CN115025779B - Olefin deoxidizer and preparation method thereof - Google Patents
Olefin deoxidizer and preparation method thereof Download PDFInfo
- Publication number
- CN115025779B CN115025779B CN202210651672.3A CN202210651672A CN115025779B CN 115025779 B CN115025779 B CN 115025779B CN 202210651672 A CN202210651672 A CN 202210651672A CN 115025779 B CN115025779 B CN 115025779B
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- Prior art keywords
- solution
- manganese
- palladium
- acidic
- deoxidizer
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 31
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 35
- 239000001301 oxygen Substances 0.000 claims description 35
- 229910052760 oxygen Inorganic materials 0.000 claims description 35
- 239000002131 composite material Substances 0.000 claims description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 28
- -1 manganese-aluminum Chemical compound 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 27
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 230000002378 acidificating effect Effects 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000005470 impregnation Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000003929 acidic solution Substances 0.000 claims description 12
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 150000002696 manganese Chemical class 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- 239000004033 plastic Substances 0.000 claims description 10
- 229920003023 plastic Polymers 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 150000002940 palladium Chemical class 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 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 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229910003445 palladium oxide Inorganic materials 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 17
- 229910000510 noble metal Inorganic materials 0.000 abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 25
- 239000005977 Ethylene Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 15
- 150000002431 hydrogen Chemical class 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000011572 manganese Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- B01J23/8986—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 manganese, technetium or rhenium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/14833—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds
- C07C7/1485—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds oxides; hydroxides; salts
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention provides an olefin deoxidizer and a preparation method thereof. The deoxidizer prepared by the invention has the advantages of simple preparation process, wide application range, deoxidization depth reaching below 0.1ppm, low noble metal content, low deoxidization temperature, low olefin hydrogenation selectivity and the like, is suitable for deoxidizing various hydrogen-containing gases such as olefin, refinery dry gas and the like, and has wide application prospect.
Description
Technical field:
the invention relates to the technical field of catalysis, in particular to a raw material deoxidizer, and particularly relates to a catalyst suitable for deep deoxidization of trace oxygen in olefin and a production method thereof.
The background technology is as follows:
with the rapid development of industries such as electronics, metallurgy, chemical industry, petroleum and the like, deoxidizers are widely applied in the industry, and simultaneously, higher requirements are put on the application field, the use condition, the deoxidizing depth and the like of the deoxidizers. Olefins are used as important basic chemical raw materials, wherein ethylene, propylene and butadiene are the main raw materials for producing high-molecular polymer materials. Various high-efficiency polyolefin catalysts and metallocene catalysts are used for producing polyethylene, polypropylene and synthetic rubber, and in order to avoid poisoning and deactivation of the catalysts and improve the product quality, strict requirements are imposed on the impurity requirements of olefin raw materials, and the oxygen content of the high-purity olefin raw materials needs to be purified to be lower than 0.1ppm. Therefore, it is significant to develop a deep and efficient deoxidizing and purifying agent for olefin treatment.
The common deoxidizers are mainly divided into three types: the first type of deoxidizer is deoxidized by adsorption only, such as activated carbon, molecular sieve and the like, and the deoxidizing agent is deoxidized by utilizing the characteristics of large specific surface and strong adsorption capacity; the second type is noble metal deoxidizer, which takes Pt, pd, ag and the like as active components, is impregnated on carriers such as alumina, silica gel, active carbon, carbon fiber, molecular sieve, titanium dioxide and the like, and oxygen in raw material gas and hydrogen react under the action of a catalyst to generate water in the presence of hydrogen so as to achieve the aim of deoxidizing, and the catalyst has the advantages of wide operating temperature, high airspeed, low residual oxygen amount and the like; the third type of deoxidizer is deoxidizing by chemical adsorption reaction, and deoxidizing by chemical reaction of active component of deoxidizer and oxygen in raw gas, and has d 5 、d 7 、d 8 、d 10 The transition metal element with the structure is often used as an active component of a deoxidizer, such as Mn, co, mo, ni, cu, cr, and the carrier is often alumina, silica, magnesia, and the like, and is prepared by an impregnation method or a kneading method, the deoxidizer is reduced by introducing hydrogen, and the reduced active component or low-valence metal oxide reacts with trace oxygen in gas to generate high-valence oxide so as to achieve the deoxidizing purpose.
The CN 1246383 of Dalian chemical and physical institute of China academy of sciences discloses a high-activity deoxidizer with Mn as an active component and high-alumina cement, diatomite or alumina as a carrier, which can be used for deeply deoxidizing ethylene and propylene in polyolefin production, and can be activated and regenerated by hydrogen at 150-400 ℃ with deoxidizing capacity of 5-18 mg/g.
The Beijing chemical institute of China petrochemical Co., ltd discloses a preparation method of an olefin deoxidizer in CN 102850166A, mn 3 O 4 、TiO 2 、Ag 2 The chemical adsorption reaction type olefin deoxidizer prepared by taking O as a main component has the advantages of high deoxidizing capacity at room temperature, low reduction temperature and the like, is mainly used for deoxidizing ethylene, and can remove 1000ppm of oxygen in the ethylene to 0.01ppm. MnO type BC-DE ethylene deoxidizers are reported in literature (petrochemical industry, 2010,39 (9): 1032-1035) to purge ethylene from 2ppm to less than 0.1ppm of oxygen at room temperature. The great CoKateli catalytic engineering Co., ltd. In CN 106378144A, a manganese-based deoxidizer using cerium-based oxide as a carrier and a method for preparing the same, using Cu and MnO as active components, ceO 2 Or CeO 2 -MO x The composite oxide is used as a carrier, kaolin, high alumina cement, pseudo-boehmite and phthalate ester are used as binders, and the composite oxide is suitable for the activation and regeneration conditions of the existing polyolefin device, and has high deoxidization capacity and long service life. The chemical adsorption deoxidization catalyst needs to be regenerated frequently in use, a double-tower switching process is often required to be arranged in an industrial device, the operation is complex, and potential safety hazards are easy to bring.
The Sedrin chemical engineering institute of China sea oil Limited company discloses a difunctional deoxidizer taking palladium and manganese as active components in CN 100341606A and a production method thereof, and the difunctional deoxidizer is mainly used for removing trace oxygen in synthesis gas, hydrogen and nitrogen. In CN 1332753A, sulfur-tolerant catalytic deoxidizing agents with platinum and molybdenum as active components are disclosed, and the sulfur-tolerant catalytic deoxidizing agents are also suitable for removing trace oxygen in synthesis gas and hydrogen. The national academy of sciences of China, dalian chemical and physical institute, CN 1070128 discloses a palladium/manganese deoxidizer, which comprises an oxide of carrier manganese added with an activity promoter and an enhancer Al 2 O 3 、CaO、SiO 2 And cement, makeThe deoxidizer has the double functions of catalytic hydrodeoxygenation and deoxidation by reaction of the carrier and oxygen, and has the advantages of deep deoxidization of raw gas at room temperature, high deoxidization airspeed, good water resistance and poison resistance in the reaction process, and the like. The noble metal deoxidizer is mainly used for deep deoxidization of hydrogen and helium, and is easy to generate polymerization reaction in an olefin system to cause deactivation of carbon deposit of the catalyst.
The Xinan chemical engineering research institute Co Ltd discloses an olefin deoxidizer which takes titanium-aluminum composite oxide with large specific surface as a carrier, one or more of palladium, platinum and silver as active components and one or more of manganese, iron, cobalt, copper and zinc as an auxiliary agent in CN 103157471A, is mainly used for deoxidizing ethylene, and has the characteristics of high low-temperature activity, long service life, no need of reduction and activation, capability of avoiding olefin addition and the like. However, the deoxidizer obtained by the method needs high-temperature (more than 100 ℃) deoxidization when the noble metal content is lower than 0.1%, and needs higher noble metal content when the deoxidizer is deoxidized at low temperature (less than or equal to 100 ℃). In addition, the catalyst is easy to cause problems such as olefin saturation and the like under the working condition of hydrogen-containing olefin.
Noble metal deoxidizer for removing trace oxygen from catalytic cracking dry gas, which takes palladium as a main active component, one or more of Ag, au, co, cr as a co-catalytic active component, aluminum oxide, activated carbon, silicon oxide or molecular sieve as a carrier, and the catalytic active component is distributed in an eggshell shape on the surface of the carrier, is disclosed in CN 101745391B by petrochemical science institute of China petrochemical industry Co. The catalyst has the characteristics of high poisoning resistance, difficult temperature runaway of a reaction bed layer and the like, and the deoxidization depth can reach 0.1ppm at high airspeed. The method has the defects of high noble metal content (Pd is more than or equal to 0.1 percent), high use temperature (100-160 ℃) and larger ethylene loss (1.3-11.3 percent).
It is considered that the deoxidizer used on the existing industrial scale has respective defects for olefin deoxidization. For the deoxidizing agent of chemical reaction, the deoxidizing amount is limited, the deoxidizing agent needs to be reduced on site before use, and hydrogen needs to be introduced again for reduction and regeneration after deactivation, and the problems of insufficient deoxidizing depth, high residual oxygen, easiness in pulverization and the like are easily caused along with the prolonging of the service period. For the existing noble metal deoxidizer, the noble metal content is high, the use temperature is high, the olefin loss is large, the olefin polymerization is easy to cause, and the like.
The invention comprises the following steps:
aiming at the defects of the prior art, the invention aims to provide a catalyst which has the advantages of low noble metal content, long service life, low deoxidizing temperature, low olefin hydrogenation selectivity, high deoxidizing precision and the like, and is suitable for removing trace oxygen in various kinds of hydrogen-containing gases such as olefin, refinery dry gas and the like, and a preparation method thereof.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
the invention provides a catalyst for removing trace oxygen from olefin, which comprises a catalytic active component and a carrier, wherein the catalytic active component consists of a main catalytic active component and a co-catalytic active component, the main catalytic active component is palladium and manganese oxide, the palladium content is 0.01-0.1% and the manganese oxide content is 1-20% by weight of the catalyst, the co-catalytic active component is one or more of copper, silver and gold, the content is 0.01-5.0%, the carrier is alumina, and the preparation method of the catalyst comprises the following steps:
1) Mixing an acidic manganese salt solution and an acidic aluminum salt solution to form an acidic solution, adding the acidic solution and an alkaline meta-aluminate solution into deionized water in parallel, neutralizing to form gel, aging, washing, drying, adding dilute nitric acid, kneading to form a plastic body, extruding strips to form, drying, and roasting to obtain a formed manganese-aluminum composite material;
2) Dissolving calculated amounts of soluble palladium salt and soluble group IB metal salt in deionized water, and uniformly stirring to obtain an impregnating solution; wherein the soluble palladium salt is selected from one or more of palladium nitrate, palladium chloride, palladium acetate and palladium acetylacetonate; the soluble IB group metal salt is selected from one of copper nitrate, silver nitrate and gold chloride;
3) Soaking the composite material in the manganese-aluminum material according to an equal volume method, and drying and roasting the composite material to obtain a deoxidizer precursor;
4) And reducing the deoxidizer precursor to obtain a deoxidizer product.
The catalyst for removing trace oxygen from olefin of the invention, wherein the content of metallic palladium is preferably 0.01 to 0.05 percent, the content of manganese oxide is 10 to 20 percent, and the total amount of copper, silver and gold is 0.01 to 2.0 percent.
The invention further provides a preparation method of the catalyst for removing trace oxygen from olefin, which comprises the following steps:
1) Mixing an acidic manganese salt solution and an acidic aluminum salt solution to form an acidic solution, adding the acidic solution and an alkaline meta-aluminate solution into deionized water in parallel, neutralizing to form gel, aging, washing, drying, adding dilute nitric acid, kneading to form a plastic body, extruding strips to form, drying, and roasting to obtain a formed manganese-aluminum composite material;
2) Dissolving calculated amounts of soluble palladium salt and soluble group IB metal salt in deionized water, and uniformly stirring to obtain an impregnating solution; wherein the soluble palladium salt is selected from one or more of palladium nitrate, palladium chloride, palladium acetate and palladium acetylacetonate; the soluble IB group metal salt is selected from one of copper nitrate, silver nitrate and gold chloride;
3) Soaking the composite material in the manganese-aluminum material according to an equal volume method, and drying and roasting the composite material to obtain a deoxidizer precursor;
4) And reducing the deoxidizer precursor to obtain a deoxidizer product.
In the preparation method of the invention, the acidic manganese salt in the step 1) is preferably selected from one or more of manganese nitrate, manganese chloride, manganese sulfate and manganese acetate, the acidic aluminum salt is selected from one or more of aluminum sulfate, aluminum nitrate and aluminum chloride, the alkaline meta-aluminate solution is selected from one or two of sodium meta-aluminate solution and potassium meta-aluminate solution, and one or more of ammonia solution, sodium hydroxide solution, sodium carbonate solution, potassium hydroxide solution and potassium carbonate solution.
Further, when preparing the acidic manganese salt solution, the acidic aluminum salt solution and the alkaline meta-aluminate solution, respectively, it is preferable that the acidic manganese salt solution has a mass concentration of 5 to 20% in terms of MnO, and the acidic aluminum salt solution has a mass concentration of Al 2 O 3 The mass concentration is 1-10%, the alkaline aluminum salt solution uses Al 2 O 3 The mass concentration is 5% -25%.
Further, the steps of neutralization and gelling, aging, separation, drying, molding and roasting in the step 1) are preferably as follows: mixing an acidic manganese salt solution and an acidic aluminum salt solution, adding the mixed solution and an alkaline meta-aluminate solution into a reaction container added with deionized water in parallel, keeping the reaction temperature at 20-60 ℃, controlling the pH value of the system at 6-9, reacting for 0.5-2.5 h, heating to 60-90 ℃ for ageing for 0.5-3 h, carrying out solid-liquid separation, fully pulping and washing with deionized water, and drying at 90-120 ℃ to obtain the manganese-aluminum composite oxide; then adding dilute nitric acid, kneading into a plastic body, extruding strips for molding, drying and roasting to obtain the manganese-aluminum composite material; wherein the mass concentration of the nitric acid is 0.5-10%; wherein the roasting temperature is 400-700 ℃.
In the preparation method of the invention, the dipping method in the step 3) is preferably normal pressure dipping or vacuum dipping, the dipping time is 0.5-12 h, the drying temperature is 60-120 ℃, the drying time is 3-24 h, the roasting temperature is 400-800 ℃, and the roasting time is 3-12 h.
In the above preparation method of the present invention, the reduction method described in step 4) is preferably liquid-phase or gas-phase reduction, wherein the liquid-phase reduction is performed by using formaldehyde or hydrazine hydrate as a reducing agent, and the gas-phase reduction is performed under a hydrogen atmosphere.
The preparation method adopts a mode of neutralizing and gelling manganese salt and aluminum salt to prepare the manganese-aluminum composite oxide, realizes the uniform recombination of manganese oxide and aluminum oxide in atomic scale, further disperses palladium and auxiliary metal on the manganese-aluminum composite material through impregnation, realizes the alloying of noble metal, auxiliary metal and manganese oxide through roasting and reduction, and ensures that the active metal plays the maximum role through the regulation of the auxiliary metal on the palladium and the manganese oxide. In the deoxidizing process of olefin raw materials containing hydrogen, manganese oxide deeply removes trace oxygen in a chemical deoxidizing mode at a lower reaction temperature, and meanwhile, noble metal and auxiliary metal adsorb hydrogen to obtain activated hydrogen atoms, so that the active hydrogen atoms can be used for reducing high-valence manganese generated by deoxidizing reaction, and in-situ regeneration of the manganese oxide is realized. Meanwhile, the lower noble metal and auxiliary metal content and the existence of a large amount of surrounding manganese oxide avoid the adsorption of olefin molecules, further avoid the activation of olefin molecules and furthest reduce the selectivity of hydrogenation reaction and polymerization reaction of olefin.
The invention prepares the highly dispersed and composite difunctional deoxidizing catalyst by dipping noble metal and auxiliary metal in the manganese-aluminum composite material, overcomes the defects of the prior art, has simple preparation process and low cost, and is easy to carry out industrial production.
The specific embodiment is as follows:
the technical scheme and technical effects of the invention are further described below with reference to specific embodiments.
Example 1
Manganese nitrate solution with MnO concentration of 16% and Al 2 O 3 Mixing 8% aluminum sulfate solution according to a mass ratio of 1:2 to obtain an acidic solution, adding 9.0kg of bottom water into a 50L stirring kettle, heating to 35-40 ℃, and adding the acidic solution and Al in parallel under the condition of rapid stirring 2 O 3 Concentration is 12%, caustic ratio alpha k The pH value of a system is controlled to be 7.0-7.5, the feeding time is controlled to be 1h, 9.0kg of acid solution and 12.8kg of sodium metaaluminate solution are added in total, then the feeding is stopped, the temperature is heated to 90 ℃, the aging is carried out for 2.5h, the solid-liquid separation is carried out, deionized water is used for full washing, the impurity removal is carried out, the solid-liquid separation is transferred to a baking oven at 120 ℃ for drying, the manganese-aluminum composite oxide is obtained, then 3% dilute nitric acid is added for kneading into a plastic body, the plastic body is extruded for molding, the plastic body is dried at 120 ℃ after being dried overnight at room temperature, the molded manganese-aluminum composite material 1 is obtained after roasting at 550 ℃ for 6h, and the water absorption rate is measured to be 70%.
Adding 0.44g of palladium nitrate and 22.0g of copper nitrate into 350g of deionized water, fully dissolving, adding the impregnating solution into an impregnating tank filled with 500g of manganese-aluminum composite material 1 by adopting an atmospheric pressure impregnating mode, fully impregnating for 2 hours, drying at 80 ℃ for 12 hours, transferring to a muffle furnace, roasting at 500 ℃ for 4 hours, reducing in 400 ℃ for 6 hours, cooling to room temperature, and obtaining deoxidizer A with Pd content of 0.04%, cu content of 1.48% and MnO content of 18.94%. 20mL of catalyst A is taken and filled into a fixed bed reactor, the feed composition is 20.0% of ethylene, 5.0% of hydrogen, 0.50% of oxygen and the balance of nitrogen, and the outlet gas composition is detected under the conditions that the pressure is 2.0MPa, the temperature is 60 ℃ and the space velocity is 10000h < -1 >, the oxygen content is 0.01ppm, and the ethylene retention rate is 99.5%.
Example 2
Adding 0.22g of palladium nitrate and 1.20g of silver nitrate into 350g of deionized water, fully dissolving, adding the impregnating solution into a vacuum impregnation tank filled with 500g of manganese-aluminum composite material 1 by adopting a vacuum impregnation mode, fully impregnating for 1h, drying at 80 ℃ for 12h, transferring to a muffle furnace, roasting at 550 ℃ for 3h, reducing in hydrogen at 350 ℃ for 6h, cooling to room temperature, and obtaining deoxidizer B with Pd content of 0.02%, ag content of 0.15% and MnO content of 19.20%. 20mL of catalyst B is taken and filled into a fixed bed reactor, the feed composition is 20.0% of ethylene, 5.0% of hydrogen, 0.50% of oxygen and the balance of nitrogen, and the outlet gas composition is detected under the conditions that the pressure is 3.0MPa, the temperature is 80 ℃ and the space velocity is 10000h < -1 >, the oxygen content is 0.03ppm, and the ethylene retention rate is 99.4%.
Example 3
Adding 0.33g of palladium nitrate and 0.23g of gold chloride into 350g of deionized water, fully dissolving, adding the impregnating solution into a vacuum impregnation tank filled with 500g of manganese-aluminum composite material 1 by adopting a vacuum impregnation mode, fully impregnating for 1h, drying for 8h at 100 ℃, transferring to a muffle furnace, roasting for 3h at 550 ℃, reducing for 4h in hydrogen at 350 ℃, and cooling to room temperature to obtain deoxidizer C with Pd content of 0.03%, au content of 0.03% and MnO content of 19.22%. 20mL of catalyst C is taken and filled into a fixed bed reactor, the feed composition is 20.0% of ethylene, 5.0% of hydrogen, 0.50% of oxygen and the balance of nitrogen, and the outlet gas composition is detected under the conditions that the pressure is 5.0MPa, the temperature is 40 ℃ and the space velocity is 5000h < -1 >, the oxygen content is 0.02ppm, and the ethylene retention rate is 98.0%.
Example 4
Manganese nitrate solution with MnO concentration of 16% and Al 2 O 3 Mixing 8% aluminum sulfate solution according to a mass ratio of 1:5 to obtain an acidic solution, adding 9.0kg of bottom water into a 50L stirring kettle, heating to 45-50 ℃, and adding the acidic solution and Al in parallel under the condition of rapid stirring 2 O 3 Concentration is 12%, caustic ratio alpha k 1.40 of sodium metaaluminate solution, controlling the pH value of the system to be 7.5-8.0, adding the materials for 1h, adding 9.0 in totalThe feeding is stopped after kg of acid solution and 11.8kg of sodium metaaluminate solution, then the mixture is heated to 90 ℃, aged for 2.0h, subjected to solid-liquid separation, fully washed by deionized water, transferred to a baking oven at 120 ℃ for drying after impurity removal, and finally manganese-aluminum composite oxide is obtained, then 2.5% dilute nitric acid is added for kneading into a plastic body, the plastic body is extruded for molding, dried at 120 ℃ after being dried overnight at room temperature, baked for 6h at 520 ℃ to obtain molded manganese-aluminum composite material 2, and the water absorption rate of the molded manganese-aluminum composite material 2 is measured to be 77%.
Adding 0.44g of palladium nitrate and 22.0g of copper nitrate into 385g of deionized water, fully dissolving, adding the impregnating solution into a vacuum impregnation tank filled with 500g of manganese-aluminum composite material 1 by adopting a vacuum impregnation mode, fully impregnating for 0.5h, drying for 6h at 120 ℃, transferring to a muffle furnace, roasting for 4h at 550 ℃, reducing for 4h in hydrogen at 350 ℃, and cooling to room temperature to obtain the deoxidizer D with the Pd content of 0.04%, the Cu content of 1.48% and the MnO content of 10.48%. 20mL of catalyst D is taken and put into a fixed bed reactor, the feed composition is 20.0% of ethylene, 5.0% of hydrogen, 0.50% of oxygen and the balance of nitrogen, and under the conditions of the pressure of 2.0MPa, the temperature of 60 ℃ and the airspeed of 10000h-1, the outlet gas composition is detected, the oxygen content is 0.07ppm, and the ethylene retention rate is 99.9%.
Example 6
Adding 0.55g of palladium nitrate and 1.20g of silver nitrate into 385g of deionized water, fully dissolving, adding the impregnating solution into a vacuum impregnation tank filled with 500g of manganese-aluminum composite material 2 by adopting a vacuum impregnation mode, fully impregnating for 1h, drying at 80 ℃ for 12h, transferring to a muffle furnace for roasting at 550 ℃ for 3h, transferring to a 10% hydrazine hydrate solution for reducing at 90 ℃ for 1h, cooling to room temperature, and drying at 120 ℃ to obtain the deoxidizer E with Pd content of 0.05%, ag content of 0.15% and MnO content of 10.62%. 20mL of catalyst E is taken and filled into a fixed bed reactor, the feed composition is 20.0% of ethylene, 5.0% of hydrogen, 0.50% of oxygen and the balance of nitrogen, and the outlet gas composition is detected under the conditions that the pressure is 2.0MPa, the temperature is 60 ℃ and the space velocity is 10000h < -1 >, the oxygen content is 0.03ppm, and the ethylene retention rate is 99.1%.
Example 6
385g of deionized water is added with 0.25g of palladium chloride and 0.23g of gold chloride, and the mixture is fullyAfter dissolution, the impregnating solution is added into an impregnating tank filled with 500g of the manganese-aluminum composite material 2 by adopting an atmospheric pressure impregnation mode, fully impregnated for 3 hours, then dried for 8 hours at 120 ℃, transferred to a muffle furnace for roasting at 550 ℃ for 6 hours, then reduced for 4 hours in hydrogen at 350 ℃, cooled to room temperature, and finally deoxidizer F with Pd content of 0.03%, au content of 0.03% and MnO content of 10.63% is obtained. 20mL of catalyst F is taken and filled into a fixed bed reactor, the feed composition is ethylene 20.0%, hydrogen 5.0%, oxygen 0.50% and the balance nitrogen, and the pressure is 2.0MPa, the temperature is 60 ℃ and the space velocity is 10000h -1 Under the conditions, the outlet gas composition was measured, the oxygen content was 0.04ppm, and the ethylene retention was 99.0%.
Life test
50mL of catalyst A is taken and filled into a fixed bed reactor, the feed composition is 20.0 percent of ethylene, 5.0 percent of hydrogen, 0.50 percent of oxygen and the balance of nitrogen, a 2000h life experiment is carried out under the conditions of 2.0MPa of pressure, 60 ℃ of temperature and 10000h < -1 > of airspeed, the content of outlet oxygen is kept below 0.03ppm, the ethylene retention rate is 99.4 to 99.7 percent, and the result is shown in Table 1.
Table 1 deoxidizer life test
Reaction time h | 192 | 384 | 576 | 768 | 960 | 1152 | 1344 | 1536 | 1728 | 1920 |
Outlet oxygen content ppm | 0.01 | 0.01 | 0.02 | 0.02 | 0.01 | 0.02 | 0.01 | 0.01 | 0.02 | 0.01 |
Ethylene retention% | 99.6 | 99.5 | 99.5 | 99.4 | 99.6 | 99.4 | 99.7 | 99.6 | 99.5 | 99.5 |
Description: in examples 1-6 and life test, ethylene retention refers to the ratio of the volume fraction of ethylene to nitrogen in the product divided by the ratio of the volume fraction of ethylene to nitrogen in the feed.
Claims (9)
1. The catalyst for removing trace oxygen from olefin is characterized by comprising a catalytic active component and a carrier, wherein the catalytic active component consists of a main catalytic active component and a co-catalytic active component, the main catalytic active component comprises palladium and manganese oxide, the palladium content is 0.01% -0.1% and the manganese oxide content is 1% -20% by weight of the catalyst, the co-catalytic active component is one or more of copper, silver and gold, the content is 0.01% -5.0%, the carrier is alumina, and the preparation method of the catalyst comprises the following steps:
1) Mixing an acidic manganese salt solution and an acidic aluminum salt solution to form an acidic solution, adding the acidic solution and an alkaline meta-aluminate solution into deionized water in parallel, neutralizing to form gel, aging, washing, drying, adding dilute nitric acid, kneading to form a plastic body, extruding strips to form, drying, and roasting to obtain a formed manganese-aluminum composite material;
2) Dissolving calculated amounts of soluble palladium salt and soluble group IB metal salt in deionized water, and uniformly stirring to obtain an impregnating solution; wherein the soluble palladium salt is selected from one or more of palladium nitrate, palladium chloride, palladium acetate and palladium acetylacetonate; the soluble IB group metal salt is selected from one or more of copper nitrate, silver nitrate and gold chloride;
3) Soaking the composite material in the manganese-aluminum material according to an equal volume method, and drying and roasting the composite material to obtain a deoxidizer precursor;
4) And reducing the deoxidizer precursor to obtain a deoxidizer product.
2. The catalyst of claim 1, wherein the metal palladium content is 0.01% -0.05%, the manganese oxide content is 10% -20%, and the total content of copper, silver and gold is 0.01% -2.0%.
3. A process for preparing a catalyst for removing trace amounts of oxygen from olefins according to claim 1, comprising the steps of:
1) Mixing an acidic manganese salt solution and an acidic aluminum salt solution to form an acidic solution, adding the acidic solution and an alkaline meta-aluminate solution into deionized water in parallel, neutralizing to form gel, aging, washing, drying, adding dilute nitric acid, kneading to form a plastic body, extruding strips to form, drying, and roasting to obtain a formed manganese-aluminum composite material;
2) Dissolving calculated amounts of soluble palladium salt and soluble group IB metal salt in deionized water, and uniformly stirring to obtain an impregnating solution; wherein the soluble palladium salt is selected from one or more of palladium nitrate, palladium chloride, palladium acetate and palladium acetylacetonate; the soluble IB group metal salt is selected from one or more of copper nitrate, silver nitrate and gold chloride;
3) Soaking the composite material in the manganese-aluminum material according to an equal volume method, and drying and roasting the composite material to obtain a deoxidizer precursor;
4) And reducing the deoxidizer precursor to obtain a deoxidizer product.
4. The preparation method according to claim 3, wherein the acidic manganese salt in the step 1) is selected from one or more of manganese nitrate, manganese chloride, manganese sulfate and manganese acetate, the acidic aluminum salt is selected from one or more of aluminum sulfate, aluminum nitrate and aluminum chloride, the alkaline meta-aluminate solution is selected from one or two of sodium meta-aluminate solution and potassium meta-aluminate solution, and one or more of ammonia solution, sodium hydroxide solution, sodium carbonate solution, potassium hydroxide solution and potassium carbonate solution.
5. The preparation method of claim 4, wherein the mass concentration of the acidic manganese salt solution is 5% -20% in terms of MnO, and the acidic aluminum salt solution is Al 2 O 3 The mass concentration is 5% -15%, and the alkaline meta-aluminate solution is prepared from Al 2 O 3 The mass concentration is 5% -25%.
6. A process according to claim 3, wherein the neutralization and gelling and aging conditions in step 1) are as follows: the neutralization and gel forming reaction temperature is 20-60 ℃, the pH value of the system is controlled to be 6-9, the reaction is carried out for 0.5-2.5 h, and then the reaction is heated to 60-90 ℃ and aged for 0.5-3 h.
7. The method according to claim 3, wherein the baking temperature in the step 1) is 400 to 700 ℃.
8. The method of claim 3, wherein the isovolumetric impregnation method in step 3) is atmospheric impregnation or vacuum impregnation, the impregnation time is 0.5-12 h, the drying temperature is 60-120 ℃, the drying time is 3-24 h, the roasting temperature is 400-800 ℃, and the roasting time is 3-12 h.
9. The method of claim 3, wherein the reduction in step 4) is a liquid-phase or gas-phase reduction using formaldehyde or hydrazine hydrate as a reducing agent, and the gas-phase reduction is carried out in a hydrogen atmosphere.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1070128A (en) * | 1991-09-06 | 1993-03-24 | 中国科学院大连化学物理研究所 | A kind of palladium/manganese oxide deoxidizing agent |
CN1724114A (en) * | 2005-06-20 | 2006-01-25 | 天津化工研究设计院 | Double functional deoxidation agent and production process thereof |
CN101703919A (en) * | 2009-11-12 | 2010-05-12 | 北京北大先锋科技有限公司 | Load type manganese and copper series deoxidizer and preparation method and application thereof |
CN110721707A (en) * | 2019-10-30 | 2020-01-24 | 大连凯特利催化工程技术有限公司 | Low-temperature deoxidation catalyst for synthesis gas and preparation and application thereof |
-
2022
- 2022-06-12 CN CN202210651672.3A patent/CN115025779B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1070128A (en) * | 1991-09-06 | 1993-03-24 | 中国科学院大连化学物理研究所 | A kind of palladium/manganese oxide deoxidizing agent |
CN1724114A (en) * | 2005-06-20 | 2006-01-25 | 天津化工研究设计院 | Double functional deoxidation agent and production process thereof |
CN101703919A (en) * | 2009-11-12 | 2010-05-12 | 北京北大先锋科技有限公司 | Load type manganese and copper series deoxidizer and preparation method and application thereof |
CN110721707A (en) * | 2019-10-30 | 2020-01-24 | 大连凯特利催化工程技术有限公司 | Low-temperature deoxidation catalyst for synthesis gas and preparation and application thereof |
Non-Patent Citations (4)
Title |
---|
Effect of preparation method on the performance of Pd‐MnOx/γ‐Al2O3 monolithic catalysts for ground‐level O3 decomposition;Chengjun Ren等;《Chinese Journal of Catalysis 》;第1883–1891页 * |
Enhanced hydrodeoxygenation of lignin-derived anisole to arenes catalyzed by Mn-doped Cu/Al2O3;Xiaofei Wang 等;《Green Energy & Environment 》;第927–937页 * |
脱氧催化剂的研究 、 工业应用及发展趋势;李小定;《湖北化工》(第2期);第2-4页 * |
脱氧剂的研究现状;景晓燕等;《应用科技》;第32卷(第8期);第62-64页 * |
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