CN114478163A - Selective hydrogenation device and selective hydrogenation method for butadiene extraction tail gas - Google Patents
Selective hydrogenation device and selective hydrogenation method for butadiene extraction tail gas Download PDFInfo
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- CN114478163A CN114478163A CN202011156909.8A CN202011156909A CN114478163A CN 114478163 A CN114478163 A CN 114478163A CN 202011156909 A CN202011156909 A CN 202011156909A CN 114478163 A CN114478163 A CN 114478163A
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 143
- 238000000605 extraction Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 91
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000001257 hydrogen Substances 0.000 claims abstract description 74
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 74
- 239000007789 gas Substances 0.000 claims abstract description 69
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000002994 raw material Substances 0.000 claims abstract description 61
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 29
- 239000003381 stabilizer Substances 0.000 claims abstract description 20
- 238000004891 communication Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 150000001345 alkine derivatives Chemical class 0.000 claims description 25
- 238000010992 reflux Methods 0.000 claims description 25
- 239000007791 liquid phase Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- 239000012071 phase Substances 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 description 29
- 239000003054 catalyst Substances 0.000 description 27
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 19
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 14
- -1 acetylene hydrocarbon Chemical class 0.000 description 11
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000001993 dienes Chemical class 0.000 description 7
- 238000007865 diluting Methods 0.000 description 7
- 208000019206 urinary tract infection Diseases 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 150000005673 monoalkenes Chemical class 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000000475 acetylene derivatives Chemical class 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- DCRIQAAPAFMPKP-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Al+3].[Ti+4] DCRIQAAPAFMPKP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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
-
- 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
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/008—Feed or outlet control devices
-
- 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
- C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
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- Oil, Petroleum & Natural Gas (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of petrochemical industry, and discloses a selective hydrogenation device and a selective hydrogenation method for butadiene extraction tail gas. The device comprises: the system comprises a raw material tank, a feed pump, a coalescer, a mixer, a hydrogenation reactor, a reactor outlet buffer tank, a circulating carbon four cooler, a stabilizer and a hydrogen feed pipeline; the raw material tank, the feed pump, the coalescer, the mixer, the hydrogenation reactor and the reactor outlet buffer tank are communicated in sequence; an outlet pipeline of the reactor outlet buffer tank is divided into two paths, and the first path is communicated with the circulating carbon four cooler, the mixer and the hydrogenation reactor in sequence; the second path is communicated with the stabilizing tower; the hydrogen feed line is divided into at least a first and optionally a second stream, the first stream being in communication with the reactor outlet surge tank and the second stream being in communication with the mixer. The device and the method can improve the selectivity of the butadiene tail gas selective hydrogenation reaction 1, 3-butadiene.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a selective hydrogenation device and a selective hydrogenation method for butadiene extraction tail gas.
Background
At present, a butadiene extraction device generally recovers 1, 3-butadiene from cracking carbon four fraction of an ethylene device by two-stage extractive distillation and common distillation methods, and meanwhile, a byproduct of tail gas rich in alkyne and diene is generated. Because of the different process technologies adopted by the butadiene extraction device, the byproduct alkyne tail gas has two states of liquid phase and gas phase, but the common characteristic is that the concentrations of Vinyl Acetylene (VA) and Ethyl Acetylene (EA) in the tail gas are higher, wherein the maximum concentration of VA can exceed 40 wt%. Currently, to ensure safety, the tail gas rich in alkynes and dienes needs to be diluted with a carbon four raffinate and then sold as liquefied gas or directly discharged to a flare for combustion. If the tail gas is recycled and utilized, good economic and social benefits can be created.
At present, for the carbon four resource rich in alkyne and dialkene, the carbon four resource is mainly converted into a product with high added value by a hydrofining method in industry, wherein one method is selective hydrofining. Although the hydrogenation activity of unsaturated hydrocarbons increases with the degree of unsaturation, the alkyne in carbon four reacts with hydrogen in preference to the diene and the monoolefin, under the action of the catalyst, the diene and the monoolefin in the carbon four component can also react with hydrogen violently at a lower temperature to generate alkane. The selective hydrogenation reaction of carbon four is a gas-liquid-solid three-phase reaction, but because the amount of hydrogen required by the reaction is small, the hydrogen is limited to be dissolved in the carbon four, and then the hydrogen and reactants in the carbon four, such as alkyne, dialkene and the like, pass through a liquid film through mass transfer to reach the surface of the catalyst for reaction. The inventor researches and discovers that: the hydrogenation reaction is limited by hydrogen, and acetylene hydrocarbon cannot be subjected to hydrogenation reaction on the surface of the catalyst in places with insufficient hydrogen, so that the acetylene hydrocarbon cannot be completely removed, and polymerization reaction is easy to occur to generate heavy components to reduce the performance of the catalyst; the excess hydrogen causes the diolefins and the butenes generated by the alkyne hydrogenation reaction to be further hydrogenated to generate the olefins and the alkanes, and causes the selectivity of the alkyne hydrogenation reaction to be reduced.
In recent years, the research work of the carbon four selective hydrogenation catalyst is more, and the activity and the selectivity of the catalyst are greatly improved. However, as mentioned above, the non-precise control and non-uniform distribution of hydrogen severely limit the exertion of catalyst selectivity, which makes it difficult for selective hydrogenation reactions to simultaneously satisfy the requirements of high conversion rate of acetylenes and dienes and high yield of mono-olefins. Compared with a laboratory pilot plant, an actual industrial plant has the advantages that the production scale is increased by hundreds of times, the accurate control of hydrogen is more difficult, the distribution is more uneven, and the improvement of selective hydrogenation reaction conditions from the aspects of process and control is more necessary according to the characteristics of the industrial plant.
CN102285859A discloses a selective hydrogenation method for a four-carbon material flow, which adopts a palladium-silver two-component or palladium-silver multi-component catalyst taking alumina as a carrier to selectively hydrogenate the four-carbon material flow with high butadiene content to obtain a product rich in 1-butene, wherein the butadiene and alkyne content in the product is lower than 10ppm, and the product can be used as a raw material of an MTBE device. The patent does not relate to butadiene tail gas rich in Vinyl Acetylene (VA) and Ethyl Acetylene (EA), and the target product is 1-butene by selective hydrogenation of acetylenes and dienes.
CN103121905A discloses a recovery method of butadiene extraction tail gas, which adopts a nickel-palladium-copper-silver multi-metal catalyst to selectively hydrogenate alkyne to obtain a product rich in butadiene, and the product is sent to a butadiene device to further recover butadiene. According to the method, hydrogen is directly added at the inlet of the reactor, the distribution is easily influenced by equipment and pipeline arrangement, the uniform distribution of the hydrogen is difficult to ensure, the selective exertion of the catalyst is further limited, and heavy components such as polymers generated by selective hydrogenation reaction are not removed from hydrogenated carbon four used for diluting a raw material, so that the accumulation in a system is easy to cause the reduction of the performance and the service life of the catalyst.
CN108863697A discloses a method for recycling butadiene through acetylene hydrocarbon selective hydrogenation, which adopts a palladium-molybdenum selective hydrogenation catalyst, the acetylene hydrocarbon in a carbon four stream is hydrogenated, the vinyl acetylene content is lower than 1.0 wt%, the butadiene selectivity is higher than 46%, and the product meets the feeding requirement of a butadiene extraction device. However, the patent adopts a palladium catalyst containing noble metal, so that the cost is higher, and the process flow of a butadiene tail gas selective hydrogenation device is not involved.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provide a selective hydrogenation device and a hydrogenation method for butadiene extraction tail gas. By improving the method for adding and metering hydrogen required by the selective hydrogenation reaction, the hydrogen is ensured to be accurately metered, the uniform distribution in the selective hydrogenation reaction is promoted, the selectivity of the selective hydrogenation reaction is improved, the occurrence of side reactions is reduced, and the service life of the catalyst is prolonged.
In order to achieve the above object, an aspect of the present invention provides a butadiene extraction tail gas selective hydrogenation apparatus, comprising: the system comprises a raw material tank, a feed pump, a coalescer, a mixer, a hydrogenation reactor, a reactor outlet buffer tank, a circulating carbon four cooler, a stabilizer and a hydrogen feed pipeline;
the raw material tank, the feeding pump, the coalescer, the mixer, the hydrogenation reactor and the reactor outlet buffer tank are communicated in sequence;
the outlet pipeline of the reactor outlet buffer tank is divided into two paths, and the first path is communicated with the circulating carbon four cooler, the mixer and the hydrogenation reactor in sequence; the second path is communicated with the stabilizing tower;
the hydrogen feed line is divided into at least a first and optionally a second stream, the first stream being in communication with the reactor outlet surge tank and the second stream being in communication with the mixer.
In another aspect of the present invention, a selective hydrogenation method for butadiene extraction tail gas is provided, which utilizes the above-mentioned butadiene extraction tail gas selective hydrogenation apparatus, and the selective hydrogenation method comprises:
(1) leading alkyne-containing tail gas from a butadiene extraction device to enter a raw material tank;
(2) pressurizing the raw material in the raw material tank to the pressure required by the reaction through a feed pump, then converging the raw material with the circulating carbon IV from the outlet buffer tank of the reactor, then entering a mixer, mixing the raw material with hydrogen in the mixer, then entering a hydrogenation reactor for hydrogenation reaction, and enabling the reaction material flow obtained by the reaction to enter the outlet buffer tank of the reactor;
hydrogen required by the reaction of the hydrogenation reactor is added in a first adding mode or a second adding mode;
the first adding mode is as follows: all hydrogen required by the reaction enters through the reactor outlet buffer tank and then enters into the hydrogenation reactor through the first path of the outlet of the reactor outlet buffer tank;
the second adding mode is as follows: part of hydrogen required by the reaction enters through the reactor outlet buffer tank and then enters into the hydrogenation reactor through the first path of the outlet of the reactor outlet buffer tank; the other part of hydrogen enters through a mixer and then enters the hydrogenation reactor;
(3) the buffer tank at the outlet of the reactor is discharged without gas phase, the liquid phase product is divided into two parts, the first part is used as the circulating carbon IV and returns to the hydrogenation reactor, and the second part is used as the feeding of the stabilizing tower;
(4) and the reaction material flow obtained by the reaction of the hydrogenation reactor enters a stabilizing tower through a reactor outlet buffer tank, and the product of the four-carbon hydrogenation is extracted after the separation of the stabilizing tower.
The technical scheme of the invention has the following beneficial effects:
(1) by adopting the device and the method, the butadiene tail gas (the alkyne-containing tail gas from the butadiene extraction device) can be fully recycled, and the selectivity of the butadiene tail gas in the selective hydrogenation reaction of 1, 3-butadiene is improved by optimizing the hydrogen distribution mode of the selective hydrogenation process.
(2) According to the invention, by optimizing the dilution mode of the raw material and adopting the 1, 3-butadiene, butene-1 and the carbon four hydrogenation product with low heavy component content to dilute the raw material, the problem of high alkyne concentration of the raw material tank is solved, the probability of re-hydrogenation of the 1, 3-butadiene and butene-1 caused by dilution carbon four back mixing is reduced, and the service life of the catalyst is further prolonged; effectively reduces the loss of 1, 3-butadiene and prolongs the service life of the catalyst.
(3) The invention adopts the catalyst without noble metal, and can effectively reduce the investment and the operation cost of the device.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Exemplary embodiments of the present invention will be described in more detail by referring to the accompanying drawings.
FIG. 1 shows a schematic diagram of a butadiene extracted tail gas selective hydrogenation unit according to one embodiment of the present invention.
Description of equipment label:
1, a raw material tank; 2, a feeding pump; 3 a coalescer; 4, a mixer; 5, a hydrogenation reactor; 6, a reactor outlet buffer tank; 7 circulating pump; 8-cycle carbo-quad coolers; 9a dilute carbon four cooler; 10 stabilizing the tower; 11 a tower top condenser; 12 a reflux tank; 13 a reflux pump; 14 tail gas condenser; 15 dilution carbon four pump; 16 a hydrogen feed line;
description of logistics labels:
101 acetylene hydrocarbon-containing tail gas (butadiene tail gas) from a butadiene extraction unit; 102 diluting carbon four; 107 hydrogenation reactor raw material; 108 hydrogenation reactor product; 109 circulating carbon four; 112 stabilizing the column feed; 115 stabilizing column reflux; 116 non-condensable gases; 117 heavy fraction; a 118 carbon four hydrogenation product; 201, reacting and supplementing hydrogen; the 202 reaction replenishes the hydrogen.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
One aspect of the present invention provides a butadiene extraction tail gas selective hydrogenation apparatus, comprising: the system comprises a raw material tank, a feed pump, a coalescer, a mixer, a hydrogenation reactor, a reactor outlet buffer tank, a circulating carbon four cooler, a stabilizer and a hydrogen feed pipeline;
the raw material tank, the feeding pump, the coalescer, the mixer, the hydrogenation reactor and the reactor outlet buffer tank are sequentially communicated;
the outlet pipeline of the reactor outlet buffer tank is divided into two paths, and the first path is communicated with the circulating carbon four cooler, the mixer and the hydrogenation reactor in sequence; the second path is communicated with the stabilizing tower;
the hydrogen feed line is split into at least a first and optionally a second stream, the first stream being in communication with the reactor outlet surge tank and the second stream being in communication with the mixer.
In the invention, the raw material tank is provided with a port for extracting the tail gas of butadiene and diluting carbon four.
According to the invention, preferably, an outlet of the stabilizer is communicated with a diluted carbon four port of the raw material tank.
According to the invention, preferably, an outlet of the stabilization tower, the diluted carbon four pump, the diluted carbon four cooler and a diluted carbon four interface of the raw material tank are communicated in sequence.
According to the present invention, preferably, the first path of the outlet line of the reactor outlet buffer tank is communicated with the recycle carbon four cooler via a circulation pump.
According to the invention, preferably, the top outlet of the stabilizer is connected with an overhead condenser and a reflux tank in sequence;
an outlet of the first reflux tank is communicated with a tail gas condenser, and an outlet of the tail gas condenser is communicated with an inlet of the first reflux tank;
and the other outlet of the reflux tank is communicated with the inlet of the stabilizing tower through a reflux pump.
According to the present invention, preferably, the hydrogenation reactor is a fixed bed reactor.
The second aspect of the present invention provides a selective hydrogenation method for butadiene extraction tail gas, which utilizes the above-mentioned butadiene extraction tail gas selective hydrogenation apparatus, and the selective hydrogenation method comprises:
(1) leading alkyne-containing tail gas from a butadiene extraction device to enter a raw material tank;
(2) pressurizing the raw material in the raw material tank to the pressure required by the reaction through a feed pump, then converging the raw material with the circulating carbon IV from the outlet buffer tank of the reactor, then entering a mixer, mixing the raw material with hydrogen in the mixer, then entering a hydrogenation reactor for hydrogenation reaction, and enabling the reaction material flow obtained by the reaction to enter the outlet buffer tank of the reactor;
hydrogen required by the reaction of the hydrogenation reactor is added in a first adding mode or a second adding mode;
the first adding mode is as follows: all hydrogen required by the reaction enters through the reactor outlet buffer tank and then enters into the hydrogenation reactor through the first path of the reactor outlet buffer tank outlet;
the second adding mode is as follows: part of hydrogen required by the reaction enters through the reactor outlet buffer tank and then enters into the hydrogenation reactor through the first path of the outlet of the reactor outlet buffer tank; the other part of hydrogen enters through a mixer and then enters the hydrogenation reactor;
(3) the buffer tank at the outlet of the reactor is discharged without gas phase, the liquid phase product is divided into two parts, the first part is used as the circulating carbon IV and returns to the hydrogenation reactor, and the second part is used as the feeding of the stabilizing tower;
(4) and the reaction material flow obtained by the reaction of the hydrogenation reactor enters a stabilizing tower through a reactor outlet buffer tank, and the product of the four-carbon hydrogenation is extracted after the separation of the stabilizing tower.
In the invention, the carbon four-hydrogenation product is extracted from the reflux tank at the top of the tower after being separated by the stabilizing tower, and the carbon four-hydrogenation product comprises 1, 3-butadiene and butene-1.
According to the invention, in step (1), the alkyne-containing tail gas in the raw material tank is diluted by adopting side-stream dilution carbon four from the stabilizer;
preferably, the mass flow ratio of the diluted carbon four to the alkyne-containing tail gas is 1-30: 1.
in the present invention, in the step (2), the raw material in the raw material tank is preferably a diluted raw material.
In the invention, the side line dilute carbon IV of the stabilizing tower mainly comprises low content of 1, 3-butadiene, butene-1 and heavy components which easily have adverse effects on the activity and the service life of the catalyst.
According to the present invention, in step (2), preferably, in the second adding mode, the mass ratio of part of hydrogen required for the reaction to hydrogen required for the hydrogenation reaction, which is the sum of part of hydrogen required for the reaction and another part of hydrogen, is not less than 0.3, preferably not less than 0.5.
In the second mode of addition, the sum of the quantities of part of the hydrogen and the other part of the hydrogen required for the reaction is equal to the total quantity of hydrogen required for the hydrogenation reaction.
In the first adding mode, hydrogen required by the hydrogenation reactor controls the pressure of a reaction system through pressure compensation, all hydrogen enters liquid-phase carbon four in a dissolving mode, and enters the hydrogenation reactor along with reactor circulating carbon four; in the second adding mode, part of hydrogen required by the reaction is added through a buffer tank at the outlet of the reactor, the part of hydrogen controls the pressure of a reaction system through pressure compensation, enters into the liquid-phase carbon IV through a dissolving mode and enters into the hydrogenation reactor along with the circulating carbon IV of the reactor.
According to the present invention, preferably, in the step (1), the operation pressure of the raw material tank is 0.5 to 1.0 MPaG;
in the step (2), the diluted raw material is pressurized to 1.0-4.0 MPaG by a feed pump, and the mass flow ratio of the circulating carbon four to the diluted carbon four raw material is 5-30: 1;
the inlet temperature of the hydrogenation reactor is 5-60 ℃ respectively and independently, and the liquid space velocity is 1-40 h-1(ii) a The pressure of the hydrogenation reactor is controlled by the pressure-supplementing hydrogen of a buffer tank at the outlet of the reactor, and the reaction pressure is 1.0-4.0 MPaG;
in the step (4), the operating pressure of the stabilizing tower is 0.4-1.0 MPaG, the number of theoretical plates is 10-40, and the position of a lateral line extraction theoretical plate is 5-35.
In the invention, in the step (4), the side-draw phase of the stabilizer is a liquid phase.
In the invention, a two-stage condenser is adopted at the top of the stabilizer to recover four carbon components carried in the non-condensable gas; a hydrogenation product with high 1, 3-butadiene and butene-1 content is extracted from the liquid phase of the tower top reflux tank; removing heavy components from the tower kettle; the low-content 1, 3-butadiene, butene-1 and the carbon four hydrogenation product of heavy components which easily have adverse effects on the activity and the service life of the catalyst are obtained from a side line and are used for diluting raw materials.
In the present invention, selective hydrogenation catalysts CN102886262, CN10886397 and/or CN104707622, etc. in the known art can be selected for selective hydrogenation reaction, preferably the selective hydrogenation catalyst disclosed in CN104707622, and the preferred catalyst comprises the following components based on the total weight of the catalyst: 5-15 wt% of copper, 0.1-3 wt% of phosphorus, 0.1-3 wt% of one or more auxiliary metals selected from nickel, zirconium, lead and tin, and the balance of a carrier, wherein the carrier is at least one carrier selected from alumina, titanium oxide, silicon oxide, titanium oxide-alumina composite oxide, titanium oxide-silica composite oxide and alumina-silica composite oxide.
In the invention, after the liquid phase butadiene tail gas is diluted and pressurized, a catalyst without noble metal is adopted for selective hydrogenation reaction, and light and heavy components are removed by a stabilizer to obtain a carbon tetraene product which has low alkyne content and is rich in 1, 3-butadiene, and the carbon tetraene product can be returned to a butadiene extraction device for further recovering the 1, 3-butadiene and the monoolefin.
The invention is further illustrated by the following examples:
the catalysts used in the following examples were: the catalyst consists of the following components in percentage by weight based on the total weight of the catalyst: copper in an amount of 7 wt%, phosphorus in an amount of 2 wt%, nickel in an amount of 3 wt%, and the balance being a carrier, the carrier being a titanium oxide-aluminum oxide composite oxide.
Example 1
As shown in fig. 1, this embodiment provides a butadiene extraction tail gas selective hydrogenation apparatus, which includes: the system comprises a raw material tank 1, a feed pump 2, a coalescer 3, a mixer 4, a hydrogenation reactor 5, a reactor outlet buffer tank 6, a circulating pump 7, a circulating carbon four-cooler 8, a diluting carbon four-cooler 9, a stabilizing tower 10, a tower top condenser 11, a reflux tank 12, a reflux pump 13, a tail gas condenser 14, a diluting carbon four-pump 15 and a hydrogen feed pipeline 16;
the device comprises a raw material tank 1, a feed pump 2, a coalescer 3, a mixer 4, a hydrogenation reactor 5 and a reactor outlet buffer tank 6, wherein the raw material tank 1 is provided with a butadiene extraction tail gas and diluted carbon four interface;
the outlet pipeline of the reactor outlet buffer tank 6 is divided into two paths, and the first path is communicated with the circulating carbon four cooler 8, the mixer 4 and the hydrogenation reactor 5 in sequence; the second path is communicated with the stabilizing tower 10; wherein, a first path of an outlet pipeline of the reactor outlet buffer tank 6 is communicated with the circulating carbon four cooler 8 through a circulating pump 7;
the hydrogen feeding line 16 is divided into at least a first stream and an optional second stream, the first stream is communicated with the top inlet of the reactor outlet buffer tank 6, and the second stream is communicated with the mixer 4;
wherein, an outlet of the stabilizing tower 10, a diluted carbon four pump 15, a diluted carbon four cooler 9 and a diluted carbon four interface of the raw material tank 1 are communicated in sequence; the top outlet of the stabilizing tower 10 is sequentially connected with an overhead condenser 11 and a reflux tank 12; an outlet of the reflux tank 12 is communicated with a tail gas condenser 14, and an outlet of the tail gas condenser 14 is communicated with an inlet of the reflux tank 12; the other outlet of the reflux tank 12 is communicated with a reflux pump 13, and the outlet of the reflux pump 13 is communicated with an inlet of the stabilizing tower 10.
Wherein, the hydrogenation reactor 5 is a fixed bed reactor.
The selective hydrogenation method for butadiene extraction tail gas by using the butadiene extraction tail gas selective hydrogenation device of the embodiment comprises the following steps:
(1) acetylene hydrocarbon-containing tail gas 101 (based on the total weight of the acetylene hydrocarbon-containing tail gas, the main components of the acetylene hydrocarbon-containing tail gas are: butylene 58.69%, butadiene 10.35%, ethyl acetylene 17.65%, vinyl acetylene 4.00%, C2.05% and above, and water 0.02%) from a butadiene extraction device enters a raw material tank 1, and the acetylene hydrocarbon-containing tail gas in the raw material tank is diluted by using diluted carbon four 102 which is cooled from a lateral line of a stabilizing tower 10; wherein the flow rate of the alkyne-containing tail gas 101 is 1825kg/h, and the pressure is 0.8 MPaG; the flow rate of the diluted carbon four 102 is 5000kg/h, the content of liquid-phase vinyl acetylene in the raw material tank 1 after dilution is 5.32%, and the content of vinyl acetylene in a gas phase is 4.75%.
(2) The diluted raw material in the raw material tank 1 is pressurized to 2.7MPaG by a feed pump, then is converged with the circulating carbon four 109 from the reactor outlet buffer tank 6, enters a mixer 4, is mixed with hydrogen in the mixer (namely the raw material 107 of the hydrogenation reactor), enters a hydrogenation reactor 5 for hydrogenation reaction, and the reaction material flow (the product 108 of the hydrogenation reactor) obtained by the reaction enters the reactor outlet buffer tank 6; the flow rate of the circulating carbon four 109 was 45000kg/h, the feed flow rate of the mixed carbon four was 46825kg/h, and the temperature was 20 ℃.
Hydrogen required by the reaction of the hydrogenation reactor 5 is added in a first adding mode;
the first adding mode is as follows: all hydrogen required by the reaction enters through the reactor outlet buffer tank 6, and then enters into the hydrogenation reactor 5 through the first path of the outlet of the reactor outlet buffer tank 6; the pressure of a reaction system is controlled by the pressure supplement of hydrogen required by the reaction of the hydrogenation reactor 5, the pressure is 2.3MPaG, the hydrogen enters the liquid-phase carbon four in a dissolving mode, the hydrogen enters the hydrogenation reactor along with the reactor circulating carbon four 109, the flow of the circulating carbon four 109 is 45000kg/h, the flow of the hydrogen dissolved in the circulating carbon four is 34.0kg/h, the hydrogen is not added into the inlet mixer 4 of the hydrogenation reactor 5, and the total airspeed of the reaction liquid phase is 15h-1(ii) a The inlet temperature of the hydrogenation reactor 5 is 20 ℃;
(3) the reactor outlet buffer tank 6 is discharged without gas phase, the liquid phase product is divided into two parts, the first part is used as the circulating carbon four 109 and returns to the hydrogenation reactor, and the second part is used as the stabilizing tower feeding 112; the flow rate of stabilizer column feed 112 was 6853 kg/h.
(4) The reactant flow (hydrogenation reactor product 108) obtained by the reaction of the hydrogenation reactor 5 enters the stabilizer 10 through the reactor outlet buffer tank 6, and the product 118 of the four carbon hydrogenation is produced after being separated by the stabilizer 10. Wherein, the stabilizer 10 removes non-condensable gas 116 from the top of the tower, removes heavy components 117 from the bottom of the tower, extracts a liquid-phase carbon four-hydrogenation product 118 rich in 1, 3-butadiene and mono-olefin from the top of the tower, and extracts diluted carbon four 102 for diluting raw materials from a side line, and the flow rate is 5000 kg/h. The number of theoretical plates of the stabilizer 10 is 30, the operation pressure is 0.5MPaG, the temperature at the top of the tower is 56.7 ℃, the temperature at the bottom of the tower is 100.2 ℃, the reflux amount (115 reflux of the stabilizer) is 5600kg/h, and the position of a lateral line extraction theoretical plate is 25.
The results of the main streams are shown in Table 1.
TABLE 1
| Number of commodity circulation | 101 | 102 | 108 | 118 | 201 | 202 |
| Phase state | Liquid for treating urinary tract infection | Liquid for treating urinary tract infection | Liquid for medical purpose | Liquid for treating urinary tract infection | Qi (Qi) | Qi (Qi) |
| Temperature [ C ]] | 40.0 | 20.1 | 35.3 | 15.0 | 15.8 | 15.8 |
| Pressure [ MPa (g)] | 0.80 | 0.65 | 2.30 | 0.50 | 2.40 | 2.40 |
| Molar composition | ％ | ％ | ％ | ％ | ％ | ％ |
| Hydrogen gas | 0.00 | 0.00 | 0.00 | 0.17 | 95.00 | 95.00 |
| Methane | 0.00 | 0.00 | 0.46 | 0.60 | 5.00 | 5.00 |
| Propane | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Propylene (PA) | 0.01 | 0.00 | 0.00 | 0.01 | 0.00 | 0.00 |
| Propyne | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| N-butane | 2.57 | 4.14 | 3.91 | 3.40 | 0.00 | 0.00 |
| Isobutane | 4.67 | 0.84 | 1.87 | 4.75 | 0.00 | 0.00 |
| Butene-1 | 14.20 | 11.32 | 14.57 | 23.10 | 0.00 | 0.00 |
| Isobutene | 22.05 | 9.32 | 12.72 | 22.57 | 0.00 | 0.00 |
| Cis-2-butene | 18.79 | 44.13 | 37.31 | 19.70 | 0.00 | 0.00 |
| Trans-2-butene | 3.65 | 11.48 | 10.47 | 8.06 | 0.00 | 0.00 |
| 1, 3-butadiene | 6.35 | 9.30 | 10.78 | 16.29 | 0.00 | 0.00 |
| 1, 2-butadiene | 4.00 | 5.06 | 3.93 | 0.91 | 0.00 | 0.00 |
| Ethyl acetylene | 4.00 | 0.31 | 0.26 | 0.12 | 0.00 | 0.00 |
| Vinyl acetylene | 17.63 | 0.76 | 0.64 | 0.31 | 0.00 | 0.00 |
| N-pentane | 1.80 | 3.21 | 2.82 | 0.00 | 0.00 | 0.00 |
| C5 | 0.25 | 0.06 | 0.27 | 0.00 | 0.00 | 0.00 |
| Water (I) | 0.02 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Molar flow rate [ kmol/h] | 32.78 | 88.56 | 1186.79 | 31.02 | 12.51 | 0.00 |
| Mass flow rate [ kg/h] | 1825.00 | 5000.00 | 66825 | 1724.50 | 34.00 | 0.00 |
As can be seen from Table 1, in the product, the content of 1, 3-butadiene is increased by about 10 percent compared with the raw material, the content of alkyne is less than 0.5 percent, the total conversion rate of alkyne is more than 97 percent, and the raw material requirement of a butadiene extraction device can be met.
Example 2
As shown in fig. 1, the present embodiment is different from embodiment 1 in the following points:
in the step (2), hydrogen required by the reaction of the hydrogenation reactor 5 is added in a second adding mode; the second adding mode is as follows: part of hydrogen required by the reaction enters through the reactor outlet buffer tank 6, and then enters into the hydrogenation reactor 5 through the first path of the outlet of the reactor outlet buffer tank 6; the other part of hydrogen enters through a mixer 4 and then enters the hydrogenation reactor 5; most of hydrogen is distributed through an outlet buffer tank 6 of the hydrogenation reactor, the pressure of the reaction system is controlled by pressure compensation, the hydrogen enters liquid phase carbon four in a dissolving mode, the hydrogen enters the reactor along with the reactor circulating carbon four 109, the flow rate of the circulating carbon four 109 is 32000kg/h, and the flow rate of the hydrogen dissolved in the circulating carbon four is 20.0 kg/h; a small part of hydrogen is distributed through a mixer 4 arranged at the inlet of the hydrogenation reactor 5, and the flow rate is 17.0 kg/h.
The results of the various main streams are shown in table 2.
TABLE 2
| Number of commodity circulation | 101 | 102 | 108 | 118 | 201 | 202 |
| Phase state | Liquid for treating urinary tract infection | Liquid for treating urinary tract infection | Liquid for treating urinary tract infection | Liquid for treating urinary tract infection | Qi (Qi) | Qi (Qi) |
| Temperature [ C ]] | 40 | 20 | 41.7 | 15 | 15.8 | 15.8 |
| Pressure [ MPa (g)] | 0.8 | 0.65 | 2.3 | 0.5 | 2.4 | 2.4 |
| Molar composition | ％ | ％ | ％ | ％ | ％ | ％ |
| Hydrogen gas | 0 | 0 | 0 | 0.18 | 95 | 95 |
| Methane | 0 | 0 | 0.50 | 0.55 | 5 | 5 |
| Propane | 0 | 0 | 0.00 | 0.00 | 0 | 0 |
| Propylene (PA) | 0.01 | 0 | 0.00 | 0.01 | 0 | 0 |
| Propyne | 0 | 0 | 0.00 | 0.00 | 0 | 0 |
| N-butane | 2.57 | 4.01 | 3.76 | 3.22 | 0 | 0 |
| Isobutane | 4.67 | 0.86 | 1.88 | 4.75 | 0 | 0 |
| Butene-1 | 14.2 | 12.06 | 15.36 | 25.20 | 0 | 0 |
| Isobutene | 22.05 | 9.52 | 12.84 | 22.55 | 0 | 0 |
| Cis-2-butene | 18.79 | 44.78 | 37.78 | 19.61 | 0 | 0 |
| Trans-2-butene | 3.65 | 12.55 | 11.40 | 8.65 | 0 | 0 |
| 1, 3-butadiene | 6.35 | 8.76 | 10.07 | 14.12 | 0 | 0 |
| 1, 2-butadiene | 4 | 4.06 | 3.16 | 0.72 | 0 | 0 |
| Ethyl acetylene | 4 | 0.41 | 0.34 | 0.13 | 0 | 0 |
| Vinyl acetylene | 17.63 | 0.96 | 0.80 | 0.33 | 0 | 0 |
| N-pentane | 1.8 | 1.93 | 1.88 | 0.00 | 0 | 0 |
| C five + C | 0.25 | 0.10 | 0.22 | 0 | 0 | 0 |
| Water (W) | 0.02 | 0 | 0 | 0 | 0 | 0 |
| Molar flow rate [ kmol/h] | 32.78 | 88.87 | 695.1 | 30.75 | 7.36 | 6.26 |
| Mass flow rate [ kg/h] | 1825 | 5000 | 38842 | 1710 | 20 | 17 |
As can be seen from Table 2, in the product, the content of 1, 3-butadiene is increased by about 7.8 percent compared with the raw material, the content of alkyne is less than 0.5 percent, the total conversion rate of alkyne is more than 97 percent, and the raw material requirement of a butadiene extraction device can be met. Compared with the example 1, in the present example, hydrogen does not completely enter the reactor by dissolution, so that the uniformity of hydrogen distribution is slightly worse than that of the example 1, and further, part of 1, 3-butadiene is consumed by hydrogenation reaction, so that the 1, 3-butadiene content in the product is reduced compared with the increase value of the raw material.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (9)
1. A butadiene extraction tail gas selective hydrogenation device is characterized by comprising: the system comprises a raw material tank, a feed pump, a coalescer, a mixer, a hydrogenation reactor, a reactor outlet buffer tank, a circulating carbon four-cooler, a stabilizer and a hydrogen feeding pipeline;
the raw material tank, the feeding pump, the coalescer, the mixer, the hydrogenation reactor and the reactor outlet buffer tank are communicated in sequence;
the outlet pipeline of the reactor outlet buffer tank is divided into two paths, and the first path is communicated with the circulating carbon four cooler, the mixer and the hydrogenation reactor in sequence; the second path is communicated with the stabilizing tower;
the hydrogen feed line is divided into at least a first and optionally a second stream, the first stream being in communication with the reactor outlet surge tank and the second stream being in communication with the mixer.
2. The butadiene extracted tail gas selective hydrogenation device of claim 1, wherein an outlet of the stabilizer is communicated with a dilute carbon four port of the raw material tank.
3. The butadiene extraction tail gas selective hydrogenation device of claim 2, wherein an outlet of the stabilizer, the diluted carbon four pump, the diluted carbon four cooler and the diluted carbon four port of the raw material tank are sequentially communicated.
4. The butadiene extraction tail gas selective hydrogenation unit of claim 1, wherein the first path of the outlet pipeline of the reactor outlet buffer tank is communicated with the recycle carbon four cooler through a circulating pump.
5. The butadiene extraction tail gas selective hydrogenation device of claim 1, wherein an overhead condenser and a reflux tank are connected to the top outlet of the stabilizer in sequence;
an outlet of the first reflux tank is communicated with a tail gas condenser, and an outlet of the tail gas condenser is communicated with an inlet of the first reflux tank;
and the other outlet of the reflux tank is communicated with the inlet of the stabilizing tower through a reflux pump.
6. The butadiene extraction tail gas selective hydrogenation device of claim 1, wherein the hydrogenation reactor is a fixed bed reactor.
7. A selective hydrogenation method of butadiene extraction tail gas, which utilizes the butadiene extraction tail gas selective hydrogenation device of any one of claims 1 to 6, characterized in that the selective hydrogenation method comprises the following steps:
(1) leading alkyne-containing tail gas from a butadiene extraction device to enter a raw material tank;
(2) pressurizing the raw material in the raw material tank to the pressure required by the reaction through a feed pump, then converging the raw material with the circulating carbon IV from the outlet buffer tank of the reactor, then entering a mixer, mixing the raw material with hydrogen in the mixer, then entering a hydrogenation reactor for hydrogenation reaction, and enabling the reaction material flow obtained by the reaction to enter the outlet buffer tank of the reactor;
hydrogen required by the reaction of the hydrogenation reactor is added in a first adding mode or a second adding mode;
the first adding mode is as follows: all hydrogen required by the reaction enters through the reactor outlet buffer tank and then enters into the hydrogenation reactor through the first path of the outlet of the reactor outlet buffer tank;
the second adding mode is as follows: part of hydrogen required by the reaction enters through the reactor outlet buffer tank and then enters into the hydrogenation reactor through the first path of the outlet of the reactor outlet buffer tank; the other part of hydrogen enters through a mixer and then enters the hydrogenation reactor;
(3) the buffer tank at the outlet of the reactor is discharged without gas phase, the liquid phase product is divided into two parts, the first part is used as the circulating carbon IV and returns to the hydrogenation reactor, and the second part is used as the feeding of the stabilizing tower;
(4) and the reaction material flow obtained by the reaction of the hydrogenation reactor enters a stabilizing tower through a reactor outlet buffer tank, and the product of the four-carbon hydrogenation is extracted after the separation of the stabilizing tower.
8. The selective hydrogenation method according to claim 7, wherein in the step (1), the alkyne-containing tail gas in the feed tank is diluted by adopting side-stream dilution carbon four from the stabilizer;
preferably, the mass flow ratio of the diluted carbon four to the alkyne-containing tail gas is 1-30: 1.
9. the selective hydrogenation process of claim 7, wherein in step (1), the feed tank is operated at a pressure of 0.5 to 1.0 MPaG;
in the step (2), the diluted raw material is pressurized to 1.0-4.0 MPaG by a feed pump, and the mass flow ratio of the circulating carbon four to the diluted carbon four raw material is 5-30: 1;
the inlet temperature of the hydrogenation reactor is 5-60 ℃, and the liquid space velocity is 1-40 h-1(ii) a The pressure of the hydrogenation reactor is buffered by the outlet of the reactorControlling the pressure of the tank by supplementing hydrogen, wherein the pressure of the reaction is 1.0-4.0 MPaG;
in the step (4), the operating pressure of the stabilizing tower is 0.4-1.0 MPaG, the number of theoretical plates is 10-40, and the position of a lateral line extraction theoretical plate is 5-35.
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| CN202011156909.8A CN114478163A (en) | 2020-10-26 | 2020-10-26 | Selective hydrogenation device and selective hydrogenation method for butadiene extraction tail gas |
| JP2023525543A JP2023546626A (en) | 2020-10-26 | 2021-10-19 | Selective hydrogenation method for butadiene extraction tail gas and its selective hydrogenation device |
| EP21884978.4A EP4238951A1 (en) | 2020-10-26 | 2021-10-19 | Method for selective hydrogenation of butadiene extraction tail gas and selective hydrogenation apparatus |
| CA3196784A CA3196784A1 (en) | 2020-10-26 | 2021-10-19 | Method for selective hydrogenation of butadiene extraction tail gas and selective hydrogenation apparatus thereof |
| PCT/CN2021/124668 WO2022089250A1 (en) | 2020-10-26 | 2021-10-19 | Method for selective hydrogenation of butadiene extraction tail gas and selective hydrogenation apparatus |
| US18/033,871 US20240076559A1 (en) | 2020-10-26 | 2021-10-19 | Method for selective hydrogenation of butadiene extraction tail gas and selective hydrogenation apparatus thereof |
| KR1020237017598A KR20230097091A (en) | 2020-10-26 | 2021-10-19 | Method for selective hydrogenation of butadiene extraction tail gas and selective hydrogenation device therefor |
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| CN103787811A (en) * | 2012-10-30 | 2014-05-14 | 中国石油化工股份有限公司 | Method for hydrotreating butadiene tail gas |
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