WO2020073853A1 - 分离低碳烃的方法及*** - Google Patents
分离低碳烃的方法及*** Download PDFInfo
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- WO2020073853A1 WO2020073853A1 PCT/CN2019/109082 CN2019109082W WO2020073853A1 WO 2020073853 A1 WO2020073853 A1 WO 2020073853A1 CN 2019109082 W CN2019109082 W CN 2019109082W WO 2020073853 A1 WO2020073853 A1 WO 2020073853A1
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- 238000000034 method Methods 0.000 title claims abstract description 61
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 58
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- 238000010521 absorption reaction Methods 0.000 claims abstract description 121
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- 238000001816 cooling Methods 0.000 claims abstract description 22
- 238000004064 recycling Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 130
- 229910052799 carbon Inorganic materials 0.000 claims description 118
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 103
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 100
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 95
- 239000005977 Ethylene Substances 0.000 claims description 95
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 65
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 49
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 28
- 150000001336 alkenes Chemical class 0.000 claims description 25
- 238000011084 recovery Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 11
- 150000001993 dienes Chemical class 0.000 claims description 9
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 9
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
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- -1 ethylene, propylene, 1-butene Chemical class 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001282 iso-butane Substances 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
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- 239000003245 coal Substances 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000009102 absorption Effects 0.000 description 86
- 239000000047 product Substances 0.000 description 54
- 239000000203 mixture Substances 0.000 description 22
- 238000005691 oxidative coupling reaction Methods 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
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- 229910052760 oxygen Inorganic materials 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 239000003921 oil Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000009103 reabsorption Effects 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
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- JVFDADFMKQKAHW-UHFFFAOYSA-N C.[N] Chemical compound C.[N] JVFDADFMKQKAHW-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/06—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by heating, cooling, or pressure treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/04—Ethylene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/11—Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/06—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil
- C10G25/11—Distillation in the presence of moving sorbents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one thermal cracking step
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/002—Cooling of cracked gases
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4081—Recycling aspects
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/28—Propane and butane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Definitions
- the invention belongs to the field of chemical industry, and in particular relates to a method and system for separating low-carbon hydrocarbons.
- Ethylene is the most important basic organic chemical raw material. For a long time, its production has relied on petroleum cracking routes, and the resulting environmental pollution and other problems have become increasingly serious. As the price of crude oil continues to rise, the price of ethylene cracking raw materials rises. At the same time, the supply of ethylene cracking raw materials is in short supply. In the face of this situation, countries around the world are adjusting the energy utilization structure and constantly looking for new ethylene production routes. In 2010, with the breakthrough of the United States in the field of shale gas, a large amount of methane that was difficult to mine was extracted, and the chemical utilization of methane has attracted the industry's great attention. Therefore, the research on the oxidative coupling of methane to ethylene and ethane has once again become Research hotspots worldwide.
- the goal of oxidative coupling of methane to ethylene is to convert methane to ethylene under the action of a catalyst.
- the reaction products are relatively complex, mainly including methane, ethylene, ethane, CO, CO 2 and O 2 .
- Many methods have been proposed in the art to separate ethylene from the reaction mixture.
- US20150368167 discloses an OCM reaction product separation method. Three product streams, a C2-rich stream, a nitrogen-rich stream, and a methane-rich stream can be obtained through a separation unit.
- the OCM reaction product first obtains the C2-rich stream and methane-nitrogen stream in the first separation column, and then obtains the nitrogen-rich stream and methane-rich stream in the second separation column. Because the separation method uses low-temperature rectification, the temperature of the entire separation unit is very low.
- the temperature of the top of the first separation tower is as low as -162 °C, and the temperature of the second separation tower is as low as -210 °C. High, greatly increasing investment costs and high energy consumption.
- CN201710006765.X discloses a process for separating reaction products of ethylene produced by oxidative coupling of methane. The process separates the reaction products one by one through compression, alcohol amine method, drying, cryogenic rectification and other processes, and finally obtains polymer grade ethylene products , Ethylene recovery rate is over 99%.
- the patent application significantly improves product quality, but the separation is still cryogenic rectification, requiring a cold box to provide a lower level of cooling capacity.
- WO2015105911 discloses a methane oxidative coupling system, which converts methane oxidative coupling to ethylene, and then converts ethylene to selectable higher hydrocarbon products.
- the separation of ethylene and other components in the OCM product gas such as unreacted methane, ethane, CO, CO 2 , nitrogen, water, etc., still uses low-temperature rectification.
- the first separator is used for Separate methane / nitrogen from components above C2.
- the operating temperature of this separator is as low as -160 °C.
- the second separator is used to separate methane and nitrogen. Its operating temperature is as low as -200 °C.
- the object of the present invention is to propose a method and system for separating low-carbon hydrocarbons.
- the method can greatly increase the operating temperature of low-carbon hydrocarbon separation, and has low energy consumption, simple process, and easy operation and control.
- the method provided by the present invention can greatly reduce the amount of supplementary absorbent added during operation through the combination of absorption and cracking.
- the present invention provides a method for separating low-carbon hydrocarbons, including the following steps:
- hydrocarbon material containing carbon one to carbon four Compress and cool the hydrocarbon materials containing carbon one to carbon four to be separated to produce compressed and cooled hydrocarbon materials, wherein the hydrocarbon material containing carbon one to carbon four contains olefins selected from carbon two or more And selected from carbon one to carbon four alkanes;
- the present invention also provides a system for separating low-carbon hydrocarbons, which can be used to implement the method of the first aspect of the present invention.
- a system for separating low-carbon hydrocarbons provided by the present invention includes:
- a compression cooling unit, an absorption unit, a desorption unit, a rectification unit, and a cracking unit wherein the absorption unit is connected to the compression cooling unit and the desorption unit, and the rectification unit is connected to the desorption unit and the A cracking unit is connected, and the cracking unit is connected to the compression cooling unit.
- the separation method provided by the present invention is simple in process and high in product quality.
- the invention makes full use of saturated resources and greatly enhances the product value.
- the present invention combines cracking and absorption-desorption for the separation of low-carbon hydrocarbon materials such as OCM reaction gas, and can directly send saturated resources, such as ethane, propane, and butane, to the cracking furnace for treatment.
- saturated resources such as ethane, propane, and butane
- the separated low-carbon hydrocarbons enter the separation device for treatment.
- the process proposed in this application can improve ethylene on the one hand Propylene production, on the other hand, the C4 and C5 hydrocarbons in the cracked gas can be used as absorbers in the absorption tower, which can reduce the amount of supplementary absorbers in the system.
- the separation method provided by the present invention can be implemented at a relatively high temperature, for example, operating above -35 ° C or even above 10 ° C, thereby reducing the requirements for the material of the equipment, and the use of propylene refrigeration compressors can meet the cooling demand of the entire process.
- the process temperature proposed by the present invention is relatively high, and the purification of the separated gas can be performed after absorption-desorption.
- the main reason is that after separating the gas into the absorption tower, the solubility of different components in the gas mixture in the solvent is used, and the gas mixture is separated.
- the solubility of CO 2 and other impurities in the solvent is very low, so it can be removed through the absorption tower Most of the CO 2 and other impurities in the incoming material greatly reduce the processing capacity of the subsequent purification unit and reduce energy consumption.
- the invention can significantly reduce the process energy consumption.
- FIG. 1 shows a schematic flow chart of a method for separating reaction gas for methane oxidative coupling to produce ethylene in Example 1 of the present invention.
- Example 2 shows a schematic flow chart of a method for separating reaction gas for methane oxidative coupling to produce ethylene in Example 2 of the present invention.
- FIG. 3 shows a schematic flow chart of a method for separating reaction gas for methane oxidative coupling to ethylene in Example 3 of the present invention.
- Example 4 shows a schematic flow chart of a method for separating reaction gas for methane oxidative coupling to produce ethylene in Example 4 of the present invention.
- Reactor for methane oxidative coupling to produce ethylene 2. Compressor; 3. Heat exchanger; 4. First absorption tower (may be called absorption tower); 5. First distillation tower (may be called desorption tower) ; 6. Second rectification tower (may be called deethanizer tower); 7. First hydrogenation reactor (may be called carbon dihydrogenation reactor); 8.
- Third rectification tower may be called ethylene) Rectification tower); 9, fourth rectification tower (may be called depropanizer tower); 10, second hydrogenation reactor (may be called carbon three hydrogenation reactor); 11, fifth rectification tower (may (Referred to as propylene rectification tower); 12, second absorption tower (may be called reabsorption tower); 13, sixth distillation tower (may be called gasoline desorption tower); 14, cracking furnace; 15, waste heat boiler; 16 1. Oil washing tower / water washing tower; 17. Oxygen or oxygen enrichment; 18. Methane; 19. Ethylene products; 20. Propylene products; 21. Carbon four products; 22. Exhaust gas; 23. Cold box; 24. Expander; 25. , Flash tank; 26, booster.
- the present invention provides a method for separating low-carbon hydrocarbons, including the following steps:
- hydrocarbon material containing carbon one to carbon four Compress and cool the hydrocarbon materials containing carbon one to carbon four to be separated to produce compressed and cooled hydrocarbon materials, wherein the hydrocarbon material containing carbon one to carbon four contains olefins selected from carbon two or more And selected from carbon one to carbon four alkanes;
- recycling the cracked gas to step (1) described in step (6) includes combining the cracked gas with the hydrocarbon material containing carbon one to carbon four to be separated Compressed and cooled together; or the cracked gas is compressed first, and then combined with the compressed hydrocarbon materials containing carbon one to carbon four for cooling; or the cracked gas is first compressed and cooled, and then combined with the compressed After cooling, the hydrocarbon materials containing carbon one to carbon four are combined.
- the hydrocarbon materials containing carbon one to carbon four come from reaction gas from methane oxidation to ethylene, refinery dry gas, coal chemical dry gas, catalytic cracking products, Fischer-Tropsch tail gas, propane dehydrogenation One or more of product, flare gas / gas separation, and shale gas separation.
- the hydrocarbon material containing carbon one to carbon four comes from the reaction gas of the methane oxidation to ethylene reactor (abbreviated as OCM reaction gas).
- the carbodicarbon or higher olefin is selected from one or more of ethylene, propylene, 1-butene, 2-butene, and 1,3-butadiene.
- the carbon-to-carbon tetraalkane is selected from one or more of methane, ethane, propane, n-butane, and isobutane.
- the saturated alkane is selected from one or more of ethane, propane, n-butane and isobutane.
- the one or more streams of liquid liquid rich in saturated alkanes include liquid materials rich in ethane.
- the one or more liquid phases rich in saturated alkanes include liquid phases rich in ethane and liquid phases rich in propane.
- one or more olefin-rich liquid or gas phases are also produced materials.
- the one or more olefin-rich liquid phase materials include ethylene-rich liquid or gas phase materials.
- the one or more olefin-rich liquid phase materials include ethylene-rich gas-phase or liquid-phase materials and propylene-rich gas-phase or liquid-phase materials.
- the term "rich” means that the molar content of components in the material accounts for more than 50%, such as more than 80%, more than 90%, more than 95%, more than 98%, more than 99%.
- the absorbent is a carbon three fraction containing carbon three alkanes, a carbon four fraction containing carbon four alkanes, and a carbon five fraction containing carbon five alkanes.
- the C3 hydrocarbon is n-propane
- the C4 hydrocarbon is n-butane
- the C5 hydrocarbon is selected from n-pentane and isopentane.
- the temperature of the cracking is 500-850 ° C, preferably 600-800 ° C.
- the cracked gas contains olefins and alkanes.
- step (1) the hydrocarbon material containing carbon one to carbon four is compressed to 2.0-5.0 MPa.
- the hydrocarbon material containing carbon one to carbon four is cooled to -40 ° C to 20 ° C, for example, 5 ° C to 20 ° C or -40 ° C to -10 ° C.
- the compressed and cooled hydrocarbon material is contacted with the absorbent in the first absorption tower, and a gas phase stream containing light components is obtained at the top of the tower
- the tower kettle obtains the solvent-rich material.
- the number of theoretical plates of the first absorption tower is 30-80, and the operating pressure is 2.0-6.0 MPa.
- the absorption liquid is sent to a first rectification tower for rectification, a gas phase material containing olefins and saturated alkanes is obtained at the top of the tower, and a lean solvent material is obtained in the tower kettle .
- the purpose of step (3) is to desorb the absorption liquid.
- the method further includes purifying the gas phase material containing olefins and saturated alkanes obtained from the top of the first rectification tower after step (3) to remove acidic components and / or Moisture and purified materials are processed in step (4).
- the method further includes purifying the compressed hydrocarbon material in step (1) to remove acidic components and / or moisture therein, and then cooling the purified material.
- the theoretical plate number of the first distillation column is 20-60, and the operating pressure is 1.0-4.0 MPa.
- the step (4) includes:
- the gas phase material containing olefins and saturated alkanes is sent to a second rectification tower for rectification, a first stream containing ethane and ethylene is obtained at the top of the tower, and a second stream containing hydrocarbons with carbon three or more is obtained at the top
- the first stream is sent to a third rectification tower for rectification, the ethylene product stream is obtained on the side, the third stream containing ethylene is obtained at the top of the tower, and the ethane-rich fourth stream is obtained in the tower kettle.
- the first stream before the first stream enters the third rectification column, it is sent to the first hydrogenation reactor for selective hydrogenation reaction to remove alkyne and / or diolefin.
- the theoretical plate number of the second rectification column is 30-80, and the operating pressure is 1.0-5.0 MPa.
- the theoretical plate number of the third distillation column is 50-130, and the operating pressure is 1.0-4.0 MPa.
- the step (4) further includes:
- the second stream is rectified in a fourth rectification column, a fifth stream containing propane and propylene is obtained at the top of the column, and a sixth stream rich in saturated alkanes is obtained in the tower kettle.
- the number of theoretical plates of the fourth distillation column is 30-80, and the operating pressure is 0.1-3.0 MPa.
- the step (4) further includes:
- the fifth stream is sent to a fifth rectification tower for rectification, a propylene product stream is obtained on the side, a seventh stream containing propylene is obtained at the top of the tower, and an eighth stream rich in propane is obtained from the tower kettle.
- the fifth stream before the fifth stream enters the fifth rectification column, it is sent to a second hydrogenation reactor for selective hydrogenation to remove alkyne and / or diolefin:
- part or all of the seventh stream is recycled to step (1);
- the number of theoretical plates of the fifth rectification tower is 100-200, and the operating pressure is 1.0-4.0 MPa.
- one or more of the fourth stream, sixth stream and eighth stream are preferably cracked to generate cracked gas.
- the resulting cracked gas contains olefins and alkanes.
- the step (4) further includes the following steps:
- the second stream is rectified in a fifth rectification column, a propylene product stream is obtained on the side, a nine stream containing propylene is obtained at the top of the column, and a tenth stream rich in saturated alkanes is obtained in the tower kettle.
- part or all of the ninth stream is recycled to step (1);
- the second stream before the second stream enters the fifth rectification column, it is sent to a third hydrogenation reactor for selective hydrogenation reaction to remove alkyne and / or diolefin;
- the number of theoretical plates of the fifth rectification tower is 100-200, and the operating pressure is 1.0-4.0 MPa.
- one or both of the fourth and sixth streams are cracked to produce cracked gas.
- the resulting cracked gas contains olefins and alkanes.
- the solvent-lean material is sent to the first absorption tower as a circulating absorbent.
- the gas phase stream containing light components from the top of the first absorption tower is sent to the second absorption tower to contact the resorbent therein to absorb the entrained absorbent And carbodicarbons not absorbed by the absorbent in the first absorption tower.
- the reabsorbent is selected from gasoline, heavy naphtha, and aromatic hydrocarbon residual oil,
- the number of theoretical plates of the second absorption tower is 15-60, and the operating pressure is 1.0-5.0 MPa.
- the tail gas obtained from the top of the second absorption tower is discharged outside the boundary area, and the liquid material obtained from the tower kettle is discharged outside the boundary area or subjected to other treatments.
- the other treatment includes: sending the liquid phase material obtained from the second absorption tower to the sixth rectification tower for rectification, and the gas phase stream obtained at the top of the tower is sent to the first absorption tower as The recycled absorbent, the liquid phase stream obtained from the tower kettle is sent to the second absorption tower as the recycled reabsorbent.
- the number of theoretical plates of the sixth rectification tower is 10-50, and the operating pressure is 0.1-2.0 MPa.
- the gas phase stream containing light components from the top of the first absorption tower is subjected to cold recovery, preferably cold recovery is performed in a cold recovery unit, preferably, the cold Quantity recovery unit includes cold box, expander, booster and flash tank.
- the gas phase stream containing light components is cooled through a cold box, and then expanded and flashed to recover unabsorbed carbon dihydrocarbons and entrained absorbent, without carbon dioxide
- the hydrocarbon tail gas is discharged after being boosted by a booster driven by an expander.
- the gas phase stream containing light components enters a cold box and is cooled to -80 ° C to -35 ° C, after which the gas is expanded by an expander, and then sent to a flash tank for flash evaporation, flash evaporation
- the gas at the top of the tank enters the cold box, and then is boosted by a booster driven by an expander to be discharged, and the liquid at the bottom of the tank returns to the top of the first absorption tower.
- the cracked gas after recovering heat through a waste heat boiler, the cracked gas enters an oil washing tower and / or a water washing tower, and then is recycled to step (1) for compression.
- a system for separating low-carbon hydrocarbons provided by the present invention includes:
- a compression cooling unit, an absorption unit, a desorption unit, a rectification unit, and a cracking unit wherein the absorption unit is connected to the compression cooling unit and the desorption unit, and the rectification unit is connected to the desorption unit and the A cracking unit is connected, and the cracking unit is connected to the compression cooling unit.
- the compression cooling unit includes a compressor (2) and a heat exchanger (3)
- the absorption unit includes a first absorption tower (4)
- the desorption unit includes a first rectification tower (5)
- the rectification unit includes a second rectification tower (6) and a third rectification tower (8)
- the cracking unit includes a cracking furnace (14).
- the type of cracking furnace used in the present invention is not particularly limited.
- the cracked gas advanced waste heat boiler recovers heat and then cools down through the water washing tower. If necessary, an oil washing tower can also be provided in the cracking step.
- the outlet of the compressor (2) is connected to the inlet of the heat exchanger (3), and the outlet of the heat exchanger (3) is connected to the first of the first absorption tower (4)
- An inlet is connected, and the outlet of the first absorption tower (4) is connected to the inlet of the first rectification tower (5), and the outlet of the top of the first rectification tower (5) is connected to the first
- the inlet of the second distillation column (6) is connected.
- the top outlet of the second rectification tower (6) is connected to the inlet of the third rectification tower (8), and the outlet of the third rectification tower (8)
- the first inlet of the cracking furnace (14) is connected.
- a first hydrogenation reactor is provided between the top of the second rectification tower (6) and the third rectification tower (8) ( 7)
- the top outlet of the third rectification column (8) is connected to the inlet of the compressor (2).
- the rectification unit further includes a fourth rectification tower (9), wherein the inlet of the fourth rectification tower (9) and the second rectification tower (6) The tower kettle outlet is connected, and the tower kettle outlet of the fourth rectification tower (9) is connected to the first inlet and / or the second inlet of the cracking furnace (14).
- the rectification unit further includes a fifth rectification tower (11), wherein the top outlet of the fourth rectification tower (9) is connected to the fifth rectification tower (11) ), A second hydrogenation reactor (10) is optionally provided between the fifth rectification tower (11) and the fourth rectification tower (9), and the tower kettle of the fifth rectification tower
- the outlet is connected to the first inlet and / or the second inlet and / or the third inlet of the cracking furnace, optionally, the top outlet of the fifth rectification column (11) and the compressor (2)
- the first entrance is connected.
- the cracking unit further includes a waste heat boiler (15) and an oil washing tower and / or water washing tower (16), wherein the outlet of the cracking furnace (14) and the waste heat boiler (15)
- the inlet of the waste heat boiler (15) is connected to the inlet of the oil washing tower and / or water washing tower (16), and the outlet of the oil washing tower and / or water washing tower (16) is connected to the compression
- the first inlet and / or the second inlet of the machine (2) are connected.
- the outlet of the first absorption tower (4) is connected to the inlet of the first rectification tower (5), and the outlet of the top of the first absorption tower (4) is connected to the first
- the first inlet of the second absorption tower (12) is connected, and the outlet of the second absorption tower (12) is optionally connected to the inlet of the sixth distillation tower (13).
- the top outlet of the sixth rectification (13) is connected to the second inlet of the first absorption tower (4), and the tower kettle of the sixth rectification tower (13) The outlet is connected to the second inlet of the second absorption tower (12).
- the outlet of the first absorption tower (4) is connected to the inlet of the first rectification tower (5), and the outlet of the top of the first absorption tower (4) is connected to the cold
- the volume recovery unit is connected.
- the cold recovery unit includes a cold box (23), an expander (24), a flash tank (25), and a booster (26), wherein the first inlet of the cold box It is connected to the top outlet of the first absorption tower (4), the first outlet of the cold box is connected to the inlet of the expander, the outlet of the expander is connected to the inlet of the flash tank, the flash The first outlet of the steam tank is connected to the second inlet of the cold box, the second outlet of the cold box is connected to the inlet of the supercharger, and optionally the second outlet of the flash tank is connected to the first The second inlet of an absorption tower is connected.
- the system further includes a purification device disposed between the first rectification tower and the second rectification tower, for removing material from the top of the first rectification tower Acid gas and / or moisture in
- the system further includes a purification device disposed between the compressor and the heat exchanger to remove acid gas and / or moisture from the material of the compressor.
- the inlets of the rectification towers including the first, second, third, fourth, fifth, and sixth rectification towers are usually provided on the side wall of the tower body, preferably in the middle of the side wall.
- the inlets of the first absorption tower and the second absorption tower are usually provided on the side wall of the tower body, preferably on the upper part of the side wall.
- the resulting OCM reaction gas is gradually increased in pressure by the compressor 2 and then cooled by the heat exchanger 3 to enter the absorption tower 4.
- the gas at the top of the absorption tower 4 is sent to the re-absorption tower 12, the material at the bottom of the absorption tower 4 enters the desorption tower 5, the tail gas 22 at the top of the re-absorption tower 12 is sent to the outside of the boundary area, and the tower kettle stream is sent to the gasoline desorption tower 13, desorption tower 5 tower After the lean solvent of the kettle exchanges heat, it returns to the absorption tower 4.
- the gas phase at the top of the desorption tower 5 is taken into the deethanizer tower 6.
- the deethanizer tower 6 is deacetylated by the carbon dihydrogenation reactor 7 and then enters the ethylene rectification tower 8.
- Ethylene rectification tower 8 The gas phase at the top of the tower returns to the compressor section, and the ethylene product 19 is produced on the side line.
- the tower kettle material is sent to the cracking furnace 14.
- the deethanizer tower 6 is fed to the depropanizer tower 9 and the depropanizer tower 9
- the top material of the tower is deacetylated by the carbon three hydrogenation reactor 10, and then enters the propylene rectification tower 11.
- the propylene rectification tower 11 returns to the compressor section with the gas phase at the top of the tower.
- the propylene product 20 is produced on the side, and the tower kettle material is sent to the cracking furnace 14.
- the materials of the depropanizer tower 9 and the kettle of the tower are recovered as the carbon four product 21, the cracked gas obtained by the cracking in the cracking furnace 14 is recovered by the waste heat boiler 15 to enter the oil washing tower / water washing tower 16, and then sent to the compressor 2 section suction tank .
- composition mol% oxygen 0.55 CO 5.69 CO 2 6.15 Methane 34.06 Ethylene 7.72 Ethane 2.52 Propane 0.55 water 42.75 Alkyne 0.01
- the number of theoretical plates of absorption tower 4 is 55, and the operating pressure is 3.8 MPa.
- the absorption solvent used is ether after carbon four.
- the absorption solvent enters the tower from the top of the absorption tower, and the OCM reaction gas enters from the 30th tray.
- the carbon two and above components in the OCM reaction gas are absorbed by the solvent, and are extracted from the tower kettle.
- the top of the tower is light components such as methane, oxygen, and CO, with a small amount of absorbent.
- the number of theoretical plates of the desorption tower 5 is 40, the operating pressure is 2.4 MPa, and the operating temperature is around 15 ° C.
- the gas phase at the top of the tower after desorption is sent to the purification unit, and the lean solvent in the tower kettle is cooled to 15 ° C and returned to the absorption tower 4 for recycling after stepwise heat exchange.
- Deethanization The purified material enters the deethanizer tower.
- the theoretical plate number of the deethanizer tower is 50, the operating pressure is 2.0 MPa, and the operating temperature is -20 ° C.
- the material rich in ethylene and ethane is produced and sent to the carbon two hydrogenation reactor, where the acetylene and other alkyne are removed by hydrogenation, and the material in the deethanizer tower is sent to Depropanizer tower.
- Ethylene rectification The material from the carbon two hydrogenation reactor enters the ethylene rectification tower 8, the theoretical plate number of the ethylene rectification tower is 90, the operating pressure is 2.0 MPa, and the operating temperature is -35 ° C.
- the gas phase at the top of the ethylene rectification tower is returned to the four-stage inlet of the compressor, and the ethylene product is extracted from the side line, and the tower kettle material is sent to the cracking furnace 14.
- Depropanization The number of theoretical plates of the depropanizer 9 is 40, the operating pressure is 0.7 MPa, and the operating temperature of the depropanizer is 16 ° C.
- the top material of the depropanizer tower is sent to the C3 hydrogenation reactor to remove the alkyne and diene, and the material of the depropanizer tower is produced as the carbon four product.
- Propylene rectification The material from the C3 hydrogenation reactor enters the propylene rectification tower.
- the theoretical plate number of the propylene rectification tower is 160, the operating pressure is 1.7 MPa, and the operating temperature is 40 ° C.
- the gas phase at the top of the propylene rectification tower is returned to the four-stage inlet of the compressor. Propylene products are produced on the side, and the main material of the tower kettle is propane, which is sent to the cracking furnace.
- Reabsorption The gas from the top of the absorption tower enters the reabsorption tower.
- the theoretical plate number of the reabsorption tower is 20, and the operating pressure is 3.8 MPa.
- the resorbent enters from the top of the tower and absorbs the absorbed absorbent And the unabsorbed carbon two components, the tail gas from the top of the reabsorption tower is sent outside the boundary area, and the tower kettle stream is sent to the gasoline desorption tower;
- Gasoline desorption The column kettle stream from the reabsorption tower enters the gasoline desorption tower.
- the theoretical number of gasoline desorption towers is preferably 28, the operating pressure is 0.5 MPa, and the operating temperature is 15 ° C.
- the gas on the top of the gasoline desorption tower is cooled and then absorbed in the absorption tower.
- the tower kettle obtains the lean gasoline solvent, and after cooling down, it is returned to the reabsorption tower.
- composition of the obtained ethylene products is shown in Table 2, and the output of ethylene products is shown in Table 12.
- the composition of the resulting propylene product is shown in Table 3.
- composition mol% Acrylic 95.2 Propane 4.8
- the purity of the ethylene product meets the specifications of polymer grade ethylene
- the purity of the propylene products meets the requirements of chemical grade propylene
- the ethylene recovery rate is 99.7%.
- the separation method shown in FIG. 2 is used to separate the reaction gas for oxidative coupling of methane to ethylene.
- the resulting OCM reaction gas is gradually increased in pressure by the compressor 2 and then cooled by the heat exchanger 3 to enter the absorption tower 4.
- the gas at the top of the absorption tower 4 is sent to the re-absorption tower 12, the material at the bottom of the absorption tower 4 enters the desorption tower 5, the tail gas 22 at the top of the re-absorption tower 12 is sent to the outside of the boundary area, and the tower kettle stream is sent to the gasoline desorption tower 13, desorption tower 5 tower After the lean solvent of the kettle exchanges heat, it returns to the absorption tower 4.
- the gas phase at the top of the desorption tower 5 is taken into the deethanizer tower 6.
- the deethanizer tower 6 is deacetylated by the carbon dihydrogenation reactor 7 and then enters the ethylene rectification tower 8.
- Ethylene rectification tower 8 The gas phase at the top of the tower returns to the compressor section, and the ethylene product 19 is produced on the side line.
- the tower kettle material is sent to the cracking furnace 14.
- the deethanizer tower 6 is fed to the depropanizer tower 9.
- the top material of the tower is deacetylated by the carbon three hydrogenation reactor 10, and then enters the propylene rectification tower 11.
- the propylene rectification tower 11 returns to the compressor section with the gas phase at the top of the tower.
- the depropanizer tower 9 kettle material is sent to the cracking furnace 14.
- the cracked gas in the cracking furnace 14 is recovered by the waste heat boiler 15 to enter the oil washing tower / water washing tower 16, and then sent to the compressor 2 section suction
- composition of the obtained ethylene products is shown in Table 4, and the output of ethylene products is shown in Table 12.
- composition mol% Acrylic 95.2 Propane 4.8
- the purity of the ethylene product meets the specifications of polymer grade ethylene
- the purity of the propylene products meets the requirements of chemical grade propylene
- the ethylene recovery rate is 99.5%.
- Example 2 The only difference from Example 2 is that the cracking furnace is not provided, and the tower material in steps (7), (8) and (9) is discharged from the boundary zone.
- Example 1 The amount of CO 2 into the absorption tower kg / h 16771 16725 Absorption tower top CO 2 amount kg / h 3081 6958 CO 2 reduction /% 18.4 41.6
- the resulting OCM reaction gas is gradually increased in pressure by the compressor 2 and then cooled by the heat exchanger 3 and enters the absorption tower 4.
- the gas at the top of the absorption tower 4 is cooled by the cold box 23, and then enters the expander 24 to expand the gas, and then is sent to the flash tank 25 for flash evaporation, and the tail gas 22 at the top of the flash tank 25 enters the cold box 23.
- the press 26 is discharged after boosting, and the bottom liquid of the flash tank 25 is returned to the top of the absorption tower 4.
- the material at the bottom of the absorption tower 4 enters the desorption tower 5, and after the lean solvent in the desorption tower 5 is heat exchanged, it returns to the top of the absorption tower 4.
- the gas produced at the top of the desorption tower 5 enters the deethanizer tower 6, and the material at the top of the deethanizer tower 6 passes
- the carbon two hydrogenation reactor 7 enters the ethylene rectification tower 8, the deethanizer 6 tower kettle material passes through the carbon three hydrogenation reactor 10, and then enters the propylene rectification tower 11, and the ethylene rectification tower 8 sideline produces ethylene products 19 ,
- the gas at the top of the tower is returned to between the two stages of the compressor, the ethane of the tower is sent to the cracking furnace 14, the propylene product 20 is produced on the side of the propylene rectification tower 11, the gas at the top of the tower is returned to the stage of the compressor, and the propane at the tower is sent to the cracking furnace 14.
- OCM reaction gas is sent to the compression system, after three stages of compression, the pressure is increased to 1.0MPa, and then sent to the amine scrubber for purification.
- Cooling The gas after purification treatment continues to be compressed, the pressure is increased to 3MPa, and then it is gradually cooled to -35 °C before entering the absorption tower.
- the number of theoretical plates of the absorption tower is 55, the operating pressure is 2.7MPa, and the tower top temperature is -27 ° C.
- the absorption solvent used is a propane-rich carbon three fraction, the solvent enters the tower from the top of the absorption tower, and the OCM reaction gas enters from the 30th tray. The carbon two and above components in the OCM reaction gas are absorbed by the solvent, and are extracted from the tower kettle.
- the top of the tower is light components such as methane, oxygen, and CO, with a small amount of absorbent.
- Deethanization The number of theoretical plates of the deethanizer is 50, and the operating pressure is 2.0 MPa.
- the top of the deethanizer tower produces a carbon two component rich in ethylene and ethane, and the tower kettle produces a carbon three component rich in propylene and propane.
- Ethylene rectification The theoretical number of ethylene rectification towers is 90, and the operating pressure is 2.0 MPa.
- the gas from the top of the deethanizer tower is first sent to the C2 hydrogenation reactor to remove the alkyne, and then sent to the ethylene rectification tower.
- the gas from the top of the ethylene rectification tower returns to the inlet of the fourth stage of the compressor and is produced on the side
- the tower kettle is rich in ethane and sent to the cracking furnace.
- Propylene rectification The number of theoretical plates of the propylene rectification tower is 140, and the operating pressure is 1.7 MPa.
- the materials from the tower kettle of the deethanizer tower are first sent to the C3 hydrogenation reactor to remove alkyne and diolefin, and then sent to the propylene rectification tower.
- Propylene products are produced on the side of the propylene rectification tower.
- the tower kettle is rich in propane and sent to the cracking furnace.
- composition of the obtained ethylene products is shown in Table 8, and the output of ethylene products is shown in Table 12.
- composition mol% Acrylic 95.2 Propane 4.8
- the separation method shown in FIG. 4 is used to separate the reaction gas for oxidative coupling of methane to ethylene.
- OCM reaction gas is sent to the compression system, after three stages of compression, the pressure is increased to 1.0MPa, and then sent to the amine scrubber for purification.
- Cooling The gas after purification treatment continues to be compressed, the pressure is increased to 3MPa, and then it is gradually cooled to -35 °C before entering the absorption tower.
- the number of theoretical plates of the absorption tower is 55, the operating pressure is 2.7MPa, and the tower top temperature is -27 ° C.
- the absorption solvent used is n-butane, the solvent enters the tower from the top of the absorption tower, and the OCM reaction gas enters from the 30th tray.
- the carbon two and above components in the OCM reaction gas are absorbed by the solvent, and are extracted from the tower kettle.
- the top of the tower is light components such as methane, oxygen, and CO, with a small amount of absorbent.
- Deethanization The number of theoretical plates of the deethanizer is 50, and the operating pressure is 2.0 MPa.
- the top of the deethanizer tower produces a carbon two component rich in ethylene and ethane, and the tower kettle produces a carbon three component rich in propylene and propane.
- Ethylene rectification The theoretical number of ethylene rectification towers is 90, and the operating pressure is 2.0 MPa.
- the gas from the top of the deethanizer tower is first sent to the C2 hydrogenation reactor to remove the alkyne, and then sent to the ethylene rectification tower.
- the gas from the top of the ethylene rectification tower returns to the inlet of the fourth stage of the compressor and is produced on the side
- the tower kettle is rich in ethane and sent to the cracking furnace.
- Depropanizer The theoretical plate number of the depropanizer is 40, and the operating pressure is 0.7 MPa.
- the top material of the depropanizer is sent to the C3 hydrogenation reactor to remove the alkyne and diene, and the material of the depropanizer is a carbon-rich four product, which is sent to the cracking furnace.
- Propylene rectification The material from the carbon three hydrogenation reactor enters the propylene rectification tower.
- the theoretical plate number of the propylene rectification tower is 160, and the operating pressure is 1.7 MPa.
- the gas phase at the top of the propylene rectification tower is returned to the four-stage inlet of the compressor.
- Propylene products are produced on the side, and the material in the tower kettle is mainly propane-rich products, which are sent to the cracking furnace.
- composition of the obtained ethylene products is shown in Table 10, and the output of ethylene products is shown in Table 12.
- composition mol% Acrylic 95.2 Propane 4.8
- Example 4 the amount of absorbent to be replenished was 2887Kg / h, and the ethylene recovery rate was 99.9%.
- Example 4 The only difference from Example 4 is that no cracking furnace is provided, the ethane-rich product obtained in step (7), the carbon-rich four product obtained in step (8), and the propane-rich product obtained in step (9) are discharged from the boundary.
- Example 4 Compared with Comparative Example 2, the amount of absorbent to be supplemented in Example 4 is reduced by 21%.
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Abstract
Description
组成 | mol% |
氧气 | 0.55 |
CO | 5.69 |
CO 2 | 6.15 |
甲烷 | 34.06 |
乙烯 | 7.72 |
乙烷 | 2.52 |
丙烷 | 0.55 |
水 | 42.75 |
炔烃 | 0.01 |
组成 | mol% |
丙烯 | 95.2 |
丙烷 | 4.8 |
组成 | mol% |
甲烷 | 0.05 |
乙烯 | 99.95 |
组成 | mol% |
丙烯 | 95.2 |
丙烷 | 4.8 |
实施例1 | 实施例2 | |
进吸收塔CO 2量kg/h | 16771 | 16725 |
吸收塔顶CO 2量kg/h | 3081 | 6958 |
CO 2减少量/% | 18.4 | 41.6 |
组成 | mol% |
甲烷 | 0.03 |
乙烯 | 99.95 |
乙烷 | 0.02 |
组成 | mol% |
丙烯 | 95.2 |
丙烷 | 4.8 |
组成 | mol% |
甲烷 | 0.03 |
乙烯 | 99.95 |
乙烷 | 0.02 |
组成 | mol% |
丙烯 | 95.2 |
丙烷 | 4.8 |
Claims (35)
- 一种用于分离低碳烃的方法,包括以下步骤:(1)将待分离的含有碳一至碳四的烃类物料进行压缩和冷却,产生压缩和冷却后的烃类物料,其中,所述含有碳一至碳四的烃类物料包含选自碳二以上烯烃和选自碳一至碳四烷烃;(2)将所述压缩和冷却后的烃类物料与吸收剂进行接触,以吸收其中的碳二以上的烃类,产生富溶剂物料;(3)将所述富溶剂物料进行精馏,产生含烯烃和饱和烷烃的气相物料和贫溶剂物料;(4)将所述含烯烃和饱和烷烃的气相物料进行一次或多次精馏,产生一股或多股富含饱和烷烃的液相物料;(5)将所述一股或多股富含饱和烷烃的液相物料进行裂解,产生裂解气;(6)将所述裂解气循环至步骤(1)。
- 根据权利要求1所述的方法,其特征在于,步骤(6)中所述的将所述裂解气循环至步骤(1)包括:将所述裂解气与所述待分离的含有碳一至碳四的烃类物料合并后一起进行压缩和冷却;或者所述裂解气先经压缩,再与压缩后的含有碳一至碳四的烃类物料合并,进行冷却;或者所述裂解气先经压缩和冷却,再与压缩和冷却后的含有碳一至碳四的烃类物料合并。
- 根据权利要求1或2所述的方法,其特征在于,所述碳二以上烯烃选自乙烯、丙烯、1-丁烯、2-丁烯、1,3-丁二烯中的一种或多种;优选地,所述碳一至碳四烷烃选自甲烷、乙烷、丙烷、正丙烷、异丙烷、正丁烷、叔丁烷和异丁烷中的一种或多种;优选地,所述饱和烷烃选自乙烷、丙烷、正丁烷和异丁烷中的一种或多种。
- 根据权利要求1-3中任一项所述的方法,其特征在于,所述吸收剂为含有碳三烷烃的碳三馏分,含有碳四烷烃的碳四馏分和含有碳五烷烃的碳五馏分,优选地,所述碳三烷烃为正丙烷,所述碳四烷烃为正丁烷,所述碳五烷烃选自正戊烷和异戊烷。
- 根据权利要求1-4中任一项所述的方法,其特征在于,所述裂解的温度为500-850℃,优选600-800℃。
- 根据权利要求1-5中任一项所述的方法,其特征在于,步骤(1)中,所述含有碳一至碳四的烃类物料被压缩至2.0-5.0MPa;和/或所述含有碳一至碳四的烃类物料被冷却到-40℃至20℃,例如5℃至20℃或者-40℃至-10℃。
- 根据权利要求1-6中任一项所述的方法,其特征在于,所述含有碳一至碳四的烃类物料来自于甲烷氧化制乙烯的反应气、炼厂干气、煤化工干气、催化裂解产物、费托尾气、丙烷脱氢产物、火炬气/瓦斯气分离和页岩气分离中的一种或多种。
- 根据权利要求1-7中任一项所述的方法,其特征在于,所述步骤(2)中,在第一吸收塔中将所述压缩和冷却后的烃类物料与吸收剂进行接触,塔顶得到含轻组分的气相料流,塔釜得到富溶剂物料,优选地,第一吸收塔的理论塔板数为30-80,操作压力为2.0-6.0MPa。
- 根据权利要求1-8中任一项所述的方法,其特征在于,所述步骤(3)中,将所述吸收液送入第一精馏塔进行精馏,塔顶得到含烯烃和饱和烷烃的气相物料,塔釜得到贫溶剂物料,优选地,第一精馏塔的理论塔板数是20-60,操作压力为1.0-4.0MPa。
- 根据权利要求1-9中任一项所述的方法,其特征在于,所述步骤(4)包括:将所述含烯烃和饱和烷烃的气相物料送入第二精馏塔进行精馏,塔顶得到含乙烷和乙烯的第一料流,塔釜得到含碳三以上烃类的第二料流;将所述第一料流送入第三精馏塔进行精馏,侧线得到乙烯产品料流,塔顶得到含乙烯的第三料流,塔釜得到富含乙烷的第四料流;任选地,在所述第一料流进入第三精馏塔之前送入第一加氢反应器进行选择性加氢反应以脱除炔烃和/或二烯烃;优选地,第二精馏塔的理论塔板数是30-80,操作压力为1.0-5.0MPa;优选地,第三精馏塔的理论塔板数是50-130,操作压力为1.0-4.0MPa。
- 根据权利要求10所述的方法,其特征在于,所述步骤(4)进一步包括:将所述第二料流在第四精馏塔中进行精馏,塔顶得到含丙烷和丙烯的第五料流,塔釜得到富含饱和烷烃的第六料流;优选地,所述第四精馏塔的理论板数为30-80,操作压力为0.1-3.0MPa。
- 根据权利要求11所述的方法,其特征在于,所述步骤(4)进一步包括:将第五料流送入第五精馏塔进行精馏,侧线得到丙烯产品料流,塔顶得到含丙烯的第七料流,塔釜得到富含富含丙烷的第八料流,任选地,在所述第五料流进入第五精馏塔之前送入第二加氢反应器进行选择性加氢反应以脱除炔烃和/或二烯烃:任选地,将所述第七料流部分或全部循环至步骤(1);优选地,所述第五精馏塔的理论板数为100-200,操作压力为1.0-4.0MPa。
- 根据权利要求10-12中任一项所述的方法,其特征在于,所述第四料流、第六料流和第八料流中的一股或多股,优选全部进行裂解,产生裂解气。
- 根据权利要求10所述的方法,其特征在于,所述步骤(4)进一步包括以下步骤:将第二料流在第五精馏塔中进行精馏,侧线得到丙烯产品料流,塔顶得到含丙烯的九料流,塔釜得到富含饱和烷烃的第十料流,任选地,将所述第九料流部分或全部循环至步骤(1);任选地,在所述第二料流进入第五精馏塔之前送入第三加氢反应器进行选择性加氢反应以脱除炔烃和/或二烯烃;优选地,所述第五精馏塔的理论板数为100-200,操作压力为1.0-4.0MPa。
- 根据权利要求10或14所述的方法,其特征在于,所述第四料流和第六料流中的一股或全部进行裂解,产生裂解气。
- 根据权利要求9-15中任一项所述的方法,其特征在于,将所述贫溶剂物料输送到第一吸收塔作为循环的吸收剂。
- 根据权利要求8-16中任一项所述的方法,其特征在于,将来自第一吸收塔塔顶的所述含轻组分的气相料流输送到第二吸收塔与其中的再吸收剂进行接触,以吸收被带出的吸收剂和未被第一吸收塔中的吸收剂吸收的碳二烃类,优选地,所述再吸收剂选自汽油、重石脑油和芳烃抽余油,优选地,所述第二吸收塔的理论板数为15-60,操作压力为1.0-5.0MPa。
- 根据权利要求17所述的方法,其特征在于,第二吸收塔塔顶得到的尾气排出界区外,塔釜得到的液相物料排出界区外或者进行其他处理。
- 根据权利要求18所述的方法,其特征在于,所述其他处理包括:将第二吸收塔塔釜得到的液相物料送入第六精馏塔进行精馏,塔顶得到的气相物流送入第一吸收塔作为循环的吸收剂,塔釜得到的液相物流输送到第二吸收塔作为循环的再吸收剂,优选地,所述第六精馏塔的理论板数为10-50,操作压力为0.1-2.0MPa。
- 根据权利要求8所述的方法,其特征在于,将来自第一吸收塔塔顶的所述含轻组分的气相料流进行冷量回收,优选冷量回收在冷量回收单元中进行,优选地,所述冷量回收单元包括冷箱、膨胀机、增压机和闪蒸罐。
- 根据权利要求20所述的方法,其特征在于,将所述含轻组分的气相料流经冷箱降温后,进行膨胀闪蒸,以回收未被吸收的碳二烃类和夹带的吸收剂,不含碳二烃类的尾气经膨胀机驱动的增压机升压后排放。
- 根据权利要求20或21所述的方法,其特征在于,所述含轻组分的气相料流进入冷箱冷却至-80℃至-35℃,之后通过膨胀机将气体膨胀,然后送入闪蒸罐闪蒸,闪蒸罐罐顶气体进入冷箱,然后经膨胀机驱动的增压机升压后排放,罐底液体返回到第一吸收塔顶部。
- 根据权利要求1-22中任一项所述的方法,其特征在于,所述裂解气经废热锅炉回收热量后,进入油洗塔和/或水洗塔,然后循环到步骤(1)进行压缩。
- 一种用于分离低碳烃的***,包括:压缩冷却单元、吸收单元、解吸单元、精馏单元以及裂解单元,其中所述吸收单元分别与所述压缩冷却单元和所述解吸单元连接,所述精馏单元分别与所述解吸单元和所述裂解单元连接,所述裂解单元与所述压缩冷却单元连接。
- 根据权利要求24所述的***,其特征在于,所述压缩冷却单元包括压缩机(2)和换热器(3),所述吸收单元包括第一吸收塔(4),所述解吸单元包括第一精馏塔(5),所述精馏单元包括第二精馏塔(6)和第三精馏塔(8),所述裂解单元包括裂解炉(14)。
- 根据权利要求25所述的***,其特征在于,所述压缩机(2)的出口与换热器(3)的入口连接,所述换热器(3)的出口与所述第一吸收塔(4)的第一入口连接,所述第一吸收塔(4)的塔釜出口与所述第一精馏塔(5)的入口连接,所述第一精馏塔(5)的塔顶出口与所述第二精馏塔(6)的入口连接。
- 根据权利要求25或26所述的***,其特征在于,所述第二精馏塔(6)的塔顶出口连接第三精馏塔(8)的入口,所述第三精馏塔(8)的塔釜出口与所述裂解炉(14)的第一入口连接,任选地,在所述第二精馏塔(6)的塔顶和第三精馏塔(8)之间设置有第一加氢反应器(7),任选地,所述第三精馏塔(8)的塔顶出口与所述压缩机(2)的入口连接。
- 根据权利要求25-27中任一项所述的***,其特征在于,所述精馏单元进一步包括第四精馏塔(9),其中,所述第四精馏塔(9)的入口与所述第二精馏塔(6)的塔釜出口连接,所述第四精馏塔(9)的塔釜出口连接所述裂解炉(14)的第一入口和/或第二入口。
- 根据权利要求28所述的***,其特征在于,所述精馏单元进一步包括第五精馏塔(11),其中,所述第四精馏塔(9)的塔顶出口连接所述第五精馏塔(11)的入口,所述第五精馏塔(11)与所述第四精馏塔(9)之间任选设置第二加氢反应器(10),所述第五精馏塔的塔釜出口与所述裂解炉的第一入口和/或第二入口和/或第三入口连接,任选地,所述第五精馏塔(11)的塔顶出口与所述压缩机(2)的第一入口连接。
- 根据权利要求25-29中任一项所述的***,其特征在于,所述裂解单元还包括废热锅炉(15)和油洗塔和/或水洗塔(16),其中所述裂解炉(14)的出口与所述废热锅炉(15)的入口连接,所述废热锅炉(15)的出口与所述油洗塔和/或水洗塔(16)的入口连接,所述油洗塔和/或水洗塔(16)的出口与所述压缩机(2)第一入口和/或第二入口连接。
- 根据权利要求25-30中任一项所述的***,其特征在于,所述第一吸收塔(4)的塔釜出口连接所述第一精馏塔(5)的入口,所述第一吸收塔(4)的塔顶出口与第二吸收塔(12)的第一入口连接,所述第二吸收塔(12)的塔釜出口任选与第六精馏塔(13)的入口连接。
- 根据权利要求31所述的***,其特征在于,所述第六精馏(13)的塔顶出口与所述第一吸收塔(4)的第二入口连接,所述第六精馏塔(13)的塔釜出口与所述第二吸收塔(12) 的第二入口连接。
- 根据权利要求25-30中任一项所述的***,其特征在于,所述第一吸收塔(4)的塔釜出口连接所述第一精馏塔(5)的入口,所述第一吸收塔(4)的塔顶出口与冷量回收单元连接。
- 根据权利要求33所述的***,其特征在于,所述冷量回收单元包括冷箱(23)、膨胀机(24)、闪蒸罐(25)和增压机(26),其中所述冷箱的第一入口与所述第一吸收塔(4)的塔顶出口连接,所述冷箱的第一出口与膨胀机的入口连接,所述膨胀机的出口与所述闪蒸罐的入口连接,所述闪蒸罐的第一出口与所述冷箱的第二入口连接,所述冷箱的第二出口与所述增压机的入口连接,任选所述闪蒸罐的第二出口与所述第一吸收塔的第二入口连接。
- 根据权利要求25-34中任一项所述的***,其特征在于,所述***还包括设置在所述第一精馏塔和所述第二精馏塔之间的净化装置,用于脱除来自第一精馏塔塔顶的物料中的酸性气体和/或水分;或者,所述***还包括设置在所述压缩机和换热器之间的净化装置,用于脱除来自压缩机的物料中的酸性气体和/或水分。
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