CN1590353A - Utilization method of butadiene extraction device residue - Google Patents
Utilization method of butadiene extraction device residue Download PDFInfo
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- CN1590353A CN1590353A CN 03159237 CN03159237A CN1590353A CN 1590353 A CN1590353 A CN 1590353A CN 03159237 CN03159237 CN 03159237 CN 03159237 A CN03159237 A CN 03159237A CN 1590353 A CN1590353 A CN 1590353A
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000000605 extraction Methods 0.000 title claims description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 150000001345 alkine derivatives Chemical class 0.000 claims description 102
- 238000005984 hydrogenation reaction Methods 0.000 claims description 101
- 239000000463 material Substances 0.000 claims description 61
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 42
- 239000001257 hydrogen Substances 0.000 claims description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims description 35
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 33
- 238000005516 engineering process Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 229910052763 palladium Inorganic materials 0.000 claims description 21
- 230000000694 effects Effects 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 16
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 238000005336 cracking Methods 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 239000011344 liquid material Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 abstract description 12
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 abstract description 12
- -1 acetylene hydrocarbon Chemical class 0.000 abstract description 8
- 239000000446 fuel Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract description 4
- 150000005673 monoalkenes Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000000926 separation method Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 10
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000001273 butane Substances 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- HHWHJTLUWTYQRR-UHFFFAOYSA-N 3-ethenylhexa-1,3-dien-5-yne Chemical group C(=C)C(=CC#C)C=C HHWHJTLUWTYQRR-UHFFFAOYSA-N 0.000 description 1
- XIUZXYIONACSDL-UHFFFAOYSA-N C#CCC.C=C Chemical group C#CCC.C=C XIUZXYIONACSDL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process for reclaiming the residue of butadiene extractor features that said residue rich in acetylene hydrocarbon is selectively hydrogenated under the action of catalyst in the fixed-bed hydrogenating reactor with circulating device to generate fuel, and recover 1-butene and monoolefin.
Description
Technical field
The present invention relates to a kind of butadiene extraction unit remnants the hydrocarbon mixture that is rich in alkynes utilize method.Relate in particular to a kind of by one, two or more fixed bed hydrogenation reactor that has circulation device, make the mixture that is rich in alkynes under the effect of catalyzer, select hydrogenation to make hydrogen and alkynes even divinyl reaction to remove alkynes even divinyl, and according to different needs by the reactor of different numbers combination and control different processing condition, making reaction product can do fuel uses, also can further reclaim 1-butylene and other monoolefine, also can only turn back to the method that the 1-butylene device reclaims 1-butylene.
Background technology
In the process of oil product thermo-cracking system alkene, can generate stable hydrocarbon, as ethane, propane, butane etc.; Unsaturated hydrocarbons is as ethene, propylene, divinyl, butylene etc.; And highly unsaturated hydro carbons, as acetylene, propine, butine, vinylacetylene etc.
When ethylene cracker coproduction carbon four hydrocarbon, contain the 1,3-butadiene of 40～60wt% in the cracking c_4 hydrocarbon of gained approximately, be the main raw material of producing synthetic rubber and resin, the polymerization-grade divinyl requires purity greater than 99.7wt%, and alkynes content is lower than 25ppm.In the cracking c_4 hydrocarbon 1, the 3-divinyl is generally made with extra care by the method for two sections solvent extraction rectifying and one section direct rectifying, alkynes concentration is higher in the residual fraction that device produces, generally greater than 20wt%, the highest 40wt% that surpasses, these residual fractions that are rich in alkynes still do not have industrial utilization at present and are worth, can only burn processing, but because the easy polymerization blast of high density alkynes, therefore these cuts must cause the very big wasting of resources so earlier with just sending torch burning after the dilution of cuts such as safe butane, butylene.In recent years, increasing along with the hydrocarbon vapours cracking severity, alkynes content is increase trend in the cracking c_4, the content of therein ethylene ethyl-acetylene rises to about 1.2wt% from about 0.5wt%, contain the 2wt% that alkynes gas has accounted for the cracking c_4 total amount, so the amount of the residual fraction that is rich in alkynes of extraction plant generation increases considerably also.If this part material is handled, perhaps the raw material that enters butadiene extraction unit is handled, make alkynes be converted into valuable cut and be used, will increase economic efficiency widely.
At present, method commonly used is before cracking c_4 enters butadiene extraction unit it to be selected hydrogenation, makes alkynes content reduce to 1.0 * 10
-5Below, we are referred to as front-end hydrogenation, and this method was introduced in " petrochemical complex " 1997 the 26th volumes 505 pages " C-4-fraction is selected the acetylene hydrogenation hydrocarbon "; The most representative in the global range is the KLP technology of the French IFP technology and the U.S..The IFP technology is that the charging of tail gas that contains high density propine, butine, vinylacetylene that described second extracting rectifying is partly removed and butadiene extraction unit mixes and selects hydrogenation, to improve the yield of divinyl.The KLP technology is that the described alkynes of hydrogenation and removing is selected in the charging of butadiene extraction unit, and alkynes content can reduce to below the 5ppm in the reaction product, thereby has saved described second abstraction distillation system.But described front-end hydrogenation process all exists same shortcoming: the treatment capacity of hydrogenation unit is big, and has lost the part divinyl inevitably.
Another kind method is that the described extraction plant residual fraction that is rich in the alkynes cut is directly selected hydrogenation, we are referred to as back end hydrogenation, alkynes is converted into divinyl and monoolefine, sends butadiene extraction unit again back to, reclaim divinyl wherein and can further reclaim 1-butylene.Because alkynes and butadiene concentration are too high in the described material, general technology is through after a while running, catalyzer can lose activity gradually, life of catalyst can only be with the moon even to count in week, and the polymerization of diolefine and alkynes is also relatively more serious in the reaction, and therefore described back end hydrogenation also seldom has report.
Summary of the invention
The invention provides and a kind of the extraction plant resistates that is rich in the alkynes cut is directly selected the technology of hydrogenation, be used for handling and contain butane, butylene, divinyl, propine, butine, vinylacetylene fraction mixture, to make full use of this part material.
Method provided by the present invention can be controlled the purposes of hydrogenation products flexibly by adopting different technical process combination and processing condition.Specifically, hydrogenation products can be used as fuel; Also can further reclaim 1-butylene and other component through downstream unit again; Also can only deliver to the 1-butylene production equipment and reclaim 1-butylene as the raw material of producing high purity butene-1.Reached the purpose that economizes on resources, improves the cracking c_4 utilization ratio like this.
To charge into alkyne hydrogenation reactor with hydrogen from the salvage stores that is rich in alkynes of butadiene extraction unit, under the effect of catalyzer, alkynes will be converted into alkene; The material that is rich in alkynes can be introduced into the interchanger heat exchange before entering alkyne hydrogenation reactor, to control the temperature in of alkyne hydrogenation reactor better.The catalyzer that adopts in the alkyne hydrogenation reactor is two-pack or the multicomponent catalyst that contains the group VIII metal, is preferably in palladium, rhodium, platinum, the nickel two or more are carried on the carrier, preferred palladium, copper or palladium, copper, silver; Carrier is selected from one or both or the two or more mixtures in titanium dioxide, silicon oxide, aluminum oxide, zinc oxide, stannic oxide, the molecular sieve, preferred aluminum oxide; One or both or two or more mixtures that catalyzer also contains in the compound that is selected from potassium, sodium, lithium, calcium, magnesium, barium, copper, silver, gold, zinc, lanthanum, cerium, molybdenum, tungsten, antimony, arsenic, vanadium are promotor.
Behind the alkynes hydrogenation product is sent into vapor-liquid separating device and separate, the non-condensable gas after the separation is discharged, and partially liq material (a) loops back alkyne hydrogenation reactor, and all the other liquid (b) enter the selective hydrogenation of butadiene device.It is 10: 1～30: 1 scope that internal circulating load (a) is controlled at fresh feed ratio with the alkyne hydrogenation reactor ingress, and material (b) is under the effect of selecting hydrogenation catalyst, and wherein divinyl is converted into 1-butylene.
Accompanying drawing has been described the synoptic diagram of two preferred versions of the present invention, below in conjunction with Fig. 1 preferred version is described in detail:
(1) material that is rich in alkynes 16 from butadiene extraction unit 1 is mixed into alkyne hydrogenation reactor 3 with hydrogen 23, and wherein alkynes is converted into alkene;
(2) send into vapor-liquid separation tank 4 from the material 13 of alkyne hydrogenation reactor 3, non-condensable gas 14 is sent into gas pipe network 28 after vapor-liquid separation, and a part of liquid material 15 loops back the alkyne hydrogenation reactor inlet, and rest materials 17 is sent hydrogenation unit;
(3) material 17 from vapor-liquid separation tank 4 is mixed into butadiene hydrogenation reactor 5 with hydrogen 24, and wherein divinyl is converted into 1-butylene, makes butadiene content≤2wt%;
(4) enter vapor-liquid separation tank 6 from material 19 behind the hydrogenation of butadiene hydrogenation reactor 5, non-condensable gas 20 is sent into gas pipe network 28 after vapor-liquid separation, part liquid material 18 loops back the selective hydrogenation of butadiene reactor inlet, and rest materials 21 is sent hydrogenation unit;
A) reclaim this part material 26, use as superior in quality domestic fuel, technological process leaves it at that;
Perhaps:
B) material 22 from vapor-liquid separation tank 6 is mixed into selective hydrogenation reaction device 7 with hydrogen 25, and wherein remaining divinyl is converted into 1-butylene, makes butadiene content≤40ppm, alkynes content≤5ppm; Here we can reclaim 1-butylene and other monoolefine, also material 27 can be sent into 1-butylene production equipment 2, produce high purity butene-1.
The raw material of the butadiene extraction unit described in the such scheme can be the material from steam cracking device, also can be the material from cat-cracker; The material 16 that is rich in alkynes is the residual fraction of butadiene extraction unit from butadiene extraction unit, contains the mixture of cuts such as butane, butylene, divinyl, propine, butine, vinylacetylene usually, and wherein the alkynes total amount is 10～40wt%.
Alkyne hydrogenation reactor 3, butadiene hydrogenation reactor 5, selective hydrogenation reaction device 7 can be single hop, two sections or multistage insulation formula bubbling bed reactor.
The hydroprocessing condition that adopts in the alkyne hydrogenation reactor 3 can suitably change according to the composition and property of material to be processed, and the selection of temperature and pressure should make material be in liquid state, and temperature is low as far as possible, to prevent the polymerization of diolefine and alkynes.Usually alkyne hydrogenation reactor 3 is operated under 1.5～4.0MPa pressure, and temperature in is 10～40 ℃, in order further to guarantee the temperature in of alkyne hydrogenation reactor, can make material at least one interchanger heat exchange of process earlier before entering reactor; The liquid phase volume air speed is 0.5～4h
-1
The flow of hydrogen should can satisfy at least makes alkynes be converted into the stoichiometric requirement of alkene, general in the scope of 2～5 mol of hydrogen/1 mole alkynes.
If 3 is single hop heat-insulating bubbling bed reactor, the mol ratio of the total alkynes amount of hydrogen and reactor inlet is 2～5 so.
If 3 is two sections or multistage insulation formula bubbling bed reactor, so the amounts of hydrogen of every section reactor feeding and the mol ratio of the total alkynes amount of this section reactor inlet are 1～2.5, simultaneously can be provided with at least one interchanger between two sections beds, be 10～40 ℃ with the temperature in of further next section of assurance bed.
The alkynes hydrogenation catalyst is two-pack or the multicomponent catalyst that contains the group VIII metal; In the preferred palladium of active ingredient, rhodium, platinum, the nickel one or more; Catalyzer also can contain promotor, promotor can be one or both or the two or more mixture in the compound of potassium, sodium, lithium, calcium, magnesium, barium, copper, silver, gold, zinc, lanthanum, cerium, molybdenum, tungsten, antimony, arsenic, vanadium, and the preferred catalyzer of the present invention is palladium copper bimetallic catalyst or palladium copper silver multimetallic catalyst; Carrier is selected from one or both or the two or more mixtures in titanium dioxide, silicon oxide, aluminum oxide, zinc oxide, stannic oxide, the molecular sieve, and the preferred carrier of the present invention is an aluminum oxide, and Preparation of catalysts can adopt method well known to those skilled in the art.
The butadiene hydrogenation reactor is operated under 1.5～4.0MPa pressure, and temperature in is 10～40 ℃, and the liquid phase volume air speed is 0.5～10h
-1
The mol ratio of hydrogen and the total divinyl amount of reactor inlet is 2～5 in the described butadiene hydrogenation reactor 5.
The amount of recycle stock was controlled at 5: 1～30: 1 with the ratio of butadiene hydrogenation reactor feed amount after the vapor-liquid separation.
The butadiene hydrogenation catalyzer is the catalyzer that contains the group VIII metal, preferably in palladium, rhodium, platinum, the nickel one or more are carried on the carrier, carrier is selected from a kind of or many clock of titanium dioxide, silicon oxide, aluminum oxide, zinc oxide, stannic oxide, molecular sieve clock; Preferred palladium catalyst, the preferred aluminum oxide of carrier, Preparation of catalysts can adopt method well known to those skilled in the art.
Selective hydrogenation reaction device 7 is operated under 1.0～3.0MPa pressure, and temperature in is 30～80 ℃, and the liquid phase volume air speed is 10～50h
-1The mol ratio of hydrogen and reactor inlet divinyl amount is 2～4 in the hydrogenator.
Selecting hydrogenation catalyst is the catalyzer that contains the group VIII metal, is preferably in palladium, rhodium, platinum, the nickel one or more are carried on the carrier preferred palladium; Carrier is selected from one or more their mixtures in titanium dioxide, silicon oxide, aluminum oxide, zinc oxide, stannic oxide, the molecular sieve, preferred aluminum oxide.Preparation of catalysts can adopt method well known to those skilled in the art.
The present invention directly selects hydrogenation to the residual fraction that is rich in alkynes of butadiene extraction unit, surprisingly, alkynes content is so high in the charging of the present invention, the alkynes hydrogenation catalyst has but kept the stability of long duration, the amount of active ingredient is not seen minimizing in the catalyzer, almost there is not dipolymer in the material behind the hydrogenation, total alkynes content is less than 0.8wt%, also lower than the alkynes content in the butadiene extraction unit charging, why good like this effect is arranged, mainly be because following 2 points: (1) the present invention has adopted the method that reaction product is looped back reactor inlet, and internal circulating load is relatively large, reduced the content of described hydrogenator inlet alkynes, reduced the temperature rise of reaction bed, thereby effectively suppressed the generation of polymkeric substance; And selected bigger backflow linear speed, and make material certain effect of washing away be arranged to catalyst surface, effectively suppressed polymkeric substance and on catalyst surface, deposited, make catalyzer can keep good performance for a long time.(2) catalyzer selected for use of the present invention is bimetal or multimetallic catalyst, and the intensive interaction has suppressed the absorption between vinylacetylene and the palladium between the metal, has effectively reduced the loss of palladium, has prolonged life of catalyst.
After alkynes reacted away, carry out the hydrogenation of divinyl again, because vinylacetylene content is very low, to not influence of the catalyzer in the follow-up flow process.Adopt present method to handle the resistates of butadiene extraction unit; directly recovered material also can be used for producing high purity butene-1 as domestic fuel, has not only improved economic benefit; and owing to reduced the amount of torch burning, the present invention has also protected environment to a certain extent.
Description of drawings
Figure of description is a process flow sheet of the present invention, is simply described as follows:
1: butadiene extraction unit; 2:1-butylene production equipment; 3: the selective acetylene hydrocarbon hydrogenation reactor; 4,6: vapor-liquid separation tank; 5: the selective hydrogenation of butadiene reactor; 7: the selective hydrogenation reaction device; 10: the material that enters butadiene extraction unit; 11: the material of after the butadiene extraction unit extracting, sending into the 1-butylene production equipment; 12,23,24,25: hydrogen; 13: the material after alkyne hydrogenation reactor is selected hydrogenation; 14,20: non-condensable gas; 15: the material part that loops back alkyne hydrogenation reactor after the vapor-liquid separation; 16: from the resistates of butadiene extraction unit; 17: the material part of sending into the butadiene hydrogenation device after the vapor-liquid separation; 18: the material part that loops back the butadiene hydrogenation reactor after the vapor-liquid separation; 19: the material that flows out the butadiene hydrogenation reactor behind the hydrogenation; 21: reclaim use or send into the material part that the selective hydrogenation reaction device is proceeded to handle as domestic fuel after the vapor-liquid separation; 27: the material of sending into the 1-butylene production equipment behind the selective hydrogenation reaction.
Embodiment
Embodiment 1
The present embodiment charging is the material that is rich in alkynes, alkyne hydrogenation reactor adopts palladium copper silver multimetallic catalyst, its content is palladium 0.2wt%, copper 9.5wt%, silver-colored 0.2wt%, support of the catalyst is an aluminum oxide, hydrogenator is two section heat-insulating fixed-bed reactor, and one section bed temperature in is 18 ℃, and two sections bed temperature ins are 25 ℃, pressure is 2.5MPa, and high alkynes feed liquid volume space velocity is 2.0h
-1, hydrogen divides two-way to enter one section bed and two sections beds respectively, and the mol ratio of every section bed hydrogen and alkynes is 1: 1～and 2: 1, recycle ratio is 18: 1, table 1 has been listed the composition of materials before and after the reaction.
Material is formed before and after table 1 reaction
| ????wt％ | 1-butylene | 1,3-butadiene | Propine | Vinylacetylene | Butine | All the other components | Total alkynes | The 1,3-butadiene yield | The alkynes transformation efficiency |
| Raw produce (500 hours) product (1000 hours) | ?7.53 ?38.78 ?39.05 | ?25.71 ?27.51 ?26.93 | ?3.91 ?- ?- | ?31.06 ?0.61 ?0.70 | ?4.65 ?0.25 ?0.27 | ?27.10 ?32.82 ?32.98 | ?39.62 ?0.86 ?0.97 | ?- ?107.0％ ?105.0％ | - 97.9％ 97.6％ |
In the hydrogenation process of alkynes, except that the hydrogenation of alkynes, 1,3-butadiene can be hydrogenated to 1-butylene, and butine is hydrogenated to 1-butylene, and vinylacetylene is hydrogenated to 1,3-butadiene.Because internal circulating load is bigger, the chance that 1,3-butadiene is hydrogenated to 1-butylene increases, so the yield of 1,3-butadiene can only remain on about 100%, but the yield of 1-butylene is than higher.By table 1 as seen, through 1000 hours running, the alkynes transformation efficiency was more than 97%, and it is stable that divinyl and 1-butylene yield keep, and illustrates that catalyzer has good activity, selectivity and stability.
The product of gained is sent into the butadiene hydrogenation reactor, adopt the catalyzer that contains palladium 0.2wt%, carrier is an aluminum oxide, and the bed temperature in is 25 ℃, and pressure is 1.5MPa, and feeding liquid phase volume air speed is 5.0h
-1, the mol ratio of hydrogen and divinyl is 2.5: 1, and recycle ratio is 15: 1, and table 2 has been listed the composition of material before and after the reaction.
Material is formed before and after table 2 reaction
| ????wt％ | 1-butylene | 1,3-butadiene | Vinylacetylene | Butine | All the other components | Total alkynes | The 1-butylene yield | Butadiene conversion |
| Raw produce (500 hours) product (1000 hours) | ??39.05 ??54.20 ??53.95 | ????26.93 ????1.86 ????1.85 | ?0.70 ?50ppm ?52ppm | ?0.27 ?10ppm ?12ppm | ??32.98 ??43.90 ??44.58 | ?0.97 ?60ppm ?64ppm | ?- ?138.8％ ?138.2％ | ?- ?93.10％ ?93.10％ |
By table 2 as seen, through 1000 hours running, catalyzer still had good activity and stable, and butadiene conversion wherein about 60% is converted into 1-butylene more than 93wt%.Because the content of remaining divinyl is below 2wt%, the residual acetylenes hydrocarbon content is below 70ppm, and reacted material can be directly used in domestic fuel, and also further hydrogenation is to butadiene content＜40ppm, and alkynes content＜5ppm is used to produce high purity butene-1.
The present embodiment charging is the material that is rich in alkynes, alkyne hydrogenation reactor adopts the palladium copper bimetallic catalyst, its content is palladium 0.2wt%, copper 9.5wt%, support of the catalyst is an aluminum oxide, and hydrogenator is single hop heat-insulating fixed-bed reactor, and the bed temperature in is 22 ℃, pressure is 2.0MPa, and high alkynes feed liquid volume space velocity is 2.0h
-1, the mol ratio of hydrogen and alkynes is 1: 1～2: 1, and recycle ratio is 13: 1, and table 2 has been listed the composition of material before and after the reaction.
Material is formed before and after table 3 reaction
| ????wt％ | 1-butylene | 1,3-butadiene | Propine | Vinylacetylene | Butine | All the other components | Total alkynes | The divinyl yield | The 1-butylene yield | The alkynes transformation efficiency |
| Raw produce (500 hours) | ??19.82 ??45.59 | 25.62 25.15 | 7.81 - | ??19.94 ??0.30 | ??9.08 ??0.22 | ??17.72 ??28.73 | ??36.83 ??0.52 | ??- ??98.2％ | ??- ??230.0％ | ?- ?98.58％ |
| Product (1000 hours) | 45.60 | 25.10 | - | ?0.42 | ??0.25 | ??28.60 | ??0.67 | ??98.0％ | ??230.0％ | ??98.53％ |
By table 3 as seen, through 1000 hours running, catalyzer still had good activity and stable, and the residual acetylenes hydrocarbon content is below 0.8w%, and the alkynes transformation efficiency is more than 98w%, and divinyl and 1-butylene are kept higher yield.
The product of gained is sent into the butadiene hydrogenation reactor, adopt the catalyzer that contains palladium 0.2w%, carrier is an aluminum oxide, and the bed temperature in is 25 ℃, and pressure is 1.5MPa, and feeding liquid phase volume air speed is 6.0h
-1, the mol ratio of hydrogen and divinyl is 3: 1, and recycle ratio is 12: 1, and table 4 has been listed the composition of material before and after the reaction.
Material is formed before and after table 4 reaction
| ????wt％ | 1-butylene | 1,3 divinyl | Vinylacetylene | Butine | All the other components | Total alkynes | The 1-butylene yield | Butadiene conversion |
| Raw produce (500 hours) product (1000 hours) | 45.60 59.79 60.30 | 25.10 1.45 1.52 | ?0.42 ?50ppm ?52ppm | ?0.25 ?10ppm ?12ppm | ?28.60 ?38.73 ?38.15 | ?0.67 ?60ppm ?64ppm | ?- ?131.1％ ?132.2％ | - 94.2％ 94.0％ |
By table 4 as seen, running through 1000 hours, catalyzer still has good activity and stable, and the 1-butylene yield is more than 130wt%, and butadiene conversion is more than 94wt%, because the content of remaining divinyl is below 2wt%, the residual acetylenes hydrocarbon content is below 70ppm, and reacted material can be directly used in domestic fuel, also further hydrogenation to butadiene content＜40ppm, alkynes content＜5ppm is used to produce high purity butene-1.
Claims (20)
- A butadiene extraction unit resistates utilize method, its step comprises:(1) salvage stores that is rich in alkynes from butadiene extraction unit charges into alkyne hydrogenation reactor with hydrogen, under the effect of catalyzer alkynes is converted into alkene;(2) from material behind the hydrogenation of step (1) after vapor-liquid separating device separates, partially liq material (a) loops back alkyne hydrogenation reactor, rest part (b) enters the selective hydrogenation of butadiene device, under the effect of catalyzer, divinyl is converted into 1-butylene.
- 2. as the method for claim 1, its step comprises:(1) salvage stores that is rich in alkynes from butadiene extraction unit charges into alkyne hydrogenation reactor with hydrogen, under the effect of catalyzer alkynes is converted into alkene;(2) from material behind the hydrogenation of step (1) after vapor-liquid separating device separates, partially liq material (a) loops back alkyne hydrogenation reactor, rest part (b) enters the selective hydrogenation of butadiene device with hydrogen, under the effect of catalyzer, most of divinyl is converted into 1-butylene;(3) will be after vapor-liquid separating device separate from the material of step (2), partially liq material (c) loops back the selective hydrogenation of butadiene reactor, and all the other liquid materials (d) reclaim.
- 3. as the method for claim 1, its step comprises:(1) salvage stores that is rich in alkynes from butadiene extraction unit charges into alkyne hydrogenation reactor with hydrogen, under the effect of catalyzer alkynes is converted into alkene;(2) from material behind the hydrogenation of step (1) after vapor-liquid separating device separates, partially liq material (a) loops back alkyne hydrogenation reactor, rest part (b) enters the selective hydrogenation of butadiene device with hydrogen, under the effect of catalyzer, most of divinyl is converted into 1-butylene;(3) will be after another vapor-liquid separating device separates from the material of step (2), partially liq material (c) loops back the selective hydrogenation of butadiene reactor, all the other liquid materials (d) are sent into follow-up selective hydrogenation reaction device with hydrogen, and the divinyl with remnants under the effect of catalyzer is converted into 1-butylene.
- 4. as the technology of claim 1, the material that is rich in alkynes in the step (1) was introduced into the interchanger heat exchange before entering alkyne hydrogenation reactor.
- 5. technology as claimed in claim 1 is rich in that the alkynes total amount is 10～40wt% in the alkynes material in the step (1).
- 6. as the technology of claim 1～3, described hydrogen is reformer hydrogen, PSA hydrogen or cracking hydrogen.
- 7. as the technology of claim 1～3, alkyne hydrogenation reactor wherein, selective hydrogenation of butadiene reactor, selective hydrogenation reaction device are single hop, two sections or multistage insulation formula bubbling bed reactor.
- 8. as the technology of claim 7, when alkyne hydrogenation reactor was single hop heat-insulating bubbling bed reactor, the mol ratio of the total alkynes amount of hydrogen and reactor inlet was 2～5.
- 9. when technology as claimed in claim 7, alkyne hydrogenation reactor were two sections or multistage insulation formula bubbling bed reactor, the mol ratio of the total alkynes amount of every section reactor inlet place amounts of hydrogen and this ingress was 1～2.5.
- 10. as the technology of claim 7, between every section of two sections or multi-stage fixed-bed hydrogenator interchanger is housed.
- 11. as the technology of claim 1～3, alkyne hydrogenation reactor is operated under 1.5～4.0MPa pressure in the step (1), temperature in is 10～40 ℃, and the liquid volume air speed is 0.5～5h -1
- 12. as the technology of claim 1～3, the recycle stock (a) in the step (2) is 10: 1～30: 1 with the mol ratio that enters the fresh material of alkyne hydrogenation reactor.
- 13. as the technology of claim 1～3, the catalyzer that adopts in the alkyne hydrogenation reactor in the step (1) is two-pack or the multicomponent catalyst that contains the group VIII metal.
- 14. technology as claim 13, described catalyzer is that in palladium, rhodium, platinum, the nickel two or more is carried on the carrier, and carrier is selected from one or more the mixture in titanium dioxide, silicon oxide, aluminum oxide, zinc oxide, stannic oxide, the molecular sieve; One or more the mixture that catalyzer also contains in the compound that is selected from potassium, sodium, lithium, calcium, magnesium, barium, copper, silver, gold, zinc, lanthanum, cerium, molybdenum, tungsten, antimony, arsenic, vanadium is a promotor.
- 15. as the technology of claim 14, described catalyzer is the palladium copper catalyst, carrier is an aluminum oxide.
- 16. as the technology of claim 14, described catalyzer is a palladium copper silver catalyst, carrier is an aluminum oxide.
- 17. as the technology of claim 1～3, the butadiene hydrogenation reactor in the step (2) is operated under 1.5～4.0MPa pressure, temperature in is 10～40 ℃, and the liquid phase volume air speed is 0.5～5h -1, the mol ratio of ingress hydrogen and material (b) is 2～5.
- 18. as the technology of claim 1～3, the internal circulating load (c) in the step (3) is 5: 1～30: 1 with the mol ratio of butadiene hydrogenation reactor feed amount (b).
- 19. technology as claim 1～3, catalyzer in selective hydrogenation of butadiene reactor and the selective hydrogenation reaction device adopts and contains the group VIII metal as active ingredient, and carrier is selected from titanium dioxide, silicon oxide, aluminum oxide, zinc oxide, stannic oxide, molecular sieve or their mixture.
- 20. technology as claimed in claim 3, the selective hydrogenation reaction device in the step (3) is operated under 1.0～3.0MPa pressure, and temperature in is 30～80 ℃, and the liquid phase volume air speed is 0.5～50h -1, the mol ratio of hydrogen and reactor inlet place material (d) is 2～4.
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| CN101993323A (en) * | 2009-08-28 | 2011-03-30 | 中国石油化工股份有限公司 | Method and equipment for using waste gas of butadiene extraction unit |
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Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2199589B (en) * | 1986-12-30 | 1991-07-24 | Labofina Sa | Improved process for the selective hydrogenation of acetylenes |
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- 2003-08-26 CN CNB031592376A patent/CN1294108C/en not_active Expired - Lifetime
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