WO2009063120A1 - Catalytic method for the production of nitriles from alcohols - Google Patents
Catalytic method for the production of nitriles from alcohols Download PDFInfo
- Publication number
- WO2009063120A1 WO2009063120A1 PCT/ES2008/070206 ES2008070206W WO2009063120A1 WO 2009063120 A1 WO2009063120 A1 WO 2009063120A1 ES 2008070206 W ES2008070206 W ES 2008070206W WO 2009063120 A1 WO2009063120 A1 WO 2009063120A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- production process
- process according
- catalyst
- glycerol
- nitrile production
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 41
- 150000002825 nitriles Chemical class 0.000 title claims description 66
- 150000001298 alcohols Chemical class 0.000 title claims description 7
- 230000003197 catalytic effect Effects 0.000 title abstract description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 191
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 13
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 12
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 5
- 150000003077 polyols Chemical class 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims 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 description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- 230000005855 radiation Effects 0.000 claims description 8
- 229910052770 Uranium Inorganic materials 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000013335 mesoporous material Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-M hydroperoxide group Chemical group [O-]O MHAJPDPJQMAIIY-UHFFFAOYSA-M 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 26
- 239000000047 product Substances 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- -1 nitriles form alcohols Chemical class 0.000 abstract description 4
- 239000002551 biofuel Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 235000011187 glycerol Nutrition 0.000 description 60
- 150000001875 compounds Chemical class 0.000 description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 17
- 239000007787 solid Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- 239000010955 niobium Substances 0.000 description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- KQEIJFWAXDQUPR-UHFFFAOYSA-N 2,4-diaminophenol;hydron;dichloride Chemical compound Cl.Cl.NC1=CC=C(O)C(N)=C1 KQEIJFWAXDQUPR-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 238000001994 activation Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910003206 NH4VO3 Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 239000012494 Quartz wool Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000037213 diet Effects 0.000 description 2
- 235000005911 diet Nutrition 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 238000006140 methanolysis reaction Methods 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011942 biocatalyst Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002483 medication Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
-
- 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
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a catalytic process for the production of nitriles from alcohols. Therefore, this invention has application in the chemical industry sector in general and, specifically, in the production of organic solvents, polymers, fibers, resins, pesticides, perfumes and medicines. STATE OF THE TECHNIQUE
- a nitrile is an organic compound that contains a cyano group, CN, such as acetonitrile, benzonitrile or acrylonitrile.
- Acetonitrile is used as a solvent for many compounds and in the production of fibers, gums and resins.
- acetonitrile is used as an intermediate in the manufacture of pesticides, perfumes and medications. It is also used in the extraction and refining of copper.
- Benzonitrile is used as a solvent and as a precursor to other compounds.
- Acrylonitrile is probably the nitrile manufactured on a larger scale.
- Acrylonitrile is a monomer that is used in the manufacture of synthetic polymers, especially polyacrylonitrile and acrylic fibers.
- Acrylic fiber has many uses, it should be noted its use as a precursor of carbon fibers. Dimerization of acrylonitrile produces adiponitrile, used in the synthesis of certain nylons. In small quantities it is also used as a fungicide. Some acrylonitrile derivatives such as 2-chloro-acrylonitrile are used in Diels-Alder reactions. Acrylonitrile is the precursor for the industrial synthesis of acrylamide and acrylic acid.
- nitriles and especially acrylonitrile
- paraffins and olefins propane and propylene
- such raw materials paraffins and / or olefins
- Glycerol also called glycerin
- glycerin is derived from methanolysis as well as the methyl esters used in diesel fuels and domestic fuel oil. It is a natural product, available in large quantities, easy to store and transport. In addition, as it is obtained as a byproduct in the manufacture of biofuels, whose demand is increasing, its price is decreasing. Therefore, interest in developing processes that use glycerol as a raw material is increasing. In recent years several patents have appeared that describe processes in this regard.
- the oxidation of glycerol leads to the obtaining of a great variety of products, used as intermediates in the synthesis of products with high added value.
- the products obtained in the glycerol oxidation reaction employ aerobic reaction conditions, either by feeding oxygen or air in the gas phase reaction, either by bubbling a stream of oxygen or air into an aqueous solution or in the presence of other solvents, for example, organic, or by the addition of hydrogen peroxide for the liquid phase reaction.
- oxidation of glycerol also takes place under anaerobic reaction conditions, by electrocatalytic oxidation of glycerol by applying an electric potential to the solution in the presence of nitroxyl radicals as catalysts (TEMPO), and using biocatalysts (enzymes and microorganisms).
- TEMPO nitroxyl radicals as catalysts
- An aspect of the present invention is the process for the production of nitriles from alcohols, hereinafter nitrile production process of the invention, which takes place by means of the amonoxidation of alcohol in the presence of an oxidant, a source of nitrogen atoms and a catalyst.
- a preferred aspect of the present invention is the nitrile production process of the invention in which the alcohol is a polyol.
- a more preferred aspect of the present invention is the process for producing nitriles of the invention in which the alcohol is glycerol.
- Another preferred aspect of the present invention is the nitrile production process of the invention in which the oxidant is molecular oxygen.
- Another preferred aspect of the present invention is the process for producing nitriles of the invention in which the oxidant is hydrogen peroxide, or a highly reactive oxygen source, such as hydroperoxides.
- Another preferred aspect of the present invention is the process for producing nitriles of the invention in which the source of nitrogen atoms is ammonia.
- A is V and / or Nb
- B is Sb, Mo and / or Nb
- C is an element selected from the group Sn, Ti, Te, W, U
- D is an element selected from the group Li, Mg, Na, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Ge, Nb, Mo, W, Cu, Tl, P, Zr, Re, Ag, Cd , Zn, Pb, D, Rb, Cs, Ta, Se, Bi, Ce, In, As, B, Al, Mn
- a more preferred aspect of the present invention is the nitrile production process of the invention in which the catalyst used does not contain elements D and E and, therefore, responds to the formula AaBbCcOx where A is V and / or Nb; B is Sb, Mo and / or
- Nb, C is an element selected from the group Sn, Ti, Te, W, U; D.
- a particular embodiment of the present invention is the nitrile production process of the invention in which the catalyst used does not contain the elements C, D and E and, therefore, responds to the formula AaBbOx where A is V and / or Nb and B is Sb, Mo and / or Nb.
- Another more preferred aspect of the present invention is the process of producing nitriles of the invention in which the catalyst is supported on metal oxides such as
- Another preferred aspect of the present invention is the production method of nitriles of the invention in which a temperature between 200 and 800 used 0 C and preferably between 350 and 550 0 C.
- Another preferred aspect of the present invention is the nitrile production process of the invention in which a pressure between 0.1 and 5 bar is used.
- Another preferred aspect of the present invention is the nitrile production process of the invention in which microwave radiation is used as the activation method, which allows working at more moderate temperatures.
- Another preferred aspect of the present invention is the production method of nitriles of the invention in which microwave activation is used with adequate power to reach a temperature between 20 and 300 0 C and preferably between 80 and 120 0 C.
- the present invention is based on the fact, observed by the inventors, that by means of the reaction of amonoxidation of an alcohol in the presence of an oxidant, a source of nitrogen atoms (eg, ammonia) and a catalyst, nitriles are obtained.
- a source of nitrogen atoms eg, ammonia
- This reaction is a completely new and attractive procedure for the preparation of nitriles at the industrial level.
- the reaction involved in this nitrile preparation process is:
- one aspect of the present invention is the process for the production of nitriles from alcohols, hereinafter the process of producing nitriles of the invention, which takes place by means of the amonoxidation of alcohol in the presence of an oxidant, a source of nitrogen atoms and a catalyst.
- a preferred aspect of the present invention is the nitrile production process of the invention in which the alcohol is a polyol.
- a more preferred aspect of the present invention is the process for producing nitriles of the invention in which the alcohol is glycerol.
- the oxidant can be molecular oxygen, which can be used in the form of air or any other gas mixture containing molecular oxygen.
- Another preferred aspect of the present invention is the nitrile production process of the invention in which the oxidant is molecular oxygen.
- Another preferred aspect of the present invention is the process for producing nitriles of the invention in which the oxidant is hydrogen peroxide, or a highly reactive oxygen source, such as hydroperoxides.
- the most common source of nitrogen atoms that can be used is ammonia. Therefore, another preferred aspect of the present invention is the process for producing nitriles of the invention in which the source of nitrogen atoms is ammonia.
- A is V and / or Nb
- B is Sb, Mo and / or Nb
- C is an element selected from the group Sn, Ti, Te, W, U
- D is an element selected from the group Li, Mg, Na, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Ge, Nb, Mo, W, Cu, Tl, P, Zr, Re, Ag, Cd , Zn, Pb, D, Rb, Cs, Ta, Se, Bi, Ce, In, As, B, Al, Mn
- a more preferred aspect of the present invention is the nitrile production process of the invention in which the catalyst used does not contain elements D and E and, therefore, responds to the formula AaBbCcOx where A is V and / or Nb; B is Sb, Mo and / or
- Nb, C is an element selected from the group Sn, Ti, Te, W, U; D.
- a particular embodiment of the present invention is the nitrile production process of the invention in which the catalyst used does not contain the elements C, D and E and, therefore, responds to the formula AaBbOx where A is V and / or Nb and B is Sb, Mo and / or Nb.
- Another more preferred aspect of the present invention is the process of producing nitriles of the invention in which the The catalyst is supported on metal oxides such as AI2O3, Nb2 ⁇ 5 , ZrÜ2, TIO2, SIO2, zeolites, mesoporous material or carbon.
- metal oxides such as AI2O3, Nb2 ⁇ 5 , ZrÜ2, TIO2, SIO2, zeolites, mesoporous material or carbon.
- the catalyst can be used pure or dissolved in some inert solid such as silicon carbide. In this way, it is easier to control the exothermicity of the reaction and therefore better control the temperature.
- Another preferred aspect of the present invention is the production method of nitriles of the invention in which a temperature between 200 and 800 used 0 C and preferably between 350 and 550 0 C. A decrease of the pressure in the medium The reaction makes it possible to evaporate the alcohol at a lower temperature, which is particularly suitable for glycerol. Therefore, another preferred aspect of the present invention is the nitrile production process of the invention in which a pressure comprised between 0.1 and 5 bar is used.
- the reaction can be carried out both in the gas phase and in the liquid phase and is accompanied by other side reactions that produce other products such as: acrolein, hydrocyanic acid, hydroxypropanone, propanaldehyde, acetaldehyde, acetone, acrolein adducts with glycerol, polycondensation products of glycerol etc.
- This decreases the yield and the selectivity towards the desired nitrile.
- suitable space velocities are between 50 and 10500 h- 1 , preferably between 300 and 3500 h- 1 .
- any inert gas such as nitrogen, argon or helium
- the composition of the food is not limited although they usually use source atomic ratios of atoms of N / source of C between 0.1 and 6, usually between 0.2 and 4;
- the oxidative atomic ratio / source of C is usually between 0.1 and 12, preferably between 0.9 and 6.
- different technologies such as fixed bed, fluid bed and fluid bed with recirculation can be used. The simplest is the fixed bed.
- the nitrile production process of the invention can be carried out in the liquid phase using microwave irradiation to activate the process.
- microwave radiation allows to shorten the reaction times, increase the selectivity of the process and decrease the presence of unwanted reactions. It also acts directly on the entire volume of the sample, and presents easy handling. Therefore, another preferred aspect of the present invention is the process for producing nitriles of the invention in which microwave radiation is used as a chemical activation method, preferably in the liquid phase.
- Another more preferred aspect of the present invention is the method of production of nitriles of the invention in which a range of temperatures between 20 and 300 0 C is used, and preferably between 80 and 120 0 C.
- the thermal activation can be performed using a conventional procedure such as a silicone bath.
- Another more preferred aspect of the present invention is the method of production of nitriles of the invention using microwave radiation in a radiation output suitable microwave is used to reach a reaction temperature between 20 and 300 0 C, and preferably between 80 and 120 0 C.
- nitriles such as acrylonitrile from an alcohol such as glycerol, available in large quantities in nature and which is also obtained as a by-product in
- glycerol is used as a carbon source, it should be borne in mind that the one that comes from methanolysis plants in basic medium may contain certain impurities such as sodium chloride or sulfate, organic matter other than glycerol and methanol. In this way, the nitrile produced can also contain such impurities and depending on the use to be given it will have to be purified.
- An oxide with empirical formula SbiViO n / AI 2 ⁇ 3 was prepared as follows. 300 ml of a solution of 0.070M NH4VO3 was mixed with 3.1 g of Sb 2 Ü3. This mixture was heated to 8O 0 C and allowed to stir continuously for one hour, then 20 g of ⁇ AI 2 Ü3 was added. The mixture was brought to dryness in a rotary evaporator with the bath at 8O 0 C and then dried in an oven at 115 0 C for 24 hours. The resulting solid was calcined at 400 0 C for four hours.
- the catalyst particles are held in two beds of quartz wool. Dead volumes before and after the catalytic bed are minimized to avoid contribution of the homogeneous reaction.
- the reactor It has a thermocouple inside it to control the temperature of the catalytic bed. An electric oven is used to heat the reactor.
- the catalyst is activated by feeding 20 ml (STP) / min (milliliters of gas under standard conditions of pressure and temperature, 1 atm and 25 0 C) from a mixture of 70% helium and 30% oxygen (volumetric percentages) and increasing The temperature from room temperature to 300 0 C at 3 ° C / min., Leaving this temperature for one hour.
- Glycerol was fed 30 ml / hour with a syringe for injection of liquid, after being introduced, there is a zone for preheating liquid at 300 0 C for vaporizing the glycerol after being vaporized is diluted in the gaseous feed also preheated to 300 0 C.
- the gaseous diet consisted of 25% oxygen, 8.6% ammonia and the rest helium (volumetric percentages). The gases are introduced with mass flow regulators.
- reaction products are analyzed at the outlet of the reactor with a gas chromatograph equipped with two detectors, a TCD (Detector of
- Glycerol Conversion (%) (moles of glycerol consumed / moles of glycerol fed) x 100
- a solid with empirical formula SbiViNb2 ⁇ n / AI 2 ⁇ 3 was prepared as follows. 280 ml of a 0.025M solution NH4VO3 was mixed with one gram of Sb2O3 and with eight grams of soluble complex of niobium and ammonium oxide. The resulting mixture was heated at 8O 0 C and kept under stirring for one hour, then 20 g of ⁇ AI2O3 was added. The mixture was brought to dryness in a rotary evaporator with the bath at 8O 0 C and then dried in an oven at 115 0 C for 24 hours. The resulting solid was calcined at 400 0 C for four hours.
- the catalyst is activated by feeding 20 ml (STP) / min (milliliters of gas under standard conditions of pressure and temperature, 1 atm and 25 0 C) from a mixture of 70% helium and 30% oxygen (volumetric percentages) and increasing the temperature from the ambient up to 300 0 C at 3 ° C / min, and leaving this temperature for one hour.
- Glycerol was fed 30 ml / hour with a syringe for injection of liquid, after being introduced, there is a zone for preheating liquid at 300 0 C for vaporizing the glycerol after being vaporized is diluted in the gaseous feed also preheated to 300 0 C.
- the gaseous diet consisted of 25% oxygen, 8.6% ammonia and the rest helium (volumetric percentages).
- the gases are introduced with mass flow regulators.
- the reaction products are analyzed at the outlet of the reactor with a gas chromatograph equipped with two detectors, a TCD (Thermal Conductivity Detector) and an FID (Ionic Flame Detector). The entire line is heated above 29O 0 C to avoid the condensation of glycerol and other reaction products.
- Glycerol Conversion (%) (moles of glycerol consumed / moles of glycerol fed) x 100
- EXAMPLE 3 Production of liquid phase acrylonitrile from glycerol using SbiViOn / AI 2 O 3 as catalyst and hydrogen peroxide oxidizing agent.
- the oxide with empirical formula Sbi ⁇ ⁇ O n / AI 2 ⁇ 3, was prepared as follows. A solution of Sb (CH3COO) 3 in 0.3M tartaric acid was prepared and kept under continuous stirring until all the antimony dissolved. Next, 300 ml of a 0.070M NH4VO3 solution and 20 g of ⁇ Al 2 ⁇ 3 were added. The mixture was brought to dryness in a rotary evaporator with the bath at 8O 0 C and then dried in an oven at 115 0 C for 24 hours. The resulting solid was calcined at 400 0 C for four hours.
- 0.5 mmol of glycerol, 15 mmol of hydrogen peroxide and 57 mmol of ammonia are introduced into a 10 ml Pyrex glass spherical flask of capacity provided with two mouths ⁇ one of them connected to the refrigerant and the other free for sampling.
- the flask with the reaction mixture immersed in a thermostated silicone bath at 100 0 C and the mixture is maintained under continuous stirring for five minutes.
- 200 mg of catalyst with particle sizes between 0.250 and 0.125 mm are added to the reaction mixture and the reaction time is counted.
- the sampling is carried out periodically, and the solid catalyst is separated from the reaction products and reagents not consumed by means of a plunger syringe provided with a filter.
- reaction products are analyzed in a gas chromatograph equipped with FID (Ionic Flame Detector).
- FID Electronic Flame Detector
- Glycerol Conversion (%) (moles of glycerol consumed / moles of glycerol fed) x 100
- EXAMPLE 4 Production of liquid phase acrylonitrile from glycerol using as catalyst Sb I V 1 O n ZAI 2 O 3 under microwave activation and as hydrogen peroxide oxidizing agent.
- the oxide with empirical formula Sb I V 1 O n ZAI 2 O 3 was prepared following both procedures described in Example 1, Sb I V 1 O n ZAI 2 O 3 (1) and in Example 3, Sb 1 V 1 O n ZAI 2 O 3 (3).
- 0.5 mmol of glycerol, 15 mmol of hydrogen peroxide and 57 mmol of ammonia are introduced into a 5 ml capacity quartz reactor and screw cap provided with a vent system to avoid overpressures. Subsequently, 200 mg of catalyst with particle sizes between 0.250 and 0.125 mm are added to the reaction mixture.
- the reactor with the reaction mixture closes tightly and is introduced into a MicroSYNTH Labstation multimode microwave equipment equipped with magnetic stirring, infrared probe temperature controller and software adapted to the equipment to monitor the reaction conditions.
- the reaction mixture in continuous stirring, is activated under microwave radiation at 100 W of power for 60 minutes, using a heating ramp of 10 ° CZmin to 100 0 C. After the reaction time has elapsed, the sample is allowed to cool to room temperature. and with a plunger syringe provided with a filter, the solid catalyst is separated from the reaction products and reagents not consumed.
- reaction products are analyzed in a gas chromatograph equipped with FID (Ionic Flame Detector).
- FID Electronic Flame Detector
- Glycerol Conversion (%) (moles of glycerol consumed / moles of glycerol fed) x 100
Abstract
The invention relates to a catalytic method for the production of nitriles form alcohols, such as polyols, for example glycerol, a reaction known as ammoxidation. For this purpose, the alcohol is reacted with a nitrogen source, such as, for example, ammonia, in the presence of an oxidising agent, such as oxygen or hydrogen peroxide, and in the presence of a catalyst. Alumina-supported catalysts containing oxides of V, Nb and Sb achieve yields above 48% in ammoxidation of glycerol to acrylonitrile. The invention is particularly suitable for obtaining high-added-value products such as acrylonitrile from glycerol which is produced as a by-product in biofuel production.
Description
PROCESO CATALÍTICO DE PRODUCCIÓN DE NITRILOS A PARTIR CATALYTIC PROCESS OF NITRILE PRODUCTION FROM
DE ALCOHOLESOF ALCOHOLS
SECTOR DE LA TÉCNICA La presente invención se refiere a un proceso catalítico para Ia producción de nitrilos a partir de alcoholes. Por tanto, esta invención tiene aplicación en el sector de Ia industria química en general y, concretamente, en Ia producción de disolventes orgánicos, polímeros, fibras, resinas, pesticidas, perfumes y medicamentos. ESTADO DE LA TÉCNICASECTOR OF THE TECHNIQUE The present invention relates to a catalytic process for the production of nitriles from alcohols. Therefore, this invention has application in the chemical industry sector in general and, specifically, in the production of organic solvents, polymers, fibers, resins, pesticides, perfumes and medicines. STATE OF THE TECHNIQUE
Un nitrilo es un compuesto orgánico que contiene un grupo ciano, CN, como acetonitrilo, benzonitrilo o acrilonitrilo. El acetonitrilo se usa como disolvente de muchos compuestos y en Ia producción de fibras, gomas y resinas. Además, el acetonitrilo se usa como intermedio en Ia fabricación de pesticidas, perfumes y medicamentos. También se usa en Ia extracción y en el refinamiento de cobre. El benzonitrilo se usa como disolvente y como precursor de otros compuestos. El acrilonitrilo es probablemente el nitrilo fabricado a mayor escala. El acrilonitrilo es un monómero que se utiliza en Ia fabricación de polímeros sintéticos, especialmente el poliacrilonitrilo y las fibras acrílicas. La fibra acrílica tiene muchos usos, conviene resaltar su uso como precursor de las fibras de carbono. La dimerización del acrilonitrilo produce adiponitrilo, usado en Ia síntesis de ciertos nylons. En pequeñas cantidades se usa también como funguicida. Algunos derivados del acrilonitrilo como el 2-cloro-acrilonitrilo se utilizan en las reacciones de Diels-Alder. El acrilonitrilo es el precursor para Ia síntesis industrial de acrilamida y de ácido acrílico.A nitrile is an organic compound that contains a cyano group, CN, such as acetonitrile, benzonitrile or acrylonitrile. Acetonitrile is used as a solvent for many compounds and in the production of fibers, gums and resins. In addition, acetonitrile is used as an intermediate in the manufacture of pesticides, perfumes and medications. It is also used in the extraction and refining of copper. Benzonitrile is used as a solvent and as a precursor to other compounds. Acrylonitrile is probably the nitrile manufactured on a larger scale. Acrylonitrile is a monomer that is used in the manufacture of synthetic polymers, especially polyacrylonitrile and acrylic fibers. Acrylic fiber has many uses, it should be noted its use as a precursor of carbon fibers. Dimerization of acrylonitrile produces adiponitrile, used in the synthesis of certain nylons. In small quantities it is also used as a fungicide. Some acrylonitrile derivatives such as 2-chloro-acrylonitrile are used in Diels-Alder reactions. Acrylonitrile is the precursor for the industrial synthesis of acrylamide and acrylic acid.
El método industrial más popular para Ia producción de nitrilos es mediante Ia amonoxidación de una olefina. En este método una olefina, como propileno o isobuteno, reaccionan en presencia de catalizador con
amoniaco y oxígeno a alta temperatura, en fase gas. Hay varias patentes que describen esté método y/o los catalizadores que llevan a cabo dicha reacción (US3895049, GB1426303, SE457506, WO03011804, JP2003260354, CN1600423, JP2004174487, entre otras). En vista del alto precio del propileno, en los últimos años se ha tratado de desarrollar el proceso de obtención del nitrilo a partir de Ia parafina, como propano o isobutano. En Ia amonoxidación de Ia parafina, ésta reacciona a alta temperatura en fase gas con oxígeno y amoniaco en presencia de catalizador. El uso del alcano disminuye Ia conversión y requiere condiciones más severas de presión y temperatura respecto al uso del alqueno. Hay varias patentes que describen esté método y/o los catalizadores que llevan a cabo dicha reacción (WO0059869, JP11310562, CN1146988, JP4275266, JP3157356, JP2258065, JP2111444, JP2075347, JP2261544, IN175744, IN172305, todas ellas asignadas a Ia Standar OiI Co).The most popular industrial method for the production of nitriles is through the amonoxidation of an olefin. In this method an olefin, such as propylene or isobutene, reacts in the presence of catalyst with ammonia and oxygen at high temperature, in gas phase. There are several patents that describe this method and / or the catalysts that carry out said reaction (US3895049, GB1426303, SE457506, WO03011804, JP2003260354, CN1600423, JP2004174487, among others). In view of the high price of propylene, in recent years attempts have been made to obtain the process of obtaining nitrile from paraffin, such as propane or isobutane. In the ammonioxidation of the paraffin, it reacts at high temperature in the gas phase with oxygen and ammonia in the presence of catalyst. The use of alkane decreases the conversion and requires more severe conditions of pressure and temperature with respect to the use of the alkene. There are several patents that describe this method and / or the catalysts that carry out said reaction (WO0059869, JP11310562, CN1146988, JP4275266, JP3157356, JP2258065, JP2111444, JP2075347, JP2261544, IN175744, IN172305, all assigned to Co Standar Oi .
Por tanto, Ia producción de nitrilos, y especialmente del acrilonitrilo, es dependiente de las correspondientes parafinas y olefinas (propano y propileno) que se obtienen del craqueo del petróleo. Además, tales materias primas (parafinas y/o olefinas), de origen fósil, contribuyen con el efecto invernadero. Se hace pues necesario disponer de un proceso de obtención de nitrilos a partir de otra materia prima.Therefore, the production of nitriles, and especially acrylonitrile, is dependent on the corresponding paraffins and olefins (propane and propylene) that are obtained from oil cracking. In addition, such raw materials (paraffins and / or olefins), of fossil origin, contribute to the greenhouse effect. It is therefore necessary to have a process to obtain nitriles from another raw material.
El glicerol (también llamado glicerina) deriva de Ia metanolisis a Ia vez que los esteres metílicos que se usan en los combustibles diesel y en el fuel-oil doméstico. Es un producto natural, disponible en gran cantidad, fácil de almacenar y transportar. Además, al obtenerse como subproducto en Ia fabricación de biocombustibles, cuya demanda está aumentando, su precio está disminuyendo. Por tanto, el interés por desarrollar procesos que utilicen glicerol como materia prima está aumentando. En los últimos años han aparecido varias patentes que describen procesos en este sentido. Se ha patentado Ia obtención de acroleína a partir de glicerol
(WO2006087083, WO2006087084, WO2007090990, asignadas a Arkema France; JP2006290815, asignada a Kao Corp; US5387720, asignada a Degussa; y WO2007058221 asignada a Nippon Catalytic Chem). También hay una patente que describe Ia obtención de ácido acrílico a partir de glicerol (WO2007090991 , asignada a Arkema France).Glycerol (also called glycerin) is derived from methanolysis as well as the methyl esters used in diesel fuels and domestic fuel oil. It is a natural product, available in large quantities, easy to store and transport. In addition, as it is obtained as a byproduct in the manufacture of biofuels, whose demand is increasing, its price is decreasing. Therefore, interest in developing processes that use glycerol as a raw material is increasing. In recent years several patents have appeared that describe processes in this regard. Obtaining acrolein from glycerol has been patented (WO2006087083, WO2006087084, WO2007090990, assigned to Arkema France; JP2006290815, assigned to Kao Corp; US5387720, assigned to Degussa; and WO2007058221 assigned to Nippon Catalytic Chem). There is also a patent describing the obtaining of acrylic acid from glycerol (WO2007090991, assigned to Arkema France).
La oxidación de glicerol conduce a Ia obtención de una gran variedad de productos, empleados como intermedios en Ia síntesis de productos de alto valor añadido. Hasta el momento, los productos obtenidos en Ia reacción de oxidación de glicerol, emplean condiciones aeróbicas de reacción, bien alimentando oxígeno o aire en Ia reacción en fase gaseosa, bien por borboteo de una corriente de oxígeno o aire en disolución acuosa o en presencia de otros disolventes, por ejemplo, orgánicos, o por adición de peróxido de hidrógeno para Ia reacción en fase líquida. La oxidación de glicerol también tiene lugar en condiciones anaeróbicas de reacción, por oxidación electrocatalítica del glicerol aplicando un potencial eléctrico a Ia solución en presencia de radicales nitroxilo como catalizadores (TEMPO), y empleando biocatalizadores (enzimas y microorganismos).The oxidation of glycerol leads to the obtaining of a great variety of products, used as intermediates in the synthesis of products with high added value. So far, the products obtained in the glycerol oxidation reaction employ aerobic reaction conditions, either by feeding oxygen or air in the gas phase reaction, either by bubbling a stream of oxygen or air into an aqueous solution or in the presence of other solvents, for example, organic, or by the addition of hydrogen peroxide for the liquid phase reaction. The oxidation of glycerol also takes place under anaerobic reaction conditions, by electrocatalytic oxidation of glycerol by applying an electric potential to the solution in the presence of nitroxyl radicals as catalysts (TEMPO), and using biocatalysts (enzymes and microorganisms).
En Ia presente invención se propone un procedimiento para Ia producción de nitrilos a partir de alcoholes, mediante Ia reacción de amonoxidación del alcohol. Esta reacción tiene lugar en fase vapor y/o en fase líquida en presencia de un catalizador sólido. Los catalizadores más adecuados en este tipo de reacciones son materiales multi-fase, insolubles en el medio de reacción. Buenos resultados se obtienen con el sistema basado en antimonio y vanadio. Dicho sistema catalítico ha sido estudiado antes para Ia reacción de amonoxidación de propano para obtener acrilonitrilo. Las primeras patentes sobre estos catalizadores están asignadas a Power Gas-I.C.I (Ger. Offen 2058004 (1971 ) and Ger. OffenIn the present invention, a process for the production of nitriles from alcohols is proposed, by means of the reaction of amonoxidation of alcohol. This reaction takes place in the vapor phase and / or in the liquid phase in the presence of a solid catalyst. The most suitable catalysts in this type of reactions are multi-phase materials, insoluble in the reaction medium. Good results are obtained with the system based on antimony and vanadium. Said catalytic system has been studied before for the reaction of amonoxidation of propane to obtain acrylonitrile. The first patents on these catalysts are assigned to Power Gas-I.C.I (Ger. Offen 2058004 (1971) and Ger. Offen
2224214 (1973)). Durante quince años no se publicaron más patentes sobre este sistema catalítico hasta que en 1998 Ia Standard OiI publicara una serie de patentes sobre el sistema V-Sb (patentes US 4,746,641 ;
4,788,317; 4,767,739 y 4,788,173). En estas patentes los catalizadores se preparaban con Ia reacción redox de Sb2O3 and V2O5 en medio acuoso, seguida de Ia adición de alúmina o sílica-alúmina como soporte, además de otros elementos como dopantes. Un método alternativo (US 4,784,979) consiste en hacer reaccionar Sb2O3 con el ion monoperoxovanadio VO(θ2)+, obtenido en Ia reacción de V2O5 con H2O2; de esta manera los catalizadores obtenidos tenían mejor resistencia. En una segunda patente, US 4,879,264, se mantenía a reflujo Ia disolución de monoperoxovanadio durante más de 16 horas antes de añadir el antimonio, de manera que se formaba primero un sol y después un gel de vanadio. Muchas patentes han aparecido sobre Ia modificación del catalizador con varios agentes dopantes (JP11 ,033,399, Patentes US 5,008,427; 5,214016; 5,432,141 ; 5,498,588; 5,994,259 y 6,043,185, y WO 95/05895).2224214 (1973)). No more patents on this catalytic system were published for fifteen years until in 1998 Ia Standard OiI published a series of patents on the V-Sb system (US patents 4,746,641; 4,788,317; 4,767,739 and 4,788,173). In these patents, the catalysts were prepared with the redox reaction of Sb2O3 and V2O5 in aqueous medium, followed by the addition of alumina or silica-alumina as a support, in addition to other elements such as dopants. An alternative method (US 4,784,979) consists in reacting Sb2O3 with the monoperoxovanadium ion VO (θ2) +, obtained in the reaction of V 2 O 5 with H 2 O 2 ; in this way the catalysts obtained had better resistance. In a second patent, US 4,879,264, the monoperoxovanadium solution was refluxed for more than 16 hours before the antimony was added, so that a sun was formed first and then a vanadium gel. Many patents have appeared on the modification of the catalyst with various doping agents (JP11, 033,399, US Patents 5,008,427; 5,214016; 5,432,141; 5,498,588; 5,994,259 and 6,043,185, and WO 95/05895).
DESCRIPCIÓN BREVE DE LA INVENCIÓNBRIEF DESCRIPTION OF THE INVENTION
Un aspecto de Ia presente invención es el procedimiento para Ia producción de nitrilos a partir de alcoholes, en adelante procedimiento de producción de nitrilos de Ia invención, que tiene lugar mediante Ia amonoxidación del alcohol en presencia de un oxidante, una fuente de átomos de nitrógeno y una catalizador.An aspect of the present invention is the process for the production of nitriles from alcohols, hereinafter nitrile production process of the invention, which takes place by means of the amonoxidation of alcohol in the presence of an oxidant, a source of nitrogen atoms and a catalyst.
Un aspecto preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que el alcohol es un poliol.A preferred aspect of the present invention is the nitrile production process of the invention in which the alcohol is a polyol.
Un aspecto más preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que el alcohol es glicerol.A more preferred aspect of the present invention is the process for producing nitriles of the invention in which the alcohol is glycerol.
Otro aspecto preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que el oxidante es oxígeno molecular.
Otro aspecto preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que el oxidante es peróxido de hidrógeno, o una fuente de oxígeno altamente reactivo, como hidroperóxidos. Otro aspecto preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que Ia fuente de átomos de nitrógeno es amoniaco.Another preferred aspect of the present invention is the nitrile production process of the invention in which the oxidant is molecular oxygen. Another preferred aspect of the present invention is the process for producing nitriles of the invention in which the oxidant is hydrogen peroxide, or a highly reactive oxygen source, such as hydroperoxides. Another preferred aspect of the present invention is the process for producing nitriles of the invention in which the source of nitrogen atoms is ammonia.
Otro aspecto preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que el catalizador responde a Ia fórmula AaBbCcDdEeOx donde A es V y/o Nb; B es Sb, Mo y/o Nb, C es un elemento seleccionado del grupo Sn, Ti, Te, W, U; D es un elemento seleccionado del grupo Li, Mg, Na, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Ge, Nb, Mo, W, Cu, Tl, P, Zr, Re, Ag, Cd, Zn, Pb, D, Rb, Cs, Ta, Se, Bi, Ce, In, As, B, Al, Mn; E es un elemento seleccionado del grupo Pd, Au, Pt, Ru, Rh, Os, Ir; y donde a y d = 0-10 , c, d y e, = 0-30, y x se determina por el estado de oxidación de los cationes presentes.Another preferred aspect of the present invention is the nitrile production process of the invention in which the catalyst responds to the formula AaBbCcDdEeOx where A is V and / or Nb; B is Sb, Mo and / or Nb, C is an element selected from the group Sn, Ti, Te, W, U; D is an element selected from the group Li, Mg, Na, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Ge, Nb, Mo, W, Cu, Tl, P, Zr, Re, Ag, Cd , Zn, Pb, D, Rb, Cs, Ta, Se, Bi, Ce, In, As, B, Al, Mn; E is an element selected from the group Pd, Au, Pt, Ru, Rh, Os, Ir; and where a and d = 0-10, c, d and e, = 0-30, and x is determined by the oxidation state of the cations present.
Un aspecto más preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que el catalizador utilizado no contiene los elementos D y E y, por tanto, responde a Ia formula AaBbCcOx donde A es V y/o Nb; B es Sb, Mo y/oA more preferred aspect of the present invention is the nitrile production process of the invention in which the catalyst used does not contain elements D and E and, therefore, responds to the formula AaBbCcOx where A is V and / or Nb; B is Sb, Mo and / or
Nb, C es un elemento seleccionado del grupo Sn, Ti, Te, W, U; D.Nb, C is an element selected from the group Sn, Ti, Te, W, U; D.
Una realización particular de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que el catalizador utilizado no contiene los elementos C, D y E y, por tanto, responde a Ia formula AaBbOx donde donde A es V y/o Nb y B es Sb, Mo y/o Nb.A particular embodiment of the present invention is the nitrile production process of the invention in which the catalyst used does not contain the elements C, D and E and, therefore, responds to the formula AaBbOx where A is V and / or Nb and B is Sb, Mo and / or Nb.
Un ejemplo particular de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que el catalizador utilizado es VzSbyOx soportado en AI2O3, donde z = 0-10, y=10-0 y x se determina por el estado de oxidación de los cationes presentes.
Otro aspecto más preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que el catalizador se encuentra soportado sobre óxidos metálicos tales comoA particular example of the present invention is the nitrile production process of the invention in which the catalyst used is VzSbyOx supported on AI2O3, where z = 0-10, y = 10-0 and x is determined by the oxidation state of The cations present. Another more preferred aspect of the present invention is the process of producing nitriles of the invention in which the catalyst is supported on metal oxides such as
AI2O3, Nb2θ5, Zrθ2, TÍO2, SÍO2, zeolitas, o material mesoporoso o carbonoso.AI2O3, Nb2θ 5 , Zrθ2, UNCLE2, SIO2, zeolites, or mesoporous or carbonaceous material.
Otro aspecto preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que se utiliza una temperatura entre 200 y 800 0C y, preferentemente, entre 350 y 550 0C. Otro aspecto preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que se utiliza una presión comprendida entre 0.1 y 5 bares.Another preferred aspect of the present invention is the production method of nitriles of the invention in which a temperature between 200 and 800 used 0 C and preferably between 350 and 550 0 C. Another preferred aspect of the present invention is the nitrile production process of the invention in which a pressure between 0.1 and 5 bar is used.
Otro aspecto preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que se utiliza radiación microondas como método de activación, Io que permite trabajar a temperaturas más moderadas.Another preferred aspect of the present invention is the nitrile production process of the invention in which microwave radiation is used as the activation method, which allows working at more moderate temperatures.
Otro aspecto preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que se utiliza activación por microondas con una potencia adecuada para alcanzar una temperatura entre 20 y 300 0C y, preferentemente, entre 80 y 120 0C.Another preferred aspect of the present invention is the production method of nitriles of the invention in which microwave activation is used with adequate power to reach a temperature between 20 and 300 0 C and preferably between 80 and 120 0 C.
DESCRIPCIÓN DETALLADADETAILED DESCRIPTION
La presente invención se basa en el hecho, observado por los inventores, de que mediante Ia reacción de amonoxidación de un alcohol en presencia de un oxidante, una fuente de átomos de nitrógeno (e.g., amoníaco) y un catalizador se obtienen nitrilos. Esta reacción es un procedimiento totalmente novedoso y atractivo para Ia preparación de nitrilos a nivel industrial.
La reacción implicada en este procedimiento de preparación de nitrilos es:The present invention is based on the fact, observed by the inventors, that by means of the reaction of amonoxidation of an alcohol in the presence of an oxidant, a source of nitrogen atoms (eg, ammonia) and a catalyst, nitriles are obtained. This reaction is a completely new and attractive procedure for the preparation of nitriles at the industrial level. The reaction involved in this nitrile preparation process is:
R-OH + NH3 + OXIDANTE → R-CN + H2O + N2 R-OH + NH 3 + OXIDIZER → R-CN + H 2 O + N 2
Por tanto, un aspecto de Ia presente invención es el procedimiento para Ia producción de nitrilos a partir de alcoholes, en adelante procedimiento de producción de nitrilos de Ia invención, que tiene lugar mediante Ia amonoxidación del alcohol en presencia de un oxidante, una fuente de átomos de nitrógeno y una catalizador.Therefore, one aspect of the present invention is the process for the production of nitriles from alcohols, hereinafter the process of producing nitriles of the invention, which takes place by means of the amonoxidation of alcohol in the presence of an oxidant, a source of nitrogen atoms and a catalyst.
Un aspecto preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que el alcohol es un poliol.A preferred aspect of the present invention is the nitrile production process of the invention in which the alcohol is a polyol.
Un aspecto más preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que el alcohol es glicerol.A more preferred aspect of the present invention is the process for producing nitriles of the invention in which the alcohol is glycerol.
En este caso, Ia reacción que tiene lugar para Ia producción de acrilonitrilo a partir de glicerol es:In this case, the reaction that takes place for the production of acrylonitrile from glycerol is:
CH2OH-CHOH-CH2OH + OXIDANTE + NH3 → CH2CHCN + H2O + N2 CH 2 OH-CHOH-CH 2 OH + OXIDIZER + NH 3 → CH 2 CHCN + H 2 O + N 2
El oxidante puede ser oxígeno molecular, que puede usarse en forma de aire o de cualquier otra mezcla de gases que contenga oxígeno molecular.The oxidant can be molecular oxygen, which can be used in the form of air or any other gas mixture containing molecular oxygen.
Otro aspecto preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que el oxidante es oxígeno molecular.Another preferred aspect of the present invention is the nitrile production process of the invention in which the oxidant is molecular oxygen.
Otro aspecto preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que el oxidante es peróxido de hidrógeno, o una fuente de oxígeno altamente reactivo, como hidroperóxidos.
La fuente de átomos de nitrógeno más usual que puede utilizarse es amoniaco. Por tanto, otro aspecto preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que Ia fuente de átomos de nitrógeno es amoniaco. Otro aspecto preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que el catalizador responde a Ia fórmula AaBbCcDdEeOx donde A es V y/o Nb; B es Sb, Mo y/o Nb, C es un elemento seleccionado del grupo Sn, Ti, Te, W, U; D es un elemento seleccionado del grupo Li, Mg, Na, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Ge, Nb, Mo, W, Cu, Tl, P, Zr, Re, Ag, Cd, Zn, Pb, D, Rb, Cs, Ta, Se, Bi, Ce, In, As, B, Al, Mn; E es un elemento seleccionado del grupo Pd, Au, Pt, Ru, Rh, Os, Ir; y donde a y d = 0-10 , c, d y e, = 0-30, y x se determina por el estado de oxidación de los cationes presentes.Another preferred aspect of the present invention is the process for producing nitriles of the invention in which the oxidant is hydrogen peroxide, or a highly reactive oxygen source, such as hydroperoxides. The most common source of nitrogen atoms that can be used is ammonia. Therefore, another preferred aspect of the present invention is the process for producing nitriles of the invention in which the source of nitrogen atoms is ammonia. Another preferred aspect of the present invention is the nitrile production process of the invention in which the catalyst responds to the formula AaBbCcDdEeOx where A is V and / or Nb; B is Sb, Mo and / or Nb, C is an element selected from the group Sn, Ti, Te, W, U; D is an element selected from the group Li, Mg, Na, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Ge, Nb, Mo, W, Cu, Tl, P, Zr, Re, Ag, Cd , Zn, Pb, D, Rb, Cs, Ta, Se, Bi, Ce, In, As, B, Al, Mn; E is an element selected from the group Pd, Au, Pt, Ru, Rh, Os, Ir; and where ayd = 0-10, c, dye, = 0-30, and x is determined by the oxidation state of the cations present.
Un aspecto más preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que el catalizador utilizado no contiene los elementos D y E y, por tanto, responde a Ia formula AaBbCcOx donde A es V y/o Nb; B es Sb, Mo y/oA more preferred aspect of the present invention is the nitrile production process of the invention in which the catalyst used does not contain elements D and E and, therefore, responds to the formula AaBbCcOx where A is V and / or Nb; B is Sb, Mo and / or
Nb, C es un elemento seleccionado del grupo Sn, Ti, Te, W, U; D.Nb, C is an element selected from the group Sn, Ti, Te, W, U; D.
Una realización particular de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que el catalizador utilizado no contiene los elementos C, D y E y, por tanto, responde a Ia formula AaBbOx donde donde A es V y/o Nb y B es Sb, Mo y/o Nb.A particular embodiment of the present invention is the nitrile production process of the invention in which the catalyst used does not contain the elements C, D and E and, therefore, responds to the formula AaBbOx where A is V and / or Nb and B is Sb, Mo and / or Nb.
Un ejemplo particular de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que el catalizador utilizado es VzSbyOx soportado en AI2O3, donde z = 0-10, y=10-0 y x se determina por el estado de oxidación de los cationes presentes.A particular example of the present invention is the nitrile production process of the invention in which the catalyst used is VzSbyOx supported on AI2O3, where z = 0-10, y = 10-0 and x is determined by the oxidation state of The cations present.
Otro aspecto más preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que el
catalizador se encuentra soportado sobre óxidos metálicos tales como AI2O3, Nb2θ5, ZrÜ2, TÍO2, SÍO2, zeolitas, material mesoporoso o carbono.Another more preferred aspect of the present invention is the process of producing nitriles of the invention in which the The catalyst is supported on metal oxides such as AI2O3, Nb2θ 5 , ZrÜ2, TIO2, SIO2, zeolites, mesoporous material or carbon.
El catalizador puede utilizarse puro o disuelto en algún sólido inerte como por ejemplo carburo de silicio. De esta manera, es más fácil controlar Ia exotermicidad de Ia reacción y por tanto controlar mejor Ia temperatura.The catalyst can be used pure or dissolved in some inert solid such as silicon carbide. In this way, it is easier to control the exothermicity of the reaction and therefore better control the temperature.
Para obtener el producto deseado es necesario utilizar temperaturas y presiones adecuadas. Otro aspecto preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que se utiliza una temperatura entre 200 y 800 0C y, preferentemente, entre 350 y 550 0C. Un descenso de Ia presión en el medio de reacción posibilita el poder evaporar el alcohol a una temperatura más baja, que es particularmente conveniente para el glicerol. Por tanto, otro aspecto preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que se utiliza una presión comprendida entre 0.1 y 5 bares.To obtain the desired product it is necessary to use appropriate temperatures and pressures. Another preferred aspect of the present invention is the production method of nitriles of the invention in which a temperature between 200 and 800 used 0 C and preferably between 350 and 550 0 C. A decrease of the pressure in the medium The reaction makes it possible to evaporate the alcohol at a lower temperature, which is particularly suitable for glycerol. Therefore, another preferred aspect of the present invention is the nitrile production process of the invention in which a pressure comprised between 0.1 and 5 bar is used.
La reacción se puede llevar a cabo tanto en fase gaseosa como en fase líquida y está acompañada por otras reacciones secundarias que producen otros productos como: acroleína, ácido cianhídrico, hidroxipropanona, propanaldehído, acetaldehído, acetona, aducios de acroleína con glicerol, productos de policondensación del glicerol etc. Esto disminuye el rendimiento y Ia selectividad hacia el nitrilo deseado. Para evitar estas reacciones secundarias y Ia formación de productos no deseados es importante limitar el tiempo de residencia en el reactor, por otro lado, cuando se aumenta el tiempo de residencia se obtienen conversiones mayores. Por tanto, velocidades espaciales adecuadas se encuentran entre 50 y 10500 h-1, preferiblemente entre 300 y 3500 h-1. Como gas disolvente para ajustar Ia velocidad espacial y Ia presión parcial de los reactivos se puede usar cualquier gas inerte, como nitrógeno, argón o helio. La composición de Ia alimentación no esta limitada aunque se
suelen utilizar relaciones atómicas fuente de átomos de N/fuente de C entre 0.1 y 6, normalmente entre 0.2 y 4; Ia relación atómica oxidante/fuente de C suele estar comprendida entre 0.1 y 12, preferentemente entre 0.9 y 6. Cuando Ia reacción tiene lugar en fase gas se pueden utilizar diferentes tecnologías tales como lecho fijo, lecho fluido y lecho fluido con recirculación. El más simple es el lecho fijo.The reaction can be carried out both in the gas phase and in the liquid phase and is accompanied by other side reactions that produce other products such as: acrolein, hydrocyanic acid, hydroxypropanone, propanaldehyde, acetaldehyde, acetone, acrolein adducts with glycerol, polycondensation products of glycerol etc. This decreases the yield and the selectivity towards the desired nitrile. To avoid these side reactions and the formation of unwanted products it is important to limit the residence time in the reactor, on the other hand, when the residence time is increased, greater conversions are obtained. Therefore, suitable space velocities are between 50 and 10500 h- 1 , preferably between 300 and 3500 h- 1 . As the solvent gas to adjust the spatial velocity and the partial pressure of the reagents, any inert gas, such as nitrogen, argon or helium, can be used. The composition of the food is not limited although they usually use source atomic ratios of atoms of N / source of C between 0.1 and 6, usually between 0.2 and 4; The oxidative atomic ratio / source of C is usually between 0.1 and 12, preferably between 0.9 and 6. When the reaction takes place in the gas phase, different technologies such as fixed bed, fluid bed and fluid bed with recirculation can be used. The simplest is the fixed bed.
El procedimiento de producción de nitrilos de Ia invención se puede llevar a cabo en fase líquida utilizando Ia irradiación de microondas para activar el proceso. De hecho, en Ia presente invención se observó que Ia radiación microondas permite acortar los tiempos de reacción, aumentar Ia selectividad del proceso y disminuir Ia presencia de reacciones no deseadas. También actúa directamente sobre todo el volumen de Ia muestra, y presenta un fácil manejo. Por tanto, otro aspecto preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que se utiliza radiación microondas como método de activación químico, preferentemente en fase líquida.The nitrile production process of the invention can be carried out in the liquid phase using microwave irradiation to activate the process. In fact, in the present invention it was observed that the microwave radiation allows to shorten the reaction times, increase the selectivity of the process and decrease the presence of unwanted reactions. It also acts directly on the entire volume of the sample, and presents easy handling. Therefore, another preferred aspect of the present invention is the process for producing nitriles of the invention in which microwave radiation is used as a chemical activation method, preferably in the liquid phase.
Otro aspecto más preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención en el que se utiliza un rango de temperaturas comprendido entre 20 y 300 0C, y preferentemente entre 80 y 120 0C. La activación térmica se puede realizar utilizando un procedimiento convencional como, por ejemplo, un baño de silicona. Otro aspecto más preferente de Ia presente invención es el procedimiento de producción de nitrilos de Ia invención utilizando radiación de microondas en el que se utiliza una potencia de irradiación de microondas adecuada para alcanzar una temperatura de reacción comprendida entre 20 y 300 0C, y preferentemente entre 80 y 120 0C.
Mediante esta invención se consigue producir nitrilos como el acrilonitrilo a partir de un alcohol como el glicerol, disponible en grandes cantidad en Ia naturaleza y que además se obtiene como subproducto enAnother more preferred aspect of the present invention is the method of production of nitriles of the invention in which a range of temperatures between 20 and 300 0 C is used, and preferably between 80 and 120 0 C. The thermal activation can be performed using a conventional procedure such as a silicone bath. Another more preferred aspect of the present invention is the method of production of nitriles of the invention using microwave radiation in a radiation output suitable microwave is used to reach a reaction temperature between 20 and 300 0 C, and preferably between 80 and 120 0 C. Through this invention it is possible to produce nitriles such as acrylonitrile from an alcohol such as glycerol, available in large quantities in nature and which is also obtained as a by-product in
Ia fabricación de biocombustibles, evitándose Ia utilización de una parafina o una olefina (propano o propileno) procedentes de los combustible fósiles.The manufacture of biofuels, avoiding the use of a paraffin or an olefin (propane or propylene) from fossil fuels.
En caso de utilizar glicerol como fuente de carbono hay que tener en cuenta que el que proviene de las plantas de metanolisis en medio básico puede contener ciertas impurezas como cloruro o sulfato sódicos, materia orgánica distinta al glicerol y metanol. De esta manera, el nitrilo producido puede contener también tales impurezas y dependiendo del uso que vaya a dársele habrá de ser purificado.If glycerol is used as a carbon source, it should be borne in mind that the one that comes from methanolysis plants in basic medium may contain certain impurities such as sodium chloride or sulfate, organic matter other than glycerol and methanol. In this way, the nitrile produced can also contain such impurities and depending on the use to be given it will have to be purified.
EJEMPLOS DE REALIZACIÓN DE LA INVENCIÓNEXAMPLES OF EMBODIMENT OF THE INVENTION
EJEMPLO 1 -Producción de Acrilonitrilo a partir de glicerol utilizando como catalizador SbiViOn/AI2θ3.EXAMPLE 1 - Acrylonitrile production from glycerol using SbiViO n / AI 2 θ3 as catalyst.
Un óxido con formula empírica SbiViOn/AI2θ3 se preparó de Ia siguiente manera. 300 mi de una solución de 0.070M NH4VO3 se mezcló con 3.1 g de Sb2Ü3. Esta mezcla se calentó a 8O0C y se dejó en agitación continua durante una hora, después, 20 g de γ AI2Ü3 fue adicionada. La mezcla se llevó a sequedad en un rotavapor con el baño a 8O0C y después se secó en una estufa a 1150C durante 24 horas. El sólido resultante fue calcinado a 4000C durante cuatro horas.An oxide with empirical formula SbiViO n / AI 2 θ3 was prepared as follows. 300 ml of a solution of 0.070M NH4VO3 was mixed with 3.1 g of Sb 2 Ü3. This mixture was heated to 8O 0 C and allowed to stir continuously for one hour, then 20 g of γ AI 2 Ü3 was added. The mixture was brought to dryness in a rotary evaporator with the bath at 8O 0 C and then dried in an oven at 115 0 C for 24 hours. The resulting solid was calcined at 400 0 C for four hours.
50 mg de catalizador SbiViOn/AI2θ3 con tamaños de partícula entre 0.250 y 0.125 mm se diluyen con 250 mg de CSi y se coloca en el interior de un reactor de lecho fijo hecho en cuarzo (DE=9mm, Dl=7.8mm, L=290 mm). Las partículas de catalizador se sostienen en dos lechos de lana de cuarzo. Los volúmenes muertos antes y después del lecho catalítico son minimizados para evitar contribución de Ia reacción homogénea. El reactor
tiene en su interior un termopar para controlar Ia temperatura del lecho catalítico. Un horno eléctrico se utiliza para calentar el reactor.50 mg of SbiViO n / AI 2 θ3 catalyst with particle sizes between 0.250 and 0.125 mm are diluted with 250 mg of CSi and placed inside a fixed bed reactor made of quartz (SD = 9mm, Dl = 7.8mm , L = 290 mm). The catalyst particles are held in two beds of quartz wool. Dead volumes before and after the catalytic bed are minimized to avoid contribution of the homogeneous reaction. The reactor It has a thermocouple inside it to control the temperature of the catalytic bed. An electric oven is used to heat the reactor.
El catalizador se activa alimentando 20 mi (STP)/min (mililitros de gas en condiciones estándar de presión y temperatura, 1 atm y 250C) de una mezcla de 70% de helio y 30% de oxígeno (porcentajes volumétricos) y aumentando Ia temperatura desde Ia ambiente hasta 3000C a 3°C/min., y dejando esta temperatura durante una hora. El glicerol se alimenta a 30 ml/hora con una jeringa para inyección de líquidos, tras ser introducido, hay una zona para precalentamiento de líquidos a 300 0C para vaporizar al glicerol que tras ser vaporizado es diluido en Ia alimentación gaseosa precalentada también a 3000C. La alimentación gaseosa consistió en 25% de oxígeno, 8.6% de amoniaco y el resto helio (porcentajes volumétricos). Los gases se introducen con reguladores de flujo másico.The catalyst is activated by feeding 20 ml (STP) / min (milliliters of gas under standard conditions of pressure and temperature, 1 atm and 25 0 C) from a mixture of 70% helium and 30% oxygen (volumetric percentages) and increasing The temperature from room temperature to 300 0 C at 3 ° C / min., Leaving this temperature for one hour. Glycerol was fed 30 ml / hour with a syringe for injection of liquid, after being introduced, there is a zone for preheating liquid at 300 0 C for vaporizing the glycerol after being vaporized is diluted in the gaseous feed also preheated to 300 0 C. The gaseous diet consisted of 25% oxygen, 8.6% ammonia and the rest helium (volumetric percentages). The gases are introduced with mass flow regulators.
Los productos de reacción se analizan a Ia salida del reactor con un cromatógrafo de gases equipado con dos detectores, un TCD (Detector deThe reaction products are analyzed at the outlet of the reactor with a gas chromatograph equipped with two detectors, a TCD (Detector of
Conductividad Térmica) y un FID (Detector Iónico de Llama). Toda Ia linea está calefactada por encima de 29O0C para evitar Ia condensación del glicerol y de otros productos de reacción.Thermal Conductivity) and an FID (Ionic Flame Detector). The entire line is heated above 29O 0 C to avoid the condensation of glycerol and other reaction products.
Las conversiones, selectividades y rendimientos se han calculado mediante las siguientes fórmulas:Conversions, selectivities and returns have been calculated using the following formulas:
Conversión de Glicerol (%) = (moles de glicerol consumido / moles de glicerol alimentado ) x 100Glycerol Conversion (%) = (moles of glycerol consumed / moles of glycerol fed) x 100
Selectividad a un compuesto (%) = ((moles formados de compuesto * átomos de carbono del compuesto)/(moles de glicerol consumido * átomos de carbono en glicerol)) x 100Selectivity to a compound (%) = ((moles formed of compound * carbon atoms of the compound) / (moles of glycerol consumed * carbon atoms in glycerol)) x 100
Rendimiento a un compuesto (%) = (selectividad a un compuesto * conversión de glicerol) / 100Yield to a compound (%) = (selectivity to a compound * glycerol conversion) / 100
Los resultados se muestran en las tablas 1 y 2.
Tabla 1. Conversión de Glicerol (%) y selectividad (%) de Ia reacción en ausencia (CSi) y presencia del sólido SbiViOn/AI2θ3.The results are shown in tables 1 and 2. Table 1. Conversion of Glycerol (%) and selectivity (%) of the reaction in absence (CSi) and presence of the solid SbiViO n / AI 2 θ3.
Convers. = conversión etil. = etileno acetonit. = acetonitrilo acrol. = acroleina acrilonit = acrilonitriloConvers. = ethyl conversion. = ethylene acetonit. = acetonitrile acrol. = acrolein acrylonit = acrylonitrile
Tabla 2. Rendimientos (%) de Ia reacción en ausencia (CSi) y presencia del sólido Sb1V1On/AI2O3.Table 2. Yields (%) of the reaction in absence (CSi) and presence of the solid Sb1V1On / AI2O3.
Se alcanzan conversiones de 71.6% en Ia amonoxidación de glicerol para Ia producción de acrilonitrilo, rendimientos similares a los obtenidos en Ia reacción de obtención del acrilonitrilo a partir de propano. El acrilonitrilo es el principal producto de esta reacción, con una selectividad del 56%, y un rendimiento del 40.1 %. El segundo producto en abundancia es Ia acroleina, que es un intermedio en Ia formación de acrilonitrilo.
EJEMPLO 2 - Producción de Acrilonitrilo a partir de glicerol utilizando como catalizador Sbi ViNb2OnZAI2O3 Conversions of 71.6% are achieved in the glycerol amonoxidation for the production of acrylonitrile, yields similar to those obtained in the reaction to obtain acrylonitrile from propane. Acrylonitrile is the main product of this reaction, with a selectivity of 56%, and a yield of 40.1%. The second product in abundance is acrolein, which is an intermediate in acrylonitrile formation. EXAMPLE 2 - Production of Acrylonitrile from glycerol using Sbi ViNb 2 O n ZAI 2 O 3 as catalyst
Un sólido con formula empírica SbiViNb2θn/AI2θ3 se preparó de Ia siguiente manera. 280 mi de una solución de 0.025M NH4VO3 se mezcló con un gramo de Sb2O3 y con ocho gramos de complejo soluble de óxido de niobio y amonio. La mezcla resultante se calentó a 8O0C y se mantuvo en agitación durante una hora, después, 20 g de γ AI2O3 fue adicionada. La mezcla se llevó a sequedad en un rotavapor con el baño a 8O0C y después se secó en una estufa a 1150C durante 24 horas. El sólido resultante fue calcinado a 4000C durante cuatro horas.A solid with empirical formula SbiViNb2θ n / AI 2 θ3 was prepared as follows. 280 ml of a 0.025M solution NH4VO3 was mixed with one gram of Sb2O3 and with eight grams of soluble complex of niobium and ammonium oxide. The resulting mixture was heated at 8O 0 C and kept under stirring for one hour, then 20 g of γ AI2O3 was added. The mixture was brought to dryness in a rotary evaporator with the bath at 8O 0 C and then dried in an oven at 115 0 C for 24 hours. The resulting solid was calcined at 400 0 C for four hours.
50 mg de catalizador SbiViNb2On/AI2θ3 con tamaños de partícula entre 0.250 y 0.125 mm se diluyen con 250 mg de CSi y se coloca en el interior de un reactor de lecho fijo hecho en cuarzo (DE=9mm, Dl=7.8mm, L=290 mm). Las partículas de catalizador se sostienen en dos lechos de lana de cuarzo. Los volúmenes muertos antes y después del lecho catalítico son minimizados para evitar contribución de Ia reacción homogénea. El reactor tiene en su interior un termopar para controlar Ia temperatura del lecho catalítico. Un horno eléctrico se utiliza para calentar el reactor. El catalizador se activa alimentando 20 mi (STP)/min (mililitros de gas en condiciones estándar de presión y temperatura, 1 atm y 250C) de una mezcla de 70% de helio y 30% de oxígeno (porcentajes volumétricos) y aumentando Ia temperatura desde Ia ambiente hasta 3000C a 3°C/min, y dejando esta temperatura durante una hora. El glicerol se alimenta a 30 ml/hora con una jeringa para inyección de líquidos, tras ser introducido, hay una zona para precalentamiento de líquidos a 300 0C para vaporizar al glicerol que tras ser vaporizado es diluido en Ia alimentación gaseosa precalentada también a 3000C. La alimentación gaseosa consistió en 25% de oxígeno, 8.6% de amoniaco y el resto helio (porcentajes volumétricos). Los gases se introducen con reguladores de flujo másico.
Los productos de reacción se analizan a Ia salida del reactor con un cromatógrafor de gases equipado con dos detectores, un TCD (Detector de Conductividad Térmica) y un FID (Detector Iónico de Llama). Toda Ia linea está calefactada por encima de 29O0C para evitar Ia condensación del glicerol y de otros productos de reacción.50 mg of SbiViNb 2 On / AI 2 θ3 catalyst with particle sizes between 0.250 and 0.125 mm are diluted with 250 mg of CSi and placed inside a quartz fixed bed reactor (SD = 9mm, Dl = 7.8 mm, L = 290 mm). The catalyst particles are held in two beds of quartz wool. Dead volumes before and after the catalytic bed are minimized to avoid contribution of the homogeneous reaction. The reactor has a thermocouple inside it to control the temperature of the catalytic bed. An electric oven is used to heat the reactor. The catalyst is activated by feeding 20 ml (STP) / min (milliliters of gas under standard conditions of pressure and temperature, 1 atm and 25 0 C) from a mixture of 70% helium and 30% oxygen (volumetric percentages) and increasing the temperature from the ambient up to 300 0 C at 3 ° C / min, and leaving this temperature for one hour. Glycerol was fed 30 ml / hour with a syringe for injection of liquid, after being introduced, there is a zone for preheating liquid at 300 0 C for vaporizing the glycerol after being vaporized is diluted in the gaseous feed also preheated to 300 0 C. The gaseous diet consisted of 25% oxygen, 8.6% ammonia and the rest helium (volumetric percentages). The gases are introduced with mass flow regulators. The reaction products are analyzed at the outlet of the reactor with a gas chromatograph equipped with two detectors, a TCD (Thermal Conductivity Detector) and an FID (Ionic Flame Detector). The entire line is heated above 29O 0 C to avoid the condensation of glycerol and other reaction products.
Las conversiones, selectividades y rendimientos se han calculado mediante las siguientes fórmulas:Conversions, selectivities and returns have been calculated using the following formulas:
Conversión de Glicerol (%) = (moles de glicerol consumido / moles de glicerol alimentado ) x 100Glycerol Conversion (%) = (moles of glycerol consumed / moles of glycerol fed) x 100
Selectividad a un compuesto (%) = (moles formados de compuesto*atomos de carbono en ese compuesto)/(moles de glicerol consumido*atomos de carbono en glicerol) x 100Selectivity to a compound (%) = (moles formed of compound * carbon atoms in that compound) / (moles of glycerol consumed * carbon atoms in glycerol) x 100
Rendimiento a un compuesto (%) = (selectividad a un compuesto * conversión de glicerol) / 100Yield to a compound (%) = (selectivity to a compound * glycerol conversion) / 100
Los resultados se muestran en las tablas 3 y 4.The results are shown in tables 3 and 4.
Tabla 3. Conversión de Glicerol (%) y selectividad (%) de Ia reacción en ausencia (CSi) y presencia del sólido SbiViNb2θn/AI2θ3.Table 3. Conversion of Glycerol (%) and selectivity (%) of the reaction in absence (CSi) and presence of the solid SbiViNb2θ n / AI 2 θ3.
Convers. = conversión etil. = etileno acetonit. = acetonitrilo acrol. = acroleina acrilonit = acrilonitriloConvers. = ethyl conversion. = ethylene acetonit. = acetonitrile acrol. = acrolein acrylonit = acrylonitrile
Tabla 4. Rendimientos (%) de Ia reacción en ausencia (CSi) y presencia del sólido SbiViNb2On/AI2O3.
Table 4. Yields (%) of the reaction in the absence (CSi) and presence of the solid SbiViNb 2 O n / AI 2 O 3 .
Con este catalizador Ia conversión es mayor; se alcanzan conversiones de 82.6% en Ia amonoxidación de glicerol para Ia producción de acrilonitrilo, rendimientos similares a los obtenidos en Ia reacción de obtención del acrilonitrilo a partir de propano. El acrilonitrilo es el principal producto de esta reacción, con una selectividad del 58.3%, y un rendimiento del 48.1 %. El segundo producto en abundancia es Ia acroleina, que es un intermedio en Ia formación de acrilonitrilo.With this catalyst the conversion is greater; Conversions of 82.6% are achieved in the glycerol amonoxidation for the production of acrylonitrile, yields similar to those obtained in the reaction to obtain acrylonitrile from propane. Acrylonitrile is the main product of this reaction, with a selectivity of 58.3%, and a yield of 48.1%. The second product in abundance is acrolein, which is an intermediate in acrylonitrile formation.
EJEMPLO 3 - Producción de Acrilonitrilo en fase líquida a partir de glicerol utilizando como catalizador SbiViOn/AI2O3 y como agente oxidante peróxido de hidrógeno.EXAMPLE 3 - Production of liquid phase acrylonitrile from glycerol using SbiViOn / AI 2 O 3 as catalyst and hydrogen peroxide oxidizing agent.
El óxido con formula empírica Sbi\ΛOn/AI2θ3, se preparó de Ia siguiente manera. Se preparó una disolución de Sb(CH3COO)3 en ácido tartárico 0.3M y se mantuvo en continua agitación hasta que todo el antimonio se disolvió. A continuación, 300 mi de una solución 0.070M NH4VO3 y 20 g de γ Al2θ3 fueron adicionados. La mezcla se llevó a sequedad en un rotavapor con el baño a 8O0C y después se secó en una estufa a 1150C durante 24 horas. El sólido resultante fue calcinado a 4000C durante cuatro horas. 0.5 mmol de glicerol, 15 mmol de peróxido de hidrógeno y 57 mmol de amoníaco se introducen en un matraz esférico de vidrio Pyrex de 10 mi
de capacidad provisto de dos bocas^ una de ellas conectada al refrigerante y Ia otra libre para Ia toma de muestras. El matraz con Ia mezcla de reacción se sumerge en un baño termostatizado de silicona a 1000C y se mantiene Ia mezcla en continua agitación durante cinco minutos. Posteriormente 200 mg de catalizador con tamaños de partícula entre 0.250 y 0.125 mm se adicionan a Ia mezcla de reacción y se empieza a contabilizar el tiempo de reacción. La toma de muestra se realiza de forma periódica, y se separan el catalizador sólido de los productos de reacción y reactivos no consumidos mediante una jeringa de émbolo provista de filtro.The oxide with empirical formula Sbi \ ΛO n / AI 2 θ3, was prepared as follows. A solution of Sb (CH3COO) 3 in 0.3M tartaric acid was prepared and kept under continuous stirring until all the antimony dissolved. Next, 300 ml of a 0.070M NH4VO3 solution and 20 g of γ Al 2 θ3 were added. The mixture was brought to dryness in a rotary evaporator with the bath at 8O 0 C and then dried in an oven at 115 0 C for 24 hours. The resulting solid was calcined at 400 0 C for four hours. 0.5 mmol of glycerol, 15 mmol of hydrogen peroxide and 57 mmol of ammonia are introduced into a 10 ml Pyrex glass spherical flask of capacity provided with two mouths ^ one of them connected to the refrigerant and the other free for sampling. The flask with the reaction mixture immersed in a thermostated silicone bath at 100 0 C and the mixture is maintained under continuous stirring for five minutes. Subsequently, 200 mg of catalyst with particle sizes between 0.250 and 0.125 mm are added to the reaction mixture and the reaction time is counted. The sampling is carried out periodically, and the solid catalyst is separated from the reaction products and reagents not consumed by means of a plunger syringe provided with a filter.
Los productos de reacción se analizan en un cromatógrafo de gases equipado con FID (Detector Iónico de Llama).The reaction products are analyzed in a gas chromatograph equipped with FID (Ionic Flame Detector).
Las conversiones, selectividades y rendimientos se han calculado mediante las siguientes fórmulas:Conversions, selectivities and returns have been calculated using the following formulas:
Conversión de Glicerol (%) = (moles de glicerol consumido / moles de glicerol alimentado ) x 100Glycerol Conversion (%) = (moles of glycerol consumed / moles of glycerol fed) x 100
Selectividad a un compuesto (%) = (moles formados de compuesto*atomos de carbono en ese compuesto)/(moles de glicerol consumido*atomos de carbono en glicerol) x 100Selectivity to a compound (%) = (moles formed of compound * carbon atoms in that compound) / (moles of glycerol consumed * carbon atoms in glycerol) x 100
Rendimiento a un compuesto (%) = (selectividad a un compuesto * conversión de glicerol) / 100Yield to a compound (%) = (selectivity to a compound * glycerol conversion) / 100
Los resultados se muestran en las tabla 5 y 6.The results are shown in tables 5 and 6.
Tabla 5. Conversión de Glicerol (%) y selectividad (%) de Ia reacción en presencia del sólido SbiViOn/AI2θ3.Table 5. Conversion of Glycerol (%) and selectivity (%) of the reaction in the presence of the solid SbiViO n / AI 2 θ3.
Tabla 6. Rendimientos (%) de Ia reacción en presencia del sólido Sb1V1OnZAI2O3.
Table 6. Yields (%) of the reaction in the presence of the solid Sb 1 V 1 O n ZAI 2 O 3 .
EJEMPLO 4 -Producción de Acrilonitrilo en fase líquida a partir de glicerol utilizando como catalizador SbIV1OnZAI2O3 bajo activación microondas y como agente oxidante peróxido de hidrógeno.EXAMPLE 4 - Production of liquid phase acrylonitrile from glycerol using as catalyst Sb I V 1 O n ZAI 2 O 3 under microwave activation and as hydrogen peroxide oxidizing agent.
El óxido con fórmula empírica SbIV1OnZAI2O3, se preparó siguiendo ambos procedimientos descritos en Ejemplo 1 , SbIV1OnZAI2O3 (1 ) y en Ejemplo 3, Sb1V1OnZAI2O3 (3).The oxide with empirical formula Sb I V 1 O n ZAI 2 O 3 , was prepared following both procedures described in Example 1, Sb I V 1 O n ZAI 2 O 3 (1) and in Example 3, Sb 1 V 1 O n ZAI 2 O 3 (3).
0.5 mmol de glicerol, 15 mmol de peróxido de hidrógeno y 57 mmol de amoníaco se introducen en un reactor de cuarzo de 5 mi de capacidad y tapón de rosca provisto de sistema de venteo para evitar sobrepresiones. Posteriormente 200 mg de catalizador con tamaños de partícula entre 0.250 y 0.125 mm se adicionan a Ia mezcla de reacción. El reactor con Ia mezcla de reacción, se cierra herméticamente y se introduce en un equipo microondas multimodo MicroSYNTH Labstation provisto de agitación magnética, controlador de temperatura por sonda de infrarrojos y software adaptado al equipo para monitorear las condiciones de reacción.0.5 mmol of glycerol, 15 mmol of hydrogen peroxide and 57 mmol of ammonia are introduced into a 5 ml capacity quartz reactor and screw cap provided with a vent system to avoid overpressures. Subsequently, 200 mg of catalyst with particle sizes between 0.250 and 0.125 mm are added to the reaction mixture. The reactor with the reaction mixture, closes tightly and is introduced into a MicroSYNTH Labstation multimode microwave equipment equipped with magnetic stirring, infrared probe temperature controller and software adapted to the equipment to monitor the reaction conditions.
La mezcla de reacción, en continua agitación, se activa bajo radiación microondas a 100 W de potencia durante 60 minutos, empleando una rampa de calentamiento de 10°CZmin hasta 1000C. Transcurrido el tiempo de reacción Ia muestra se deja enfriar a temperatura ambiente y con una jeringa de émbolo provista de filtro, se separan el catalizador sólido de los productos de reacción y reactivos no consumidos.The reaction mixture, in continuous stirring, is activated under microwave radiation at 100 W of power for 60 minutes, using a heating ramp of 10 ° CZmin to 100 0 C. After the reaction time has elapsed, the sample is allowed to cool to room temperature. and with a plunger syringe provided with a filter, the solid catalyst is separated from the reaction products and reagents not consumed.
Los productos de reacción se analizan en un cromatógrafo de gases equipado con FID (Detector Iónico de Llama).The reaction products are analyzed in a gas chromatograph equipped with FID (Ionic Flame Detector).
Las conversiones, selectividades y rendimientos se han calculado mediante las siguientes fórmulas:
Conversión de Glicerol (%) = (moles de glicerol consumido / moles de glicerol alimentado ) x 100Conversions, selectivities and returns have been calculated using the following formulas: Glycerol Conversion (%) = (moles of glycerol consumed / moles of glycerol fed) x 100
Selectividad a un compuesto (%) = (moles formados de compuesto*atomos de carbono en ese compuesto)/(moles de glicerol consumido*atomos de carbono en glicerol) x 100Selectivity to a compound (%) = (moles formed of compound * carbon atoms in that compound) / (moles of glycerol consumed * carbon atoms in glycerol) x 100
Rendimiento a un compuesto (%) = (selectividad a un compuesto * conversión de glicerol) / 100Yield to a compound (%) = (selectivity to a compound * glycerol conversion) / 100
Los resultados se muestran en las tabla 7 y 8.The results are shown in tables 7 and 8.
Tabla 5. Conversión de Glicerol (%) y selectividad (%) de Ia reacción en presencia del sólido SbIV1OnZAI2O3.Table 5. Conversion of Glycerol (%) and selectivity (%) of the reaction in the presence of the solid Sb I V 1 O n ZAI 2 O 3 .
(1 ) = procedimiento de preparación del sólido (Ejemplo 1 )(1) = solid preparation procedure (Example 1)
(3) = procedimiento de preparación del sólido (Ejemplo 3)(3) = solid preparation procedure (Example 3)
Tabla 6. Rendimientos (%) de Ia reacción en presencia del sólidoTable 6. Yields (%) of the reaction in the presence of the solid
SbiViOn/AI2O3.SbiViO n / AI 2 O 3 .
Claims
1. Procedimiento para Ia producción de nitrilos a partir de alcoholes caracterizado porque tiene lugar mediante Ia amonoxidación del alcohol en presencia de un oxidante, una fuente de átomos de nitrógeno y un catalizador.1. Procedure for the production of nitriles from alcohols characterized in that it takes place by means of ammonoxidation of alcohol in the presence of an oxidant, a source of nitrogen atoms and a catalyst.
2. Procedimiento de producción de nitrilos según reivindicación 1 caracterizado porque el alcohol es un poliol.2. Nitrile production process according to claim 1 characterized in that the alcohol is a polyol.
3. Procedimiento de producción de nitrilos según reivindicación 1 caracterizado porque el poliol es un es glicerol.3. Nitrile production process according to claim 1 characterized in that the polyol is a glycerol.
4. Procedimiento de producción de nitrilos según reivindicaciones 1 caracterizado porque el oxidante es oxígeno molecular.4. Nitrile production process according to claims 1 characterized in that the oxidant is molecular oxygen.
5. Procedimiento de producción de nitrilos según reivindicación 1 caracterizado porque el oxidante es un hidroperóxido.5. Nitrile production process according to claim 1 characterized in that the oxidant is a hydroperoxide.
6. Procedimiento de producción de nitrilos según reivindicación 5 caracterizado porque el hidroperóxido es peróxido de hidrógeno6. Nitrile production process according to claim 5 characterized in that the hydroperoxide is hydrogen peroxide
7. Procedimiento de producción de nitrilos según reivindicación 1 caracterizado porque Ia fuente de átomos de nitrógeno es amoniaco.7. Nitrile production process according to claim 1 characterized in that the source of nitrogen atoms is ammonia.
8. Procedimiento de producción de nitrilos según reivindicación 1 caracterizado porque el catalizador responde a Ia fórmula AaBbCcDdEeOx donde A es V y/o Nb; B es Sb, Mo y/o Nb, C es un elemento seleccionado del grupo Sn, Ti, Te, W , U; D es un elemento seleccionado del grupo Li, Mg, Na, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Ge, Nb, Mo, W, Cu, Tl, P, Zr, Re, Ag, Cd, Zn, Pb, D, Rb, Cs, Ti, Ta, Se, Bi, Ce, In, As, B, Al, Mn; E es un elemento seleccionado del grupo Pd, Au, Pt, Ru, Rh, Os, Ir; y donde a y d = 0-10, c, d y e, = 0-30, y x se determina por el estado de oxidación de los cationes presentes.8. Nitrile production process according to claim 1 characterized in that the catalyst responds to the formula AaBbCcDdEeOx where A is V and / or Nb; B is Sb, Mo and / or Nb, C is an element selected from the group Sn, Ti, Te, W, U; D is an element selected from the group Li, Mg, Na, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Ge, Nb, Mo, W, Cu, Tl, P, Zr, Re, Ag, Cd , Zn, Pb, D, Rb, Cs, Ti, Ta, Se, Bi, Ce, In, As, B, Al, Mn; E is a selected item from the group Pd, Au, Pt, Ru, Rh, Os, Ir; and where ayd = 0-10, c, dye, = 0-30, and x is determined by the oxidation state of the cations present.
9. Procedimiento de producción de nitrilos según reivindicación 8 caracterizado porque el catalizador no contiene los elementos D y E y, por tanto, responde a Ia formula AaBbCcOx donde A es V y/o Nb; B es Sb, Mo y/o Nb, C es un elemento seleccionado del grupo Sn, Ti, Te, W , U.9. Nitrile production process according to claim 8 characterized in that the catalyst does not contain elements D and E and, therefore, responds to the formula AaBbCcOx where A is V and / or Nb; B is Sb, Mo and / or Nb, C is an element selected from the group Sn, Ti, Te, W, U.
10. Procedimiento de producción de nitrilos según reivindicación 9 caracterizado porque el catalizador no contiene el elemento C y, por tanto, responde a Ia formula AaBbOx donde donde A es V y/o Nb y B es Sb, Mo y/o Nb.10. Nitrile production process according to claim 9 characterized in that the catalyst does not contain element C and, therefore, responds to the formula AaBbOx where A is V and / or Nb and B is Sb, Mo and / or Nb.
11. Procedimiento de producción de nitrilos según reivindicación 10 caracterizado porque el catalizador utilizado es VzSbyOx soportado en AI2O3, donde z = 0-10, y=10-0 y x se determina por el estado de oxidación de los cationes presentes.11. Nitrile production process according to claim 10 characterized in that the catalyst used is VzSbyOx supported on AI2O3, where z = 0-10, y = 10-0 and x is determined by the oxidation state of the cations present.
12. Procedimiento de producción de nitrilos según reivindicaciones 8-11 caracterizado porque el catalizador se encuentra soportado sobre óxidos metálicos, zeolitas, o material mesoporoso o carbonoso.12. Nitrile production process according to claims 8-11 characterized in that the catalyst is supported on metal oxides, zeolites, or mesoporous or carbonaceous material.
13. Procedimiento de producción de nitrilos según reivindicación 1 caracterizado porque se utiliza una temperatura entre 200 y 800 0C y, preferentemente, entre 350 y 550 0C.13. Nitrile production process according to claim 1 characterized in that a temperature between 200 and 800 0 C and, preferably, between 350 and 550 0 C is used.
14. Procedimiento de producción de nitrilos según reivindicación 1 caracterizado porque se utiliza una presión comprendida entre 0.1 y 5 bares. 14. Nitrile production method according to claim 1 characterized in that a pressure between 0.1 and 5 bar is used.
15. Procedimiento de producción de nitrilos según reivindicación 1 caracterizado porque se utiliza radiación microondas como método de activación químico, preferentemente en fase líquida.15. Nitrile production process according to claim 1 characterized in that microwave radiation is used as a chemical activation method, preferably in the liquid phase.
i 16. Procedimiento de producción de nitrilos según reivindicación 15 caracterizado porque se usa Ia potencia de Ia radiación de microondas necesaria para alcanzar una temperatura de reacción entre 20 y 300 0C, y preferiblemente, entre 80 y 120 0C. i 16. Process for producing nitriles according to claim 15 characterized in that the power of microwave radiation necessary Ia is used to reach a reaction temperature between 20 and 300 0 C, and preferably between 80 and 120 0 C.
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-
2007
- 2007-11-13 ES ES200702992A patent/ES2319949B1/en not_active Expired - Fee Related
-
2008
- 2008-11-13 WO PCT/ES2008/070206 patent/WO2009063120A1/en active Application Filing
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| US20040220434A1 (en) * | 2003-05-02 | 2004-11-04 | Brophy John H. | Process for converting a hydrocarbon to an oxygenate or a nitrile |
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| WO2008113927A1 (en) * | 2007-02-16 | 2008-09-25 | Arkema France | Method for the synthesis of acrylonitrile from glycerol |
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| US9415375B2 (en) * | 2010-04-09 | 2016-08-16 | Dow Global Technologies Llc | Catalyst compositions for producing mixed alcohols |
| WO2014170604A1 (en) * | 2013-04-17 | 2014-10-23 | Centre National De La Recherche Scientifique | Method for producing nitriles using a catalyst made from antimony and iron |
| FR3004713A1 (en) * | 2013-04-17 | 2014-10-24 | Centre Nat Rech Scient | PROCESS FOR THE PRODUCTION OF NITRILES USING A CATALYST BASED ON ANTIMONY AND IRON |
| CN105308019A (en) * | 2013-04-17 | 2016-02-03 | 科学研究国家中心 | Method for producing nitriles using a catalyst made from antimony and iron |
| US9676705B2 (en) | 2013-04-17 | 2017-06-13 | Ecole Centrale De Lille | Process for the production of nitriles using a catalyst based on antimony and iron |
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Also Published As
| Publication number | Publication date |
|---|---|
| ES2319949A1 (en) | 2009-05-14 |
| ES2319949B1 (en) | 2010-03-17 |
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