CN112794784A - Pyrolysis gas separation system and method adopting absorption-desorption - Google Patents
Pyrolysis gas separation system and method adopting absorption-desorption Download PDFInfo
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- 238000003795 desorption Methods 0.000 title claims abstract description 70
- 238000000926 separation method Methods 0.000 title claims abstract description 33
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000010521 absorption reaction Methods 0.000 claims abstract description 81
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 67
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000005261 decarburization Methods 0.000 claims abstract description 25
- 238000000746 purification Methods 0.000 claims abstract description 24
- 238000005262 decarbonization Methods 0.000 claims abstract description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 44
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 38
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 36
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 32
- 239000005977 Ethylene Substances 0.000 claims description 32
- 238000005336 cracking Methods 0.000 claims description 20
- 230000002745 absorbent Effects 0.000 claims description 18
- 239000002250 absorbent Substances 0.000 claims description 18
- 239000001294 propane Substances 0.000 claims description 18
- 230000006835 compression Effects 0.000 claims description 16
- 238000007906 compression Methods 0.000 claims description 16
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 9
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 8
- 239000003502 gasoline Substances 0.000 claims description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 6
- 150000001345 alkine derivatives Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000001282 iso-butane Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 12
- 239000007789 gas Substances 0.000 description 67
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 15
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 239000002737 fuel gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IFYDWYVPVAMGRO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)NCCCN(C)C IFYDWYVPVAMGRO-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- 238000004227 thermal cracking Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
-
- 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
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
-
- 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
- C10G5/00—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas
- C10G5/04—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas with liquid absorbents
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention discloses a pyrolysis gas separation system and method adopting absorption-desorption. The system comprises: the system comprises a compressor, a purification system, a four-decarbonization tower, an absorption tower, a desorption tower, a depropanization tower, a de-heavy tower, a carbon-two hydrogenation reactor and a carbon-four hydrogenation reactor; wherein, the compressor section is sequentially connected with a purification system and a four decarburization towers, the top of the four decarburization towers is connected with the rear section of the compressor and then connected with an absorption tower, and the kettle of the four decarburization towers is connected with a heavy component removal tower; the top of the heavy component removal tower is connected with a carbon four hydrogenation reactor, and an outlet pipeline of the carbon four hydrogenation reactor is combined with an outlet pipeline of the tower kettle of the desorption tower and then connected with the upper part of the absorption tower; the tower kettle of the absorption tower is connected with a desorption tower; the top of the desorption tower is connected with a depropanization tower, and the tower kettle of the desorption tower is combined with an outlet pipeline of the four-carbon hydrogenation reactor and then connected with the upper part of the absorption tower; the top of the depropanizing tower is connected with a carbo-hydrogenation reactor. The invention has the characteristics of investment saving, low energy consumption and obvious benefit.
Description
Technical Field
The invention relates to the technical field of pyrolysis gas separation, in particular to a pyrolysis gas separation system and method adopting absorption-desorption.
Background
A large amount of tail gas is generated in the oil refining and chemical production processes, wherein some tail gas, such as tail gas generated in the production processes of catalytic cracking, thermal cracking, delayed coking, hydrocracking and the like, contains a plurality of components of carbon and carbon, and particularly, the ethane/propane content in some tail gas is higher. At present, carbon two and three concentrated gases recovered from refinery tail gas are mainly sent to different sections of an ethylene plant to increase the yield of ethylene and propylene, however, for a refinery without an ethylene production device at the periphery, the direction of the concentrated gases is a main problem, so that carbon two and three resources in dry gases cannot be fully utilized, and great waste is caused.
The most important utilization mode of saturated alkanes such as ethane/propane is to produce high-quality basic chemical raw materials such as ethylene and propylene by thermal cracking. After being mixed with steam, cracking raw materials such as saturated alkane, light hydrocarbon, naphtha, hydrogenated tail oil, light diesel oil and the like undergo a thermal cracking reaction in a cracking furnace to generate cracking products such as hydrogen, methane, carbon two, carbon three, carbon four and the like. Separating and purifying the cracking product in a subsequent separation system to obtain fractions with different carbon atoms, and separating ethylene and propylene products from the carbon two and carbon three fractions.
At present, the separation and purification of the cracking products in the industry mainly adopts a sequential separation method, a front depropanization process, a front deethanization process and the like, and the obtained products comprise polymer-grade ethylene, polymer-grade propylene and the like. However, no matter what separation process is adopted, if a rectification method is adopted to separate out light components such as methane, a cold box is required to provide lower cold energy, the investment is large, and the energy consumption is high. In addition, the equipment quantity, energy consumption and the like required for obtaining polymer-grade ethylene products and polymer-grade propylene products are large.
For refineries without ethylene production devices around, the amount of saturated resources is not large enough, and if cracking and traditional cryogenic separation methods are adopted to utilize the resources, the investment recovery rate is low and the energy consumption is high. Therefore, it is urgently needed to develop a separation method and utilization of cracked gas to reduce the problems of large investment, high energy consumption and the like of the separation process of the cracked gas.
Disclosure of Invention
The invention provides a pyrolysis gas separation system and method adopting absorption-desorption to solve the problems of large process investment, high energy consumption and the like in the prior art. Has the characteristics of investment saving, low energy consumption and remarkable benefit.
It is an object of the present invention to provide a cracked gas separation system employing absorption-desorption.
The system comprises:
the system comprises a compressor, a purification system, a four-decarbonization tower, an absorption tower, a desorption tower, a depropanization tower, a de-heavy tower, a carbon-two hydrogenation reactor and a carbon-four hydrogenation reactor; wherein,
the purification system and the four decarburization towers are sequentially connected between the compressor sections, the four decarburization towers are connected with the rear section of the compressor and then connected with the absorption tower, and the four decarburization tower kettles are connected with the heavy component removal tower; the top of the heavy component removal tower is connected with a carbon four hydrogenation reactor, and an outlet pipeline of the carbon four hydrogenation reactor is combined with an outlet pipeline of the tower kettle of the desorption tower and then connected with the upper part of the absorption tower;
the tower kettle of the absorption tower is connected with a desorption tower; the top of the desorption tower is connected with a depropanization tower, and the tower kettle of the desorption tower is combined with an outlet pipeline of the four-carbon hydrogenation reactor and then connected with the upper part of the absorption tower; the top of the depropanizing tower is connected with a carbo-hydrogenation reactor.
Preferably, the first and second liquid crystal materials are,
the bottom of the depropanization tower is connected with a carbon three hydrogenation reactor, the carbon three hydrogenation reactor is connected with a propylene rectifying tower, and the top of the propylene rectifying tower is connected with a compressor section.
A reboiler is arranged at the tower kettle of the absorption tower; and/or the presence of a gas in the gas,
the tower kettle of the desorption tower is provided with a reboiler.
And an outlet pipeline of the tower kettle of the desorption tower is divided into two paths, one path is extracted, and the other path is combined with an outlet pipeline of the four-carbon hydrogenation reactor and then connected with the upper part of the absorption tower.
The second purpose of the invention is to provide a method for separating cracked gas.
The method comprises the following steps:
(1) after compression, pressure increase and purification, the pyrolysis gas enters a four-tower decarburization device to remove more than four carbon components;
(2) compressing the top material flow of the four decarbonization towers, then sending the material flow into an absorption tower to remove light components, and sending the kettle material flow of the four decarbonization towers into a de-weighting tower;
(3) extracting light components from the top of the absorption tower, feeding the material flow in the bottom of the absorption tower into a desorption tower, and feeding the material at the top of the desorption tower into a depropanizing tower; returning the material in the tower kettle of the desorption tower to the absorption tower;
(4) extracting a gasoline product from the tower kettle of the de-heavy tower, enabling the material flow at the top of the de-heavy tower to enter a carbon four hydrogenation reactor, combining the material flow at the outlet of the carbon four hydrogenation reactor with the material flow at the tower kettle of the desorption tower, and then enabling the combined material flow to enter an absorption tower;
(5) removing alkyne from the material at the top of the depropanizing tower by a carbo-hydrogenation reactor, and then extracting a crude ethylene product; the propane product is extracted from the tower bottom of the depropanizing tower.
Preferably, the first and second liquid crystal materials are,
the method further comprises (6),
the material in the bottom of the depropanizing tower enters a carbon-three hydrogenation reactor for reaction and then enters a propylene rectifying tower, a propylene product is extracted at the side line, a propane product is extracted at the bottom of the depropanizing tower, and the tower top returns to the space between compressor sections.
Adopting five-section compression to increase the pressure of the cracking gas to 2-5 MPag, then cooling to 10-15 ℃, and then feeding into an absorption tower;
the purification is carried out between compression sections, preferably after three-section compression, the pyrolysis gas purification is carried out.
The absorbent of the absorption tower 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 depropanizer overhead stream controls the propylene content to be less than 0.5% mol.
The number of theoretical plates of the four decarburization towers is 25-80, and the operating pressure is 0.5-2.5 MPa;
the number of theoretical plates of the absorption tower is 25-60, the operating pressure is 2.0-6.0 MPa, and the temperature of the tower top is 10-40 ℃;
the number of theoretical plates of the desorption tower is 20-60, and the operating pressure is 1.0-4.0 MPa;
the number of theoretical plates of the depropanizing tower is 20-80, and the operating pressure is 0.5-4.0 MPa;
the number of theoretical plates of the de-weighting tower is 20-80, and the operating pressure is 0.1-2 MPa;
the number of theoretical plates of the propylene rectifying tower is 80-280, and the operating pressure is 0.1-4.0 MPa.
The invention can adopt the following technical scheme:
a cracked gas separation system, comprising: the system comprises a compressor, a purification system, a four-decarbonization tower, an absorption tower, a desorption tower, a depropanization tower, a de-heavy tower, a carbon-two hydrogenation reactor and a carbon-four hydrogenation reactor; wherein,
the purification system and the four decarburization towers are sequentially connected between the compressor sections, the four decarburization towers are connected with the rear section of the compressor and then connected with the absorption tower, and the four decarburization tower kettles are connected with the heavy component removal tower; the tower kettle of the absorption tower is connected with the desorption tower; the top of the desorption tower is connected with a depropanization tower, and the tower kettle of the desorption tower is connected with the top of the absorption tower; the top of the depropanizing tower is connected with a carbo-hydrogenation reactor and then connected with a product extraction line; the top of the heavy component removal tower is connected with the carbon four hydrogenation reactor and then connected with the top of the absorption tower, and the tower kettle of the heavy component removal tower is connected with a gasoline product line.
In the invention, the tower kettle of the absorption tower and/or the tower kettle of the desorption tower are/is preferably provided with a reboiler to ensure that light components such as methane, hydrogen and the like in the tower kettle of the absorption tower are reduced below the set requirement. Wherein, the heating medium of the reboiler at the tower bottom of the absorption tower and the reboiler at the tower bottom of the desorption tower can adopt low-pressure steam or hot oil, preferably hot oil, which can not only fully utilize the abundant heat of a refinery, but also reduce the process energy consumption.
According to the invention, the material at the outlet of the four-carbon hydrogenation reactor completely enters the absorption tower, and in order to ensure the stable dosage of the absorbent in the system and prevent the accumulation of heavy components, part of the absorbent is preferably extracted from the tower kettle of the desorption tower, so that the tower kettle of the desorption tower is preferably provided with a solvent extraction pipeline.
A method of separating a cracked gas, comprising: the cracking gas enters a compressor to be pressurized, an intersegment outlet is purified and then enters a four-tower decarburization device to remove components with four or more carbons, then enters the rear section of the compressor to be compressed continuously, the compressed cracking gas enters an absorption tower to remove light components and then enters a desorption tower, the material at the top of the desorption tower enters a depropanizing tower, the material at the bottom of the depropanizing tower returns to the absorption tower, and the material at the top of the depropanizing tower is firstly removed alkyne by a carbon dioxide hydrogenation reactor and then is sent out of a battery compartment as a product. And (3) feeding a four-carbon hydrogenation reactor at the top of the de-heavy tower, hydrogenating olefin and alkadiene in the four-carbon hydrogenation reactor into alkane, returning the alkane to the absorption tower to serve as a supplementary absorbent, and extracting a gasoline product from the tower bottom.
In the present invention, the light components include methane and hydrogen.
According to a preferred embodiment of the invention, the method comprises the steps of:
(1) compression: after the pressure of the cracking gas is increased and the cracking gas is cooled, the cracking gas enters an absorption tower;
(2) purifying: purifying the cracked gas between the compression sections;
(3) and fourthly, decarburization: the purified cracking gas is cooled and then enters a decarburization four-tower, heavy components with more than four carbon atoms are extracted from a tower kettle and sent to a de-heavy tower, and the material flow at the top of the tower enters the rear section of a compressor to be continuously boosted.
(4) Absorption: cooling the boosted cracked gas to enter an absorption tower, and allowing an absorbent to enter the tower from the top of the absorption tower to absorb components C2 and above in the cracked gas; the material flow in the tower bottom of the absorption tower is sent to a desorption tower, the gas which is not absorbed in the tower top is cooled, and part of absorbent is recovered and taken out as fuel gas;
(5) desorbing: the top of the desorption tower obtains carbon dioxide three concentrated gas, the bottom of the desorption tower obtains a poor solvent, and the poor solvent returns to the top of the absorption tower after being cooled;
(6) depropanizing: sending the carbon dioxide three-concentrated gas obtained from the top of the desorption tower to a depropanizing tower, obtaining crude ethylene gas from the top of the depropanizing tower, sending the crude ethylene gas to a carbon dioxide hydrogenation reactor, removing alkyne, extracting the product, and sending the product to a styrene device to be used as a raw material.
(7) Removing weight: and (3) feeding the material at the bottom of the four-tower decarbonizing tower into a heavy component removing tower, extracting more than five carbon components from the tower bottom, feeding the four-carbon fraction at the tower top into a four-carbon hydrogenation reactor, completely hydrogenating unsaturated hydrocarbon into saturated hydrocarbon, and feeding the saturated hydrocarbon serving as a supplementary absorbent into the top of the absorption tower.
In the compression step, the number of stages to be compressed is not particularly limited in the present invention, and five-stage compression is preferably employed. Preferably, the compression specifically means that the pressure of the cracking gas is increased to 2-5 MPag, and then the gas is sent to an absorption tower after being cooled to 10-15 ℃.
In the purification step, the purification of the pyrolysis gas is performed between compression sections, preferably after three-section compression, and preferably, the purification comprises acid gas removal, drying and the like.
In the four decarburization steps, according to the invention, the number of theoretical plates of the four decarburization towers is preferably 25 to 80, and the operating pressure is preferably 0.5 to 2.5 MPa.
In the absorption step, the amount of the absorbent used in the absorption column is not particularly limited in the present invention, and can be determined by those skilled in the art based on the general knowledge of the prior art. The absorbent can be 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 carbon four-cut fraction containing n-butane and isobutane is preferred.
Preferably, the number of theoretical plates of the absorption tower is 25-60, the operating pressure is 2.0-6.0 MPa, and the tower top temperature is 10-40 ℃.
In the desorption step, the desorbed absorbent obtained at the bottom of the desorption tower can be cooled step by step and then returned to the absorption tower for recycling.
According to the invention, the number of theoretical plates of the desorption tower is preferably 20-60, and the operating pressure is preferably 1.0-4.0 MPa.
In the depropanization step, the invention has no particular limitation on the form of the carbohydrogenator and the catalyst, and the skilled person can determine the form according to the general knowledge in the prior art.
According to the invention, the number of theoretical plates of the depropanizer is preferably 20-80, and the operating pressure is preferably 0.5-4.0 MPa.
According to the present invention, preferably the depropanizer overhead stream controls the propylene content below 0.5% mol, preferably the depropanizer overhead stream is sent to the styrene plant as feed.
According to the present invention, if the cracked gas feed is high in propylene content, it is preferred to further refine the depropanizer bottoms, which preferably comprises:
(8) and (3) propylene rectification: the material at the tower bottom of the depropanizing tower firstly enters a carbon-three hydrogenation reactor and then enters a propylene rectifying tower, a propylene product is extracted at the side line, a propane product is extracted at the tower bottom, and the tower top returns to the space between compressor sections.
According to the present invention, the form and catalyst of the hydrocarbon three hydrogenation reactor are not particularly limited, and those skilled in the art can determine the form and catalyst based on the general knowledge of the prior art.
According to the invention, the number of theoretical plates of the propylene rectifying tower is preferably 80-280, and the operating pressure is preferably 0.1-4.0 MPa.
According to the present invention, preferably, the propane product is returned to the cracking furnace for use as a cracking feedstock.
In the de-heavy step, the invention has no special limitation on the form of the carbon four hydrogenation reactor and the catalyst, and the skilled person can determine the form according to the common knowledge in the prior art.
According to the invention, the theoretical plate number of the heavy component removing tower is preferably 20-80, and the operating pressure is preferably 0.1-2 MPa.
In the present invention, all the pressures are gauge pressures unless otherwise specified.
The separation method and the system of the pyrolysis gas have the following characteristics that:
(1) because the absorption-desorption method is adopted to remove light components such as methane, hydrogen and the like, a complete set of equipment such as a cold box and an ethylene refrigeration compressor is not needed, the energy consumption is saved, and the investment is obviously reduced.
(2) The carbon four fraction is fully hydrogenated and then used as a supplementary absorbent of the absorption tower, so that the supplementary absorbent is not needed to be purchased, and the device independence is strong.
(3) Because the absorption-desorption step removes light components such as methane, hydrogen and the like, the ethylene content in the crude ethylene product is high, and the obtained crude ethylene product is a high-quality raw material of a styrene device and can be continuously and finely separated. In addition, the propylene content in the product can be strictly controlled in the depropanizing step, so that the propylene content in the crude ethylene is low, the energy consumption of the device is effectively saved, and the energy consumption of the styrene device is effectively reduced.
(4) The pyrolysis gas separation method provided by the invention has the characteristics of low investment, low energy consumption and remarkable benefit.
Drawings
FIG. 1 is a schematic diagram of a cracked gas separation system of example 1;
FIG. 2 is a schematic diagram of a cracked gas separation system of example 2;
description of reference numerals:
1-1 compressor front section; 1-2 compressor rear section; 2, a purification system; 3, decarbonizing four towers; 4, an absorption tower; 5 a desorption tower; 6 a depropanizer; 7, a heavy component removing tower; 8, a hydrogenation reactor for carbon dioxide; a 9-carbon four-hydrogenation reactor; 10 a propylene rectification column; 11-carbon three-hydrogenation reactor; 20 cracking gas; 21 a crude ethylene product; 22 a propylene product; a 23 propane product; 24 a fuel gas; a 25 carbon four product; 26 gasoline products.
Detailed Description
While the present invention will be described in detail and with reference to the specific embodiments thereof, it should be understood that the following detailed description is only for illustrative purposes and is not intended to limit the scope of the present invention, as those skilled in the art will appreciate numerous insubstantial modifications and variations therefrom.
Example 1:
a cracked gas separation system as shown in fig. 1 is employed, comprising: a compressor (a compressor front section 1-1 and a compressor rear section 1-2); a purification system 2; a decarburization four tower 3; an absorption tower 4; a desorption tower 5; a depropanizer 6; a de-weighting tower 7; a carbo-hydrogenation reactor 8; a carbon four hydrogenation reactor 9.
The purification system 2 and the four decarbonization 7 towers 3 are sequentially connected between the compressor sections, the tops of the four decarbonization towers 3 are connected with the rear sections 1-2 of the compressors and then connected with the absorption tower 4, and the kettle 3 of the four decarbonization towers is connected with the de-weighting tower; the top of the heavy component removal tower 7 is connected with a carbon four hydrogenation reactor 9, and an outlet pipeline of the carbon four hydrogenation reactor 9 is combined with an outlet pipeline of the tower bottom of the desorption tower 5 and then connected with the upper part of the absorption tower 4;
the tower kettle of the absorption tower 4 is connected with a desorption tower 5; the top of the desorption tower 5 is connected with a depropanization tower 6, and the bottom of the desorption tower 5 is combined with an outlet pipeline of the four-carbon hydrogenation reactor 9 and then connected with the upper part of the absorption tower 4; the top of the depropanizer 6 is connected with a carbo-hydrogenation reactor 8.
A reboiler is arranged at the tower kettle of the absorption tower; the tower kettle of the desorption tower is provided with a reboiler.
The charge amount of the pyrolysis gas is 42000 kg/h. N-butane was chosen as absorbent.
The separation method of the pyrolysis gas comprises the following steps:
(1) compression: the cracked gas is compressed in five stages, the pressure is increased to 3.6MPag, and then the cracked gas is cooled to 15 ℃ and enters an absorption tower 4. (2) Purifying: cracked gas at the outlet of the three sections of the compressor enters a purification system 2 to remove acid gas, water and other impurities in the cracked gas.
(3) And fourthly, decarburization: the theoretical plate number of the four decarbonization towers is 40, and the operating pressure is 1 MPag. The purified cracking gas enters the middle part of a four-tower decarburization system, after more than four carbon components are removed, the gas phase at the top of the tower enters the rear section of a compressor to continuously increase the pressure, and the material at the bottom of the tower enters a heavy component removal tower.
(4) Absorption: the theoretical plate number of the absorption column 4 was 40, the operating pressure was 3.5MPag, and the column top temperature was 20 ℃. The used absorption solvent is saturated carbon four, the solvent enters the absorption tower from the top of the absorption tower 4, and the cracked gas enters from the 15 th tower plate. C2 and its heavy components in the cracked gas are absorbed by solvent and extracted from tower bottom, the tower top contains light components of methane, hydrogen, etc. and small amount of absorbent, and the absorbent is recovered through cooling and is used as fuel gas.
(5) Desorbing: the theoretical plate number of the desorption column 5 was 42, and the operating pressure was 2.3 MPag. The rich solvent absorbing the components such as C2 in the cracking gas enters a desorption tower from the 15 th tower plate, the desorbed C2 concentrated gas is extracted from the top of the tower, and after part of the lean solvent is extracted, the rest lean solvent is cooled to 15 ℃ after gradual heat exchange and returns to the absorption tower 4 for recycling.
(6) Depropanizing: the carbon two carbon three concentrated gas obtained from the top of the desorption tower 5 is sent to a depropanizer 6, the theoretical plate number of the depropanizer 6 is 35, and the operation pressure is 2.0 MPag. Crude ethylene gas is extracted from the tower top and sent to a carbon dioxide hydrogenation reactor 8 to be extracted as a crude ethylene product, and a propane product is extracted from the tower bottom.
(7) Removing weight: the theoretical plate number of the de-heavies column 7 was 39 and the operating pressure was 0.45 MPag. The material at the top of the heavy component removal tower is firstly hydrogenated into saturated hydrocarbon by a carbon four hydrogenation reactor, and then the saturated hydrocarbon is returned to the top of the absorption tower to be used as a supplementary absorbent, and the material at the bottom of the tower is extracted as a gasoline product.
The incoming pyrolysis gas composition is shown in table 1.
TABLE 1 cracked gas composition
| Composition of | Wt％ |
| Hydrogen gas | 1.15 |
| CO | 0.10 |
| CO2 | 0.02 |
| H2S | 0.01 |
| Methane | 14.92 |
| Acetylene | 0.52 |
| Ethylene | 29.57 |
| Ethane (III) | 3.77 |
| MAPD | 0.86 |
| Propylene (PA) | 10.31 |
| Propane | 0.50 |
| Butadiene | 3.09 |
| Butene (butylene) | 1.50 |
| Butane | 1.30 |
| C5+ | 6.45 |
| Water (W) | 25.92 |
The composition of the crude ethylene product obtained is shown in Table 2.
TABLE 2 crude ethylene product composition
| Composition of | mol％ |
| Methane | 13 |
| Ethylene | 77.4 |
| Ethane (III) | 8.9 |
| Propylene (PA) | 0.4 |
The other individual stream mass compositions are shown in table 3.
TABLE 3 Mass composition of the different streams
| 20 | 21 | 22 | 23 | 24 | 25 | |
| Hydrogen gas | 1.15 | 0.00 | 7.58 | 0.00 | 0.00 | 0.00 |
| CO | 0.10 | 0.00 | 0.69 | 0.00 | 0.00 | 0.00 |
| CO2 | 0.02 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| H2S | 0.01 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Methane | 14.92 | 7.79 | 80.82 | 0.00 | 0.00 | 0.01 |
| Acetylene | 0.52 | 0.28 | 0.07 | 3.20 | 0.00 | 0.00 |
| Ethylene | 29.57 | 81.28 | 0.91 | 0.48 | 0.00 | 0.04 |
| Ethane (III) | 3.77 | 10.01 | 0.00 | 1.23 | 0.00 | 0.01 |
| MAPD | 0.86 | 0.00 | 0.24 | 6.83 | 0.46 | 0.01 |
| Propylene (PA) | 10.31 | 0.63 | 0.25 | 83.37 | 0.24 | 0.06 |
| Propane | 0.50 | 0.00 | 0.05 | 4.09 | 0.06 | 0.00 |
| Butadiene | 3.09 | 0.00 | 0.00 | 0.00 | 0.00 | 0.08 |
| Butene (butylene) | 1.50 | 0.00 | 0.00 | 0.00 | 0.00 | 0.03 |
| Butane | 1.30 | 0.00 | 9.39 | 0.80 | 99.23 | 0.05 |
| C5+ | 6.45 | 0.00 | 0.00 | 0.00 | 0.01 | 99.71 |
| Water (W) | 25.92 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
In this example, the ethylene recovery was 99.0%.
Example 2:
a cracked gas separation system as shown in fig. 2 is employed, comprising: a compressor (a compressor front section 1-1 and a compressor rear section 1-2); a purification system 2; a decarburization four tower 3; an absorption tower 4; a desorption tower 5; a depropanizer 6; a de-weighting tower 7; a carbo-hydrogenation reactor 8; a carbon four hydrogenation reactor 9; a propylene rectifying column 10; a carbon three hydrogenation reactor 11.
The purification system 2 and the four decarbonization 7 towers 3 are sequentially connected between the compressor sections, the tops of the four decarbonization towers 3 are connected with the rear sections 1-2 of the compressors and then connected with the absorption tower 4, and the kettle 3 of the four decarbonization towers is connected with the de-weighting tower; the top of the heavy component removal tower 7 is connected with a carbon four hydrogenation reactor 9, and an outlet pipeline of the carbon four hydrogenation reactor 9 is combined with an outlet pipeline of the tower bottom of the desorption tower 5 and then connected with the upper part of the absorption tower 4;
the tower kettle of the absorption tower 4 is connected with a desorption tower 5; the top of the desorption tower 5 is connected with a depropanization tower 6, and the bottom of the desorption tower 5 is combined with an outlet pipeline of the four-carbon hydrogenation reactor 9 and then connected with the upper part of the absorption tower 4; the top of the depropanizing tower 6 is connected with a carbo-hydrogenation reactor 8; the bottom of the depropanizing tower 6 is connected with a carbon three hydrogenation reactor 11, the carbon three hydrogenation reactor 11 is connected with a propylene rectifying tower 10, and the top of the propylene rectifying tower 10 is connected with a compressor section.
A reboiler is arranged at the tower kettle of the absorption tower; the tower kettle of the desorption tower is provided with a reboiler.
The charge amount of pyrolysis gas was also 42000kg/h, and the specific composition is shown in Table 1. N-butane was chosen as absorbent.
The specific separation steps are the same as the first seven steps of the embodiment 1, and the difference is that the method comprises the following steps:
(8) and (3) propylene rectification: the material at the bottom of the depropanizing tower is firstly fed into a carbon-three hydrogenation reactor to remove the alkyne, dialkene and other impurities, and then fed into a propylene rectifying tower 10. The theoretical plate number of the propylene rectifying column 10 was 170, and the operating pressure was 1.7 MPag. The propylene product is extracted from the side line of the propylene rectifying tower, the top of the tower returns to the space between the compressor sections, and the propane product is extracted from the bottom of the tower.
The composition of the crude ethylene product obtained is shown in Table 4.
TABLE 4 crude ethylene product composition
| Composition of | mol％ |
| Methane | 13 |
| Ethylene | 77.4 |
| Ethane (III) | 8.9 |
| Propylene (PA) | 0.4 |
The composition of the propylene product obtained is shown in Table 5.
TABLE 5 propylene product composition
| Composition of | mol％ |
| Ethylene | 0.2 |
| Propylene (PA) | 99.7 |
| Propane | 0.1 |
The other individual stream mass compositions are shown in table 6.
TABLE 6 Mass composition of the different streams
| 20 | 21 | 22 | 23 | 24 | 25 | 26 | |
| Hydrogen gas | 1.15 | 0.01 | 0.00 | 0.00 | 7.65 | 0.00 | 0.00 |
| CO | 0.10 | 0.00 | 0.00 | 0.00 | 0.70 | 0.00 | 0.00 |
| CO2 | 0.02 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| H2S | 0.01 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Methane | 14.92 | 7.99 | 0.00 | 0.00 | 80.77 | 0.00 | 0.01 |
| Acetylene | 0.52 | 0.00 | 0.00 | 0.00 | 0.07 | 0.00 | 0.00 |
| Ethylene | 29.57 | 81.16 | 0.13 | 0.00 | 0.94 | 0.00 | 0.04 |
| Ethane (III) | 3.77 | 10.21 | 0.00 | 0.00 | 0.00 | 0.00 | 0.01 |
| MAPD | 0.86 | 0.00 | 0.00 | 0.00 | 0.20 | 0.39 | 0.01 |
| Propylene (PA) | 10.31 | 0.63 | 99.77 | 1.83 | 0.17 | 0.16 | 0.06 |
| Propane | 0.50 | 0.00 | 0.10 | 81.72 | 0.04 | 0.04 | 0.00 |
| Butadiene | 3.09 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.08 |
| Butene (butylene) | 1.50 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.03 |
| Butane | 1.30 | 0.00 | 0.00 | 16.44 | 9.47 | 99.41 | 0.05 |
| C5+ | 6.45 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 99.71 |
| Water (W) | 25.92 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
In this example, the ethylene recovery was 99.0% and the propylene recovery was 98%.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not 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 described embodiments.
Claims (10)
1. A cracked gas separation system using absorption-desorption, the system comprising:
the system comprises a compressor, a purification system, a four-decarbonization tower, an absorption tower, a desorption tower, a depropanization tower, a de-heavy tower, a carbon-two hydrogenation reactor and a carbon-four hydrogenation reactor; wherein,
the purification system and the four decarburization towers are sequentially connected between the compressor sections, the four decarburization towers are connected with the rear section of the compressor and then connected with the absorption tower, and the four decarburization tower kettles are connected with the heavy component removal tower; the top of the heavy component removal tower is connected with a carbon four hydrogenation reactor, and an outlet pipeline of the carbon four hydrogenation reactor is combined with an outlet pipeline of the tower kettle of the desorption tower and then connected with the upper part of the absorption tower;
the tower kettle of the absorption tower is connected with a desorption tower; the top of the desorption tower is connected with a depropanizing towerSuction deviceThe tower kettle and the outlet pipeline of the four-carbon hydrogenation reactor are combined and then connected with the upper part of the absorption tower; the top of the depropanizing tower is connected with a carbo-hydrogenation reactor.
2. The cracked gas separation system of claim 1, wherein:
the bottom of the depropanization tower is connected with a carbon three hydrogenation reactor, the carbon three hydrogenation reactor is connected with a propylene rectifying tower, and the top of the propylene rectifying tower is connected with a compressor section.
3. The cracked gas separation system of claim 1, wherein:
a reboiler is arranged at the tower kettle of the absorption tower; and/or the presence of a gas in the gas,
the tower kettle of the desorption tower is provided with a reboiler.
4. The cracked gas separation system of claim 1, wherein:
and an outlet pipeline of the tower kettle of the desorption tower is divided into two paths, one path is extracted, and the other path is combined with an outlet pipeline of the four-carbon hydrogenation reactor and then connected with the upper part of the absorption tower.
5. A cracked gas separation method using the system as claimed in any one of claims 1 to 4, characterized in that the method comprises:
(1) after compression, pressure increase and purification, the pyrolysis gas enters a four-tower decarburization device to remove more than four carbon components;
(2) compressing the top material flow of the four decarbonization towers, then sending the material flow into an absorption tower to remove light components, and sending the kettle material flow of the four decarbonization towers into a de-weighting tower;
(3) extracting light components from the top of the absorption tower, feeding the material flow in the bottom of the absorption tower into a desorption tower, and feeding the material at the top of the desorption tower into a depropanizing tower; returning the material in the tower kettle of the desorption tower to the absorption tower;
(4) extracting a gasoline product from the tower kettle of the de-heavy tower, enabling the material flow at the top of the de-heavy tower to enter a carbon four hydrogenation reactor, combining the material flow at the outlet of the carbon four hydrogenation reactor with the material flow at the tower kettle of the desorption tower, and then enabling the combined material flow to enter an absorption tower;
(5) removing alkyne from the material at the top of the depropanizing tower by a carbo-hydrogenation reactor, and then extracting a crude ethylene product; the propane product is extracted from the tower bottom of the depropanizing tower.
6. The pyrolysis gas separation method according to claim 5, characterized in that:
the method further comprises (6),
the material in the bottom of the depropanizing tower enters a carbon-three hydrogenation reactor for reaction and then enters a propylene rectifying tower, a propylene product is extracted at the side line, a propane product is extracted at the bottom of the depropanizing tower, and the tower top returns to the space between compressor sections.
7. The pyrolysis gas separation method according to claim 5, characterized in that:
adopting five-section compression to increase the pressure of the cracking gas to 2-5 MPag, then cooling to 10-15 ℃, and then feeding into an absorption tower;
the purification is carried out between compression sections, preferably after three-section compression, the pyrolysis gas purification is carried out.
8. The pyrolysis gas separation method according to claim 5, characterized in that:
the absorbent of the absorption tower 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 depropanizer overhead stream controls the propylene content to be less than 0.5% mol.
9. The pyrolysis gas separation method according to claim 5, characterized in that:
the number of theoretical plates of the four decarburization towers is 25-80, and the operating pressure is 0.5-2.5 MPa;
the number of theoretical plates of the absorption tower is 25-60, the operating pressure is 2.0-6.0 MPa, and the temperature of the tower top is 10-40 ℃;
the number of theoretical plates of the desorption tower is 20-60, and the operating pressure is 1.0-4.0 MPa;
the number of theoretical plates of the depropanizing tower is 20-80, and the operating pressure is 0.5-4.0 MPa;
the number of theoretical plates of the de-heavy tower is 20-80, and the operating pressure is 0.1-2 MPa.
10. The pyrolysis gas separation method according to claim 6, characterized in that:
the number of theoretical plates of the propylene rectifying tower is 80-280, and the operating pressure is 0.1-4.0 MPa.
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| CN109678635A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of utilization method of saturated hydrocarbons cracking gas separating system and rich ethane/propane saturated hydrocarbons |
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| GB1236164A (en) * | 1969-05-19 | 1971-06-23 | Harold Newby | Separation of pyrolysis gases |
| CN101353286A (en) * | 2007-07-25 | 2009-01-28 | 上海惠生化工工程有限公司 | Non-copious cooling lower carbon number hydrocarbons separation method containing light gas |
| CN103159581A (en) * | 2011-12-12 | 2013-06-19 | 中国石油化工股份有限公司 | System and method for preparing polymer-grade propylene through absorption and separation of catalytic cracking product gas |
| CN109678635A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of utilization method of saturated hydrocarbons cracking gas separating system and rich ethane/propane saturated hydrocarbons |
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