CN108863696A - Method for recovering butene by selective hydrogenation of alkyne - Google Patents
Method for recovering butene by selective hydrogenation of alkyne Download PDFInfo
- Publication number
- CN108863696A CN108863696A CN201710338485.9A CN201710338485A CN108863696A CN 108863696 A CN108863696 A CN 108863696A CN 201710338485 A CN201710338485 A CN 201710338485A CN 108863696 A CN108863696 A CN 108863696A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- alkynes
- palladium
- molybdenum
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 79
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 50
- 150000001345 alkine derivatives Chemical class 0.000 title claims description 84
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title abstract description 5
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 title abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 157
- 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 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 150000001993 dienes Chemical class 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 17
- -1 acetylene hydrocarbon Chemical class 0.000 claims abstract description 17
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 17
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 63
- 239000000203 mixture Substances 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 43
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 42
- 238000002360 preparation method Methods 0.000 claims description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 34
- 229910001593 boehmite Inorganic materials 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims description 34
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 34
- 229910052763 palladium Inorganic materials 0.000 claims description 21
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 229910052709 silver Inorganic materials 0.000 claims description 18
- 239000004332 silver Substances 0.000 claims description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims description 16
- 239000011733 molybdenum Substances 0.000 claims description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims description 14
- 150000001340 alkali metals Chemical class 0.000 claims description 14
- 238000000465 moulding Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 13
- 238000010790 dilution Methods 0.000 claims description 13
- 239000012895 dilution Substances 0.000 claims description 13
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 238000002441 X-ray diffraction Methods 0.000 claims description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 229910003303 NiAl2O4 Inorganic materials 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 claims 1
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 claims 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 32
- 230000000694 effects Effects 0.000 abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052799 carbon Inorganic materials 0.000 abstract description 17
- 238000000605 extraction Methods 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 11
- 230000009467 reduction Effects 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000011112 process operation Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- 229910001868 water Inorganic materials 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000001569 carbon dioxide Substances 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 230000032683 aging Effects 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 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 8
- 238000012854 evaluation process Methods 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- 150000002815 nickel Chemical class 0.000 description 6
- 150000002940 palladium Chemical class 0.000 description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 5
- 239000011609 ammonium molybdate Substances 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 229940010552 ammonium molybdate Drugs 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- 238000005336 cracking Methods 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
- 239000011148 porous material Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000002803 maceration Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000010187 selection method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004575 stone Substances 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
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- 230000013011 mating Effects 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- OHBTULDTCSOWOY-UHFFFAOYSA-N [C].C=C Chemical compound [C].C=C OHBTULDTCSOWOY-UHFFFAOYSA-N 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003676 hair preparation Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229940071264 lithium citrate Drugs 0.000 description 1
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for recovering butene by acetylene hydrocarbon selective hydrogenation takes carbon four-fraction rich in acetylene hydrocarbon after butadiene extraction as raw material, and adopts an adiabatic reactor to selectively hydrogenate acetylene hydrocarbon and diene into butene in the presence of a catalyst, and the adopted process operation conditions are as follows: the inlet temperature of the reactor is 25-100 ℃, the reaction pressure is 0.6-2.5 MPa, and the liquid airspeed is 15-25 h‑1. The catalyst is a palladium-molybdenum-silver selective hydrogenation catalyst prepared by a nickel-containing alumina carrier with a specific crystal form, so that the dispersion degree and the utilization rate of active metals can be greatly improved, and the hydrogenation performance of the catalyst is improved. 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 methods of the selection plus hydrogen retrieval butylene of the height unsaturated hydrocarbons in a kind of C-4-fraction, especially relate to
A kind of and method of selective acetylene hydrocarbon hydrogenation recycling butylene.
Background technique
1,3-butadiene is the important monomer of synthetic rubber, industrially mainly with the cracking of by-product when hydrocarbon cracking ethylene
Carbon four is raw material, is produced using the method for solvent extraction.The 1,3-butadiene containing 40~60wt% is removed in cracking c_4
Outside, the alkynes usually also containing 1~2wt% (predominantly vinylacetylene), in order to obtain polymer grade 1,3-butadiene (butadiene
Purity >=99.5%, alkynes content<100ppm), generalling use two-stage extracting rectifying adds the mode of two-stage conventional distillation to extract fourth
Diene.Four alkynes of carbon as impurity is mainly discharged in the second extractive distillation column, with a set of 800,000 tons/year of ethylene unit
For, four alkynes of carbon discharged every year is at 30,000 tons or so.Industrially for the purpose of safety, this four alkynes of part carbon is being discharged
Before, it needs that alkynes is diluted to safe range with fractions such as butylene, butane, alkynes content is high in this partial material after dilution
(15~30wt% of vinylacetylene, 10~25wt% of 1,3-butadiene, remaining is butylene, butane), does not utilize way suitably
Diameter usually direct emission torch or is sold as low-value fuel, therefore causes the huge wasting of resources and environmental pollution.
With the enlargement of ethylene unit scale, the discharge amount of four alkynes of carbon is also increasing.How rationally efficient benefit
It is the research puzzle that lot of domestic and foreign research institution faces with this part resource, adds the method for hydrogen by this partial discharge using selection
Four alkynes of carbon handled, so that vinylacetylene and butadiene therein is converted into monoolefine, can not only eliminate because of this stock
The discharge of material runs bring security risk to butadiene extraction device, but also can recycle a large amount of monoolefine, reaches
Turn waste into wealth, energy-saving purpose.
ZL201010182736.7 discloses the selection method of hydrotreating of alkynes and alkadienes in a kind of C_4 hydrocarbon logistics, the party
Method use fixed bed reactors, the process condition used for：Reacting inlet temperature is 10~80 DEG C, and reaction pressure is
The molar ratio of the sum of 0.1~4.0MPa, hydrogen and alkynes and alkadienes is 1~10.The catalyst used is palladium series catalyst, is adopted
It is prepared with spraying hair, and uses ionizing radiation palladium catalyst precursor.Containing only butadiene in the C 4 materials that embodiment uses,
Without containing alkynes.
CN201110315384.2 discloses a kind of method of hydrotreating containing alkynes and alkadienes C-4-fraction, and this method uses
Two series connection isotherm formula fixed bed reactors, the process condition used for：Reacting inlet temperature is 20~60 DEG C, reaction pressure
Power is 0.5~4.0MPa, 1.0~30h of liquid air speed-1, the molar ratio of the sum of first reactor hydrogen and alkynes and alkadienes
It is 1~6, the molar ratio of the sum of second reactor hydrogen and alkynes and alkadienes is 1~6.The catalyst used be palladium base or
Copper-based catalysts, and contain IB element, IIIB element and alkali metal/alkaline-earth metal.Raw material is the fourth rich in alkynes and alkadienes
Diene extraction device remnants C 4 materials and MTBE device residue C 4 materials, remaining C 4 materials be rich in alkynes and alkadienes
Remaining C 4 materials weight ratio be 1~4:1.
ZL201010182720.6 discloses the selection method of hydrotreating of alkynes and alkadienes in a kind of olefin stream, this method
The fixed bed reactors of use, the process condition used for：Reacting inlet temperature is 10~80 DEG C, reaction pressure 0.1
The molar ratio of the sum of~4.0MPa, hydrogen and alkynes and alkadienes is 1~10.The catalyst used is palladium series catalyst, is used
Spraying hair preparation, and use ionizing radiation palladium catalyst precursor.Embodiment uses material for C3 fraction, contains propine and third
Diene.
Following three aspects (1) that focus on for improving palladium series hydrocatalyst comprehensive performance develop a kind of novel be applicable in
In the carrier material of palladium series hydrocatalyst；(2) modulation palladium series hydrocatalyst active component content；(3) auxiliary agent and work is added
Property ingredient dispersion agents improve active component comprehensive utilization ratio.
Hydrated alumina such as boehmite and boehmite etc. are widely used as the raw material for preparing alumina support,
Although in carrying alumina production procedure can using as the methods of pH value swing method, the organic expanding agent of addition, hydro-thermal process come
Improve the property of the aluminium oxide as carrier, but the aluminium oxide of catalyst carrier for hydrgenating material is improved by these methods
Performance is limited.The property for preparing aqua oxidation aluminum feedstock used in alumina support is to produce excellent properties carrying alumina
One of body most critical factor.
CN1123392C describes a kind of alumina carrier containing Ni and preparation method thereof, by alkali-treated nickeliferous chemical combination
The mixture of object and carbon black and aluminum hydroxide solid elastomer powder kneading, be made through extruded moulding and drying, roasting it is a kind of it is nickeliferous be 2.0
~14.0% alumina support, it is 0.4~1.0cm which, which holds,3/ g, specific surface area are 160~420m2/ g, average pore size
For 8.0~15.0nm, the 85% more of its total hole is accounted for greater than the ratio in the hole 6.0nm, Kong Rong, average pore size are larger, shared by macropore
Ratio is more, is particularly suitable for use as the carrier of hydrorefining catalyst for heavy oil.
CN200710179630.X discloses a kind of preparation method of nickel-coated alumina powder, it is characterised in that will be added and divide
Suspension is made in the mixed liquor of the nano aluminium oxide of powder, is added with stirring nickel salt solution, after mixing evenly, drips in mixed liquor
Enter ammonium hydroxide, add distilled water, obtains navy blue nickel amine complex ([Ni (NH3)6]2+)-Aluminium oxide mixed solution C, using water
Heat ageing is filtered, washed, dries, and obtains coating product among green；Roasting is restored again, the oxidation of black nickel coated is obtained
Aluminium powder body.
CN1102862C discloses a kind of nickel-containing hydrogenationcatalysts, contains：In terms of nickel oxide, 65~80% nickel, with two
Silica meter, 10~25% silicon, in terms of zirconium oxide, 2~10% zirconium, in terms of aluminium oxide, 0~10% aluminium, premise item
Part is that the sum of content of silica and aluminium oxide is at least 15% (weight %, based on the total weight of catalyst), this
Catalyst is by the way that by nickel, zirconium, if necessary, there are also the acidic aqueous solutions of the salt of aluminium to be added to silicon, and if necessary, there are also aluminium
In the alkaline aqueous solution or suspension of compound, the pH of the mixture so obtained is made to be reduced at least 6.5, then by into one
Step addition alkaline solution adjusts pH value to 7-8, separate the solid so deposited, dry, form and be sintered.Additionally
It discloses the method for preparing catalyst and it is preparing medicinal white oils, high-purity medical paraffin and low boiling point low arene content
Or the method for aromatic free hydrocarbon mixture.The preparation method of the catalyst is commonly used to prepare the catalysis of high-activity component content
Agent, but use the catalyst activity of this method preparation poor.
Article " the changes induced by calcination temperature in of Agudo A L etc.
hydrodesulfurization activity of NiCo-Mo/Al2O3Catalysis, Applied Catalysis,
1987,30:185-188 " has investigated maturing temperature to NiCoMo/A12O3The active influence of catalyst rhohene desulfiirization.As a result table
Bright, the desulphurizing activated of the catalyst activated at 500 DEG C is significantly higher than the catalyst activated under the conditions of 600 DEG C, this is because
In 600 DEG C of activation, strong interaction generation spinel structure occurs for metal and alumina support so as to cause catalysis in catalyst
Agent activity is remarkably decreased.Activation temperature is higher, and the nickel aluminate phase content of generation is higher, and the activity decline of catalyst is brighter
It is aobvious."Influence of support-interaction on the sulfidation behavior and
hydrodesulfurization activity of Al2O3Support W, CoW and NiW model catalysts, J
Phys Chem B, 2002,106:5897-5906 " equally obtains similar conclusion.Since nickel and alumina support are roasted in high temperature
Strong interaction can occur during burning and generate spinel structure, be remarkably decreased so as to cause catalyst activity, therefore in high temperature
It is all as prudent using the two as possible before roasting, avoid the generation of spinel structure.It is different from other metals, it is rare it is nickeliferous intend it is thin
Diaspore report generally requires to carry out high-temperature roasting when because preparing catalyst carrier with it.
The active component of Typical precious metal catalyst is easy to reunite and be poisoned and inactivate during the reaction, point of palladium metal
Divergence is even more that numerous researchers attempt to solve the problems, such as.
Summary of the invention
The object of the present invention is to provide a kind of methods of selective acetylene hydrocarbon hydrogenation recycling butylene, specifically provide a kind of fourth two
The selection method of hydrotreating of C-4-fraction rich in alkynes after alkene extracting, contains butane, butylene, butadiene, vinyl for handling
The C-4-fractions such as acetylene, butine improve resource added value to recycle butylene, reduce investment, improve device economic benefit.
A kind of method of selective acetylene hydrocarbon hydrogenation recycling butylene provided by the invention, this method includes to hydrogenation material and H2Into
Enter adiabatic reactor, palladium-molybdenum-silver system selective hydrogenation catalyst, hydrogen and the total alkynes of reactor inlet are mounted in adiabatic reactor
Hydrocarbon+diene content molar ratio is 1.5~6.0；25~100 DEG C of reactor inlet temperature, reaction pressure be 0.6~
2.5MPa, liquid volume air speed are 15~25h-1, reaction product enters knockout drum after cooling and separated；It is described to be added
Hydrogen material is the mixture of the C-4-fraction rich in alkynes, the C-4-fraction rich in alkynes and dilution material；Palladium-molybdenum-silver system selection
Hydrogenation catalyst is active component with palladium-molybdenum-silver using nickeliferous aluminium oxide as carrier, is palladium in terms of 100% by total catalyst weight
Content (in terms of simple substance) 0.1~0.5wt%, silver content (in terms of simple substance) 0.3~1.5wt%, 0.5~3wt% of molybdenum oxide, nickel contain
Measuring (in terms of simple substance) is 1~4wt%；0.5~3wt% of alkali metal and/or alkaline earth oxide；Cerium oxide and/or lanthana 0
~4wt%.50~150m of specific surface area of catalyst2/ g, hole hold 0.40~0.65ml/g.The presoma of alumina carrier containing Ni is
Nickeliferous boehmite has acid-base neutralization and plastic process in the preparation process of the nickeliferous boehmite；It is molten containing active component
Liquid impregnates alumina carrier containing Ni, and through drying, roasting, palladium-molybdenum-silver system selective hydrogenation catalyst is made.
The method disclosed in the present, it is described to hydrogenation material be the C-4-fraction rich in alkynes or the carbon rich in alkynes four
The mixture of fraction and dilution material.Wherein the C-4-fraction rich in alkynes comes from butadiene extraction device, after being Butadiene Extraction
The remaining higher C-4-fraction of alkynes content, usually contains butylene, butane, butadiene, vinylacetylene, butine mainly group
Point.Alkynes is mainly the content of vinylacetylene in C-4-fraction rich in alkynes, and the mass content of vinylacetylene is usually 7
~25wt%, butadiene mass content are usually 5~20wt%.
The method disclosed in the present, when to hydrogenation material and H2When into adiabatic reactor, in hydrogenation material
Alkynes and alkadienes mass content are preferably not higher than 4wt%.For the C-4-fraction rich in alkynes or alkynes is rich in hydrogenation material
C-4-fraction and dilution material mixture；When alkynes and alkadienes mass content are higher than in the C-4-fraction rich in alkynes
When 4wt%, the C-4-fraction dilution material dilution of alkynes, the weight of C-4-fraction and dilution material rich in alkynes preferably will be enriched in
Than being preferably 1:10~1:20；Most common dilution material is carbon four or itself hydrogenated products after carbon-4, ether.
The method disclosed in the present, the adiabatic reactor be heat-insulating fixed bed reactors, preferably single hop or
Multistage insulation formula fixed bed reactors.For single stage adiabatic formula fixed bed reactors, hydrogen and the total alkynes+diene of reactor inlet
The molar ratio of hydrocarbon content is preferably 2.0~6.0.The multistage insulation formula fixed bed reactors refer to containing double sections or double sections with
On adiabatic reactor, when using multistage insulation formula fixed bed reactors, every section of inlet amounts of hydrogen is waited for this section of inlet
Alkynes+alkadienes total amount molar ratio is preferably 1.5~3.0 in hydrogenation material.The method disclosed in the present, adiabatic reactor
In can according to raw material difference, select different reaction conditions, due to the reaction be liquid phase reactor, the selection of temperature and pressure
Raw material should be all set to be in liquid；Reaction inlet temperature is generally 25~100 DEG C, preferably 25~80 DEG C；Reaction pressure is generally
0.6~2.5MPa, preferably 0.6~2.0MPa；Liquid air speed is 15~25h-1, preferably 15~20h-1；Raw material and dilution are expected
Weight ratio be preferably 1:10~1:20.
The method disclosed in the present, palladium-molybdenum-silver system selective hydrogenation catalyst therein using nickeliferous aluminium oxide as carrier,
Be active component with palladium-molybdenum-silver, by total catalyst weight be 100% in terms of, 0.1~0.5wt% of palladium content, preferably 0.2~
0.5wt%；0.3~1.5wt% of silver content, preferably 0.3~1.0wt%；0.5~3wt% of molybdenum oxide, preferably 0.5~2wt%；
1~4wt% of nickel content, preferably 2~4wt%；Alkali metal and/or alkaline earth oxide 0.5~3wt%, preferably 0.5~
2wt%；Cerium oxide and/or lanthana 0~4wt%, preferably 1~2wt%.50~150m of specific surface area of catalyst2/ g, preferably 60
~120m2/g；Hole holds 0.40~0.65ml/g.The presoma of alumina carrier containing Ni is nickeliferous boehmite, this is nickeliferous quasi-
There are acid-base neutralization and plastic process in the preparation process of boehmite；Alumina carrier containing Ni, warp are impregnated containing active component solution
Dry, roasting, is made palladium-molybdenum-silver system selective hydrogenation catalyst.If it is the alumina carrier containing Ni of other methods preparation, i.e.,
It is of the invention to be that same catalyst composition can not achieve the effect that.
Palladium-molybdenum-silver system selective hydrogenation catalyst used in the method for selective acetylene hydrocarbon hydrogenation recycling butylene of the present invention is most prominent
Out the characteristics of is to be catalyst using nickeliferous aluminium oxide as carrier, and the presoma of alumina carrier containing Ni is nickeliferous to intend thin water aluminium
Stone has acid-base neutralization and plastic process in the preparation process of the nickeliferous boehmite, can nickel and boehmite organically
Combine, while pore structure to nickeliferous boehmite and acidity have preferable adjustment effect.This is nickeliferous to intend thin water aluminium
Stone is mainly used for catalyst carrier, especially carrier of hydrogenating catalyst, by the nickeliferous boehmite and its load of preparation
Body has suitable pore-size distribution simultaneously.
The present invention also provides a kind of catalyst suitable for C-4-fraction selection plus hydrogen retrieval butylene rich in alkynes, the catalysis
Agent has excellent hydrogenation activity and butylene selectivity.
Carrier of the present invention is prepared using general technology, and the present invention is not limited thereto.Catalyst carrier extrusion at
One of alkali metal, alkaline-earth metal, cerium, lanthanum or a variety of can be added before and after type.Recommend to obtain using the method for one of the following：
Method one：By nickeliferous boehmite and nitric acid, water mixer kneader, extruded moulding, 80~140 DEG C are dried, 900~
1050 DEG C of 3~6h of roasting, obtain catalyst carrier.
Method two：By the way that alkali metal, alkaline-earth metal and/or lanthanum, cerium are added before extruded moulding when alumina carrier containing Ni
Predecessor, nitric acid, water mixer kneader, extruded moulding, 80~140 DEG C of drying, 900~1050 DEG C of 3~6h of roasting are catalyzed
Agent carrier.
Method three：After addition nitric acid, water are mediated in nickeliferous boehmite, extruded moulding, 80~140 DEG C of bakings
Dry, then it is molten to impregnate the predecessors such as the soluble-salt of alkali metal, alkaline-earth metal and/or lanthanum, cerium by 300~600 DEG C of 3~6h of roasting
Liquid, 80~140 DEG C of drying, 900~1050 DEG C of 3~6h of roasting obtain catalyst carrier.
The present invention also provides the preparation methods that a kind of palladium-molybdenum-silver is selective hydrogenation catalyst, using conventional dipping side
Method preparation, the dip loading of Metal Palladium are identical as common lamella catalyst dipping technique.Palladium-molybdenum of the invention-silver system selection adds
The preparation method that hydrogen catalyst can be recommended using the present invention obtains：It will contain palladium, silver and molybdenum solution impregnated catalyst support, palladium,
Silver and molybdenum can use step impregnation, can also be used while impregnating, and through drying, roasting, palladium-molybdenum-silver system selection is made plus hydrogen is urged
Agent.Palladium-molybdenum of the invention-silver system selective hydrogenation catalyst is not excluded for outside palladium removing, silver, molybdenum also other catalyst modifications members
Element.
Rare-earth element cerium and/or lanthanum and alkali metal and/or alkaline-earth metal can be added in carrier forming process；?
It can be added in advance into carrier before dipping active component after carrier molding；It can also be when impregnating active component, with
Activity component impregnation solution is added simultaneously.
I.e. alkali metal and/or alkaline-earth metal, lanthanum and/or cerium can the addition when preparing carrier, can also carrier at
After type, palladium, silver, molybdenum are added into carrier in advance before being added, then will contain palladium, silver, molybdenum solution and be impregnated in alumina carrier containing Ni
On, 3~6h is roasted at 300~500 DEG C after dry, and catalyst is made.It can also be in palladium-impregnated, silver, molybdenum, with palladium, silver, molybdenum
It is added simultaneously, i.e., alkali metal, alkaline-earth metal and/or lanthanum, cerium is added to palladium, silver, molybdenum solution and is impregnated in alumina carrier containing Ni
On, 3~6h is roasted at 300~500 DEG C after dry, and catalyst is made.
Palladium-molybdenum-silver of the present invention is the preparation method of selective hydrogenation catalyst, active component solution can be palladium,
The soluble salt solutions of silver and molybdenum.Palladium salt can be palladium nitrate, palladium chloride, palladium acetate, preferably palladium chloride；Silver salt is silver nitrate；
Molybdenum used can be ammonium molybdate, molybdenum trioxide.In the present invention alkali metal and/or alkaline-earth metal preferably with soluble nitrate,
What the form of acetate or citrate was added.Cerium and/or lanthanum are preferably added in the form of soluble nitrate in the present invention
's.
Nickeliferous boehmite of the invention is not the simple object for being boehmite and nickel compound containing or nickel salt solution
Reason blending or cladding, but acid-base reaction occurs, there is plastic process, it is final that the load with specific nickel and aluminium mixing crystal form is made
Body.
The present invention also provides the preparation method that a kind of more specific palladium-molybdenum-silver is selective hydrogenation catalyst, with containing palladium,
The solution of molybdenum and silver impregnates alumina carrier containing Ni by one or more steps, obtains catalyst by drying, roasting；Nickeliferous oxidation
Alumina supporter by nickeliferous boehmite at least through molding, drying, roasting process and obtain；Wherein nickeliferous boehmite preferably by
Following methods obtain, and detailed process includes the following steps：
(1) it neutralizes in kettle and bottom water is added, bottom water is deionized water, is heated to 50~90 DEG C；
(2) acid aluminum saline solution, acid nickel salt aqueous solution are prepared respectively, by acid aluminium salt aqueous solution and acid nickel salt water
Solution is uniformly mixed, and obtains the acidic mixed solution of aluminium containing salt and nickel salt, and adjusting the acidic mixed solution temperature is 50~90 DEG C,
Wherein acid aluminium salt concentration of aqueous solution is 10~80gAl2O3/ L, acid nickel salt aqueous solution concentration are 3~50gNiO/L；
(3) alkali metal aluminate solution is prepared, alkali metal aluminate solution concentration is 50~300gAl2O3/L；
(4) the acidic mixed solution that step (2) obtains and the alkali metal aluminate solution cocurrent that step (3) obtains are added
In neutralization kettle in step (1), constant ventilation stirring, until plastic；
(5) 50~90 DEG C of gelling temperature of rate-determining steps (4), plastic pH value 7~10；
(6) it after cemented into bundles, through aging, is filtered, washed, dries nickeliferous boehmite is made.
It is in terms of 100% by nickeliferous boehmite total weight, nickel contains in nickeliferous boehmite using this method preparation
Amount is 0.1~10wt%, preferably 0.5wt~5wt%.300~420m of specific surface area20.7~1.2cm of/g, Kong Rongwei3/ g, hole
Diameter is 5~10nm；50~90 DEG C of gelling temperature, preferably 60~80 DEG C；Plastic pH value 7~10, preferably 7~9；Aging temperature
It is 50~80 DEG C, ageing time is 10~60min.
Alumina carrier containing Ni of the present invention preferably contains δ-Al2O3、δ-NiAl26O40、NiAl2O4Crystal form, and XRD
0.45≤B1/B2≤0.85 in spectrogram, B1 refer to that the integrated intensity at the peak that 2 θ are 34.2~39.8 ° in XRD spectra, B2 refer to
The integrated intensity at the peak that 2 θ are 43.3~48.5 ° in XRD spectra.
In alumina carrier containing Ni of the present invention, preferably contain δ-Al2O3、δ-NiAl26O40、NiAl2O4Crystal form mixes
Crystalline substance, best δ-Al2O3、δ-NiAl26O40And NiAl2O4Account for the 50%~100% of alumina carrier containing Ni total weight.In carrier also
θ-Al can be contained2O3、α-Al2O3And/or γ-Al2O3, best α-Al2O3Lower than 30wt%.
Contain alkali metal and/or alkaline-earth metal in palladium-molybdenum provided by the invention-silver system selective hydrogenation catalyst, is adjusted
The acid-base property of catalyst support surface improves the Hydrogenation and stabilized hydrogenation of catalyst, advantageously reduces in hydrogenation process
Carbonaceous, the deposition of colloid, to extend the service life of catalyst.The addition of cerium and/or lanthanum is urged when being able to suppress high-temperature roasting
Agent carrier crystal grain is grown up, and the dispersion degree of active component is improved, and improves the hydrogenation selectivity and stability of catalyst.
The method disclosed in the present directly carries out selection plus hydrogen to the C-4-fraction for being rich in alkynes after Butadiene Extraction,
In the process since catalyst has used the alumina carrier containing Ni with specific crystal formation to be prepared, so that catalyst has
Suitable acidity and pore structure improves the hydrogenation activity and selectivity of catalyst.Method of the invention by alkynes therein and
Di-olefins are butylene, improve the added value of this strand of material.Even if the alkynes and diene content of raw material are greater than 4wt%,
It still is able to run well for a long time using method provided by the present invention, almost without dimer production, alkynes in the material after adding hydrogen
Hydrocarbon and alkadienes mass content are less than 1.0wt%.Method major advantage of the invention is：(1) present invention process simulation industry
Device, using heat-insulating fixed bed reactors, Catalyst packing goes into operation and regenerative operation is convenient, invest it is small, be very beneficial for
Commercial plant is promoted.(2) the matching used catalyst of the present invention is with the alumina carrier containing Ni preparation with specific crystal formation
Bimetallic or multimetal reforming catalyst, the absorption between strong interaction ethene suppressing ethyl-acetylene and palladium between metal, effectively subtract
Few active component palladium loss, extends the service life of catalyst, it is ensured that hydrogenation technique is run steadily in the long term.
Method of the invention is suitable for C-4-fraction selection plus hydrogen retrieval butylene rich in alkynes, compared with prior art,
This method has hydrogenation activity good, and butylene selectivity is high, and stabilized hydrogenation and anticoking capability are strong, can operating condition range it is wide etc.
Advantage.When using method of hydrotreating of the invention, and palladium-molybdenum-silver prepared by the mating alumina carrier containing Ni using specific crystal formation
It is selective hydrogenation catalyst, hydrogenation activity and butylene selectivity are high, and chemical stability and thermostabilization are good, and anticoking capability is strong and makes
It is long with the service life.
Specific embodiment
Raw material sources and analysis method：
C-4-fraction rich in alkynes：It is derived from Lanzhou Petrochemical ethylene plant, contains vinylacetylene (VA) 7~25wt%, fourth two
5~20wt% of alkene；
Catalyst activity component content assaying method：Using national standard《Atomic absorption spectroscopy general rule》GB/
T15337-94 and《Chemical reagent flame atom absorption spectrophotography method general rule》GB19723-88 analysis；
Specific surface area (m2/ g) and Kong Rong (ml/g)：Using national standard catalyst and adsorbent surface product measuring method
GB/T 5816 is analyzed；
Crystalline form analysis：Using D8Advance type x-ray powder diffraction instrument (XRD) measurement of German Bruker company production
The crystal form of carrier, actual conditions：CuK α radiation, 40 kilovolts, 40 milliamperes, 0.02 ° of scanning speed/step, 0.5 second/step, B1 referred to
The integrated intensity at the peak that 2 θ are 34.2~39.8 ° in XRD spectra, B2 refer to the product at the peak that 2 θ are 43.3~48.5 ° in XRD spectra
Divide intensity；
Raw material and product form：It is analyzed using the composition measuring SH-T 1141-92 of industrial cracking c_4.
The present invention is further illustrated below by embodiment, but is not regarded as that present invention is limited only by this.
The preparation of embodiment catalyst 1~6
The preparation of catalyst C1：
It is 50g Al by 4L concentration2O3The sodium aluminate solution of/L is placed in belt stirrer and tank bottom can be passed through the stainless of gas
In steel container, prepares nickel nitrate solution and be packed into the container of high level, be passed through the mixed gas of carbon dioxide and air, open simultaneously
Prepared nickel nitrate solution is added dropwise in dynamic peristaltic pump coutroi velocity, and carbon dioxide in gas mixture concentration is 60v%, flow
3Nm3/ h, 30 DEG C of reaction temperature, reaction end pH value 10.0, stopping is passed through carbon dioxide, aging 30 minutes, is separated by filtration mother
Nickeliferous boehmite is made in liquid, washing, 120 DEG C of dry 5h.
By nickeliferous boehmite and nitric acid, water mixer kneader, extruded moulding, 120 DEG C are dried, 500 DEG C of roasting 4h, then
It is saturated impregnated carrier, 120 DEG C of drying with lithium citrate solution, nickeliferous and lithium alumina support is made in 950 DEG C of roasting 4h.
Palladium chloride and ammonium molybdate are configured to activity component impregnation liquid, solution ph is adjusted to 2.5, is impregnated into 100g carrier
On, extraction raffinate is removed after 25 minutes, is washed with distilled water, before aged, 120 DEG C of dry 3h, 480 DEG C of roasting 4h obtain catalyst
Body；Then silver nitrate solution is prepared again, is immersed on catalyst precarsor, aged, 120 DEG C of dry 3h, 520 DEG C of roasting 4h, system
Obtain catalyst C1.
The preparation of catalyst C2：
It is 50g Al by 4L concentration2O3The sodium aluminate solution of/L is placed in belt stirrer and tank bottom can be passed through the stainless of gas
In steel container, prepares nickel nitrate solution and be packed into the container of high level, be passed through the mixed gas of carbon dioxide and air, open simultaneously
Prepared nickel nitrate solution is added dropwise in dynamic peristaltic pump coutroi velocity, and carbon dioxide in gas mixture concentration is 70v%, flow
4Nm3/ h, 35 DEG C of reaction temperature, reaction end pH value 9.5, stopping is passed through carbon dioxide, aging 35 minutes, is separated by filtration mother liquor,
Washing, drying, are made nickeliferous boehmite.
By nickeliferous boehmite and nitric acid, magnesium nitrate and water mixer kneader, extruded moulding, 120 DEG C of drying, 1000 DEG C of roastings
4h is burnt, nickeliferous and magnesium alumina support is made.
Palladium nitrate and silver nitrate are configured to activity component impregnation liquid, solution ph is adjusted to 2.4, is then impregnated into 100g
On carrier, extraction raffinate is removed after 25 minutes, is washed with distilled water, aged, 120 DEG C of dry 2h, 420 DEG C of roasting 4h obtain catalyst
Precursor；Then molybdenum oxide is configured to mixed solution again, be immersed on catalyst precarsor, aged, 120 DEG C of dry 3h, 500 DEG C
4h is roasted, catalyst C2 is made.
The preparation of catalyst C3：
It is 50g Al by 1L concentration2O3The aluminum sulfate solution of/L and the nickel nitrate solution of preparation are uniformly mixed and are packed into high level
Container in, compound concentration be 100g Al2O3/ L sodium aluminate solution 1.5L is packed into the container of high level, while being started two and being held
The peristaltic pump of device connection, coutroi velocity is added dropwise to the belt stirrer equipped with 1L bottom water and tank bottom can be passed through the rustless steel container of gas
Interior, 60 DEG C of reaction temperature, it is 9.0 that control flow, which adjusts pH value of reaction system, is 9.5 by the way that ammonium hydroxide is added dropwise to adjust slurry pH value,
Aging 30 minutes after reaction, are separated by filtration mother liquor, and nickeliferous boehmite is made in washing, drying.
By nickeliferous boehmite and nitric acid, water mixer kneader, extruded moulding, 120 DEG C are dried, 550 DEG C of roasting 4h, then
It is saturated impregnated carrier, 120 DEG C of drying with magnesium nitrate solution, nickeliferous and magnesium alumina support is made in 1020 DEG C of roasting 4h.
Palladium chloride, ammonium molybdate and cerous nitrate are configured to activity component impregnation liquid, solution ph is adjusted to 2.6, will prepare
Good maceration extract is impregnated on 100g carrier, and extraction raffinate is removed after 25 minutes, is washed with distilled water, aged, 120 DEG C of dry 3h,
420 DEG C of roasting 4h obtain catalyst precarsor；Then silver nitrate solution is prepared again, is immersed on catalyst precarsor, it is aged, 120
DEG C dry 3h, 480 DEG C of roasting 4h, obtained catalyst C3.
The preparation of catalyst C4：
It is 50g Al by 1L concentration2O3The aluminum sulfate solution of/L and the nickel nitrate solution of preparation are uniformly mixed and are packed into high level
Container in, compound concentration be 75g Al2O3/ L sodium aluminate solution 2L is packed into the container of high level, while starting two containers
The peristaltic pump of connection, coutroi velocity is added dropwise to the belt stirrer equipped with 1L bottom water and tank bottom can be passed through the rustless steel container of gas
Interior, 60 DEG C of reaction temperature, it is 7.5 that control flow, which adjusts pH value of reaction system, is 8.0 by the way that ammonium hydroxide is added dropwise to adjust slurry pH value,
Aging 30 minutes after reaction, are separated by filtration mother liquor, and nickeliferous boehmite is made in washing, drying.
By nickeliferous boehmite and nitric acid, water mixer kneader, extruded moulding, 120 DEG C are dried, 480 DEG C of roasting 4h, then
It is saturated impregnated carrier, 110 DEG C of drying with magnesium nitrate and potassium nitrate solution, the oxidation of nickeliferous, magnesium and potassium is made in 900 DEG C of roasting 4h
Alumina supporter.
Palladium acetate is configured to activity component impregnation liquid, is then impregnated on 100g carrier, removes extraction raffinate after forty minutes, is passed through
Ageing, 120 DEG C of dry 2h, 450 DEG C of roasting 3h obtain catalyst precarsor；Then it is molten that silver nitrate, ammonium molybdate and lanthanum nitrate are prepared again
Liquid is immersed on catalyst precarsor, and aged, 120 DEG C of dry 3h, 520 DEG C of roasting 4h obtain catalyst C4.
The preparation of catalyst C5：
It is 50g Al by 4L concentration2O3The sodium aluminate solution of/L is placed in belt stirrer and tank bottom can be passed through the stainless of gas
In steel container, it is passed through the mixed gas of carbon dioxide and air, carbon dioxide in gas mixture concentration is 70v%, flow 4Nm3/
h.40 DEG C of reaction temperature, reaction end pH value 10, stopping is passed through carbon dioxide.Under blowing air stirring condition, the nitre of preparation is added
Sour nickel solution is 8.5 by the way that ammonium hydroxide is added dropwise to adjust slurry pH value after stablizing 30 minutes, after reaction aging 30 minutes, filtering
Mother liquor is separated, nickeliferous boehmite is made in washing, drying.
By nickeliferous boehmite and nitric acid, water mixer kneader, extruded moulding, 120 DEG C are dried, 450 DEG C of roasting 4h, then
It is saturated impregnated carrier, 110 DEG C of drying with lanthanum nitrate hexahydrate, nickeliferous and lanthanum alumina support is made in 1050 DEG C of roasting 4h.
Palladium chloride, ammonium molybdate, potassium carbonate are configured to activity component impregnation liquid, solution ph is adjusted to 2.7, will prepare
Maceration extract be impregnated on 100g carrier, remove extraction raffinate after 30 minutes, be washed with distilled water, aged, 120 DEG C of dry 3h, 460
DEG C roasting 4h obtain catalyst precarsor；Then prepare silver nitrate solution again, be immersed on catalyst precarsor, it is aged, 120 DEG C it is dry
Catalyst C5 is made in dry 3h, 520 DEG C of roasting 4h.
The preparation of catalyst C6：
It is 40g Al by 5L concentration2O3The sodium aluminate solution of/L is placed in belt stirrer and tank bottom can be passed through the stainless of gas
In steel container, prepares nickel nitrate solution and be packed into the container of high level, be passed through the mixed gas of carbon dioxide and air, open simultaneously
Prepared nickel nitrate solution is added dropwise in dynamic peristaltic pump coutroi velocity, and carbon dioxide in gas mixture concentration is 70v%, flow
5Nm3/ h, 40 DEG C of reaction temperature, reaction end pH value 10, stopping is passed through carbon dioxide, aging 35 minutes, is separated by filtration mother liquor,
Washing, drying, are made nickeliferous boehmite.
The nickeliferous boehmite for weighing preparation, with nitric acid, water mixer kneader, extruded moulding is dried, 980 DEG C at 110 DEG C
4h is roasted, nickeliferous alumina support is made.
Palladium chloride, molybdenum oxide, potassium carbonate are configured to activity component impregnation liquid, solution ph is adjusted to 2.5, will prepare
Maceration extract be impregnated on 100g carrier, remove extraction raffinate after 25 minutes, be washed with distilled water, aged, 120 DEG C of dry 3h, 400
DEG C roasting 4h obtain catalyst precarsor；Then prepare silver nitrate solution again, be immersed on catalyst precarsor, it is aged, 120 DEG C it is dry
Catalyst C6 is made in dry 3h, 550 DEG C of roasting 4h.
The physico-chemical property of catalyst 1~6 is as shown in table 1.
The physico-chemical property of 1 embodiment of table catalyst C1~C6
Embodiment 1
The C-4-fraction that will be enriched in alkynes is diluted with carbon-4, C-4-fraction and carbon-4 rich in alkynes
Weight ratio is 1:20.Adiabatic reactor uses single stage adiabatic formula fixed bed, and using catalyst C1, catalyst passes through in a hydrogen atmosphere
120 DEG C of reduction 6h.40 DEG C of inlet temperature, reaction pressure 2.0MPa, liquid air speed 15h of reaction-1, hydrogen and alkynes+alkadienes
Molar ratio is 5.0, and table 2 is the composition of reaction front and back material.
The reaction of table 2 front and back material composition
Embodiment 2
Carbon four is diluted after will be enriched in the C-4-fraction ether of alkynes, carbon four after C-4-fraction and ether rich in alkynes
Weight ratio is 1:18.Adiabatic reactor uses single stage adiabatic formula fixed bed, and using catalyst C2, catalyst passes through in a hydrogen atmosphere
120 DEG C of reduction 6h.38 DEG C of inlet temperature, reaction pressure 1.5MPa, liquid air speed 17h of reaction-1, hydrogen and alkynes+alkadienes
Molar ratio is 4.0, and table 3 is the composition of reaction front and back material.
The reaction of table 3 front and back material composition
Embodiment 3
The C-4-fraction carbon-4 and itself hydrogenated products that will be enriched in alkynes are diluted, and the carbon four rich in alkynes evaporates
Dividing with the weight ratio of (carbon-4+itself hydrogenated products) is 1:13, adiabatic reactor is using double section heat-insulating fixed beds, catalysis
Agent is in a hydrogen atmosphere through 120 DEG C of reduction 6h.One section uses catalyst C3, and two sections use catalyst C1, one section of reaction entrance temperature
40 DEG C of degree, second-stage reaction inlet temperature are 25 DEG C, reaction pressure 2.0MPa, liquid air speed 22h-1, one section of bed hydrogen and alkynes+two
The molar ratio of alkene is 2.5, and two sections of bed hydrogen and alkynes+alkadienes molar ratio are 1.5, and table 4 is the group of reaction front and back material
At.
The reaction of table 4 front and back material composition
Embodiment 4
Carbon four is with the dilution of itself hydrogenated products row after will be enriched in the C-4-fraction ether of alkynes, the C-4-fraction rich in alkynes
Weight ratio with (carbon-4+itself hydrogenated products) is 1:15.Adiabatic reactor uses single stage adiabatic formula fixed bed, using urging
Agent C4, catalyst is in a hydrogen atmosphere through 120 DEG C of reduction 6h.30 DEG C of inlet temperature, reaction pressure 0.8MPa of reaction, liquid-containing air
Fast 20h-1, hydrogen and alkynes+alkadienes molar ratio are 2.5, and table 5 is the composition of reaction front and back material.
The reaction of table 5 front and back material composition
Embodiment 5
The C-4-fraction that will be enriched in alkynes is diluted with carbon-4, C-4-fraction and carbon-4 rich in alkynes
Weight ratio is 1:10, adiabatic reactor is using double section heat-insulating fixed beds, and catalyst is in a hydrogen atmosphere through 120 DEG C of reduction 6h.
One section uses catalyst C5, and two sections use catalyst C2, and one section 30 DEG C of inlet temperature of reaction, second-stage reaction inlet temperature is 30
DEG C, reaction pressure 1.0MPa, liquid air speed 25h-1, one section of bed hydrogen and alkynes+alkadienes molar ratio are 2.0, two sections of bed hydrogen
Gas and alkynes+alkadienes molar ratio are 1.5, and table 6 is the composition of reaction front and back material.
The reaction of table 6 front and back material composition
Embodiment 6
The C-4-fraction carbon-4 and itself hydrogenated products that will be enriched in alkynes are diluted, and the carbon four rich in alkynes evaporates
Dividing with the weight ratio of (carbon-4+itself hydrogenated products) is 1:15, adiabatic reactor uses single stage adiabatic formula fixed bed, catalysis
Agent is in a hydrogen atmosphere through 120 DEG C of reduction 6h.Using catalyst C3,40 DEG C of inlet temperature, reaction pressure 1.2MPa are reacted, liquid
Air speed 18h-1, hydrogen and alkynes+alkadienes molar ratio are 3.0, and table 7 is the composition of reaction front and back material.
The reaction of table 7 front and back material composition
Embodiment 7
Carbon four is diluted after will be enriched in the C-4-fraction ether of alkynes, carbon four after C-4-fraction and ether rich in alkynes
Weight ratio is 1:12, adiabatic reactor uses single stage adiabatic formula fixed bed, and catalyst is in a hydrogen atmosphere through 120 DEG C of reduction 6h.
Using catalyst C6,30 DEG C of inlet temperature, reaction pressure 0.6MPa, liquid air speed 23h are reacted-1, hydrogen and alkynes+alkadienes
Molar ratio is 2.5, and table 8 is the composition of reaction front and back material.
The reaction of table 8 front and back material composition
In the selection hydrogenation process rich in alkynes C-4-fraction, main reaction is alkynes and diolefin hydrogenate fourth
Alkene.In order to recycle butylene to the greatest extent, it is desirable that the hydrogenation activity and selectivity of catalyst will be got well.
For the data from table 2,3,4,5,6,7 and 8, it is apparent that under the conditions of high-speed, the removal efficiency of alkadienes is super
98% is crossed, the removal efficiency of alkynes is up to 99% or more, and alkynes content is lower than 30ppm in hydrogenated products, and diene content is lower than
100ppm, butene recovery rate more than 100%, show catalyst of the invention have preferable hydrogenation activity, selectivity and surely
It is qualitative.
Comparative example 1
1 used catalyst of comparative example is identical as catalyst C1 preparation method, the difference is that intending thin water aluminium in comparative example 1
Nickel is not added in the preparation process of stone.The evaluation process conditions of catalyst are same as Example 1.Table 9 is the group of reaction front and back material
At.
The reaction of table 9 front and back material composition
Comparative example 2
2 used catalyst of comparative example is identical as catalyst C2 preparation method, the difference is that 2 used catalyst of comparative example
In be free of component molybdenum oxide.The evaluation process conditions of catalyst are same as Example 2.Table 10 is the composition of reaction front and back material.
The reaction of table 10 front and back material composition
Comparative example 3
3 used catalyst of comparative example is identical as catalyst C2 preparation method, the difference is that 2 used catalyst of comparative example
Middle oxidation molybdenum content is 4.0wt%.The evaluation process conditions of catalyst are same as Example 2.Table 11 is reaction front and back material
Composition.
The reaction of table 11 front and back material composition
Comparative example 4
4 used catalyst of comparative example is identical as catalyst C4 preparation method, the difference is that 4 used catalyst of comparative example
Middle nickel content (in terms of simple substance) 5.0wt%, the evaluation process conditions of catalyst are same as Example 4.Table 12 is reaction front and back object
The composition of material.
The reaction of table 12 front and back material composition
Comparative example 5
5 one sections of bed used catalysts of comparative example are identical as catalyst C3 preparation method, the difference is that 5 one sections of comparative example
Magnesia is free of in bed used catalyst.Two sections of bed catalysts equally use catalyst C1, the evaluation process conditions of catalyst with
Embodiment 3 is identical.Table 13 is the composition of reaction front and back material.
The reaction of table 13 front and back material composition
Comparative example 6
6 used catalyst of comparative example is identical as catalyst C1 preparation method, the difference is that 6 used catalyst of comparative example
Middle nickel content (in terms of simple substance) 0.6wt%, the evaluation process conditions of catalyst are same as Example 1.Table 14 is reaction front and back object
The composition of material.
The reaction of table 14 front and back material composition
Comparative example 7
7 used catalyst of comparative example is identical as catalyst C6 preparation method, the difference is that 7 used catalyst of comparative example
The evaluation process conditions of not argentiferous, catalyst are same as Example 7.Table 15 is the composition of reaction front and back material.
The reaction of table 15 front and back material composition
Comparative example 8
Method preparation of the nickeliferous carrier of 8 used catalyst of comparative example using embodiment description in CN1123392C, carrier
In nickel content, method for preparing catalyst and catalyst composition it is identical with catalyst C4 as embodiment.The evaluation technique of catalyst
Condition is same as Example 4.Table 16 is the composition of reaction front and back material.
The reaction of table 16 front and back material composition
Comparative example 9
The nickeliferous carrier of 9 used catalyst of comparative example is urged using the method preparation of embodiment description in CN103372432A
Agent composition is identical with catalyst C1 as embodiment, but B1/B2 is 0.89.The evaluation process conditions of catalyst and 1 phase of embodiment
Together.Table 17 is the composition of reaction front and back material.
The reaction of table 17 front and back material composition
Method of hydrotreating of the invention is used it can be seen from the analysis of the data of embodiment and comparative example, and mating with this
Palladium-molybdenum-silver the series catalysts for the alumina carrier containing Ni load that invention uses, under the conditions of high-speed, the removal efficiency of alkadienes
More than 98%, the removal efficiency of alkynes is up to 99% or more, and butene recovery rate is more than 100%, and alkynes content is low in hydrogenated products
In 30ppm, diene content is lower than 100ppm, can be used as etherificate or raw material for alkylation, improves the added value of four alkynes of carbon.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (10)
1. a kind of method of selective acetylene hydrocarbon hydrogenation recycling butylene, it is characterised in that this method includes to hydrogenation material and H2Into exhausted
Thermal reactor is mounted with palladium-molybdenum-silver system selective hydrogenation catalyst, hydrogen and the total alkynes+two of reactor inlet in adiabatic reactor
The molar ratio of olefin(e) centent is 1.5~6.0；25~100 DEG C of reactor inlet temperature, reaction pressure is 0.6~2.5MPa, liquid
Volume space velocity is 15~25h-1, reaction product enters knockout drum after cooling and separated；It is described to hydrogenation material be richness
The mixture of C-4-fraction and dilution material containing alkynes；Palladium-molybdenum-silver system selective hydrogenation catalyst using nickeliferous aluminium oxide as carrier,
It is active component with palladium-molybdenum-silver, is in terms of 100% by total catalyst weight, palladium content 0.1~0.5wt% in terms of simple substance, silver contains
0.3~1.5wt% in terms of simple substance, 0.5~3wt% of molybdenum oxide are measured, nickel content is calculated as 1~4wt% with simple substance；Alkali metal and/or
0.5~3wt% of alkaline earth oxide, cerium oxide and/or lanthana 0~4wt%, 50~150m of specific surface area of catalyst2/ g,
Hole holds 0.40~0.65ml/g；It is preferred that palladium-molybdenum-silver series catalysts include 0.2~0.5wt% of palladium, 0.3~1.0wt% of silver content,
0.5~2wt% of molybdenum oxide, 2~4wt% of nickel content, 0.5~2wt% of alkali metal and/or alkaline earth oxide, cerium oxide and/
Or 1~2wt% of lanthana；60~120m of specific surface area of catalyst2/ g, hole hold 0.40~0.65ml/g；Alumina carrier containing Ni
Presoma be nickeliferous boehmite, have acid-base neutralization and plastic process in the preparation process of the nickeliferous boehmite；Contain
Active component solution impregnates alumina carrier containing Ni, and through drying, roasting, palladium-molybdenum-silver system selective hydrogenation catalyst is made.
2. according to the method described in claim 1, it is characterized in that 25~80 DEG C of reactor inlet temperature；Reaction pressure 0.6~
2.0MPa；15~20h of liquid volume air speed-1。
3. according to the method described in claim 1, it is characterized in that the alkynes and alkadienes quality in hydrogenation material contains
Amount is not higher than 4wt%.
4. according to the method described in claim 1, it is characterized in that in the C-4-fraction rich in alkynes, vinylacetylene matter
Amount content is 7~25wt%, and butylene mass content is 5~20wt%.
5. according to the method described in claim 1, it is characterized in that being C-4-fraction and dilution rich in alkynes to hydrogenation material
The weight ratio of the mixture of material, C-4-fraction and dilution material rich in alkynes is 1:10~1:20.
6. according to the method described in claim 1, it is characterized in that adiabatic reactor is that single stage adiabatic formula reactor or multistage are exhausted
Hot type reactor.
7. according to the method described in claim 6, it is characterized in that single stage adiabatic formula reactor, hydrogen and the total alkynes of reactor inlet
Hydrocarbon+diene content molar ratio is 2.0~6.0；Multistage insulation formula reactor, every section of inlet amounts of hydrogen and this section of inlet
It is 1.5~3.0 to alkynes in hydrogenation material+alkadienes total amount molar ratio.
8. according to the method described in claim 1, it is characterized in that：Alumina carrier containing Ni by nickeliferous boehmite through at
Type, roasting and obtain, contain δ-Al2O3、δ-NiAl26O40、NiAl2O4Crystal form, and 0.45≤B1/B2≤0.85 in XRD spectra,
B1 refers to that the integrated intensity at the peak that 2 θ are 34.2~39.8 ° in XRD spectra, B2 refer to that 2 θ are 43.3~48.5 ° in XRD spectra
The integrated intensity at peak.
9. according to the method described in claim 1, it is characterized in that：δ-Al in alumina carrier containing Ni2O3、δ-NiAl26O40With
NiAl2O4Account for the 30%~100% of alumina carrier containing Ni total weight.
10. according to the method described in claim 1, it is characterized in that palladium-molybdenum-silver system selective hydrogenation catalyst is by that will contain
The solution of palladium, silver and molybdenum is impregnated on alumina carrier containing Ni by one or more steps, roasts 3~6h after drying at 300~500 DEG C
It is obtained；Rare-earth element cerium and/or lanthanum and alkali metal and/or alkaline-earth metal are added in carrier forming process；Or
After carrier molding, it is added in advance into carrier before dipping active component；Either when impregnating active component, with active component
Dipping solution is added simultaneously.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710338485.9A CN108863696B (en) | 2017-05-15 | 2017-05-15 | Method for recovering butene by selective hydrogenation of alkyne |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710338485.9A CN108863696B (en) | 2017-05-15 | 2017-05-15 | Method for recovering butene by selective hydrogenation of alkyne |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108863696A true CN108863696A (en) | 2018-11-23 |
| CN108863696B CN108863696B (en) | 2021-07-02 |
Family
ID=64320150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710338485.9A Active CN108863696B (en) | 2017-05-15 | 2017-05-15 | Method for recovering butene by selective hydrogenation of alkyne |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108863696B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113797907A (en) * | 2021-10-13 | 2021-12-17 | 润和科华催化剂(上海)有限公司 | Selective hydrogenation catalyst with spinel structure and preparation method and application thereof |
| CN114315498A (en) * | 2020-09-28 | 2022-04-12 | 中国石油天然气股份有限公司 | A kind of alkyne-rich carbon four fraction selective hydrogenation method |
| CN116037084A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Alkyne selective hydrogenation catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102139217A (en) * | 2010-02-03 | 2011-08-03 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst and preparation method thereof |
| CN102285859A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Selective hydrogenation process for C4 material flow with high concentration of butadiene |
-
2017
- 2017-05-15 CN CN201710338485.9A patent/CN108863696B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102139217A (en) * | 2010-02-03 | 2011-08-03 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst and preparation method thereof |
| CN102285859A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Selective hydrogenation process for C4 material flow with high concentration of butadiene |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114315498A (en) * | 2020-09-28 | 2022-04-12 | 中国石油天然气股份有限公司 | A kind of alkyne-rich carbon four fraction selective hydrogenation method |
| CN113797907A (en) * | 2021-10-13 | 2021-12-17 | 润和科华催化剂(上海)有限公司 | Selective hydrogenation catalyst with spinel structure and preparation method and application thereof |
| CN116037084A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Alkyne selective hydrogenation catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108863696B (en) | 2021-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108855127A (en) | Hydrogenation catalyst and preparation method thereof | |
| CN105732288B (en) | Selective hydrogenation method of carbon four-fraction | |
| CN108927173A (en) | A kind of alkynes selective hydrocatalyst and its preparation method and application | |
| CN108863706A (en) | Selective hydrogenation method for alkyne-containing four-fraction | |
| CN108855106A (en) | Nickel-zinc series hydrogenation catalyst and preparation method thereof | |
| CN108863696A (en) | Method for recovering butene by selective hydrogenation of alkyne | |
| CN108855128A (en) | Selective hydrogenation catalyst and preparation method thereof | |
| CN108262047B (en) | Nickel-molybdenum series hydrogenation catalyst and preparation method thereof | |
| CN108250010A (en) | Selective hydrogenation method for methanol-to-olefin product | |
| CN108865239B (en) | Pyrolysis gasoline selective hydrogenation method | |
| CN105214677B (en) | nickel-base catalyst | |
| CN108863697A (en) | Method for increasing yield of butadiene | |
| CN108863699A (en) | Method for recycling butadiene through selective hydrogenation of alkyne | |
| CN106552640A (en) | Reformer feed catalyst for pre-hydrogenation and preparation method thereof | |
| CN108865243B (en) | Pre-hydrogenation treatment method of carbon tetra-alkylation raw material | |
| CN108264586A (en) | Hydrogenation method of C-V petroleum resin | |
| CN106928004B (en) | Carbon three-fraction selective hydrogenation method | |
| CN113663687B (en) | Acetylene-containing carbon four hydrogenation catalyst | |
| CN108855129A (en) | Nickel-silver hydrogenation catalyst and preparation method thereof | |
| CN108865242B (en) | Selective hydrogenation method | |
| CN108865241B (en) | Selective hydrogenation method for cracked gasoline carbon eight fractions | |
| CN106928012A (en) | Acetylene removal method by using carbon dioxide post-hydrogenation process | |
| CN108863695A (en) | Hydrotreatment method of mixed C-C raw material | |
| CN108864368A (en) | Hydrogenation method for C-V petroleum resin | |
| CN108865240B (en) | A kind of pyrolysis gasoline selective hydrogenation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |