CN105732289A - Method for recycling butadiene through selective hydrogenation of alkyne - Google Patents
Method for recycling butadiene through selective hydrogenation of alkyne Download PDFInfo
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- CN105732289A CN105732289A CN201410768145.6A CN201410768145A CN105732289A CN 105732289 A CN105732289 A CN 105732289A CN 201410768145 A CN201410768145 A CN 201410768145A CN 105732289 A CN105732289 A CN 105732289A
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- catalyst
- alkynes
- fraction
- butadiene
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 75
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 41
- 150000001345 alkine derivatives Chemical class 0.000 title claims description 70
- 238000004064 recycling Methods 0.000 title abstract 2
- 239000003054 catalyst Substances 0.000 claims abstract description 162
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 11
- -1 acetylene hydrocarbon Chemical class 0.000 claims abstract description 11
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010955 niobium Substances 0.000 claims abstract description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 58
- 239000000463 material Substances 0.000 claims description 54
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 37
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 34
- 229910052763 palladium Inorganic materials 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 230000005587 bubbling Effects 0.000 claims description 21
- 229910052783 alkali metal Inorganic materials 0.000 claims description 14
- 150000001340 alkali metals Chemical class 0.000 claims description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 14
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 14
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 claims description 12
- 238000010790 dilution Methods 0.000 claims description 12
- 239000012895 dilution Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Inorganic materials O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- BFRGSJVXBIWTCF-UHFFFAOYSA-N niobium monoxide Inorganic materials [Nb]=O BFRGSJVXBIWTCF-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 229910006415 θ-Al2O3 Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000000605 extraction Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000011112 process operation Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000243 solution Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910001593 boehmite Inorganic materials 0.000 description 12
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 12
- 238000000465 moulding Methods 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- 238000012854 evaluation process Methods 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 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 description 5
- 238000005336 cracking Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 150000002822 niobium compounds Chemical class 0.000 description 4
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229940046892 lead acetate Drugs 0.000 description 3
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000006396 nitration reaction Methods 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- 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 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical compound [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- AZYFWOPFILSZRA-UHFFFAOYSA-N buta-1,3-diene but-1-en-3-yne Chemical compound C=CC=C.C=CC#C AZYFWOPFILSZRA-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012962 cracking technique Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 231100000817 safety factor Toxicity 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 238000010187 selection method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for recycling butadiene through acetylene hydrocarbon selective hydrogenation takes carbon four-fraction which is rich in acetylene hydrocarbon after butadiene extraction as a raw material, and 1, 3-butadiene is obtained through selective hydrogenation by adopting an isothermal reactor in the presence of a catalyst, wherein the adopted process operation conditions are as follows: the reaction temperature is 30-80 ℃, the reaction pressure is 1.0-3.0 MPa, and the liquid space velocity is 7-18 h-1. The catalyst is a palladium-lead catalyst taking niobium oxide-alumina as a carrier. The method has obvious good effects on effective utilization of the acetylene hydrocarbon-rich carbon four-fraction after butadiene extraction, reduction of resource waste and improvement of economic benefits.
Description
Technical field
The present invention relates to the method that the selection of the height unsaturated hydrocarbons in a kind of C-4-fraction adds hydrogen retrieval butadiene.
Background technology
Usually containing the butadiene of mass fraction 40%～60% in the cracking c_4 fraction of hydrocarbons pyrolysis ethylene by-product, butadiene is the important monomer of China Synthetic Rubber Industry.From cracking c_4 fraction, extract butadiene generally adopt solvent extraction process, such as acetonitrile method, N methylpyrrolidone process and dimethylformamide method.Owing in the C-4-fraction after extracting, alkyne concentration is higher, and there is no industrial utility value at present, burn processing can only be made, but because high concentration alkynes has the danger of blast, therefore in the industrial production for the consideration of safety factors, to discharge the butadiene of equivalent when separating alkynes simultaneously, and just need to can send torch burning with after the fraction dilutions such as appropriate butylene, butane.This not only causes the very big wasting of resources, also pollutes environment.These factors have resulted in traditional carbon four solvent extraction apparatus energy consumption and have risen, and butadiene loss is serious, and economy is deteriorated.Due to the impact of the factor such as cracking severity and cracking technique, in cracking c_4 fraction, alkynes content is in being gradually increased trend, causes that the loss increase of butadiene in extractive process and energy consumption increase.Meanwhile, along with the development of organic synthesis industrial technology, alkynes in butadiene is also more strict containing quantitative limitation, and these factors all cause that the economy of BEU is deteriorated.When extracting butadiene, by recovery section butadiene after selective acetylene hydrocarbon hydrogenation, it is possible not only to the purpose reaching to turn waste into wealth, and to reducing alkynes discharge and preventing the pollution of the environment and also function to important function.
Carbon four acetylene hydrogenation technique is broadly divided into front-end hydrogenation technique and back end hydrogenation technique.Front-end hydrogenation technique is to be stripped butadiene again after chosen for the alkynes in C-4-fraction hydrogenation；Back end hydrogenation technique is to carry out selecting hydrogenation to the C-4-fraction rich in alkynes of discharge after extracting butadiene, returns extraction device and reclaim butadiene after vinylacetylene is converted into 1,3-butadiene.
ZL200810239462.3 discloses a kind of method of selective acetylene hydrocarbon hydrogenation, the fixed bed reactors that the method adopts are single hop or multistage isotherm formula bubbling bed reactor, the process condition adopted is: reaction temperature is 30～90 DEG C, and reaction pressure is 1.0～4.0MPa, and liquid air speed is 7～20h-1.The catalyst used is palladium system Cu-contained catalyst.
CN102731240A discloses a kind of method that carbon four selects hydrogenation to produce butadiene, this technique is front-end hydrogenation technique, adopting two sections of fixed bed adiabatic formula reactors, process conditions are: reaction inlet temperature 30～60 DEG C, reaction pressure 0.6～2.0MPa, carbon four liquid air speed 10～60h-1, hydrogen alkynes is than 0.2～10mol/mol.It is one or more in the rare-earth elements La of 0.01～10wt%, Pr, Nd that the catalyst adopted includes alumina support, 0.01～1wt%Pd, 0.01～5wt%Pb and total content.
ZL03159238.4 discloses the selection hydrogenation technique of a kind of hydrocarbon material flow rich in alkynes, and the fixed bed reactors that this technique adopts are single hop or multistage insulation formula bubbling bed reactor, and inlet temperature 10～40 DEG C, liquid air speed is 0.5～5h-1, the recycle ratio of product circulation amount and fresh material is 6:1～30:1.Under these process conditions, the conversion ratio of alkynes is more than 98%, and the yield of 1,3-butadiene is about 98%.But the liquid air speed of this technique is less, product circulation amount is higher with the recycle ratio of fresh material, and equipped with heat exchanger between every section of multi-stage fixed-bed reactor.
CN85106117A discloses alkynes and alkadienes catalysis selective hydrogenation technique in a kind of monoolefine, adopts single stage adiabatic formula trickle bed reactor, in order to α-Al2O3For the palladium catalyst of carrier, mainly for the treatment of C3Fraction, after hydrogenation reaction, alkynes and diene content are below 5%.
Summary of the invention
It is an object of the invention to provide a kind of method that selective acetylene hydrocarbon hydrogenation reclaims butadiene, rich in the selection method of hydrotreating of the C-4-fraction of alkynes after a kind of Butadiene Extraction of concrete offer, for processing containing C-4-fractions such as butane, butylene, butadiene, vinylacetylene, butine, to reclaim butadiene, improve resource added value, reduce investment, improve device economic benefit.
A kind of selective acetylene hydrocarbon hydrogenation of the present invention reclaims the method for butadiene, and the method includes treating hydrogenation material and H2Entering isothermal reactor, the mol ratio being mounted with selective hydrocatalyst, hydrogen and the total alkynes content of reactor inlet in isothermal reactor is 1.0～3.0；Reaction temperature 30～80 DEG C, reaction pressure is 1.0～3.0MPa, and liquid volume air speed is 7～18h-1, product enters knockout drum after cooling and is easily separated；Described treat hydrogenation material be the C-4-fraction rich in alkynes, the mixture of C-4-fraction and dilution material rich in alkynes；The carrier of selective hydrocatalyst is the complex carrier of aluminium oxide and niobium oxide, counts with total catalyst weight for 100wt%, and catalyst comprises palladium 0.1～1.0wt%, it is preferable that 0.2～0.6wt%；Plumbous 2～10wt%, it is preferable that 3～8wt%；Niobium oxide 0.5～3wt%, it is preferable that 1～3wt%, aluminium oxide 80～97wt%.
The method disclosed in the present, described treats that hydrogenation material is the C-4-fraction rich in alkynes or the mixture of C-4-fraction and dilution material rich in alkynes.Wherein rich in the C-4-fraction of alkynes from BEU, it is the C-4-fraction that alkynes content remaining after Butadiene Extraction is higher, usually contains butylene, butane, butadiene, vinylacetylene, butine key component.Be mainly the content of vinylacetylene rich in alkynes in the C-4-fraction of alkynes, the mass content of vinylacetylene is generally 15～25wt%, and butadiene mass content is generally 12～20wt%.
The method disclosed in the present, when treating hydrogenation material and H2When entering isotherm formula reactor, treat that the alkynes mass content in hydrogenation material is preferably not higher than 10wt%.Treat hydrogenation material be the C-4-fraction rich in alkynes or rich in alkynes C-4-fraction with dilution material mixture；When alkynes content is higher than 10wt% in rich in the C-4-fraction of alkynes, it is desirable to will be enriched in the dilution material dilution of the C-4-fraction of alkynes, the weight ratio expected rich in C-4-fraction and the dilution of alkynes is preferably 1:0.5～3；The most frequently used dilution material is carbon-4.
The method disclosed in the present, described isothermal reactor is trickle bed isothermal reactor or bubbling bed isothermal reactor two kinds.The present invention recommends bubbling bed isothermal reactor, it is desirable to for single hop or multistage isotherm formula bubbling bed reactor.Mol ratio for single hop isotherm formula bubbling bed reactor, hydrogen and the total alkynes content of reactor inlet is preferably 1.0～3.0.Described multistage isotherm formula bubbling bed reactor refers to the isotherm formula bubbling bed reactor more than containing double; two sections or double; two section, when adopting multistage isotherm formula bubbling bed reactor, with this section of porch, every section of porch amounts of hydrogen treats that in hydrogenation material, the mol ratio of alkynes total amount is preferably 1.0～2.0.The method disclosed in the present, can be different according to raw material in isothermal reactor, select different reaction conditions, owing to this reaction is liquid phase reactor, therefore the selection of temperature and pressure all should make raw material be in liquid, and temperature can not be too high, to prevent the polymerization of alkene and alkynes；Reaction temperature is generally 30～80 DEG C, it is desirable to be 30～70 DEG C；Reaction pressure is generally 1.0～3.0MPa, it is desirable to be 1.0～2.0MPa；Liquid air speed is 7～18h-1, it is desirable to it is 8～15h-1；The weight ratio that raw material is expected with dilution is preferably 1:0.5～1:3.
The method disclosed in the present, the carrier of selective hydrocatalyst therein is the complex carrier of aluminium oxide and niobium oxide, counts with total catalyst weight for 100wt%, and catalyst comprises palladium 0.1～1.0wt%, it is preferable that 0.2～0.6wt%；Plumbous 2～10wt%, it is preferable that 3～8wt%；Niobium oxide 0.5～3wt%, it is preferable that 1～3wt%, aluminium oxide 80～97wt%；Described aluminium oxide is θ-Al2O3And/or δ-Al2O3。
The method disclosed in the present, described selective hydrocatalyst, its carrier is the complex carrier of aluminium oxide and niobium oxide, no matter catalyst activity component is reduction-state or oxidation state, metal niobium exists with oxidation states all the time, and forms complex carrier with aluminium oxide.Its existing forms is described by the present invention with niobium oxide, and actually the niobium in niobium oxide has multiple chemical valence state, for instance have niobium pentaoxide (Nb2O5), columbium sesquioxide (Nb2O3), columbium dioxide (NbO2) and columbium monoxide (NbO), the niobium oxide in the present invention can be niobium pentaoxide, columbium dioxide, it is preferable that niobium pentaoxide.
The method disclosed in the present, the content of described niobium oxide is 0.5～3wt%.When content is lower than 0.5wt%, introduce niobium oxide the performance effect improving catalyst carrier is inconspicuous；When content is higher than 3wt%, the membership that adds of niobium oxide is greatly improved the acidity of catalyst carrier, and especially B-acid amount increases, and this can cause catalyst selectivity poor and easy gum deposit inactivation, is highly detrimental to the selection hydrogenation of catalyst.
The method disclosed in the present, selective hydrocatalyst therein comprises alkali metal and/or alkaline-earth metal 0.5～5wt%, it is preferable that 1～4wt%；Also can comprise in auxiliary agent gold, cobalt, molybdenum, tungsten, lanthanum, silver, cerium one or more, content is 0～2wt%, it is preferable that 0.2～1.8wt%.The specific surface area of catalyst is 20～80m2/ g, specific pore volume is 0.2～0.7ml/g.
The method disclosed in the present, described catalyst can adopt the following concrete preparation method of special recommendation of the present invention but catalyst used in the present invention is not limited in obtaining by the method, and the preparation method concrete steps of catalyst include:
The preparation of A catalyst carrier
By boehmite with containing niobium compound mixer kneader, extruded moulding, 100～130 DEG C of dry, 800～1100 DEG C of roasting 2～6h, prepare catalyst carrier；
The impregnated activated component of B
Preparing the solution plumbous containing 0.1～1.0wt% palladium and 2～10wt%, adjust pH value to 1.0～5.0, substep or co-impregnation are on catalyst complex carrier, through 100～130 DEG C of dry 2～6h, 300～700 DEG C of roasting 3～6h.
The preparation of catalyst carrier of the present invention can also be: by boehmite with containing niobium compound mixer kneader, extruded moulding, 100～130 DEG C of dry, 400～700 DEG C of roasting 2～6h, prepares niobium oxide and alumina composite carrier.
The preparation method of catalyst of the present invention, when in catalyst containing alkali metal and/or alkaline-earth metal, alkali metal and/or alkaline-earth metal load are on aluminium oxide and niobium oxide complex carrier.Obtain containing alkali metal or/and the catalyst carrier of alkaline-earth metal is the technology of non-normal open, prior art common are two kinds of approach: one is that addition alkali metal is or/and alkaline-earth metal before carrier molding, and a kind of passing through after carrier shaping and roasting prepares dry after corresponding soluble salt solutions impregnates, roasting acquisition.The present invention is not any limitation as.The method that can adopt one of the following obtains: method one: aluminium oxide and niobium oxide complex carrier be impregnated in the solution of alkali metal containing and/or alkaline-earth metal, through 100～130 DEG C of dry 2～6h, 800～1100 DEG C of roasting 3～8h, prepare the catalyst carrier of alkali metal containing and/or alkaline-earth metal.Method two: by the compound of alkali metal containing and/or alkaline-earth metal and boehmite, be mixed together containing niobium compound, nitric acid and water, through kneading, molding, then through 100～130 DEG C of dry 2～6h, 800～1100 DEG C of roasting 3～8h, make the catalyst carrier of alkali metal containing and/or alkaline-earth metal.
The preparation method of catalyst of the present invention, when catalyst is containing one or more promoter metal being selected from gold, cobalt, molybdenum, tungsten, lanthanum, silver, cerium, after step B activity metal impregnation, dry, roasting, impregnation aids metal, its process conditions are: the product obtained with one or more the soluble salt solutions substep in gold, cobalt, molybdenum, tungsten, lanthanum, silver, cerium or co-impregnation step B, through 100～130 DEG C of dry 2～6h, 300～700 DEG C of roasting 3～6h prepare catalyst.
The preparation method of catalyst of the present invention, when in catalyst containing alkali metal and/or alkaline-earth metal, one or more promoter metal in gold, cobalt, molybdenum, tungsten, lanthanum, silver, cerium, first prepare the catalyst carrier containing alkali metal and/or alkaline-earth metal, impregnated activated component, then impregnation aids metal again.
In method for preparing catalyst of the present invention, it is selected from the one in niobium pentaoxide, niobium oxalate, niobium hydroxide or ammonium niobium oxalate containing niobium compound.
In method for preparing catalyst of the present invention, palladium is to introduce with the form of soluble-salt, such as Palladous chloride., Palladous nitrate. or palladium.
Method for preparing catalyst of the present invention, lead is to introduce with the form of nitrate or acetate.
In method for preparing catalyst of the present invention, alkali metal is one or more in Li, Na, K and Cs, it is preferable that Li and/or K, and the form that alkali metal is the soluble nitrate with it or acetate introduces；Alkaline-earth metal is one or more in Be, Mg, Ca and Sr, it is preferable that Mg, and the form that alkaline-earth metal is the soluble nitrate with it or acetate introduces.
In method for preparing catalyst of the present invention, promoter metal is one or more in gold, cobalt, molybdenum, tungsten, lanthanum, silver, cerium.The form that promoter metal is the soluble-salt with it introduces.
The pH value of Catalyst Preparation Impregnation liquid of the present invention can adjust with ammonia, sodium bicarbonate or sodium carbonate liquor.
In the present invention, boehmite can use prepared by the methods such as carbonizatin method, ammonium method, nitrate method it is best to use prepared by ammonium method.
The method disclosed in the present, described catalyst carrier is the complex carrier of niobium oxide and aluminium oxide, because niobium oxide can improve the Acidity of catalyst carrier, improves the heat stability of catalyst carrier, extends the service life of catalyst.It is simultaneously introduced niobium oxide and can also stablize the chain carrier of lower valency.It needs to be noted in described catalyst not cupric, when catalyst contains niobia-alumina, when active component palladium, lead, time in catalyst containing copper, reaction temperature is relatively higher, it is easy to cause the unsaturated hydrocarbons in C-4-fraction to be polymerized, and produces green oil, cause that catalyst gum deposit inactivates, affect the service life of catalyst.And the existence of copper component can make catalyst regeneration conditions complexity harsh, security performance is not high.
The method disclosed in the present, C-4-fraction rich in alkynes after Butadiene Extraction is made directly selection hydrogenation, employ the catalyst containing niobium oxide and the complex carrier of aluminium oxide in the process, the existence of niobium oxide, improve the Acidity of catalyst carrier preferably, the existence of niobium oxide and other components and synergism so that catalyst has good heat stability, it is provided that stablizes the chain carrier weapons of lower valency and has longer service life；The method of hydrotreating of the present invention is by vinylacetylene butadiene therein and monoolefine, and hydrogenation products can return to extraction device and continues extracting butadiene, increases the yield of butadiene, improves the added value of this strand of material.Even if when the alkynes content of raw material is more than 5wt%, method provided by the present invention is adopted still to be able to long-term normal operation, catalyst activity component palladium is substantially free of loss, produces almost without dimer in the material after hydrogenation, and vinylacetylene content is less than 1.0wt%.The method of the present invention has a major advantage in that: (1) adopts isotherm formula reactor.Owing to carbon four selective acetylene hydrocarbon hydrogenation is the reaction that thermal discharge is higher, heat is easily assembled, cause bed temperature rise, unsaturated hydrocarbons is easily made to be polymerized gum deposit in course of reaction, blocking catalyst duct, causes catalysqt deactivation, and side reaction also can be made to aggravate simultaneously, and adopt isotherm formula reactor, these undesirable elements can be avoided.So can effectively suppress the generation of polymer, make a small amount of low-molecular-weight polymer that catalyst surface deposits be rinsed by reactant rapidly to take away, so that effective contact area of catalyst and reactant increases, the activity and selectivity of catalyst is enable all fully to be showed in long-time.(2) catalyst that the present invention uses is bimetallic or multimetal reforming catalyst, the absorption between strong interaction ethene suppressing ethyl-acetylene and palladium between metal, effectively reduce active component palladium loss, extend the life-span of catalyst, it is ensured that the smooth long term running of hydrogenation technique.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of embodiment 1～7 catalyst carrier, the XRD spectra of these carriers is basically identical, 2 θ values are mainly the diffraction maximum that interval is niobium oxide of 22～26 ° and 53～56 °, and 2 θ values are mainly the diffraction maximum that interval is aluminium oxide of 30～42 °, 42～49 ° and 64～70 °.
Detailed description of the invention
Raw material sources and the method for analysis:
C-4-fraction rich in alkynes: take from Lanzhou Petrochemical ethylene plant, containing vinylacetylene (VA) 15～25wt%, butadiene 12～20wt%；
Boehmite: catalyst carrier company limited of Nanjing Olympic Thailand；
Specific surface area (m2/ g) and pore volume (ml/g): adopt national standard catalyst and the long-pending assay method GB/T5816 of adsorbent surface to analyze；
Raw material and product composition: adopt the composition measuring SH-T1141-92 of industrial cracking c_4 to analyze；
Catalyst agent active component content assay method: adopt national standard " atomic absorption spectroscopy general rule " GB/T15337-94 and " chemical reagent flame atom absorption spectrophotography method general rule " GB19723-88 to analyze.
Embodiment
The preparation of catalyst 1～7
The preparation of catalyst 1:
By boehmite, niobium pentaoxide, nitric acid, water mixer kneader, extruded moulding, 120 DEG C of dry, 980 DEG C of roasting 3h, prepare catalyst carrier；Preparing palladium nitrate solution again, regulating pH value with sodium carbonate is 2.6, is impregnated in catalyst carrier, removes remaining liquid after 20 minutes, and with distilled water wash, aged, 120 DEG C of dry 2h, 420 DEG C of roasting 3h obtain the catalyst precarsor containing palladium；Finally prepare lead acetate solution again, be immersed on catalyst precarsor, 120 DEG C of dry 4h, 480 DEG C of roasting 4h, prepare selective hydrocatalyst 1.
The preparation of catalyst 2:
By boehmite, niobium oxalate, nitric acid, water mixer kneader, extruded moulding, 120 DEG C of dry, 1020 DEG C of roasting 4h, prepare catalyst carrier；Then preparing palladium chloride solution, regulate pH to 2.7 with sodium bicarbonate, be impregnated in catalyst carrier, remove remaining liquid after 20 minutes, with distilled water wash, aged, 120 DEG C of dry 2h, 450 DEG C of roasting 3h obtain the catalyst precarsor containing palladium；Prepare lead nitrate solution again, be immersed on the catalyst precarsor containing palladium, 120 DEG C of dry 2h, 450 DEG C of roasting 4h, prepare selective hydrocatalyst 2.
The preparation of catalyst 3:
By boehmite, niobium oxalate, magnesium nitrate, nitric acid, water mixer kneader, extruded moulding, 120 DEG C of dry, 1050 DEG C of roasting 4h, prepare catalyst carrier；Then preparing palladium chloride solution, regulate pH to 2.7 with sodium carbonate, be impregnated in catalyst carrier, remove remaining liquid after 20 minutes, with distilled water wash, aged, 120 DEG C of dry 2h, 450 DEG C of roasting 3h obtain the catalyst precarsor containing palladium；Prepare lead acetate solution again, be immersed on the catalyst precarsor containing palladium, 120 DEG C of dry 2h, 460 DEG C of roasting 4h, prepare selective hydrocatalyst 2.
The preparation of catalyst 4:
By boehmite, niobium oxalate, nitric acid, water mixer kneader, extruded moulding, 120 DEG C of dry, 600 DEG C of roasting 3h, prepare niobium oxide and alumina composite carrier；Then being impregnated on a catalyst support by a certain amount of potassium nitrate solution, 110 DEG C of dry 4h, 1050 DEG C of roasting 5h make the catalyst carrier containing magnesium；Then preparation palladium solution, regulates pH to 2.8 with sodium carbonate, is impregnated in the catalyst carrier containing magnesium, removes remaining liquid after 20 minutes, and with distilled water wash, aged, 120 DEG C of dry 3h, 440 DEG C of roasting 3h obtain the catalyst precarsor containing palladium；Prepare lead nitrate solution again, be immersed on the catalyst precarsor containing palladium, 120 DEG C of dry 3h, 500 DEG C of roasting 4h, prepare selective hydrocatalyst 3.
The preparation of catalyst 5:
By boehmite, niobium hydroxide, nitric acid, water mixer kneader, extruded moulding, 120 DEG C of dry, 550 DEG C of roasting 3h, prepare niobium oxide and alumina composite carrier；Then a certain amount of potassium nitrate and magnesium nitrate solution being impregnated on a catalyst support, 110 DEG C of dry 4h, 980 DEG C of roasting 5h make the catalyst carrier containing potassium；Preparing the mixed solution of palladium and lead acetate again, regulating pH value with sodium bicarbonate is 2.9, is impregnated in the catalyst carrier containing potassium, remaining liquid is removed after 20 minutes, with distilled water wash, aged, 120 DEG C of dry 2h, 450 DEG C of roasting 3h, prepare selective hydrocatalyst 4.
The preparation of catalyst 6:
By boehmite, ammonium niobium oxalate, magnesium nitrate, nitric acid, water mixer kneader, extruded moulding, 120 DEG C of dry, 1000 DEG C of roasting 3h, prepare the catalyst carrier containing magnesium；Then preparing palladium chloride solution, regulate pH to 2.6 with sodium bicarbonate, be impregnated in catalyst carrier, remove remaining liquid after 20 minutes, with distilled water wash, aged, 120 DEG C of dry 2h, 450 DEG C of roasting 3h obtain the catalyst precarsor containing palladium；Preparing lead nitrate solution again, be immersed on the catalyst precarsor containing palladium, 120 DEG C of dry 2h, 550 DEG C of roasting 4h obtain the catalyst precarsor containing palladium and lead；Finally prepare silver nitrate solution, be immersed on catalyst precarsor, 120 DEG C of dry 2h, 500 DEG C of roasting 3h, prepare selective hydrocatalyst 5.
The preparation of catalyst 7:
By boehmite, niobium pentaoxide, nitric acid, water mixer kneader, extruded moulding, 120 DEG C of dry, 620 DEG C of roasting 3h, prepare niobium oxide and alumina composite carrier；Then being immersed in by a certain amount of magnesium nitrate solution on niobium oxide and alumina composite carrier, 120 DEG C of dry 4h, 1100 DEG C of roasting 3h make the catalyst carrier containing magnesium；Prepare the mixed solution of palladium and plumbi nitras again, regulating pH value with ammonia is 2.8, is impregnated in the catalyst carrier containing magnesium, removes remaining liquid after 20 minutes, with distilled water wash, aged, 120 DEG C of dry 2h, 440 DEG C of roasting 5h obtain the catalyst precarsor containing palladium and lead；Finally prepare ammonium metatungstate solution, be jointly immersed on catalyst precarsor, 120 DEG C of dry 4h, 550 DEG C of roasting 4h, prepare selective hydrocatalyst 6.
The physico-chemical property of catalyst 1～7 is as shown in table 1.
The physico-chemical property of the catalyst prepared by table 1 embodiment
Embodiment 1
Will be enriched in the C-4-fraction carbon-4 of alkynes to be diluted, be 1:2.5 rich in the C-4-fraction of alkynes and the weight ratio of carbon-4.Isothermal reactor adopts single hop isotherm formula bubbling bed, adopts catalyst 1, and catalyst is in a hydrogen atmosphere through 120 DEG C of reduction 6h.Reaction temperature 50 DEG C, reaction pressure 1.2MPa, liquid air speed 8.5h-1, the mol ratio of hydrogen and alkynes is 1.5, and table 2 is the composition of material before and after reaction.
Material composition before and after table 2 reaction
Embodiment 2
Will be enriched in the C-4-fraction carbon-4 of alkynes to be diluted, be 1:3 rich in the C-4-fraction of alkynes and the weight ratio of carbon-4.Isothermal reactor adopts single hop isotherm formula bubbling bed, adopts catalyst 2, and catalyst is in a hydrogen atmosphere through 120 DEG C of reduction 6h.Reaction temperature 45 DEG C, reaction pressure 1.5MPa, liquid air speed 9.0h-1, the mol ratio of hydrogen and alkynes is 1.5, and table 3 is the composition of material before and after reaction.
Material composition before and after table 3 reaction
Embodiment 3
Will be enriched in the C-4-fraction carbon-4 of alkynes to be diluted, be 1:3 rich in the C-4-fraction of alkynes and the weight ratio of carbon-4, isothermal reactor adopts single hop isotherm formula bubbling bed, adopts catalyst 3, and catalyst is in a hydrogen atmosphere through 120 DEG C of reduction 6h.Reaction temperature 45 DEG C, reaction pressure 2.0MPa, liquid air speed 10.0h-1, the mol ratio of hydrogen and alkynes is 2.0, and table 4 is the composition of material before and after reaction.
Material composition before and after table 4 reaction
Embodiment 4
Will be enriched in the C-4-fraction carbon-4 of alkynes to be diluted, be 1:0.5 rich in the C-4-fraction of alkynes and the weight ratio of carbon-4, isothermal reactor adopts single hop isotherm formula bubbling bed, adopts catalyst 4, and catalyst is in a hydrogen atmosphere through 120 DEG C of reduction 6h.Reaction temperature 40 DEG C, reaction pressure 2.0MPa, liquid air speed 12h-1, the mol ratio of hydrogen and alkynes is 3.0, and table 5 is the composition of material before and after reaction.
Material composition before and after table 5 reaction
Embodiment 5
Will be enriched in the C-4-fraction carbon-4 of alkynes to be diluted, be 1:2 rich in the C-4-fraction of alkynes and the weight ratio of carbon-4, isothermal reactor adopts double; two section isotherm formula bubbling bed, and catalyst is in a hydrogen atmosphere through 120 DEG C of reduction 6h.One section adopts catalyst 5, and two-stage nitration adopts catalyst 6, and one section of reaction temperature 40 DEG C, second-stage reaction temperature is 40 DEG C, reaction pressure 1.5MPa, liquid air speed 15.0h-1, the mol ratio of every section of bed hydrogen and alkynes is 3.0, and table 6 is the composition of material before and after reaction.
Material composition before and after table 6 reaction
Embodiment 6
Will be enriched in the C-4-fraction carbon-4 of alkynes to be diluted, be 1:2.5 rich in the C-4-fraction of alkynes and the weight ratio of carbon-4.Isothermal reactor adopts double; two section isotherm formula bubbling bed, and catalyst is in a hydrogen atmosphere through 120 DEG C of reduction 6h.The employing catalyst 7 of two sections, one section of reaction temperature 35 DEG C, second-stage reaction temperature is 45 DEG C, reaction pressure 1.5MPa, liquid air speed 12h-1, the mol ratio of every section of bed hydrogen and alkynes is 2.0, and table 7 is the composition of material before and after reaction.
Material composition before and after table 7 reaction
Embodiment 7
Will be enriched in the C-4-fraction carbon-4 of alkynes to be diluted, be 1:3 rich in the C-4-fraction of alkynes and the weight ratio of carbon-4, isothermal reactor adopts double; two section isotherm formula bubbling bed, and catalyst is in a hydrogen atmosphere through 120 DEG C of reduction 6h.One section adopts catalyst 3, and two-stage nitration adopts catalyst 6, and one section of reaction temperature 40 DEG C, second-stage reaction temperature is 40 DEG C, reaction pressure 2.0MPa, liquid air speed 18.0h-1, the mol ratio of every section of bed hydrogen and alkynes is 2.0, and table 8 is the composition of material before and after reaction.
Material composition before and after table 8 reaction
Embodiment 8
Will be enriched in the C-4-fraction carbon-4 of alkynes to be diluted, be 1:1 rich in the C-4-fraction of alkynes and the weight ratio of carbon-4, isothermal reactor adopts double; two section isotherm formula bubbling bed, and catalyst is in a hydrogen atmosphere through 120 DEG C of reduction 6h.One section adopts catalyst 1, and two-stage nitration adopts catalyst 3, and catalyst is in a hydrogen atmosphere through 120 DEG C of reduction 6h.One section of reaction temperature 35 DEG C, second-stage reaction temperature is 40 DEG C, reaction pressure 2.0MPa, liquid air speed 10.0h-1, the mol ratio of every section of bed hydrogen and alkynes is 2.0, and table 9 is the composition of material before and after reaction.
Material composition before and after table 9 reaction
In the selection hydrogenation process of carbon four alkynes, main reaction is that vinylacetylene selects to be hydrogenated to 1,3-butadiene.In order to farthest reclaim butadiene, it is desirable to selectivity of catalyst to be got well.Data from table 2,3,4,5,6,7,8 are it is apparent that catalyst has good hydrogenation activity, selectivity and stability, and product medium vinyl acetylene content is lower than 1.0wt%, butadiene selective is all more than 45%, the 1,3-butadiene response rate is higher, has all exceeded 100%.
Comparative example 1
Comparative example 1 used catalyst is identical with catalyst 1 preparation method, is different in that in comparative example 1 used catalyst without niobium oxide.The evaluation process conditions of catalyst are identical with embodiment 1.Table 10 is the composition of material before and after reaction.
Material composition before and after table 10 reaction
Comparative example 2
Comparative example 2 used catalyst is identical with catalyst 2 preparation method, is different in that in comparative example 2 used catalyst plumbous without component.The evaluation process conditions of catalyst are identical with embodiment 2.Table 11 is the composition of material before and after reaction.
Material composition before and after table 11 reaction
Comparative example 3
Comparative example 2 used catalyst is identical with catalyst 2 preparation method, and being different in that in comparative example 2 used catalyst, lead content is 12.0wt%.The evaluation process conditions of catalyst are identical with embodiment 2.Table 12 is the composition of material before and after reaction.
Material composition before and after table 12 reaction
Comparative example 4
Comparative example 4 used catalyst is identical with catalyst 4 preparation method, and being different in that in comparative example 4 used catalyst, niobium oxide content is 4.5wt%.The evaluation process conditions of catalyst are identical with embodiment 4.Table 13 is the composition of material before and after reaction.
Material composition before and after table 13 reaction
Comparative example 5
Comparative example 5 used catalyst is identical with catalyst 3 preparation method, is different in that in comparative example 3 used catalyst without niobium oxide.The evaluation process conditions of catalyst are identical with embodiment 3.Table 14 is the composition of material before and after reaction.
Material composition before and after table 14 reaction
Comparative example 6
Comparative example 1 used catalyst is identical with catalyst 1 preparation method, and being different in that in comparative example 1 used catalyst, niobium oxide content is 0.35wt%.The evaluation process conditions of catalyst are identical with embodiment 1.Table 15 is the composition of material before and after reaction.
Material composition before and after table 15 reaction
Comparative example 7
Comparative example 7 used catalyst preparation method is with the embodiment 7 of CN101428228B.Consisting of of comparative example 7 used catalyst: carrier is aluminium oxide, 0.45wt%Pd, 1.25wt%Mg, 3.65wt%Pb, 3.05wt%Cu.The evaluation process conditions of catalyst are identical with embodiment 2.Table 16 is the composition of material before and after reaction.
Material composition before and after table 16 reaction
Be can be seen that by the data analysis of embodiment and comparative example, adopt the method for hydrotreating of the present invention, and the supporting palladium lead series catalysts of niobia-alumina composite carrier load adopted with the present invention, hydrogenated products medium vinyl acetylene content is lower than 1.0wt%, butadiene selective is high, can farthest reclaiming butadiene, hydrogenated products meet BEU feed needs.
Claims (10)
1. the method that a selective acetylene hydrocarbon hydrogenation reclaims butadiene, it is characterised in that the method includes treating hydrogenation material and H2Entering isothermal reactor, the mol ratio being mounted with selective hydrocatalyst, hydrogen and the total alkynes content of reactor inlet in isothermal reactor is 1.0～3.0；Reaction temperature 30～80 DEG C, reaction pressure is 1.0～3.0MPa, and liquid volume air speed is 7～18h-1, product enters knockout drum after cooling and is easily separated；Described treat hydrogenation material be the C-4-fraction rich in alkynes, the mixture of C-4-fraction and dilution material rich in alkynes；The carrier of selective hydrocatalyst is the complex carrier of aluminium oxide and niobium oxide, counts with total catalyst weight for 100wt%, and catalyst comprises palladium 0.1～1.0wt%, plumbous 2～10wt%, niobium oxide 0.5～3wt%, aluminium oxide 80～97wt%；Described aluminium oxide is θ-Al2O3And/or δ-Al2O3。
2. method according to claim 1, it is characterised in that described catalyst comprises palladium 0.2～0.6wt%, plumbous 3～8wt%, niobium oxide 1～3wt%.
3. method according to claim 1, it is characterised in that niobium oxide represents that metal niobium exists with oxidation states all the time, and niobium oxide is one or more in niobium pentaoxide, columbium sesquioxide, columbium dioxide, columbium monoxide.
4. method according to claim 1, it is characterised in that this catalyst contains alkali metal and/or alkaline-earth metal, its content is 0.5～5wt% of total catalyst weight；Containing one or more in auxiliary agent gold, cobalt, molybdenum, tungsten, lanthanum, silver, cerium, described auxiliary agent content is 0～2wt% of total catalyst weight.
5. method according to claim 1, it is characterised in that the described alkynes mass content treated in hydrogenation material is not higher than 10wt%.
6. method according to claim 1, it is characterised in that the described C-4-fraction rich in alkynes, vinylacetylene mass content is 15～25wt%, and butadiene mass content is 12～20wt%.
7. method according to claim 5, it is characterised in that treat the mixture that hydrogenation material is the C-4-fraction rich in alkynes and dilution material, is 1:0.5～3 rich in the C-4-fraction of alkynes and the weight ratio of dilution material.
8. method according to claim 1, it is characterised in that isothermal reactor is single hop isotherm formula bubbling bed reactor or multistage isotherm formula bubbling bed reactor.
9. the mol ratio of method according to claim 8, it is characterised in that single hop isotherm formula bubbling bed reactor, hydrogen and the total alkynes content of reactor inlet is 1.0～3.0；Multistage isotherm formula bubbling bed reactor, with this section of porch, every section of porch amounts of hydrogen treats that in hydrogenation material, the mol ratio of alkynes total amount is 1.0～2.0.
10. method according to claim 1, it is characterised in that reaction temperature 30～70 DEG C；Reaction pressure 1.0～2.0MPa；Liquid air speed 8～15h-1。
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| CN105732289B (en) | 2018-07-13 |
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