CN114478161A - Apparatus and process for selective hydrogenation of mixed C4 stream - Google Patents
Apparatus and process for selective hydrogenation of mixed C4 stream Download PDFInfo
- Publication number
- CN114478161A CN114478161A CN202011148024.3A CN202011148024A CN114478161A CN 114478161 A CN114478161 A CN 114478161A CN 202011148024 A CN202011148024 A CN 202011148024A CN 114478161 A CN114478161 A CN 114478161A
- Authority
- CN
- China
- Prior art keywords
- selective hydrogenation
- mixed
- butadiene
- stream
- material flow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 182
- 238000000034 method Methods 0.000 title claims abstract description 46
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 119
- 239000000463 material Substances 0.000 claims abstract description 92
- 238000005192 partition Methods 0.000 claims abstract description 44
- 238000000895 extractive distillation Methods 0.000 claims abstract description 43
- 238000000926 separation method Methods 0.000 claims abstract description 43
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000009833 condensation Methods 0.000 claims abstract description 11
- 230000005494 condensation Effects 0.000 claims abstract description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 240
- 238000000605 extraction Methods 0.000 claims description 73
- 239000007788 liquid Substances 0.000 claims description 69
- 239000001257 hydrogen Substances 0.000 claims description 55
- 229910052739 hydrogen Inorganic materials 0.000 claims description 55
- 239000003054 catalyst Substances 0.000 claims description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 46
- 150000001345 alkine derivatives Chemical class 0.000 claims description 36
- 150000002431 hydrogen Chemical class 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- 238000004230 steam cracking Methods 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- -1 acetylene hydrocarbon Chemical class 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 6
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000000475 acetylene derivatives Chemical class 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 235000013844 butane Nutrition 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 244000286663 Ficus elastica Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- 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
- C07C5/05—Partial hydrogenation
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
-
- 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
- C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
- C07C7/08—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by extractive distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of petrochemical industry, in particular to a device and a method for selective hydrogenation of a mixed C4 material flow. The device for selectively hydrogenating the mixed C4 material flow adopts a separating wall tower which is provided with an external condensation part and is divided into a selective hydrogenation area and an extractive distillation area, the selective hydrogenation area and the extractive distillation area are limited to be separated by a partition plate, the condenser is arranged outside the shell and above the selective hydrogenation area, and selective hydrogenation reaction, material separation and extractive distillation are integrated in one reactor, so that the process flow is simplified, the retention time of the material is shortened, the equipment investment is saved, and the operation safety is improved. Meanwhile, the selective hydrogenation method of the mixed C4 material flow provided by the invention adopts a process of selective hydrogenation and extractive distillation, so that the butene separation efficiency is greatly improved, and the content and the conversion rate of 1-butene in the butene-rich material flow are effectively improved.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a device and a method for selective hydrogenation of a mixed C4 material flow.
Background
1-butene is an olefin with relatively active chemical properties, is mainly used for producing branched chain or straight chain olefins such as polybutene, heptene, octene and the like, maleic anhydride, ethylene oxide, acetic acid, pesticides and the like, has increasing demand for 1-butene at home and abroad, and has become one of the fastest-developing chemical products.
The petroleum hydrocarbon cracking ethylene preparing device produces a large amount of mixed carbon four as a byproduct, wherein the cracking mixed carbon four contains about 40-60 wt% of 1, 3-butadiene, 0.5-2 wt% of Vinyl Acetylene (VA) and Ethyl Acetylene (EA), and the balance of butane, butylene and a small amount of 1, 2-butadiene, carbon three and carbon five. Usually, this portion of 1, 3-butadiene is separated from C.sub.four by extraction or the like. Certain ethylene production plants, particularly small and medium-scale ethylene plants, do not require 1, 3-butadiene but require large amounts of high purity 1-butene when no associated synthetic rubber plants are downstream. Therefore, for projects which do not need 1, 3-butadiene and need a large amount of 1-butene products, the construction of a 1, 3-butadiene extraction device is not economical, and the conversion of 1, 3-butadiene in the cracking carbon four into 1-butene through selective hydrogenation is an economical process route which reasonably utilizes the carbon four resources.
Butadiene and acetylenes in the C4 stream are converted to butenes and small amounts of butanes by hydrogenation using a selective hydrogenation catalyst. Butadiene and alkyne in the C4 material flow react in the presence of a selective hydrogenation catalyst and hydrogen, the hydrogenation reaction is an exothermic reaction, and a large amount of heat is released in the reaction process, so that the reaction temperature rises sharply. In addition, substances such as butadiene, alkyne and the like in the C4 material flow are extremely unstable, polymerization reaction can be carried out on the catalyst, so that the catalyst is blocked and deactivated, the reaction temperature is increased due to the heat release of the hydrogenation reaction, the speed of polymer deposition is further increased due to the increase of the reaction temperature, and the selective hydrogenation process for butadiene and alkyne is not only extremely unsafe to operate but also has short service life of the catalyst. The consequences are even more severe if the acetylenes and butadiene concentration in the C4 stream is higher. Therefore, the development of selective hydrogenation catalyst is really important, but the selection of proper selective hydrogenation process is more important.
CN1872819A provides a counter-current selective hydrogenation method, mixed C4 hydrocarbon raw material and hydrogen respectively enter a tower from the upper part and the lower part of a counter-current reactor through a distributor, a downward flowing hydrocarbon fraction and upward flowing hydrogen are in counter-current contact on the surface of a catalyst, the pressure is 0.1-3MPa, the reaction temperature is 40-100 ℃, and the volume space velocity is 1-20h-1While the light gas in the mixed C4 enters into the gas phase under the stripping action of hydrogen and flows out from the top of the reactor together with the unreacted hydrogen; the refined mixed C4 product flowed out of the bottom of the reactor. In the method, the mixed C4 hydrocarbon raw material is a C4 mixture (diolefin is more than or equal to 100ppm) from an MTBE device.
CN102285859A provides a selective hydrogenation process for C4 stream, which is to pass C4 stream containing high concentration of butadiene through one or more fixed bed hydrogenation reactors with recycle line, remove butadiene and alkyne under the action of hydrogenation catalyst, and further remove residual butadiene and alkyne from C4 stream containing low concentration of butadiene through a terminal reactor without recycle line.
Accordingly, there is a need for an apparatus and method for the selective hydrogenation of a mixed C4 stream.
