CN115364876A - Hydrogenation catalyst, preparation method and application thereof, and hydrogenation reaction method of polystyrene - Google Patents
Hydrogenation catalyst, preparation method and application thereof, and hydrogenation reaction method of polystyrene Download PDFInfo
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- CN115364876A CN115364876A CN202110546377.7A CN202110546377A CN115364876A CN 115364876 A CN115364876 A CN 115364876A CN 202110546377 A CN202110546377 A CN 202110546377A CN 115364876 A CN115364876 A CN 115364876A
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- earth metal
- hydrogenation catalyst
- metal element
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- 239000003054 catalyst Substances 0.000 title claims abstract description 161
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 155
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 52
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 32
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 30
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 23
- 239000003607 modifier Substances 0.000 claims abstract description 23
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 22
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 20
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- 150000002367 halogens Chemical class 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims description 46
- 238000001035 drying Methods 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005470 impregnation Methods 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000000306 component Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004914 cyclooctane Substances 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000002184 metal Substances 0.000 description 9
- 238000002791 soaking Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 5
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- -1 Polycyclohexylethylene Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002539 nanocarrier Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000004383 yellowing Methods 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- 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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- 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)
Abstract
The invention relates to the field of hydrogenation catalysts, and discloses a hydrogenation catalyst, a preparation method and application thereof, and a hydrogenation reaction method of polystyrene, wherein the hydrogenation catalyst comprises a carrier, and an active component, an auxiliary agent and a modifier which are loaded on the carrier; the active component contains Pt element, the modifier contains halogen element, the auxiliary agent contains IVA group element, IVB group element and rare earth metal element, and optionally, the auxiliary agent also contains alkali metal element and/or alkaline earth metal element; wherein the content molar ratio of the IVA group element to the Pt element is 1-5:1. the catalyst has excellent hydrogenation activity for unsaturated polymers such as polystyrene, the dosage of the catalyst is small, the hydrogenation efficiency is high, and the hydrogenated polymers can not be degraded.
Description
Technical Field
The invention relates to the field of hydrogenation catalysts, in particular to a hydrogenation catalyst, a preparation method and application thereof, and a hydrogenation reaction method of polystyrene.
Background
The general unsaturated high molecular material usually contains unsaturated double bonds (such as benzene ring double bonds, diene double bonds and the like), so that the heat resistance, ultraviolet resistance and yellowing resistance of the general unsaturated high molecular material are poor, and the hydrogenation of the existing unsaturated polymer is a rapid and effective way for improving the performance of the general unsaturated high molecular material.
The fully saturated Polycyclohexylethylene (PVCH) is obtained after hydrogenation of double bonds of benzene rings in the atactic Polystyrene (PS), and compared with the PS, the fully saturated PVCH has the glass transition temperature of about 105 ℃ and can be increased to 147 ℃, and the heat resistance, ultraviolet light resistance and other properties of the PS are obviously improved. PVCH maintains the high light transmittance of PS while having a low dielectric constant, refractive index, and low moisture absorption rate. In addition, the tensile strength is also improved, and the optical film can be used in the fields of optical materials, optical storage media, electronics and the like.
The hydrogenation of double bonds in benzene rings in polystyrene is more difficult than that of olefin-C = C-double bonds, and generally requires harsh process conditions such as high temperature and high pressure, and the traditional homogeneous catalyst is difficult to hydrogenate, so that the main current PS hydrogenation method is a heterogeneous hydrogenation method, and the hydrogenation catalyst is generally a heterogeneous catalyst.
Elias H G, etter O. With Raney Ni catalyst, at 200-270 ℃ and 210-260atm pressure, for 24 hours, the degree of hydrogenation can reach 42% -100%, but the polymer is severely degraded (Tg =80 ℃) (Glass temperature of hydrogenated polystyrene [ J ]. Journal of Macromolecular Science-Chemistry, 1967,1 (5): 943-953.).
Gehlsen et al use Pd/BaSO 4 The polystyrene cyclohexane solution is hydrogenated under the conditions of 140 ℃ and 35atm pressure by using the catalyst, the mass ratio of the catalyst to the polymer is 2.5/1, the reaction is carried out for 12 hours, the fully hydrogenated PVCH is obtained, and the polymer has partial chain scission degradation (Tg =140 ℃).
Zhou Hongyong and the like, the metal Ru is loaded on a magnetic nano carrier, and the magnetic nano catalyst is prepared and used for the hydrogenation reaction of polystyrene. The reaction temperature is above 120 ℃, the hydrogen pressure is 8MPa, and the reaction time is 5h, the hydrogenation degree of the polystyrene can reach above 90%, but the hydrogenated polystyrene is degraded to generate benzene, toluene, cyclohexane, methylcyclohexane and other micromolecules.
