CN108863699B - Method for recycling butadiene through selective hydrogenation of alkyne - Google Patents
Method for recycling butadiene through selective hydrogenation of alkyne Download PDFInfo
- Publication number
- CN108863699B CN108863699B CN201710342669.2A CN201710342669A CN108863699B CN 108863699 B CN108863699 B CN 108863699B CN 201710342669 A CN201710342669 A CN 201710342669A CN 108863699 B CN108863699 B CN 108863699B
- Authority
- CN
- China
- Prior art keywords
- nickel
- catalyst
- palladium
- molybdenum
- alkyne
- 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.)
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims abstract description 79
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 70
- 150000001345 alkine derivatives Chemical class 0.000 title claims description 47
- 238000004064 recycling Methods 0.000 title abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 186
- 239000003054 catalyst Substances 0.000 claims abstract description 158
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 93
- 238000006243 chemical reaction Methods 0.000 claims abstract description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 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 74
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 74
- -1 acetylene hydrocarbon Chemical class 0.000 claims abstract description 42
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 41
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 41
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 34
- 239000011733 molybdenum Substances 0.000 claims abstract description 34
- 239000013078 crystal Substances 0.000 claims abstract description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 55
- 239000000243 solution Substances 0.000 claims description 52
- 239000000463 material Substances 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 47
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 40
- 229910052763 palladium Inorganic materials 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 19
- 230000032683 aging Effects 0.000 claims description 18
- 230000002378 acidificating effect Effects 0.000 claims description 17
- 230000005587 bubbling Effects 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000005470 impregnation Methods 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
- 229910001868 water Inorganic materials 0.000 claims description 15
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 150000001340 alkali metals Chemical class 0.000 claims description 13
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 12
- 239000003085 diluting agent Substances 0.000 claims description 11
- 229910052746 lanthanum Inorganic materials 0.000 claims description 10
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 10
- 150000002815 nickel Chemical class 0.000 claims description 10
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 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
- 238000007598 dipping method Methods 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 6
- 229910003303 NiAl2O4 Inorganic materials 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- 238000005336 cracking Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 229910052761 rare earth metal 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
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 238000000605 extraction Methods 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000011112 process operation Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- 239000007789 gas Substances 0.000 description 15
- 239000001569 carbon dioxide Substances 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 12
- 238000000197 pyrolysis Methods 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 238000012854 evaluation process Methods 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
- 238000004898 kneading Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 238000007865 diluting Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000012153 distilled water Substances 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
- 239000012452 mother liquor Substances 0.000 description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 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
- 229940010552 ammonium molybdate Drugs 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical class 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
- 239000002002 slurry Substances 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-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
- 239000004411 aluminium Substances 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 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
- 239000012266 salt solution Substances 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 238000009738 saturating Methods 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 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
- 238000004458 analytical method Methods 0.000 description 2
- 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 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 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 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229940071264 lithium citrate Drugs 0.000 description 2
- 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 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 150000005673 monoalkenes Chemical class 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
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 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
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000005303 weighing 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
- 229910016523 CuKa Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 125000003118 aryl group 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
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000009826 distribution 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
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- DOARWPHSJVUWFT-UHFFFAOYSA-N lanthanum nickel Chemical compound [Ni].[La] DOARWPHSJVUWFT-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- 150000002940 palladium Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 231100000817 safety factor Toxicity 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000725 suspension Substances 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
- 229930192474 thiophene Natural products 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
- 229910006415 θ-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
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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Abstract
A method for recycling butadiene by acetylene hydrocarbon selective hydrogenation takes carbon four-fraction which is rich in acetylene hydrocarbon after butadiene extraction as raw material, and 1, 3-butadiene is obtained by selective hydrogenation in the presence of a catalyst by adopting an adiabatic reactor, wherein the adopted process operation conditions are as follows: the temperature of a reaction inlet is 20-60 ℃, the reaction pressure is 0.6-2.5 MPa, and the liquid airspeed is 10-25 h‑1. The catalyst is a palladium-molybdenum catalyst prepared from 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 invention relates to a method for recovering butadiene through acetylene hydrocarbon selective hydrogenation, in particular to a method for recovering butadiene through selective hydrogenation of residual high acetylene carbon four tail gas after butadiene extraction.
Background
The four fractions of the cracking carbon by-product from the ethylene preparation by hydrocarbon pyrolysis usually contain 40-60% by mass of butadiene, which is an important monomer in the synthetic rubber industry. Butadiene is generally extracted from the cracked C.sub.four fraction by solvent extraction methods such as acetonitrile, N-methylpyrrolidinone and dimethylformamide. Because the acetylene hydrocarbon concentration in the extracted carbon four fraction is high and the industrial utilization value is not available at present, the extracted carbon four fraction can only be used for combustion treatment, but because the high-concentration acetylene hydrocarbon has the danger of explosion, the same amount of butadiene needs to be discharged simultaneously when the acetylene hydrocarbon is separated in the industrial production due to the consideration of safety factors, and the acetylene hydrocarbon can be sent to a torch for combustion after being diluted by using a proper amount of fractions such as butylene, butane and the like. This not only causes a great waste of resources but also pollutes the environment. These factors all lead to an increase in energy consumption, severe butadiene loss and poor economics in conventional carbon four solvent extraction plants. Due to the influence of factors such as cracking depth, cracking technology and the like, the alkyne content in the cracked carbon four-fraction gradually increases, so that the loss of butadiene in the extraction process is increased and the energy consumption is increased. Meanwhile, with the development of the organic synthesis industrial technology, the limitation on the alkyne content in butadiene is more strict, and the economic efficiency of a butadiene extraction device is deteriorated due to the factors. When the butadiene is extracted, acetylene hydrocarbon is selectively hydrogenated and then part of the butadiene is recovered, so that the aim of changing waste into valuable is fulfilled, and the method plays an important role in reducing acetylene hydrocarbon emission and preventing environmental pollution.
The hydrocarbon four-hydrogenation alkyne-removing process is mainly divided into a pre-hydrogenation process and a post-hydrogenation process. The pre-hydrogenation process is to extract butadiene after selective hydrogenation of alkyne in the carbon four-fraction; the post-hydrogenation process is to perform selective hydrogenation on acetylene hydrocarbon-rich carbon four-fraction discharged after butadiene extraction, convert vinyl acetylene into 1, 3-butadiene and then return the 1, 3-butadiene to the extraction device to recover butadiene.
ZL200810239462.3 discloses a method for selective hydrogenation of alkyne, the method adopts a single-stage or multi-stage adiabatic bubbling bed reactor, and adopts the following technological conditions: the temperature of a reaction inlet is 30-90 ℃, the reaction pressure is 1.0-4.0 MPa, and the liquid airspeed is 7-20 h-1. The catalyst used is a palladium-based copper-containing catalyst.
CN102731240A discloses a method for producing butadiene by selective hydrogenation of C4, which is a pre-hydrogenation process, adopts a two-section fixed bed adiabatic reactor, and has the following process conditions: the reaction inlet temperature is 30-60 ℃, the reaction pressure is 0.6-2.0 MPa, and the airspeed of the carbon four-liquid is 10-60 h-1And the ratio of hydrogen to alkyne is 0.2-10 mol/mol. The adopted catalyst comprises an alumina carrier, 0.01-1 wt% of Pd, 0.01-5 wt% of Pb and one or more of La, Pr and Nd which are rare earth elements and have the total content of 0.01-10 wt%.
ZL03159238.4 discloses a selective hydrogenation process for hydrocarbon streams rich in alkynes, wherein a fixed bed reactor adopted in the process is a single-section or multi-section adiabatic bubbling bed reactor, the inlet temperature is 10-40 ℃, and the liquid space velocity is 0.5-5 h-1And the circulation ratio of the product circulation amount to the fresh material is 6: 1-30: 1. Under the process condition, the conversion rate of alkyne is above 98%, and the yield of 1, 3-butadiene is about 98%. But the liquid space velocity of the process is small, the product circulation quantity and the fresh material circulation ratio are high, and a heat exchanger is arranged between each section of the multi-section fixed bed reactor.
CN85106117A discloses a catalytic selective hydrogenation process for alkynes and dienes in monoolefins, which adopts a single-stage adiabatic trickle bed reactor for alpha-Al2O3Supported palladium catalyst, primarily for treatment C3The acetylene hydrocarbon and diene content of the fraction after hydrogenation reaction is lower than 5 percent.
The key point of improving the comprehensive performance of the palladium hydrogenation catalyst is to develop a novel carrier material suitable for the palladium hydrogenation catalyst in the following three aspects of (1); (2) adjusting the content of active components of the palladium hydrogenation catalyst; (3) and the addition of an auxiliary agent and an active component dispersing agent improves the comprehensive utilization rate of the active component.
Hydrated aluminas such as pseudo-boehmite, and the like are widely used as raw materials for preparing alumina carriers, and although methods such as a pH swing method, addition of an organic pore-expanding agent, hydrothermal treatment, and the like may be employed in the preparation of alumina carriers to improve the properties of alumina as a carrier, there is a limit to the improvement of the properties of alumina of a hydrogenation catalyst support material by these methods. The nature of the hydrated alumina feedstock used to prepare the alumina support is one of the most critical factors in producing an alumina support with superior performance.
CN1123392C describes a nickel-containing alumina carrier and a preparation method thereof, the mixture of an alkali-treated nickel-containing compound and carbon black is kneaded with aluminum hydroxide dry glue powder, and the mixture is extruded, formed, dried and roasted to prepare the alumina carrier containing 2.0-14.0% of nickel, the pore volume of the carrier is 0.4-1.0 cm3A specific surface area of 160 to 420m2The catalyst has the advantages of high specific surface area, large pore volume, large average pore diameter and large proportion of macropores, has the average pore diameter of 8.0-15.0 nm, accounts for more than 85 percent of total pores, and is particularly suitable for being used as a carrier of a heavy oil hydrofining catalyst.
CN200710179630.X discloses a method for preparing nickel-coated alumina powder, which is characterized in that a mixed solution of nano alumina added with a dispersant is prepared into a suspension, a nickel salt solution is added under stirring, ammonia water is dropped into the mixed solution after uniform stirring, and distilled water is added to obtain a dark blue nickel-ammonia complex ([ Ni (NH)3)6]2+)-Carrying out hydrothermal aging, filtering, washing and drying on the alumina mixed solution C to obtain a green intermediate coating product; and then carrying out reduction roasting to obtain black nickel-coated alumina powder.
CN1102862C discloses a nickel-containing hydrogenation catalyst, which contains: 65 to 80% nickel, calculated as nickel oxide, 10 to 25% silicon, calculated as silicon dioxide, 2 to 10% zirconium, calculated as zirconium oxide, 0 to 10% aluminium, calculated as aluminium oxide, with the proviso that the sum of the contents of silicon dioxide and aluminium oxide is at least 15% by weight, based on the total weight of the catalyst, which catalyst is obtainable by adding an acidic aqueous solution of a salt of nickel, zirconium and, if necessary, aluminium to an alkaline aqueous solution or suspension of silicon and, if necessary, a compound of aluminium, reducing the pH of the mixture thus obtained to at least 6.5, then adjusting the pH to 7 to 8 by further adding an alkaline solution, separating the solid thus deposited, drying, shaping and sintering. Also disclosed are methods of making the catalyst and its use in making medicinal white oils, high purity medicinal paraffins and low boiling, low aromatic content or aromatic-free hydrocarbon mixtures. The preparation method of the catalyst is usually used for preparing the catalyst with high active component content, but the catalyst prepared by the method has poor activity.
The article "changes induced by catalysis in the hydrolysis activity of NiCo-Mo/Al" by Agudo A L et Al2O3Catalysis, Applied Catalysis, 1987,30:185-2O3Influence of the desulfurization activity of the catalyst thiophene. The results show that the desulfurization activity of the catalyst activated at 500 ℃ is significantly higher than that of the catalyst activated at 600 ℃, which is caused by the strong interaction of the metal in the catalyst and the alumina carrier to form a spinel structure when activated at 600 ℃, resulting in a significant decrease in the catalyst activity. The higher the activation temperature is, the higher the content of the generated nickel aluminate spinel phase is, and the more obvious the activity of the catalyst is reduced. "infection of support-interaction of the support latent developer and hydrolysis activity of Al2O3similar conclusions were also drawn for support W, CoW and NiW model catalysts, J Phys Chem B, 2002, 106: 5897-. Because the nickel and the alumina carrier can generate strong interaction to generate a spinel structure in the high-temperature roasting process, the activity of the catalyst is obviously reduced, and the nickel and the alumina carrier are used as carefully as possible before the high-temperature roasting, so that the spinel structure is avoided. Unlike other metals, nickel-containing pseudo-boehmite has been reported only to a lesser extent because it is often calcined at high temperatures to prepare catalyst supports.
The active components of the conventional noble metal catalyst are easy to agglomerate and poison to deactivate in the reaction process, and the dispersity of palladium metal is the problem which many researchers try to solve.
Disclosure of Invention
The invention aims to provide a method for recovering butadiene by acetylene hydrocarbon selective hydrogenation, in particular to a selective hydrogenation method of acetylene hydrocarbon-rich carbon four-fraction after butadiene extraction, which is used for treating butane, butylene, butadiene, vinyl acetylene, butyne and other carbon four-fraction to recover butadiene, improve the additional value of resources, reduce investment and improve the economic benefit of a device.
The invention relates to a method for recovering butadiene by selective hydrogenation of alkyne, which comprises a material to be hydrogenated and H2Entering an adiabatic reactor, wherein a palladium-molybdenum selective hydrogenation catalyst is loaded in the adiabatic reactor, and the molar ratio of hydrogen to the total alkyne content at the inlet of the reactor is 0.8-3.0; the temperature of a reaction inlet is 20-60 ℃, the reaction pressure is 0.6-2.5 MPa, and the liquid volume space velocity is 10-25 h-1Cooling the reaction product, and separating in a gas-liquid separating tank; the material to be hydrogenated is a mixture of acetylene hydrocarbon-rich carbon four fraction, acetylene hydrocarbon-rich carbon four fraction and diluent; the palladium-molybdenum selective hydrogenation catalyst takes nickel-containing alumina as a carrier, takes palladium-molybdenum as an active component, and takes the total weight of the catalyst as 100%, wherein the palladium content (by simple substance) is 0.1-0.7 wt%, the molybdenum oxide content is 1-5 wt%, and the nickel content (by simple substance) is 0.5-3 wt%; 1-8 wt% of an alkali metal and/or alkaline earth metal oxide; 0-5 wt% of cerium oxide and/or lanthanum oxide. The specific surface area of the catalyst is 20-120 m2The pore volume is 0.30-0.65 ml/g. The precursor of the nickel-containing alumina carrier is nickel-containing pseudo-boehmite, and the preparation process of the nickel-containing pseudo-boehmite comprises acid-base neutralization and gelling processes; dipping the nickel-containing alumina carrier in the solution containing the active components, drying and roasting to prepare the palladium-molybdenum hydrogenation catalyst.
According to the method disclosed by the invention, the material to be hydrogenated is acetylene hydrocarbon-rich carbon four fraction or a mixture of acetylene hydrocarbon-rich carbon four fraction and diluent. The acetylene hydrocarbon-rich carbon four fraction is from a butadiene extraction device, is a residual acetylene hydrocarbon-rich carbon four fraction after butadiene extraction, and usually contains main components of butylene, butane, butadiene, vinylacetylene and butyne. The alkyne in the alkyne-rich carbon four fraction is mainly the content of vinyl acetylene, the mass content of the vinyl acetylene is usually 7-25 wt%, and the mass content of the butadiene is usually 5-20 wt%.
The method disclosed in the invention is used when the material to be hydrogenated and H2When entering the adiabatic reactor, the alkyne mass content in the material to be hydrogenated is preferably not higher than 10 wt%. The material to be hydrogenated is acetylene hydrocarbon-rich carbon four fraction or a mixture of acetylene hydrocarbon-rich carbon four fraction and diluent; when the alkyne content in the alkyne-rich carbon four fraction is higher than 10wt%, the alkyne-rich carbon four fraction is preferably diluted by a diluent, and the weight ratio of the alkyne-rich carbon four fraction to the diluent is preferably 1: 1-1: 8; the most commonly used diluent is raffinate carbon four or pyrolysis carbon four. In addition, the butadiene content of the material to be hydrogenated is required to be more than or equal to 8 wt%.
In the method disclosed by the invention, the adiabatic reactor is a trickle bed adiabatic reactor or a bubbling bed adiabatic reactor. The present invention preferably uses a bubbling bed adiabatic reactor, preferably a single or multi-stage adiabatic bubbling bed reactor. For a single-stage adiabatic bubble column reactor, the molar ratio of hydrogen to the total alkyne content at the reactor inlet is preferably 1.0 to 3.0. The multistage adiabatic bubbling bed reactor is characterized by comprising two or more stages, and when the multistage adiabatic bubbling bed reactor is adopted, the molar ratio of the hydrogen amount at each inlet to the total alkyne amount in the material to be hydrogenated at the inlet is preferably 0.8-2.0. In the method disclosed by the invention, different reaction conditions can be selected in the adiabatic reactor according to different raw materials, and because the reaction is a liquid phase reaction, the raw materials are in a liquid state by selecting the temperature and the pressure, and the temperature cannot be too high, so that the polymerization of olefin and alkyne is prevented; the temperature of the reaction inlet is generally 20-60 ℃, preferably 25-50 ℃; the reaction pressure is generally 0.6 to 2.5MPa, preferably 1.0 to 2.0 MPa; the liquid airspeed is 10-25 h-1Preferably 12 to 18 hours-1(ii) a The weight ratio of the raw materials to the diluent is preferably 1: 1-1: 8.
The invention discloses a method, wherein the palladium-molybdenum selective hydrogenation catalyst uses nickel-containing alumina as a carrier, uses palladium-molybdenum as an active component and uses the total weight of the catalystThe palladium content (calculated by a simple substance) is 0.1-0.7 wt%, preferably 0.2-0.6 wt% calculated as 100%; 1-5 wt% of molybdenum oxide, preferably 3-5 wt%; the content of nickel (calculated by simple substance) is 0.5-3 wt%, preferably 0.5-2 wt%; 1-8 wt%, preferably 2-5 wt% of alkali metal and/or alkaline earth metal oxide; cerium oxide and/or lanthanum oxide in an amount of 0 to 5wt%, preferably 0.5 to 3 wt%. The specific surface area of the catalyst is 20-120 m2A specific ratio of 20 to 80 m/g2(ii)/g; the pore volume is 0.30 to 0.65ml/g, preferably 0.40 to 0.65 ml/g. The precursor of the nickel-containing alumina carrier is nickel-containing pseudo-boehmite, and the preparation process of the nickel-containing pseudo-boehmite comprises acid-base neutralization and gelling processes; dipping the nickel-containing alumina carrier in the solution containing the active components, drying and roasting to prepare the palladium-molybdenum hydrogenation catalyst. In the case of the nickel-containing alumina carrier prepared by other methods, the effects of the present invention cannot be achieved even with the same catalyst composition.
The palladium-molybdenum selective hydrogenation catalyst used in the method for recovering butadiene by acetylene hydrocarbon selective hydrogenation is characterized in that the catalyst takes nickel-containing alumina as a carrier, a precursor of the nickel-containing alumina carrier is nickel-containing pseudo-boehmite, and the preparation process of the nickel-containing pseudo-boehmite comprises acid-base neutralization and gelling processes, so that nickel and the pseudo-boehmite can be organically combined, and meanwhile, the method has a good adjusting effect on the pore structure and acidity of the nickel-containing pseudo-boehmite. The nickel-containing pseudo-boehmite is mainly used for catalyst carriers, particularly for hydrotreating catalyst carriers, and the nickel-containing pseudo-boehmite and the carrier prepared by the nickel-containing pseudo-boehmite simultaneously have proper pore size distribution.
The invention also provides a catalyst suitable for acetylene hydrocarbon-rich carbon four-fraction selective hydrogenation to recover butadiene, and the catalyst has excellent hydrogenation activity and butadiene selectivity.
The vectors of the present invention are prepared using general techniques, and the present invention is not limited thereto. One or more of alkali metal, alkaline earth metal, cerium and lanthanum can be added into the catalyst carrier before and after extrusion molding. Preferably, the method comprises one of the following steps:
the method comprises the following steps: mixing and kneading the nickel-containing pseudo-boehmite with nitric acid and water, extruding into strips, forming, drying at 80-140 ℃, and roasting at 900-1100 ℃ for 3-6 hours to obtain the catalyst carrier.
The second method comprises the following steps: when the nickel-containing alumina carrier is used, the catalyst carrier is obtained by adding precursors of alkali metal, alkaline earth metal and/or lanthanum and cerium, nitric acid and water to mix and knead before extrusion molding, drying at 80-140 ℃, and roasting at 900-1100 ℃ for 3-6 hours.
The third method comprises the following steps: adding nitric acid and water into the nickel-containing pseudo-boehmite for kneading, extruding and forming, drying at 80-140 ℃, roasting at 300-600 ℃ for 3-6 h, then impregnating precursor solutions of soluble salts of alkali metals, alkaline earth metals and/or lanthanum and cerium and the like, drying at 80-140 ℃, and roasting at 900-1100 ℃ for 3-6 h to obtain the catalyst carrier.
The invention also provides a preparation method of the palladium-molybdenum selective hydrogenation catalyst, which adopts a conventional impregnation method to prepare the catalyst, and the impregnation load of the metal palladium is the same as that of the common shell catalyst. The palladium-molybdenum selective hydrogenation catalyst can be obtained by adopting the preparation method recommended by the invention: the palladium-molybdenum series hydrogenation catalyst is prepared by dipping a catalyst carrier in a solution containing palladium and molybdenum, wherein the palladium and the molybdenum can be dipped step by step or simultaneously, and then drying and roasting are carried out. The palladium-molybdenum-based hydrogenation catalyst of the present invention does not exclude other catalyst-modifying elements in addition to palladium and molybdenum.
The rare earth elements cerium and/or lanthanum and alkali metal and/or alkaline earth metal can be added in the carrier forming process; or the active component can be added into the carrier before being impregnated after the carrier is formed; it can also be added simultaneously with the active ingredient impregnation solution when the active ingredient is impregnated.
That is, alkali metal and/or alkaline earth metal, lanthanum and/or cerium can be added during preparation of the carrier, or can be added into the carrier before palladium and molybdenum are added after the carrier is formed, then the solution containing palladium and molybdenum is soaked on the nickel-containing alumina carrier, and the catalyst is prepared by drying and roasting at 300-500 ℃ for 3-6 h. And the catalyst can also be prepared by adding palladium and molybdenum simultaneously during palladium and molybdenum impregnation, namely adding alkali metal, alkaline earth metal and/or lanthanum and cerium into a palladium and molybdenum solution, impregnating the palladium and molybdenum solution on a nickel-containing alumina carrier, drying the nickel-containing alumina carrier, and roasting the dried nickel-containing alumina carrier for 3 to 6 hours at the temperature of 300 to 500 ℃.
In the preparation method of the palladium-molybdenum hydrogenation catalyst, the active component solution can be a soluble salt solution of palladium and molybdenum. The palladium salt can be palladium nitrate, palladium chloride and palladium acetate, and is preferably palladium chloride. The molybdenum can be ammonium molybdate and molybdenum trioxide. In the present invention, the alkali metal and/or alkaline earth metal is preferably added in the form of a soluble nitrate, acetate or citrate. In the present invention, cerium and/or lanthanum are preferably added in the form of soluble nitrates.
The nickel-containing pseudo-boehmite is not simple physical blending or coating of the pseudo-boehmite and a nickel-containing compound or a nickel salt solution, but generates an acid-base reaction, has a gelling process, and finally prepares the carrier with a specific nickel and aluminum mixed crystal form.
The invention also provides a preparation method of the more specific palladium-molybdenum series selective hydrogenation catalyst, which comprises the steps of dipping the nickel-containing alumina carrier by using a solution containing palladium and molybdenum in one step or multiple steps, drying and roasting to obtain the catalyst; the nickel-containing alumina carrier is obtained by at least forming, drying and roasting nickel-containing pseudo-boehmite; the nickel-containing pseudo-boehmite is preferably obtained by the following method, and the specific process comprises the following steps:
(1) adding bottom water into the neutralization kettle, wherein the bottom water is deionized water, and heating to 50-90 ℃;
(2) respectively preparing an acidic aluminum salt aqueous solution and an acidic nickel salt aqueous solution, uniformly mixing the acidic aluminum salt aqueous solution and the acidic nickel salt aqueous solution to obtain an acidic mixed solution containing aluminum salt and nickel salt, and adjusting the temperature of the acidic mixed solution to be 50-90 ℃, wherein the concentration of the acidic aluminum salt aqueous solution is 10-80 g of Al2O3The concentration of the acidic nickel salt aqueous solution is 3-50 gNiO/L;
(3) preparing alkali metal aluminate solution with the concentration of 50-300 gAl2O3/L；
(4) Adding the acidic mixed solution obtained in the step (2) and the alkali metal aluminate solution obtained in the step (3) into the neutralization kettle in the step (1) in a concurrent flow manner, and continuously ventilating and stirring until colloid is formed;
(5) controlling the gelling temperature of the step (4) to be 50-90 ℃, and controlling the gelling pH value to be 7-10;
(6) after the cementing, the nickel-containing pseudo-boehmite is prepared by aging, filtering, washing and drying.
The nickel-containing pseudo-boehmite prepared by the method contains 0.1-10 wt%, preferably 0.5-5 wt% of nickel based on 100% of the total weight of the nickel-containing pseudo-boehmite. The specific surface area is 300-420 m2A pore volume of 0.7 to 1.2 cm/g3(ii)/g, the pore diameter is 5-10 nm; the gelling temperature is 50-90 ℃, preferably 60-80 ℃; the pH value of the gel is 7-10, preferably 7-9; the aging temperature is 50-80 ℃, and the aging time is 10-60 min.
The nickel-containing alumina carrier of the present invention preferably contains delta-Al2O3、δ-NiAl26O40、NiAl2O4The crystal form is a crystal form, wherein B1/B2 is more than or equal to 0.45 and less than or equal to 0.85 in an XRD spectrogram, B1 refers to the integral intensity of a peak with the 2 theta of 34.2-39.8 degrees in the XRD spectrogram, and B2 refers to the integral intensity of a peak with the 2 theta of 43.3-48.5 degrees in the XRD spectrogram.
The nickel-containing alumina carrier of the present invention preferably contains delta-Al2O3、δ-NiAl26O40、NiAl2O4Mixed crystals of crystal forms, preferably delta-Al2O3、δ-NiAl26O40And NiAl2O4Accounting for 50-100% of the total weight of the nickel-containing alumina carrier. The carrier may further contain theta-Al2O3、α-Al2O3And/or gamma-Al2O3Preferably alpha-Al2O3Less than 30 wt%.
The palladium-molybdenum selective hydrogenation catalyst provided by the invention contains alkali metal and/or alkaline earth metal, can adjust the acidity and alkalinity of the surface of the catalyst carrier, improves the hydrogenation performance and hydrogenation stability of the catalyst, and is beneficial to reducing the deposition of carbon and colloid in the hydrogenation process, thereby prolonging the service life of the catalyst. The addition of cerium and/or lanthanum can inhibit the growth of catalyst carrier grains during high-temperature roasting, improve the dispersion degree of active components and improve the hydrogenation selectivity and stability of the catalyst.
The method disclosed by the invention directly carries out selective hydrogenation on the acetylene hydrocarbon-rich carbon four-fraction after butadiene extraction, and in the process, the catalyst is prepared by using a nickel-containing alumina carrier with a specific crystal form, so that the catalyst has proper acidity and pore structure, and the hydrogenation activity and selectivity of the catalyst are improved. The hydrogenation method of the invention converts alkyne in the acetylene hydrocarbon into butadiene and mono-olefin, and the hydrogenation product can return to the extraction device to continuously extract butadiene, thereby increasing the yield of butadiene and improving the added value of the material. Even when the alkyne content of the raw material is more than 5wt%, the method provided by the invention can still normally operate for a long time, the palladium serving as the active component of the catalyst is basically not lost, the dimer is hardly produced in the hydrogenated material, and the vinyl acetylene content is less than 1.0 wt%. The method of the invention has the main advantages that: (1) the process simulation industrial device adopts the adiabatic fixed bed reactor, is convenient for catalyst filling, start-up and regeneration operation, has small investment, and is very favorable for popularization to the industrial device. (2) The catalyst used in the invention is a bimetallic or multi-metal catalyst prepared by nickel-containing alumina carrier with a specific crystal form, the strong interaction between metals inhibits the adsorption between vinyl acetylene and palladium, effectively reduces the loss of active component palladium, prolongs the service life of the catalyst and ensures the long-term stable operation of the hydrogenation process.
The method is suitable for selective hydrogenation of acetylene hydrocarbon-rich carbon four-fraction, and compared with the prior art, the method has the advantages of good hydrogenation activity, high butadiene selectivity, strong hydrogenation stability and coking resistance, wide operable condition range and the like. When the hydrogenation method is used, a specific selective hydrogenation catalyst is adopted, so that the hydrogenation activity and the butadiene selectivity are high, the chemical stability and the thermal stability are good, the anti-coking performance is strong, and the service life is long.
Detailed Description
Raw material source and analysis method:
acetylene rich carbon four fraction: the catalyst is prepared from Lanzhou petrochemical ethylene plants, contains 7-25 wt% of Vinyl Acetylene (VA) and 5-20 wt% of butadiene;
the method for measuring the content of the active components of the catalyst comprises the following steps: analyzing by using national standard GB/T15337-94 of general rules of atomic absorption Spectroscopy and GB19723-88 of general rules of chemical reagent flame atomic absorption Spectroscopy;
specific surface area (m)2Per g) and pore volume (ml/g): analyzing by using a national standard catalyst and adsorbent surface area determination method GB/T5816;
and (3) crystal form analysis: the crystal form of the carrier is determined by an X-ray powder diffractometer (XRD) of D8Advance model produced by Bruker company in Germany, and the specific conditions are as follows: CuKa radiation, 40 kilovolts, 40 milliamperes, a scanning speed of 0.02 DEG/step and 0.5 seconds/step, wherein B1 refers to the integral intensity of a peak with the 2 theta of 34.2-39.8 DEG in an XRD spectrogram, and B2 refers to the integral intensity of a peak with the 2 theta of 43.3-48.5 DEG in the XRD spectrogram;
the raw materials and the product composition are as follows: and (4) adopting the composition determination of industrial cracking carbon four to analyze SH-T1141-92.
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto.
EXAMPLES preparation of catalysts 1 to 6
Preparation of catalyst C1:
4L of Al with a concentration of 50g2O3Putting the/L sodium metaaluminate solution into a stainless steel container with a stirrer and a gas-permeable tank bottom, preparing a nickel nitrate solution, putting the nickel nitrate solution into a high-level container, introducing a mixed gas of carbon dioxide and air, starting a peristaltic pump to control the flow rate of the mixed gas, and dropwise adding the prepared nickel nitrate solution, wherein the concentration of the carbon dioxide in the mixed gas is 70 v%, and the flow rate is 3Nm3And h, the reaction temperature is 35 ℃, the pH value at the end of the reaction is 9.5, the introduction of carbon dioxide is stopped, the aging is carried out for 30 minutes, mother liquor is filtered and separated, the washing is carried out, and the drying is carried out for 5 hours at the temperature of 120 ℃, so that the nickel-containing pseudo-boehmite is prepared.
Mixing and kneading the nickel-containing pseudo-boehmite with nitric acid and water, extruding into strips, drying at 120 ℃, roasting at 500 ℃ for 4h, then saturating and impregnating the carrier with a magnesium nitrate solution, drying at 120 ℃, and roasting at 1040 ℃ for 4h to prepare the nickel-and-magnesium-containing alumina carrier.
Preparing active component impregnation liquid from palladium chloride and ammonium molybdate, adjusting the pH value of the solution to 2.8, impregnating the solution on 100g of carrier, removing residual liquid after 25 minutes, washing the residual liquid with distilled water, aging, drying at 120 ℃ for 3 hours, and roasting at 480 ℃ for 4 hours to obtain the catalyst C1.
Preparation of catalyst C2:
5L of Al with a concentration of 40g2O3Putting the/L sodium metaaluminate solution into a stainless steel container with a stirrer and a gas-permeable tank bottom, preparing a nickel nitrate solution, putting the nickel nitrate solution into a high-level container, introducing a mixed gas of carbon dioxide and air, starting a peristaltic pump to control the flow rate of the mixed gas, and dropwise adding the prepared nickel nitrate solution, wherein the concentration of the carbon dioxide in the mixed gas is 65 v%, and the flow rate is 4Nm3And h, the reaction temperature is 30 ℃, the pH value at the end of the reaction is 10, the introduction of carbon dioxide is stopped, the aging is carried out for 35 minutes, mother liquor is filtered and separated, and the nickel-containing pseudo-boehmite is prepared by washing and drying.
Mixing and kneading the nickel-containing pseudo-boehmite with nitric acid, lithium citrate and water, extruding and forming, drying at 120 ℃, and roasting at 1070 ℃ for 4 hours to prepare the nickel-and-lithium-containing alumina carrier.
Preparing palladium nitrate into an active component impregnation liquid, adjusting the pH value of the solution to 2.4, then impregnating the solution on a 100g carrier, removing residual liquid after 25 minutes, washing the residual liquid with distilled water, aging, drying at 120 ℃ for 2 hours, and roasting at 420 ℃ for 4 hours to obtain a catalyst precursor; then preparing a mixed solution of molybdenum oxide and potassium nitrate, soaking the mixed solution on a catalyst precursor, aging, drying at 120 ℃ for 3h, and roasting at 500 ℃ for 4h to obtain the catalyst C2.
Preparation of catalyst C3:
1L of Al with a concentration of 50g2O3The aluminum sulfate solution and the prepared nickel nitrate solution are mixed evenly and put into a container at a high position, and the prepared concentration is 100g Al2O3Putting 1.5L of sodium metaaluminate solution into a container at a high position, simultaneously starting a peristaltic pump connected with the two containers, and dropwise adding the solution at a controlled flow rate1L of bottom water is provided with a stirrer, the bottom of the stainless steel container can be filled with gas, the reaction temperature is 55 ℃, the flow is controlled to adjust the pH value of the reaction system to be 8.5, ammonia water is dripped to adjust the pH value of the slurry to be 9.0, the slurry is aged for 30 minutes after the reaction is finished, mother liquor is filtered and separated, and the nickel-containing pseudo-boehmite is prepared by washing and drying.
Weighing the prepared nickel-containing pseudo-boehmite, mixing and kneading with magnesium nitrate, nitric acid and water, extruding into strips, drying at 110 ℃, and roasting at 1065 ℃ for 4 hours to prepare the nickel-and-magnesium-containing alumina carrier.
Preparing palladium chloride, ammonium molybdate and lanthanum nitrate into an active component impregnation liquid, adjusting the pH value of the solution to 2.6, impregnating the prepared impregnation liquid on 100g of a carrier, removing residual liquid after 25 minutes, washing with distilled water, aging, drying at 120 ℃ for 3 hours, and roasting at 520 ℃ for 4 hours to obtain the catalyst C3.
Preparation of catalyst C4:
1L of Al with a concentration of 50g2O3The aluminum sulfate solution and the prepared nickel nitrate solution are mixed evenly and put into a container at a high position, and the prepared concentration is 50g Al2O3Putting 3L of sodium metaaluminate solution into a high-position container, simultaneously starting a peristaltic pump connected with the two containers, controlling the flow rate to be dripped into a stainless steel container which is provided with 1L of bottom water and is provided with a stirrer, and the bottom of the stainless steel container can be filled with gas, controlling the reaction temperature to be 65 ℃, controlling the flow to adjust the pH value of a reaction system to be 7.0, adjusting the pH value of slurry to be 7.5 by dripping ammonia water, aging for 25 minutes after the reaction is finished, filtering and separating mother liquor, washing and drying to obtain the nickel-containing pseudo-boehmite.
Mixing and kneading the nickel-containing pseudo-boehmite with nitric acid and water, extruding and forming, drying at 120 ℃, roasting at 480 ℃ for 4h, then saturating and impregnating the carrier with magnesium nitrate and lithium citrate solution, drying at 110 ℃, and roasting at 1090 ℃ for 4h to prepare the alumina carrier containing nickel, lithium and magnesium.
Preparing palladium acetate into an active component impregnation solution, then impregnating the impregnation solution on 100g of a carrier, removing residual liquid after 40 minutes, aging, drying at 120 ℃ for 2 hours, and roasting at 450 ℃ for 3 hours to obtain a catalyst precursor; then preparing ammonium molybdate and cerium nitrate solution, dipping the solution on the catalyst precursor, aging, drying at 120 ℃ for 3h, and roasting at 450 ℃ for 4h to obtain the catalyst C4.
Preparation of catalyst C5:
2L of Al with a concentration of 100g2O3Putting the/L sodium metaaluminate solution into a stainless steel container which is provided with a stirrer and can be filled with gas at the bottom of the tank, filling mixed gas of carbon dioxide and air, wherein the concentration of the carbon dioxide in the mixed gas is 60 v%, and the flow rate is 3Nm3H is used as the reference value. The reaction temperature is 35 ℃, the pH value at the end of the reaction is 10, and the introduction of carbon dioxide is stopped. Adding the prepared nickel nitrate solution under the condition of air stirring, stabilizing for 30 minutes, adjusting the pH value of the slurry to 8.5 by dropwise adding ammonia water, aging for 30 minutes after the reaction is finished, filtering and separating mother liquor, washing and drying to obtain the nickel-containing pseudo-boehmite.
Mixing and kneading the nickel-containing pseudo-boehmite with nitric acid and water, extruding and forming, drying at 120 ℃, roasting at 450 ℃ for 4h, then saturating and impregnating the carrier with a lanthanum nitrate solution, drying at 110 ℃, and roasting at 1100 ℃ for 4h to prepare the nickel-and lanthanum-containing alumina carrier.
Preparing active component impregnation liquid from palladium chloride, ammonium molybdate and potassium carbonate, adjusting the pH value of the solution to 2.8, impregnating the prepared impregnation liquid on 100g of carrier, removing residual liquid after 25 minutes, washing with distilled water, aging, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours to obtain the catalyst C5.
Preparation of catalyst C6:
4L of Al with a concentration of 50g2O3Putting the/L sodium metaaluminate solution into a stainless steel container with a stirrer and a gas-permeable tank bottom, preparing a nickel nitrate solution, putting the nickel nitrate solution into a high-level container, introducing a mixed gas of carbon dioxide and air, starting a peristaltic pump to control the flow rate of the mixed gas, and dropwise adding the prepared nickel nitrate solution, wherein the concentration of the carbon dioxide in the mixed gas is 70 v%, and the flow rate is 6Nm3And h, the reaction temperature is 40 ℃, the pH value at the end of the reaction is 9.5, the introduction of carbon dioxide is stopped, the aging is carried out for 35 minutes, mother liquor is filtered and separated, and the nickel-containing pseudo-boehmite is prepared by washing and drying.
Weighing the prepared nickel-containing pseudo-boehmite, mixing and kneading with nitric acid and water, extruding into strips, forming, drying at 110 ℃, and roasting at 1055 ℃ for 4h to prepare the nickel-containing alumina carrier.
Preparing palladium chloride, molybdenum oxide and potassium carbonate into an active component impregnation liquid, adjusting the pH value of the solution to 2.8, impregnating the prepared impregnation liquid on 100g of a carrier, removing residual liquid after 25 minutes, washing with distilled water, aging, drying at 120 ℃ for 4 hours, and roasting at 560 ℃ for 4 hours to obtain the catalyst C6.
The physicochemical properties of catalysts 1 to 6 are shown in Table 1.
TABLE 1 physicochemical Properties of catalysts C1-C6 for examples
Example 1
Diluting the alkyne-rich carbon four fraction with raffinate carbon four, wherein the weight ratio of the alkyne-rich carbon four fraction to the raffinate carbon four is 1: 1. The adiabatic reactor adopts a single-section adiabatic bubbling bed and adopts a catalyst C1, and the catalyst is reduced for 6 hours at 120 ℃ in a hydrogen atmosphere. The reaction inlet temperature is 45 ℃, the reaction pressure is 1.0MPa, and the liquid space velocity is 10h-1The molar ratio of hydrogen to alkyne was 3.0, and table 2 shows the composition of the materials before and after the reaction.
TABLE 2 Material composition before and after reaction
Example 2
Diluting the acetylene hydrocarbon-rich carbon four fraction with raffinate carbon four and pyrolysis carbon four, wherein the weight ratio of the acetylene hydrocarbon-rich carbon four fraction to (raffinate carbon four + pyrolysis carbon four) is 1: 2. The adiabatic reactor adopts a single-section adiabatic bubbling bed and adopts a catalyst C2, and the catalyst is reduced for 6 hours at 120 ℃ in a hydrogen atmosphere. The reaction inlet temperature is 30 ℃, the reaction pressure is 1.5MPa, and the liquid space velocity is 15h-1The molar ratio of hydrogen to alkyne was 3.0, and table 3 shows the composition of the materials before and after the reaction.
TABLE 3 Material composition before and after reaction
Example 3
Diluting the acetylene hydrocarbon-rich carbon four fraction with raffinate carbon four and pyrolysis carbon four, wherein the weight ratio of the acetylene hydrocarbon-rich carbon four fraction to (raffinate carbon four + pyrolysis carbon four) is 1:3, a two-section adiabatic bubbling bed is adopted in an adiabatic reactor, and a catalyst is reduced for 6 hours at 120 ℃ in a hydrogen atmosphere. The catalyst C3 is adopted in the first section, the catalyst C1 is adopted in the second section, the temperature of the first section reaction inlet is 40 ℃, the temperature of the second section reaction inlet is 30 ℃, the reaction pressure is 0.8MPa, and the liquid space velocity is 18h-1The molar ratio of hydrogen to alkyne in the first stage bed was 2.0, the molar ratio of hydrogen to alkyne in the second stage bed was 0.8, and table 4 shows the composition of the materials before and after the reaction.
TABLE 4 Material composition before and after reaction
Example 4
Diluting the acetylene hydrocarbon-rich carbon four fraction with raffinate carbon four and pyrolysis carbon four, wherein the weight ratio of the acetylene hydrocarbon-rich carbon four fraction to (raffinate carbon four + pyrolysis carbon four) is 1: 5. The adiabatic reactor adopts a single-section adiabatic bubbling bed and adopts a catalyst C4, and the catalyst is reduced for 6 hours at 120 ℃ in a hydrogen atmosphere. The reaction inlet temperature is 25 ℃, the reaction pressure is 1.5MPa, and the liquid space velocity is 18h-1The molar ratio of hydrogen to alkyne was 3.0, and table 5 shows the composition of the materials before and after the reaction.
TABLE 5 Material composition before and after reaction
Example 5
Diluting the carbon four fraction rich in alkyne with the raffinate carbon four, wherein the weight ratio of the carbon four fraction rich in alkyne to the raffinate carbon four is 1:1, a two-section adiabatic bubbling bed is adopted in an adiabatic reactor, and the catalyst is reduced for 6 hours at 120 ℃ in a hydrogen atmosphere. Catalyst C5 is used in the first stage and catalyst is used in the second stageCatalyst C2, the temperature of the first-stage reaction inlet is 35 ℃, the temperature of the second-stage reaction inlet is 25 ℃, the reaction pressure is 2.0MPa, and the liquid space velocity is 15h-1The molar ratio of hydrogen to alkyne in the first stage bed was 2.5, the molar ratio of hydrogen to alkyne in the second stage bed was 1.2, and Table 6 shows the composition of the materials before and after the reaction.
TABLE 6 Material composition before and after reaction
Example 6
Diluting the four carbon fractions rich in alkyne with raffinate four and pyrolysis four carbon in a weight ratio of 1:8, wherein the adiabatic reactor adopts a single-stage adiabatic bubbling bed, and the catalyst is reduced for 6 hours at 120 ℃ in a hydrogen atmosphere. Adopts a catalyst C3, the reaction inlet temperature is 40 ℃, the reaction pressure is 1.2MPa, and the liquid space velocity is 22h-1The molar ratio of hydrogen to alkyne was 1.5, and the compositions of the materials before and after the reaction are shown in Table 7.
TABLE 7 Material composition before and after reaction
Example 7
Diluting the acetylene hydrocarbon-rich carbon four fraction with raffinate carbon four and pyrolysis carbon four, wherein the weight ratio of the acetylene hydrocarbon-rich carbon four fraction to (raffinate carbon four + pyrolysis carbon four) is 1:6, a single-section adiabatic bubbling bed is adopted in an adiabatic reactor, and a catalyst is reduced for 6 hours at 120 ℃ in a hydrogen atmosphere. Adopts catalyst C6, the reaction inlet temperature is 40 ℃, the reaction pressure is 1.5MPa, and the liquid space velocity is 20h-1The molar ratio of hydrogen to alkyne was 2.0, and table 8 shows the composition of the materials before and after the reaction.
TABLE 8 Material composition before and after reaction
In the selective hydrogenation process of the alkyne-rich carbon four fraction, the main reaction is the selective hydrogenation of vinyl acetylene into 1, 3-butadiene. To maximize butadiene recovery, the catalyst is required to have good hydrogenation activity and selectivity. The higher the butadiene content of the feed to be hydrogenated, the lower the selectivity of conversion of vinylacetylene to butadiene, limited by the kinetic equilibrium. As is apparent from the data in tables 2, 3, 4, 5, 6, 7 and 8, under the condition that the content of butadiene in the raw material to be hydrogenated exceeds 8wt%, the vinyl acetylene content in the product is lower than 1.0 wt%, and the butadiene selectivity is higher than 47%, which shows that the catalyst of the invention has better hydrogenation activity, selectivity and stability.
Comparative example 1
Comparative example 1 the catalyst used was prepared in the same manner as catalyst C1 except that no nickel was added during the preparation of the pseudoboehmite of comparative example 1. The evaluation process conditions of the catalyst were the same as in example 1. Table 9 shows the composition of the materials before and after the reaction.
TABLE 9 Material composition before and after reaction
Comparative example 2
The catalyst used in comparative example 2 was prepared in the same manner as catalyst C2, except that the catalyst used in comparative example 2 did not contain molybdenum oxide as a component. The evaluation process conditions of the catalyst were the same as in example 2. Table 10 shows the composition of the materials before and after the reaction.
TABLE 10 Material composition before and after reaction
Comparative example 3
The catalyst used in comparative example 3 was prepared in the same manner as catalyst C2 except that the molybdenum oxide content in the catalyst used in comparative example 2 was 6.0 wt%. The evaluation process conditions of the catalyst were the same as in example 2. Table 11 shows the composition of the materials before and after the reaction.
TABLE 11 Material composition before and after reaction
Comparative example 4
The catalyst used in comparative example 4 was prepared in the same manner as catalyst C4 except that the catalyst used in comparative example 4 had a nickel content (as a simple substance) of 4.0 wt% and the evaluation process conditions of the catalyst were the same as in example 4. Table 12 shows the composition of the materials before and after the reaction.
TABLE 12 Material composition before and after reaction
Comparative example 5
Comparative example 5 the catalyst used in the first stage bed was prepared according to the same procedure as catalyst C3 except that the catalyst used in the first stage bed of comparative example 5 did not contain magnesium oxide. The two-stage bed catalyst was also used as catalyst C1, and the evaluation process conditions for the catalyst were the same as in example 3. Table 13 shows the composition of the materials before and after the reaction.
TABLE 13 Material composition before and after reaction
Comparative example 6
The catalyst used in comparative example 6 was prepared in the same manner as catalyst C1 except that the catalyst used in comparative example 6 had a nickel content (as a simple substance) of 0.3 wt% and the evaluation process conditions of the catalyst were the same as in example 1. Table 14 shows the composition of the materials before and after the reaction.
TABLE 14 Material composition before and after reaction
Comparative example 7
Comparative example 7 the catalyst used was prepared as in example 7 of CN 101428228B. The composition of the catalyst used in comparative example 7 was: the carrier was alumina, 0.45 wt% Pd, 4.5 wt% molybdenum oxide, 3.5 wt% magnesium oxide, 1.0 wt% lithium oxide, 2.0 wt% cerium oxide. The evaluation process conditions of the catalyst were the same as in example 4. Table 15 shows the composition of the materials before and after the reaction.
TABLE 15 Material composition before and after reaction
Comparative example 8
Comparative example 8 the catalyst used was prepared as in example 12 of CN 105727951A. The composition of the catalyst used in comparative example 8 was: the carrier was alumina, 0.32 wt% Pd, 1.42 wt% molybdenum oxide, 1.45 wt% potassium oxide. The evaluation process conditions of the catalyst were the same as in example 7. Table 16 shows the composition of the materials before and after the reaction.
TABLE 16 Material composition before and after reaction
Comparative example 9
The nickel-containing carrier of the catalyst used in comparative example 9 was prepared by the method described in the example of CN1123392C, and the nickel content in the carrier, the catalyst preparation method and the catalyst composition were the same as those of the catalyst C4 used in the example, except that B1/B2 was 0.95. The evaluation process conditions of the catalyst were the same as in example 4. Table 17 shows the compositions of the materials before and after the reaction.
TABLE 17 Material composition before and after reaction
It can be seen from the examples and the data analysis of the proportion that, by adopting the hydrogenation method of the invention and matching with the nickel-containing alumina carrier-supported palladium-molybdenum-based catalyst adopted by the invention, under the condition that the butadiene content in the material to be hydrogenated is higher than 8wt%, the vinylacetylene content in the hydrogenated product is lower than 1.0 wt%, the butadiene selectivity is higher than 46%, the butadiene can be recovered to the maximum extent, and the hydrogenated product meets the feeding requirement of a butadiene extraction device.
Claims (11)
1. A method for recovering butadiene through selective hydrogenation of alkyne is characterized in that the method comprises a material to be hydrogenated and H2Entering an adiabatic reactor, wherein a palladium-molybdenum selective hydrogenation catalyst is loaded in the adiabatic reactor, and the molar ratio of hydrogen to the total alkyne content at the inlet of the reactor is 0.8-3.0; the temperature of a reaction inlet is 20-60 ℃, the reaction pressure is 0.6-2.5 MPa, and the liquid volume space velocity is 10-25 h-1Cooling the reaction product, and separating in a gas-liquid separating tank; the material to be hydrogenated is acetylene hydrocarbon-rich carbon four fraction or a mixture of acetylene hydrocarbon-rich carbon four fraction and a diluent, and the diluent is raffinate carbon four or cracking carbon four; the palladium-molybdenum selective hydrogenation catalyst takes nickel-containing alumina as a carrier, takes palladium-molybdenum as an active component, and takes the total weight of the catalyst as 100%, wherein the content of palladium in terms of simple substances is 0.1-0.7 wt%, the content of molybdenum oxide is 1-5 wt%, and the content of nickel in terms of simple substances is 0.5-3 wt%; 1-8 wt% of an alkali metal and/or alkaline earth metal oxide; 0-5 wt% of cerium oxide and/or lanthanum oxide; the specific surface area of the catalyst is 20-120 m2The pore volume is 0.30-0.65 ml/g; the precursor of the nickel-containing alumina carrier is nickel-containing pseudo-boehmite, and the preparation process of the nickel-containing pseudo-boehmite comprises acid-base neutralization and gelling processes; dipping a nickel-containing alumina carrier in a solution containing active components, drying and roasting to prepare a palladium-molybdenum hydrogenation catalyst; the nickel-containing pseudo-boehmite is obtained by the following method, and the specific process comprises the following steps:
(1) adding bottom water into the neutralization kettle, wherein the bottom water is deionized water, and heating to 50-90 ℃;
(2) respectively preparing an acidic aluminum salt aqueous solution and an acidic nickel salt aqueous solution, uniformly mixing the acidic aluminum salt aqueous solution and the acidic nickel salt aqueous solution to obtain an acidic aqueous solution containing aluminum salt and nickel salt, and adjusting the temperature of the mixed solution to be 50-90 ℃, wherein the concentration of the acidic aluminum salt aqueous solution is 10-80 g of Al2O3The concentration of the acidic nickel salt aqueous solution is 3-50 gNiO/L;
(3) preparing alkali metal aluminate solution, wherein the concentration of the alkali metal aluminate solution is 50-300 g of Al2O3/L；
(4) Adding the (2) and the (3) into the (1) in a concurrent flow manner, and continuously ventilating and stirring;
(5) controlling the gelling temperature of the step (4) to be 50-90 ℃, and controlling the gelling pH value to be 7-10;
(6) after the cementing, the nickel-containing pseudo-boehmite is prepared by aging, filtering, washing and drying.
2. The method of claim 1, wherein the palladium-molybdenum-based selective hydrogenation catalyst comprises 0.2 to 0.6wt% of palladium, 3 to 5wt% of molybdenum oxide, 0.5 to 2wt% of nickel, 2 to 5wt% of an alkali metal and/or alkaline earth metal oxide, 0.5 to 3wt% of cerium oxide and/or lanthanum oxide, and a specific surface area of the catalyst is 20 to 80m2The pore volume is 0.40-0.65 ml/g.
3. The method according to claim 1, characterized in that the process conditions of the method are: the temperature of a reaction inlet is 25-50 ℃; the reaction pressure is 1.0-2.0 MPa; liquid volume airspeed of 12-18 h-1。
4. The process according to claim 1, characterized in that the mass content of alkynes in the feed to be hydrogenated is not higher than 10 wt%.
5. The method according to claim 1, wherein the alkyne-rich carbon four fraction has a vinylacetylene mass content of 7-25 wt% and a butadiene mass content of 5-20 wt%.
6. The method according to claim 1, wherein the material to be hydrogenated is a mixture of the alkyne-rich carbon four fraction and the diluent, and the weight ratio of the alkyne-rich carbon four fraction to the diluent is 1: 1-1: 8.
7. The method of claim 1, wherein the adiabatic reactor is a single-stage adiabatic bubble bed reactor or a multi-stage adiabatic bubble bed reactor.
8. The method according to claim 7, wherein the single-stage adiabatic bubbling bed reactor has a molar ratio of hydrogen to total alkyne content at the reactor inlet of 1.0 to 3.0; the mol ratio of the hydrogen amount at each section of inlet to the total alkyne amount in the material to be hydrogenated at the section of inlet in the multi-section adiabatic bubbling bed reactor is 0.8-2.0.
9. The method as claimed in claim 1, wherein the nickel-containing alumina carrier is obtained by molding and calcining nickel-containing pseudo-boehmite, and contains delta-Al2O3、δ-NiAl26O40、NiAl2O4The crystal form is a crystal form, wherein B1/B2 is more than or equal to 0.45 and less than or equal to 0.85 in an XRD spectrogram, B1 refers to the integral intensity of a peak with the 2 theta of 34.2-39.8 degrees in the XRD spectrogram, and B2 refers to the integral intensity of a peak with the 2 theta of 43.3-48.5 degrees in the XRD spectrogram.
10. The method as claimed in claim 9, wherein the nickel containing alumina support is delta-Al2O3、δ-NiAl26O40And NiAl2O4The nickel-containing alumina carrier accounts for 30-100% of the total weight of the nickel-containing alumina carrier.
11. The method of claim 1, wherein the palladium-molybdenum selective hydrogenation catalyst is prepared by one or more steps of dipping a solution containing palladium and molybdenum on a nickel-containing alumina carrier, drying, and roasting at 300-500 ℃ for 3-6 h; the rare earth elements cerium and/or lanthanum and alkali metal and/or alkaline earth metal are added in the carrier forming process; or after the carrier is formed, the active components are firstly added into the carrier before being impregnated; or when the active component is impregnated, the active component and the active component impregnation solution are added simultaneously.
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| CN114315498B (en) * | 2020-09-28 | 2024-06-25 | 中国石油天然气股份有限公司 | Alkyne-rich carbon four-fraction selective hydrogenation method |
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| CN105732255A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Selective hydrogenation method for alkyne |
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| CN1665761A (en) * | 2002-08-08 | 2005-09-07 | 催化蒸馏技术公司 | Selective hydrogenation of acetylenes |
| CN105732288A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Selective hydrogenation method of carbon four-fraction |
| CN105732255A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Selective hydrogenation method for alkyne |
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