JP6242920B2 - 気相および液体−気体相ニトリル化法 - Google Patents
気相および液体−気体相ニトリル化法 Download PDFInfo
- Publication number
- JP6242920B2 JP6242920B2 JP2015558432A JP2015558432A JP6242920B2 JP 6242920 B2 JP6242920 B2 JP 6242920B2 JP 2015558432 A JP2015558432 A JP 2015558432A JP 2015558432 A JP2015558432 A JP 2015558432A JP 6242920 B2 JP6242920 B2 JP 6242920B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- catalyst
- metal
- group
- metal oxide
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title claims description 52
- 239000003054 catalyst Substances 0.000 claims description 71
- 229910044991 metal oxide Inorganic materials 0.000 claims description 46
- 150000004706 metal oxides Chemical class 0.000 claims description 46
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 36
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 36
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 30
- 239000000194 fatty acid Substances 0.000 claims description 30
- 229930195729 fatty acid Natural products 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 20
- 150000004665 fatty acids Chemical class 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 150000002148 esters Chemical class 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- -1 fatty acid esters Chemical class 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 15
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 15
- 239000011949 solid catalyst Substances 0.000 claims description 15
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 12
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 11
- 230000000737 periodic effect Effects 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 9
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 7
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 7
- 229910001887 tin oxide Inorganic materials 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 230000001546 nitrifying effect Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 3
- 230000000802 nitrating effect Effects 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- 239000012071 phase Substances 0.000 description 25
- 150000002825 nitriles Chemical class 0.000 description 16
- 150000001408 amides Chemical class 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000004702 methyl esters Chemical class 0.000 description 4
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000007037 hydroformylation reaction Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000005649 metathesis reaction Methods 0.000 description 3
- MGJXBDMLVWIYOQ-UHFFFAOYSA-N methylazanide Chemical compound [NH-]C MGJXBDMLVWIYOQ-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000003466 anti-cipated effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000003631 expected effect Effects 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- ANLABNUUYWRCRP-UHFFFAOYSA-N 1-(4-nitrophenyl)cyclopentane-1-carbonitrile Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1(C#N)CCCC1 ANLABNUUYWRCRP-UHFFFAOYSA-N 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- XTWJVMPEOYBUME-UHFFFAOYSA-N 2-methylundec-10-enoic acid Chemical compound OC(=O)C(C)CCCCCCCC=C XTWJVMPEOYBUME-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004165 Methyl ester of fatty acids Substances 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical class NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical class O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010316 high energy milling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006140 methanolysis reaction Methods 0.000 description 1
- SBIGSHCJXYGFMX-UHFFFAOYSA-N methyl dec-9-enoate Chemical compound COC(=O)CCCCCCCC=C SBIGSHCJXYGFMX-UHFFFAOYSA-N 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000010641 nitrile hydrolysis reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- XPQPWPZFBULGKT-UHFFFAOYSA-N undecanoic acid methyl ester Natural products CCCCCCCCCCC(=O)OC XPQPWPZFBULGKT-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/22—Preparation of carboxylic acid nitriles by reaction of ammonia with carboxylic acids with replacement of carboxyl groups by cyano groups
-
- 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8474—Niobium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8476—Tantalum
-
- 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
- B01J35/613—10-100 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
- 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
- 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
- B01J35/643—Pore diameter less than 2 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
- 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
- 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
- B01J35/66—Pore distribution
-
- 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
- B01J37/04—Mixing
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nanotechnology (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
− 酸化アルミニウム、酸化ジルコニウム、酸化ニオブ、酸化タンタルおよび酸化スズから選択される少なくとも1種の金属酸化物との混合物として、
− 少なくとも1種の金属酸化物を含むものであり、前記金属酸化物の金属は周期律表の8族に属し、
前記8族に属する金属の金属酸化物が、全金属酸化物の混合物の体積に対して0.1から0.6の体積比で存在する方法である。
本発明は、気相または気−液混合相において連続して動作する反応器中で、180から400℃の温度範囲で、固体触媒の存在下アンモニアを反応させることにより、場合により不飽和である脂肪酸または脂肪酸エステルをニトリル化する方法であって、該固体触媒は、酸化アルミニウム、酸化ジルコニウム、酸化ニオブ、酸化タンタルおよび酸化スズから選択される少なくとも1種の金属酸化物との混合物として、少なくとも1種の金属酸化物を含み、前記金属酸化物の金属は周期律表の8族に属し、前記8族に属する金属の金属酸化物が、全金属酸化物の混合物の体積に対して0.1から0.6の体積比で存在する方法に関する。
CH2=CH−(CH2)n−COOR
式中、nは整数7または8を表し、およびRは水素原子又は、1から4個の炭素原子を有するアルキル基のいずれかを表す。
第1の実施形態では、2つの反応剤を気体状態(純粋な気相)で反応器に導入することができる。
好ましくは、混合相ニトリル化方法は脂肪酸を用いて行われる。
また、本発明の主題は固体触媒に関する。
触媒を調製する方法としていくつかの方法が適切であり得る。即ち、塩または塩の混合物の共沈;一般的に塩、酸化物または水酸化物の形の前駆体の混合;1つの化合物の、別の化合物による含浸、例えば、酸化鉄の前駆体を含む溶液による、酸化アルミニウム、酸化ジルコニウムまたは酸化ニオブの含浸;反応性粉砕、ここで2つの酸化物が高エネルギー粉砕によってよく混合され、それにより新たな化合物が形成される;または微粒化である。様々な形態の酸化物の前駆体を、特に、酸化物、硝酸塩、炭酸塩、塩化物、硫酸塩(オキシ硫酸塩を含む)、リン酸塩、有機金属化合物、酢酸塩またはアセチルアセトネートの形態で使用することができる。好適例では、オキシ硫酸ジルコニウムからの触媒の調製により、本発明の方法に適した触媒が得られる。
ラウリン酸メチルエステルについて試験を実施した。
アセンブリは、蠕動ポンプを介して液体状態のエステルが連続的に供給される蒸発室からなっていた。乾燥窒素の制御された流れが、エステルを同伴し、それを下の触媒床に搬送する。アンモニアの制御された流れは、ステンレス鋼フリット上に保持された直径8mm×30mmの円筒である触媒床で、エステル+窒素の流れに出会う。流出する流れは、ラウリン酸化合物(ニトリル、アミド、酸、メチルアミド等)を回収するために最初150〜170℃で凝結され、2度目は12℃で、次いで−77℃(ドライアイストラップを使用して)にされ、軽質化合物を凝結する。凝結物を除去し、エステル、ニトリル、および場合によりアミドおよびN−メチルアミドの濃度が算出されるGC−FIDおよびGC−MSにより分析する。
1.Fe2O3およびAl2O3触媒を用いて
3つの異なる触媒、即ち、アルミナ単独Al2O3、酸化鉄単独Fe2O3およびFe2O3/(Al2O3+Fe2O3)体積比0.5のAl2O3およびFe2O3の混合物、を用いてこの実験を実施した。
結果を下の表3および図1に示す。
3つの異なる触媒、即ち、ジルコニア単独ZrO2、酸化鉄単独Fe2O3およびFe2O3/(ZrO2+Fe2O3)体積比0.5のZrO2およびFe2O3の混合物、を用いてこの実験を実施した。
結果を以下の表4に示す。
結果を以下の表5および図2に示す。
Al2O3支持体上のFe2O3触媒を用いてウンデセン酸のメチルエステルに対し試験を実施した。手順は上記実施例1で示されたものと同じである。
3つの異なる触媒、即ち、アルミナ単独Al2O3、酸化鉄単独Fe2O3およびFe2O3/(Al2O3+Fe2O3)体積比0.5のAl2O3/Fe2O3混合物、を用いてこの実験を実施した。
結果を以下の表6に示す。
結果を以下の表7に示す。
Claims (15)
- 気相または気−液混合相において連続して動作する反応器中で、180から400℃の温度範囲で固体触媒の存在下アンモニアを反応させることにより、場合により不飽和である脂肪酸または脂肪酸エステルをニトリル化する方法であって、前記固体触媒は
− 酸化アルミニウム、酸化ジルコニウム、酸化ニオブ、酸化タンタルおよび酸化スズから選択される少なくとも1種の金属酸化物との混合物として、
− 少なくとも1種の金属酸化物を含むものであり、前記金属酸化物の金属は周期律表の8族に属し、
前記8族に属する金属の金属酸化物が、全金属酸化物の混合物の体積に対して0.1から0.6の体積比で存在する方法。 - 前記触媒が、周期律表の8族に属する金属の金属酸化物として、少なくとも酸化第二鉄を含む、請求項1に記載の方法。
- 前記触媒が、酸化第二鉄(Fe2O3)および五酸化ニオブ(Nb2O5)を含む、請求項1または2に記載の方法。
- 前記触媒が、酸化第二鉄(Fe2O3)および酸化アルミニウム(Al2O3)を含む、請求項1または2に記載の方法。
- 前記触媒が、酸化第二鉄(Fe2O3)および酸化ジルコニウム(ZrO2)を含む、請求項1または2に記載の方法。
- 前記方法の反応剤が、以下の式
CH2=CH−(CH2)n−COOR
[式中、nは整数7または8を表し、およびRは水素原子又は1から4個の炭素原子を有するアルキル基のいずれかを表す。]
を有するω−不飽和酸またはエステルである、請求項1から5のいずれか一項に記載の方法。 - 反応温度が、200から300℃の範囲である、請求項1から6のいずれか一項に記載の方法。
- − 酸化アルミニウム、酸化ジルコニウム、酸化ニオブ、酸化タンタルおよび酸化スズから選択される少なくとも1種の金属酸化物との混合物として、
− 少なくとも1種の金属酸化物を含み、前記金属酸化物の金属は、周期律表の8族に属するものである
固体触媒であって、
前記8族に属する金属の金属酸化物が、全金属酸化物の混合物の体積に対して0.1から0.6の体積比で存在し、
前記触媒の比表面積が10から500m 2 /gの範囲であることを特徴とする、
固体触媒。 - 周期律表の8族に属する金属の金属酸化物が酸化第二鉄である、請求項8に記載の触媒。
- 酸化第二鉄(Fe2O3)および五酸化ニオブ(Nb2O5)を含む、請求項9に記載の触媒。
- 酸化第二鉄(Fe2O3)および酸化アルミニウム(Al2O3)を含む、請求項9に記載の触媒。
- 酸化第二鉄(Fe2O3)および酸化ジルコニウム(ZrO2)を含む、請求項9に記載の触媒。
- 前記触媒が、細孔容積の20%未満が、2nm未満の直径を有する細孔内にあるような細孔径分布によって特徴付けられる、請求項8から12のいずれか一項に記載の触媒。
- 請求項8から13のいずれか一項に定義された触媒の調製方法であって、前記金属酸化物の機械的混合ステップを含む方法。
- 脂肪酸エステルまたは脂肪酸のニトリル化方法のための、請求項8から13のいずれか一項に定義された触媒の使用。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1351432A FR3002227B1 (fr) | 2013-02-20 | 2013-02-20 | Procede de nitrilation en phase gaz et liquide gaz |
FR1351432 | 2013-02-20 | ||
PCT/EP2014/053213 WO2014128154A1 (fr) | 2013-02-20 | 2014-02-19 | Procédé de nitrilation en phase gaz et liquide-gaz |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2016513119A JP2016513119A (ja) | 2016-05-12 |
JP6242920B2 true JP6242920B2 (ja) | 2017-12-06 |
Family
ID=48692596
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2015558432A Active JP6242920B2 (ja) | 2013-02-20 | 2014-02-19 | 気相および液体−気体相ニトリル化法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US10287238B2 (ja) |
EP (1) | EP2958673A1 (ja) |
JP (1) | JP6242920B2 (ja) |
CN (1) | CN105246594B (ja) |
FR (1) | FR3002227B1 (ja) |
WO (1) | WO2014128154A1 (ja) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10349678B2 (en) * | 2015-06-30 | 2019-07-16 | Shenzhen Smoore Technology Limited | Electronic cigarette, atomizer device thereof, method for assembling the atomizer device |
RU2020123756A (ru) | 2017-12-20 | 2022-01-20 | Басф Се | Катализатор и способ получения диметилового эфира |
CN111655667A (zh) | 2018-02-06 | 2020-09-11 | 东丽株式会社 | 腈的制造方法 |
Family Cites Families (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2794043A (en) * | 1955-01-13 | 1957-05-28 | Goodrich Co B F | Preparation of aliphatic nitriles |
US3012060A (en) * | 1958-04-15 | 1961-12-05 | Robert S Aries | Conversion of higher fatty acids into shorter chain length nitriles |
US3661970A (en) * | 1969-05-20 | 1972-05-09 | Kraftco Corp | Method for reacting a mixture of carboxylic acids with ammonia to provide nitriles |
NL178870C (nl) | 1979-03-06 | 1986-06-02 | Inst Neftekhim Protsessov | Werkwijze voor de bereiding van ftalonitrillen, alsmede de daarbij te gebruiken katalysator. |
JPS5938541B2 (ja) * | 1979-12-22 | 1984-09-18 | 松下電工株式会社 | 可燃性ガス検知素子 |
US4575434A (en) * | 1984-09-28 | 1986-03-11 | Akzona Incorporated | Process for the separation of amides from nitriles |
DE3639857A1 (de) | 1986-11-21 | 1988-06-01 | Hoechst Ag | Verfahren zur herstellung von fettsaeurenitrilen und glycerin aus glyceriden |
JP2893216B2 (ja) * | 1990-11-30 | 1999-05-17 | ライオン株式会社 | 脂肪族ニトリルの製造方法 |
JPH04283549A (ja) | 1991-03-13 | 1992-10-08 | Lion Corp | 色調を改良した脂肪族ニトリルの製造方法 |
JPH10195035A (ja) * | 1997-01-14 | 1998-07-28 | Lion Corp | 脂肪族ニトリルの製造方法 |
JPH11117990A (ja) | 1997-10-20 | 1999-04-27 | Kinugawa Rubber Ind Co Ltd | ダイナミックダンパー |
JP4219481B2 (ja) | 1998-04-27 | 2009-02-04 | 花王株式会社 | 脂肪族ニトリルの製造方法 |
US6005134A (en) | 1998-06-25 | 1999-12-21 | Kao Corporation | Process for the preparation of aliphatic nitriles |
EP1495160B1 (en) * | 2002-04-16 | 2005-11-09 | MOLTECH Invent S.A. | Non-carbon anodes for aluminium electrowinning and other oxidation resistant components with slurry-applied coatings |
JP4283549B2 (ja) | 2003-01-16 | 2009-06-24 | 株式会社鶴見製作所 | 竪型水中電動ポンプの浸水検知機構 |
JP4409238B2 (ja) | 2003-09-17 | 2010-02-03 | 花王株式会社 | 脂肪族ニトリルの製造方法 |
EP2132165B1 (de) * | 2007-03-01 | 2014-04-23 | Basf Se | Verfahren zur herstellung von ethylendiamin |
JP2009240874A (ja) * | 2008-03-28 | 2009-10-22 | Hopit:Kk | カーボンナノコイル製造用触媒 |
FR2938533B1 (fr) * | 2008-11-17 | 2010-11-19 | Arkema France | Procede de synthese d'un omega-aminoacide ou ester a partir d'un acide ou ester gras mono-insature |
FR2941694B1 (fr) * | 2009-02-05 | 2011-02-11 | Arkema France | Procede de synthese d'un omega-aminoacide ou ester a partir d'un acide ou ester gras mono-insature. |
JP5690250B2 (ja) | 2010-09-24 | 2015-03-25 | 日本特殊陶業株式会社 | スパークプラグの製造方法 |
KR101258870B1 (ko) * | 2011-03-16 | 2013-04-29 | 동도바잘트산업(주) | 코크스 오븐 상승관 내화물 제조방법 |
FR2978147B1 (fr) * | 2011-07-19 | 2015-01-09 | Arkema France | Procede de synthese d'acides omega-fonctionnalises a partir d'acides ou esters gras hydroxyles |
FR2978764B1 (fr) * | 2011-08-01 | 2013-08-16 | Arkema France | Procede de synthese d'un omega-aminoacide ou ester a partir d'un acide ou ester gras mono-insature |
FR2979342B1 (fr) * | 2011-08-26 | 2013-08-09 | Arkema France | Procede de synthese d'esters d'acides omega-amino-alcanoiques en c11 et c12 comportant une etape de metathese |
FR2983477B1 (fr) * | 2011-12-01 | 2013-12-27 | Arkema France | Procede de coupure de chaines grasses insaturees |
-
2013
- 2013-02-20 FR FR1351432A patent/FR3002227B1/fr active Active
-
2014
- 2014-02-19 EP EP14705194.0A patent/EP2958673A1/fr not_active Ceased
- 2014-02-19 WO PCT/EP2014/053213 patent/WO2014128154A1/fr active Application Filing
- 2014-02-19 CN CN201480009622.9A patent/CN105246594B/zh active Active
- 2014-02-19 US US14/769,312 patent/US10287238B2/en active Active
- 2014-02-19 JP JP2015558432A patent/JP6242920B2/ja active Active
Also Published As
Publication number | Publication date |
---|---|
CN105246594A (zh) | 2016-01-13 |
CN105246594B (zh) | 2018-07-13 |
US20160016153A1 (en) | 2016-01-21 |
EP2958673A1 (fr) | 2015-12-30 |
WO2014128154A1 (fr) | 2014-08-28 |
FR3002227A1 (fr) | 2014-08-22 |
JP2016513119A (ja) | 2016-05-12 |
FR3002227B1 (fr) | 2021-10-01 |
US10287238B2 (en) | 2019-05-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2029513B1 (fr) | Procede de transformation de composes nitriles en acides carboxyliques et esters correspondants | |
CN101186584B (zh) | 通过在含二氧化锰的催化剂存在下水解羧酸腈制备羧酸酰胺的方法 | |
US8835661B2 (en) | Process for the synthesis of C11 and C12 omega-aminoalkanoic acid esters comprising a nitrilation step | |
JP6242920B2 (ja) | 気相および液体−気体相ニトリル化法 | |
EP0443758A1 (en) | A process for preparing alkylene carbonates | |
TW201323402A (zh) | α-羥基羧酸酯類之製備方法 | |
JP6025831B2 (ja) | 3−シアノ−3,5,5−トリメチルシクロヘキサノンの製造方法 | |
JPH11508251A (ja) | N−アシル−n−アルキルカルボキシラートの合成 | |
JPS6247857B2 (ja) | ||
JP3251525B2 (ja) | 3−オキソカルボン酸エステルの製造方法 | |
US3320305A (en) | Process for converting nitriles | |
IL199839A (en) | A method for making cinematic esters is stored in position 2 - cyan | |
US3876691A (en) | Process for the hydrolysis of nitriles | |
TW201518270A (zh) | 製造α-羥基羧酸酯的方法 | |
EP1842844B1 (en) | Continuous process for the production of monocarboxylic acid alkyl amides | |
JPH10195035A (ja) | 脂肪族ニトリルの製造方法 | |
CA2004959A1 (en) | Manufacture of 5-cyanovaleric acid and its esters | |
JPS59118745A (ja) | アミンの製法 | |
JPH04208260A (ja) | 脂肪族ニトリルの製造方法 | |
EP0435445A1 (en) | Method for preparing alpha beta-unsaturated nitriles | |
US3542822A (en) | Hydrolysis of nitriles to carboxylic acids | |
TW200306966A (en) | Continuous process for the manufacture of 3-hydroxy propionitrile | |
EP1305280A2 (en) | Process for making 3-hydroxyalkanenitriles and hydroxyaminoalkanes | |
JP3974709B2 (ja) | リンゴ酸モノアミド類組成物の製造方法 | |
CN117658827A (zh) | 烷基环己基乙胺的合成方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20161124 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170517 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170523 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170821 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20171010 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20171108 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6242920 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |