JP2019501760A - コバルトをベースとする触媒であって、コバルトは、メソ細孔性酸化物マトリクスに中に捕捉され、少なくとも1種のモノマー前駆体から得られたものである触媒の存在下に合成ガスから炭化水素を合成する方法 - Google Patents
コバルトをベースとする触媒であって、コバルトは、メソ細孔性酸化物マトリクスに中に捕捉され、少なくとも1種のモノマー前駆体から得られたものである触媒の存在下に合成ガスから炭化水素を合成する方法 Download PDFInfo
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- JP2019501760A JP2019501760A JP2018526170A JP2018526170A JP2019501760A JP 2019501760 A JP2019501760 A JP 2019501760A JP 2018526170 A JP2018526170 A JP 2018526170A JP 2018526170 A JP2018526170 A JP 2018526170A JP 2019501760 A JP2019501760 A JP 2019501760A
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- Prior art keywords
- catalyst
- range
- cobalt
- weight
- mixture
- 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.)
- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 109
- 239000002243 precursor Substances 0.000 title claims abstract description 88
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 60
- 239000010941 cobalt Substances 0.000 title claims abstract description 60
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000011159 matrix material Substances 0.000 title claims abstract description 44
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 24
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 title claims description 51
- 238000003786 synthesis reaction Methods 0.000 title description 39
- 239000000178 monomer Substances 0.000 title description 6
- 238000000034 method Methods 0.000 claims abstract description 73
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 239000007787 solid Substances 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 26
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- 238000011282 treatment Methods 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 230000008569 process Effects 0.000 claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 24
- 238000005470 impregnation Methods 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000443 aerosol Substances 0.000 claims description 13
- 238000001694 spray drying Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 150000003839 salts Chemical group 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003125 aqueous solvent Substances 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 35
- 239000007789 gas Substances 0.000 description 25
- 239000011148 porous material Substances 0.000 description 16
- 239000012071 phase Substances 0.000 description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 229920002415 Pluronic P-123 Polymers 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
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- 238000000265 homogenisation Methods 0.000 description 9
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- 238000012360 testing method Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 239000002028 Biomass Substances 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 150000004703 alkoxides Chemical group 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000011066 ex-situ storage Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- -1 alkoxy chloride Chemical compound 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
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- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000012686 silicon precursor Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920002359 Tetronic® Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical class [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 229910001942 caesium oxide Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- MQIKJSYMMJWAMP-UHFFFAOYSA-N dicobalt octacarbonyl Chemical group [Co+2].[Co+2].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] MQIKJSYMMJWAMP-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical group O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000009666 routine test Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
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Abstract
Description
本発明は、メソ細孔性酸化物マトリクスと、元素コバルトとを含む触媒の存在下に、一酸化炭素と二水素とを含む供給原料から線状パラフィン系炭化水素を合成する方法であって、前記触媒の全重量に対する金属の重量%として表される元素コバルトの重量含有率が0.5重量%〜60重量%の範囲内であり、前記触媒は、少なくとも以下の工程:
a) 水性溶媒または水−有機性溶媒(hydro-organic solvent)中、コバルトを含む少なくとも1種の分子前駆体と、ケイ素、アルミニウム、チタン、ジルコニウム、セリウムおよびそれらの混合物によって構成される群から選択される少なくとも1種の元素Xを含む前記メソ細孔性酸化物マトリクスの少なくとも1種の分子前駆体とを混合する工程であって、前記分子前駆体は、前記水性溶媒または水−有機性溶媒に溶解させられる、工程;
b) 工程a)において得られた混合物をエアロゾル噴霧乾燥させて、結果として、球状液滴を形成させる工程;
c) 前記球状液滴を10℃〜300℃の範囲内の温度で乾燥させて固体粒子を得る工程;
d) 酸化状態が0であるコバルトのナノ粒子を形成するように、還元処理によって前記固体粒子を活性にする工程
を含む方法に従って調製される、方法に関する。
一態様において、本発明は、フィッシャー・トロプシュ法において従来から採用される触媒を製造するための方法の前例のない単純化を呈する調製方法に従って調製された触媒の存在下にパラフィン系炭化水素を合成する方法(フィッシャー・トロプシュ法)を提案し、このことは、得られた合成炭化水素の製造のコストが低減させられ得、最近の数十年の一層より厳しい環境上の制約が適合され得ることを意味する。このような単純化は、噴霧乾燥によって前記触媒を調製する方法を開発することによって達成され、メソ細孔性酸化物マトリクスの形成の間に、活性相の少なくとも1種の前駆体、すなわち、元素コバルトの少なくとも1種の前駆体を完全にまたは部分的に組み込むために用いられ得る。マトリクスは、通常、従来の合成方法において「担体」と称される。
(FT合成法)
線状パラフィン系炭化水素の合成方法は、フィッシャー・トロプシュ法とも呼ばれ、この方法は、本質的に線状の飽和C5+炭化水素を製造するために用いられ得る。本発明によると、用語「本質的に線状の飽和C5+炭化水素」は、炭化水素であって、分子当たり少なくとも5個の炭素原子を含有する炭化水素化合物の割合が、形成された炭化水素の全体の最低50重量%、好ましくは最低80重量%を示し、分子当たり少なくとも5個の炭素原子を含有する前記炭化水素化合物中に存在するオレフィン性化合物の全含有率が、15重量%未満であるものを意味する。本発明の方法により製造される炭化水素は、それ故に、本質的にパラフィンである炭化水素であり、最高沸点を有するフラクションは、接触水素化転化方法、例えば、水素化分解および/または水素化異性化によって中間留分(ガスオイルおよびケロセン留分)に高収率で転化され得る。
本発明によると、線状パラフィン系炭化水素の合成方法は、メソ細孔性酸化物マトリクスと、元素コバルトとを含む触媒の存在下に行われ、元素コバルトの重量含有率は、前記触媒の全重量に対する金属の重量%として表されて0.5〜60重量%であり、前記触媒は、少なくとも以下の工程:
a) 水性または水−有機性の溶媒中、コバルトを含む少なくとも1種の分子前駆体と、ケイ素、アルミニウム、チタン、ジルコニウム、セリウムおよびそれらの混合物によって構成される群から選択される少なくとも1種の元素Xを含む前記メソ細孔性酸化物マトリクスの少なくとも1種の分子前駆体とを混合する工程であって、前記分子前駆体は、前記水性溶媒または水−有機性溶媒に溶解させられている、工程;
b) 工程a)において得られた混合物をエアロゾル噴霧乾燥させて、その結果として球状液滴を形成させる工程;
c) 前記球状液滴を10℃〜300℃の範囲内の温度で乾燥させて固体粒子を得る工程;
d) 工程c)から(場合によっては工程c1)から)得られた固体粒子を活性にする工程であって、有利には高純度のまたは希釈された水素中、高温での還元処理により行われ、ゼロの酸化状態を有する、すなわち、金属形態にあるコバルトの粒子、すなわち、本発明により用いられる触媒の活性相を形成するようにする、工程
を連続的に含む調製方法に従って調製される。
本発明は、メソ細孔性酸化物マトリクスと少なくとも元素コバルトとを含む触媒を用いて実施される炭化水素の合成のためのフィッシャー・トロプシュ法であって、前記元素は、前記マトリクスの形成の間に、コバルトを含む少なくとも1種の分子前駆体と、ケイ素、アルミニウム、チタン、ジルコニウム、セリウムおよびこれらの混合物によって構成される群から選択される少なくとも1種の元素Xを含む前記メソ細孔性酸化物マトリクスの少なくとも1種の分子前駆体とによって組み入れられる、方法に関する。
以下の実施例において、使用されたエアロゾル技術は、本発明の開示において上述されたものであった。触媒は、FT合成法を表す触媒試験の前に現場外(ex situ)で活性にされた。使用された噴霧乾燥機は、Buchiによって供給された市販B290装置であり、超音波噴霧乾燥ノズルを有する。
触媒の全重量に対して15重量%の元素Coと、シリカマトリクスとを含み、メソ構造化シリカマトリクスの形成の間に元素コバルトの分子前駆体Co(NO3)2を組み入れることによって得られた非活性化触媒Aの調製。
触媒の全重量に対して15重量%の元素Coと、シリカマトリクスとを含み、メソ構造化シリカマトリクスの形成の間に元素コバルトの分子前駆体Co(NO3)2を組み入れることによって得られる非活性化触媒Bの調製。
触媒の全重量に対して15重量%の元素Coと、マトリクスの全重量に対して5重量%のシリカを含有するアルミノシリカートマトリクスとを含み、メソ細孔アルミノシリカートマトリクスの形成の間に元素Coの分子前駆体Co(NO3)2を組み入れることによって得られる非活性化触媒Cの調製。
触媒の全重量に対して15重量%の元素Coと、シリカマトリクスとを含み、メソ構造化シリカマトリクスの形成の間に元素コバルトの分子前駆体Co(NO3)2の一部を組み入れ、次いで、第1の工程の間に得られた固体上への乾式含浸によって元素Coの分子前駆体Co(NO3)2の一部を組み入れることによって得られる非活性化触媒Dの調製。
触媒の全重量に対して15重量%の元素Coと、シリカマトリクスとを含み、メソ細孔性酸化ケイ素マトリクスを形成し、次いで、第1の工程の間に得られた固体上への乾式含浸によって元素コバルトの分子前駆体Co(NO3)2を組み入れることによって得られる非活性化触媒Eの調製。
フィッシャー・トロプシュ合成における触媒A〜Eの使用。
Claims (11)
- メソ細孔性酸化物マトリクスと、元素コバルトとを含む触媒の存在下に、一酸化炭素と二水素とを含む供給原料から線状パラフィン系炭化水素を合成する方法であって、元素コバルトの重量含有量は、前記触媒の全重量に対する金属の重量%として表されて0.5重量%〜60重量%の範囲内であり、前記触媒は、少なくとも以下の工程:
a) 水性溶媒または水−有機性溶媒中、コバルトを含む少なくとも1種の分子前駆体と、ケイ素、アルミニウム、チタン、ジルコニウム、セリウムおよびこれらの混合物によって構成される群から選択される少なくとも1種の元素Xを含む前記メソ細孔性酸化物マトリクスの少なくとも1種の分子前駆体とを混合する工程であって、前記分子前駆体は、前記水性溶媒または水−有機溶媒に溶解させられている、工程;
b) 工程a)において得られた混合物をエアロゾル噴霧乾燥させて、その結果として球状液滴を形成させる工程;
c) 前記球状液滴を10℃〜300℃の範囲内の温度で乾燥させて固体粒子を得る工程;
d) 還元処理により、0の酸化状態を有するコバルトのナノ粒子を形成するようにして前記固体粒子を活性にする工程
を含む調製方法により調製される、方法。 - 前記工程a)による前記混合物は、前記メソ細孔性酸化物マトリクスの唯一の分子前駆体として元素ケイ素を含む分子前駆体を含む、請求項1に記載の方法。
- 前記工程a)による前記混合物は、前記細孔性酸化物マトリクスの唯一の分子前駆体として、元素ケイ素を含む分子前駆体と、元素アルミニウムを含む分子前駆体とを、シリカ含有率が、前記酸化物マトリクスの全重量に対して0.5重量%〜95重量%になるように含む、請求項1に記載の方法。
- 第VIIB族、第IA族、第IIA族およびIIIA族から選択される少なくとも1種の元素、および単独または混合物としての元素Rh、Pd、Ag、Os、Ir、Pt、Auが、工程a)の混合物に加えられ、前記触媒が含む前記少なくとも1種の元素の重量含有率が、前記触媒の全重量に対する元素の重量%として表されて、20重量ppm〜10重量%の範囲内になるようにされる、請求項1〜3のいずれか1つに記載の方法。
- 工程a)による前記混合物は、少なくとも1種の界面活性剤も含む、請求項1〜4のいずれか1つに記載の方法。
- 前記調製方法は、工程c)から得られた固体粒子の熱処理のための工程c1)を含み、130℃〜1000℃の範囲内の温度で、72時間未満、好ましくは24時間未満の期間にわたって、工程d)の上流で実施される、請求項1〜5のいずれか1つに記載の方法。
- 前記調製方法は、工程c)から得られた固体粒子の水熱処理のための工程c’)を含み、工程d)の上流で、水蒸気中、110℃〜900℃の範囲内の温度で、好ましくは30分〜12時間の期間にわたって、空気/水蒸気の混合物により実施され、前記混合物は、2%〜80%(モル)の範囲内の水を水蒸気の形態で含む、請求項1〜5のいずれか1つに記載の方法。
- 前記調製方法は、工程c1)から得られた固体粒子の水熱処理のための工程c’)を含み、水蒸気中、110℃〜900℃の範囲内の温度で、好ましくは30分〜12時間の期間にわたって、空気/水蒸気混合物を用いて、工程d)の上流で実施され、前記混合物は、2%〜80%(モル)の水を水蒸気の形態で含む、請求項6に記載の方法。
- 工程d)の直前に、得られた固体粒子に、コバルト、ニッケル、ルテニウムおよび鉄によって構成される群から選択される第VIII族からの金属の少なくとも1種の塩を含む水性または有機性の溶液を含浸させ、かつ、得られた生成物を60℃〜200℃の範囲内の温度で乾燥させるための工程c”)を含む、請求項1〜8のいずれか1つに記載の方法。
- 第VIIB族、第IA族、第IIA族および第IIIA族から選択される少なくとも1種の元素、および単独または混合物としての元素Rh、Pd、Ag、Os、Ir、Pt、Auを、含浸工程c”)の間に、前記触媒が、前
記少なくとも1種の元素を、前記触媒の全重量に対する元素の重量%として表されて20重量ppm〜10重量%の範囲内の重量含有率で含むように添加する、請求項9に記載の方法。 - H2/COモル比が0.5〜4の範囲内であり、0.1〜15MPaの範囲内の全圧、150℃〜350℃の範囲内の温度、触媒の体積当たりかつ時間当たりの供給原料の体積100〜20000の範囲内の毎時空間速度で操作される、請求項1〜10のいずれか1つに記載のパラフィン系炭化水素の合成方法。
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PCT/EP2016/076881 WO2017089111A1 (fr) | 2015-11-23 | 2016-11-07 | Procede de synthese d'hydrocarbures a partir de gaz de synthese en presence d'un catalyseur a base de cobalt piege dans une matrice oxyde mesoporeuse et obtenu a partir d'au moins un precurseur monomerique |
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