JP2019523127A - 遷移金属系触媒用の担体としての表面修飾炭酸カルシウム - Google Patents
遷移金属系触媒用の担体としての表面修飾炭酸カルシウム Download PDFInfo
- Publication number
- JP2019523127A JP2019523127A JP2019503674A JP2019503674A JP2019523127A JP 2019523127 A JP2019523127 A JP 2019523127A JP 2019503674 A JP2019503674 A JP 2019503674A JP 2019503674 A JP2019503674 A JP 2019503674A JP 2019523127 A JP2019523127 A JP 2019523127A
- Authority
- JP
- Japan
- Prior art keywords
- pdcl
- calcium carbonate
- transition metal
- ptcl
- metal compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 474
- 239000003054 catalyst Substances 0.000 title claims abstract description 122
- 229910052723 transition metal Inorganic materials 0.000 title claims description 59
- 150000003624 transition metals Chemical class 0.000 title claims description 44
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 146
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 114
- 238000000034 method Methods 0.000 claims abstract description 82
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 52
- 239000007787 solid Substances 0.000 claims abstract description 44
- 230000008569 process Effects 0.000 claims abstract description 15
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 11
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 11
- 238000005859 coupling reaction Methods 0.000 claims abstract description 8
- 230000008878 coupling Effects 0.000 claims abstract description 7
- 238000010168 coupling process Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 130
- 101150003085 Pdcl gene Proteins 0.000 claims description 116
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 105
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims description 88
- 239000007788 liquid Substances 0.000 claims description 77
- 239000010949 copper Substances 0.000 claims description 62
- 239000002245 particle Substances 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 50
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 42
- 239000000725 suspension Substances 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000011148 porous material Substances 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 229910021532 Calcite Inorganic materials 0.000 claims description 30
- 229910052763 palladium Inorganic materials 0.000 claims description 25
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 229910052802 copper Inorganic materials 0.000 claims description 24
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 24
- 229910052753 mercury Inorganic materials 0.000 claims description 24
- 229910052697 platinum Inorganic materials 0.000 claims description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 21
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims description 19
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 claims description 18
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 claims description 17
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 239000007795 chemical reaction product Substances 0.000 claims description 17
- 238000006880 cross-coupling reaction Methods 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 238000004438 BET method Methods 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 238000002459 porosimetry Methods 0.000 claims description 15
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 14
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 14
- 239000002798 polar solvent Substances 0.000 claims description 14
- 238000001704 evaporation Methods 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000012454 non-polar solvent Substances 0.000 claims description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 10
- 239000005749 Copper compound Substances 0.000 claims description 10
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- HWZRXCHJIQVTPX-UHFFFAOYSA-N acetic acid;triphenylphosphanium;acetate Chemical compound CC(O)=O.CC(O)=O.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 HWZRXCHJIQVTPX-UHFFFAOYSA-N 0.000 claims description 10
- 150000001880 copper compounds Chemical class 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- 150000002941 palladium compounds Chemical class 0.000 claims description 10
- 150000003058 platinum compounds Chemical class 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 8
- 229910016509 CuF 2 Inorganic materials 0.000 claims description 7
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 claims description 7
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims description 7
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- CGMRCMMOCQYHAD-UHFFFAOYSA-J dicalcium hydroxide phosphate Chemical compound [OH-].[Ca++].[Ca++].[O-]P([O-])([O-])=O CGMRCMMOCQYHAD-UHFFFAOYSA-J 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- SFJMFSWCBVEHBA-UHFFFAOYSA-M copper(i)-thiophene-2-carboxylate Chemical compound [Cu+].[O-]C(=O)C1=CC=CS1 SFJMFSWCBVEHBA-UHFFFAOYSA-M 0.000 claims description 5
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 150000001345 alkine derivatives Chemical class 0.000 claims description 4
- 229910052586 apatite Inorganic materials 0.000 claims description 4
- 229910052589 chlorapatite Inorganic materials 0.000 claims description 4
- PROQIPRRNZUXQM-ZXXIGWHRSA-N estriol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H]([C@H](O)C4)O)[C@@H]4[C@@H]3CCC2=C1 PROQIPRRNZUXQM-ZXXIGWHRSA-N 0.000 claims description 4
- 229910052587 fluorapatite Inorganic materials 0.000 claims description 4
- 238000007327 hydrogenolysis reaction Methods 0.000 claims description 4
- 229910000392 octacalcium phosphate Inorganic materials 0.000 claims description 4
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 4
- YIGWVOWKHUSYER-UHFFFAOYSA-F tetracalcium;hydrogen phosphate;diphosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[Ca+2].OP([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YIGWVOWKHUSYER-UHFFFAOYSA-F 0.000 claims description 4
- 238000006757 chemical reactions by type Methods 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 150000001502 aryl halides Chemical class 0.000 claims description 2
- HBYOLNPZXLHVQA-UHFFFAOYSA-J dicalcium dicarbonate Chemical compound [Ca+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HBYOLNPZXLHVQA-UHFFFAOYSA-J 0.000 claims 1
- 238000007363 ring formation reaction Methods 0.000 claims 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 21
- 238000004517 catalytic hydrocracking Methods 0.000 abstract description 6
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 4
- 235000010216 calcium carbonate Nutrition 0.000 description 134
- 239000002609 medium Substances 0.000 description 66
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 60
- 150000002500 ions Chemical class 0.000 description 58
- 239000011734 sodium Substances 0.000 description 45
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 33
- 239000002253 acid Substances 0.000 description 32
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 29
- 239000002002 slurry Substances 0.000 description 29
- 239000000463 material Substances 0.000 description 26
- 238000002156 mixing Methods 0.000 description 24
- -1 transition metal salts Chemical class 0.000 description 24
- 150000003839 salts Chemical class 0.000 description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 19
- 239000007900 aqueous suspension Substances 0.000 description 15
- 238000009826 distribution Methods 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 11
- 150000001450 anions Chemical class 0.000 description 11
- 239000000523 sample Substances 0.000 description 11
- 235000011054 acetic acid Nutrition 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000004062 sedimentation Methods 0.000 description 8
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 7
- 229910001424 calcium ion Inorganic materials 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 239000004579 marble Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 235000006408 oxalic acid Nutrition 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910052762 osmium Inorganic materials 0.000 description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
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Classifications
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
Description
(i)窒素及びISO 9277:2010に従うBET法を用いて測定される場合15〜200m2/gの比表面積;
(ii)水銀ポロシメトリー測定から計算される場合0.1〜2.3cm3/gの範囲の粒子内圧入比細孔容積;及び
(iii)1:99〜99:1の範囲の、少なくとも1つの水不溶性カルシウム塩とカルサイト、アラゴナイト及び/又はバテライトとの比、
を示す。
(a)粉砕天然炭酸カルシウム(GNCC)又は沈降炭酸カルシウム(PCC)及び炭酸カルシウム以外の少なくとも1つの水不溶性カルシウム塩を含む少なくとも1つの表面反応炭酸カルシウムを提供する工程;
(b)少なくとも1つの遷移金属化合物を提供する工程;及び
(c)液体媒体中、工程(a)で提供される表面反応炭酸カルシウム及び工程(b)で提供される遷移金属化合物を接触させて、表面反応炭酸カルシウム及び遷移金属化合物を含む混合物を得る工程、
を含み、
この表面反応炭酸カルシウムは、
(i)窒素及びISO9277:2010に従うBET法を用いて測定される場合15〜200m2/gの比表面積;
(ii)水銀ポロシメトリー測定から計算される場合0.1〜2.3cm3/gの範囲の粒子内圧入比細孔容積;及び
(iii)1:99〜99:1の範囲の、少なくとも1つの水不溶性カルシウム塩とカルサイト、アラゴナイト及び/又はバテライトとの比、
を示す。
(a)1つ以上の反応物を提供する工程;
(b)本発明の触媒系を提供する工程;
(c)工程(b)で提供される触媒系の存在下で、工程(a)で提供される1つ以上の反応物を化学反応に供する工程、
を含む方法におけるこの触媒系の使用に関する。
本発明の意味において「粉砕天然炭酸カルシウム」(GNCC)は、天然源、例えば石灰岩、大理石、又はチョークから得られ、湿式及び/又は乾式処理、例えば粉砕、スクリーニング及び/又は分別、例えばサイクロン又は分類機によるものを通して加工処理された炭酸カルシウムである。
(i)窒素及びISO 9277:2010によるBET法を用いて測定される場合27〜180m2/g、好ましくは25〜160m2/g、より好ましくは30〜150m2/gの範囲の比表面積;
(ii)1〜75μm、好ましくは2〜50μm、より好ましくは3〜40μm、さらにより好ましくは4〜30μm、最も好ましくは5〜15μmの範囲のd50(体積);
(iii)2〜150μm、好ましくは4〜100μm、より好ましくは6〜80μm、さらにより好ましくは8〜60μm、最も好ましくは10〜30μmの範囲のd98(体積);及び/又は
(iv)水銀ポロシメトリー測定から計算される場合0.2〜2.0cm3/g、好ましくは0.4〜1.8cm3/g、最も好ましくは0.6〜1.6cm3/gの範囲の粒子内圧入比細孔容積。
(i)工程(a)の少なくとも1つの表面反応炭酸カルシウムは懸濁液の形態で液体媒体中に提供される;及び/又は
(ii)工程(b)の少なくとも1つの遷移金属化合物は、溶液又は懸濁液の形態で、好ましくは溶液の形態で液体媒体中に提供される。
本発明の方法の工程(a)によれば、表面反応炭酸カルシウムが提供される。表面反応炭酸カルシウムはまた、官能化炭酸カルシウム(FCC)とも呼ばれる。
(a)粉砕天然炭酸カルシウム(GNCC)又は沈降炭酸カルシウム(PCC)の懸濁液を提供する工程;
(b)工程(a)で提供される懸濁液に、20℃で0以下のpKa値を有する又は20℃で0〜2.5のpKa値を有する少なくとも1つの酸を添加する工程;及び
(c)工程(a)で提供される懸濁液を工程(b)の前、工程(b)の間又は工程(b)の後にCO2で処理する工程。
(a)粉砕天然炭酸カルシウム(GNCC)又は沈降炭酸カルシウム(PCC)を提供する工程;
(b)少なくとも1つの水溶性酸を提供する工程;
(c)ガス状のCO2を提供する工程;及び
(d)工程(a)で提供されるこのGNCC又はPCC、工程(b)で提供される少なくとも1つの酸及び工程(c)で提供されるガス状CO2を接触させる工程;
(i)工程(b)で提供される少なくとも1つの酸が、その第1の利用可能な水素のイオン化に関連して、20℃で2.5を超えて7以下のpKaを有し、対応するアニオンが、水溶性カルシウム塩を形成でき、この第1の利用可能な水素の損失時に形成されること;及び(ii)工程(b)で提供される少なくとも1つの水溶性酸と工程(a)で提供されるGNCC又はPCCとを接触させた後、水素含有塩の場合この第1の利用可能な水素のイオン化に関連して、20℃で7を超えるpKaを有し、その塩アニオンが水不溶性カルシウム塩を形成できる少なくとも1つの水溶性塩がさらに提供されることを特徴とする。
本発明による製造方法の工程(b)において、少なくとも1つの遷移金属化合物が提供される。
本発明による製造方法の工程(c)では、工程(a)で提供される表面反応炭酸カルシウム及び工程(b)で提供される遷移金属化合物を液体媒体中で接触させて、表面反応炭酸カルシウム及び遷移金属化合物を含む混合物を得る。
本発明による方法は、工程(c)で得られる混合物から液体媒体を除去する工程(d)を任意選択的に含んでもよい。
本発明の触媒系を製造する方法の工程(e)によれば、工程(c)の混合物又は任意の工程(d)の濃縮混合物は、400℃以下、好ましくは約170℃〜400℃、より好ましくは200℃〜300℃、さらにより好ましくは250〜310℃、最も好ましくは280℃〜320℃の温度で熱処理される。
本発明による触媒系は固体担体上の遷移金属化合物を含み、ここで固体担体は粉砕天然炭酸カルシウム(GNCC)又は沈降炭酸カルシウム(PCC)及び炭酸カルシウム以外の少なくとも1つの水不溶性カルシウム塩を含む表面反応炭酸カルシウムである。この表面反応炭酸カルシウムは、CO2及び1つ以上のH3O+イオン供与体で処理された粉砕天然炭酸カルシウム(GNCC)又は沈降炭酸カルシウム(PCC)の反応生成物であり、ここでこのCO2は、H3O+イオン供与体処理によってインサイチュで形成され及び/又は外部供給源から供給される。
(i)窒素及びISO 9277:2010に従うBET法を用いて測定される場合15〜200m2/gの比表面積;
(ii)水銀ポロシメトリー測定から計算される場合0.1〜2.3cm3/gの範囲の粒子内圧入比細孔容積;及び
(iii)重量で、1:99〜99:1の範囲の、少なくとも1つの水不溶性カルシウム塩とカルサイト、アラゴナイト及び/又はバテライトとの比。
(i)窒素及びISO 9277:2010に従うBET法を用いて測定される場合15〜200m2/gの比表面積;
(ii)水銀ポロシメトリー測定から計算される場合0.1〜2.3cm3/gの範囲の粒子内圧入比細孔容積;及び
(iii)重量で1:99〜99:1の範囲の、少なくとも1つの水不溶性カルシウム塩とカルサイト、アラゴナイト及び/又はバテライトとの比。
(i)窒素及びISO 9277:2010に従うBET法を用いて測定される場合15〜200m2/gの比表面積;
(ii)水銀ポロシメトリー測定から計算される場合0.1〜2.3cm3/gの範囲の粒子内圧入比細孔容積;及び
(iii)重量で、1:99〜99:1の範囲の、少なくとも1つの水不溶性カルシウム塩とカルサイト、アラゴナイト及び/又はバテライトとの比、
ここで遷移金属化合物は、パラジウム化合物、白金化合物、銅化合物及びそれらの混合物からなる群から選択され、好ましくは遷移金属化合物は遷移金属塩又は遷移金属錯体である。
(i)窒素及びISO 9277:2010に従うBET法を用いて測定される場合15〜200m2/gの比表面積;
(ii)水銀ポロシメトリー測定から計算される場合0.1〜2.3cm3/gの範囲の粒子内圧入比細孔容積;及び
(iii)重量で1:99〜99:1の範囲の、少なくとも1つの水不溶性カルシウム塩とカルサイト、アラゴナイト及び/又はバテライトとの比、
遷移金属化合物は、パラジウム化合物、白金化合物、銅化合物及びそれらの混合物からなる群から選択され、好ましくは遷移金属化合物は、遷移金属塩又は遷移金属錯体である。
本発明の触媒系は、多くの触媒反応において特に有用であることがわかった。例えば、C−Cクロスカップリング反応におけるより高い転化率及びグリセロール水素化分解におけるより高い収率が達成された。
(a)1つ以上の反応物を提供する工程;
(b)本発明の触媒系を提供する工程;
(c)工程(b)で提供される触媒系の存在下で、工程(a)で提供される1つ以上の反応物を化学反応に供する工程。
本願を通じて定義され、以下の実施例において決定されるパラメータは、以下の測定方法に基づく:
固形分含有量
懸濁液固形分含有量(「乾燥重量」としても知られている)を、以下の設定を伴ったMoisture Analyser MJ33(Mettler−Toledo,Switzerland)を使用して決定した:150℃の乾燥温度、質量が30秒間にわたって1mg超えて変化しない場合に自動でスイッチオフ、5gの懸濁液の標準乾燥。
本明細書における表面反応炭酸カルシウムの粒径は、体積に基づく粒径分布dx(体積)として記載される。Malvern Mastersizer 2000 Laser Diffraction System(Malvern Instruments Plc.,Great Britain)を用いて、体積で決定されたメジアン粒径d50(体積)及び体積で決定されたトップカット粒径d98(体積)を評価した。d50(体積)又はd98(体積)の値は、粒子のそれぞれ50体積%又は98体積%がこの値未満の直径を有するような直径値を示す。測定によって得られた生データは、1.57の粒子屈折率及び0.005の吸収指数で、ミー理論を使用して分析された。方法及び機器は、当業者に既知であり、充填剤及び顔料の粒径分布を決定するために一般に使用される。
比細孔容積は、ラプラススロート直径0.004μm(〜nm)に等しい水銀414MPa(60000psi)の最大印加圧力を有するMicromeritics Autopore V 9620水銀ポロシメータを使用する水銀圧入ポロシメトリー測定を用いて測定される。各圧力工程で使用される平衡時間は20秒である。サンプル材料を、分析のために3cm3チャンバ粉末ペネトロメータに密封する。データは、ソフトウェアPore−Compを用いて、水銀圧縮、ペネトロメータ拡張及びサンプル材料圧縮について補正する(Gane,P.A.C.,Kettle,J.P.,Matthews,G.P.and Ridgway,C.J.,「Void Space Structure of Compressible Polymer Spheres and Consolidated Calcium Carbonate Paper−Coating Formulations」,Industrial and Engineering Chemistry Research,35(5),1996,p1753−1764)。
本明細書を通して、表面反応炭酸カルシウム又は他の材料の比表面積(m2/g)は、当業者に周知のBET法(吸着ガスとして窒素を使用)を用いて決定する(ISO 9277:2010)。次いで、充填剤材料の総表面積(m2単位)は、処理対応サンプルの比表面積及び質量(g単位)との乗算によって得られる。
XRD実験は、回転可能なPMMAホルダーリングを用いてサンプルに対して実施される。サンプルは、Braggの法則に従うBruker D8 Advance粉末回折計で分析される。この回折計は、2.2kWのX線管、サンプルホルダー、θ−θゴニオメータ及びVANTEC−1検出器からなる。ニッケルフィルタCu Kα線をすべての実験に用いる。プロファイルは2θで毎分0.7°の走査速度を用いて自動的に記録されたチャートである。得られた粉末回折パターンを、ICDD PDF 2データベースの基準パターンに基づいて、DIFFRACsuiteソフトウェアパッケージEVA及びSEARCHを用いて鉱物含有量によって容易に分類できる。
Suzuki反応:サンプルを、Dionex UVD3400検出器、Dionex ASi−100オートサンプラ(10μL注入)、Dionex TCC−100 HPLCカラムサーモスタット(40℃)及びDG1210脱ガス装置を備えたDionex P680 HPLCポンプ(1.0ml・分−1)を用いて、Waters Symmetry Shield(商標)カラム(RP−8、3.5μM、4.6x50mM)で分析した。水相中の0〜100%のアセトニトリルの勾配(脱塩水中の0.1%ギ酸及び5%アセトニトリル)を溶離剤として使用した。
SRCC1(d 50 (体積)=4.4μm、d 98 (体積)=8.6μm、SSA=39.9m 2 g −1 )
SRCC1は、沈降法によって決定される場合に2μm未満の90%の質量基準の粒径分布を有するHustadmarmor,Norwayからの粉砕大理石炭酸カルシウムの固形分含有量を、水性懸濁液の総重量に基づいて15重量%の固形分含有量が得られるように調整することによって、混合容器中で粉砕炭酸カルシウムの水性懸濁液10リットルを調製することによって得られた。加えて、30重量%のリン酸を含有する溶液を調製した。スラリーを混合しながら、0.83kgのリン酸溶液を70℃の温度で10分間かけてこの懸濁液に添加した。最後に、リン酸を添加した後、スラリーを容器から取り出し、濾過し、乾燥する前に、スラリーをさらに5分間撹拌した。
SRCC2は、沈降法によって決定される場合に2μm未満の90%の質量基準の粒径分布を有するHustadmarmor,Norwayからの粉砕大理石炭酸カルシウムの固形分含有量を、水性懸濁液の総重量に基づいて15重量%の固形分含有量が得られるように調整することによって、混合容器中で粉砕炭酸カルシウムの水性懸濁液10リットルを調製することによって得られた。加えて、希リン酸と硫酸アルミニウム十六水和物とをブレンドすることによって溶液を調製したが、ここで、リン酸は30重量%の濃度を有し、硫酸アルミニウム十六水和物はニートなリン酸の質量5%で投与した。スラリーを混合しながら、1.7kgのリン酸/硫酸アルミニウム溶液を70℃の温度で10分間かけてこの懸濁液に添加した。最後に、リン酸を添加した後、スラリーを容器から取り出し、濾過し、乾燥する前に、スラリーをさらに5分間撹拌した。
SRCC3は、沈降法によって決定される場合に2μm未満の90%の質量基準の粒径分布を有するHustadmarmor,Norwayからの粉砕大理石炭酸カルシウムの固形分含有量を、水性懸濁液の総重量に基づいて10重量%の固形分含有量が得られるように調整することによって、混合容器中で粉砕炭酸カルシウムの水性懸濁液10リットルを調製することによって得られた。加えて、希リン酸とクエン酸とをブレンドすることによって溶液を調製し、ここでリン酸は29重量%の濃度を有し、クエン酸はニートなリン酸の質量10%で投与された。スラリーを混合しながら、1.65kgのリン酸/クエン酸溶液を70℃の温度で10分間かけてこの懸濁液に添加した。最後に、リン酸を添加した後、スラリーを容器から取り出し、濾過し、乾燥する前に、スラリーをさらに5分間撹拌した。
SRCC4は、沈降法によって決定される場合に2μm未満の90%の質量基準の粒径分布を有するHustadmarmor,Norwayからの粉砕大理石炭酸カルシウムの固形分含有量を、水性懸濁液の総重量に基づいて10重量%の固形分含有量が得られるように調整することによって、混合容器中で粉砕炭酸カルシウムの水性懸濁液10lを調製することによって得られた。加えて、30重量%のリン酸を含有する溶液を調製し、一方5重量%のクエン酸を含有する別の溶液を調製した。スラリーを混合しながら、1.60kgのリン酸溶液を70℃の温度で10分間かけてこの懸濁液に添加した。また、リン酸添加開始から2分後から0.05kgのクエン酸溶液もスラリーに添加した。最後に、リン酸を添加した後、スラリーを容器から取り出し、濾過し、乾燥する前に、スラリーをさらに5分間撹拌した。
SRCC5は、沈降法によって決定される場合に2μm未満の90%の質量基準の粒径分布を有するHustadmarmor,Norwayからの粉砕大理石炭酸カルシウムの固形分含有量を、水性懸濁液の総重量に基づいて10重量%の固形分含有量が得られるように調整することによって、混合容器中で粉砕炭酸カルシウムの水性懸濁液10リットルを調製することによって得られた。加えて、30重量%のリン酸を含有する溶液を調製し、一方5重量%のクエン酸を含有する別の溶液を調製した。スラリーを混合しながら、1.60kgのリン酸溶液を70℃の温度で10分間かけてこの懸濁液に添加した。また、リン酸添加開始から3分後から0.05kgのクエン酸溶液もスラリーに添加した。最後に、リン酸を添加した後、スラリーを容器から取り出し、濾過し、乾燥する前に、スラリーをさらに5分間撹拌した。
方法1:エタノール中の非水性含浸
担体(0.5g)のスラリーを、金属塩が既に溶解している有機溶媒(20ml)中で調製する。次いでスラリーを撹拌し(18時間)、濾過し、真空下に周囲温度で18時間乾燥する。この手順は、触媒充填量を増やすために一度繰り返すことができる。
担体(2g)のスラリーを、金属塩も溶解している有機溶媒(25ml)中で調製する。次いで、溶媒を一定の撹拌下で蒸発させて触媒を担体上に含浸させ、均一な粉末を得る。次いで、この材料を周囲温度で18時間真空下で乾燥し、300℃で焼成する。
金属の水溶性塩を最初に水(4ml)に溶解し、NaHCO3(飽和)を使用することによりpHを5.5〜6に調整する。溶液を水(8〜12ml)中の担体(1.8〜2.0g)のスラリーに添加する。混合物を30〜90分間70℃に加熱し、次いで室温に冷却する。触媒を濾別し、水(3×4ml)ですすぎ、周囲温度で18時間真空乾燥し、次いで300℃で3時間焼成する。この手順は、触媒充填量を増やすために数回繰り返すことができる。
水性含浸物C19(SRCC4)からの濾液溶液を、すべての可溶性金属塩が黒色物質として沈殿するまで(すなわち、溶液の完全な脱色まで)静置した。沈殿物を計量し、触媒充填量をこの値から計算して4.6重量%のPtとした。計算は金属白金から行った。
Suzuki反応(実施例A1〜A10、比較例CA1〜CA5)
ヨードベンゼンとフェニルボロン酸との間のカップリング反応は、様々な触媒充填量及び触媒タイプを用いて、Letters in Organic Chemistry,4,2007,13−15に従って行われた。典型的な反応では、0.45gのフェニルボロン酸(1.5当量、3.7mmol)を100mlの丸底フラスコに計量した。炭酸カリウム(2.9当量、7.3mmol、1.0g)を80mLの溶媒(水中40%エタノール)と共に混合物に添加した。フラスコをセプタムで閉じ、撹拌を開始し、フラスコを窒素流でパージした。次いでヨードベンゼン(0.50g、2.5mmol)を添加し、続いて予め計量した触媒を加えた(密閉バイアル中)。窒素パージを10〜15分間続けた。アリコート(約0.5ml)を混合物から一定間隔で取り出し、1mlのヘプタンで抽出し、UVダイオードアレイ検出器(238nm)を用いてHPLCによって分析した。転化率を表4にまとめる。
反応は、Catalysis Communications,13,2011,1−5に従って実施した。水(100mM)中の触媒(グリセロールに対して5モル%の活性金属)と20mlのグリセロールとの混合物を40バールの水素圧下に置き、次いで800rpmで撹拌しながら18時間200℃に加熱した。室温に冷却した後、サンプルを分析のために採取した。サンプルを濾過し、等量の5mMのH2SO4と混合した。触媒を濾別し、水(3×1ml)ですすぎ、真空乾燥した。反応混合物をHPLCにより分析して、出発材料(グリセロール)の量及び4つの主要反応生成物;乳酸(LA)、1,2−プロパンジオール(12−PD)、エチレングリコール(EG)及びエタノール(EtOH)の量を決定した。すべての場合において、これらの化合物は総ピーク面積の95%以上を占める。結果を表6にまとめる。
Claims (22)
- 固体担体上に遷移金属化合物を含む触媒系であって、前記固体担体は、粉砕天然炭酸カルシウム(GNCC)又は沈降炭酸カルシウム(PCC)及び炭酸カルシウム以外の少なくとも1つの水不溶性カルシウム塩を含む表面反応炭酸カルシウムであり、前記表面反応炭酸カルシウムが、
(i)窒素及びISO 9277:2010に従うBET法を用いて測定される場合15〜200m2/gの比表面積;
(ii)水銀ポロシメトリー測定から計算される場合0.1〜2.3cm3/gの範囲の粒子内圧入比細孔容積;及び
(iii)重量で、1:99〜99:1の範囲の、前記少なくとも1つの水不溶性カルシウム塩とカルサイト、アラゴナイト及び/又はバテライトとの比、
を示す触媒系。 - 前記少なくとも1つの水不溶性カルシウム塩が、リン酸オクタカルシウム、ヒドロキシルアパタイト、クロルアパタイト、フルオロアパタイト、カーボネートアパタイト及びそれらの混合物からなる群から選択され、好ましくは前記少なくとも1つの水不溶性カルシウム塩がヒドロキシルアパタイトである、請求項1に記載の触媒系。
- 前記少なくとも1つの水不溶性カルシウム塩と、カルサイト、アラゴナイト及び/又はバテライト、好ましくはカルサイトとの前記比が、重量で、1:9〜9:1、好ましくは1:7〜8:1、より好ましくは1:5〜7:1、さらにより好ましくは1:4〜7:1の範囲である、請求項1又は2に記載の触媒系。
- 前記遷移金属化合物が、パラジウム化合物、白金化合物、銅化合物及びそれらの混合物からなる群から選択される、請求項1〜3のいずれか一項に記載の触媒系。
- 前記遷移金属化合物が、元素状パラジウム、Pd(acac)2、Na2PdCl4、Pd(OAc)2、Pd(PPh3)4、PdCl2(PPh3)2、(dppf)PdCl2、(dppe)PdCl2、(dppp)PdCl2、(dppb)PdCl2、PdCl2、(C3H5PdCl)2、ビス(アセテート)−トリフェニル−ホスフィン−パラジウム(II)、Pd(dba)2、Pd(H2NCH2CH2NH2)Cl2、元素状白金、Na2PtCl6Pt(acac)2、Na2PtCl4、H2PtCl6、(NH4)2[PtCl6]、PtO2・H2O、PtCl4、元素状銅、Cu2O、Cu2S、銅(I)−チオフェン−2−カルボキシレート、CuBr、CuCN、CuCl、CuF、CuI、CuH、CuSCN、CuBr2、CuCO3、CuCl2、CuF2、Cu(NO3)2、Cu3(PO4)2、CuO、CuO2、Cu(OH)2、CuI2、CuS、CuSO4、Cu2(OAc)4及びそれらの混合物からなる群から選択され、好ましくは前記遷移金属化合物が、元素状パラジウム、Pd(acac)2、Na2PdCl4、Pd(OAc)2、Pd(PPh3)4、PdCl2(PPh3)2、(dppf)PdCl2、(dppe)PdCl2、(dppp)PdCl2、(dppb)PdCl2、PdCl2、(C3H5PdCl)2、ビス(アセテート)−トリフェニル−ホスフィン−パラジウム(II)、Pd(dba)2、Pd(H2NCH2CH2NH2)Cl2、元素状白金、Na2PtCl6Pt(acac)2、Na2PtCl4、H2PtCl6、(NH4)2[PtCl6]、PtO2・H2O、PtCl4及びそれらの混合物からなる群から選択される、請求項1〜4のいずれか一項に記載の触媒系。
- 前記表面反応炭酸カルシウムが、
(i)窒素及びISO 9277:2010に従うBET法を用いて測定される場合27〜180m2/g、好ましくは25〜160m2/g、より好ましくは30〜150m2/gの範囲の比表面積;
(ii)1〜75μm、好ましくは2〜50μm、より好ましくは3〜40μm、さらにより好ましくは4〜30μm、最も好ましくは5〜15μmの範囲のd50(体積);
(iii)2〜150μm、好ましくは4〜100μm、より好ましくは6〜80μm、さらにより好ましくは8〜60μm、最も好ましくは10〜30μmの範囲のd98(体積);及び/又は
(iv)水銀ポロシメトリー測定から計算される場合0.2〜2.0cm3/g、好ましくは0.4〜1.8cm3/g、最も好ましくは0.6〜1.6cm3/gの範囲の粒子内圧入比細孔容積、
を有する、請求項1〜5のいずれか一項に記載の触媒系。 - 前記触媒系が、遷移金属化合物と表面反応炭酸カルシウムとの反応によって得られる1つ以上の反応生成物をさらに含む、請求項1〜6のいずれか一項に記載の触媒系。
- 前記遷移金属化合物及び/又は前記1つ以上の反応生成物の含有量が、前記触媒系の総重量あたりの前記遷移金属化合物の重量に基づいて、0.1〜60重量%、好ましくは0.1〜30重量%、より好ましくは0.1〜20重量%、さらにより好ましくは0.1〜10重量%、最も好ましくは0.2〜5重量%の範囲である、請求項1〜7のいずれか一項に記載の触媒系。
- 固体担体上に遷移金属化合物を含む触媒系を製造するための方法であって、
(a)粉砕天然炭酸カルシウム(GNCC)又は沈降炭酸カルシウム(PCC)及び炭酸カルシウム以外の少なくとも1つの水不溶性カルシウム塩を含む少なくとも1つの表面反応炭酸カルシウムを提供する工程;
(b)少なくとも1つの遷移金属化合物を提供する工程;及び
(c)液体媒体中、工程(a)で提供される前記表面反応炭酸カルシウム及び工程(b)で提供される前記遷移金属化合物を接触させて、表面反応炭酸カルシウム及び遷移金属化合物を含む混合物を得る工程;
を含み、
前記表面反応炭酸カルシウムは、
(i)窒素及びISO9277:2010に従うBET法を用いて測定される場合15〜200m2/gの比表面積;
(ii)水銀ポロシメトリー測定から計算される場合0.1〜2.3cm3/gの範囲の粒子内圧入比細孔容積;及び
(iii)重量で1:99〜99:1の範囲の、前記少なくとも1つの水不溶性カルシウム塩とカルサイト、アラゴナイト及び/又はバテライトとの比
を示す、方法。 - (i)工程(a)の前記少なくとも1つの表面反応炭酸カルシウムが、懸濁液の形態で液体媒体中に提供される;及び/又は
(ii)工程(b)の前記少なくとも1つの遷移金属化合物が、溶液又は懸濁液の形態で、好ましくは溶液の形態で液体媒体中に提供される、
請求項9に記載の方法。 - 前記方法が、工程(c)の前記混合物に含有される前記液体媒体の少なくとも一部を蒸発及び/又は濾過によって除去して濃縮混合物を得る工程(d)をさらに含む、請求項9又は10に記載の方法。
- 前記方法が、工程(c)の混合物又は工程(d)の濃縮混合物を、400℃以下の温度で、好ましくは170℃〜400℃、より好ましくは200℃〜300℃、さらにより好ましくは250℃〜310℃、最も好ましくは280℃〜320℃の範囲の温度で熱処理する工程(e)をさらに含む、請求項9〜11のいずれか一項に記載の方法。
- 前記遷移金属化合物が、パラジウム化合物、白金化合物、銅化合物及びそれらの混合物からなる群から選択される、請求項9〜12のいずれか一項に記載の方法。
- 前記遷移金属化合物が、元素状パラジウム、Pd(acac)2、Na2PdCl4、Pd(OAc)2、Pd(PPh3)4、PdCl2(PPh3)2、(dppf)PdCl2、(dppe)PdCl2、(dppp)PdCl2、(dppb)PdCl2、PdCl2、(C3H5PdCl)2、ビス(アセテート)−トリフェニル−ホスフィン−パラジウム(II)、Pd(dba)2、Pd(H2NCH2CH2NH2)Cl2、元素状白金、Na2PtCl6Pt(acac)2、Na2PtCl4、H2PtCl6、(NH4)2[PtCl6]、PtO2・H2O、PtCl4、元素状銅、Cu2O、Cu2S、銅(I)−チオフェン−2−カルボキシレート、CuBr、CuCN、CuCl、CuF、CuI、CuH、CuSCN、CuBr2、CuCO3、CuCl2、CuF2、Cu(NO3)2、Cu3(PO4)2、CuO、CuO2、Cu(OH)2、CuI2、CuS、CuSO4、Cu2(OAc)4及びそれらの混合物からなる群から選択され、好ましくは前記遷移金属化合物が、元素状パラジウム、Pd(acac)2、Na2PdCl4、Pd(OAc)2、Pd(PPh3)4、PdCl2(PPh3)2、(dppf)PdCl2、(dppe)PdCl2、(dppp)PdCl2、(dppb)PdCl2、PdCl2、(C3H5PdCl)2、ビス(アセテート)−トリフェニル−ホスフィン−パラジウム(II)、Pd(dba)2、Pd(H2NCH2CH2NH2)Cl2、元素状白金、Na2PtCl6Pt(acac)2、Na2PtCl4、H2PtCl6、(NH4)2[PtCl6]、PtO2・H2O、PtCl4及びそれらの混合物からなる群から選択される、請求項9〜13のいずれか一項に記載の方法。
- 前記液体媒体が、非極性溶媒、極性溶媒又はそれらの混合物であり、好ましくは前記非極性溶媒は、ペンタン、シクロペンタン、ヘキサン、シクロヘキサン、ベンゼン、トルエン、1,4−ジオキサン、クロロホルム、ジエチルエーテル、ジクロロメタン及びそれらの混合物からなる群から選択され、及び/又は前記極性溶媒は、テトラヒドロフラン、酢酸エチル、アセトン、ジメチルホルムアミド、アセトニトリル、ジメチルスルホキシド、ニトロメタン、プロピレンカーボネート、ギ酸、n−ブタノール、イソプロパノール、n−プロパノール、エタノール、メタノール、酢酸、水及びそれらの混合物からなる群から選択される、請求項9〜14のいずれか一項に記載の方法。
- 前記遷移金属化合物が、Na2PdCl4及び/又はNa2PtCl4であり、前記液体媒体が極性溶媒、好ましくは水であり;及び/又は前記遷移金属化合物がPd(acac)2及び/又はPt(acac)2であり、前記液体媒体は非極性溶媒、好ましくはトルエンである、請求項9〜15のいずれか一項に記載の方法。
- 請求項9〜16のいずれか一項に記載の方法に従って得られることができる触媒系。
- (a)1つ以上の反応物を提供する工程;
(b)請求項1〜8又は17のいずれか一項に記載の前記触媒系を提供する工程;
(c)工程(b)で提供される前記触媒系の存在下で、工程(a)で提供される前記1つ以上の反応物を化学反応に供する工程、
を含む方法における請求項1〜8又は17のいずれか一項に記載の触媒系の使用。 - 前記方法が、工程(c)の前記化学反応の後に前記触媒系を回収し、前記遷移金属をリサイクルする工程(d)をさらに含む、請求項18に記載の使用。
- 工程(c)の前記化学反応が、水素化分解反応、C−Cカップリング及びC−Cクロスカップリング、C−Nクロスカップリング、C−Oクロスカップリング、C−Sクロスカップリング、付加環化反応、アルケン水素化及びアルキン水素化、アリル置換、ニトロ基の還元及びハロゲン化アリールのヒドロカルボニル化、好ましくは水素化分解、C−Cカップリング及びC−Cクロスカップリング、の反応タイプの1つ以上から選択される、請求項18又は19に記載の使用。
- 遷移金属系触媒用の担体としての、請求項1〜3又は6のいずれか一項に記載の表面反応炭酸カルシウムの使用。
- 請求項1〜8又は17のいずれか一項に記載の触媒系を含む顆粒、成形品又は押出物。
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DK2386682T3 (da) * | 2010-04-27 | 2014-06-23 | Omya Int Ag | Fremgangsmåde til fremstilling af strukturerede materialer under anvendelse af nano-fibrillære cellulosegeler |
EP3542897A1 (en) * | 2018-03-23 | 2019-09-25 | Omya International AG | Method for transesterification of carboxylic acid esters |
JP2022549645A (ja) * | 2019-09-26 | 2022-11-28 | オムヤ インターナショナル アクチェンゲゼルシャフト | 金属種の触媒担体としてのsrcc |
BR112022005560A2 (pt) * | 2019-09-26 | 2022-06-21 | Omya Int Ag | Sistema catalítico, método para fabricar um sistema catalítico, usos de um sistema catalítico e de um carreador sólido, e, grânulos, peças moldadas ou extrudados |
CN110743582B (zh) * | 2019-10-23 | 2020-10-02 | 广东海洋大学 | 海洋生物废弃物牡蛎壳负载钯催化剂的制备及应用 |
WO2023285198A1 (en) * | 2021-07-12 | 2023-01-19 | Omya International Ag | Process for preparing an alcohol using a surface-reacted calcium carbonate catalyst |
EP4306210A1 (en) * | 2022-07-12 | 2024-01-17 | Omya International AG | High surface area pcc as a catalyst carrier for platinum compounds |
CN116351476A (zh) * | 2022-12-18 | 2023-06-30 | 石河子大学 | 一种用于催化乙炔氢氯化反应的配体-铜基催化剂及其制备方法和应用 |
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WO2018019630A1 (en) | 2018-02-01 |
KR20190033583A (ko) | 2019-03-29 |
DK3487619T3 (da) | 2023-11-06 |
BR112019001472A2 (pt) | 2019-05-07 |
US20190262807A1 (en) | 2019-08-29 |
EP3487619B1 (en) | 2023-10-04 |
JP6979056B2 (ja) | 2021-12-08 |
AU2017304362B2 (en) | 2021-08-05 |
CN109475849A (zh) | 2019-03-15 |
BR112019001472B1 (pt) | 2022-10-04 |
RU2742335C2 (ru) | 2021-02-04 |
RU2019104891A (ru) | 2020-08-25 |
CA3030065A1 (en) | 2018-02-01 |
PL3487619T3 (pl) | 2024-02-19 |
KR102401444B1 (ko) | 2022-05-25 |
RU2019104891A3 (ja) | 2020-08-25 |
AU2017304362A1 (en) | 2019-01-03 |
EP3487619A1 (en) | 2019-05-29 |
US10875014B2 (en) | 2020-12-29 |
EP3275537A1 (en) | 2018-01-31 |
MX2019001061A (es) | 2019-04-25 |
FI3487619T3 (fi) | 2023-10-18 |
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