CN111004079B - Separation method and device for reaction gas for preparing ethylene by oxidative coupling of methane - Google Patents
Separation method and device for reaction gas for preparing ethylene by oxidative coupling of methane Download PDFInfo
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- CN111004079B CN111004079B CN201811168501.5A CN201811168501A CN111004079B CN 111004079 B CN111004079 B CN 111004079B CN 201811168501 A CN201811168501 A CN 201811168501A CN 111004079 B CN111004079 B CN 111004079B
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000005977 Ethylene Substances 0.000 title claims abstract description 88
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000926 separation method Methods 0.000 title claims abstract description 35
- 239000012495 reaction gas Substances 0.000 title claims abstract description 31
- 238000005691 oxidative coupling reaction Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 74
- 238000010521 absorption reaction Methods 0.000 claims abstract description 67
- 238000003795 desorption Methods 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000000746 purification Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 77
- 230000009102 absorption Effects 0.000 claims description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 62
- 229910052799 carbon Inorganic materials 0.000 claims description 62
- 238000005336 cracking Methods 0.000 claims description 57
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 49
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 49
- 230000009103 reabsorption Effects 0.000 claims description 44
- 239000000047 product Substances 0.000 claims description 40
- 238000005984 hydrogenation reaction Methods 0.000 claims description 33
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 230000002745 absorbent Effects 0.000 claims description 23
- 239000002250 absorbent Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 16
- 239000001294 propane Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000002918 waste heat Substances 0.000 claims description 12
- 230000006835 compression Effects 0.000 claims description 10
- 238000007906 compression Methods 0.000 claims description 10
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 9
- 150000001345 alkine derivatives Chemical class 0.000 claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 5
- 238000005057 refrigeration Methods 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- 239000013589 supplement Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 239000001282 iso-butane Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 15
- 239000012071 phase Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 230000020335 dealkylation Effects 0.000 description 4
- 238000006900 dealkylation reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 208000005156 Dehydration Diseases 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000000475 acetylene derivatives Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- JVFDADFMKQKAHW-UHFFFAOYSA-N C.[N] Chemical compound C.[N] JVFDADFMKQKAHW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- -1 alcohol amine Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KOWXKIHEBFTVRU-UHFFFAOYSA-N nga2 glycan Chemical compound CC.CC KOWXKIHEBFTVRU-UHFFFAOYSA-N 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013014 purified material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of chemical industry, and discloses a separation method and a separation device for preparing ethylene reaction gas by oxidative coupling of methane. The invention is a new method for separating reaction gas of preparing ethylene by oxidative coupling of methane, which can greatly improve the operation temperature, has low energy consumption and simple flow, and is easy to operate and control. The separation method has the advantages that the temperature is higher, so that the requirement of the whole separation method on equipment materials is greatly reduced, the energy consumption and the investment are obviously reduced, and meanwhile, the purification of the OCM reaction gas is carried out after the absorption and desorption temperature is higher, so that the treatment capacity of a purification unit is greatly reduced, the energy consumption is reduced, the saturated resources are fully utilized, and the product value is greatly improved.
Description
Technical Field
The invention belongs to the field of chemical industry, and in particular relates to a separation method and a separation device for reaction gas for preparing ethylene by oxidative coupling of methane.
Background
Ethylene is used as the most important basic organic chemical raw material, and the production of ethylene is always dependent on petroleum cracking routes for a long time, so that the problems of environmental pollution and the like are also becoming serious. Along with the continuous rising of the price of crude oil, the rising of the price of ethylene cracking raw materials is initiated, meanwhile, the phenomenon of the supply and shortage of ethylene cracking raw materials is also very prominent, and in the face of the current situation, the energy utilization structure is regulated in all countries of the world, and new ethylene production routes are continuously searched. In 2010, along with the breakthrough of the united states in the shale gas field, a large amount of methane which is difficult to mine is mined, and chemical utilization of methane attracts great importance in the industry, so that research on ethylene and ethane prepared by oxidative coupling of methane becomes a research hotspot worldwide again.
The purpose of preparing ethylene by oxidative coupling of methane is to convert methane into ethylene under the action of catalyst, and the reaction products are complex and mainly comprise methane, ethylene, ethane, CO and CO 2 、O 2 And the like, a number of methods for separating ethylene from the reaction mixture have been proposed in the art.
US20150368167 discloses a process for separating OCM reaction products, whereby three product streams, a C2-rich stream, a nitrogen-rich stream and a methane-rich stream, are obtained by means of a separation unit. The OCM reaction product is first separated in a first separation column to obtain a C2-rich stream and a methane nitrogen stream, and then separated in a second separation column to obtain a nitrogen-rich stream and a methane-rich stream. As the separation methods all adopt low-temperature rectification, the temperature of the whole separation unit is very low, the temperature of the first separation tower top is as low as-162 ℃ and the temperature of the second separation tower top is as low as-210 ℃, the requirements on equipment materials are very high, the investment cost is greatly increased, and the energy consumption is high.
CN201710006765.X discloses a separation process of reaction products of methane oxidative coupling for preparing ethylene, wherein the reaction products are subjected to processes of compression, alcohol amine method, drying, cryogenic rectification and the like to separate components one by one, so that a polymerization grade ethylene product is finally obtained, and the ethylene recovery rate is more than 99%. This patent application significantly improves product quality, but the separation is still a cryogenic rectification requiring a cold box to provide a lower level of refrigeration.
WO2015105911 discloses a methane oxidative coupling system for the oxidative coupling of methane to ethylene and then ethylene to an alternative higher hydrocarbon product. However, in this patent application, the ethylene in the OCM product gas is combined with other components, such as unreacted methane, ethane, CO 2 Cryogenic rectification is still employed for separation of nitrogen, water, etc., with the first separator being used to separate methane/nitrogen from components above C2, the separator operating at temperatures as low as about-160℃, and the second separator being used to separate methane from nitrogen, the temperature being as low as about-200℃.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide a novel separation method for preparing ethylene reaction gas by oxidative coupling of methane, which can greatly improve the operation temperature, has low energy consumption and simple flow, and is easy to operate and control.
The invention provides a separation method of reaction gas for preparing ethylene by oxidative coupling of methane, which comprises the following steps:
(1) Compression: boosting the pressure of the reaction gas by using a compressor;
(2) And (3) cooling: cooling the compressed gas obtained in the step (1) to 5-20 ℃, and then sending the cooled compressed gas to an absorption tower;
(3) Absorption: the absorbent enters from the top of the absorption tower to absorb the carbon two fractions and above components in the reaction gas, the tower bottom material flow of the absorption tower is sent to a desorption tower, and the tower top gas is sent to a reabsorption tower;
(4) And (3) desorption: feeding a material flow from the tower bottom of the absorption tower into a desorption tower, feeding the gas obtained from the tower top into a purification unit, cooling the lean solvent obtained from the tower bottom, and returning to the top of the absorption tower;
(5) Purifying: sequentially deacidifying and dehydrating the gas at the top of the desorption tower;
(6) Deethanizing: sending the gas subjected to the purification treatment in the step (5) to a deethanizer, obtaining a carbon bi-component rich in ethylene and ethane at the top of the deethanizer, sending the carbon bi-component to a carbon bi-hydrogenation reactor to remove alkyne, and sending the bottom material flow of the deethanizer to a depropanizer;
(7) Ethylene rectification: feeding the material flow from the carbon two hydrogenation reactor into an ethylene rectifying tower, extracting ethylene products from the side line of the ethylene rectifying tower, returning tower top gas to the space between compressor sections, and feeding the tower bottom material flow into a cracking furnace;
(8) Removing propane: feeding the material flow from the tower bottom of the deethanizer into a depropanizer, obtaining carbon three components rich in propylene and propane at the tower top of the depropanizer, delivering the carbon three components into a carbon three hydrogenation reactor to remove alkyne and diene, and feeding the material flow from the tower bottom of the depropanizer into a cracking furnace or extracting the material flow as a carbon four product;
(9) Propylene rectification: feeding the material flow from the carbon three hydrogenation reactor into a propylene rectifying tower, extracting propylene products from the side line of the propylene rectifying tower, returning tower top gas to the space between the compressor sections, and feeding the tower bottom material flow into a cracking furnace;
(10) Cracking: delivering tower kettle material flows in the step (7), the step (9) and the optional step (8) to a cracking furnace for cracking, and delivering the obtained cracking gas to an oil washing tower/water washing tower after heat is recovered by a waste heat boiler, and then delivering the cracking gas to a compressor section of a suction tank;
(11) And (3) reabsorption: the gas from the top of the absorption tower enters a reabsorption tower, the reabsorber enters from the top of the absorption tower, the absorbed absorbent and the unabsorbed carbon two components are absorbed, the tail gas from the top of the reabsorption tower is sent to the outside of the boundary region, and the bottom material flow is sent to the gasoline desorber or the outside of the boundary region.
When the reabsorption tower bottom material flow is sent to the gasoline desorber, the method also preferably comprises the following steps:
(12) Gasoline desorption: the tower bottom material flow from the reabsorption tower enters a gasoline desorption tower, gas at the top of the gasoline desorption tower returns to the top of the absorption tower after being cooled, and the lean gasoline solvent is obtained at the tower bottom and returns to the reabsorption tower after being cooled.
According to the present invention, in the compression step (1), the OCM reaction gas is generally required to be increased in pressure step by step, preferably to 3.0 to 5.0MPa, and the number of stages of compression is not particularly limited, and five stages of compression are preferably used.
In the cooling step (2), the required cooling capacity can be provided by a propylene refrigeration compressor or a lithium bromide refrigeration unit.
In the absorption step (3), the theoretical plate number of the absorption tower is preferably 30-80, and the operation pressure is 2.0-6.0MPa; the absorbent is a carbon three-fraction containing propane, a carbon four-fraction containing n-butane and isobutane, or a carbon five-fraction containing n-pentane and isopentane, and further, preferably, a carbon four-fraction containing n-butane and isobutane, and the amount of the absorbent is not particularly limited in the present invention, and can be determined by a person skilled in the art according to the general knowledge of the prior art.
In the desorption step (4), the theoretical plate number of the desorption tower is preferably 20-60, and the operation pressure is 1.0-4.0MPa; the produced gas at the top of the desorption tower is sent to a purification unit, and the desorbed absorbent obtained at the bottom of the desorption tower is returned to the absorption tower for recycling after being cooled step by step. Part of the absorbent enters the reabsorption tower along with the gas phase at the top of the absorption tower, and a strand of absorbent is preferably introduced into the tower bottom of the desorption tower to supplement the absorbent so as to ensure the consumption of the absorbent in the absorption tower in the system.
In the purification step (5), which mainly includes deacidification gas and dehydration, the specific process conditions of this step are not particularly limited in the present invention, and a person skilled in the art can determine suitable specific operation conditions thereof according to a conventional method.
In the deethanizer step (6), the theoretical plate number of the deethanizer is preferably 30-80, and the operating pressure is 1.0-5.0MPa; the deethanizer overhead is fed to a carbon dioxide hydrogenation reactor to remove acetylenes therefrom, and the catalyst and process conditions for the deethanization are not particularly limited in this invention, and those skilled in the art can determine the appropriate specific operating conditions according to conventional methods. The material in the bottom of the deethanizer is sent to a depropanizer.
In the ethylene rectification step (7), the theoretical plate number of the ethylene rectification tower is preferably 50-130, and the operation pressure is 1.0-4.0MPa; ethylene products are extracted from the side line of the ethylene rectifying tower, the gas at the top of the tower returns to the space between the compressor sections, and the materials at the tower bottom are sent to the cracking furnace.
In the depropanizing step (8), the theoretical plate number of the depropanizer is preferably 30-80, and the operating pressure is 0.1-3.0MPa; the depropanizer overhead is sent to a carbon three hydrogenation reactor to remove acetylenes and dienes therefrom, and the catalyst and process conditions used in the depropanization are not particularly limited in this invention, and those skilled in the art can determine the appropriate specific operating conditions according to conventional methods. The material at the bottom of the depropanizer can be extracted as a product and can also be sent to a cracking furnace.
In the propylene rectification step (9), the theoretical plate number of the propylene rectification tower is preferably 100-200, and the operating pressure is 1.0-4.0MPa; propylene products are extracted from the side line of the propylene rectifying tower, the gas at the top of the tower returns to the space between the compressor sections, and the materials at the tower bottom are sent to the cracking furnace.
In the cracking step (10), the present invention is not particularly limited as to the type of cracking furnace. The pyrolysis gas is recovered by an advanced waste heat boiler and then cooled by a water scrubber. An oil scrubber may also be provided in the cracking step if desired.
In the reabsorption step (11), the theoretical plate number of the reabsorption tower is preferably 15 to 60, and the operation pressure is 1.0 to 5.0MPa; the gas at the top of the absorption tower enters a reabsorption tower, the reabsorber enters from the top of the absorption tower, the absorbed absorbent and the unabsorbed carbon two components are absorbed, the gas phase tail gas at the top of the reabsorption tower is sent out of an external area, and the liquid phase at the bottom of the absorption tower can be extracted and sent out of a boundary area and also can be sent to a gasoline desorption tower; the reabsorber is preferably gasoline, heavy naphtha or aromatic raffinate oil, and further preferably refinery stable gasoline.
In the gasoline desorption step (12), the theoretical plate number of the gasoline desorption tower is preferably 10-50, and the operating pressure is 0.1-2.0MPa; the lean absorbent obtained from the tower bottom of the gasoline desorber is cooled step by step and then returned to the reabsorber for recycling. Preferably, a strand of reabsorber is introduced into the kettle of the gasoline desorption tower to be used as supplement, and the top material flow of the gasoline desorption tower is returned to the absorption tower for recycling after being cooled.
According to a preferred embodiment of the invention, the separation method comprises the steps of:
(1) Compression: gradually increasing the pressure of OCM reaction gas to 3.0-5.0MPa;
(2) And (3) cooling: cooling the compressed OCM reaction gas obtained in the step (1) to 10-20 ℃;
(3) Absorption: the cooled OCM reaction gas is sent to an absorption tower, and an absorbent enters from the top of the absorption tower to absorb carbon two fractions and above components in the OCM reaction gas; the tower bottom material flow of the absorption tower is sent to a desorption tower for treatment, and the tower top gas is sent to a reabsorption tower;
(4) And (3) desorption: the material flow from the tower bottom of the absorption tower enters a desorption tower, the lean solvent obtained from the tower bottom is cooled and returned to the top of the absorption tower to be used as an absorbent for recycling, and the gas obtained from the tower top is sent to a purification unit;
(5) Purifying: sequentially carrying out deacidification gas and dehydration treatment on the gas from the top of the desorption tower;
(6) Deethanizing: the purified gas is sent to a deethanizer, the top of the deethanizer is a carbon two component rich in ethylene and ethane, the carbon two component is sent to a carbon two hydrogenation reactor, alkyne in the carbon two component is removed, and the bottom material flow of the deethanizer is sent to a depropanizer;
(7) Ethylene rectification: feeding the material flow from the carbon two hydrogenation reactor into an ethylene rectifying tower, extracting ethylene products from the side line of the ethylene rectifying tower, returning tower top gas to the space between the compressor sections, and feeding tower bottom materials into a cracking furnace;
(8) Removing propane: the materials from the tower bottom of the deethanizer are sent to a depropanizer, the top of the depropanizer is rich in propylene and propane, the carbon three components are sent to a carbon three hydrogenation reactor, alkyne and diene in the carbon three components are removed, and the materials from the tower bottom can be sent to a cracking furnace or can be extracted as a carbon four product;
(9) Propylene rectification: the material flow from the carbon three hydrogenation reactor enters a propylene rectifying tower, propylene products are extracted from the side line of the propylene rectifying tower, the gas at the top of the tower returns to the space between the compressor sections, and the material at the bottom of the tower is sent to a cracking furnace.
(10) Cracking: delivering tower kettle material flows in the step (7), the step (9) and the optional step (8) to a cracking furnace for cracking, and delivering cracking gas to an oil washing tower/water washing tower after heat is recovered by a waste heat boiler, and then delivering to a compressor section of a suction tank;
(11) And (3) reabsorption: the gas from the top of the absorption tower enters a reabsorption tower, the unabsorbed C2 fraction and the entrained absorbent are recovered, the tail gas after reabsorption is sent to the outside of the boundary region, and the bottom material flow of the reabsorption tower is sent to the outside of the gasoline desorption tower or the boundary region;
(12) Gasoline desorption: the materials from the tower bottom of the reabsorption tower are sent to a gasoline desorber, the top of the gasoline desorber obtains the recovered absorbent, the recovered absorbent is sent to an absorption tower, the tower bottom obtains the lean gasoline solvent, and the lean gasoline solvent returns to the reabsorption tower after being cooled.
In another aspect, the invention provides a separation device for the separation method, the device comprises a compressor, a heat exchanger, an absorption tower, a desorption tower, a deethanizer, a carbon two hydrogenation reactor, an ethylene rectifying tower, a depropanizer, a carbon three hydrogenation reactor, a propylene rectifying tower, a cracking furnace, a waste heat boiler and an oil washing tower/water washing tower;
wherein the OCM reactor is sequentially connected with the compressor, the heat exchanger and the absorption tower;
the tower bottom of the absorption tower is connected with the desorption tower, and the tower top of the absorption tower is connected with the reabsorption tower;
the top of the reabsorption tower is connected with the outside of the boundary region, and the tower bottom is optionally connected with a gasoline desorption tower; when the gas stripping tower is connected, the top of the gas stripping tower is connected with the top of the absorption tower, and the bottom of the gas stripping tower is connected with the top of the reabsorber;
the top of the desorption tower is connected with the deethanizer, and the tower bottom is connected with the absorption tower;
the top of the deethanizer is connected with a carbon dioxide hydrogenation reactor and an ethylene rectifying tower in sequence;
the top of the ethylene rectifying tower is connected with the compressor, the tower kettle is connected with the cracking furnace, and the side part of the ethylene rectifying tower is connected with an ethylene product extraction line;
the deethanizer tower kettle is connected with a depropanizer, the top of the depropanizer tower is sequentially connected with a carbon three hydrogenation reactor and a propylene rectifying tower, and the tower kettle is optionally connected with the cracking furnace;
the tower kettle of the propylene rectifying tower is connected with the cracking furnace;
the cracking furnace is sequentially connected with a waste heat boiler, an oil scrubber/water scrubber and a compressor.
1) The separation process has higher temperature, greatly reduces the requirement on equipment materials by the whole process, and obviously reduces the energy consumption and the investment.
2) Because the absorption and desorption temperature is higher, the purification of the OCM reaction gas is carried out after the desorption tower, so that the treatment capacity of a purification unit is greatly reduced, and the energy consumption is reduced.
3) The invention has simple process flow and high product quality.
4) The invention makes full use of saturated resources and greatly improves the product value.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular descriptions of exemplary embodiments of the invention as illustrated in the accompanying drawings wherein like reference numbers generally represent like parts throughout the exemplary embodiments of the invention.
FIG. 1 is a schematic flow chart showing a separation method of reaction gas for preparing ethylene by oxidative coupling of methane in example 1 of the present invention.
FIG. 2 is a schematic flow chart showing the separation method of the reaction gas for preparing ethylene by oxidative coupling of methane in example 2 of the present invention.
Reference numerals illustrate:
1. a reactor for preparing ethylene by oxidative coupling of methane; 2. a compressor; 3. a heat exchanger; 4. an absorption tower; 5. a desorption tower; 6. a deethanizer; 7. a carbon two hydrogenation reactor; 8. an ethylene rectifying tower; 9. a depropanizer; 10. a carbon three hydrogenation reactor; 11. a propylene rectifying column; 12. a reabsorption tower; 13. a gasoline desorber; 14. a pyrolysis furnace; 15. a waste heat boiler; 16. an oil/water scrubber; 17. oxygen or oxygen enrichment; 18. methane; 19. an ethylene product; 20. a propylene product; 21. a carbon four product; 22. tail gas.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein.
Example 1
The separation method shown in figure 1 is adopted to separate the reaction gas of methane oxidative coupling ethylene production.
The process flow comprises the following steps:
after methane 18 and oxygen or oxygen-enriched 17 react in the reactor 1 for preparing ethylene by oxidative coupling of methane, the obtained OCM reaction gas is gradually pressurized by a compressor 2, cooled by a heat exchanger 3 and then enters an absorption tower 4. The top gas of the absorption tower 4 is sent to the reabsorption tower 12, the bottom material of the absorption tower 4 enters the desorption tower 5, the top tail gas 22 of the reabsorption tower 12 is sent to the outside of the boundary region, the tower bottom material is sent to the gasoline desorption tower 13, the lean solvent in the tower bottom of the desorption tower 5 exchanges heat and returns to the absorption tower 4, the top gas phase of the desorption tower 5 enters the deethanizer 6, the top material of the deethanizer 6 is sent to the ethylene rectifying tower 8 after being subjected to the dealkylation by the carbon two hydrogenation reactor 7, the top gas phase of the ethylene rectifying tower 8 returns to the compressor section, the side line is used for extracting ethylene products 19, the tower bottom material is sent to the cracking furnace 14, the top material of the deethanizer 6 is sent to the depropanizer 9, the top material of the depropanizer 9 is sent to the propylene rectifying tower 11 after being subjected to the dealkylation by the carbon three hydrogenation reactor 10, the top gas phase of the propylene rectifying tower 11 returns to the compressor section, the side line is used for extracting propylene products 20, the tower bottom material is sent to the cracking furnace 14, the bottom material of the depropanizer 9 is sent to the cracking furnace 14 as a carbon four products 21, the cracking gas obtained after the cracking is subjected to the cracking is sent to the waste heat 15, the waste heat and enters the oil/water washing tower 16 and is sent to the compressor 2.
The composition of the outlet of the reactor for preparing ethylene by oxidative coupling of methane is shown in table 1.
TABLE 1
| Composition of the composition | mol％ |
| Oxygen gas | 0.55 |
| CO | 5.69 |
| CO 2 | 6.15 |
| Methane | 34.06 |
| Ethylene | 7.72 |
| Ethane (ethane) | 2.52 |
| Propane | 0.55 |
| Water and its preparation method | 42.75 |
The specific operation steps are as follows:
(1) Compression: the OCM reaction gas is sent to a compression system, and after five stages of compression, the pressure is increased to 4.2MPa.
(2) And (3) cooling: the OCM reaction gas after pressure boosting is cooled to 15 ℃ and then enters an absorption tower.
(3) Absorption: the theoretical plate number of the absorption tower is 55, and the operating pressure is 3.8MPa. The absorption solvent is C-IV after ether, the absorption solvent enters the tower from the top of the absorption tower, and the OCM reaction gas enters from the 30 th tower plate. The second and more components of OCM reaction gas are absorbed by solvent, extracted from tower bottom, the top of tower is light component of methane, oxygen and CO, etc. and small quantity of absorbent is entrained.
(4) And (3) desorption: the theoretical plate number of the desorption tower is 40, and the operation pressure is 2.4MPa. The desorbed top gas phase is sent to a purifying unit, and the lean solvent in the tower bottom is cooled to 15 ℃ after step-by-step heat exchange and then returned to the absorption tower for recycling.
(5) Purifying: after deacidification gas treatment in the amine washing/alkali washing tower, the OCM reaction gas is dried.
(6) Deethanizing: the purified material enters a deethanizer, the theoretical plate number of the deethanizer is 50, and the operating pressure is 2.0MPa. The materials rich in ethylene and ethane are extracted from the top of the deethanizer, sent to a carbon two hydrogenation reactor, acetylene and other alkyne in the materials are removed through hydrogenation, and the materials in the bottom of the deethanizer are sent to a depropanizer.
(7) Ethylene rectification: the materials from the carbon two hydrogenation reactor are fed into an ethylene rectifying tower, the theoretical plate number of the ethylene rectifying tower is 90, and the operating pressure is 2.0MPa. The gas phase at the top of the ethylene rectifying tower returns to the four-section inlet of the compressor, ethylene products are extracted from the side line, and ethane is sent to the cracking furnace at the tower bottom.
(8) Removing propane: the number of theoretical plates of the depropanizer was 40 and the operating pressure was 0.7MPa. The tower top material of the depropanizer is sent to a carbon three hydrogenation reactor to remove alkyne and diene, and the tower bottom material of the depropanizer is taken as a carbon four product to be extracted.
(9) Propylene rectification: the material from the carbon three hydrogenation reactor enters a propylene rectifying tower, the theoretical plate number of the propylene rectifying tower is 160, and the operating pressure is 1.7MPa. The gas phase at the top of the propylene rectifying tower returns to the four-section inlet of the compressor, propylene products are extracted from the side line, and the materials at the tower bottom are mainly propane and are sent to the cracking furnace.
(10) Cracking: the alkane such as ethane, propane, n-butane and the like enters the cracking furnace, the heat of the cracking gas is recovered by the waste heat boiler, and the cracking gas is sent to the first-stage inlet of the compressor after being cooled by the water scrubber.
(11) And (3) reabsorption: the gas from the top of the absorption tower enters a reabsorption tower, the theoretical plate number of the reabsorption tower is 20, the operating pressure is 3.8MPa, the reabsorption agent enters from the top of the tower, the carried absorbent and the unabsorbed carbon two components are absorbed, the tail gas from the top of the reabsorption tower is sent to the outside of the boundary region, and the tower bottom material flow is sent to a gasoline desorption tower;
(12) Gasoline desorption: the tower bottom material flow from the reabsorption tower enters a gasoline desorption tower, the theoretical plate number of the gasoline desorption tower is preferably 28, the operating pressure is 0.5MPa, the gas at the top of the gasoline desorption tower is cooled and then is absorbed by the absorption tower, the lean gasoline solvent is obtained at the tower bottom, and the lean gasoline solvent is cooled and then returns to the reabsorption tower.
The composition of the ethylene product obtained is shown in Table 2.
TABLE 2
| Composition of the composition | mol％ |
| Methane | 0.05 |
| Ethylene | 99.95 |
The composition of the propylene product obtained is shown in Table 3.
TABLE 3 Table 3
| Composition of the composition | mol％ |
| Propylene | 95.2 |
| Propane | 4.8 |
In this example, the ethylene product purity meets the polymerization grade ethylene specification, the propylene product purity meets the chemical grade propylene specification, and the ethylene recovery is 99.7%.
Example 2
The separation method shown in figure 2 is adopted to separate the reaction gas of methane oxidative coupling ethylene production.
The process flow comprises the following steps: after methane 18 and oxygen or oxygen-enriched 17 react in the reactor 1 for preparing ethylene by oxidative coupling of methane, the obtained OCM reaction gas is gradually pressurized by a compressor 2, cooled by a heat exchanger 3 and then enters an absorption tower 4. The top gas of the absorption tower 4 is sent to the reabsorption tower 12, the bottom material of the absorption tower 4 enters the desorption tower 5, the top tail gas 22 of the reabsorption tower 12 is sent to the outside of the boundary region, the tower bottom material is sent to the gasoline desorption tower 13, the lean solvent in the tower bottom of the desorption tower 5 exchanges heat and returns to the absorption tower 4, the top gas phase of the desorption tower 5 enters the deethanizer 6, the top material of the deethanizer 6 is sent to the ethylene rectifying tower 8 after being subjected to the dealkylation by the carbon two hydrogenation reactor 7, the top gas phase of the ethylene rectifying tower 8 returns to the compressor section, the side gas phase is used for obtaining ethylene products 19, the tower bottom material is sent to the cracking furnace 14, the top material of the deethanizer 6 is sent to the depropanizer 9, the top material of the depropanizer 9 is sent to the propylene rectifying tower 11 after being subjected to the dealkylation by the carbon three hydrogenation reactor 10, the top gas phase of the propylene rectifying tower 11 returns to the compressor section, the side gas phase is used for obtaining propylene products 20, the tower bottom material is sent to the cracking furnace 14, the bottom material of the deethanation 9 is sent to the cracking furnace 14, the pyrolysis gas obtained after the cracking is subjected to the thermal recovery by the boiler 15, and enters the oil/water washing tower 16, and the compressor section 2 is sent to the compressor section 2.
The specific operation steps are as follows: the only differences between this embodiment and embodiment 1 are: n-butane was selected as the absorbent; the depropanizer 9 bottoms feed is sent to a cracker 14.
The composition of the ethylene product obtained is shown in Table 4.
TABLE 4 Table 4
| Composition of the composition | mol％ |
| Methane | 0.05 |
| Ethylene | 99.95 |
The composition of the propylene product obtained is shown in Table 5.
TABLE 5
| Composition of the composition | mol％ |
| Propylene | 95.2 |
| Propane | 4.8 |
In this example, the ethylene product purity meets the polymerization grade ethylene specification, the propylene product purity meets the chemical grade propylene specification, and the ethylene recovery is 99.5%.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
Claims (6)
1. The separation method of the reaction gas for preparing ethylene by oxidative coupling of methane is characterized by comprising the following steps:
(1) Compression: the reaction gas is boosted to 3.0-5.0MPa by a compressor;
(2) And (3) cooling: cooling the compressed gas obtained in the step (1) to 5-20 ℃, and then sending the cooled compressed gas to an absorption tower;
(3) Absorption: the absorbent enters from the top of the absorption tower to absorb the carbon two fractions and above components in the reaction gas, the tower bottom material flow of the absorption tower is sent to a desorption tower, and the tower top gas is sent to a reabsorption tower; the absorbent is a carbon three-fraction containing propane, a carbon four-fraction containing n-butane and isobutane, or a carbon five-fraction containing n-pentane and isopentane; the theoretical plate number of the absorption tower is 30-80, and the operating pressure is 2.0-6.0MPa;
(4) And (3) desorption: feeding a material flow from the tower bottom of the absorption tower into a desorption tower, feeding the gas obtained from the tower top into a purification unit, cooling the lean solvent obtained from the tower bottom, and returning to the top of the absorption tower;
(5) Purifying: sequentially deacidifying and dehydrating the gas at the top of the desorption tower;
(6) Deethanizing: sending the gas subjected to the purification treatment in the step (5) to a deethanizer, obtaining a carbon bi-component rich in ethylene and ethane at the top of the deethanizer, sending the carbon bi-component to a carbon bi-hydrogenation reactor to remove alkyne, and sending the bottom material flow of the deethanizer to a depropanizer;
(7) Ethylene rectification: feeding the material flow from the carbon two hydrogenation reactor into an ethylene rectifying tower, extracting ethylene products from the side line of the ethylene rectifying tower, returning tower top gas to the space between compressor sections, and feeding the tower bottom material flow into a cracking furnace;
(8) Removing propane: feeding the material flow from the tower bottom of the deethanizer into a depropanizer, obtaining carbon three components rich in propylene and propane at the tower top of the depropanizer, delivering the carbon three components into a carbon three hydrogenation reactor to remove alkyne and diene, and feeding the material flow from the tower bottom of the depropanizer into a cracking furnace or extracting the material flow as a carbon four product;
(9) Propylene rectification: feeding the material flow from the carbon three hydrogenation reactor into a propylene rectifying tower, extracting propylene products from the side line of the propylene rectifying tower, returning tower top gas to the space between the compressor sections, and feeding the tower bottom material flow into a cracking furnace;
(10) Cracking: delivering tower kettle material flows in the step (7), the step (9) and the optional step (8) to a cracking furnace for cracking, and delivering the obtained cracking gas to an oil washing tower/water washing tower after heat is recovered by a waste heat boiler, and then delivering the cracking gas to a compressor section of a suction tank;
(11) And (3) reabsorption: the gas from the top of the absorption tower enters a reabsorption tower, the reabsorber enters from the top of the absorption tower, the absorbed absorbent and the unabsorbed carbon two components are absorbed, the tail gas from the top of the reabsorption tower is sent to the outside of the boundary area, and the bottom material flow of the reabsorption tower is sent to the outside of the gasoline desorption tower or the boundary area;
when the tower bottom material flow of the reabsorption tower is sent to the gasoline desorber, the method further comprises the following steps:
(12) Gasoline desorption: the tower bottom material flow from the reabsorption tower enters a gasoline desorption tower, gas at the top of the gasoline desorption tower returns to the top of the absorption tower after being cooled, a lean gasoline solvent is obtained at the tower bottom, and the lean gasoline solvent returns to the reabsorption tower after being cooled;
the theoretical plate number of the desorption tower is 20-60, and the operating pressure is 1.0-4.0MPa;
the theoretical plate number of the deethanizer is 30-80, and the operating pressure is 1.0-5.0MPa;
the theoretical plate number of the ethylene rectifying tower is 50-130, and the operating pressure is 1.0-4.0MPa;
the theoretical plate number of the depropanizer is 30-80, and the operating pressure is 0.1-3.0MPa;
the theoretical plate number of the propylene rectifying tower is 100-200, and the operating pressure is 1.0-4.0MPa;
the theoretical plate number of the reabsorption tower is 15-60, and the operating pressure is 1.0-5.0MPa;
the theoretical plate number of the gasoline desorber is 10-50, and the operating pressure is 0.1-2.0MPa.
2. The separation method according to claim 1, wherein in the step (4), a stream of absorbent is introduced into the bottom of the desorption column as a supplement.
3. The separation process of claim 1 wherein in step (11) the reabsorber is gasoline, heavy naphtha or aromatic raffinate.
4. The separation process according to claim 1, wherein in step (12), a strand of reabsorber is introduced as a supplement into the gasoline desorber bottoms.
5. The separation process of claim 1, wherein the cooling requirement of step (2) is provided by a propylene refrigeration compressor or by a lithium bromide refrigeration unit.
6. The separation method according to any one of claims 1 to 5, wherein the separation device for producing ethylene reaction gas by oxidative coupling of methane comprises a compressor, a heat exchanger, an absorber, a desorber, a deethanizer, a carbon di-hydrogenation reactor, an ethylene rectifying column, a depropanizer, a carbon tri-hydrogenation reactor, a propylene rectifying column, a cracking furnace, a waste heat boiler, an oil scrubber/water scrubber;
wherein the OCM reactor is sequentially connected with the compressor, the heat exchanger and the absorption tower;
the tower bottom of the absorption tower is connected with the desorption tower, and the tower top of the absorption tower is connected with the reabsorption tower;
the top of the reabsorption tower is connected with the outside of the boundary region, and the tower bottom is optionally connected with a gasoline desorption tower; when the gas stripping tower is connected, the top of the gas stripping tower is connected with the top of the absorption tower, and the bottom of the gas stripping tower is connected with the top of the reabsorber;
the top of the desorption tower is connected with the deethanizer, and the tower bottom is connected with the absorption tower;
the top of the deethanizer is connected with a carbon dioxide hydrogenation reactor and an ethylene rectifying tower in sequence;
the top of the ethylene rectifying tower is connected with the compressor, the tower kettle is connected with the cracking furnace, and the side part of the ethylene rectifying tower is connected with an ethylene product extraction line;
the deethanizer tower kettle is connected with a depropanizer, the top of the depropanizer tower is sequentially connected with a carbon three hydrogenation reactor and a propylene rectifying tower, and the tower kettle is optionally connected with the cracking furnace;
the tower kettle of the propylene rectifying tower is connected with the cracking furnace;
the cracking furnace is sequentially connected with a waste heat boiler, an oil scrubber/water scrubber and a compressor.
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| MYPI2021001910A MY203258A (en) | 2018-10-08 | 2019-09-29 | Method and system for separating light hydrocarbons |
| JP2021520300A JP7546555B2 (en) | 2018-10-08 | 2019-09-29 | Method and system for separating light hydrocarbons |
| US17/283,606 US11649406B2 (en) | 2018-10-08 | 2019-09-29 | Method and system for separating light hydrocarbons |
| PCT/CN2019/109082 WO2020073853A1 (en) | 2018-10-08 | 2019-09-29 | Method and system for separating light hydrocarbons |
| SA521421693A SA521421693B1 (en) | 2018-10-08 | 2021-04-08 | Method and system for separating light hydrocarbons |
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