooling, compression, purification and filtration and then enters a plate-fin heat exchanger EX-101 of a separation system, is cooled and condensed to the temperature of minus 10 ℃ and then enters a gas-liquid separation tank V101, the separated liquid phase enters a carbon three-product tank V-105, the gas phase enters the plate-fin heat exchanger EX-102, is further cooled and condensed to the temperature of minus 38 ℃ and then enters the gas-liquid separation tank V-102, the separated liquid phase carbon three is mixed with the liquid phase carbon three separated at the next stage and then enters the plate-fin heat exchanger EX-102, is subjected to reheating in the plate-fin heat exchanger EX-102 by self pressure and then enters the plate-fin heat exchanger EX-105, the gas phase enters the plate-fin heat exchanger EX-103, is further cooled and condensed and then enters the gas-liquid separation tank V-103, and the separated liquid phase carbon three separated from the next stage EX-104 is sequentially subjected to reheating in the plate-fin heat exchanger EX-103 and then enters the plate-fin heat exchanger EX-102. Dry gas and circulating gas are obtained at the top of a final-stage gas-liquid separation tank V-104, wherein the dry gas sequentially returns to plate-fin heat exchange EX-104, EX103, EX-102 and EX-101, and is sent out of a boundary region after being reheated to 30 ℃; the circulating gas and fresh propane feed are mixed at the inlet of each stage of plate-fin heat exchanger along the direction of the circulating gas input into the cold box system, and then are reheated to 30 ℃ by the plate-fin heat exchangers EX-104, EX-103, EX-102 and EX-101 and then are sent out of the boundary region. The tail gas at the top of the deethanizer is cooled to-115 ℃ in multiple stages through a cold box system, throttled to 255KPaG, returned to the cold box system, reheated to 25 ℃ and sent out of the cold box system.
In this example, the reaction product gas underwent four gas-liquid separations in total, and the recycle gas was also subjected to four mixes with the feed propane. The flow distribution ratio of propane at the mixing point in the order of the temperature from high to low is about: 7:2:0.7:0.3, wherein 90% of the fresh propane flow is allocated to the pre-cooling section. The liquid phase products separated by each level of gas-liquid separation tank are collected to a carbon three product tank V-105, flash gas at the top of the carbon three product tank V-105 is condensed by a falling film condenser E-201, flash gas which is not condensed is sent out of a boundary region after being reheated by plate-fin heat exchangers EX-102 and EX-101 in sequence, the condensed liquid flows back to the carbon three product tank V-105 due to self gravity, and finally is pressurized to the plate-fin heat exchanger EX-101 by a carbon three product pump P-101A/B to be reheated to 35 ℃ and then is sent into a deethanizer for hydrogen/carbon one/carbon two and carbon three separation.
The refrigeration capacity required to be provided outside the separation system is obtained by adopting two refrigeration cycle systems of propylene precooling and mixed refrigerant deep cooling. The propylene pre-cooling refrigeration cycle system can provide propylene refrigerant with two temperature levels of-41 ℃ and-15 ℃, wherein the propylene refrigerant with the temperature of-15 ℃ is used by a deethanizer condenser, and the propylene refrigerant with the temperature of-41 ℃ is used by a plate fin heat exchanger EX-102 and a falling film condenser E-201 on the top of a carbon three product tank V-105. The propylene refrigerating compressor adopts a centrifugal type, the outlet pressure is 1.77MPaG, and the outlet gas-phase propylene is cooled to 43 ℃ through circulating cooling water.
The mixed refrigerant cryogenic refrigeration cycle system adopts methane, ethylene and propane as refrigerants, and after the mixed refrigerant compressor is pressurized to 2.19MPaG, the mixed refrigerant is cooled to 43 ℃ by cooling circulating water, and then enters plate-fin heat exchangers EX-101 and EX-102 in sequence, and after being precooled to-38 ℃, the mixed refrigerant enters a gas-liquid separation tank V-201. The tank top gas-phase refrigerant sequentially enters the plate-fin heat exchanger EX-103 and the EX-104 to be cooled to the final separation temperature and then throttled to 320KPaG, then enters the plate-fin heat exchanger EX-104 for reheating, and is mixed with tank bottom liquid-phase refrigerant cooled by the plate-fin heat exchanger EX-103 to enter the plate-fin heat exchanger EX-103 for reheating to the temperature of minus 40 ℃ and then enters a mixed refrigerant refrigerating compressor suction tank to be compressed to the outlet pressure, thus completing the refrigerating cycle.
Example 2
As shown in figure 3, the reaction product gas at the outlet of the propane dehydrogenation reactor is subjected to pretreatment such as cooling, compression, purification and filtration and then enters a separation system plate-fin heat exchanger EX-101, is cooled and condensed to the temperature of minus 8 ℃ and then enters a gas-liquid separation tank V101, the separated liquid phase enters a carbon three product tank V-105, the gas phase enters the plate-fin heat exchanger EX-102, is further cooled and condensed to the temperature of minus 37 ℃ and then enters the gas-liquid separation tank V-102, the separated liquid phase carbon three is mixed with the liquid phase carbon three separated at the next stage and then is subjected to reheating in the gas-liquid separation tank V-105 by utilizing the self pressure, the gas phase enters the plate-fin heat exchanger EX-103, is further cooled and condensed and then enters the gas-liquid separation tank V-103, and the separated liquid phase carbon three is mixed with the liquid phase carbon three separated at the next stage and then subjected to reheating in the plate-fin heat exchanger EX-104, and then enters the gas-liquid separation tank V-105 after the gas phase enters the plate-fin heat exchanger EX-102, and is subjected to the gas-liquid separation tank V-104 after the gas phase is cooled and separated by the plate-fin heat exchanger EX-104. Dry gas is obtained at the top of a final-stage gas-liquid separation tank V-104 and sequentially returns to plate-fin heat exchange EX-104, EX103, EX-102 and EX-101, and is sent out of a boundary region after being reheated to 15 ℃; since the preset hydrogen/hydrocarbon ratio is zero, the fresh propane feed is withdrawn 80% after being pre-cooled to-8 ℃ by EX-101, mixed with propane after being cooled to-37 ℃ by EX-102 and returned to EX-102 for reheating, and sent out of the boundary zone after being reheated to 33 ℃ by EX-101, wherein 100% of the fresh propane flow is distributed to the pre-cooling section. The tail gas at the top of the deethanizer is cooled to-122 ℃ in multiple stages through a cold box system, throttled to 285KPaG, returned to the cold box system, reheated to 33 ℃ and sent out of the cold box system.
In this embodiment, the reaction product gas undergoes four gas-liquid separations altogether, and the fourth-stage separation tank does not generate circulating gas because the preset hydrogen/hydrocarbon ratio is zero, and the raw propane is vaporized by two stages in the pre-cooling stage. The flow distribution ratio of propane in two places in the order from high to low temperature is about: 8:2. The liquid phase products separated by each level of gas-liquid separation tank are collected to a carbon three product tank V-105, flash gas at the top of the carbon three product tank V-105 is condensed by a falling film condenser E-201, flash gas which is not condensed is sent out of a boundary region after being reheated by plate-fin heat exchangers EX-102 and EX-101 in sequence, the condensed liquid flows back to the carbon three product tank V-105 due to self gravity, and finally is pressurized to a plate-fin heat exchanger EX-101 by a carbon three product pump P-101A/B, and is sent to a deethanizer for hydrogen/carbon one/carbon two and carbon three separation after being reheated to 33 ℃.
The refrigeration capacity required to be provided outside the separation system is obtained by adopting two refrigeration cycle systems of propylene precooling and mixed refrigerant deep cooling. The propylene pre-cooling refrigeration cycle system can provide propylene refrigerant with two temperature levels of-41 ℃ and-15 ℃, wherein the propylene refrigerant with the temperature of-15 ℃ is used by a deethanizer condenser, and the propylene refrigerant with the temperature of-41 ℃ is used by a plate fin heat exchanger EX-102 and a falling film condenser E-201 on the top of a carbon three product tank V-105. The propylene refrigerating compressor adopts a centrifugal type, the outlet pressure is 1.65MPaG, and the outlet gas-phase propylene is cooled to 40 ℃ through circulating cooling water.
The mixed refrigerant cryogenic refrigeration cycle system adopts nitrogen, ethylene and propylene as refrigerants, and after the mixed refrigerant compressor is pressurized to 2.21MPaG, the mixed refrigerant is cooled to 40 ℃ by cooling circulating water, and then enters plate-fin heat exchangers EX-101 and EX-102 in sequence, and after being precooled to-37 ℃, the mixed refrigerant enters a gas-liquid separation tank V-201. The tank top gas-phase refrigerant sequentially enters the plate-fin heat exchanger EX-103 and the EX-104 to be cooled to the final separation temperature and then throttled to 345KPaG, then enters the plate-fin heat exchanger EX-104 for reheating, and is mixed with tank bottom liquid-phase refrigerant cooled by the plate-fin heat exchanger EX-103 to enter the plate-fin heat exchanger EX-103 for reheating to the temperature of minus 41 ℃ and then enters a mixed refrigerant refrigerating compressor suction tank to be compressed to the outlet pressure, thus completing the refrigerating cycle.
Example 3
As shown in figure 4, the reaction product gas at the outlet of the propane dehydrogenation reactor is pretreated by cooling, compressing, purifying, filtering and the like, then enters a plate-fin heat exchanger EX-101 of a separation system, is cooled and condensed to the temperature of minus 15 ℃ and then enters a gas-liquid separation tank V101, the separated liquid phase enters a carbon three-product tank V-105, the gas phase enters the plate-fin heat exchanger EX-102, is further cooled and condensed to the temperature of minus 30 ℃ and then enters the gas-liquid separation tank V102, the separated liquid phase carbon three is mixed with the carbon three separated at the next stage and reheated in the plate-fin heat exchanger EX-103, and is reheated in the plate-fin heat exchanger EX-102 and summarized to the carbon three-product tank V-105 by utilizing the pressure of the gas phase, and the gas phase enters the plate-fin heat exchanger EX-103, and is cooled to the temperature of minus 130 ℃ and then enters the gas-liquid separation tank V-103. Dry gas and circulating gas are obtained at the top of a final-stage gas-liquid separation tank V-103, wherein the dry gas sequentially returns to plate-fin heat exchange EX-103, EX-102 and EX-101, and is sent out of a boundary region after reheating to 35 ℃; the circulating gas and fresh propane feed are mixed at the inlet of each stage of plate-fin heat exchanger along the direction of the circulating gas input into the cold box system, and then are reheated to 40 ℃ by the plate-fin heat exchangers EX-103, EX-102 and EX-101 and then are sent out of the boundary region. The tail gas at the top of the deethanizer is cooled to minus 130 ℃ in multiple stages through a cold box system, throttled to 300KPaG, returned to the cold box system, reheated to 40 ℃ and sent out of the cold box system.
In this example, the reactants underwent three gas-liquid separations altogether, and the recycle gas was also subjected to three mixes with the feed propane. The flow distribution ratio of propane at the mixing point in the order of the temperature from high to low is about: 6.5:2:1.5, wherein 85% of the fresh propane flow is allocated to the pre-cooling section. The liquid phase products separated by each level of gas-liquid separation tank are collected to a carbon three product tank V-105, flash gas at the top of the carbon three product tank V-105 is condensed by a falling film condenser E-201, flash gas which is not condensed is sent out of a boundary region after being reheated by plate-fin heat exchangers EX-102 and EX-101 in sequence, the condensed liquid flows back to the carbon three product tank V-105 due to self gravity, and finally is pressurized to the plate-fin heat exchanger EX-101 by a carbon three product pump P-101A/B, and is sent to a deethanizer for hydrogen/carbon one/carbon two and carbon three separation after being reheated to 36 ℃.
The refrigeration capacity required to be provided outside the separation system is obtained by adopting two sets of refrigeration circulation systems of ammonia precooling and mixed refrigerant deep cooling. The ammonia pre-cooling refrigeration cycle system can provide cold energy at two temperature levels of minus 33 ℃ and minus 15 ℃, wherein the cold energy at minus 15 ℃ is used by a deethanizer condenser, and the cold energy at minus 33 ℃ is used by a plate-fin heat exchanger EX-102 and a falling film condenser E-201 on the tank top of V-105. The ammonia refrigeration compressor adopts a centrifugal type, the outlet pressure is 1.54MPaG, and the outlet gas phase ammonia is cooled to 40 ℃ through circulating cooling water.
The mixed refrigerant cryogenic refrigeration cycle system adopts nitrogen, ethane and propylene as refrigerants, after the mixed refrigerant compressor is pressurized to 2.08MPaG, the mixed refrigerant is cooled to 40 ℃ by cooling circulating water, and then enters the plate-fin heat exchangers EX-101, EX-102 and EX-103 in sequence, after precooled to the final separation temperature, throttled to 285KPaG, enters the plate-fin heat exchanger EX-103 for reheating to-38 ℃ and then enters the mixed refrigerant refrigerating compressor suction tank, and is compressed to the outlet pressure, thus the refrigeration cycle is completed.
Example 4
The flow of this embodiment is the same as that of embodiment 1, as shown in fig. 5, except that:
the flow distribution ratio of propane in the order from high to low is: 6:2.5:1:0.5, wherein 85% of the fresh propane flow is allocated to the pre-cooling section. The gas phase in the separation system enters a plate-fin heat exchanger EX-104 to be cooled to minus 138 ℃ and then enters a gas-liquid separation tank V-104. The tail gas at the top of the deethanizer is cooled to-138 ℃ in multiple stages through a cold box system, throttled to 225KPaG, returned to the cold box system, reheated to 20 ℃ and sent out of the cold box system. The precooling refrigeration cycle system adopts a mixed refrigerant of propane and propylene, and simultaneously provides cold energy at two temperature levels of-40 ℃ and-15 ℃. The mixed refrigerant of the cryogenic refrigeration cycle system adopts nitrogen, methane, ethane, propane and butane as refrigerants, is pressurized to 2.11MPaG by a cryogenic mixed refrigerant compressor, is cooled to 42 ℃ by cooling circulating water, sequentially enters into a plate-fin heat exchanger EX-101 and EX-102, is precooled to-37 ℃ and then enters into a gas-liquid separation tank V-201. The tank top gas-phase refrigerant sequentially enters the plate-fin heat exchangers EX-103 and EX-104 to be cooled to minus 138 ℃, throttled to 285KPaG, enters the plate-fin heat exchanger EX-104 to be reheated, is mixed with tank bottom liquid-phase refrigerant cooled by the plate-fin heat exchanger EX-103, sequentially passes through the fin heat exchangers EX-103, EX-102 and EX-101 to be reheated to 25 ℃, enters the mixed refrigerant refrigerating compressor to be sucked into the tank, and is compressed to the outlet pressure, thus the refrigeration cycle is completed.
According to the embodiment, the method for reheating the mixed refrigerant to the normal temperature can effectively reduce the requirements of the inlet pipeline of the mixed refrigerant compressor and the materials of the compressor body, so that the equipment investment is saved, and the operation stability of the mixed refrigerant compressor is improved. The energy consumption of the pre-cooling refrigeration cycle compressor can also be reduced as compared to embodiments 1 and 2.
Example 5
Example 5 as shown in fig. 6, the procedure is substantially identical to example 4, with the main difference that:
the flow distribution ratio of propane in the order from high to low is: 3.2:2.8:2.2:1.8, wherein 60% of the fresh propane flow is allocated to the pre-cooling section. The gas phase in the separation system enters a plate-fin heat exchanger EX-104 to be cooled to minus 148 ℃ and then enters a gas-liquid separation tank V-104. The tail gas at the top of the deethanizer is cooled to-148 ℃ in multiple stages through a cold box system, throttled to 310KPaG, returned to the cold box system, reheated to 35 ℃ and sent out of the cold box system. The precooling refrigeration cycle system adopts a mixed refrigerant of ethylene, propylene and pentane. And (3) cooling the precooling mixed compressor to 45 ℃ by using an outlet water cooler, sequentially entering into a plate-fin heat exchanger EX-101 and an EX-102, condensing and cooling to-55 ℃, then reducing the pressure to 175kPaG by using a throttle, returning to the plate-fin heat exchanger EX-102 and the EX-101, reheating to normal temperature, entering into a first-stage suction tank of the precooling mixed compressor, and then performing two-stage compression to 2.15MPaG to complete the refrigeration cycle.
Methane, ethylene and propylene are adopted as refrigerants in the cryogenic refrigeration cycle system, after the cryogenic mixed refrigerant is pressurized to 2.38MPaG by a compressor, the refrigerant is cooled to 45 ℃ by cooling circulating water, and then the refrigerant enters plate-fin heat exchangers EX-101 and EX-102 in sequence, is precooled to-55 ℃ and then enters a gas-liquid separation tank V-201. The tank top gas-phase refrigerant sequentially enters the plate-fin heat exchangers EX-103 and EX-104 to be cooled to minus 148 ℃ and throttled to 335KPaG, then enters the plate-fin heat exchanger EX-104 for reheating, is mixed with tank bottom liquid-phase refrigerant cooled by the plate-fin heat exchanger EX-103, sequentially passes through the fin heat exchangers EX-103, EX-102 and EX-101 for reheating to 27 ℃, then enters the mixed refrigerant refrigerating compressor to be sucked into the tank, and is compressed to the outlet pressure, thus the refrigeration cycle is completed.
The precooling circulation system of the embodiment adopts mixed refrigerant, and can reduce the irreversibility and the heat transfer process by reducing the temperature difference in the precooling heat transfer processThe loss is reduced, the energy consumption of the pre-cooling circulating compressor is reduced, and the gain effect of reducing the energy consumption of the whole separation device is achieved.
Meanwhile, in the specific embodiment, by adopting the double-circulation mixed refrigerant for refrigeration and adjusting the formulas of the two sets of mixed refrigerants, the power consumption of the two mixed refrigerant compressors is consistent, so that the power devices with the same specification can be matched, and the gain effects of reducing the complete difficulty of the compressor unit and the running operation difficulty are achieved.
Comparative example 1
The separation scheme and apparatus for the propane dehydrogenation reaction product shown in FIG. 7 was used, and the constitution of the separation apparatus was kept the same as in example 1.
The process parameters of comparative example 1 were also consistent with those of example 1, with the main differences: 1. comparative example 1 did not employ the design of a multiple-point mixed throttling evaporation of fresh feed propane and recycle gas; 2. comparative example 1 does not employ design of deethanizer overhead tail gas temperature reduction throttling and reheat to provide refrigeration to the separation system.
The shaft power of the two refrigeration compressors in example 1 versus comparative example 1 is compared as follows:
| unit (B) | Comparative example 1 | Example 1 | |
| Precooling cycle compressor shaft power | kW | 9235 | 2455 |
| Cryogenic cycle compressor shaft power | kW | 2471 | 1765 |
| Total load of refrigeration cycle cooler | MW | 28.95 | 10.43 |
As can be seen from the comparison, in comparative example 1, since the cold energy of the raw propane and the tail gas from the top of the deethanizer is not coupled into the separation system, the shaft power of the two external refrigeration compressors is larger than that in example 1, and the total load of the refrigeration cycle cooler is also much larger than that in example 1, which shows that example 1 has great advantages in saving the energy consumption of the separation system.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (5)
1. A method for separating a coupled alkane catalytic dehydrogenation reaction product, which is characterized by comprising the following steps:
inputting reaction product gas at the outlet of the alkane catalytic dehydrogenation reactor into a cold box system to obtain a cooled product;
and inputting the cooled product into N-stage serial gas-liquid separation tanks for gas-liquid separation, and then:
re-inputting the gas-phase product obtained in the 1 st to N-1 st stages into a cold box system;
collecting the liquid-phase products obtained in the 1-N stages, then reheating and sending out of a cold box system, and then separating products with different carbon numbers from the liquid-phase products through a separation tower;
mixing circulating gas obtained from the top of an N-th-stage gas-liquid separation tank with fresh propane according to a preset hydrogen/hydrocarbon ratio through M stages, and performing throttle evaporation in a cold box system to provide cold energy for the cold box system, and delivering the cold box system after reheating, wherein M is less than or equal to N;
introducing tail gas at the top of the deethanizer into a cold box system, providing cold energy for the cold box system, and delivering the cold box system after reheating;
the cold energy of the cold box system is also from an external refrigeration cycle system;
the series level of the heat exchangers in the cold box system is equal to the level of the N-level separation tanks and is matched step by step, the cold box system comprises a pre-cooling section by one or more levels, and the rest of the cold box system comprises a deep cooling section;
60% -100% of the fresh propane flow is distributed to the pre-cooling section, the rest is distributed to the deep cooling section, and the distribution flow and the fresh propane temperature grade are matched according to negative correlation;
the external refrigeration cycle system includes: a precooling refrigeration cycle system for providing cold energy to the precooling section and a cryogenic refrigeration cycle system for providing cold energy to the cryogenic section.
2. The method for separating a coupled catalytic dehydrogenation reaction product according to claim 1, wherein the refrigerant in the precooling refrigeration cycle system is one or more of ammonia, ethane, ethylene, propylene, propane, butane, and pentane;
the refrigerant in the cryogenic refrigeration cycle system is a combination of a plurality of nitrogen, methane, ethane, ethylene, propane, propylene and butane.
3. The method for separating a coupled alkane catalytic dehydrogenation reaction product according to claim 1, wherein the flow of the recycle gas is directly proportional to the preset hydrogen/hydrocarbon ratio;
when the preset hydrogen/hydrocarbon ratio is zero, the circulating gas flow is set to zero, and the fresh propane is throttled and evaporated only in the corresponding stage number of the pre-cooling section.
4. The method for separating the coupled alkane catalytic dehydrogenation reaction product according to claim 1, wherein the tail gas at the top of the deethanizer is cooled to the temperature of the Nth stage separation by a cold box system, throttled and returned to the cold box system, and sent out of the cold box system after reheating.
5. A device for separating the product of a catalytic dehydrogenation reaction of an alkane coupled thereto, comprising:
the cold box system is respectively connected with an alkane catalytic dehydrogenation reactor outlet and a separation tower top tail gas outlet and is connected with a fresh propane storage tank, and the cold box system comprises a pre-cooling section and a deep cooling section;
the precooling refrigeration circulation system is in heat exchange connection with the precooling section and provides cooling capacity for the precooling cooling separation process of the reaction product gas at the outlet of the alkane catalytic dehydrogenation reactor;
the cryogenic refrigeration circulation system is connected with the cryogenic section in a heat exchange mode and provides cooling capacity for the cryogenic cooling separation process of the reaction product gas at the outlet of the alkane catalytic dehydrogenation reactor;
the N-stage separation tank is connected with the cold box system and matched step by step, circulating gas obtained from the tank top of the Nth separation tank is mixed with fresh propane according to a preset hydrogen/hydrocarbon ratio through M stages and is input into the cold box system, wherein M is less than or equal to N, and an outlet of a liquid-phase product obtained from the separation tank 1-N stages is sequentially connected with the liquid product tank and the separation tower, so that separation of products with different carbon numbers is realized;
the top of the liquid product tank is also provided with a falling film condenser;
the separation tower is a deethanizer;
the cold box system comprises a multi-stage plate-fin heat exchanger;
the precooling refrigeration cycle system is also respectively connected with a condenser of the deethanizer, a falling film condenser and a cryogenic refrigeration cycle system in a heat exchange mode.
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