Furthermore, although US5700878 discloses a large pore silica support with an average pore size of up to 380nm developed by the Dow chemical company, which is loaded with the active component Pt (5% Pt/SiO) 2 ) The catalyst/polymer mass ratio is 0.27/1, the reaction is carried out for 6 hours at 140 ℃ and 105atm pressure, the polystyrene hydrogenation degree reaches 99.9 percent, however, the loading capacity of the noble metal is large, the catalyst consumption is large, and the cost is high.
Therefore, the existing heterogeneous hydrogenation catalyst still has the defects of low catalytic activity, excessive catalyst dosage, harsh reaction conditions, easy degradation of the polymer obtained by hydrogenation and the like.
Disclosure of Invention
The invention aims to overcome the defects of low catalytic activity, excessive catalyst consumption, harsh reaction conditions and easy degradation of a polymer obtained by hydrogenation in the prior art of heterogeneous hydrogenation catalysts, and provides a hydrogenation catalyst and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a hydrogenation catalyst comprising a carrier, and an active component, an auxiliary and a modifier supported on the carrier; the active component contains Pt element, the modifier contains halogen element, the auxiliary agent contains IVA group element, IVB group element and rare earth metal element, and optionally, the auxiliary agent also contains alkali metal element and/or alkaline earth metal element; wherein the content molar ratio of the IVA group element to the Pt element is 1-5:1.
in a second aspect, the present invention provides a process for preparing the aforementioned hydrogenation catalyst, which process comprises: active components, auxiliary agents and modifiers are introduced to the carrier by adopting an impregnation method, and then roasting is carried out.
In a third aspect, the present invention provides the use of the hydrogenation catalyst of the first aspect described above in a hydrogenation reaction of an unsaturated bond-containing polymer.
The fourth aspect of the present invention provides a hydrogenation reaction method of polystyrene, comprising: contacting a polystyrene-containing polymer solution, hydrogen and the hydrogenation catalyst of the first aspect under hydrogenation reaction conditions.
Compared with the prior art, the invention has at least the following advantages:
(1) The supported hydrogenation catalyst provided by the invention has high catalyst activity.
(2) The supported hydrogenation catalyst provided by the invention is used for hydrogenation reaction of polymers containing unsaturated bonds such as polystyrene, the catalyst dosage is small, the reaction efficiency is high, the reaction condition is mild, and the catalyst can be recycled.
(3) The hydrogenation catalyst provided by the invention is used in hydrogenation reaction of unsaturated bond-containing polymers such as polystyrene, can adopt polymer solution with wider concentration range, and has wide applicable polystyrene molecular weight range.
(4) The hydrogenation catalyst provided by the invention is used for hydrogenation reaction of unsaturated bond-containing polymers such as polystyrene, and the polymers obtained after hydrogenation can not be degraded.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
In the present invention, the term "optionally" means that a certain component may or may not be contained, and may or may not be subjected to a certain step.
As described above, the first aspect of the present invention provides a hydrogenation catalyst comprising a carrier and an active component, a co-agent and a modifier supported on the carrier; the active component contains Pt element, the modifier contains halogen element, the auxiliary agent contains IVA group element, IVB group element and rare earth metal element, and optionally, the auxiliary agent also contains alkali metal element and/or alkaline earth metal element; wherein the content molar ratio of the IVA group element to the Pt element is 1-5:1.
preferably, in the hydrogenation catalyst, the molar ratio of the group IVA element to the Pt element is from 2 to 4:1. the inventors of the present invention have found that a hydrogenation catalyst containing the preferred content ratio in particular has a higher catalytic activity.
According to the present invention, preferably, the content of the Pt element is 0.1 to 0.8 wt%, the content of the group IVA element is 0.2 to 4 wt%, the content of the group IVB element is 0.05 to 2 wt%, the content of the rare earth metal element is 0.05 to 2 wt%, the content of the alkali metal element is 0 to 2 wt%, the content of the alkaline earth metal element is 0 to 2 wt%, and the content of the halogen element is 0.05 to 0.5 wt%, based on the total weight of the hydrogenation catalyst.
More preferably, based on the total weight of the hydrogenation catalyst, the content of the Pt element is 0.3 to 0.5 wt%, the content of the group IVA element is 0.5 to 1.5 wt%, the content of the group IVB element is 0.1 to 1 wt%, the content of the rare earth metal element is 0.1 to 1 wt%, the content of the alkali metal element is 0.5 to 2 wt%, the content of the alkaline earth metal element is 0.5 to 2 wt%, and the content of the halogen element is 0.1 to 0.4 wt%.
In the invention, when the hydrogenation catalyst only contains a carrier and an active component, an auxiliary agent and a modifier which are loaded on the carrier, the balance except the active component, the auxiliary agent and the modifier is the content of the carrier; however, the present invention is not limited thereto, and the hydrogenation catalyst of the present invention may further comprise other functional additives that do not affect the catalytic effect of the hydrogenation catalyst, for example, the hydrogenation catalyst may comprise an impurity scavenger, etc., and will not be described in detail herein, and those skilled in the art should not be construed as limiting the present invention.
With the above preferred catalyst composition, even in the case where the content of the active component is small, the activity of the catalyst can be further improved by the synergistic effect of the components.
According to the present invention, preferably, the group IVA element is selected from at least one of C, si, ge, sn, and Pb elements; preferably at least one of Si, ge and Sn, and most preferably Sn. The Sn element is matched with other components in the catalyst, so that the catalytic performance of the catalyst is improved.
According to the present invention, preferably, the group IVB element is a Ti element and/or a Zr element, more preferably a Zr element.
According to the present invention, preferably, the rare earth metal element is at least one selected from La, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb and Lu elements, more preferably at least one selected from La, ce and Pr elements, more preferably La element and/or Ce element, and most preferably La element. The La element is matched with other components in the catalyst, so that the catalytic performance of the catalyst is improved.
According to the present invention, preferably, the alkali metal element is selected from at least one of elements of Li, na, K, rb and Cs, more preferably at least one of elements of Li, na and K.
According to the present invention, preferably, the alkaline earth metal element is at least one element selected from Be, mg, ca, sr and Ba, more preferably Mg element and/or Ca element, and further preferably Mg element, and the Mg element is adopted to cooperate with other components in the hydrogenation catalyst, so as to Be more beneficial for improving the catalytic performance of the hydrogenation catalyst.
In the present invention, the hydrogenation catalyst may contain an alkali metal element, may not contain an alkali metal element, and preferably contains an alkali metal element.
In the present invention, the hydrogenation catalyst may or may not contain an alkaline earth metal element, and preferably contains an alkaline earth metal element.
According to the present invention, preferably, the halogen element is at least one selected from F, cl, br and I elements, and more preferably a Cl element.
Preferably, the support is selected from at least one of refractory inorganic oxides.
More preferably, the support is selected from at least one of alumina, silica, zirconia, magnesia and titania, more preferably alumina.
Preferably, the specific surface area of the carrier is 100 to 400m 2 (iv) g; the average pore diameter of the carrier is 10-20nm.
According to the invention, preferably, the hydrogenation catalyst has a specific surface area of 50 to 500m 2 A/g, more preferably 100 to 300m 2 (ii)/g; the average pore diameter of the hydrogenation catalyst is 5-40nm, and more preferably 10-20nm.
According to a particularly preferred embodiment of the present invention, the hydrogenation catalyst comprises: the active component is Pt element, the auxiliary agent contains IVA group elements, IVB group elements, rare earth elements, optional alkali metal elements and optional alkaline earth metal elements, the IVA group elements are Sn elements, the IVB group elements are Zr elements, the rare earth elements are La elements, the alkali metal elements are K elements, the alkaline earth metal elements are Mg elements, and the modifier is Cl elements, wherein the molar ratio of the IVA group elements to the Pt elements is 2-4:1. The active component, the modifier and the auxiliary agent which are specially composed are matched with the alumina carrier, so that the catalyst has a higher effective specific surface, and is used in the hydrogenation reaction of polystyrene, the catalyst dosage is less, the reaction condition is milder, the hydrogenation speed is higher, the hydrogenation efficiency is higher, and the hydrogenated polymer is not degraded.
As previously mentioned, a second aspect of the present invention provides a process for preparing the aforementioned hydrogenation catalyst, which process comprises: active components, auxiliary agents and modifiers are introduced to the carrier by adopting an impregnation method, and then roasting is carried out.
The present invention is not particularly limited in type and specific operation of the impregnation method, and may be various impregnation methods conventionally used in the art, as long as it is possible to introduce an active component precursor, an assistant precursor and a modifier precursor onto a support. For example, the impregnation method may be co-impregnation, or may be stepwise impregnation, and preferably is stepwise impregnation.
According to a preferred embodiment of the present invention, in the method, the step of introducing the active ingredient, the auxiliary agent and the modifier onto the support by impregnation comprises:
(1) Introducing rare earth metal elements to the carrier by a dipping method to obtain a carrier containing the rare earth metal elements;
(2) Introducing a Pt element, an IVA group element, an IVB group element and a halogen element to the carrier containing the rare earth metal element by an impregnation method;
optionally, the method further comprises: before the step (2), an alkali metal element and/or an alkaline earth metal element is introduced to the support containing a rare earth metal element by an impregnation method, and then the step (2) is performed.
The inventor of the invention finds that by adopting the preferred embodiment, the carrier is modified by the rare earth metal element, and then the active component, the auxiliary agent and the modifier are introduced, which is more beneficial to improving the catalytic performance of the catalyst.
According to a more preferred embodiment of the invention, the method comprises:
(a) Dipping a carrier by adopting a solution containing a rare earth metal element precursor, and then carrying out first drying to obtain the carrier containing the rare earth metal element;
(b) Dipping the carrier containing the rare earth metal element by adopting a solution containing an alkali metal element precursor and/or an alkaline earth metal element precursor, and then carrying out second drying to obtain a catalyst intermediate;
(c) And (3) soaking the catalyst intermediate by adopting a solution containing a Pt element precursor, an IVA group metal element precursor, an IVB group metal element precursor and a modifier precursor, and then carrying out third drying and roasting.
In the present invention, the type of the precursor of each component is not particularly limited, and each of the precursors may be independently a soluble compound, for example, a soluble salt, of the component. By soluble is meant either directly soluble in a solvent (e.g., water) or soluble in a solvent in the presence of a co-solvent. For example, the Pt element precursor is chloroplatinic acid, and the group IVA metal element precursor may be a chloride and/or nitrate of an IVA element, preferably stannous chloride and/or stannic chloride; the precursor of the IVB group metal element may be a chloride and/or a nitrate of the IVB element, preferably zirconium nitrate and/or zirconyl nitrate, and the precursor of the rare earth metal element, the precursor of the alkali metal element, and the precursor of the alkaline earth metal element may be, independently, a chloride and/or a nitrate of the rare earth metal element, the alkali metal element, and the alkaline earth metal element, which may be appropriately selected by a person skilled in the art, and the present invention is not described herein again.
In the present invention, the modifier precursor is a halogen-containing compound, and may be at least one of hydrochloric acid, HBr, HI, and HF, for example, and is preferably hydrochloric acid.
Preferably, the carrier, the rare earth metal precursor, the alkali metal precursor, the alkaline earth metal precursor, the platinum precursor, the group IVA metal precursor, the group IVB metal precursor, and the modifier precursor are used in amounts such that the contents of the respective elements in the obtained hydrogenation catalyst are correspondingly the same as those in the hydrogenation catalyst of the first aspect. In light of the present disclosure, one skilled in the art would know how to set the amount of each precursor.
In the second aspect of the present invention, the properties of the carrier and the rare earth metal elements, alkali metal elements, alkaline earth metal elements, group IVA metal elements, group IVB metal elements, and halogen elements, such as species selection, are the same as those of the first aspect, and thus, the description thereof is omitted.
The concentration of the solution in step (a), step (b) and step (c) is not particularly limited, and can be determined according to the water absorption of the carrier and the target content of each component, which is not described herein again.
In the present invention, the solvent of the solution of step (a), step (b) and step (c) is each independently selected from the group consisting of water, hydrochloric acid and organic solvents. The organic solvent includes, but is not limited to, ethanol, isopropanol, butanol.
Preferably, the solvent of the solution in step (a) and step (b) is water.
In a preferred aspect, the solvent of the solution of step (c) is ethanol (absolute ethanol). By adopting the preferred embodiment, the catalyst components are uniformly dispersed, and the activity of the catalyst is stabilized.
In another preferred case, the solvent of the solution in step (c) is hydrochloric acid ethanol solution, wherein the volume ratio of hydrochloric acid to ethanol (absolute ethanol) is 1:1-5. The inventors have found in particular that, with this preferred embodiment, it is more advantageous to disperse the catalyst components uniformly and stabilize the catalyst activity.
According to the present invention, the conditions of the first drying, the second drying, and the third drying may be the same or different.
Preferably, the conditions of the first drying, the second drying, and the third drying each independently include: the temperature is 50-200 deg.C for 1-10 hours, more preferably 80-150 deg.C for 2-8 hours.
Preferably, the conditions of the calcination include: the temperature is 400-650 deg.C, and the time is 1-10 hr. More preferably, the conditions of the calcination include: the temperature is 400-600 ℃, and the time is 2-8 hours.
As described above, the third aspect of the present invention provides the use of the hydrogenation catalyst according to the first aspect in the hydrogenation of an unsaturated bond-containing polymer.
Preferably, the unsaturated bond-containing polymer is polystyrene. The inventor of the invention finds that the hydrogenation catalyst provided by the invention is particularly used in the hydrogenation reaction of polystyrene, the catalyst is low in dosage, can be recycled, has high reaction efficiency and mild reaction conditions, can adopt a polymer solution with a wider concentration range, is applicable to polystyrene with a wide molecular weight range, and particularly, the hydrogenated polymer can not be degraded.
As previously mentioned, a fourth aspect of the present invention provides a hydrogenation reaction method of polystyrene, the method comprising: under hydrogenation reaction conditions, a polystyrene-containing polymer solution, hydrogen and the hydrogenation catalyst of the first aspect are contacted.
Preferably, the polystyrene is polymerized by free radical and/or by anionic polymerization.
Because the viscosity of the polymer solution is far greater than that of the small molecule solution, the traditional heterogeneous powder catalyst is adopted for hydrogenation reaction, the concentration of the polymer solution is limited, the concentration is too high, the hydrogenation efficiency is very low, and the concentration of the polymer solution is usually below 5 weight percent. The hydrogenation catalyst provided by the invention has high reaction activity, so that the concentration of the polymer solution can reach 20 wt%, preferably the concentration of the polymer solution is 2-20 wt%, and more preferably 5-15 wt%.
According to the present invention, it is preferable that the solvent in the polymer solution is at least one selected from the group consisting of cyclohexane, methylcyclohexane, n-hexane, cyclooctane, cycloheptane, acetone, n-butanone, decahydronaphthalene, and tetrahydrofuran.
In addition, the activity of the conventional heterogeneous powder catalyst in the hydrogenation reaction is usually 100 to 800 wt% based on the mass of polystyrene, because of its low activity. Due to the high reactivity of the catalyst provided by the invention, the dosage of the hydrogenation catalyst is preferably 1-20g, more preferably 2-10g, relative to 100g of the polystyrene.
The catalyst provided by the invention can be applied to hydrogenation of polystyrene with relatively wide molecular weight, and the number average molecular weight of the polystyrene is preferably 1 ten thousand to 25 ten thousand, more preferably 6 ten thousand to 20 ten thousand.
Preferably, the hydrogenation reaction conditions include: the hydrogenation reaction temperature is 50-200 deg.C, preferably 120-180 deg.C, and more preferably 120-150 deg.C. The pressure of the hydrogenation reaction is 0.1 to 10MPa, preferably 0.5 to 5MPa. The hydrogenation catalyst provided by the invention has high reaction activity, so that the hydrogenation reaction method provided by the invention can be carried out under a relatively mild condition.
According to the invention, the hydrogenation reaction judges the reaction degree by the consumption of hydrogen or the reduction of hydrogen pressure, the reaction is stopped usually without reducing the hydrogen pressure, and the total hydrogenation reaction time is 0.5-10h, preferably 0.5-6h, more preferably 0.5-3h.
According to the present invention, before the hydrogenation reaction is performed by using the hydrogenation catalyst, the hydrogenation catalyst is preferably reduced, so that the active component (e.g., pt element) and/or the promoter (e.g., group IVA element, group IVB element, rare earth metal element) contained in the hydrogenation catalyst is reduced to a simple substance to have higher catalytic activity, and then the hydrogenation reaction is performed by contacting with the polymer solution containing the unsaturated bond polymer (e.g., polystyrene) and hydrogen.
Preferably, the reduction is carried out in a hydrogen-containing atmosphere, more preferably in a hydrogen atmosphere.
Preferably, the reducing conditions include: the temperature is 150-550 deg.C, preferably 550-550 deg.C, and the time is 1-10h.
The method of the present invention may further include conventional post-treatment operations such as washing, drying, separation, solvent removal, etc., and the present invention has no particular limitation on the specific steps of these post-treatment operations, and may be performed in a manner conventional in the art, such as separation by filtration, etc., and those skilled in the art should not be construed as limiting the present invention.
The hydrogenation catalyst provided by the invention has the advantages of simple preparation method and mild preparation conditions, and when the hydrogenation catalyst is used in the hydrogenation reaction of polystyrene, the catalyst consumption is small, the catalyst can be repeatedly used, the reaction efficiency is high, the reaction conditions are mild, in addition, a polymer solution with a wider concentration range can be adopted, and the applicable polystyrene molecular weight range is wide. In particular, the hydrogenation catalyst prepared by the invention is used for hydrogenation of polystyrene, and the polymer obtained by hydrogenation is not degraded.
In the present invention, the pressure means a gauge pressure unless otherwise specified.
The present invention will be described in detail below by way of examples.
In the following examples, the amounts of the respective precursors and the concentrations of the respective precursor solutions are determined in accordance with the weight of the hydrogenation catalyst and the contents of the respective elements in the hydrogenation catalyst, unless otherwise specified.
In the following examples, the weight of the hydrogenation catalyst to be prepared was 10g, unless otherwise specified.
In the following examples, a γ -alumina carrier having a specific surface area of 350m was used without particular mention 2 In g, the mean pore diameter is 20nm.
The properties referred to in the following examples were tested as follows:
(1) Degree of hydrogenation of benzene ring in polymer: and (4) measuring by using a nuclear magnetic resonance hydrogen spectrum.
(2) Molecular weight and distribution before and after polymer hydrogenation: the measurement was carried out by gel permeation chromatography.
(3) Glass transition temperature: measured using a Differential Scanning Calorimeter (DSC).
Example 1
This example is intended to provide a hydrogenation catalyst having the composition shown in table 1.
(1) Impregnating a gamma-alumina carrier with a cerium nitrate aqueous solution in the same volume, and drying at 120 ℃ for 8 hours to obtain a cerium-containing alumina carrier;
(2) Soaking the alumina carrier containing the cerium element obtained in the step (1) by using an aqueous solution containing potassium nitrate and magnesium nitrate in the same volume, and drying at 120 ℃ for 8 hours to obtain a catalyst intermediate;
(3) Soaking the catalyst intermediate obtained in the step (2) in hydrochloric acid ethanol solution (the volume ratio of hydrochloric acid to absolute ethyl alcohol is 1:2) containing chloroplatinic acid, tin chloride and zirconium chloride in equal volume, and drying at 120 ℃ for 8 hoursThen roasting for 6 hours at 600 ℃ to obtain the hydrogenation catalyst C-1. The specific surface area of the hydrogenation catalyst C-1 is 300m 2 In terms of a/g, the mean pore diameter is 17.6nm.
Example 2
This example is intended to provide a catalyst having the composition shown in table 1.
A hydrogenation catalyst C-2 was obtained in a similar manner to example 1, except that the amount of the precursor for each component was changed. The specific surface area of the hydrogenation catalyst C-2 is 290m 2 In terms of/g, the mean pore diameter is 18.3nm.
Example 3
This example is intended to provide a catalyst having the composition shown in table 1.
A hydrogenation catalyst C-3 was obtained in a similar manner to example 1, except that the amounts of the precursors of the respective components were different. The specific surface area of the hydrogenation catalyst C-3 is 280m 2 In terms of/g, the mean pore diameter is 19.8nm.
Example 4
This example is intended to provide a catalyst having the composition shown in table 1.
A similar procedure as in example 1 was followed, except that the amounts of the precursors of the respective components were varied, to obtain hydrogenation catalyst C-4. The specific surface area of the hydrogenation catalyst C-4 is 295m 2 In terms of/g, the mean pore diameter is 18.2nm.
Example 5
This example is intended to provide a catalyst having the composition shown in table 1.
A hydrogenation catalyst C-5 was obtained in a similar manner to example 1, except that the amounts of the precursors of the respective components were changed. The specific surface area of the hydrogenation catalyst C-5 is 290m 2 In terms of/g, the mean pore diameter is 18.5nm.
Example 6
This example is intended to provide a catalyst having the composition shown in table 1.
A hydrogenation catalyst C-6 was obtained in a similar manner to example 1, except that the amounts of the precursors of the respective components were different. The specific surface area of the hydrogenation catalyst C-6 is 280m 2 In terms of/g, the mean pore diameter is 18.9nm.
Example 7
This example is intended to provide a catalyst having the composition shown in table 1.
A hydrogenation catalyst C-7 was obtained by following the procedure of example 1, except that the step (2) was not conducted, and the cerium-containing alumina support obtained in the step (1) was impregnated directly with an equal volume of an ethanol hydrochloride solution containing chloroplatinic acid, tin chloride and zirconium chloride, and the amounts of the precursors of the respective components were adjusted. The specific surface area of the hydrogenation catalyst C-7 is 280m 2 In terms of a/g, the mean pore diameter is 18.7nm.
Example 8
This example is intended to provide a catalyst having the composition shown in table 1.
(1) Soaking gamma-alumina in an aqueous solution containing potassium nitrate and magnesium nitrate in the same volume, and drying at 120 ℃ for 8 hours to obtain an alumina carrier containing potassium and magnesium;
(2) Soaking the alumina carrier containing potassium and magnesium obtained in the step (1) in an aqueous solution containing cerium nitrate in an equal volume, and drying at 120 ℃ for 8 hours to obtain a catalyst intermediate;
(3) Soaking the catalyst intermediate obtained in the step (2) in hydrochloric acid ethanol solution (the volume ratio of hydrochloric acid to absolute ethyl alcohol is 1:2) containing chloroplatinic acid, tin chloride and zirconium chloride in the same volume, drying at 120 ℃ for 8 hours, and roasting at 600 ℃ for 6 hours to obtain the hydrogenation catalyst C-8. The specific surface area of the hydrogenation catalyst C-8 is 260m 2 In terms of/g, the mean pore diameter is 19.8nm.
Example 9
This example is intended to provide a catalyst having the composition shown in table 1.
(1) Soaking gamma-alumina in cerium nitrate water solution in the same volume, and drying at 120 deg.c for 8 hr to obtain cerium containing alumina carrier;
(2) Soaking the cerium-containing alumina carrier obtained in the step (1) in an aqueous solution containing potassium nitrate and magnesium nitrate in the same volume, and drying at 120 ℃ for 8 hours to obtain a catalyst intermediate;
(3) The catalyst intermediate obtained in the step (2) is impregnated by hydrochloric acid aqueous solution (the volume ratio of hydrochloric acid to water is 1:2) containing chloroplatinic acid, stannic chloride and zirconium chloride in equal volume,drying at 120 deg.C for 4 hr, and calcining at 600 deg.C for 6 hr to obtain hydrogenation catalyst C-9. The specific surface area of the hydrogenation catalyst C-9 is 200m 2 In terms of/g, the mean pore diameter is 19.8nm.
Example 10
This example is intended to provide a catalyst having the composition shown in table 1.
A hydrogenation catalyst C-10 was obtained in a similar manner to example 1, except that the amounts of the precursors of the respective components were different. The specific surface area of the hydrogenation catalyst C-10 is 280m 2 In terms of/g, the mean pore diameter is 18.8nm.
Example 11
This example is intended to provide a catalyst having the composition shown in table 1.
A hydrogenation catalyst C-11 was obtained in a similar manner to example 1, except that the amounts of the precursors of the respective components were changed. The specific surface area of the hydrogenation catalyst C-11 is 280m 2 In terms of/g, the mean pore diameter was 17.9nm.
Comparative example 1
Soaking a gamma-alumina carrier in a nickel nitrate solution in the same volume, and drying at 120 ℃ for 8 hours to obtain a catalyst containing a nickel element;
and reducing the catalyst containing the nickel element for 6 hours at 500 ℃ in a hydrogen atmosphere to obtain the catalyst D-1. Wherein the loading of the active metal nickel is 10 weight percent, and the active metal nickel is directly used in the follow-up process.
Comparative example 2
This comparative example is intended to provide a catalyst having the composition shown in table 1.
According to a similar method to that of example 1, except that the amount of the precursor of each component was different and the ethanol hydrochloric acid solution in the step (3) did not contain zirconium chloride, a hydrogenation catalyst D-2 was obtained. The specific surface area of the hydrogenation catalyst D-2 was 200m 2 /g。
Comparative example 3
This comparative example is intended to provide a catalyst having the composition shown in table 1.
A hydrogenation catalyst D-3 was obtained in a similar manner to example 1, except that the amounts of the precursors of the respective components were varied. The specific surface area of the hydrogenation catalyst D-3 is 230m 2 /g。
TABLE 1
Note: the content of each element is based on the total weight of the hydrogenation catalyst.
Test example
Hydrogenation tests were conducted using the catalysts prepared in the above examples, respectively, wherein the catalysts prepared in the above examples and comparative examples 2 to 3 were reduced under conditions including: under a hydrogen atmosphere, the temperature was 150 ℃ and the time was 2 hours.
A0.5L autoclave equipped with a stirrer was charged with 200g of a polystyrene solution (20 g of polystyrene and 180g of cyclohexane solvent, the number average molecular weight of polystyrene is shown in Table 2), 1g of the reduced catalyst was added, and then hydrogen gas was introduced to conduct hydrogenation. The hydrogenation reaction conditions comprise: the temperature is 150 ℃, the hydrogen pressure is 3MPa, the reaction time is 1h, and the stirring speed is 800rpm. And after the reaction is finished, filtering and separating the hydrogenated product to obtain a hydrogenated polystyrene (polycyclohexylethylene) solution on the upper layer, and removing the solvent to obtain the polycyclohexylethylene dry glue. The results of the degree of hydrogenation, molecular weight and distribution analysis are shown in Table 2. And collecting the separated catalyst, washing the catalyst by using a hexane solvent, and drying the catalyst in vacuum to remove the solvent for recycling.
TABLE 2
The catalyst has excellent hydrogenation catalytic activity on unsaturated polymers such as polystyrene, the using amount of the catalyst is small, the hydrogenation efficiency is high, the reaction time is 1 hour, the hydrogenation degree can reach nearly 100mol%, and the full hydrogenation of the polystyrene can be realized; in addition, the hydrogenation reaction condition is relatively mild, the molecular weight of the hydrogenated Polystyrene (PVCH) is not obviously reduced, and the molecular weight distribution is basically kept unchanged, which shows that the catalyst provided by the invention is used for hydrogenating the polystyrene without degrading polymer molecular chains.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (14)
1. A hydrogenation catalyst is characterized by comprising a carrier, and an active component, an auxiliary agent and a modifier which are loaded on the carrier; the active component contains Pt element, the modifier contains halogen element, the auxiliary agent contains IVA group element, IVB group element and rare earth metal element, and optionally, the auxiliary agent also contains alkali metal element and/or alkaline earth metal element; wherein the content molar ratio of the IVA group element to the Pt element is 1-5:1.
2. the hydrogenation catalyst according to claim 1, wherein the hydrogenation catalyst contains the group IVA element and the Pt element at a molar ratio of 2-4:1;
preferably, the content of the Pt element is 0.1 to 0.8 wt%, the content of the IVA group element is 0.2 to 4 wt%, the content of the IVB group element is 0.05 to 2 wt%, the content of the rare earth metal element is 0.05 to 2 wt%, the content of the alkali metal element is 0 to 2 wt%, the content of the alkaline earth metal element is 0 to 2 wt%, and the content of the halogen group element is 0.05 to 0.5 wt% based on the total weight of the hydrogenation catalyst;
more preferably, based on the total weight of the hydrogenation catalyst, the content of the Pt element is 0.3 to 0.5 wt%, the content of the group IVA element is 0.5 to 1.5 wt%, the content of the group IVB element is 0.1 to 1 wt%, the content of the rare earth metal element is 0.1 to 1 wt%, the content of the alkali metal element is 0.5 to 2 wt%, the content of the alkaline earth metal element is 0.5 to 2 wt%, and the content of the halogen element is 0.1 to 0.4 wt%.
3. The hydrogenation catalyst according to claim 1 or 2, wherein the group IVA element is selected from at least one of C, si, ge, sn and Pb elements, more preferably Sn element;
preferably, the group IVB element is a Ti element and/or a Zr element;
preferably, the rare earth metal element is at least one element selected from La, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb and Lu elements, preferably at least one element selected from La, ce and Pr elements, more preferably La element and/or Ce element;
preferably, the alkali metal element is selected from at least one of elements of Li, na, K, rb and Cs, more preferably at least one of elements of Li, na and K;
preferably, the alkaline earth metal element is at least one element selected from Be, mg, ca, sr and Ba elements, more preferably Mg element and/or Ca element;
preferably, the halogen element is at least one selected from F, cl, br and I elements, preferably a Cl element.
4. A hydrogenation catalyst according to any one of claims 1 to 3, wherein the support is selected from at least one of refractory inorganic oxides;
preferably, the support is selected from at least one of alumina, silica, zirconia, magnesia and titania, more preferably alumina.
5. The hydrogenation catalyst according to any one of claims 1 to 4, wherein the hydrogenation catalyst has a specific surface area of 50 to 500m 2 A/g, more preferably 100 to 300m 2 (ii)/g; the average pore diameter of the hydrogenation catalyst is 5-40nm, and more preferably 10-20nm.
6. A process for preparing a hydrogenation catalyst as claimed in any one of claims 1 to 5, characterized in that it comprises: active components, auxiliary agents and modifiers are introduced to the carrier by adopting an impregnation method, and then roasting is carried out.
7. The method of claim 6, wherein the step of introducing the active ingredient, the adjuvant and the modifier onto the support using an impregnation method comprises:
(1) Introducing rare earth metal elements to the carrier by a dipping method to obtain a carrier containing the rare earth metal elements;
(2) Introducing a Pt element, an IVA group element, an IVB group element and a halogen element to the carrier containing the rare earth metal element by an impregnation method;
optionally, the method further comprises: before the step (2), an alkali metal element and/or an alkaline earth metal element is introduced to the support containing a rare earth metal element by an impregnation method, and then the step (2) is performed.
8. The method of claim 7, wherein the method comprises:
(a) Impregnating a carrier with a solution containing a precursor of a rare earth metal element, and then carrying out first drying to obtain the carrier containing the rare earth metal element;
(b) Dipping the carrier containing the rare earth metal element by adopting a solution containing an alkali metal element precursor and/or an alkaline earth metal element precursor, and then carrying out secondary drying to obtain a catalyst intermediate;
(c) And dipping the catalyst intermediate by adopting a solution containing a Pt element precursor, an IVA group element precursor, an IVB group element precursor and a modifier precursor, and then carrying out third drying and roasting.
9. The method of any of claims 6-8, wherein the firing conditions comprise: the temperature is 400-650 ℃, and the time is 1-10 hours;
preferably, the conditions of the calcination include: the temperature is 400-600 ℃, and the time is 2-8 hours.
10. Use of a hydrogenation catalyst according to any one of claims 1 to 5 in a hydrogenation reaction of a polymer containing unsaturated bonds;
preferably, the unsaturated bond-containing polymer is polystyrene.
11. A hydrogenation reaction method of polystyrene is characterized by comprising the following steps: contacting a polystyrene-containing polymer solution, hydrogen and the hydrogenation catalyst of any one of claims 1 to 5 under hydrogenation reaction conditions.
12. The method according to claim 11, wherein the concentration of polystyrene in the polymer solution is 2-20 wt%, preferably 5-15 wt%;
preferably, the solvent in the polymer solution is selected from at least one of cyclohexane, methylcyclohexane, n-hexane, cyclooctane, cycloheptane, acetone, n-butanone, decahydronaphthalene, and tetrahydrofuran.
13. The process according to claim 11 or 12, wherein the hydrogenation catalyst is used in an amount ranging from 1 to 20g, preferably from 2 to 10g, with respect to 100g of the polystyrene;
preferably, the polystyrene has a number average molecular weight of 1 to 25 ten thousand, preferably 6 to 20 ten thousand.
14. The method of any of claims 11-13, wherein the hydrogenation reaction conditions comprise: the hydrogenation reaction temperature is 50-200 ℃, and preferably 120-180 ℃; the hydrogenation reaction pressure is 0.1-10MPa, preferably 0.5-5MPa.
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