Disclosure of Invention
The invention aims to solve the problems of long reaction flow, low separation efficiency, low safety, complex operation and the like of the selective hydrogenation reaction of butadiene in C4 material flow in the prior art, and provides a device and a method for selective hydrogenation of mixed C4 material flow, wherein the selective hydrogenation and the product separation of the C4 material flow are simultaneously completed by utilizing a device containing a dividing wall tower, the retention time is short, the equipment investment is reduced, and the operation is simplified; meanwhile, the method effectively improves the content and the conversion rate of the 1-butene in the butene-rich material flow.
In order to achieve the above object, a first aspect of the present invention provides an apparatus for the selective hydrogenation of a mixed C4 stream, the apparatus comprising: the separation wall tower comprises a shell and a condenser, a partition plate parallel to the central axis of the shell is arranged in the shell, the partition plate is connected with the top of the separation wall tower and the tower wall and is not connected with the bottom of the separation wall tower, and the partition plate partitions the interior of the shell into a selective hydrogenation zone and an extractive distillation zone;
the selective hydrogenation zone is provided with a selective hydrogenation catalyst bed layer and is used for carrying out a selective hydrogenation reaction by carrying out countercurrent contact on a mixed C4 material flow containing alkyne and butadiene and an extraction liquid with hydrogen to saturate alkyne and butadiene into butene so as to obtain a selective hydrogenation product, and simultaneously, under the stripping action of the hydrogen, separating a light component and unreacted butadiene from the mixed C4 material flow;
the condenser is arranged outside the shell and above the selective hydrogenation zone and is used for mixing and condensing the light components, the selective hydrogenation product and unreacted hydrogen to obtain a butene-rich material flow;
the extraction and rectification zone is used for carrying out extraction and rectification on mixed liquor containing unreacted butadiene and extraction liquid to obtain a butadiene-containing material flow and an extraction liquid-rich material flow.
In a second aspect, the present invention provides a process for the selective hydrogenation of a mixed C4 stream, the process comprising the steps of:
(1) in the presence of a selective hydrogenation catalyst, carrying out a selective hydrogenation reaction by countercurrent contact of a mixed C4 material flow containing alkyne and butadiene and an extraction liquid with hydrogen to saturate alkyne and butadiene into butene, so as to obtain a selective hydrogenation product, and simultaneously, under the stripping action of the hydrogen, separating light components and unreacted butadiene from the mixed C4 material flow;
(2) mixing the light components, the selective hydrogenation product and unreacted hydrogen, and carrying out condensation separation to obtain a butene-rich material flow;
(3) carrying out extractive distillation on a mixed solution containing unreacted butadiene and an extraction liquid to obtain a butadiene-containing material flow and an extraction liquid-rich material flow;
wherein the method is carried out in the apparatus provided in the first aspect.
Through the technical scheme, the device for selectively hydrogenating the mixed C4 material flow, provided by the invention, adopts the separation wall tower which is provided with the outer condensation part and is divided into the selective hydrogenation area and the extractive distillation area, the selective hydrogenation area and the extractive distillation area are limited to be separated by the partition plate, the condenser is arranged outside the shell and above the selective hydrogenation area, and the selective hydrogenation reaction, the material separation and the extractive distillation are integrated in one reactor, so that the process flow is simplified, the retention time of the material is shortened, the equipment investment is saved, and the operation safety is improved.
Meanwhile, the selective hydrogenation method of the mixed C4 material flow provided by the invention adopts a process of firstly selective hydrogenation and then extractive distillation, namely, acetylene hydrocarbon and butadiene in the mixed C4 material flow are removed before extractive distillation, so that the butene separation efficiency is greatly improved, and the content and the conversion rate of 1-butene in the butene-rich material flow are effectively improved.
Drawings
FIG. 1 is a schematic diagram of an apparatus for the selective hydrogenation of a mixed C4 stream provided by the present invention;
FIG. 2 is a schematic diagram of an apparatus for the selective hydrogenation of a mixed C4 stream provided in comparative example 4.
Description of the reference numerals
1. Hydrogen 2, mixed C4 stream 3, extract
4. Tail gas 5, butene-rich stream 6, butadiene-containing stream
7. Rich extract liquid stream 8, selective hydrogenation catalyst bed layer 9 and partition plate
10. Extracting agent and butadiene mixed liquor I, selective hydrogenation zone II and extractive rectification zone
III, a condenser IV, a fixed bed reactor V and an extractive distillation tower
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the "top" of the container referred to in the specification means 0 to 10% of the position of the container from the top to the bottom without specific description; the "upper" portion of the vessel refers to the 0-30% position of the vessel from top to bottom; the "lower part" of the container means 70-100% of the position of the container from top to bottom; the "bottom" of the container refers to 90-100% of the container from top to bottom.
In a first aspect, the present invention provides an apparatus for the selective hydrogenation of a mixed C4 stream, the apparatus comprising: the separation wall tower comprises a shell and a condenser, a partition plate parallel to the central axis of the shell is arranged in the shell, the partition plate is connected with the top of the separation wall tower and the tower wall and is not connected with the bottom of the separation wall tower, and the partition plate partitions the interior of the shell into a selective hydrogenation zone and an extractive distillation zone;
the selective hydrogenation zone is provided with a selective hydrogenation catalyst bed layer and is used for carrying out a selective hydrogenation reaction by carrying out countercurrent contact on a mixed C4 material flow containing alkyne and butadiene and an extraction liquid with hydrogen to saturate alkyne and butadiene into butene so as to obtain a selective hydrogenation product, and simultaneously, under the stripping action of the hydrogen, separating a light component and unreacted butadiene from the mixed C4 material flow;
the condenser is arranged outside the shell and above the selective hydrogenation zone and is used for mixing and condensing the light components, the selective hydrogenation product and unreacted hydrogen to obtain a butene-rich material flow;
the extraction and rectification zone is used for carrying out extraction and rectification on mixed liquor containing unreacted butadiene and extraction liquid to obtain a butadiene-containing material flow and an extraction liquid-rich material flow.
In the present invention, there is no particular case where one end of the partition is connected to the top of the divided wall column and the other end of the partition is not connected to the bottom of the divided wall column.
In the present invention, the selective hydrogenation product is butene, preferably 1-butene, unless otherwise specified.
In the present invention, the light component refers to unreacted alkyne, C1-C3 alkane and butene in the mixed C4 stream without specific indication.
According to the present invention, preferably, the selective hydrogenation zone is further provided with an extract liquid inlet, a mixed C4 stream inlet and a hydrogen inlet.
To fully embody the countercurrent contacting of the mixed C4 stream and the extract with hydrogen, and to increase the saturation ratio of acetylenes and butadiene in the mixed C4 stream. Preferably, the extract inlet and the mixed C4 stream inlet are each independently disposed above the hydrogen inlet.
According to the invention, preferably, the height ratio of the bed of selective hydrogenation catalyst to the selective hydrogenation zone is between 0.4 and 0.9:1, preferably 0.6 to 0.8: 1. in the present invention, the height of the selective hydrogenation zone corresponds to the height of the partition, unless otherwise specified. The preferred conditions are adopted to facilitate the conversion of the acetylenes and butadiene in the mixed C4 stream to butenes and increase the conversion.
In some embodiments of the present invention, preferably, the bed of selective hydrogenation catalyst is disposed below the inlet of the mixed C4 stream and the inlet of the extraction liquid, and above the inlet of the hydrogen gas.
In the present invention, the mixed C4 stream inlet and the extract liquid inlet are not limited, and preferably, the extract liquid inlet is disposed above the mixed C4 stream inlet.
According to a preferred device of the invention, the selective hydrogenation zone is provided with an extract liquid inlet, a mixed C4 stream inlet, a selective hydrogenation catalyst bed and a hydrogen gas inlet, wherein the mixed C4 stream is arranged below the extract liquid inlet, and the selective hydrogenation catalyst bed is arranged below the mixed C4 stream inlet and above the hydrogen gas inlet.
According to the invention, preferably, the ratio of the radii of the selective hydrogenation zone and the extractive distillation zone is between 0.5 and 1.5: 1, preferably 0.8 to 1.2: 1. the optimized conditions are adopted, so that the sufficiency of selective hydrogenation and extractive distillation is ensured.
Preferably, the ratio of the height of the partition to the height of the divided wall column is from 0.5 to 0.9:1, preferably 0.7 to 0.9: 1. preferred conditions are used to better facilitate the simultaneous selective hydrogenation of the mixed C4 feed and stripping of the upper hydrogen on the left side of the dividing wall column.
In the present invention, the partition has a wide range of options as long as the partition wall column is partitioned into a selective hydrogenation zone and a butadiene extraction zone.
Preferably, the extractive distillation zone is provided with an extract-rich stream outlet and a butadiene-containing stream outlet; further preferably, the butadiene-containing stream outlet is arranged above the extract rich stream outlet.
According to the present invention, preferably, the apparatus further comprises: and the extraction liquid-rich material flow outlet arranged in the extraction rectification zone is communicated with the extraction liquid inlet arranged in the selective hydrogenation zone and is used for returning the extraction liquid-rich material flow to be mixed into the extraction liquid.
The invention provides a device for selective hydrogenation of a mixed C4 material flow, which comprises the following components in percentage by weight as shown in figure 1: the separation wall tower comprises a shell and a condenser III, a partition plate 9 parallel to the central axis of the shell is arranged in the shell, the partition plate 9 is connected with the top of the separation wall tower and the tower wall and is not connected with the bottom of the separation wall tower, and the partition plate 9 partitions the interior of the shell into a selective hydrogenation zone I and an extractive distillation zone II;
the selective hydrogenation zone I is provided with a selective hydrogenation catalyst bed layer 8 for carrying out a selective hydrogenation reaction by countercurrent contact of a mixed C4 material flow 2 containing alkyne and butadiene and an extraction liquid 3 with hydrogen to saturate alkyne and butadiene into butene and obtain a selective hydrogenation product, and simultaneously, under the stripping action of the hydrogen, light components and unreacted butadiene are separated from the mixed C4 material flow 2;
the condenser III is arranged outside the shell and above the selective hydrogenation zone I, and is used for mixing and condensing the light components, the selective hydrogenation products and unreacted hydrogen to obtain a butene-rich material flow 5 and a tail gas 4;
and the extractive distillation area II is used for carrying out extractive distillation on the mixed solution containing unreacted butadiene and the extraction liquid to obtain a butadiene-containing material flow 6 and an extraction liquid-rich material flow 7.
Preferably, the selective hydrogenation zone I is further provided with an extract inlet, a mixed C4 stream and a hydrogen inlet, wherein the bed 8 of selective hydrogenation catalyst is arranged below the mixed C4 stream inlet and the extract inlet and above the hydrogen inlet.
Preferably, the extractive distillation area II is provided with a butadiene-containing material flow outlet and a rich extraction liquid outlet from top to bottom in sequence.
Preferably, the rich extract stream outlet arranged in the extractive distillation zone II is communicated with the extract inlet arranged in the selective hydrogenation zone I, and is used for returning and mixing the rich extract stream 7 into the extract 3.
In a second aspect, the present invention provides a process for the selective hydrogenation of a mixed C4 stream, the process comprising the steps of:
(1) in the presence of a selective hydrogenation catalyst, carrying out a selective hydrogenation reaction by countercurrent contact of a mixed C4 material flow containing alkyne and butadiene and an extraction liquid with hydrogen to saturate alkyne and butadiene into butene, so as to obtain a selective hydrogenation product, and simultaneously, under the stripping action of the hydrogen, separating light components and unreacted butadiene from the mixed C4 material flow;
(2) mixing the light components, the selective hydrogenation product and unreacted hydrogen, and carrying out condensation separation to obtain a butene-rich material flow;
(3) carrying out extractive distillation on a mixed solution containing unreacted butadiene and an extraction liquid to obtain a butadiene-containing material flow and an extraction liquid-rich material flow;
wherein the method is carried out in the apparatus provided in the first aspect.
The inventor of the invention researches and finds that: aiming at the method for selectively hydrogenating the mixed C4 material flow, a process flow of firstly selectively hydrogenating and then extracting and rectifying is adopted, namely alkyne is removed before extracting and rectifying, and gas-liquid separation of a selectively hydrogenated product and unreacted butadiene is realized by utilizing the steam stripping effect of hydrogen, so that the separation efficiency of the selectively hydrogenated product is improved; meanwhile, the extraction liquid is introduced in the selective hydrogenation stage, so that the separation of the unreacted butadiene and the selective hydrogenation product is effectively improved.
In the present invention, the butadiene means 1, 3-butadiene and/or 1, 4-butadiene without specific description.
In some embodiments of the present invention, it is preferred that the butadiene content is ≧ 10 wt%, preferably 20-60 wt%, based on the weight of the mixed C4 stream; the content of the alkyne is 20 to 50 wt%, preferably 20 to 30 wt%. In the present invention, the contents of butadiene and alkyne are both determined by gas chromatography methods.
In the present invention, the alkyne is selected from at least one of ethylacetylene, vinylacetylene and methylacetylene without specific indication.
In the present invention, there is a wide range of choices for the source of the mixed C4 stream, as long as the butadiene and alkyne content of the mixed C4 stream meets the above requirements. Preferably, the mixed C4 stream is from a butadiene extraction unit and/or a hydrocarbon steam cracking unit. Wherein the hydrocarbon steam cracking device may be an ethylene cracking device.
In the present invention, the selective hydrogenation catalyst has a wide selection range, so long as acetylene hydrocarbon and butadiene in the mixed C4 material flow are subjected to selective hydrogenation reaction with hydrogen to convert into butene. Preferably, the selective hydrogenation catalyst contains an active component and a carrier; further preferably, the active component comprises a main active component and optionally a co-active component.
According to the present invention, preferably, the main active component is present in an amount of 0.01 to 1 wt%, preferably 0.1 to 0.3 wt%, based on the weight of the selective hydrogenation catalyst; the content of the auxiliary active component is 0-20 wt%, preferably 0-10 wt%.
In some embodiments of the present invention, preferably, the main active component is selected from at least one of palladium, silver, rhodium, platinum and nickel, preferably palladium and/or silver; the auxiliary active component is at least one of potassium, sodium, lithium, calcium, magnesium, copper, gold, lead, zinc, manganese and rare earth elements.
According to the present invention, preferably, the specific surface area of the carrier is 1 to 200m2A/g, preferably from 80 to 200m2(ii)/g; the average pore diameter is 5-300nm, preferably 50-200 nm; the pore volume is 0.2-1mL/g, preferably 0.3-0.7 mL/g.
According to the present invention, preferably, the support is selected from at least one of alumina, silica, spinel, diatomaceous earth, titania, zinc oxide, tin oxide, and molecular sieves, preferably alumina and/or silica.
In the present invention, there is a wide range of choices for the shape of the selective hydrogenation catalyst. Preferably, the shape of the selective hydrogenation catalyst is selected from at least one of a granular shape, a spherical shape, a gear shape, a blade shape and a bar shape.
In the present invention, the selective hydrogenation catalyst can be obtained commercially or prepared; wherein, the preparation method of the selective hydrogenation catalyst is a method well known by the technical personnel in the field.
In the present invention, the extract is directed to separating unreacted butadiene from the C4 stream, increasing the efficiency of the separation of selectively hydrogenated products. Preferably, the extraction solution is an aqueous solution containing an extractant.
In some embodiments of the present invention, the water content of the extract is preferably 1-20 wt%, e.g., 1 wt%, 5 wt%, 7 wt%, 9 wt%, 11 wt%, 13 wt%, 15 wt%, 17 wt%, 20 wt%, and any two ranges of values, preferably 5-15 wt%.
In the present invention, the extractant has a wide selection range as long as the selective hydrogenation product is effectively separated from the unreacted butadiene without adversely affecting the selective hydrogenation catalyst. Preferably, the extractant is selected from at least one of N-methylpyrrolidone, acetonitrile, furfural, formylmorpholine, dimethylacetamide and dimethylformamide.
According to the present invention, preferably, the conditions of selective hydrogenation include: the temperature is 25-80 ℃, preferably 35-60 ℃; the pressure is 0.1-5MPa, preferably 0.6-3 MPa; the volume space velocity is 10-100h-1Preferably 10-50h-1. And the preferable condition range is adopted, so that the selective hydrogenation reaction of the acetylene hydrocarbon and the butadiene in the C4 material flow is more favorably carried out, and the hydrogenation efficiency is improved.
Preferably, the molar ratio of the mixed C4 stream to hydrogen is 1: 1-10, preferably 1: 1-5, wherein the molar amount of the mixed C4 stream is based on the molar amount of acetylenes and butadiene in the mixed C4 stream.
According to the invention, preferably, the weight ratio of the extract to the mixed C4 stream is from 0.3 to 5: 1, preferably 0.5 to 1.5: 1.
in the invention, in the step (1), the countercurrent contact is more favorable for promoting the selective hydrogenation reaction of the acetylene hydrocarbon and the butadiene in the C4 material flow and the hydrogen, so that the selective hydrogenation efficiency is improved.
In the invention, the condensation separation aims to mix and carry out condensation separation on light components, selective hydrogenation products and unreacted hydrogen in the mixed C4 stream to obtain a butene-rich stream; preferably, the condensation separation also yields a tail gas.
According to the present invention, preferably, in step (2), the butene-rich stream has a 1-butene content of ≥ 40 wt%, preferably 40-60 wt%.
Preferably, the conversion of 1-butene in the butene rich stream is 55% or more, preferably 55 to 70%.
Further preferably, the butene rich stream has an alkyne and butadiene content of each independently ≦ 20ppm, preferably 5 to 10 ppm.
In the present invention, the conditions for the extractive distillation may be selected from a wide range, and the mixed solution containing the extract and the unreacted butadiene mixture may be separated. Preferably, the conditions of the extractive distillation include: the theoretical plate number is 50-95, preferably 60-85; the pressure is 0.1-1MPa, preferably 0.5-0.6 MPa; the temperature of the top of the tower is 25-60 ℃, and the preferable temperature is 35-50 ℃; the temperature of the tower bottom is 120-150 ℃, preferably 125-145 ℃. The preferable conditions are adopted, so that the separation efficiency of a small amount of butadiene in the selective hydrogenation product is improved.
In some embodiments of the present invention, it is preferred that the butadiene content of the butadiene-containing stream is in the range of from 0 to 10 wt%, preferably from 0 to 5 wt%.
According to the present invention, preferably, the method further comprises: the rich extract stream is returned to and mixed into the extract. The purpose of the arrangement can effectively improve the utilization rate of the extraction liquid.
The present invention will be described in detail below by way of examples.
In the selective hydrogenation catalysts in the examples and the comparative examples, the active components are palladium and silver, and the carrier is alumina; based on the weight of the selective hydrogenation catalyst, the content of palladium is 0.5 wt%, and the content of silver is 0.18 wt%; the specific surface area of the alumina is 150m2(ii)/g, average pore diameter was 250nm, and pore volume was 0.6 mL/g.
Example 1
(1) An apparatus for the selective hydrogenation of a mixed C4 stream is shown in FIG. 1 and comprises: the separation wall tower comprises a shell and a condenser III, a partition plate 9 parallel to the central axis of the shell is arranged in the shell, the partition plate 9 is connected with the top of the separation wall tower and the tower wall and is not connected with the bottom of the separation wall tower, the partition plate 9 partitions the interior of the shell into a selective hydrogenation zone I and an extractive distillation zone II, and the condenser III is arranged outside the shell and above the selective hydrogenation zone I;
the selective hydrogenation zone I is provided with an extract liquid inlet, a mixed C4 material flow inlet, a selective hydrogenation catalyst bed layer 8 and a hydrogen gas inlet, wherein the mixed C4 material flow inlet is arranged below the extract liquid inlet, the selective hydrogenation catalyst bed layer 8 is arranged below the extract liquid inlet and above the hydrogen gas inlet, and the height ratio of the selective hydrogenation catalyst bed layer to the selective hydrogenation zone is 0.6: 1;
the extractive distillation zone II is sequentially provided with a butadiene-containing material flow outlet and an extract-rich material flow outlet from top to bottom;
the radius ratio of the selective hydrogenation zone I to the extractive distillation zone II is 1:1, and the height ratio of the partition plate 9 to the partition wall tower is 0.7: 1;
and the extraction liquid-rich material flow outlet arranged in the extraction and rectification zone II is communicated with the extraction liquid inlet arranged in the selective hydrogenation zone I and is used for returning the extraction liquid-rich material flow 7 and mixing the extraction liquid 3.
(2) A process for the selective hydrogenation of a mixed C4 stream, the process comprising:
a. a mixed C4 stream (hydrocarbon cracker, butadiene content 51 wt%, alkyne content 20 wt%, 1-butene content 15 wt%) and a N-methyl pyrrolidone solution with water content 5 wt% are subjected to a selective hydrogenation reaction with hydrogen in the presence of a selective hydrogenation catalyst, wherein the weight ratio of the N-methyl pyrrolidone solution to the mixed C4 stream is 1:1, and the molar ratio of the mixed C4 stream to the hydrogen is 1:2, and the conditions of the selective hydrogenation reaction comprise: the temperature is 35 ℃, the pressure is 2MPa, and the volume space velocity is 15h-1Obtaining selective hydrogenation products, and simultaneously separating light components and unreacted butadiene from the mixed C4 material flow under the stripping action of the hydrogen;
b. mixing the light components, the selective hydrogenation product and unreacted hydrogen, and carrying out condensation separation to obtain a butene-rich material flow S1;
c. performing extractive distillation on a mixed solution containing unreacted butadiene and an extraction liquid, wherein the extractive distillation conditions comprise: the theoretical plate number is 70, the pressure is 0.6MPa, the temperature at the top of the tower is 48 ℃, the temperature at the bottom of the tower is 125 ℃, a stream P1 containing butadiene is obtained, and the obtained extractant-rich stream is returned and mixed into the extraction liquid;
wherein, in the butene-rich stream S1, the content of alkynes and butadiene are both 6ppm, the content of 1-butene is 58 wt%, and the conversion rate of 1-butene is 60%;
the butadiene content of the butadiene-containing stream P1 was 5 ppm.
Example 2
(1) Mixed C4 stream selective additionThe hydrogen plant is shown in FIG. 1 and comprises: the separation wall tower comprises a shell and a condenser III, a partition plate 9 parallel to the central axis of the shell is arranged in the shell, the partition plate 9 is connected with the top of the separation wall tower and the tower wall and is not connected with the bottom of the separation wall tower, the partition plate 9 partitions the interior of the shell into a selective hydrogenation zone I and an extractive distillation zone II, and the condenser III is arranged outside the shell and above the selective hydrogenation zone I;
the selective hydrogenation zone I is provided with an extract liquid inlet, a mixed C4 material flow inlet, a selective hydrogenation catalyst bed layer 8 and a hydrogen gas inlet, wherein the mixed C4 material flow inlet is arranged below the extract liquid inlet, the selective hydrogenation catalyst bed layer 8 is arranged below the extract liquid inlet and above the hydrogen gas inlet, and the height ratio of the selective hydrogenation catalyst bed layer to the selective hydrogenation zone is 0.7: 1;
the extraction and rectification zone II is sequentially provided with a butadiene-containing material flow outlet and an extract-rich material flow outlet from top to bottom;
the radius ratio of the selective hydrogenation zone I to the extractive distillation zone II is 1:1, and the height ratio of the partition plate 9 to the partition wall tower is 0.9: 1;
and the extraction liquid-rich material flow outlet arranged in the extraction and rectification zone II is communicated with the extraction liquid inlet arranged in the selective hydrogenation zone I and is used for returning the extraction liquid-rich material flow 7 and mixing the extraction liquid 3.
(2) A process for the selective hydrogenation of a mixed C4 stream, the process comprising:
a. counter-current contacting a mixed C4 stream (butadiene extraction unit, butadiene content of 19 wt%, alkyne content of 36 wt%, 1-butene content of 8 wt%) and an N-methylpyrrolidone solution with a water content of 9 wt% with hydrogen in the presence of a selective hydrogenation catalyst and carrying out selective hydrogenation, wherein the weight ratio of the N-methylpyrrolidone solution to the mixed C4 stream is 1:1, and the molar ratio of the mixed C4 stream to the hydrogen is 1:1.5, and the conditions of the selective hydrogenation reaction comprise: the temperature is 55 ℃, the pressure is 3MPa, and the volume space velocity is 23h-1To obtainSelectively hydrogenating the product while separating light components and unreacted butadiene from the mixed C4 stream under the stripping action of the hydrogen;
b. mixing the light components, the selective hydrogenation product and unreacted hydrogen, and carrying out condensation separation to obtain a butene-rich material flow S2;
c. carrying out extractive distillation on a mixed solution containing unreacted butadiene and an extraction liquid, wherein the extractive distillation conditions comprise: the theoretical plate number is 80, the pressure is 0.55MPa, the temperature at the top of the tower is 45 ℃, the temperature at the bottom of the tower is 140 ℃, a stream P2 containing butadiene is obtained, and the obtained extractant-rich stream is returned and mixed into the extraction liquid;
wherein, in the butene-rich stream S2, the content of alkynes and butadiene are both 7ppm, the content of 1-butene is 40 wt%, and the conversion rate of 1-butene is 58%;
the butadiene content of the butadiene-containing stream P1 was 7 ppm.
Example 3
(1) An apparatus for the selective hydrogenation of a mixed C4 stream is shown in FIG. 1 and comprises: the separation wall tower comprises a shell and a condenser III, a partition plate 9 parallel to the central axis of the shell is arranged in the shell, the partition plate 9 is connected with the top of the separation wall tower and the tower wall and is not connected with the bottom of the separation wall tower, the partition plate 9 partitions the interior of the shell into a selective hydrogenation zone I and an extractive distillation zone II, and the condenser III is arranged outside the shell and above the selective hydrogenation zone I;
the selective hydrogenation zone I is provided with an extract liquid inlet, a mixed C4 material flow inlet, a selective hydrogenation catalyst bed layer 8 and a hydrogen gas inlet, wherein the mixed C4 material flow inlet is arranged below the extract liquid inlet, the selective hydrogenation catalyst bed layer 8 is arranged below the extract liquid inlet and above the hydrogen gas inlet, and the height ratio of the selective hydrogenation catalyst bed layer to the selective hydrogenation zone is 0.8: 1;
the extraction and rectification zone II is sequentially provided with a butadiene-containing material flow outlet and an extract-rich material flow outlet from top to bottom;
the radius ratio of the selective hydrogenation zone I to the extractive distillation zone II is 1:1, and the height ratio of the partition plate 9 to the partition wall tower is 0.9: 1;
and the extraction liquid-rich material flow outlet arranged in the extraction and rectification zone II is communicated with the extraction liquid inlet arranged in the selective hydrogenation zone I and is used for returning the extraction liquid-rich material flow 7 and mixing the extraction liquid 3.
(2) A process for the selective hydrogenation of a mixed C4 stream, the process comprising:
a. a mixed C4 stream (containing 45 wt% of butadiene, 15 wt% of alkyne and 11 wt% of 1-butene) and a solution of N-methyl pyrrolidone with a water content of 7 wt% are subjected to a selective hydrogenation reaction with hydrogen in the presence of a selective hydrogenation catalyst, the weight ratio of the solution of N-methyl pyrrolidone to the mixed C4 stream is 1:1, and the molar ratio of the mixed C4 stream to hydrogen is 1:1.8, wherein the conditions of the selective hydrogenation reaction comprise: the temperature is 40 ℃, the pressure is 2.5MPa, and the volume space velocity is 19h-1Obtaining selective hydrogenation products, and simultaneously separating light components and unreacted butadiene from the mixed C4 material flow under the stripping action of the hydrogen;
b. mixing the light components, the selective hydrogenation product and unreacted hydrogen, and carrying out condensation separation to obtain a butene-rich material flow S3;
c. carrying out extractive distillation on a mixed solution containing unreacted butadiene and an extraction liquid, wherein the extractive distillation conditions comprise: the theoretical plate number is 75, the pressure is 0.58MPa, the temperature at the top of the tower is 50 ℃, the temperature at the bottom of the tower is 130 ℃, a stream P3 containing butadiene is obtained, and the obtained extractant-rich stream is returned and mixed into the extraction liquid;
wherein, in the butene-rich stream S3, the content of acetylene hydrocarbon and butadiene are both 5ppm, the content of 1-butene is 47 wt%, and the conversion rate of 1-butene is 59%;
the butadiene content of the butadiene-containing stream P1 was 6 ppm.
Comparative example 1
The feed and catalyst of example 1 were subjected to selective hydrotreatment according to the method disclosed in CN102285859A to obtain a 1-butene stream D1, namely:
mixing a fresh mixed C4 material flow and C4 circulated from the back of the second-stage reactor, and allowing the mixture to enter the first-stage reactor, and allowing the product of the first-stage reactor to enter the second-stage reactor; the outlet part C4 of the second-stage reactor is recycled to the inlet of the first-stage reactor, and the rest part is output as a hydrogenation product with the recycle ratio of 11.5; the inlet temperature of the first-stage reactor is 30 ℃, the pressure is 2MPa, and the hydrogen acetylene ratio is 0.81; the inlet temperature of the second-stage reactor is 37 ℃, the pressure is 1.8MPa, and the hydrogen alkyne ratio is 2.3; the final 1-butene content at the outlet of the first stage reactor was 16.22 wt%, the 1-butene content at the outlet of the second stage reactor was 14.76 wt%, and the 1-butene conversion was 5.5%;
wherein the 1-butene stream D1 had a 1-butene content of 14.76 wt% and a 1-butene conversion of 5.5%.
Comparative example 2
The feed and catalyst of example 1 were subjected to selective hydrogenation according to the method disclosed in CN1872819A to give a 1-butene stream D2;
wherein the 1-butene stream D2 had a 1-butene content of 20 wt% and a 1-butene conversion of 7.2%.
Comparative example 3
According to the process of example 1, except that a solution of N-methylpyrrolidone with a water content of 5% by weight is added in stage (2), obtaining a butene-rich stream DS3, according to stage (3), obtaining a butadiene-containing stream DP 3;
wherein, in the butene-rich stream DS3, the content of alkyne and butadiene are both 10ppm, the content of 1-butene is 54 wt%, and the conversion rate of 1-butene is 55%;
the butadiene content of the butadiene-containing stream DP3 was 8 ppm.
Comparative example 4
The feed and catalyst of example 1 were carried out in a selective hydrogenation unit as shown in FIG. 2 to give a butene-rich stream DS4 and a butadiene-containing stream DP 4;
wherein, in the butene-rich stream DS4, the content of alkyne and butadiene are both 30ppm, the content of 1-butene is 22 wt%, and the conversion rate of 1-butene is 10%;
the butadiene content of the butadiene-containing stream DP4 was 25 ppm.
As can be seen from the data of the examples and the comparative examples, the device for selectively hydrogenating the mixed C4 material flow provided by the invention is adopted, namely, a dividing wall tower which is externally condensed and is provided with a dividing wall which is divided into a selective hydrogenation area and an extractive distillation area is adopted, and the selective hydrogenation and the extractive distillation of the C4 material flow are simultaneously realized, so that the operation flow is simplified; meanwhile, the method provided by the invention can effectively improve the separation efficiency of 1-butene in the C4 material flow, and particularly, in the material flow rich in butene, the content of 1-butene is more than or equal to 40 wt%, the conversion rate of 1-butene is more than or equal to 55%, and the content of alkyne and butadiene are less than or equal to 20 ppm.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. An apparatus for the selective hydrogenation of a mixed C4 stream, the apparatus comprising: the separation wall tower comprises a shell and a condenser, a partition plate parallel to the central axis of the shell is arranged in the shell, the partition plate is connected with the top of the separation wall tower and the tower wall and is not connected with the bottom of the separation wall tower, and the partition plate partitions the interior of the shell into a selective hydrogenation zone and an extractive distillation zone;
the selective hydrogenation zone is provided with a selective hydrogenation catalyst bed layer and is used for carrying out a selective hydrogenation reaction by carrying out countercurrent contact on a mixed C4 material flow containing alkyne and butadiene and an extraction liquid with hydrogen to saturate alkyne and butadiene into butene so as to obtain a selective hydrogenation product, and simultaneously, under the stripping action of the hydrogen, separating a light component and unreacted butadiene from the mixed C4 material flow;
the condenser is arranged outside the shell and above the selective hydrogenation zone and is used for mixing and condensing the light components, the selective hydrogenation product and unreacted hydrogen to obtain a butene-rich material flow;
the extraction and rectification zone is used for carrying out extraction and rectification on mixed liquor containing unreacted butadiene and extraction liquid to obtain a butadiene-containing material flow and an extraction liquid-rich material flow.
2. The apparatus of claim 1, wherein the selective hydrogenation zone is further provided with an extract inlet, a mixed C4 stream inlet, and a hydrogen inlet;
preferably, the extract inlet and the mixed C4 stream inlet are each independently disposed above the hydrogen inlet;
preferably, the height ratio of the selective hydrogenation catalyst bed layer to the selective hydrogenation zone is 0.4-0.9: 1, preferably 0.6 to 0.8: 1;
preferably, the bed of selective hydrogenation catalyst is disposed below the inlet of the mixed C4 stream and the inlet of the extraction liquid, and above the inlet of the hydrogen gas.
3. The apparatus of claim 1 or 2, wherein the ratio of the radii of the selective hydrogenation zone and the extractive rectification zone is from 0.5 to 1.5: 1, preferably 0.8 to 1.2: 1;
preferably, the ratio of the height of the partition to the height of the divided wall column is from 0.5 to 0.9:1, preferably 0.7 to 0.9: 1.
4. the apparatus of any one of claims 1-3, wherein the extractive distillation zone is provided with an extract rich stream outlet and a butadiene containing stream outlet;
preferably, the butadiene-containing stream outlet is disposed above the rich extract stream outlet;
preferably, the apparatus further comprises: and the extraction liquid-rich material flow outlet arranged in the extraction rectification zone is communicated with the extraction liquid inlet arranged in the selective hydrogenation zone and is used for returning the extraction liquid-rich material flow to be mixed into the extraction liquid.
5. A process for the selective hydrogenation of a mixed C4 stream, the process comprising the steps of:
(1) in the presence of a selective hydrogenation catalyst, carrying out a selective hydrogenation reaction by countercurrent contact of a mixed C4 material flow containing alkyne and butadiene and an extraction liquid with hydrogen to saturate alkyne and butadiene into butene, so as to obtain a selective hydrogenation product, and simultaneously, under the stripping action of the hydrogen, separating light components and unreacted butadiene from the mixed C4 material flow;
(2) mixing the light components, the selective hydrogenation product and unreacted hydrogen, and carrying out condensation separation to obtain a butene-rich material flow;
(3) carrying out extractive distillation on a mixed solution containing unreacted butadiene and an extraction liquid to obtain a butadiene-containing material flow and an extraction liquid-rich material flow;
wherein the process is carried out in an apparatus according to any one of claims 1 to 4.
6. The process of claim 5, wherein the butadiene content is ≥ 10 wt%, preferably from 20-60 wt%, based on the weight of the mixed C4 stream; the content of the alkyne is 20-50 wt%, preferably 20-30 wt%; the content of the 1-butene is 5 to 30 wt%, preferably 5 to 15 wt%;
preferably, the mixed C4 stream is from a butadiene extraction unit and/or a hydrocarbon steam cracking unit.
7. The process of claim 5 or 6, wherein the selective hydrogenation catalyst comprises an active component and a support;
preferably, the active component comprises a primary active component and optionally a co-active component;
preferably, the main active component is present in an amount of from 0.01 to 1 wt%, preferably from 0.1 to 0.3 wt%, based on the weight of the selective hydrogenation catalyst; the content of the auxiliary active component is 0-20 wt%, preferably 0-10 wt%;
preferably, the specific surface area of the carrier is 1 to 200m2A/g, preferably from 80 to 200m2(ii)/g; the average pore diameter is 5-300nm, preferably 50-200 nm; the pore volume is 0.2-1mL/g,preferably 0.3 to 0.7 mL/g.
8. The method according to any one of claims 5 to 7, wherein the extraction liquid is an aqueous solution containing an extractant;
preferably, the extract has a water content of 1 to 20 wt%, preferably 5 to 15 wt%;
preferably, the extractant is selected from at least one of N-methylpyrrolidone, acetonitrile, furfural, formylmorpholine, dimethylacetamide and dimethylformamide;
preferably, the conditions of the selective hydrogenation reaction include: the temperature is 25-80 ℃, preferably 35-60 ℃; the pressure is 0.1-5MPa, preferably 0.6-3 MPa; the volume space velocity is 10-100h-1Preferably 10-50h-1；
Preferably, the molar ratio of the mixed C4 stream to hydrogen is 1: 1-10, preferably 1: 1-5.
9. Process according to any one of claims 5-8, wherein the butene-rich stream has a 1-butene content of ≥ 40 wt%, preferably 40-60 wt%;
preferably, the butene rich stream has an alkyne and butadiene content of each independently ≦ 20ppm, preferably 5 to 10 ppm.
10. The method of any of claims 5-9, wherein the conditions of extractive distillation comprise: the theoretical plate number is 50-95, preferably 60-85; the pressure is 0.1-1MPa, preferably 0.5-0.6 MPa; the temperature of the top of the tower is 25-60 ℃, and the preferable temperature is 35-50 ℃; the temperature of the tower kettle is 120-150 ℃, preferably 125-145 ℃;
preferably, the butadiene-containing stream has a butadiene content of from 0 to 10 wt.%, preferably from 0 to 5 wt.%;
preferably, the method further comprises: the rich extract stream is returned to and mixed into the extract.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011148024.3A CN114478161A (en) | 2020-10-23 | 2020-10-23 | Apparatus and process for selective hydrogenation of mixed C4 stream |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011148024.3A CN114478161A (en) | 2020-10-23 | 2020-10-23 | Apparatus and process for selective hydrogenation of mixed C4 stream |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114478161A true CN114478161A (en) | 2022-05-13 |
Family
ID=81470424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011148024.3A Pending CN114478161A (en) | 2020-10-23 | 2020-10-23 | Apparatus and process for selective hydrogenation of mixed C4 stream |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114478161A (en) |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5969203A (en) * | 1996-12-23 | 1999-10-19 | Institut Francais Du Petrole | Process for the production of high purity isobutene combining reactive distillation with hydroisomerization, distillation and skeletal isomerization |
| CN1235947A (en) * | 1998-03-27 | 1999-11-24 | Basf公司 | Preparation of olefins |
| KR20020095254A (en) * | 2000-05-09 | 2002-12-20 | 바스프 악티엔게젤샤프트 | Method and Device For Treating a C4 Fraction |
| CN1433392A (en) * | 2000-05-09 | 2003-07-30 | 巴斯福股份公司 | Method and device for treating C4 fraction |
| CN1671638A (en) * | 2002-07-24 | 2005-09-21 | 巴斯福股份公司 | Continuous method for separating a c4 cut |
| CN1872819A (en) * | 2005-05-31 | 2006-12-06 | 中国石油化工股份有限公司 | Counter flow typed selective method for adding hydrogen |
| US20070055088A1 (en) * | 2003-10-27 | 2007-03-08 | Basf Aktiengesellschaft | Method for producing 1-butene |
| CN1965063A (en) * | 2004-04-09 | 2007-05-16 | 法国石油公司 | Method and device for processing a butadiene-containing feedstock |
| CN101133006A (en) * | 2005-02-01 | 2008-02-27 | 催化剂蒸馏技术公司 | Process and catalyst for selective hydrogenation of dienes and acetylenes |
| CN101665399A (en) * | 2008-09-05 | 2010-03-10 | 中国石油化工股份有限公司 | Method for producing butadiene |
| CN102285859A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Selective hydrogenation process for C4 material flow with high concentration of butadiene |
| CN103086831A (en) * | 2011-11-02 | 2013-05-08 | 中国石油化工股份有限公司 | Butadiene production system and method for improving butadiene yield and sufficiently utilizing C4 hydrocarbon |
| CN104926584A (en) * | 2014-03-19 | 2015-09-23 | 中国石化工程建设有限公司 | System and method for preparing isobutane |
| US20170029348A1 (en) * | 2015-07-30 | 2017-02-02 | Exxonmobil Chemical Patents Inc. | Process and Apparatus for Recovering Aromatic Hydrocarbons |
| CN106608791A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Method for preparing propylene through integrated utilization of C4 hydrocarbon |
-
2020
- 2020-10-23 CN CN202011148024.3A patent/CN114478161A/en active Pending
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5969203A (en) * | 1996-12-23 | 1999-10-19 | Institut Francais Du Petrole | Process for the production of high purity isobutene combining reactive distillation with hydroisomerization, distillation and skeletal isomerization |
| CN1235947A (en) * | 1998-03-27 | 1999-11-24 | Basf公司 | Preparation of olefins |
| KR20020095254A (en) * | 2000-05-09 | 2002-12-20 | 바스프 악티엔게젤샤프트 | Method and Device For Treating a C4 Fraction |
| CN1433392A (en) * | 2000-05-09 | 2003-07-30 | 巴斯福股份公司 | Method and device for treating C4 fraction |
| CN1671638A (en) * | 2002-07-24 | 2005-09-21 | 巴斯福股份公司 | Continuous method for separating a c4 cut |
| US20070055088A1 (en) * | 2003-10-27 | 2007-03-08 | Basf Aktiengesellschaft | Method for producing 1-butene |
| CN1965063A (en) * | 2004-04-09 | 2007-05-16 | 法国石油公司 | Method and device for processing a butadiene-containing feedstock |
| CN101133006A (en) * | 2005-02-01 | 2008-02-27 | 催化剂蒸馏技术公司 | Process and catalyst for selective hydrogenation of dienes and acetylenes |
| CN1872819A (en) * | 2005-05-31 | 2006-12-06 | 中国石油化工股份有限公司 | Counter flow typed selective method for adding hydrogen |
| CN101665399A (en) * | 2008-09-05 | 2010-03-10 | 中国石油化工股份有限公司 | Method for producing butadiene |
| CN102285859A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Selective hydrogenation process for C4 material flow with high concentration of butadiene |
| CN103086831A (en) * | 2011-11-02 | 2013-05-08 | 中国石油化工股份有限公司 | Butadiene production system and method for improving butadiene yield and sufficiently utilizing C4 hydrocarbon |
| CN104926584A (en) * | 2014-03-19 | 2015-09-23 | 中国石化工程建设有限公司 | System and method for preparing isobutane |
| US20170029348A1 (en) * | 2015-07-30 | 2017-02-02 | Exxonmobil Chemical Patents Inc. | Process and Apparatus for Recovering Aromatic Hydrocarbons |
| CN106608791A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Method for preparing propylene through integrated utilization of C4 hydrocarbon |
Non-Patent Citations (1)
| Title |
|---|
| 刘诗尧等: "隔壁塔应用于萃取精馏技术的研究进展", 《现代化工》, vol. 39, no. 06, 30 June 2019 (2019-06-30), pages 65 - 69 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109485536B (en) | Selective hydrogenation method for alkyne and/or diene in carbon four fraction | |
| JP5327485B2 (en) | Method for separating 1,3-butadiene from crude C4 fraction using acetylene conversion | |
| CN101133006B (en) | Process and catalyst for selective hydrogenation of dienes and acetylenes | |
| CN105566032B (en) | The selection hydrogenation technique of rich alkynes carbon four | |
| CN102695690B (en) | Process and system for the production of isoprene | |
| CN102285860B (en) | Selective hydrogenation process for C4 material flow with high concentration of alkyne | |
| CN100400482C (en) | Process for the selective hydrogenation of alkynes | |
| CN110325496A (en) | The manufacturing method and manufacturing device of hydrocarbon | |
| CN101613621B (en) | Method for selective hydrogenation and separation for pyrolysis gas | |
| CN103146428B (en) | Full hydrogenation process of unsaturated hydrocarbon fraction | |
| CN101451077A (en) | Selective hydrogenation method of acetylene hydrocarbon and dialkene in cracking gas | |
| CN106008820A (en) | Production system of low-chromaticity C5/C9 copolymerization hydrogenation resin and method | |
| CN101104573A (en) | Method for separating isoprene by combined rectification | |
| CN114478161A (en) | Apparatus and process for selective hydrogenation of mixed C4 stream | |
| CN109485534B (en) | Tail gas hydrogenation method for butadiene extraction device by DMF (dimethyl formamide) method | |
| CN101100412A (en) | Postheating dimerization method for separating C5 diene | |
| CN103946187A (en) | Procedure for manufacturing oligomers of butene | |
| CN114479935B (en) | Hydrogenation device and hydrogenation method for mixed C4 material flow | |
| CN114471375B (en) | Device and method for fully hydrogenating mixed C4 material flow | |
| CN101423452A (en) | Selective hydrogenation method for foreshot high unsaturated hydrocarbons mixed phase | |
| CN103086831B (en) | A kind of butadiene production system and method improving butadiene yield and make full use of C_4 hydrocarbon | |
| CN114478162B (en) | Butadiene extraction tail gas selective hydrogenation device and selective hydrogenation method | |
| US20240076559A1 (en) | Method for selective hydrogenation of butadiene extraction tail gas and selective hydrogenation apparatus thereof | |
| CN109485538B (en) | Selective hydrogenation method for alkyne in carbon four fraction | |
| CN111978141B (en) | Cracking mixed C 4 Material selective hydrogenation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |