CN114225940A - Heterogeneous catalyst for hydrogenation of styrene thermoplastic elastomer - Google Patents
Heterogeneous catalyst for hydrogenation of styrene thermoplastic elastomer Download PDFInfo
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- CN114225940A CN114225940A CN202111610922.0A CN202111610922A CN114225940A CN 114225940 A CN114225940 A CN 114225940A CN 202111610922 A CN202111610922 A CN 202111610922A CN 114225940 A CN114225940 A CN 114225940A
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- China
- Prior art keywords
- heterogeneous catalyst
- slurry
- thermoplastic elastomer
- hydrogenation
- styrene
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 65
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 34
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- 229920001400 block copolymer Polymers 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 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 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 4
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 150000004687 hexahydrates Chemical class 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 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 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 claims 6
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
- 239000012018 catalyst precursor Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 239000002174 Styrene-butadiene Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 230000005311 nuclear magnetism Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229920006132 styrene block copolymer Polymers 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 nickel acetylacetonate dihydrate Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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Classifications
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- 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
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/02—Hydrogenation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a heterogeneous catalyst for hydrogenation of a styrene thermoplastic elastomer, which comprises, by mass, 5-80 wt% of an active component nickel, 0.01-5 wt% of a second active component, 5-80 wt% of a silicon source and 5-80 wt% of an aluminum source. The heterogeneous catalyst obtained by the invention not only has higher hydrogenation reaction activity, but also is easy to separate from the product after reaction, avoids the problems of separation and recycling of the catalyst and the product existing in the use of the homogeneous catalyst, and has good industrial application prospect.
Description
Technical Field
The invention relates to the field of catalyst preparation and high-molecular catalytic hydrogenation, in particular to a heterogeneous catalyst for hydrogenation of a styrene thermoplastic elastomer.
Background
Styrene-based thermoplastic elastomers (SBCs), also known as styrene block copolymers, are mainly block copolymers with styrene, butadiene or isoprene as polymerization monomers, and the SBCs are mainly of the types styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS) and styrene-butadiene copolymer (SBR).
SIS is a styrene thermoplastic elastomer prepared by anionic polymerization of styrene and isoprene as raw materials. SIS is widely used in materials such as automobile parts, parts of rubber mechanical products, rubber shoes, adhesives, electric wires and cables, paints, and hoses.
SBS is widely applied to rubber products, and the sole made of SBS as a main material is not only pure in color but also comfortable and wear-resistant, so that SBS is a mainstream material for producing white sports shoe soles at present and is widely applied to various large sports brands.
SBR is the most commonly used synthetic rubber in the world, and the excellent wear resistance and aging resistance of the SBR enables the SBR to be widely applied to the manufacturing and processing fields of tires, football, hose belts, wires, cables and the like.
However, the three styrene thermoplastic elastomer material blocks all have a large number of C = C bonds, so that the styrene thermoplastic elastomer material has poor aging resistance such as heat resistance, oxygen resistance, ozone resistance, ultraviolet radiation resistance and the like, is easy to degrade when exposed to oxygen, ozone and ultraviolet radiation, and limits the application of the styrene thermoplastic elastomer material in high-tech fields under high temperature and other extreme conditions. Therefore, catalytic hydrogenation modification of the catalyst is an important approach to solve the problem.
In addition to the C = C double bond, the above styrene-based thermoplastic elastomer also contains a large number of benzene rings, and a novel Copolymer, a Cyclic Block Copolymer (CBC for short), is obtained by hydrogenating all the double bonds of the benzene rings and the conjugated olefin. Compared with SBC, CBC has the advantages of extremely clean and ultrahigh visible light and Ultraviolet (UV) transparency (including deep ultraviolet UVC), excellent chemical resistance, Gamma (Gamma) resistance, electron beam irradiation sterilization and the like, and CBC has the characteristics of excellent thermal oxidation stability, low water absorption rate, low density and the like in the aspect of processing and is suitable for processing procedures such as extrusion, injection molding, blow molding and the like, so that the SBC has a wide application prospect in the field of medical consumables, and is expected to be applied to prefilled injectors, small medicine bottles/ampoules, detection consumables-UV cuvettes, microporous plates UV, high-flux microporous plates, microporous plates for fluorescent markers, microfluidic chips and the like.
Many studies on heterogeneous hydrogenation catalysts have been reported, and conventional catalysts include nickel-based catalysts, noble metals such as platinum and palladium. For example, patent CN10245689B reports a heterogeneous nickel-based catalyst prepared by slurrying a support alumina and or silica with active metal nickel and an auxiliary agent, and then reacting with a precipitant, and used for hydrogenation of petroleum resin. Patent CN 109482189 a reports a preparation method of a nickel-based C5 petroleum resin hydrogenation catalyst, the catalyst prepared by the preparation method has the advantages of high catalyst activity, small dosage, safe use and the like, and compared with a homogeneous catalyst, the catalyst has the advantage that the product and the catalyst are easy to separate, and the separation cost can be significantly reduced in industrial production. The patent CN101700494B uses noble metal Pd/Ru/Rh catalyst for hydrogenation reaction.
At present, the catalyst for hydrogenation modification of the styrene thermoplastic elastomer is mainly a homogeneous catalyst. For example, patent CN 107828000 a reports a method for preparing SEPS by homogeneous catalytic hydrogenation of styrene-isoprene-styrene triblock copolymer, and the homogeneous catalyst prepared by the method has the advantages of simple and easy experimental operation, high catalytic efficiency, and the like. However, a significant disadvantage of homogeneous catalysts is the difficulty in separating the catalyst from the product, which greatly increases the production cost. While most commercial processes are heterogeneous catalyst catalyzed reactions, this is mainly due to the advantage of heterogeneous catalysts that the products can be easily separated from the catalyst. At present, no report is found about the application of nickel-based bimetallic catalyst in the hydrogenation modification of styrene thermoplastic elastomer to prepare cyclic block copolymer.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a heterogeneous catalyst which is easy to separate from a product and is used for hydrogenation of a styrene thermoplastic elastomer.
In order to solve the above problems, the heterogeneous catalyst for hydrogenation of styrene thermoplastic elastomer according to the present invention is characterized in that: the catalyst comprises, by mass, 5-80 wt% of an active component nickel, 0.01-5 wt% of a second active component, 5-80 wt% of a silicon source and 5-80 wt% of an aluminum source.
The active component nickel is one or more of nickel nitrate, nickel chloride, nickel acetylacetonate and nickel carbonyl.
The second active component is one or more of metal palladium, platinum, copper and cobalt; the palladium is derived from one or more of palladium nitrate, palladium chloride and palladium acetate; the platinum is derived from one or more of chloroplatinic acid hexahydrate and platinum acetylacetonate; the copper is selected from one or more of copper nitrate, copper chloride and copper sulfate pentahydrate; the cobalt is derived from one or more of cobalt nitrate hexahydrate, cobalt chloride and cobalt acetylacetonate.
The silicon source is one or more of sodium silicate, fumed silica and silica sol.
The aluminum source is one or more of aluminum nitrate nonahydrate, aluminum chloride, aluminum oxide and sodium metaaluminate.
The preparation method of the heterogeneous catalyst for hydrogenation of the styrene thermoplastic elastomer comprises the following steps:
dissolving a silicon source and a surfactant in a solvent to form slurry A; the mass ratio of the silicon source, the surfactant and the solvent is 1: 0.5-5: 25 to 500 parts by weight;
dissolving soluble salts of active components, namely nickel, soluble salts of a second active component and soluble salts of an aluminum source in water to obtain slurry B containing the active components, namely nickel and the second active component; the molar mass ratio of the active component nickel to the second active component to water is 1: 0.0002 to 0.48: 5000-50000;
heating the slurry A to 50-80 ℃; then adding the slurry B and 0.5-5 wt% of aqueous solution of alkaline soluble salt into the slurry A in a parallel flow manner, and controlling the pH of the slurry in the reaction kettle to be 7.0-11.0 in the process; the alkaline soluble salt is one or more of ammonia water, sodium hydroxide, sodium carbonate and urea;
fourthly, continuously stirring the solution for 12 hours after the slurry B is dropwise added to obtain slurry C;
filtering, washing and drying the slurry C to obtain a precursor of the heterogeneous catalyst;
sixthly, fully roasting the precursor of the heterogeneous catalyst in the air, and reducing the precursor in a hydrogen atmosphere to obtain the heterogeneous catalyst.
The method comprises the step of preparing the surface active agent by using one or more of ethylene glycol, polyethylene glycol, polyvinyl pyrrolidone and urea.
The solvent in the step is water.
The application of the heterogeneous catalyst for hydrogenation of the styrene thermoplastic elastomer is characterized in that: under the action of the heterogeneous catalyst, 1.0-10.0 wt% of styrene thermoplastic elastomer and H2Carrying out hydrogenation reaction at the reaction temperature of 353-433K, the reaction time of 3-15 h and the reaction pressure of 0.1-8.0 MPa to generate a cyclic block copolymer; the molar ratio of the heterogeneous catalyst to the styrene thermoplastic elastomer is 1 x 10-3~1×10-1：1。
The styrene thermoplastic elastomer is one of styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS) and styrene-butadiene copolymer (SBR).
Compared with the prior art, the invention has the following advantages:
1. the heterogeneous catalyst prepared by the invention has the advantages that the reduction temperature of the catalyst is obviously reduced due to the introduction of the second metal, the dispersion degree of the nickel metal is improved, and the sintering resistance of the catalyst can be improved due to the coating of the carrier, so that the heterogeneous catalyst has higher hydrogenation reaction activity.
2. Compared with a homogeneous catalyst, the prepared heterogeneous catalyst is easy to separate from a product after reaction, the problems of separation and recycling of the catalyst and the product existing in the use of the homogeneous catalyst are solved, and the method has a good industrial application prospect.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a nuclear magnetic resonance spectrum of the raw material SIS in example 7 of the present invention.
FIG. 2 is a nuclear magnetic resonance spectrum of a cyclic block copolymer obtained by hydrogenation of the SIS starting material in example 7 of the present invention.
FIG. 3 is the nuclear magnetic resonance spectrum of SBS of example 12.
FIG. 4 is the NMR spectrum of the product of hydrogenation of SBS in example 12 of the present invention.
Detailed Description
The heterogeneous catalyst for hydrogenation of the styrene thermoplastic elastomer comprises, by mass (g), 5-80 wt% of active component nickel, 0.01-5 wt% of a second active component, 5-80 wt% of a silicon source and 5-80 wt% of an aluminum source.
Wherein: the active component nickel is one or more of nickel nitrate, nickel chloride, nickel acetylacetonate and nickel carbonyl.
The second active component is one or more of metal palladium, platinum, copper and cobalt; the palladium is one or more of palladium nitrate, palladium chloride and palladium acetate; the platinum is selected from one or more of chloroplatinic acid hexahydrate and platinum acetylacetonate; the copper is selected from one or more of copper nitrate, copper chloride and copper sulfate pentahydrate; the cobalt is selected from one or more of cobalt nitrate hexahydrate, cobalt chloride and cobalt acetylacetonate.
The silicon source is one or more of sodium silicate, fumed silica and silica sol.
The aluminum source is one or more of aluminum nitrate nonahydrate, aluminum chloride, aluminum oxide and sodium metaaluminate.
The preparation method of the heterogeneous catalyst comprises the following steps:
dissolving a silicon source and a surfactant in a solvent to form slurry A; the mass ratio (g/g) of the silicon source, the surfactant and the solvent is 1: 0.5-5: 25 to 500.
Wherein: the surfactant is one or more of ethylene glycol, polyethylene glycol, polyvinylpyrrolidone and urea. The solvent is water.
Dissolving soluble salts of active components, namely nickel, soluble salts of a second active component and soluble salts of an aluminum source in water to obtain slurry B containing the active components, namely nickel and the second active component; the molar mass ratio of the active component nickel to the second active component to water is 1: 0.0002 to 0.48: 5000-50000.
Heating the slurry A to 50-80 ℃; and then adding the slurry B and 0.5-5 wt% of aqueous solution of alkaline soluble salt into the slurry A in a parallel flow manner, and controlling the pH of the slurry in the reaction kettle to be 7.0-11.0 in the process. During the concurrent dropwise addition, the pH during the dropwise addition was kept constant by controlling the dropwise addition rate.
Wherein: the alkaline soluble salt is one or more of ammonia water, sodium hydroxide, sodium carbonate and urea.
After the slurry B is completely added, the solution is continuously stirred for 12 hours to obtain slurry C.
And filtering, washing and drying the slurry C to obtain a precursor of the heterogeneous catalyst.
Wherein: filtering and washing by suction filtration or centrifugation until the pH value is 7.0.
Drying is carried out by adopting an oven, the drying temperature is 333K-393K, and the drying time is 6-12 h.
Sixthly, fully roasting a precursor of the heterogeneous catalyst in the air to remove the surfactant; roasting is carried out by adopting a muffle furnace, the roasting temperature is 573K-773K, and the roasting time is 2-6 h. And reducing the mixture in hydrogen atmosphere to obtain the heterogeneous catalyst. The reduction is carried out by adopting a tubular atmosphere furnace, the reduction atmosphere is hydrogen atmosphere, the gas flow rate is 10-100 ml/min, the reduction temperature is 573K-873K, and the reduction time is 2-10 h.
The application of a heterogeneous catalyst for hydrogenation of styrene thermoplastic elastomer comprises the following steps: under the action of the heterogeneous catalyst, 1.0-10.0 wt% of styrene thermoplastic elastomer and H2Carrying out hydrogenation reaction at 353-433K for 3-15 h under 0.1-8.0 MPa to obtain the cyclic block copolymer.
Wherein: the molar ratio of the heterogeneous catalyst to the styrene thermoplastic elastomer is 1 x 10-3~1×10-1：1。
The styrene-based thermoplastic elastomer is one of styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), and styrene-butadiene copolymer (SBR).
Reagents, materials, devices and the like used in the following examples are commercially available unless otherwise specified.
Example 1 a method for preparing a heterogeneous catalyst comprising the steps of:
first, 1.8 g of sodium silicate and 1.5 g of ethylene glycol were dissolved in 50 ml of water to obtain slurry a containing carrier component silicon.
Weighing 3.0 g of nickel chloride, 0.50 mg of palladium chloride and 0.27 g of gamma-Al2O3And dissolved in 50 ml of deionized water to obtain slurry B containing active components of nickel and palladium and containing a carrier component of aluminum.
Heating the slurry A to 50 ℃; then, slurry B and an aqueous ammonia solution having a mass fraction of 5 wt% were added concurrently to the slurry A, during which the pH of the reaction tank slurry was controlled to 7.0. During the concurrent dropwise addition, the pH during the dropwise addition was kept constant by controlling the dropwise addition rate.
After the slurry B is completely added, the solution is continuously stirred for 12 hours to obtain slurry C.
And fifthly, carrying out suction filtration and deionized water washing on the slurry C to be neutral, and drying 373K in an oven for 12h to obtain a precursor of the heterogeneous catalyst.
Sixthly, heterogeneous catalysisAnd roasting the precursor of the catalyst in a muffle furnace at 573K for 6h to obtain the catalyst precursor. The precursor is put in a tube furnace at H2Reducing for 6 hours under 773K in the atmosphere, wherein the hydrogen flow rate is 50 ml/min, and obtaining 60Ni-0.01Pd/SiO after reduction2-Al2O3A heterogeneous catalyst.
Example 2 a method of preparing a heterogeneous catalyst comprising the steps of:
first, 7.6 g of silica Sol (SiO)2Content 40 wt%), 3.8 g of polyethylene glycol was dissolved in 210 ml of water to obtain slurry A containing carrier component silicon.
Weighing 1.0 g of nickel acetylacetonate dihydrate, 0.20g of palladium acetate and 0.50g of sodium metaaluminate, and dissolving in 210 ml of deionized water to obtain slurry B containing active components of nickel and palladium and a carrier component of aluminum.
Heating the slurry A to 80 ℃; then, the slurry B and a 0.50 wt% sodium hydroxide solution by mass fraction were concurrently added to the slurry a, during which the pH of the reaction tank slurry was controlled to 11.0. During the concurrent dropwise addition, the pH during the dropwise addition was kept constant by controlling the dropwise addition rate.
After the slurry B is completely added, the solution is continuously stirred for 12 hours to obtain slurry C.
And fifthly, carrying out suction filtration and deionized water washing on the slurry C to be neutral, and drying the obtained filter cake in an oven for 333K for 12h to obtain a precursor of the heterogeneous catalyst.
Sixthly, roasting the precursor of the heterogeneous catalyst in a muffle furnace at 773K for 2 hours to obtain the catalyst precursor. The precursor is put in a tube furnace at H2Reducing for 2h under the atmosphere of 573K, wherein the hydrogen flow rate is 10 ml/min, and obtaining 5Ni-2.4Pd/SiO after reduction2-Al2O3A heterogeneous catalyst.
Example 3 a method of preparing a heterogeneous catalyst comprising the steps of:
first, 3.0 g of silica Sol (SiO)2Content 40 wt%), 1.5 g of polyvinylpyrrolidone was dissolved in 120 ml of water to obtain slurry A containing carrier component silicon.
Weighing 3.0 g of nickel acetylacetonate dihydrate, 0.15g of palladium acetate and 13 g of anhydrous aluminum trichloride, and dissolving in 120 ml of deionized water to obtain slurry B containing active components of nickel and palladium and a carrier component of aluminum.
Heating the slurry A to 50 ℃; subsequently, slurry B and a 5.0 wt% sodium carbonate solution were added concurrently to the slurry a, during which the pH of the reaction tank slurry was controlled to 9.0. During the concurrent dropwise addition, the pH during the dropwise addition was kept constant by controlling the dropwise addition rate.
After the slurry B is completely added, the solution is continuously stirred for 12 hours to obtain slurry C.
And fifthly, carrying out suction filtration and deionized water washing on the slurry C to be neutral, and drying the obtained filter cake in a baking oven 393K for 6h to obtain a precursor of the heterogeneous catalyst.
Sixthly, roasting the precursor of the heterogeneous catalyst in a muffle furnace at 673K for 4 hours to obtain the catalyst precursor. The precursor is put in a tube furnace at H2Reducing for 6h under 673K in the atmosphere with the hydrogen flow rate of 50 ml/min to obtain 10Ni-0.5Pd/SiO2-Al2O3A heterogeneous catalyst.
Example 4 a method of preparing a heterogeneous catalyst comprising the steps of:
first, 0.4 g of fumed silica and 2.0 g of polyvinylpyrrolidone were dissolved in 200 ml of water to obtain slurry a containing carrier component silicon.
Weighing 10.5 g of nickel nitrate hexahydrate, 0.03g of chloroplatinic acid hexahydrate and 0.5 g of aluminum nitrate nonahydrate, and dissolving in 200 ml of deionized water to obtain slurry B containing active components of nickel and palladium and a carrier component of aluminum.
Heating the slurry A to 50 ℃; subsequently, slurry B and a 5.0 wt% urea solution were added concurrently to the slurry A, during which the pH of the reactor slurry was controlled to 7.5. During the concurrent dropwise addition, the pH during the dropwise addition was kept constant by controlling the dropwise addition rate.
After the slurry B is completely added, the solution is continuously stirred for 12 hours to obtain slurry C.
And fifthly, carrying out suction filtration and deionized water washing on the slurry C to be neutral, and drying 373K in an oven for 12h to obtain a precursor of the heterogeneous catalyst.
Sixthly, roasting the precursor of the heterogeneous catalyst in a muffle furnace for 6 hours under 573K to obtain the catalyst precursor. And roasting the precursor in a muffle furnace at 673K for 4 h to obtain the catalyst precursor. The precursor is put in a tube furnace at H2Reducing for 10 hours under the condition of 673K in the atmosphere, wherein the flow rate of hydrogen is 100 ml/min, and obtaining 80Ni-0.4Pt/SiO after reduction2-Al2O3A heterogeneous catalyst.
Example 5 a method of preparing a heterogeneous catalyst comprising the steps of:
first, 0.6 g of sodium silicate and 1.5 g of ethylene glycol were dissolved in 100 ml of water to obtain slurry a containing carrier component silicon.
Weighing 2.9 g of nickel nitrate hexahydrate, 0.45g of copper sulfate pentahydrate and 5.5 g of aluminum nitrate nonahydrate, and dissolving in 100 ml of deionized water to obtain slurry B containing active components of nickel and palladium and a carrier component of aluminum.
Heating the slurry A to 50 ℃; subsequently, slurry B and a 5.0 wt% sodium hydroxide solution were added concurrently to the slurry a, during which the pH of the reaction tank slurry was controlled to 7.0. During the concurrent dropwise addition, the pH during the dropwise addition was kept constant by controlling the dropwise addition rate.
After the slurry B is completely added, the solution is continuously stirred for 12 hours to obtain slurry C.
And fifthly, carrying out suction filtration and deionized water washing on the slurry C to be neutral, and drying 373K in an oven for 12h to obtain a precursor of the heterogeneous catalyst.
Sixthly, roasting the precursor of the heterogeneous catalyst in a muffle furnace at 673K for 4 hours to obtain the catalyst precursor. The precursor is put in a tube furnace at H2Reducing for 6 hours under the condition of 673K in the atmosphere, wherein the hydrogen flow rate is 50 ml/min, and obtaining 25Ni-4.9Cu/SiO after reduction2-Al2O3A heterogeneous catalyst.
Example 6 a method of preparing a heterogeneous catalyst comprising the steps of:
first layer 1.07 g of silica Sol (SiO)240 percent by weight) of ethylene glycol, 1.5 g of ethylene glycol is dissolved in 250 ml of water,slurry a containing the carrier component silicon is obtained.
5.8 g of nickel nitrate hexahydrate, 0.50g of cobalt nitrate hexahydrate and 1.0 g of aluminum nitrate nonahydrate are weighed and dissolved in 250 ml of deionized water, so that slurry B containing active components of nickel and palladium and a carrier component of aluminum is obtained.
Heating the slurry A to 50 ℃; then, the slurry B and an aqueous ammonia solution having a mass fraction of 0.5 wt% were concurrently added to the slurry A, during which the pH of the reaction tank slurry was controlled to 8.0. During the concurrent dropwise addition, the pH during the dropwise addition was kept constant by controlling the dropwise addition rate.
After the slurry B is completely added, the solution is continuously stirred for 12 hours to obtain slurry C.
And fifthly, carrying out suction filtration and deionized water washing on the slurry C to be neutral, and drying 373K in an oven for 12h to obtain a precursor of the heterogeneous catalyst.
Sixthly, roasting the precursor of the heterogeneous catalyst in a muffle furnace at 673K for 4 hours to obtain the catalyst precursor. The precursor is put in a tube furnace at H2Reducing for 6 hours under the condition of 673K in the atmosphere, wherein the hydrogen flow rate is 50 ml/min, and obtaining 76Ni-2.9Co/SiO after reduction2-Al2O3A heterogeneous catalyst.
Example 7
10 mg of the nickel-based catalyst obtained in example 1 was added to a batch reactor, 0.078g of the raw material SIS (the nuclear magnetic spectrum of which is shown in FIG. 1) was added to the batch reactor, 10 ml of cyclohexane was added as a solvent, 4 MPa of hydrogen was charged into the reactor, the reaction was carried out at 413K for 12 hours, the reaction product was centrifuged to obtain a supernatant, and the supernatant was analyzed by liquid nuclear magnetic resonance, and as a result, as shown in FIG. 2, H having a shift of 4.5 to 5.5 ascribed to the benzene ring and H having a shift of 6.0 to 7.5 ascribed to the unsaturated double bond on the main chain disappeared completely, indicating that the degree of hydrogenation was more than 99%. The specific analysis results are shown in Table 1.
Example 8
2.5 mg of the nickel-based catalyst obtained in example 2 was added to a batch reactor, 0.172g of SBS as a raw material was added to the batch reactor, 10 ml of cyclohexane was added as a solvent, 6 MPa of hydrogen was charged to the reactor, the reaction was carried out at 433K for 10 hours, the product after the reaction was centrifuged to obtain a supernatant, which was analyzed by liquid nuclear magnetism, and the analysis results are shown in Table 1.
Example 9
200 mg of the nickel-based catalyst obtained in example 3 was added to a batch reactor, 0.234g of SBR as a raw material was added to the batch reactor, 6 ml of cyclohexane was added as a solvent, 6 MPa of hydrogen was charged into the reactor, and the reaction was carried out at 353K for 12 hours, and the product after the reaction was centrifuged to obtain a supernatant, which was analyzed by liquid nuclear magnetism, and the analysis results are shown in Table 1.
Example 10
20 mg of the nickel-based catalyst obtained in example 4 was added to a batch reactor, 0.234g of SBS was added to the batch reactor, 6 ml of cyclohexane was added as a solvent, then 0.1 MPa of hydrogen was charged to the reactor, and the reaction was carried out at 433K for 15 hours, and the resultant was centrifuged to obtain a supernatant, which was analyzed by liquid nuclear magnetic resonance, and the analysis results are shown in Table 1.
Example 11
20 mg of the nickel-based catalyst obtained in example 5 was charged into a batch reactor, 0.234g of SIS as a raw material was charged into the batch reactor, 6 ml of cyclohexane was added as a solvent, 2 MPa of hydrogen was charged into the reactor, and the reaction was carried out at 393K for 8 hours, and the product after the reaction was centrifuged to obtain a supernatant, which was analyzed by liquid nuclear magnetism, and the analysis results are shown in Table 1.
Example 12
20 mg of the nickel-based catalyst obtained in example 6 was added to a batch reactor, 0.234g of raw material SBS (the nuclear magnetic spectrum of which is shown in FIG. 3) was added to the batch reactor, 6 ml of cyclohexane was added as a solvent, then 8 MPa of hydrogen was charged to the reactor, reaction was carried out at 413K for 10 hours, the reaction product was centrifuged to obtain a supernatant, and analysis was carried out by liquid nuclear magnetic resonance, and as a result, as shown in FIG. 4, H having a shift of 4.5 to 5.5 ascribed to the benzene ring and H having a shift of 6.0 to 7.5 ascribed to the unsaturated double bonds in the main chain (1, 4-mer and 3, 4-mer) were completely disappeared, indicating that the degree of hydrogenation was more than 99%. The specific analysis results are shown in Table 1.
Comparative example 1
Weighing 0.6 g of sodium silicate, 2.9 g of nickel nitrate hexahydrate and 5.5 g of aluminum nitrate nonahydrate, and dissolving in 100 ml of deionized water to obtain slurry containing an active component nickel and carrier components silicon and aluminum; and stirring the solution overnight, uniformly mixing, carrying out rotary evaporation and drying at 50 ℃, continuously drying the obtained sample in an oven at 373K for 12h, and then roasting in a muffle furnace at 673K for 4 h to obtain the catalyst precursor. The precursor is put in a tube furnace at H2Reducing for 6h under 773K in atmosphere, wherein the hydrogen flow rate is 50 ml/min, and obtaining the single-metal control sample catalyst after reduction.
Comparative example 2
Adding 20 mg of nickel acetylacetonate into a batch type reaction kettle, adding 0.234g of raw material SBS into the batch type reaction kettle, adding 6 ml of cyclohexane as a solvent, then filling 4 MPa of hydrogen into the reaction kettle, reacting for 10 hours at 413K, centrifuging the reacted product to obtain a supernatant, and analyzing by liquid nuclear magnetism, wherein the analysis result is shown in Table 1.
Comparative example 3
20 mg of the catalyst obtained in comparative example 1 was added to a batch reactor, 0.234g of SBS was added to the batch reactor, 6 ml of cyclohexane was added as a solvent, 4 MPa of hydrogen was charged to the reactor, the reaction was carried out at 413K for 10 hours, the product after the reaction was centrifuged to obtain a supernatant, which was analyzed by liquid nuclear magnetism, and the analysis results are shown in Table 1.
Table 1: evaluation results of catalysts used in examples 7 to 12 and comparative examples 2 to 3
From the above results in table 1, it can be seen that the prepared catalysts all have certain activity under the evaluation conditions, while the activity in comparative example 2 is lower, which may be because the homogeneous catalyst in comparative example 2 is not activated, the catalyst in comparative example 3 is a single active metal catalyst, and sintering of the catalyst occurs during the reduction process, resulting in reduction of catalytic reaction activity, whereas the introduction of the noble metal of the nickel-based bimetallic catalyst protected in the present invention not only serves as a promoter, but also helps to reduce the reduction temperature and avoid catalyst sintering to improve the dispersion degree of metallic nickel.
Claims (10)
1. A heterogeneous catalyst for hydrogenation of styrene thermoplastic elastomer is characterized in that: the catalyst comprises, by mass, 5-80 wt% of an active component nickel, 0.01-5 wt% of a second active component, 5-80 wt% of a silicon source and 5-80 wt% of an aluminum source.
2. The heterogeneous catalyst for hydrogenation of a styrenic thermoplastic elastomer according to claim 1, wherein: the active component nickel is one or more of nickel nitrate, nickel chloride, nickel acetylacetonate and nickel carbonyl.
3. The heterogeneous catalyst for hydrogenation of a styrenic thermoplastic elastomer according to claim 1, wherein: the second active component is one or more of metal palladium, platinum, copper and cobalt; the palladium is derived from one or more of palladium nitrate, palladium chloride and palladium acetate; the platinum is derived from one or more of chloroplatinic acid hexahydrate and platinum acetylacetonate; the copper is selected from one or more of copper nitrate, copper chloride and copper sulfate pentahydrate; the cobalt is derived from one or more of cobalt nitrate hexahydrate, cobalt chloride and cobalt acetylacetonate.
4. The heterogeneous catalyst for hydrogenation of a styrenic thermoplastic elastomer according to claim 1, wherein: the silicon source is one or more of sodium silicate, fumed silica and silica sol.
5. The heterogeneous catalyst for hydrogenation of a styrenic thermoplastic elastomer according to claim 1, wherein: the aluminum source is one or more of aluminum nitrate nonahydrate, aluminum chloride, aluminum oxide and sodium metaaluminate.
6. The method for preparing the heterogeneous catalyst for hydrogenation of the styrene-based thermoplastic elastomer as claimed in claim 1, comprising the steps of:
dissolving a silicon source and a surfactant in a solvent to form slurry A; the mass ratio of the silicon source, the surfactant and the solvent is 1: 0.5-5: 25 to 500 parts by weight;
dissolving soluble salts of active components, namely nickel, soluble salts of a second active component and soluble salts of an aluminum source in water to obtain slurry B containing the active components, namely nickel and the second active component; the molar mass ratio of the active component nickel to the second active component to water is 1: 0.0002 to 0.48: 5000-50000;
heating the slurry A to 50-80 ℃; then adding the slurry B and 0.5-5 wt% of aqueous solution of alkaline soluble salt into the slurry A in a parallel flow manner, and controlling the pH of the slurry in the reaction kettle to be 7.0-11.0 in the process; the alkaline soluble salt is one or more of ammonia water, sodium hydroxide, sodium carbonate and urea;
fourthly, continuously stirring the solution for 12 hours after the slurry B is dropwise added to obtain slurry C;
filtering, washing and drying the slurry C to obtain a precursor of the heterogeneous catalyst;
sixthly, fully roasting the precursor of the heterogeneous catalyst in the air, and reducing the precursor in a hydrogen atmosphere to obtain the heterogeneous catalyst.
7. The method for preparing a heterogeneous catalyst for hydrogenation of a styrene-based thermoplastic elastomer, according to claim 6, wherein the method comprises the following steps: the method comprises the step of preparing the surface active agent by using one or more of ethylene glycol, polyethylene glycol, polyvinyl pyrrolidone and urea.
8. The method for preparing a heterogeneous catalyst for hydrogenation of a styrene-based thermoplastic elastomer, according to claim 6, wherein the method comprises the following steps: the solvent in the step is water.
9. The use of a heterogeneous catalyst according to claim 1 for hydrogenation of a styrenic thermoplastic elastomer, wherein: under the action of the heterogeneous catalyst, 1.0-10.0 wt% of styrene thermoplastic elastomer and H2Carrying out hydrogenation reaction at the reaction temperature of 353-433K, the reaction time of 3-15 h and the reaction pressure of 0.1-8.0 MPa to generate a cyclic block copolymer; the molar ratio of the heterogeneous catalyst to the styrene thermoplastic elastomer is 1 x 10-3~1×10-1：1。
10. The use of a heterogeneous catalyst according to claim 9 for hydrogenation of a styrenic thermoplastic elastomer, wherein: the styrene thermoplastic elastomer is one of styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer and styrene-butadiene copolymer.
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| US4532351A (en) * | 1982-06-16 | 1985-07-30 | Exxon Research And Engineering Co. | Process for hydrogenating organic compounds by use of Group VIII aluminum-silicate catalysts |
| CN102451689A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of nickel-based catalyst precursor |
| CN102764656A (en) * | 2012-08-06 | 2012-11-07 | 久泰能源科技有限公司 | High-efficiency hydrogenation catalyst and method for preparing same |
| CN105682797A (en) * | 2013-07-17 | 2016-06-15 | 巴斯夫公司 | Process and catalyst for resin hydrogenation |
| CN104190426A (en) * | 2014-09-02 | 2014-12-10 | 山东巨业精细化工有限公司 | Preparation method of nickel-based hydrogenation catalyst for unsaturated oils and fats |
| CN105126845A (en) * | 2015-08-28 | 2015-12-09 | 天津大学 | Oxalate hydrogenation catalyst for producing ethanol and preparation method of catalyst |
| CN108160103A (en) * | 2017-12-08 | 2018-06-15 | 华东师范大学 | The preparation of high dispersive transition metal nanoparticles support type porous zeotile aggregation |
| CN113164926A (en) * | 2018-12-28 | 2021-07-23 | 韩华思路信株式会社 | Catalyst for hydrogenation reaction and preparation method thereof |
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