CN106883098B - Application of multi-active-component catalyst in preparation of 1, 3-propylene glycol by hydrogenolysis of glycerol - Google Patents
Application of multi-active-component catalyst in preparation of 1, 3-propylene glycol by hydrogenolysis of glycerol Download PDFInfo
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- CN106883098B CN106883098B CN201510933866.2A CN201510933866A CN106883098B CN 106883098 B CN106883098 B CN 106883098B CN 201510933866 A CN201510933866 A CN 201510933866A CN 106883098 B CN106883098 B CN 106883098B
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- Prior art keywords
- oxide
- catalyst
- glycerol
- carrier
- tungsten oxide
- Prior art date
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 35
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 34
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims abstract description 19
- 229940035437 1,3-propanediol Drugs 0.000 claims abstract description 19
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 11
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 239000010948 rhodium Substances 0.000 claims abstract description 8
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 6
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910003449 rhenium oxide Inorganic materials 0.000 claims abstract description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 4
- FYKIBYPMFVOSPN-UHFFFAOYSA-N [W+2]=O.[O-2].[Al+3] Chemical compound [W+2]=O.[O-2].[Al+3] FYKIBYPMFVOSPN-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 17
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 14
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims 4
- 150000003077 polyols Chemical class 0.000 claims 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 229960004063 propylene glycol Drugs 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 6
- 229910052741 iridium Inorganic materials 0.000 abstract description 5
- 229910052763 palladium Inorganic materials 0.000 abstract description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 239000010949 copper Substances 0.000 abstract description 4
- 239000010931 gold Substances 0.000 abstract description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052709 silver Inorganic materials 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract description 3
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001195 gallium oxide Inorganic materials 0.000 abstract description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052737 gold Inorganic materials 0.000 abstract description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001947 lithium oxide Inorganic materials 0.000 abstract description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000395 magnesium oxide Substances 0.000 abstract description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001950 potassium oxide Inorganic materials 0.000 abstract description 3
- 239000004332 silver Substances 0.000 abstract description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001948 sodium oxide Inorganic materials 0.000 abstract description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 3
- 239000011787 zinc oxide Substances 0.000 abstract description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 3
- 235000011187 glycerol Nutrition 0.000 description 32
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- AKXKFZDCRYJKTF-UHFFFAOYSA-N 3-Hydroxypropionaldehyde Chemical compound OCCC=O AKXKFZDCRYJKTF-UHFFFAOYSA-N 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000006315 carbonylation Effects 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000193403 Clostridium Species 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- CMDGQTVYVAKDNA-UHFFFAOYSA-N propane-1,2,3-triol;hydrate Chemical compound O.OCC(O)CO CMDGQTVYVAKDNA-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6567—Rhenium
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The patent relates to a catalyst for preparing 1, 3-propanediol by hydrogenolysis of glycerol and a preparation method thereof, wherein the catalyst comprises tungsten oxide-aluminum oxide (WO)3‑Al2O3) The composite carrier and one of the active components ruthenium, rhodium, palladium, iridium and platinum (marked as A) and one of gold, silver, copper, nickel, sodium oxide, lithium oxide, potassium oxide, magnesium oxide, gallium oxide, zinc oxide, iron oxide, molybdenum oxide, lanthanum oxide, zirconium oxide, cobalt oxide, rhenium oxide, tin oxide and manganese oxide (marked as component B). The catalyst prepared by the patent can be used for hydrogenolyzing glycerol at a certain hydrogen pressure and temperature with high conversion rate and high selectivity to generate 1, 3-propylene glycol.
Description
Technical Field
The invention relates to a catalyst for preparing 1, 3-propylene glycol by hydrogenolysis of glycerol, in particular to WO3-Al2O3The carrier supports one of active components ruthenium, rhodium, palladium, iridium and platinum (marked as A) and one of gold, silver, copper, nickel, sodium oxide, lithium oxide, potassium oxide, magnesium oxide, gallium oxide, zinc oxide, iron oxide, molybdenum oxide, lanthanum oxide, zirconium oxide, cobalt oxide, rhenium oxide, tin oxide and manganese oxide (marked as component B).
The invention relates to a preparation method and application of the catalyst, in particular to a method for preparing WO by adopting wet impregnation3-Al2O3The method comprises the following steps of preparing a carrier, preparing multi-active-component catalysts with different loading sequences, and observing the activity and selectivity of the catalyst in the preparation of 1, 3-propanediol by hydrogenolysis of glycerol under different preparation conditions.
Technical Field
Along with the rapid development of the biodiesel industry, a large amount of glycerin is also produced as a byproduct, and crude glycerin obtained by biodiesel production contains more impurities and thus has low value, the crude glycerin purification step is more complicated, the energy consumption is high, and the demand of pure glycerin is limited; therefore, the conversion of raw glycerol to more value-added chemicals has received much attention in recent years. Glycerol can generate 1, 3-propanediol through hydrogenolysis reaction, the 1, 3-propanediol can be used as a chemical raw material with high added value, can be directly used as a synthetic raw material of an antifreeze agent, a plasticizer, a detergent, a preservative and an emulsifier, can also be used in the industries of food, cosmetics, pharmacy and the like, and the most main application of the glycerol and terephthalic acid react to generate novel polyester PTT with great development prospect. PTT is a novel polyester fiber with biodegradability, overcomes the defects that polyethylene terephthalate (PET) is too hard and polybutylene terephthalate (PBT) is too soft, has excellent rebound resilience, easy dyeing property, biodegradability and the like, and has huge development potential in the industries of carpets, textile engineering plastics and the like. Currently, the commercial production of 1, 3-propanediol is carried out by ethylene oxide carbonylation hydrogenation from Shell and acrolein hydration hydrogenation from Degussa.
The ethylene oxide carbonylation hydrogenation method (Chinese patent CN1201407A) adopts a method that ethylene oxide and synthesis gas generate 3-hydroxypropionaldehyde under the action of a cobalt-based catalyst, and then the 3-hydroxypropionaldehyde and hydrogen are hydrogenated under the action of a hydrogenation catalyst to generate 1, 3-propylene glycol. The acrolein hydration hydrogenation method (Chinese patent CN93114516.3) adopts gas glycerol hydrate to dehydrate under the action of solid acid catalyst to generate acrolein, the generated acrolein is hydrated under the action of acid catalyst to generate 3-hydroxypropionaldehyde, and the generated 3-hydroxypropionaldehyde is hydrogenated under the action of conventional hydrogenation catalyst to prepare 1, 3-propylene glycol. In addition, chinese patent CN02100233.9 discloses a technology for preparing 1, 3-propanediol by condensing formaldehyde and acetaldehyde and hydrogenating 3-hydroxypropionaldehyde, in which formaldehyde and acetaldehyde are condensed under an alkaline condition to generate 3-hydroxypropionaldehyde, and the 3-hydroxypropionaldehyde reacts with hydrogen in the presence of a catalyst to generate 1, 3-propanediol.
The ethylene oxide carbonylation hydrogenation method has large equipment investment, high technical difficulty, rigorous and unstable preparation process and extremely toxic ligand. The acrolein hydration hydrogenation method has high cost, and particularly, the acrolein belongs to extremely toxic, flammable and explosive articles and is difficult to store and transport.
The literature (appl. Microbiol. Biotechnol.1992,36,592-597) reports a process for preparing 1, 3-propanediol by bioconversion of the strain Clostridium species, in which a 110g/l glycerol solution can be converted after 29h to 56g/l 1, 3-propanediol, which is affected by the activity of the biological metabolism, is less efficient and requires a high energy consumption for the purification and isolation of 1, 3-propanediol due to the low product concentration.
The literature (Catal. Commun.2008,9, 1360-.
The group of Tomishige subjects in Japan reported Re-modified Rh/SiO2And Ir/SiO2Catalyst, the authors in Ir-Re/SiO2Adding liquid sulfuric acid (H) under the action of catalyst+Re ═ 1), initial pressure of hydrogen 8MPa, reaction temperature 120 ℃, after 36h of reaction in 20% aqueous glycerol, yields of 1, 3-propanediol up to 38.0% were obtained.
Korean Jinho Oh reported that Pt is supported on sulfuric acid-acidified ZrO2In the method, DMI is used as a reaction medium, and the yield of the 1, 3-propylene glycol is up to 55.6 percent after the reaction is carried out for 24 hours under the conditions that the initial pressure of hydrogen is 7.3MPa and the reaction temperature is 170 ℃.
The reaction adopts an organic solvent as a reaction medium or a method of adding liquid acid, and does not meet the requirement of green chemistry.
The direct hydrogenolysis of glycerol to 1, 3-propanediol has received considerable attention in recent years because of its simple process and inexpensive raw materials. Noble metal catalysts (such as platinum, palladium, rhodium, iridium, ruthenium and the like) have strong catalytic activity, but have poor tolerance to impurities in crude glycerol, and are easy to be poisoned to cause catalyst deactivation.
Disclosure of Invention
Compared with the prior art, the invention effectively improves the conversion rate of the glycerol and the selectivity of the 1, 3-propanediol.
The invention provides a catalyst for preparing 1, 3-propanediol by direct hydrogenolysis of glycerol, and a catalyst carrier is WO prepared by wet impregnation3-Al2O3The composite carrier comprises an active component which is one of ruthenium, rhodium, palladium, iridium and platinum (marked as A) and one of gold, silver, copper, nickel, sodium oxide, lithium oxide, potassium oxide, magnesium oxide, gallium oxide, zinc oxide, iron oxide, molybdenum oxide, lanthanum oxide, zirconium oxide, cobalt oxide, rhenium oxide, tin oxide and manganese oxide (marked as component B). The mass contents of the active components A and B are respectively 0.001-20% and 0.001-20%.
Support for the catalyst of the invention WO3-Al2O3The preparation method comprises the following steps:
soaking a precursor solution (ammonium metatungstate or ammonium paratungstate aqueous solution) of tungsten oxide on alumina in an equal volume by a wet method for 10-18h, drying in an oven at 120 ℃ for more than 10h, and calcining in a muffle furnace at 400-900 ℃ for 1-10 h to obtain the tungsten oxide-alumina composite carrier, which is recorded as WO3-Al2O3。
Preparing multi-active component catalyst A/B/WO with different loading sequences3-Al2O3，B/A/WO3-Al2O3And A-B/WO3-Al2O3；
Firstly, dipping a carrier with a precursor solution of an active component A to carry the active component A, dipping overnight, drying in a 120 ℃ oven for more than 10h, and calcining in a muffle furnace at 200-700 ℃ for 1-10 h to prepare A/WO3-Al2O3A catalyst;
then A/WO is added3-Al2O3Adding the catalyst into a precursor solution of an active component B, soaking overnight, drying in a 120 ℃ oven for more than 10h, and calcining in a muffle furnace at 200-700 ℃ for 1-10 h to obtain the catalyst B/A/WO3-Al2O3；
Reversing the order of A and B loading to produce A/B/WO3-Al2O3Catalyst, or A and B are loaded on carrier simultaneously to prepare A-B/WO3-Al2O3A catalyst.
The catalyst is applied to the reaction for preparing the 1, 3-propanediol by hydrogenolysis of the glycerol aqueous solution, and the reaction conditions are as follows: the reaction is carried out in an intermittent kettle type reactor, the reaction raw material is glycerol aqueous solution, wherein the mass concentration of the raw material is 1-100%, the hydrogen pressure is 0.1-10MPa, the reaction temperature is 80-300 ℃, and the reaction time is 0.2-80 hours. After cooling, the liquid product was analyzed by gas chromatography using Agilent7890B equipped with InnoWax capillary column and the gas product was analyzed by gas chromatography using Agilent B equipped with HayeSep packed column.
Compared with the prior art, the invention can obviously improve the conversion rate of the glycerol and the selectivity of the 1, 3-propylene glycol.
The present invention will be further illustrated by the following specific examples and comparative examples.
Detailed Description
Example 1
The catalyst used is WO3-Al2O3The carrier (the mass fraction of tungsten oxide is 20%) is loaded with active components of platinum and lanthanum oxide. The catalyst consists of Pt (5 wt%), La (0.5 wt%) and WO (the rest)3-Al2O3And (3) a carrier. WO3-Al2O3The carrier is prepared by a wet impregnation method, and the specific preparation steps comprise: a) soaking precursor solution (ammonium metatungstate or ammonium paratungstate aqueous solution) of tungsten oxide on alumina by a wet method for 18h, drying in an oven at 120 ℃ for more than 10h, and calcining in a muffle furnace at 900 ℃ for 10h to obtain the tungsten oxide-alumina composite carrier, wherein the obtained tungsten oxide-alumina composite carrier is recorded as WO3-Al2O3. b) Impregnating chloroplatinic acid solution in equal volume into WO3-Al2O3Soaking the carrier overnight, drying in a 120 ℃ oven for 12h, and calcining in a muffle furnace at 500 ℃ for 10h to obtain Pt/WO3-Al2O3The mass content of Pt in the catalyst is 5 percent; then adding Pt/WO3-Al2O3Adding the catalyst into a lanthanum nitrate solution, soaking overnight, drying in a 120 ℃ oven for 12 hours, calcining in a muffle furnace at 500 ℃ for 10 hours, and reducing and activating in a hydrogen reduction furnace at 500 ℃ for 3 hours to obtain the catalyst La2O3/Pt/WO3-Al2O3(ii) a An intermittent reaction kettle is selected, the mass concentration of the glycerol aqueous solution is 50 percent (30 g of the solution), the catalyst amount is 2g, the reaction temperature is 200 ℃, the reaction pressure is 7MPa, and the reaction time is 10 hours.
Example 2
The order of Pt and La loading was reversed, and the other conditions were the same as in example 1 and were recorded as Pt/La2O3/WO3-Al2O3。
Example 3
Pt and La are simultaneously loaded on a carrier WO3-Al2O3Otherwise, the same conditions as in example 1 are described as Pt-La2O3/WO3-Al2O3。
Example 4
The Pt was replaced by Ru under the same conditions as in example 1.
Example 5
The Pt was replaced with Rh under the same conditions as in example 1.
Example 6
Pt was replaced with Pd, and other conditions were the same as in example 1.
Example 7
The Pt was changed to Ir and the other conditions were the same as in example 1.
Example 8
La was changed to K, and the other conditions were the same as in example 1.
Example 9
The La was changed to Li, and other conditions were the same as in example 1.
Example 10
La was replaced with Mg and the other conditions were the same as in example 1.
Example 11
The La was replaced by Ga and the other conditions were the same as in example 1.
Example 12
La was replaced with Au, and the other conditions were the same as in example 1.
Example 13
La was replaced by Ag and the other conditions were the same as in example 1.
Example 14
The La was replaced by Cu and the other conditions were the same as in example 1.
Example 15
La was replaced by Zn and the other conditions were the same as in example 1.
Example 16
La was replaced by Fe and the other conditions were the same as in example 1.
Example 17
La was replaced by Mo, and the other conditions were the same as in example 1.
Example 18
La was replaced by La and the other conditions were the same as in example 1.
Example 19
La was replaced by Zr and the other conditions were the same as in example 1.
Example 20
La was replaced by Co and the other conditions were the same as in example 1.
Example 21
La was replaced with Ni and the other conditions were the same as in example 1.
Example 22
La was replaced with Re and the other conditions were the same as in example 1.
Example 23
La was replaced by Sn and the other conditions were the same as in example 1.
Example 24
La was changed to Mn and other conditions were the same as in example 1.
Example 25
The other conditions were the same as in example 1 except that the mass content of La was changed to 0.1%.
Example 26
The other conditions were the same as in example 1 except that the mass content of La was changed to 0.3%.
Example 27
The other conditions were the same as in example 1 except that the mass content of La was changed to 0.7%.
Example 28
The mass fraction of tungsten oxide in the carrier was changed to 5%, and the other conditions were the same as in example 1.
Example 29
The mass fraction of tungsten oxide in the carrier was changed to 10%, and the other conditions were the same as in example 1.
Example 30
The mass fraction of tungsten oxide in the carrier was changed to 30%, and the other conditions were the same as in example 1.
Example 31
The mass fraction of tungsten oxide in the carrier was changed to 40%, and the other conditions were the same as in example 1.
Example 32
The reaction materials were replaced with crude glycerin (glycerin content: 80% by mass), and the other conditions were the same as in example 1.
Comparative example 1
La-free Pt/WO3-Al2O3The catalyst and other conditions were the same as in example 1.
Comparative example 2
La without Pt2O3/WO3-Al2O3The catalyst and other conditions were the same as in example 1.
Comparative example 3
WO free of La and Pt3-Al2O3The catalyst and other conditions were the same as in example 1.
Comparative example 4
By using Pt/WO3-Al2O3The catalyst was prepared by replacing the reaction raw material with crude glycerin (glycerin content: 80% by mass), and the other conditions were the same as in example 1.
As can be seen from comparative examples 1 to 3, the noble metal Pt plays a crucial role in the catalytic performance of the catalyst, and the catalyst containing no Pt has no activity at all. As can be seen from example 1 and comparative example 1, La2O3The introduction of the catalyst obviously improves the conversion rate of the glycerol and the selectivity of the target product 1, 3-propylene glycol. Examples 1 to 3 examined La2O3And Pt, and we can see from the results that Pt is loaded first and La is loaded later2O3Is optimal. Examples 1,4,5,6,7 examinedAs the result of the influence of noble metal on the reaction, the activities of Ru, Pd and Ir are not as good as those of Pt and Rh, the conversion rate of glycerol is higher, but the selectivity of the target product 1, 3-propanediol is lower. Examples 1, 8-24 examined the effect of different promoters on the reactivity, and from table 1 we can see that the catalyst activity is highest when lanthanum oxide is introduced, and secondly the conversion rate of manganese oxide to glycerol and the selectivity of 1, 3-propanediol are both improved; after the rhenium oxide is introduced, the selectivity of the target product 1, 3-propylene glycol is obviously improved, but the conversion rate of the glycerol is reduced. Examples 1, 25, 26 and 27 examined the effect of different lanthanum contents on the catalytic activity, and the reaction results showed that the catalyst had the highest reactivity at a lanthanum mass content of 0.5%. Examples 1,28,29,30,31 examined the effect of the content of tungsten oxide in the carrier on the reaction results, and found that the reactivity was the best when the mass fraction of tungsten oxide was 20%. Comparative examples 1 and 4 examined the influence of different reaction raw materials, and found that the reaction activity was significantly reduced after pure glycerin was replaced with crude glycerin. From comparative examples 1 and 4 and example 32, it can be seen that the tolerance of the catalyst to impurities in crude glycerol is significantly improved by introducing the second active component, lanthanum oxide.
TABLE 1 comparison of catalytic Performance for the hydrogenolysis of glycerol to 1, 3-propanediol
Others include small amounts of propane, methanol, ethanol, ethylene glycol, overall material conservation.
Claims (6)
1. The application of a multi-active-component catalyst for preparing 1, 3-propylene glycol by hydrogenolysis of glycerol is characterized in that: the catalyst takes a tungsten oxide-aluminum oxide composite oxide as a carrier, and the active component is one or two of rhodium and platinum, which is marked as a component A, and one or more of molybdenum oxide, lanthanum oxide, rhenium oxide and manganese oxide, which is marked as a component B; wherein the mass fraction of tungsten oxide in the carrier is 1-99%, and the mass fraction of aluminum oxide is 1-99%; the content of the active component A is 0.001-20% of the weight of the catalyst, and the content of the active component B is 0.001-20% of the weight of the catalyst;
the preparation process of the composite oxide of the carrier alumina-tungsten oxide comprises the following steps: the precursor solution of tungsten oxide is ammonium metatungstate or ammonium paratungstate aqueous solution, is soaked on alumina by a wet method, is calcined for 1 to 10 hours at the temperature of 900 ℃ in a muffle furnace after being dried, and the obtained tungsten oxide-alumina composite carrier is marked as WO3-Al2O3(ii) a The carrier alumina-tungsten oxide composite oxide is prepared by a wet impregnation method, and the specific process comprises the following steps:
soaking a precursor solution of tungsten oxide on alumina by a wet method for 10-18h, drying in an oven at 120 ℃ for more than 10h, calcining in a muffle furnace at 400-900 ℃ for 1-10 h to obtain the tungsten oxide-alumina composite carrier, and recording the tungsten oxide-alumina composite carrier as WO3-Al2O3；
Prepared multi-active component catalyst B/A/WO3-Al2O31) impregnating a carrier with a precursor solution of an active component A to carry the active component A, impregnating overnight, drying in an oven at 120 ℃ for more than 10 hours, and calcining in a muffle furnace at 200-700 ℃ for 1-10 hours to prepare A/WO3-Al2O3A catalyst;
2) then A/WO is added3-Al2O3Adding the catalyst into a precursor solution of an active component B, soaking overnight, drying in a 120 ℃ oven for more than 10h, and calcining in a muffle furnace at 200-700 ℃ for 1-10 h to prepare the catalyst A/B/WO3-Al2O3。
2. Use according to claim 1, characterized in that: the final catalyst is prepared in H2And (3) reducing at the temperature of 200-600 ℃ for 0.5-5 h.
3. Use according to claim 1, characterized in that: the catalyst is used in the reaction for preparing 1, 3-propylene glycol by hydrogenolysis of glycerol, the reaction raw material is glycerol aqueous solution, the mass concentration of the glycerol is 1-100%, the hydrogen pressure is 0.1-10MPa, the reaction temperature is 80-300 ℃, the reaction time is 0.2-80h, and the dosage of the catalyst is 0.01-5g/30g of the glycerol aqueous solution.
4. Use according to claim 3, characterized in that: the catalyst is also used for the reaction of preparing the lower polyol by the hydrogenolysis of other polyols, namely the glycerol can be replaced by other polyols, and the other polyols are 1, 2-propylene glycol or 1, 4-butanediol.
5. Use according to claim 3, characterized in that: the reaction is carried out in a batch tank reactor, a fixed bed or a fluidized bed reactor.
6. Use according to claim 4, to obtain a selectivity of 1, 3-propanediol of 30-60% and a glycerol conversion of 10-70%.
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Effective date of registration: 20231225 Address after: 450001 b930-931, building 2, entrepreneurship center, No.96 Ruida Road, high tech Industrial Development Zone, Zhengzhou City, Henan Province Patentee after: Zhongke baiyijin (Zhengzhou) New Energy Technology Co.,Ltd. Address before: 116023 No. 457, Zhongshan Road, Liaoning, Dalian Patentee before: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES |