WO2004015030A1 - Method of oxidising mercaptans, thiophenic compounds and derivatives thereof in petrol, kerosene and diesel fractions - Google Patents
Method of oxidising mercaptans, thiophenic compounds and derivatives thereof in petrol, kerosene and diesel fractions Download PDFInfo
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- WO2004015030A1 WO2004015030A1 PCT/ES2003/000399 ES0300399W WO2004015030A1 WO 2004015030 A1 WO2004015030 A1 WO 2004015030A1 ES 0300399 W ES0300399 W ES 0300399W WO 2004015030 A1 WO2004015030 A1 WO 2004015030A1
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- 238000000034 method Methods 0.000 title claims abstract description 68
- 150000001875 compounds Chemical class 0.000 title claims abstract description 13
- 239000003350 kerosene Substances 0.000 title claims abstract description 13
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 239000007787 solid Substances 0.000 claims abstract description 26
- 239000007800 oxidant agent Substances 0.000 claims abstract description 25
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007791 liquid phase Substances 0.000 claims abstract description 8
- 150000002978 peroxides Chemical class 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002432 hydroperoxides Chemical class 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 36
- 150000003464 sulfur compounds Chemical class 0.000 claims description 33
- 230000003647 oxidation Effects 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical group CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 26
- 239000003502 gasoline Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 17
- 239000000446 fuel Substances 0.000 claims description 15
- 229910018540 Si C Inorganic materials 0.000 claims description 12
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 6
- 238000006884 silylation reaction Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 150000003577 thiophenes Chemical class 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000011949 solid catalyst Substances 0.000 claims description 3
- GQNOPVSQPBUJKQ-UHFFFAOYSA-N 1-hydroperoxyethylbenzene Chemical compound OOC(C)C1=CC=CC=C1 GQNOPVSQPBUJKQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 2
- 241001292274 Eumenes Species 0.000 claims 1
- 229910021485 fumed silica Inorganic materials 0.000 claims 1
- 229910052809 inorganic oxide Inorganic materials 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
- 239000010936 titanium Substances 0.000 description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 239000012071 phase Substances 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- -1 peroxyacetic acid Chemical class 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910003471 inorganic composite material Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 241000282376 Panthera tigris Species 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000002051 biphasic effect Effects 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 150000002019 disulfides Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000007319 Avena orientalis Nutrition 0.000 description 1
- 244000075850 Avena orientalis Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000010364 biochemical engineering Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- JKALIJGJDGORBL-UHFFFAOYSA-N ethane;hydrogen peroxide Chemical compound CC.OO JKALIJGJDGORBL-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000001706 oxygenating effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J21/18—Carbon
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/80—Catalysts, in general, characterised by their form or physical properties characterised by their amorphous structures
-
- 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
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- 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
- B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
-
- 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
- B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- B01J2235/05—Nuclear magnetic resonance [NMR]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Definitions
- the present invention relates to the technical field of heterogeneous catalysis, especially to the hydrocarbon refining sector and specifically to the refining of the gasoline, kerosene and diesel fractions.
- Sulfur compounds, disulfides, mercaptans, thiophene and their alkylated derivatives, as well as benzothiophene among others, are among the most common sulfur compounds present in gasoline cuts.
- the predominant sulfur compounds are benzothiophene, dibenzothiophene and their respective alkylated derivatives. All of them cause corrosion in refining equipment and combustion engines, and poisoning of catalysts used in refineries or catalytic converters of gaseous effluents. Further, These compounds are one of the major causes of pollution, because when they are subject to combustion they become sulfur oxides, which released into the atmosphere give rise to the formation of oxy acids that contribute to the phenomenon known as acid rain.
- Heteropolyacids of the peroxotungstophosphate type in biphasic systems are capable of oxidizing mercaptans, dibenzothiophenes and alkyl dibenzothiophenes although they are less effective with the thiogenic and benzothiophene compounds (FM Collins et al. J. Mol. Catal. A: Chem., 117, 397, 1997).
- the use of solid catalysts of the type T-silicalites in liquids containing sulfur compounds achieves low levels of conversion to the corresponding sulfones (T. Kabe JP 11140462 A2, 1999).
- the catalysts of the TS-1 and TS-2 type based on microporous titanosilicates with zeolitic structure (M. Taramasso et al. US-A-, 410, 501, 1983), allow selective oxidation of various sulfides with water oxygenated (RS Reddy et al. J. Chem. Soc, Chem. Commun., 84, 1992; V. Hulea et al. "J. Mol. Catal.
- the present invention relates to a procedure for the oxidation of sulfur compounds selected from mercaptans, thiophene compounds and derivatives thereof present in gasoline, kerosene and diesel fractions comprising subjecting said sulfur compounds to an oxidation reaction.
- an oxidizing agent selected from peroxides and organic hydroperoxides the process comprising the steps of preparing a single liquid phase, comprising said antioxidant agent and a fraction of fuel selected from gasoline, kerosene and diesel fractions, and contacting said liquid phase with a catalyst selected from solid amorphous X-ray and macroporous catalysts, which incorporate at least Si and Ti.
- amorphous solid refers to solids without an ordered or crystalline structure, so that, when subjected to short or long distance X-rays, they do not generate diffraction peaks.
- the invention is based on the surprising fact that catalysts based on amorphous materials of the inorganic silica type containing Ti, and preferably amorphous materials of the inorganic silica type containing Ti and carbon compounds, allow the oxidation of thiogenic compounds and their derivatives with excellent conversions by weight of catalyst, these catalysts being able to operate in a single phase system instead of the two phase system described in the patent application.
- FR-A-99 16559 (1999). The fact that they allow working in a single-phase system instead of the two-phase system and without using a co-solvent, such as acetonitrile, gives greater flexibility to the process of the present invention.
- a catalyst based on a "composite” type material formed of a carbon organic compound or compounds bonded to the amorphous inorganic component is more active than pure inorganic material.
- the resulting “composite” is an organic-inorganic hybrid material containing Ti that not only produces good results when working with H 2 0 2 and without any solvent, but also produces excellent levels of oxidation of sulfur compounds when working on a single phase and an organic hydroperoxide, such as tert-butyl hydroperoxide (TBHP), is used as the oxidizing agent.
- TBHP tert-butyl hydroperoxide
- organic-inorganic "composites” based on amorphous materials containing Si and Ti, and Si-C bonds, are also more active than the corresponding component inorganic both when working with H 2 0 2 as an oxidizing agent, and a cosolvent, such as acetonitrile.
- a cosolvent such as acetonitrile.
- the process of the present application is especially suitable for the oxidation of the sulfur compounds remaining in hydrotreated fractions of the gasoline, kerosene and diesel type, and with sulfur contents less than 300 ppm
- This invention claims an oxidation process of mercaptans, thiophene compounds and their derivatives contained in gasoline, kerosene or diesel fractions, or the corresponding hydrotreated fractions, which comprises carrying out an oxidation reaction of said sulfur compounds, in one phase or in two phases, using as catalysts: macroporous organic-inorganic hybrid amorphous solid materials characterized by containing Si, Ti, and, preferably at the same time Si bonded to carbon (Si-C bonds); and using organic peroxides as oxidizing agents, such as t-butyl hydroperoxide, or inorganic peroxides, such as H 2 0 2 , without these limiting examples.
- the materials of the present invention are amorphous to X-ray diffraction, and are macroporous, further facilitating the diffusion of larger molecules.
- said amorphous organic-inorganic hybrid solid materials comprising at least Si, Ti and silicon bonded to carbon are obtained by a process comprising silylation during synthesis, or by a method comprising silylation of the material inorganic in a post-synthesis stage.
- Said organic-inorganic "composites” comprising at least Si, Ti and silicon bonded to carbon may consist of amorphous inorganic siliceous solids chemically combined with Ti in proportions between 0.5 and 8% by weight of Ti in the form of oxide on the total catalyst, and that contain silicon bonded to carbon.
- Said material can be synthesized in the presence of compounds containing Si-C groups, or it is subjected to a post-synthesis silylation step creating Si-C bonds, and therefore an organic-inorganic "composite" material.
- the oxidizing agents may be organic peroxides such as, for example, t-butyl hydroperoxide, ethylbenzene hydroperoxide or ethane hydroperoxide, or inorganic peroxides, such as, for example, Hydrogen Peroxide (aqueous H 2 0 2 ), perborates, or the urea complex - Hydrogen peroxide (H 2 N-NH 2 - H 2 0 2 ), without these limiting examples.
- the catalyst works in a single-phase system, from the point of view of liquid components, and in any case without the need to use a solvent, such as acetonitrile, as described in the FR patent application -A-99 16559.
- the sulfur compounds present in gasoline, kerosene and diesel fractions are transformed into other oxidized products with different boiling point and different polarity, which they have a boiling point above the cut of the fractions in question and / or that can be more easily extracted by distillation or extraction following conventional techniques.
- high conversions and selectivities in the oxidation of said sulfur compounds are achieved.
- Our catalysts are also active and selective when you want to work in the presence of solvent.
- the oxidation of the sulfur compounds present in the liquid fuels is carried out by contacting a reactive mixture containing the fuel fraction and the organic or inorganic peroxide, in a single phase and, preferably , in the absence of solvent, with the solid amorphous silica catalyst with anchored Ti, or the silica-titanium co-gel, or preferably the organic-inorganic hybrid solid material containing Si-C species, or a mixture thereof at a temperature between 10 and 120 ° C during reaction times that can vary between 2 minutes and 24 hours depending on the catalyst and the reaction conditions employed.
- the weight ratio of the fuel fraction to catalyst is between 5 and 600, and preferably between 10 and 300, the weight ratio being between the fuel fraction and oxidizing agent between 300 and 10, and preferably between 200 and 20
- the incorporation of titanium in the amorphous siliceous materials can be carried out by direct synthesis of a silica and titanium cogel, or through the anchoring of titanium compounds on the surface of the materials, giving rise to isolated Ti species after a calcination process. .
- Solid amorphous catalysts can be based on amorphous silicas such as those marketed under the names CAB-O-SIL (a chain-shaped colloidal amorphous silica, marketed by Cabot Corporation, USA) and AEROSIL (a pyrogenic amorphous silica marketed by Degussa-Hüls AG, Frankfurt aM, Germany).
- CAB-O-SIL a chain-shaped colloidal amorphous silica, marketed by Cabot Corporation, USA
- AEROSIL a pyrogenic amorphous silica marketed by Degussa-Hüls AG, Frankfurt aM, Germany.
- suitable amorphous solid catalysts those formed by Thi-aerosil and Ti-aerosil containing Si-C groups, and silicon and titanium cogels and said cogels containing Si-C groups are described below. The latter are compared with cogels reported by other research groups (JL Fierro et al., Chem. Commun., 855, 2000; and A. Baiker et al., Catal. Lett., 75, 131, 2001).
- the sulfur compound oxidation catalyst may be an organic-inorganic composite consisting of amorphous inorganic siliceous solids, chemically combined with Ti in proportions between 0.2 and 8% by weight of Ti in oxide form on the total catalyst, and containing silicon bonded to carbon.
- Said amorphous inorganic siliceous solids comprise at least 80% silica, and are preferably pyrogenic silicas selected between cab-o-sil and Aerosil with specific surfaces between 40 and 450 rr ⁇ .g "1 and particle size between about 0.007 and 0.05 microns
- Other preferred amorphous inorganic siliceous solids are silicon and titanium cogels
- These catalysts are amorphous solids containing at least Si and Ti, and may also contain other elements selected from V, B,
- these catalysts may contain amounts between 0.01 and 4% in weight of promoters of the group of alkali metals, alkaline earth metals or mixtures thereof, in the form of oxides.
- a preferred method, for preparing Ti-Si0 2 catalysts suitable for the oxidation of sulfur compounds of the gasoline fraction is to treat an amorphous silica, for example of the aerosol type with a compound of Ti, oxides, oxyhydroxides, alkoxides, halides or any of its salts, and preferably tetraethoxide, tetrapropoxide or tetrabutoxide of Ti.
- Another preferred method for preparing amorphous catalysts of the type reinvindicated in the present patent involves the formation of a silicon and titanium cogel, by the interaction of a suitable source of titanium, for example Ti alkoxides and preferably Ti tetraethoxide, tetrapropoxide or tetrabutoxide ( IV), with the corresponding source of silicon, tetraethylorthosilicate, among others.
- a suitable source of titanium for example Ti alkoxides and preferably Ti tetraethoxide, tetrapropoxide or tetrabutoxide ( IV)
- tetraethylorthosilicate tetraethylorthosilicate
- the oxidation step can be carried out in a batch reactor, a continuous stirred tank reactor (CSTR), in a continuous fixed bed reactor, in a fluidized bed reactor, or a boiling bed reactor, using organic or inorganic peroxides as oxidizing agents, in a single organic phase and in the absence of solvent.
- CSTR continuous stirred tank reactor
- the weight ratio of the fuel fraction to catalyst is conveniently between 5 and 600, and preferably between 10 and 300, the weight ratio being between the fraction of fuel and oxidizing agent preferably between 300 and 10, and preferably between 200 and 20.
- the process temperature may be between 10 and 120 ° C, and preferably between 20 and 80 ° C; and the reaction time usually ranges from 2 minutes to 24 hours.
- the products of the oxidation reaction can be separated by distillation, extraction with suitable solvent, or by adsorption on an adsorption column that allows selectively adsorbing the more polar compounds (sulfoxides and sulfones) formed during the oxidation stage of the sulfur compounds; the unreacted remainder being able to be totally or partially recycled to the reactor.
- the process of the present invention can be carried out using the H 2 0 2 -Urea complex as oxidizing agent .
- the process of the present invention can also operate in the presence of a solvent, such as acetonitrile, especially suitable for catalytic oxidations with molecular sieves containing Ti in a previous publication (A. Corma et al., J. Catal., 161, 11, 1996), and H 2 0 2 in aqueous solution (preferably 35% by weight).
- a solvent such as acetonitrile
- FIGURES As an integral part of the present specification, a figure is attached showing the UV-Visible spectra of diffuse reflectance of several samples whose characteristics will be described in more detail in some examples. MODES OF CARRYING OUT THE INVENTION
- Example 1 Preparation of a material of the amorphous Si0 2 type containing Ti in its composition.
- a Titanium compound is anchored on the surface, according to the following procedure: 5 g of Si0 2 is dehydrated at 300 ° C and 10 "3 mm Hg for 2 hours, adding a solution containing 0.079 g of titanocene dichloride in 45 g of anhydrous chloroform. The resulting suspension is stirred at room temperature for 1 hour under Ar. To this suspension is added a solution containing 0.063 g of triethylamine in 10 g of chloroform. White gas evolution is observed and the color of the solution changes from red-orange to yellow-orange.
- the solid is recovered by filtration and the excess reagents are removed by thorough washing with dichloromethane and drying at 60 ° C for 12 hours.
- the Ti content of the amorphous material determined by chemical analysis is 2.23% by weight, expressed as Ti0 2 , showing its UV-Visible spectrum in Figure 1.
- the solid obtained has a specific surface area of 328 m 2 -g _1 .
- Example 2 Preparation of an amorphous organic-inorganic composite material.
- 2.0 g of the sample obtained in example 1 are dehydrated at 100 ° C and 10 ⁇ 3 Tor for 2 hours.
- the sample is cooled, and at room temperature a solution of 1.88g of hexamethyldisilazane (CH 3 ) 3 Si-NH-Si (CH 3 ) 3 ) in 30g of toluene is added.
- the resulting mixture is refluxed at 120 ° C for 90 minutes and washed with toluene.
- the final product is dried at 60 ° C.
- This solid has a specific surface area of 268 ir ⁇ -g "1 , in addition the spectrum of 29 Si-MAS-NMR has a resonance band at 14 ppm assigned to the presence of Si-C bonds.
- Example 3 Preparation of an amorphous material based on a tiger type Ti0 2 -Si0 2 -
- tetraethylorthosilicate TEOS
- HCl 0.1N aqueous solution of HCl
- 15 g of water at room temperature for one hour and 45 minutes with constant stirring.
- a solution of 1.02 g of Ti tetrabutoxide in 82.5 g of isopropanol is then added, and the mixture is allowed to stir under the same conditions for approximately 15 minutes.
- TPAOH tetrapropylammonium hydroxide
- the solid obtained is dried at 100 ° C in an oven, the Ti content of the amorphous material determined by chemical analysis is 2.32% by weight, expressed as Ti0 2 , showing its UV-Visible spectrum in Figure 1. Subsequently calcined in an air atmosphere at 500 ° C for 5 hours. The solid obtained has a specific surface area of 686 rr ⁇ -g "1 .
- Example 4 Preparation of an amorphous organic-inorganic composite material.
- This solid has a specific surface area of 505 rr ⁇ -g -1 , in addition the spectrum of 29 Si-MAS-NMR has a resonance band at 14 ppm assigned to the presence of Si-C bonds.
- Example 5 Preparation of an amorphous material based on a tiger type Ti0 2 -Si0 2 , according to the methodology used by JL Fierro et al. (Cheai. Co- ⁇ nnu-n., 855, 2000).
- tetraethylorthosilicate TEOS
- HCl 0.1N aqueous solution of HCl
- the solid obtained is washed first with ethanol and then with hexane, dried at 100 ° C in an oven, the Ti content of the amorphous material determined by chemical analysis is 2.16% by weight, expressed as Ti0 2 , showing its spectrum of UV-Visible in Figure 1. Subsequently it is calcined in an air atmosphere at 500 ° C for 3 hours.
- the solid obtained has a specific surface area of 854 m 2 -g -1 .
- Example 6 Preparation of an amorphous organic-inorganic composite material.
- This solid has a specific surface area of 509 ⁇ ⁇ -g "1 , in addition the spectrum of 29 Si-MAS-NMR has a resonance band at 14 ppm assigned to the presence of Si-C bonds.
- Example 7 In this example, the activity for the selective oxidation of sulfur compounds present in synthetic gasoline with 35% H 2 0 2 by weight as an oxidizing agent and in the absence of solvent is compared, using catalysts based on amorphous silica materials containing Ti according to Examples 1, 3 and 5, and according to Examples 2, 4 and 6.
- Example 8 In this example, the activity for the selective oxidation of sulfur compounds present in synthetic Gasoline with TBHP as an oxidizing agent and in a single liquid phase, in the absence of solvent, is compared using catalysts based on amorphous silica materials containing Ti according to Examples 1, 3 and 5, and according to Examples 2, 4 and 6.
- Example 9 In this example, the catalytic activity for the selective oxidation of sulfur compounds present in Simulated Diesel is compared to catalysts based on amorphous siliceous materials containing Ti according to Examples 1, 3 and 5, and according to Examples 2, 4 and 6, using H 2 0 2 at 35% by weight as oxidizing agent and in the absence of solvent.
- Example 1 50 mg of one of the amorphous materials described (examples 1 and 2) are introduced into a glass reactor at 80 ° C containing 120 mg of hydrogen peroxide (H 2 0 2 , Sol. 35% by weight) and 15000 mg of Simulated Diesel.
- the reaction mixture is stirred and sample is taken at 7 hours of reaction.
- the samples are analyzed by GC with a special S detector, the initial and final compositions being in the content of non-oxidized sulfur compounds for the reaction mixtures and the conversions obtained for each of the catalysts tested the following:
- Example 10 In this example, the catalytic activity for the selective oxidation of sulfur compounds present in Simulated Diesel is compared to catalysts based on amorphous siliceous materials containing Ti according to Examples 1, 3 and 5, and according to Examples 2, 4 and 6, using TBHP as an oxidizing agent and in the absence of solvent.
- Example 11 In this example, the catalytic activity for the selective oxidation of sulfur compounds present in Diesel (Low S Diesel) of the catalysts based on amorphous siliceous materials containing Ti according to Examples 1, 3 and 5, and according to Examples 2, is compared. 4 and 6, using H 2 0 2 at 35% by weight as oxidizing agent and in the absence of solvent. 30 mg of one of the amorphous materials described
- Example 12 In this example, the catalytic activity for the selective oxidation of sulfur compounds present in Diesel (Low S Diesel) of the catalysts based on amorphous siliceous materials containing Ti according to Examples 1, 3 and 5, and according to Examples 2, is compared. 4 and 6, using TBHP as an oxidizing agent and in the absence of solvent. 30 mg of one of the amorphous materials described (examples 1 to 6) are introduced into a 80 ° C glass reactor containing 80 mg of t-butyl hydroperoxide (TBHP, Sol. 80% by weight) and 9000 mg of a diesel fraction. The reaction mixture is stirred and sample is taken at 7 hours of reaction. The samples are analyzed by GC with a special S detector, the initial and final compositions being in the content of non-oxidized sulfur compounds for the reaction mixtures and the conversions obtained for each of the catalysts tested the following:
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Abstract
The invention relates to a method of oxidising mercaptans, thiophenic compounds and the derivatives thereof present in petrol, kerosene and diesel fractions. The inventive method is characterised in that it consists in oxidising sulphur compounds using organic or inorganic peroxides in a single liquid phase which comprises one of said fractions and an oxidising agent selected from peroxides and hydroperoxides and which is brought into contact with a catalyst based on solids which are amorphous to X-rays and which contain at least Si and Ti and, preferably, silicon bound to carbon.
Description
PROCESO PARA LA OXIDACIÓN DE MERCAPTANOS, COMPUESTOS TIOFÉNICOS Y SUS DERIVADOS, EN LAS FRACCIONES GASOLINA, PROCESS FOR OXIDATION OF MERCAPTANS, THIOPHENIC COMPOUNDS AND THEIR DERIVATIVES, IN GASOLINE FRACTIONS,
QUEROSENO Y DIESEL CAMPO TÉCNICO DE LA INVENCIÓN La presente invención se refiere al campo técnico de la catálisis heterogénea, especialmente al sector del refino de hidrocarburos y específicamente al refino de las fracciones gasolina, queroseno y diesel.KEROSENE AND DIESEL TECHNICAL FIELD OF THE INVENTION The present invention relates to the technical field of heterogeneous catalysis, especially to the hydrocarbon refining sector and specifically to the refining of the gasoline, kerosene and diesel fractions.
ESTADO DE LA TÉCNICA ANTERIOR A LA INVENCIÓN Hasta hace poco tiempo, los procesos de hidrodesulfurización (HDS) han dominado ampliamente la desulfurización de combustibles líquidos. Sin embargo, su costo, prohibitivo para la mayoría de las pequeñas y medianas refinerías, y la necesidad de. mayores disminuciones en los niveles de Azufre en la composición de las fracciones gasolina y diesel, se han conjuntado para motivar el desarrollo de tecnologías alternativas, que por sí solas o en combinación con las ya existentes produzcan una fuerte disminución del contenido de S hasta un rango de 10-100 ppm.STATE OF THE PRIOR ART OF THE INVENTION Until recently, hydrodesulfurization (HDS) processes have largely dominated the desulfurization of liquid fuels. However, its cost, prohibitive for most small and medium refineries, and the need for. major decreases in sulfur levels in the composition of the gasoline and diesel fractions, have been combined to motivate the development of alternative technologies, which alone or in combination with existing ones produce a sharp decrease in the content of S to a range from 10-100 ppm.
Entre los compuestos de azufre más comunes presentes en cortes de gasolina se pueden citar sulfuros, disulfuros, mercaptanos, tiofeno y sus derivados alquilados, además de benzotiofeno entre otros. En el caso de las fracciones del destilado de petróleo generalmente utilizadas como alimentación diesel, cuya temperatura inicial de destilación es superior a 160 °C normalmente, los compuestos de azufre predominantes son benzotiofeno, dibenzotiofeno y sus respectivos derivados alquilados. Todos ellos son causantes de corrosión en los equipos de refino y en los motores de combustión, y de envenenamiento de catalizadores utilizados en refinerías o en convertidores catalíticos de efluentes gaseosos. Además,
estos compuestos son una de las mayores causas de polución, debido a que sometidos a combustión se convierten en óxidos de azufre, los cuales liberados en la atmósfera dan lugar a la formación de oxi-ácidos que contribuyen al fenómeno conocido como lluvia acida.Sulfur compounds, disulfides, mercaptans, thiophene and their alkylated derivatives, as well as benzothiophene among others, are among the most common sulfur compounds present in gasoline cuts. In the case of the petroleum distillate fractions generally used as diesel feed, whose initial distillation temperature is normally higher than 160 ° C, the predominant sulfur compounds are benzothiophene, dibenzothiophene and their respective alkylated derivatives. All of them cause corrosion in refining equipment and combustion engines, and poisoning of catalysts used in refineries or catalytic converters of gaseous effluents. Further, These compounds are one of the major causes of pollution, because when they are subject to combustion they become sulfur oxides, which released into the atmosphere give rise to the formation of oxy acids that contribute to the phenomenon known as acid rain.
Se han explorado diversos procesos alternativos o complementarios para desulfurización de gasolina y diesel, como adsorción directa (Nagi et al . Patente estadounidense US-A-4,830, 733 , 1983), bio-procesado (M. J. Grossman et al. US Pat . 5,910,440 , 1999; A. P. Borole et al. ACS Div. Pet . Chem . Preprints, 45, 2000) y oxidación selectiva (S. E. Bonde et al. ACS Div. Pet . Chem. Preprints, 44 [2] , 199, 1998; E. D. Guth et al. US Pat . 3,919,405 , 1975; J. F. Ford et al: US Pat . 3,341,448 , 1967); además de la aplicación de tecnologías alternativas a procesos ya conocidos, como es el caso del nuevo proceso OATS (proceso de alquilación de BP, Hydrocarbon Processing, Feb. 2001) .Various alternative or complementary processes for desulfurization of gasoline and diesel have been explored, such as direct adsorption (Nagi et al. US Pat. No. 4,830, 733, 1983), bioprocessing (MJ Grossman et al. US Pat. 5,910,440, 1999; AP Borole et al. ACS Div. Pet. Chem. Preprints, 45, 2000) and selective oxidation (SE Bonde et al. ACS Div. Pet. Chem. Preprints, 44 [2], 199, 1998; ED Guth et al. US Pat. 3,919,405, 1975; JF Ford et al: US Pat. 3,341,448, 1967); In addition to the application of alternative technologies to known processes, such as the new OATS process (BP alkylation process, Hydrocarbon Processing, Feb. 2001).
En el caso de los procesos de desulfurización oxidativa (ODS) , se busca un sistema económico que sea suficientemente selectivo para oxidar los compuestos con Azufre, incrementando así su polaridad y peso molecular para facilitar su posterior separación por extracción o destilación. Hasta el momento no ha sido desarrollado ningún proceso comercial de desulfurización oxidativa debido fundamentalmente a la combinación de requerimientos regulatorios y económicos a escala industrial, si bien existe una gran variedad de ellos en desarrollo (S. E.In the case of oxidative desulfurization (ODS) processes, an economic system that is sufficiently selective to oxidize the compounds with Sulfur is sought, thus increasing its polarity and molecular weight to facilitate its subsequent separation by extraction or distillation. So far, no commercial oxidative desulfurization process has been developed due mainly to the combination of regulatory and economic requirements on an industrial scale, although there is a great variety of them under development (S. E.
Bonde et al. ACS Div. Pet . Chem . Preprints, 45, 375, 2000).Bonde et al. ACS Div. Pet. Chem Preprints, 45, 375, 2000).
Se ha reportado la utilización de peroxiácidos orgánicos, como el ácido peroxiacético, para la eliminación de sulfuros, disulfuros y mercaptanos presentes en combustibles líquidos consiguiendo disminuciones del 95% en el contenido de azufre de algunas gasolinas trabajando a
temperaturas entre 2 y 100 °C (S. E. Bonde et al. ACS Div. Pet . Chem . