CN117003610A - Acetonitrile method hydrogenation rectifying butadiene extraction device and method - Google Patents
Acetonitrile method hydrogenation rectifying butadiene extraction device and method Download PDFInfo
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- CN117003610A CN117003610A CN202210468047.5A CN202210468047A CN117003610A CN 117003610 A CN117003610 A CN 117003610A CN 202210468047 A CN202210468047 A CN 202210468047A CN 117003610 A CN117003610 A CN 117003610A
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 246
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 128
- 238000000605 extraction Methods 0.000 title claims abstract description 127
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 53
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 130
- 238000007670 refining Methods 0.000 claims abstract description 58
- 238000005406 washing Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims description 65
- 238000007599 discharging Methods 0.000 claims description 59
- 238000010992 reflux Methods 0.000 claims description 48
- 239000007789 gas Substances 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 20
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- 238000005336 cracking Methods 0.000 claims description 7
- 150000005673 monoalkenes Chemical class 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- -1 acetylene hydrocarbon Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims 2
- LPVADQSSULMHLG-UHFFFAOYSA-N acetonitrile buta-1,3-diene Chemical compound CC#N.C=CC=C LPVADQSSULMHLG-UHFFFAOYSA-N 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- 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
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- 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
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00006—Large-scale industrial plants
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- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention belongs to the field of butadiene extraction devices by an acetonitrile method, and relates to a device and a method for extracting butadiene by hydrogenation rectification by the acetonitrile method. The device comprises a first extraction tower system, a first stripping tower system, an alkyne selective hydrogenation reaction rectification system, a second extraction tower system, a water washing tower system and a butadiene refining system; the bottom discharge pipeline of the first extraction tower system is connected with the first stripping tower system, the side discharge pipeline of the first stripping tower system is connected with the alkyne selective hydrogenation reaction rectifying system, and the bottom discharge pipeline of the first stripping tower system is connected with the second extraction tower system; the top discharge pipeline of the second extraction tower system is sequentially connected with the water washing tower system and the butadiene refining system, and the bottom discharge pipeline of the second extraction tower system is connected with the first stripping tower system. According to the invention, the alkyne couples the selective hydrogenation rectification system with the traditional acetonitrile butadiene extraction device, so that the stability of the operation of the extraction device is ensured, and the purpose of canceling the second stripping system is realized.
Description
Technical Field
The invention belongs to the field of acetonitrile method butadiene extraction devices, and particularly relates to an acetonitrile method hydrogenation rectifying butadiene extraction device and method.
Background
The butadiene extraction device is used for extracting butadiene through two-stage extraction and four-carbon refining process flows, an acetonitrile method is taken as an example, a typical flow is shown in figure 1, the primary extraction is to separate mono-olefin and alkane from di-olefin and alkyne, the secondary extraction is to further separate di-olefin from alkyne to remove alkyne, the water washing system is to remove solvent, and the refining system is to remove light and heavy components. The traditional butadiene extraction device adopts a two-stage extraction process, the process flow is long, and the energy consumption and the investment are relatively high. In addition, the traditional alkyne tail gas treatment method is a newly added fixed bed hydrogenation system, and a certain equipment investment is required.
Along with the development and application maturity of the selective hydrogenation catalyst, if the catalyst is applied to the flow of the butadiene extraction device, a hydrogenation system is not added independently, and a second stripping tower can be omitted, so that about 10% -15% of energy consumption of the whole device is saved, the reaction rectifying tower is coupled with the traditional butadiene extraction device in a reasonable range while the alkyne removal rate and the butadiene loss rate are controlled, the economical efficiency and the environmental protection of the device are greatly improved, the comprehensive energy consumption of the device is reduced, and the comprehensive utilization value of four carbon is increased.
Three key problems exist in alkyne selective hydrogenation technology: the selectivity and the conversion rate of alkyne are ensured through the catalyst and the operation condition, and meanwhile, the loss of butadiene is reduced; heavy component and purge gas generated by hydrogenation reaction are discharged; reducing the equipment in the butadiene extraction process flow and the problem of equipment quantity increase caused by hydrogenation. Meanwhile, three problems can be solved, namely industrialization can be realized, investment is reduced, and project economy is guaranteed.
The current method for producing butadiene-rich products by alkyne selective hydrogenation of a butadiene extraction device mainly comprises three steps, wherein alkyne-containing materials extracted from the side line of a debutanizer of a first ethylene device are hydrogenated and then returned to the debutanizer, cracking carbon four raw materials of a second butadiene extraction device are selectively hydrogenated and then enter the extraction device, and the alkyne-containing materials extracted from a high alkyne position in the butadiene extraction device are selectively hydrogenated.
CN102381920 hydrotreats alkyne-containing materials from the side line of a debutanizer of an ethylene unit, CN101172929 converts alkynes into butadiene-rich materials by pre-hydrotreating cracking carbon four materials, but both approaches require a fixed bed hydrogenation system to be separately arranged, thus increasing equipment investment; meanwhile, no matter side-draw materials or cracking carbon four raw materials contain high-concentration butadiene, and the loss of butadiene in the hydrogenation process is difficult to avoid. And the boiling point of vinyl acetylene is very close to that of butadiene, the acetylene is difficult to realize separation hydrogenation from a side line, alkyne still enters a butadiene extraction device from the top of a debutanizer, and the product qualification is difficult to ensure.
The process for extracting butadiene by using the NMP method through the US2003181772 realizes the selective hydrogenation of alkyne-containing materials through a dividing wall tower and a coupling rectifying tower, the method realizes the purposes of removing alkyne and increasing butadiene yield through reactive distillation, the process flow is simple, a single dividing wall tower can realize the purposes of extractive distillation, alkyne separation and alkyne selective hydrogenation, but the dividing wall tower of the process equipment is more complicated, the increase of internal components causes easy polymerization of diene and alkyne, coking and material loss are caused, the industrialization difficulty is high, and the process flow is only aimed at NMP solvent.
Aiming at the problems, the invention develops a hydrogenation reaction rectification system aiming at the process flow of extracting butadiene by an acetonitrile method, which not only can realize that a fixed bed hydrogenation system is not added, but also can simplify the structure of process equipment, saves energy and reduces consumption, and simultaneously is convenient for realizing industrial application.
Disclosure of Invention
The invention aims to solve the problems of long flow, high energy consumption and low raw material utilization rate of the existing butadiene device, and provides an acetonitrile method hydrogenation rectifying butadiene extraction device and method.
In order to achieve the above object, a first aspect of the present invention provides an acetonitrile method hydrofracterized butadiene extraction device, comprising a first extraction tower system, a first stripping tower system, an alkyne selective hydrogenation rectification system, a second extraction tower system, a water washing tower system and a butadiene refining system;
the first extraction tower system is provided with a raw material feeding pipeline, a first extraction tower system top discharging pipeline and a first extraction tower system bottom discharging pipeline, the first extraction tower system bottom discharging pipeline is connected with a first stripping tower system, the first stripping tower system is provided with a first stripping tower system top discharging pipeline, a first stripping tower system bottom discharging pipeline and a first stripping tower system side line discharging pipeline, the first stripping tower system top discharging pipeline is connected with the lower part of a second extraction tower system, and the first stripping tower system side line discharging pipeline is connected with an alkyne selective hydrogenation rectifying system;
the alkyne selective hydrogenation rectification system is provided with a hydrogen feeding pipeline, an alkyne selective hydrogenation rectification system top discharging pipeline, an alkyne selective hydrogenation rectification system bottom discharging pipeline and an alkyne selective hydrogenation rectification system lateral line discharging pipeline, the alkyne selective hydrogenation rectification system lateral line discharging pipeline is connected with the upper part of the first stripping tower, and the alkyne selective hydrogenation rectification system bottom discharging pipeline is connected with the lower part of the first stripping tower system;
the discharging pipeline at the bottom of the first stripping tower system is divided into two branches, one branch is connected with the upper part of the first extraction tower system, and the other branch is connected with the upper part of the second extraction tower system;
the second extraction tower system is provided with a second extraction tower system top discharge pipeline and a second extraction tower system bottom discharge pipeline, the second extraction tower system top discharge pipeline is connected with the water washing tower system and the butadiene refining system in sequence, and the second extraction tower system bottom discharge pipeline is connected with the upper part of the first stripping tower system.
The second aspect of the invention provides a method for extracting butadiene by acetonitrile method hydrogenation rectification, which is carried out by adopting the device for extracting butadiene by acetonitrile method hydrogenation rectification, and comprises the following steps:
feeding the acetylene-containing cracking carbon four raw materials into a first extraction tower system, extracting raffinate containing mono-olefin and alkane from the tower top, feeding a solvent rich in di-olefin and alkyne extracted from the tower bottom into the first stripping tower system to separate the solvent and the carbon four, feeding the material at the top of the first stripping tower system into the lower part of a second extraction system, feeding the material with higher vinyl acetylene concentration extracted from the side line of the first stripping tower system into an alkyne selective hydrogenation reaction rectification system to carry out alkyne selective hydrogenation and rectification reaction with hydrogen;
the carbon four materials with higher butadiene concentration are extracted from the lateral line of the alkyne selective hydrogenation reaction rectification system and returned to the upper part of the first stripping tower system, the purge gas at the top of the alkyne selective hydrogenation reaction rectification system is sent out of the boundary, and the materials at the bottom of the alkyne selective hydrogenation reaction rectification system are sent to the lower part of the first stripping tower;
the bottom material of the first stripping tower system is divided into two parts, one part is sent to the upper part of the first extraction tower system, the other part is sent to the upper part of the second extraction tower system, the top material of the second extraction tower system is sequentially sent to the water washing tower system and the butadiene refining system, and the bottom material of the second extraction tower system is returned to the first stripping tower system.
The invention has the beneficial effects that:
1) The selective hydrogenation reaction rectification system is arranged to increase the comprehensive utilization efficiency of the carbon four;
2) The vinyl acetylene is converted into butadiene by arranging an alkyne selective hydrogenation reaction rectification system, so that the yield of butadiene is increased, and the economy of the device is improved;
3) The second stripping tower system is omitted by arranging the alkyne selective hydrogenation reaction rectification system, and meanwhile, a fixed bed hydrogenation system is not added, so that the comprehensive energy consumption is reduced, and the investment is saved;
4) The alkyne selective hydrogenation rectification system is arranged, so that noncondensable gas, carbon five, polymer and other heavy components generated in the reaction process can be removed, the operation stability of the extraction device is ensured, and the polymerization risk is reduced;
5) The concentration of vinyl acetylene can be reduced by arranging an alkyne selective hydrogenation reaction rectification system, so that the operation safety of the device is ensured;
6) The invention is preferably nickel-based catalyst, and has outstanding economic benefit;
7) The second extraction tower and alkyne selective hydrogenation rectification system can realize that alkyne does not enter the refining system, and the qualified butadiene product is ensured.
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 flow chart of a conventional butadiene extraction device by acetonitrile method.
FIG. 2 is a flow chart of the apparatus for extracting butadiene by hydro-rectifying acetonitrile method of the invention.
FIG. 3 is a detailed view of the alkyne selective hydrogenation rectification system of the present invention.
Reference numerals illustrate:
the device comprises a first extraction tower system 1, a first stripping tower system 2, a second extraction tower system 3, a second stripping tower system 4, a water washing tower system 5, a butadiene refining system light component removal tower 6, a butadiene refining system heavy component removal tower 7, an alkyne selective hydrogenation reaction rectifying tower 8, a tower top condenser 9, a tower top reflux tank 10, a tail gas cooler 11 and a reflux pump 12.
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. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
In order to achieve the above object, a first aspect of the present invention provides an acetonitrile method hydrofracterized butadiene extraction device, comprising a first extraction tower system, a first stripping tower system, an alkyne selective hydrogenation rectification system, a second extraction tower system, a water washing tower system and a butadiene refining system;
the first extraction tower system is provided with a raw material feeding pipeline, a first extraction tower system top discharging pipeline and a first extraction tower system bottom discharging pipeline, the first extraction tower system bottom discharging pipeline is connected with a first stripping tower system, the first stripping tower system is provided with a first stripping tower system top discharging pipeline, a first stripping tower system bottom discharging pipeline and a first stripping tower system side line discharging pipeline, the first stripping tower system top discharging pipeline is connected with the lower part of a second extraction tower system, and the first stripping tower system side line discharging pipeline is connected with an alkyne selective hydrogenation rectifying system;
the alkyne selective hydrogenation rectification system is provided with a hydrogen feeding pipeline, an alkyne selective hydrogenation rectification system top discharging pipeline, an alkyne selective hydrogenation rectification system bottom discharging pipeline and an alkyne selective hydrogenation rectification system lateral line discharging pipeline, the alkyne selective hydrogenation rectification system lateral line discharging pipeline is connected with the upper part of the first stripping tower, and the alkyne selective hydrogenation rectification system bottom discharging pipeline is connected with the lower part of the first stripping tower system;
the discharging pipeline at the bottom of the first stripping tower system is divided into two branches, one branch is connected with the upper part of the first extraction tower system, and the other branch is connected with the upper part of the second extraction tower system;
the second extraction tower system is provided with a second extraction tower system top discharge pipeline and a second extraction tower system bottom discharge pipeline, the second extraction tower system top discharge pipeline is connected with the water washing tower system and the butadiene refining system in sequence, and the second extraction tower system bottom discharge pipeline is connected with the upper part of the first stripping tower system.
In the invention, the first extraction tower system, the first stripping tower system, the second extraction tower system, the water washing tower system and the butadiene refining system of the butadiene extraction device are all typically arranged in a conventional butadiene extraction device.
According to the invention, preferably, the alkyne selective hydrogenation rectification system comprises an alkyne selective hydrogenation rectification column, a top condenser, a top reflux tank, a tail gas cooler and a reflux pump;
the lateral line extraction pipeline of the first stripping tower system is connected with an alkyne selective hydrogenation reaction rectifying tower, and the alkyne selective hydrogenation reaction rectifying tower is provided with an alkyne selective hydrogenation reaction rectifying tower top discharge pipeline, an alkyne selective hydrogenation reaction rectifying tower lateral line discharge pipeline and an alkyne selective hydrogenation reaction rectifying tower bottom discharge pipeline; the top discharge pipeline of the alkyne selective hydrogenation reaction rectifying tower is sequentially connected with a tower top condenser and a tower top reflux tank, the tower top reflux tank is provided with a top discharge pipeline of the tower top reflux tank and a bottom discharge pipeline of the tower top reflux tank, and the top discharge pipeline of the tower top reflux tank is connected with a tail gas cooler; the tail gas cooler is provided with a top discharge pipeline of the tail gas cooler and a bottom discharge pipeline of the tail gas cooler, the bottom discharge pipeline of the tail gas cooler is connected with a top reflux tank, and the bottom discharge pipeline of the top reflux tank is sequentially connected with a reflux pump and the lower part of the alkyne selective hydrogenation rectifying tower; the discharging pipeline at the bottom of the alkyne selective hydrogenation reaction rectifying tower is connected with the lower part of the first stripping tower system; and a lateral line discharge pipeline of the alkyne selective hydrogenation rectifying tower is connected with the upper part of the first stripping tower system.
According to the present invention, preferably, the butadiene refining system includes a butadiene refining system light ends removal column and a butadiene refining system heavy ends removal column;
the light-off tower of the butadiene refining system is provided with a light-off tower top discharge pipeline of the butadiene refining system and a light-off tower bottom discharge pipeline of the butadiene refining system, and the light-off tower bottom discharge pipeline of the butadiene refining system is connected with the heavy-off tower of the butadiene refining system;
the heavy-removal tower of the butadiene refining system is provided with a heavy-removal tower top discharge pipeline of the butadiene refining system and a heavy-removal tower bottom discharge pipeline of the butadiene refining system.
The second aspect of the invention provides a method for extracting butadiene by acetonitrile method hydrogenation rectification, which is carried out by adopting the device for extracting butadiene by acetonitrile method hydrogenation rectification, and comprises the following steps:
feeding the acetylene-containing cracking carbon four raw materials into a first extraction tower system, extracting raffinate containing mono-olefin and alkane from the tower top, feeding a solvent rich in di-olefin and alkyne extracted from the tower bottom into the first stripping tower system to separate the solvent and the carbon four, feeding the material at the top of the first stripping tower system into the lower part of a second extraction system, feeding the material with higher vinyl acetylene concentration extracted from the side line of the first stripping tower system into an alkyne selective hydrogenation reaction rectification system to carry out alkyne selective hydrogenation and rectification reaction with hydrogen;
the carbon four materials with higher butadiene concentration are extracted from the lateral line of the alkyne selective hydrogenation reaction rectification system and returned to the upper part of the first stripping tower system, the purge gas at the top of the alkyne selective hydrogenation reaction rectification system is sent out of the boundary, and the materials at the bottom of the alkyne selective hydrogenation reaction rectification system are sent to the lower part of the first stripping tower;
the bottom material of the first stripping tower system is divided into two parts, one part is sent to the upper part of the first extraction tower system, the other part is sent to the upper part of the second extraction tower system, the top material of the second extraction tower system is sequentially sent to the water washing tower system and the butadiene refining system, and the bottom material of the second extraction tower system is returned to the first stripping tower system.
According to the invention, the materials at the top of the first stripping tower system are returned to the second extraction tower system, and the solvent is used for extracting and returning the alkyne-containing materials which are not fed into the hydrogenation reaction rectification system to the first stripping tower system again, so that no alkyne is contained in the subsequent butadiene product.
According to the invention, preferably, the material with higher vinyl acetylene concentration extracted from the side line of the first stripping tower system and hydrogen are sent into an alkyne selective hydrogenation rectifying tower, the material at the top of the alkyne selective hydrogenation rectifying tower sequentially enters a tower top condenser and a tower top reflux tank, the material at the top of the tower top reflux tank enters a tail gas cooler for cooling, the uncondensed gas phase material is discharged out of the side line from the top, and the material at the bottom of the tail gas cooler returns to the tower top reflux tank; the material at the bottom of the tower top reflux tank is sequentially connected with a reflux pump and an alkyne selective hydrogenation rectifying tower; the acetylene hydrocarbon selective hydrogenation reaction rectifying tower side line is used for extracting carbon four materials with higher butadiene concentration and returns to the upper part of the first stripping tower; and feeding the material at the bottom of the alkyne selective hydrogenation rectifying tower into the lower part of the first stripping tower.
According to the invention, preferably, the top material of the water washing tower system is sent to a light component removing tower of a butadiene refining system, light components are separated from the tower top and sent to the outside, the bottom material of the light component removing tower of the butadiene refining system is sent to a heavy component removing tower of the butadiene refining system, heavy components are separated from the tower bottom, and a butadiene product is obtained from the tower top.
According to the invention, preferably, the alkyne-containing cracked carbon tetraraw material comprises alkynes, diolefins, and mono-olefins and/or alkanes; wherein the butadiene content is 20-70 wt% and the vinyl acetylene content is 0.1-10 wt%.
According to the present invention, preferably, the butadiene content is 40wt% to 55wt% and the vinyl acetylene content is 0.5wt% to 5wt%.
According to the invention, preferably, the catalyst of the alkyne selective hydrogenation rectifying tower is positioned in the rectifying section, and a catalyst cloth bag is used for filling a tray or a supported catalyst is used; the catalyst is a nickel-based catalyst and/or a palladium-based catalyst, preferably a nickel-based catalyst.
According to the present invention, preferably, wherein the selective hydroprocessing conditions comprise: the operation temperature is 35-90 ℃, the operation pressure is 0-1.0 MPaG, the reaction temperature rise is 5-25 ℃, the mole ratio of the hydrogen and the alkyne is 0.5-5, the number of the tower plates is 20-100, and the reflux ratio is 5-50.
Example 1
The embodiment adopts an acetonitrile method hydrogenation rectifying butadiene extraction device shown in fig. 2 and 3, and comprises a first extraction tower system, a first stripping tower system, an alkyne selective hydrogenation rectifying system, a second extraction tower system, a water washing tower system and a butadiene refining system;
the first extraction tower system is provided with a raw material feeding pipeline, a first extraction tower system top discharging pipeline and a first extraction tower system bottom discharging pipeline, the first extraction tower system bottom discharging pipeline is connected with the first stripping tower system, the first stripping tower system is provided with a first stripping tower system top discharging pipeline, a first stripping tower system bottom discharging pipeline and a first stripping tower system side discharging pipeline, the first stripping tower system top discharging pipeline is connected with the lower part of the second extraction tower system, the first stripping tower system side discharging pipeline is connected with the first stripping tower system side discharging pipeline and is connected with an alkyne selective hydrogenation rectifying tower, and the alkyne selective hydrogenation rectifying tower is provided with an alkyne selective hydrogenation rectifying tower top discharging pipeline, an alkyne selective hydrogenation rectifying tower side discharging pipeline and an alkyne selective hydrogenation rectifying tower bottom discharging pipeline; the top discharge pipeline of the alkyne selective hydrogenation reaction rectifying tower is sequentially connected with a tower top condenser and a tower top reflux tank, the tower top reflux tank is provided with a top discharge pipeline of the tower top reflux tank and a bottom discharge pipeline of the tower top reflux tank, and the top discharge pipeline of the tower top reflux tank is connected with a tail gas cooler; the tail gas cooler is provided with a top discharge pipeline of the tail gas cooler and a bottom discharge pipeline of the tail gas cooler, the bottom discharge pipeline of the tail gas cooler is connected with a top reflux tank, and the bottom discharge pipeline of the top reflux tank is sequentially connected with a reflux pump and the lower part of the alkyne selective hydrogenation rectifying tower; the discharging pipeline at the bottom of the alkyne selective hydrogenation reaction rectifying tower is connected with the lower part of the first stripping tower system; the lateral line discharge pipeline of the alkyne selective hydrogenation rectifying tower is connected with the upper part of the first stripping tower system;
the discharging pipeline at the bottom of the first stripping tower system is divided into two branches, one branch is connected with the upper part of the first extraction tower system, and the other branch is connected with the upper part of the second extraction tower system;
the second extraction tower system is provided with a second extraction tower system top discharge pipeline and a second extraction tower system bottom discharge pipeline, the second extraction tower system bottom discharge pipeline is connected with the upper part of the first stripping tower system, the second extraction tower system top discharge pipeline is sequentially connected with a water washing tower system and a butadiene refining system light ends removal tower, the butadiene refining system light ends removal tower is provided with a butadiene refining system light ends removal tower top discharge pipeline and a butadiene refining system light ends removal tower bottom discharge pipeline, and the butadiene refining system light ends removal tower bottom discharge pipeline is connected with the butadiene refining system heavy ends removal tower; the heavy-removal tower of the butadiene refining system is provided with a heavy-removal tower top discharge pipeline of the butadiene refining system and a heavy-removal tower bottom discharge pipeline of the butadiene refining system.
The method for extracting the hydrocracked butadiene by the acetonitrile method comprises the following steps of:
feeding the acetylene-containing cracking carbon four raw materials into a first extraction tower system, extracting raffinate containing mono-olefin and alkane from the tower top, feeding a solvent rich in di-olefin and alkyne extracted from the tower bottom into the first stripping tower system to separate the solvent and the carbon four, feeding a material at the top of the first stripping tower system into the lower part of a second extraction system, feeding a material with higher vinyl acetylene concentration extracted from the side line of the first stripping tower system and hydrogen into an alkyne selective hydrogenation reaction rectifying tower, feeding a material at the top of the alkyne selective hydrogenation reaction rectifying tower into a tower top condenser and a tower top reflux tank in sequence, feeding a material at the top of the tower top reflux tank into a tail gas cooler to be cooled, discharging uncondensed gas phase materials out of the boundary from the top, and feeding a material at the bottom of the tail gas cooler into the tower top reflux tank; the material at the bottom of the tower top reflux tank is sequentially connected with a reflux pump and an alkyne selective hydrogenation rectifying tower; the acetylene hydrocarbon selective hydrogenation reaction rectifying tower side line is used for extracting carbon four materials with higher butadiene concentration and returns to the upper part of the first stripping tower; feeding the material at the bottom of the alkyne selective hydrogenation rectifying tower into the lower part of the first stripping tower;
the method comprises the steps that a material at the bottom of a first stripping tower system is divided into two parts, one part is sent to the upper part of the first extraction tower system, the other part is sent to the upper part of a second extraction tower system, alkyne-containing material at the bottom of the second extraction tower system is extracted and returned to the first stripping tower system again, material at the top of the second extraction tower system is sequentially sent to a water washing tower system, material at the top of the water washing tower system is sent to a butadiene refining system light component removing tower, light components are separated from the tower top and sent to the tower bottom of the butadiene refining system light component removing tower, heavy components are separated from the tower bottom of the butadiene refining system light component removing tower, and butadiene products are obtained from the tower top.
The composition of the cracked C4 feedstock is shown in Table 1 below (an example is a 20 ten thousand ton/year butadiene unit)
TABLE 1
The catalyst adopts a nickel-based catalyst, the selective hydrogenation operation condition temperature is 80 ℃, the operation pressure is 0.07MPaG, the reaction temperature rise is 5-25 ℃, and the molar ratio of the alkyne (the sum of alkyne and diene) is 1; the overhead operating temperature was 70 ℃, the number of trays was 40, and the reflux ratio was 10.
Because the second extraction tower can ensure that high-concentration carbon tetrayne is positioned in the middle of the first stripping tower, the requirement of the selective hydrogenation rectification system on the single-pass conversion rate is not high (the single-pass conversion rate reaches 80 percent, the final conversion rate is close to 100 percent), the selectivity can reach more than 40 percent, and the economic benefit is considerable.
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 (10)
1. The device is characterized by comprising a first extraction tower system, a first stripping tower system, an alkyne selective hydrogenation reaction rectification system, a second extraction tower system, a water washing tower system and a butadiene refining system;
the first extraction tower system is provided with a raw material feeding pipeline, a first extraction tower system top discharging pipeline and a first extraction tower system bottom discharging pipeline, the first extraction tower system bottom discharging pipeline is connected with a first stripping tower system, the first stripping tower system is provided with a first stripping tower system top discharging pipeline, a first stripping tower system bottom discharging pipeline and a first stripping tower system side line discharging pipeline, the first stripping tower system top discharging pipeline is connected with the lower part of a second extraction tower system, and the first stripping tower system side line discharging pipeline is connected with an alkyne selective hydrogenation rectifying system;
the alkyne selective hydrogenation rectification system is provided with a hydrogen feeding pipeline, an alkyne selective hydrogenation rectification system top discharging pipeline, an alkyne selective hydrogenation rectification system bottom discharging pipeline and an alkyne selective hydrogenation rectification system lateral line discharging pipeline, the alkyne selective hydrogenation rectification system lateral line discharging pipeline is connected with the upper part of the first stripping tower, and the alkyne selective hydrogenation rectification system bottom discharging pipeline is connected with the lower part of the first stripping tower system;
the discharging pipeline at the bottom of the first stripping tower system is divided into two branches, one branch is connected with the upper part of the first extraction tower system, and the other branch is connected with the upper part of the second extraction tower system;
the second extraction tower system is provided with a second extraction tower system top discharge pipeline and a second extraction tower system bottom discharge pipeline, the second extraction tower system top discharge pipeline is connected with the water washing tower system and the butadiene refining system in sequence, and the second extraction tower system bottom discharge pipeline is connected with the upper part of the first stripping tower system.
2. The acetonitrile method hydro-rectifying butadiene extraction device according to claim 1, wherein the alkyne selective hydrogenation rectifying system comprises an alkyne selective hydrogenation rectifying tower, a tower top condenser, a tower top reflux tank, a tail gas cooler and a reflux pump;
the lateral line extraction pipeline of the first stripping tower system is connected with an alkyne selective hydrogenation reaction rectifying tower, and the alkyne selective hydrogenation reaction rectifying tower is provided with an alkyne selective hydrogenation reaction rectifying tower top discharge pipeline, an alkyne selective hydrogenation reaction rectifying tower lateral line discharge pipeline and an alkyne selective hydrogenation reaction rectifying tower bottom discharge pipeline; the top discharge pipeline of the alkyne selective hydrogenation reaction rectifying tower is sequentially connected with a tower top condenser and a tower top reflux tank, the tower top reflux tank is provided with a top discharge pipeline of the tower top reflux tank and a bottom discharge pipeline of the tower top reflux tank, and the top discharge pipeline of the tower top reflux tank is connected with a tail gas cooler; the tail gas cooler is provided with a top discharge pipeline of the tail gas cooler and a bottom discharge pipeline of the tail gas cooler, the bottom discharge pipeline of the tail gas cooler is connected with a top reflux tank, and the bottom discharge pipeline of the top reflux tank is sequentially connected with a reflux pump and the lower part of the alkyne selective hydrogenation rectifying tower; the discharging pipeline at the bottom of the alkyne selective hydrogenation reaction rectifying tower is connected with the lower part of the first stripping tower system; and a lateral line discharge pipeline of the alkyne selective hydrogenation rectifying tower is connected with the upper part of the first stripping tower system.
3. The acetonitrile method hydrocracked butadiene extraction device of claim 1, wherein the butadiene refining system comprises a butadiene refining system light ends removal column and a butadiene refining system heavy ends removal column;
the light-off tower of the butadiene refining system is provided with a light-off tower top discharge pipeline of the butadiene refining system and a light-off tower bottom discharge pipeline of the butadiene refining system, and the light-off tower bottom discharge pipeline of the butadiene refining system is connected with the heavy-off tower of the butadiene refining system;
the heavy-removal tower of the butadiene refining system is provided with a heavy-removal tower top discharge pipeline of the butadiene refining system and a heavy-removal tower bottom discharge pipeline of the butadiene refining system.
4. An acetonitrile method for extracting butadiene through hydrofraction, which is characterized in that the method is carried out by adopting the acetonitrile method for extracting butadiene through hydrofraction, which is characterized by comprising the following steps:
feeding the acetylene-containing cracking carbon four raw materials into a first extraction tower system, extracting raffinate containing mono-olefin and alkane from the tower top, feeding a solvent rich in di-olefin and alkyne extracted from the tower bottom into the first stripping tower system to separate the solvent and the carbon four, feeding the material at the top of the first stripping tower system into the lower part of a second extraction system, feeding the material with higher vinyl acetylene concentration extracted from the side line of the first stripping tower system into an alkyne selective hydrogenation reaction rectification system to carry out alkyne selective hydrogenation and rectification reaction with hydrogen;
the carbon four materials with higher butadiene concentration are extracted from the lateral line of the alkyne selective hydrogenation reaction rectification system and returned to the upper part of the first stripping tower system, the purge gas at the top of the alkyne selective hydrogenation reaction rectification system is sent out of the boundary, and the materials at the bottom of the alkyne selective hydrogenation reaction rectification system are sent to the lower part of the first stripping tower;
the bottom material of the first stripping tower system is divided into two parts, one part is sent to the upper part of the first extraction tower system, the other part is sent to the upper part of the second extraction tower system, the top material of the second extraction tower system is sequentially sent to the water washing tower system and the butadiene refining system, and the bottom material of the second extraction tower system is returned to the first stripping tower system.
5. The method for extracting butadiene by acetonitrile method according to claim 4, wherein the material with higher vinyl acetylene concentration extracted from the side line of the first stripping tower system and hydrogen are fed into an alkyne selective hydrogenation rectifying tower, the material at the top of the alkyne selective hydrogenation rectifying tower sequentially enters a tower top condenser and a tower top reflux tank, the material at the top of the tower top reflux tank enters a tail gas cooler for cooling, the uncondensed gas phase material is discharged out of the boundary from the top, and the material at the bottom of the tail gas cooler returns to the tower top reflux tank; the material at the bottom of the tower top reflux tank is sequentially connected with a reflux pump and an alkyne selective hydrogenation rectifying tower; the acetylene hydrocarbon selective hydrogenation reaction rectifying tower side line is used for extracting carbon four materials with higher butadiene concentration and returns to the upper part of the first stripping tower; and feeding the material at the bottom of the alkyne selective hydrogenation rectifying tower into the lower part of the first stripping tower.
6. The method for extracting butadiene by acetonitrile method according to claim 4, wherein the material at the top of the water washing tower system is sent to a light component removing tower of a butadiene refining system, the light component separated from the top of the tower is sent to the outside, the material at the bottom of the light component removing tower of the butadiene refining system separated from the bottom of the tower is sent to a heavy component removing tower of the butadiene refining system, the heavy component is separated from the bottom of the tower, and the butadiene product is obtained from the top of the tower.
7. The process for the extraction of hydrocracked butadiene from acetonitrile according to claim 4, wherein the alkyne-containing cracked carbon four feedstock comprises alkynes, diolefins, and mono-olefins and/or alkanes; wherein the butadiene content is 20-70 wt% and the vinyl acetylene content is 0.1-10 wt%.
8. The method for extracting butadiene by hydrocatalytic distillation according to claim 7, wherein the content of butadiene is 40-55wt% and the content of vinylacetylene is 0.5-5wt%.
9. The method for extracting butadiene by acetonitrile method according to claim 4, wherein the catalyst of the alkyne selective hydrogenation reaction rectifying tower is positioned in a rectifying section, and a catalyst cloth bag is used for filling a tray or a supported catalyst is used; the catalyst is a nickel-based catalyst and/or a palladium-based catalyst, preferably a nickel-based catalyst.
10. The process for extracting butadiene by hydrocatalytic distillation with acetonitrile as claimed in claim 4 wherein the selective hydrogenation operating conditions comprise: the operation temperature is 35-90 ℃, the operation pressure is 0-1.0 MPaG, the reaction temperature rise is 5-25 ℃, the mole ratio of the hydrogen and the alkyne is 0.5-5, the number of the tower plates is 20-100, and the reflux ratio is 5-50.
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