CN110963878A - Recovery method of C4 alkyne tail gas - Google Patents
Recovery method of C4 alkyne tail gas Download PDFInfo
- Publication number
- CN110963878A CN110963878A CN201811156827.6A CN201811156827A CN110963878A CN 110963878 A CN110963878 A CN 110963878A CN 201811156827 A CN201811156827 A CN 201811156827A CN 110963878 A CN110963878 A CN 110963878A
- Authority
- CN
- China
- Prior art keywords
- tail gas
- alkyne
- compressor
- stage
- reactor
- 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.)
- Granted
Links
- 150000001345 alkine derivatives Chemical class 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 80
- 238000011084 recovery Methods 0.000 title abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 116
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 109
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 82
- 239000000463 material Substances 0.000 claims abstract description 63
- 238000000605 extraction Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000012535 impurity Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000007599 discharging Methods 0.000 claims abstract description 13
- 239000003085 diluting agent Substances 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 208000028659 discharge Diseases 0.000 claims description 41
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 claims description 28
- 239000012071 phase Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000007791 liquid phase Substances 0.000 claims description 16
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 claims description 10
- 230000006835 compression Effects 0.000 claims description 10
- 238000007906 compression Methods 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000001273 butane Substances 0.000 claims description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 5
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 5
- 239000000539 dimer Substances 0.000 claims description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- -1 acetylene hydrocarbon Chemical class 0.000 abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 76
- 239000000047 product Substances 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 239000012752 auxiliary agent Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000004064 recycling Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 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
- 238000003795 desorption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical group 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a recovery method of C4 alkyne tail gas, the C4 alkyne tail gas is generated by a DMF method 1, 3-butadiene extraction device, and the impurities in the C4 alkyne tail gas comprise: butadiene dimer, solvent DMF and water, comprising the steps of: (1) tail gas liquefaction: c4 acetylene hydrocarbon tail gas is compressed and boosted by the first stage of the compressor and the second stage of the first stage of the compressor; (2) impurity removal: s1, discharging the material from the second-stage cooler of the compressor, entering a second-stage discharge buffer tank of the compressor, and removing impurities to obtain a liquefied C4 alkyne material; s2, mixing the liquefied C4 alkyne material with the raffinate carbon IV, removing impurities to obtain a coalescer discharge; (3) hydrogenation reaction: mixing the coalescer discharge with hydrogen and then carrying out selective hydrogenation reaction; (4) removing light components: and removing light weight of the hydrogenated material, sending one part of the hydrogenated material to the inlet of the reactor to be used as a circulating diluent, sending the other part of the hydrogenated material to a product cooler to be cooled to obtain a hydrogenated product, and sending the hydrogenated product to a mixing C4 storage tank.
Description
Technical Field
The invention belongs to the field of petrochemical industry, relates to a method for recycling high-concentration alkyne tail gas in C4 fraction, and particularly relates to a method for recycling C4 alkyne tail gas generated by a DMF (dimethyl formamide) method 1, 3-butadiene extraction device.
Background
Along with the increase of the ethylene cracking depth in China, the alkyne content in the cracking mixed carbon four is obviously increased, and the alkyne content in the cracking mixed carbon four of part of manufacturers is even more than 2.0 percent (weight). The increase of alkyne content and the improvement of downstream requirement on butadiene purity obviously increase the operation difficulty and energy consumption of a secondary extraction system of a butadiene extraction device, and simultaneously increase the loss of butadiene. A large amount of carbon-tetra-alkyne tail gas (rich in ethyl acetylene, vinyl acetylene and propyne) can be generated after butadiene extraction, and when the concentration of alkyne in the tail gas exceeds a certain range, the risk of decomposition and explosion exists, so that alkyne is usually diluted to a safe range by using a large amount of butene and butane and then is directly discharged into a torch system or sold at a low price, along with the expansion of the scale of domestic ethylene and the increase of the requirement on the purity of butadiene, the quantity of the carbon-tetra-alkyne tail gas discharged by a butadiene extraction device is gradually increased, and the carbon-tetra-alkyne tail gas is discharged into a torch for treatment or sold at a low price, so that great economic loss and environmental pollution are caused. Meanwhile, with the rapid development of the rubber industry, the short supply and short demand phenomenon of butadiene is more obvious, and butadiene of a plurality of manufacturers has a certain gap seriously, so that the butadiene is recovered from the carbon-tetra-alkyne tail gas discharged by the extraction device after selective hydrogenation, the economic benefit of the device can be obviously improved, the operation stability of the device is improved, and the environmental pollution caused by tail gas discharge is reduced.
For selective hydrogenation of alkyne in cracking mixed C4, there are pre-hydrogenation process and post-hydrogenation process. The pre-hydrogenation is to perform selective hydrogenation on all four fractions of the cracking carbon to remove alkyne, and then perform extraction of butadiene. And the post hydrogenation is to perform selective hydrogenation on the high-concentration alkyne separated by the second extraction system to convert the alkyne into 1, 3-butadiene, and the hydrogenated fraction is returned to the mixed C-C raw material storage tank or the extraction device for butadiene extraction again.
The KLP technology of the U.S. UOP company is the most representative pre-hydrogenation process in the world at present, and the method has large treatment capacity of a hydrogenation device and inevitably loses part of butadiene. The IFP technology of French Petroleum institute belongs to the post-hydrogenation technology, and the alkyne concentration in the hydrogenation material is high, so that the catalyst has high hydrogenation activity requirement.
Chinese patent No. 103768896 discloses a tail gas recovery system and method for butadiene extraction device. The system comprises: the absorption tower comprises an absorption tower, a hydrogenation reactor I section and an analytical tower, wherein an absorbent inlet is formed in the upper part of the absorption tower, a butadiene tail gas inlet is formed in the lower part of the absorption tower, and an outlet at the bottom of the absorption tower is connected with a pump, combined with a hydrogen pipeline and then connected with the bottom of the hydrogenation reactor I section; the outlet at the top of the I-section hydrogenation reactor is connected with the middle part of the desorption tower, the bottom of the desorption tower is connected with the absorbent inlet of the absorption tower, and the top of the desorption tower is connected with the outside. The method comprises the following steps: butadiene tail gas is absorbed, hydrogenated and resolved in the section I. The invention can safely realize the recycling of the butadiene tail gas.
Chinese patent CN102336626 discloses a method for utilizing waste gas of butadiene extraction device, in which the waste gas is reacted with hydrogen gas, so that the alkyne in the waste gas is selectively hydrogenated to produce diolefin, and the reaction product is returned to butadiene extraction device to recover 1, 3-butadiene. The problem of difficult utilization of the butadiene tail gas is solved by adopting the process of a compressor and a cold box.
Chinese patent CN102381920 discloses a method for removing alkynes in C4 fraction by selective hydrogenation. Liquid in the tower is introduced into the C4 alkyne hydrogenation reactor from a proper position below the feeding plate, and the reacted material flow returns to the rectifying tower, so that the aim of removing alkyne is fulfilled in the separation process. The method has the advantages that the concentration of butadiene entering the C4 hydrogenation reactor is low, the concentration of EA and VA is high by adjusting the liquid phase extraction position and the reflux ratio of the debutanizer, the reaction probability of butadiene conversion to butylene and butane is reduced, the selectivity of C4 alkyne conversion to butadiene is improved, the purposes of butadiene yield increase and alkyne removal are realized, and meanwhile, because the C4 alkyne hydrogenation is carried out on a fixed bed outside the tower, the regeneration and replacement of the catalyst are easier, and the requirement of long-period operation of an ethylene device can be met. The method can reduce the alkyne concentration in the carbon four-fraction entering the butadiene extraction device, reduce partial energy consumption of secondary extraction, save C4 hydrocarbon for dilution and reduce environmental pollution.
The key point of the recycling of the C4 alkyne tail gas generated by the DMF 1, 3-butadiene extraction device is as follows:
(1) the vinyl acetylene contained in the tail gas is easy to polymerize and explode, and the tail gas is liquefied on the premise of ensuring safety;
(2) a method for removing impurities which affect the activity of the hydrogenation catalyst, such as water, dimer, solvent DMF and the like contained in tail gas;
(3) a method for separating light components such as hydrogen, methane and the like in a hydrogenation product.
The prior art adopts a method for solving the problems, but the control is not ideal, the tail gas liquefaction process is complex, and the energy consumption is high; the impurity content in the tail gas does not meet the requirement, and the long-period operation of the catalyst is influenced; light components in the hydrogenated product are not effectively removed, so that the operation stability of the whole butadiene extraction device is influenced.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a method for recovering C4 alkyne tail gas, in particular to a method for recovering C4 alkyne tail gas generated by a DMF (dimethyl formamide) method 1, 3-butadiene extraction device. The method can realize safe, stable and long-period utilization of tail gas.
Therefore, the invention provides a method for recovering C4 alkyne tail gas, the C4 alkyne tail gas is generated by a DMF method 1, 3-butadiene extraction device, and the impurities in the C4 alkyne tail gas comprise: butadiene dimer, solvent DMF and water, comprising the steps of:
(1) tail gas liquefaction: c4 alkyne tail gas is compressed and boosted by the first stage of the compressor, cooled by the compressor inter-stage cooler, enters the inter-stage buffer tank, heavier butadiene dimer and solvent DMF components are discharged from the bottom of the tank in a condensed liquid form, gas phase at the top of the tank enters the second stage of the compressor for second-stage compression and boosting, and is cooled by the cooler at the outlet of the second stage of the compressor to obtain the discharge of the second stage of the compressor cooler;
(2) impurity removal:
s1, discharging the discharged material of the compressor secondary cooler into a compressor secondary discharge buffer tank, discharging the heavier butadiene dimer and the solvent DMF component from the tank bottom to an impurity storage tank in a condensate form, and feeding the gas phase at the tank top into a tail gas condenser to obtain the discharged material of the condenser, namely the liquefied C4 alkyne material;
s2, mixing the liquefied C4 alkyne material with the raffinate carbon four, then feeding the mixture into a front buffer tank of a reactor, primarily diluting vinyl acetylene in the material, simultaneously separating free water in the material in the buffer tank, boosting the pressure of an oil phase through a booster pump of the reactor, and then feeding the oil phase into a coalescer to separate residual water to obtain the discharge of the coalescer;
(3) hydrogenation reaction: mixing the discharge of the coalescer with a circulating diluent to obtain a reaction material, cooling the reaction material by a reactor inlet cooler, mixing the reaction material with hydrogen, and entering a hydrogenation reactor for selective hydrogenation reaction;
(4) removing light components: and (3) feeding the hydrogenated material into a light component removal tower, discharging the non-condensable gas at the tower top into a torch system, boosting the liquid phase at the tower bottom by a tower bottom booster pump, sending one part of the liquid phase to the inlet of the reactor as a circulating diluent, and sending the other part of the liquid phase to a product cooler for cooling to obtain a hydrogenated product, and sending the hydrogenated product to a mixed C4 storage tank.
According to the recovery method of C4 alkyne tail gas, in the step (1), the outlet pressure of the first section of the compressor is preferably 0.10-0.15 MPa, and the temperature is preferably 50-70 ℃; the outlet pressure of the second section of the compressor is preferably 0.30-0.5 MPa, and the temperature is preferably 50-70 ℃.
According to the recovery method of C4 alkyne tail gas, in the step (1), the compression ratio of the first section of the compressor and the second section of the compressor is preferably 1.2-2.5.
According to the recovery method of C4 alkyne tail gas, in the step (1), the temperature of the compressor inter-segment cooler is preferably 30-50 ℃; the temperature of the two-section outlet cooler of the compressor is preferably 30-50 ℃.
In the method for recovering the acetylene hydrocarbon tail gas of C4, in step (2) of S2, the mass concentration of the vinyl acetylene in the buffer tank before the reactor is preferably 5% to 15%.
According to the recovery method of C4 alkyne tail gas, in the S2 of the step (2), the outlet pressure of the reactor booster pump is preferably 1.0-4.0 MPa.
According to the recovery method of the C4 alkyne tail gas, in the S2 in the step (2), the mass concentration of water in the discharge of the coalescer is preferably 0-100 mu g/g, the mass concentration of the dimer is preferably 0-0.5%, and the mass concentration of a solvent DMF is preferably 0-100 mu g/g.
In the method for recovering the C4 alkyne tail gas, in the step (3), the hydrogenation reactor is preferably a two-stage adiabatic reactor, and the hydrogenation reactor preferably includes a first-stage hydrogenation reactor and a second-stage hydrogenation reactor.
In the method for recovering C4 alkyne tail gas, in the step (3), the preferred temperature of the inlet of the first-stage hydrogenation reactor is 20-60 ℃ and the mass space velocity is 5-15 h‐1The molar ratio of the hydrogen to the acetylene is 0.5-5, and the mass concentration of the vinyl acetylene in the inlet material flow of the first-stage hydrogenation reactor is 2-10%; the inlet temperature of the two-stage hydrogenation reactor is 20-60 ℃, and the mass space velocity is 5-15 h‐1And the molar ratio of the hydrogen to the alkyne is 0.5-5.
In the method for recovering the C4 alkyne tail gas, in the step (3), the volume concentration of the hydrogen is preferably more than or equal to 85%, wherein CO + CO2≤5ml/m3。
In the method for recovering the alkyne tail gas of C4 of the present invention, in the step (4), preferably, the lightness-removing column is provided with a top cooler of the lightness-removing column, and the top cooler of the lightness-removing column is internally or externally arranged.
In the recovery method of C4 alkyne tail gas, in the step (4), the tower pressure of the light component removal tower is preferably 0.4-1 MPa, the tower top temperature is preferably 40-80 ℃, the tower bottom temperature is preferably 40-80 ℃, the number of theoretical plates is preferably 3-15, the reflux ratio is preferably 2-20, and the position of a feed plate is preferably 2-14.
In the method for recovering C4 alkyne tail gas according to the present invention, in step (1), the composition of the C4 alkyne tail gas is preferably: 1-4% of water, 1-4% of C2-C3, 5-20% of butane, 20-50% of butene, 10-30% of 1, 3-butadiene, 10-20% of vinyl acetylene, 1-4% of butadiene dimer, 1-4% of butyne, 0-1% of C5 and 0-0.001% of DMF (a solvent).
Wherein, the meaning of each component mole percentage takes water in tail gas as an example: the total molar flow of the tail gas is calculated as 100, the molar flow of water is 1-4, and the molar percentage of water is 1-4%.
The method of the invention can be described in detail as follows:
the invention relates to a method for recovering C4 alkyne tail gas obtained by a DMF (dimethyl formamide) method 1, 3-butadiene extraction device, wherein the C4 alkyne tail gas comprises the following components: the method comprises the following steps of liquefying C4 alkyne tail gas, removing impurities, and then carrying out selective hydrogenation to recover butadiene, wherein the mol percent of water is 1-4%, the mol percent of C2-C3 is 1-4%, the mol percent of butane is 5-20%, the mol percent of butene is 20-50%, the mol percent of 1, 3-butadiene is 10-30%, the mol percent of vinyl acetylene is 10-20%, the mol percent of butadiene dimer is 1-4%, the mol percent of butyne is 1-4%, the mol percent of C5 is 0-1%, and the mol percent of DMF (dimethyl formamide) is 0-0.001%.
(1) Tail gas liquefaction
C4 alkyne tail gas from a DMF (dimethyl formamide) method 1, 3-butadiene extraction device enters a two-section compressor for boosting, firstly, C4 alkyne tail gas enters a first section of the compressor for first-stage compression and boosting, and then enters an intersegment buffer tank after being cooled by a cooler between the sections of the compressor, heavier butadiene dimer and solvent DMF components are discharged from the bottom of the tank in a condensate form, a gas phase at the top of the tank enters a second section of the compressor for second-stage compression and boosting, and the gas phase is cooled by a cooler at the outlet of the second section of the compressor to obtain the discharge of the cooler at the second section of the compressor;
wherein the outlet pressure of the first section of the compressor is 0.10-0.15 MPa (gauge pressure), and the temperature is 50-70 ℃; the outlet pressure (gauge pressure) of the second section is 0.30-0.5 MPa, the temperature is 50-70 ℃, and the compression ratio of the first section of the compressor and the second section of the compressor is 1.2-2.5. The temperature of the compressor inter-segment cooler is 30-50 ℃; the temperature of the cooler at the second-stage outlet of the compressor is 30-50 ℃. The method strictly controls the partial pressure of VA (vinyl acetylene) to be lower than 0.1MPa (absolute pressure), the content of VA is below 20% (mol), the operating temperature is controlled to be below 80 ℃, and simultaneously, sodium nitrite is not used in the whole process, thereby ensuring the process safety of the method.
(2) Impurity removal
S1, discharging the discharged material of the compressor secondary cooler into a compressor secondary discharge buffer tank, discharging the heavier butadiene dimer and the solvent DMF component from the tank bottom to an impurity storage tank in a condensate form, and feeding the gas phase at the tank top into a tail gas condenser to obtain the discharged material of the condenser, namely the liquefied C4 alkyne material;
s2, mixing the liquefied C4 alkyne material with the raffinate carbon four, then feeding the mixture into a reactor front buffer tank, primarily diluting vinyl acetylene in the material, simultaneously separating free water in the material in the tank, discharging the separated free water phase into a sewage treatment system, boosting the pressure of an oil phase through a reactor booster pump, and then feeding the oil phase into a coalescer to separate the residual water to obtain a coalescer discharge;
the mass concentration of vinyl acetylene in a buffer tank in front of a reactor is controlled to be 5-15%, the concentration of water in a flow of C4 at an outlet of a coalescer is 0-100 mu g/g, the mass concentration of a dimer is 0-0.5%, and the mass concentration of a solvent DMF is 0-100 mu g/g. The outlet pressure of the booster pump of the reactor is 1.0-4.0 MPa (gauge pressure).
(3) Hydrogenation reaction
Mixing the discharged material of the coalescer with a circulating diluent, further diluting the concentration of vinyl acetylene in the material to obtain a reaction material, cooling the reaction material by a reactor inlet cooler, and then mixing the reaction material with hydrogen (the volume concentration of the hydrogen is more than or equal to 85 percent, and the concentration of CO and CO is more than or equal to 85 percent)2≤5ml/m3) Mixing to obtain a first-stage reactor feed (the mass concentration of vinyl acetylene is 2-10%), feeding the first-stage reactor feed into a first stage of a heat-insulated hydrogenation reactor, wherein the temperature of a first-stage inlet of the hydrogenation reactor is 20-60 ℃, the mass space velocity is 5-15 h < -1 >, and the molar ratio of hydrogen to acetylene is 0.5-5;
and cooling the discharged material of the first hydrogenation reactor section by using the inter-reactor-section cooler, and then feeding the cooled material into the second adiabatic hydrogenation reactor section, wherein the inlet temperature of the second hydrogenation reactor section is 20-60 ℃, the mass airspeed is 5-15 h < -1 >, and the molar ratio of the hydrogen to the alkyne is 0.5-5.
The hydrogenation processes are all selective hydrogenation, the catalyst selects alumina as a carrier, and comprises an active component palladium, an auxiliary agent copper, an auxiliary agent X1, an auxiliary agent X2 and an auxiliary agent metal, wherein the total weight of the catalyst is 100 percent: 0.1-0.5% of palladium, 2.0-5.5% of copper, 10.5-15% of X, 20.5-5% of X and 0-2% of auxiliary metal; wherein, the auxiliary metal is selected from one or more of cobalt, nickel, molybdenum, tungsten, lanthanum, silver, cerium, samarium and neodymium; x1 is selected from IVA element, X2 is selected from alkali metal, alkaline earth metal or their mixture.
(4) Light component removal
The hydrogenated material directly enters a light component removal tower, and the non-condensable gas at the top of the tower is discharged into a torch system. And after the liquid phase at the bottom of the tower is boosted by a tower bottom booster pump, one part of the liquid phase is sent to a pipeline in front of a reactor inlet cooler to be used as a circulating diluent to dilute reaction feed, and the other part of the liquid phase is sent to a product cooler to be cooled to obtain a hydrogenated product and sent to a mixed C4 storage tank.
Wherein, the top cooler of the light component removal tower can be internally arranged or externally arranged. The tower pressure is 0.4-1 MPa (G), the tower top temperature is 40-80 ℃, the tower bottom temperature is 40-80 ℃, the number of theoretical plates is 3-15, the reflux ratio is 2-20, and the position of the feeding plate is 2-14.
The recovery method for the C4 alkyne tail gas generated by the DMF 1, 3-butadiene extraction device provided by the invention can convert vinyl acetylene in the C4 alkyne tail gas generated by the DMF 1, 3-butadiene extraction device into 1, 3-butadiene, and simultaneously recycle the 1, 3-butadiene lost in the tail gas, thereby increasing great economic benefit for enterprises. Compared with the prior art, the method has the following advantages:
1. the C4 alkyne tail gas liquefaction method provided by the invention is safe, simple in process and low in energy consumption.
2. The method can effectively remove impurities which influence the activity of the hydrogenation catalyst in the tail gas, and maintains the activity of the catalyst.
3. The invention can effectively separate the residual light components in the hydrogenated product and ensure the operation stability of the whole butadiene extraction device.
4. The method has simple process flow and low investment, can convert the C4 alkyne tail gas into butadiene with high added value for recycling, reduces the waste of resources and brings great economic benefit for enterprises.
Drawings
FIG. 1 is a schematic diagram of a technological process of recycling acetylene hydrocarbon tail gas of a DMF 1, 3-butadiene extraction device C4;
wherein:
1-C4 alkyne tail gas, 2-compressor first-stage discharge, 3-compressor inter-stage cooler discharge, 4-compressor second-stage discharge, 5-compressor second-stage cooler discharge, 6-condenser discharge, 7-reactor booster pump discharge, 8-carbon four, 9-hydrogen gas extraction, 10-coalescer discharge, 11-reaction material, 12-first-stage reactor feed, 13-second-stage reactor discharge, 14-circulating diluent, 15-hydrogenation product, 17-reactor front buffer tank, 19-lightness-removing tower;
16-1, a compressor section; 16-2, a second compressor section;
18-1, a hydrogenation reactor section; 18-2, a hydrogenation reactor second section;
101, a compressor interstage cooler; 102, a compressor second-stage outlet cooler; 103, a tail gas condenser; 104, reactor inlet cooler; 105, a reactor interstage cooler; 106, a product cooler;
201, a second-stage discharge buffer tank of a compressor; 202, a reactor booster pump; 203, a coalescer; 204, a tower bottom booster pump; 206, an intersegment buffer tank.
Detailed Description
Embodiments of the invention are described in further detail below with reference to the following figures: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
Referring to fig. 1, the method for recovering C4 alkyne tail gas of the present invention, the C4 alkyne tail gas is generated by a DMF method 1, 3-butadiene extraction apparatus, and the impurities in the C4 alkyne tail gas include: butadiene dimer, solvent DMF and water, specifically, C4 alkyne tail gas comprises: the mole percent of water is 1-4%, the mole percent of C2-C3 is 1-4%, the mole percent of butane is 5-20%, the mole percent of butene is 20-50%, the mole percent of 1, 3-butadiene is 10-30%, the mole percent of vinyl acetylene is 10-20%, the mole percent of butadiene dimer is 1-4%, the mole percent of butyne is 1-4%, the mole percent of C5 is 0-1%, and the mole percent of solvent DMF is 0-0.001%.
The recovery method specifically comprises the following steps:
(1) tail gas liquefaction: c4 alkyne tail gas 1 is compressed and boosted by the first stage of the compressor section 16-1, then cooled by the compressor section cooler 101, enters the section buffer tank 206, heavier butadiene dimer and solvent DMF components are discharged from the bottom of the tank in a condensate form, gas phase at the top of the tank enters the second stage of the compressor section 16-2 for second stage compression and boosting, and is cooled by the second stage of the compressor section outlet cooler 102 to obtain the discharge 5 of the second stage of the compressor cooler;
wherein the outlet pressure of the first section 16-1 of the compressor is 0.10-0.15 MPa, and the temperature is 50-70 ℃; the outlet pressure of the compressor second section 16-2 is 0.30-0.5 MPa, and the temperature is 50-70 ℃;
the compression ratio of the first compressor section 16-1 and the second compressor section 16-2 is 1.2-2.5;
the temperature of the compressor inter-stage cooler 206 is 30-50 ℃; the temperature of the second-stage outlet cooler 102 of the compressor is 30-50 ℃.
(2) Impurity removal:
s1, discharging 5 of a second-stage cooler of the compressor into a second-stage discharge buffer tank 201 of the compressor, discharging heavier butadiene dimer and DMF (dimethyl formamide) solvent components into an intersegment buffer tank 206 from the bottom of the tank in a condensate form, and feeding gas phase at the top of the tank into a tail gas condenser 103 to obtain a condenser discharging 6, namely liquefied C4 alkyne material;
s2, mixing the liquefied C4 alkyne material with the raffinate carbon IV 8, then feeding the mixture into a reactor front buffer tank 17, primarily diluting vinyl acetylene in the material, simultaneously separating free water in the material in the tank, boosting the pressure of an oil phase by a reactor booster pump 202, and then feeding the oil phase into a coalescer 203 to separate the residual water to obtain a coalescer discharge 10;
wherein the mass concentration of the vinyl acetylene in the buffer tank 17 in front of the reactor is 5-15%;
the outlet pressure of the reactor booster pump 202 is 1.0-4.0 MPa;
the mass concentration of water in the coalescer discharge 10 is 0-100 mug/g, the mass concentration of the dimer is 0-0.5%, and the mass concentration of the solvent DMF is 0-100 mug/g.
(3) Hydrogenation reaction: mixing the coalescer discharge 10 with a circulating diluent 14 to obtain a reaction material 11, cooling the reaction material by a reactor inlet cooler 104, mixing the reaction material with hydrogen 9, and entering a hydrogenation reactor for selective hydrogenation reaction;
the hydrogenation reactor is a two-section adiabatic reactor and comprises a first-section hydrogenation reactor 18-1 and a second-section hydrogenation reactor 18-2, and a reactor inter-section cooler 105 is arranged between the first-section hydrogenation reactor 18-1 and the second-section hydrogenation reactor 18-2;
the inlet temperature of the first-stage hydrogenation reactor 18-1 is 20-60 ℃, the mass space velocity is 5-15 h < -1 >, the hydrogen acetylene molar ratio is 0.5-5, and the mass concentration of vinyl acetylene in the inlet material flow of the first-stage hydrogenation reactor 18-1 is 2-10%; the inlet temperature of the second-stage hydrogenation reactor 18-2 is 20-60 ℃, the mass space velocity is 5-15 h < -1 >, and the hydrogen alkyne molar ratio is 0.5-5;
the volume concentration of the hydrogen 9 is more than or equal to 85 percent, wherein, the CO + CO2≤5ml/m3。
The hydrogenation processes are all selective hydrogenation, the catalyst selects alumina as a carrier, and comprises an active component palladium, an auxiliary agent copper, an auxiliary agent X1, an auxiliary agent X2 and an auxiliary agent metal, wherein the total weight of the catalyst is 100 percent: 0.1-0.5% of palladium, 2.0-5.5% of copper, 10.5-15% of X, 20.5-5% of X and 0-2% of auxiliary metal; wherein, the auxiliary metal is selected from one or more of cobalt, nickel, molybdenum, tungsten, lanthanum, silver, cerium, samarium and neodymium; x1 is selected from IVA element, X2 is selected from alkali metal, alkaline earth metal or their mixture.
(4) Removing light components: the hydrogenated material 13 enters a light component removal tower 19, the top non-condensable gas is discharged into a torch system, the bottom liquid phase is boosted by a bottom booster pump 204, one part of the liquid phase is sent to the inlet of the reactor to be used as a circulating diluent, and the other part of the liquid phase is sent to a product cooler 106 to be cooled to obtain a hydrogenated product 15 and sent to a mixed C4 storage tank;
wherein, the light component removing tower 19 is provided with a light component removing tower top cooler (not shown), and the light component removing tower top cooler is internally arranged or externally arranged;
the tower pressure of the light component removal tower 19 is 0.4-1 MPa, the tower top temperature is 40-80 ℃, the tower bottom temperature is 40-80 ℃, the number of theoretical plates is 3-15, the reflux ratio is 2-20, and the position of the feeding plate is 2-14.
Example 1
1. Tail gas liquefaction:
c4 alkyne tail gas 1 from a DMF (dimethyl formamide) 1, 3-butadiene extraction device has the flow rate of 638kg/h, the temperature of 30 ℃ and the pressure of 0.01MPa (gauge pressure), enters a first section 16-1 of a compressor to obtain a first section discharge 2 of the compressor, has the temperature of 64.2 ℃ and the pressure of 0.13MPa (gauge pressure), is cooled by a compressor section cooler 101 to obtain a second section discharge 3 of the compressor section cooler, has the temperature of 38 ℃, enters an intersegment buffer tank 206, discharges heavier butadiene dimers and solvent DMF components in a condensate form from the bottom of the tank, enters a second section 16-2 of the compressor to perform second-stage compression and pressure boosting to obtain a second section discharge 4 of the compressor, has the temperature of 67.1 ℃ and the pressure of 0.4MPa (gauge pressure), then enters a second section outlet cooler 102 of the compressor to obtain a second section cooler discharge 5 of the compressor, has the temperature of 50 ℃, and then enters a second section discharge buffer, the heavier butadiene dimer and solvent DMF components are discharged from the bottom of the tank to the interstage surge tank 206 in the form of condensate, the gas phase at the top of the tank enters the tail gas condenser 103 to obtain the condenser discharge 6 (i.e. liquefied C4 alkyne material), the temperature is 40 ℃, and the pressure is 0.4MPa (gauge pressure);
2. removing impurities:
the liquefied C4 alkyne material 6 and 500kg/h of raffinate carbon four 8 are mixed and then enter a reactor front buffer tank 17, free water in the material is separated out in the tank, vinyl acetylene in the material is diluted for the first time, the mol percentage of the vinyl acetylene in the material is 10.7%, then the liquefied C4 alkyne material 6 is boosted to 1.68MPa (gauge pressure) by using a reactor booster pump 202 in an oil phase to obtain a reactor booster pump discharge 7, and then the liquefied C4 alkyne material enters a coalescer 203 to separate the residual water, so that a coalescer discharge 10 is obtained.
3. Hydrogenation reaction:
mixing a coalescer discharge 10 with 2700kg/h of circulating diluent 14 to obtain a reaction material 11 (namely a reactor inlet cooler feed), controlling the mole percentage of vinyl acetylene in the reactor inlet cooler feed 11 to be 3.6%, then mixing with hydrogen 9 to obtain a first-section reactor feed 12, feeding the first-section reactor feed 12 into a first section 18-1 of an adiabatic hydrogenation reactor, wherein the hydrogen distribution amount of the first section 18-1 of the hydrogenation reactor is 4.2kg/h, the inlet temperature is 33.6 ℃, the pressure is 1.6MPa (gauge pressure), the outlet temperature is 68.5 ℃, the pressure is 1.55MPa (gauge pressure), the temperature of the discharge of the first section 18-1 of the hydrogenation reactor is reduced to 35 ℃ after being cooled by a reactor inter-section cooler 105, then feeding the discharge into a second section 18-2 of the adiabatic hydrogenation reactor, the hydrogen distribution amount of the second section 18-2 of the hydrogenation reactor is 3kg/h, the outlet temperature is 58 ℃, the pressure is 1.5MPa (gauge pressure), and a second-stage discharge 13 of the hydrogenation reactor is obtained. Hydrogenation ofThe reaction adopts a multi-metal selective hydrogenation catalyst, and the catalyst carrier is Al2O3The metal component content is as follows: 0.8 wt% of lithium, 0.5 wt% of palladium, 10.8 wt% of lead, 5.4 wt% of copper and the balance of a carrier.
4. Removing light components:
the two-stage discharge 13 of the hydrogenation reactor enters a light component removal tower 19, the operating conditions of the tower are that the temperature of the tower top is 55.5 ℃, 0.6MPaG, the temperature of the tower bottom is 57.8 ℃, 0.61MPaG, the number of theoretical plates is 10, the reflux ratio is 15.28, the tower top is fed, the gas phase at the tower top enters a built-in tower top cooler, the condensed material returns to the tower as reflux through self gravity, and the non-condensable gas is discharged into a torch system; the liquid phase at the bottom of the column is boosted to 1.65MPaG by a booster pump 204 at the bottom of the column, wherein one part of the liquid phase is sent to a cooler 104 at the inlet of the reactor to be used as a circulating diluent 14, and the other part of the liquid phase is sent to a product cooler 106 to be cooled to 40 ℃, so as to obtain a cooled hydrogenation product 15 which is sent to a mixed C4 storage tank.
The molar composition of the above main streams (stream numbers indicated in the table) is shown in table 1.
TABLE 1
As can be seen from the above table, the method for recovering C4 alkyne tail gas generated by the DMF method 1, 3-butadiene extraction device provided by the present invention can convert vinyl acetylene in C4 alkyne tail gas generated by the DMF method 1, 3-butadiene extraction device into 1, 3-butadiene, and simultaneously recycle 1, 3-butadiene lost in the tail gas, so as to increase great economic benefits for enterprises. Compared with the prior art, the method has the following advantages:
1. the C4 alkyne tail gas liquefaction method provided by the invention is safe, simple in process and low in energy consumption.
2. The method can effectively remove impurities which influence the activity of the hydrogenation catalyst in the tail gas, and maintains the activity of the catalyst.
3. The invention can effectively separate the residual light components in the hydrogenated product and ensure the operation stability of the whole butadiene extraction device.
4. The method has simple process flow and low investment, can convert the C4 alkyne tail gas into butadiene with high added value for recycling, reduces the waste of resources and brings great economic benefit for enterprises.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (13)
1. A method for recovering C4 alkyne tail gas, the C4 alkyne tail gas being produced by a DMF process 1, 3-butadiene extraction apparatus, the impurities in the C4 alkyne tail gas comprising: butadiene dimer, solvent DMF and water, characterized by comprising the following steps:
(1) tail gas liquefaction: c4 alkyne tail gas is compressed and boosted by the first stage of the compressor, cooled by the compressor inter-stage cooler, enters the inter-stage buffer tank, heavier butadiene dimer and solvent DMF components are discharged from the bottom of the tank in a condensed liquid form, gas phase at the top of the tank enters the second stage of the compressor for second-stage compression and boosting, and is cooled by the cooler at the outlet of the second stage of the compressor to obtain the discharge of the second stage of the compressor cooler;
(2) impurity removal:
s1, discharging the discharged material of the compressor secondary cooler into a compressor secondary discharge buffer tank, discharging the heavier butadiene dimer and the solvent DMF component from the tank bottom to an impurity storage tank in a condensate form, and feeding the gas phase at the tank top into a tail gas condenser to obtain the discharged material of the condenser, namely the liquefied C4 alkyne material;
s2, mixing the liquefied C4 alkyne material with the raffinate carbon four, then feeding the mixture into a front buffer tank of a reactor, primarily diluting vinyl acetylene in the material, simultaneously separating free water in the material in the buffer tank, boosting the pressure of an oil phase through a booster pump of the reactor, and then feeding the oil phase into a coalescer to separate residual water to obtain the discharge of the coalescer;
(3) hydrogenation reaction: mixing the discharge of the coalescer with a circulating diluent to obtain a reaction material, cooling the reaction material by a reactor inlet cooler, mixing the reaction material with hydrogen, and entering a hydrogenation reactor for selective hydrogenation reaction;
(4) removing light components: and (3) feeding the hydrogenated material into a light component removal tower, discharging the non-condensable gas at the tower top into a torch system, boosting the liquid phase at the tower bottom by a tower bottom booster pump, sending one part of the liquid phase to the inlet of the reactor as a circulating diluent, and sending the other part of the liquid phase to a product cooler for cooling to obtain a hydrogenated product, and sending the hydrogenated product to a mixed C4 storage tank.
2. The method for recovering the C4 alkyne tail gas according to claim 1, wherein in the step (1), the outlet pressure of the first stage of the compressor is 0.10-0.15 MPa, and the temperature is 50-70 ℃; the outlet pressure of the second compressor section is 0.30-0.5 MPa, and the temperature is 50-70 ℃.
3. The method for recovering C4 alkyne tail gas according to claim 1, wherein in step (1), the compression ratio between the first compressor section and the second compressor section is 1.2-2.5.
4. The method for recovering the C4 alkyne tail gas according to claim 1, wherein in the step (1), the temperature of the compressor inter-segment cooler is 30-50 ℃; the temperature of the cooler at the two-section outlet of the compressor is 30-50 ℃.
5. The method for recovering C4 alkyne tail gas as recited in claim 1, wherein in step (2) S2, the mass concentration of vinyl acetylene in the buffer tank before the reactor is 5-15%.
6. The method for recovering C4 alkyne tail gas as set forth in claim 1, wherein in S2 of step (2), the outlet pressure of the reactor booster pump is 1.0-4.0 MPa.
7. The method for recovering C4 alkyne tail gas as claimed in claim 1, wherein in step (2) S2, the mass concentration of water in the coalescer output is 0-100 μ g/g, the mass concentration of dimer is 0-0.5%, and the mass concentration of DMF solvent is 0-100 μ g/g.
8. The method for recovering C4 alkyne tail gas as recited in claim 1, wherein in step (3), the hydrogenation reactor is a two-stage adiabatic reactor, and the hydrogenation reactor comprises a first-stage hydrogenation reactor and a second-stage hydrogenation reactor.
9. The method for recovering the C4 alkyne tail gas according to claim 1, wherein in the step (3), the inlet temperature of the first-stage hydrogenation reactor is 20-60 ℃ and the mass space velocity is 5-15 h‐1The molar ratio of the hydrogen to the acetylene is 0.5-5, and the mass concentration of the vinyl acetylene in the inlet material flow of the first-stage hydrogenation reactor is 2-10%; the inlet temperature of the two-stage hydrogenation reactor is 20-60 ℃, and the mass space velocity is 5-15 h‐1And the molar ratio of the hydrogen to the alkyne is 0.5-5.
10. The method for recovering C4 alkyne tail gas as recited in claim 1, wherein the volume concentration of hydrogen in step (3) is 85% or more, wherein CO + CO2≤5ml/m3。
11. The method for recovering the C4 alkyne tail gas as recited in claim 1, wherein in the step (4), the lightness-removing column is provided with a lightness-removing column top cooler, and the lightness-removing column top cooler is internally or externally arranged.
12. The method for recovering C4 alkyne tail gas according to claim 1, wherein in step (4), the lightness-removing column has a column pressure of 0.4-1 MPa, a column top temperature of 40-80 ℃, a column bottom temperature of 40-80 ℃, a theoretical plate number of 3-15, a reflux ratio of 2-20, and a feed plate position of 2-14.
13. The method for recovering C4 alkyne tail gas as set forth in claim 1, wherein in step (1), the C4 alkyne tail gas consists of: 1-4% of water, 1-4% of C2-C3, 5-20% of butane, 20-50% of butene, 10-30% of 1, 3-butadiene, 10-20% of vinyl acetylene, 1-4% of butadiene dimer, 1-4% of butyne, 0-1% of C5 and 0-0.001% of DMF (a solvent).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811156827.6A CN110963878B (en) | 2018-09-30 | 2018-09-30 | Recovery method of C4 alkyne tail gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811156827.6A CN110963878B (en) | 2018-09-30 | 2018-09-30 | Recovery method of C4 alkyne tail gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110963878A true CN110963878A (en) | 2020-04-07 |
| CN110963878B CN110963878B (en) | 2022-08-02 |
Family
ID=70029036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811156827.6A Active CN110963878B (en) | 2018-09-30 | 2018-09-30 | Recovery method of C4 alkyne tail gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110963878B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102886262A (en) * | 2011-07-21 | 2013-01-23 | 北京石油化工学院 | C4 alkyne selective hydrogenation catalyst and preparation method and application thereof |
| CN104370679A (en) * | 2014-10-17 | 2015-02-25 | 中国石油集团东北炼化工程有限公司吉林设计院 | Separation process and device for removing butadiene dimer |
| CN105585411A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Hydrogenation method of butadiene extraction tail gas |
| CN109485534A (en) * | 2017-09-12 | 2019-03-19 | 中国石化扬子石油化工有限公司 | A kind of method of DMF method butadiene extraction device tail gas hydrogenation |
-
2018
- 2018-09-30 CN CN201811156827.6A patent/CN110963878B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102886262A (en) * | 2011-07-21 | 2013-01-23 | 北京石油化工学院 | C4 alkyne selective hydrogenation catalyst and preparation method and application thereof |
| CN104370679A (en) * | 2014-10-17 | 2015-02-25 | 中国石油集团东北炼化工程有限公司吉林设计院 | Separation process and device for removing butadiene dimer |
| CN105585411A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Hydrogenation method of butadiene extraction tail gas |
| CN109485534A (en) * | 2017-09-12 | 2019-03-19 | 中国石化扬子石油化工有限公司 | A kind of method of DMF method butadiene extraction device tail gas hydrogenation |
Non-Patent Citations (1)
| Title |
|---|
| 赵玉龙: "丁二烯抽提装置尾气回收系统改造", 《炼油与化工》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110963878B (en) | 2022-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5327485B2 (en) | Method for separating 1,3-butadiene from crude C4 fraction using acetylene conversion | |
| CN103787815B (en) | A kind of method of hydrotreating of divinyl tail gas | |
| CN105585411A (en) | Hydrogenation method of butadiene extraction tail gas | |
| CN101172929B (en) | One-stage extraction method for butadiene by NMP method | |
| CN101475429A (en) | Method for comprehensive utilization of cracking C4 | |
| CN109456139B (en) | Oil absorption separation method for reaction product of preparing ethylene from methane | |
| CN103041699B (en) | Butadiene tail gas hydrogenation unit and method | |
| CN110963878B (en) | Recovery method of C4 alkyne tail gas | |
| CN107602325B (en) | Separation method of methanol-to-olefin reaction gas | |
| CN114478173A (en) | Method, system and application for recovering refinery dry gas | |
| CN109485534B (en) | Tail gas hydrogenation method for butadiene extraction device by DMF (dimethyl formamide) method | |
| CN103041700B (en) | Butadiene tail gas hydrogenation unit and hydrogenation method | |
| CN111004079B (en) | Separation method and device for reaction gas for preparing ethylene by oxidative coupling of methane | |
| CN111320525A (en) | Non-low temperature separation process for ethylene-rich catalytic cracking gas | |
| CN112723976A (en) | Method and system for recycling refinery dry gas as ethylene raw material by using metal organic framework material | |
| CN112707786B (en) | Pyrolysis gas separation system and separation method | |
| CN107602331B (en) | Separation method of methanol-to-olefin reaction gas | |
| CN112707787B (en) | Pyrolysis gas separation system with purification function and utilization method | |
| CN103086831B (en) | A kind of butadiene production system and method improving butadiene yield and make full use of C_4 hydrocarbon | |
| CN112723972B (en) | Method for recycling refinery dry gas as ethylene raw material | |
| CN111943796A (en) | Process and system for hydrogenation and extractive distillation of crude benzene | |
| CN103768896B (en) | A kind of BEU exhaust gas recovery system and method | |
| CN112920008B (en) | Method and device for separating hydrocarbon pyrolysis gas and producing ethylbenzene by using hydrocarbon pyrolysis gas | |
| CN112723974B (en) | Cracking gas separation system and separation method capable of reducing energy consumption | |
| CN112920830B (en) | Method for recovering C2 fraction in refinery dry gas |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |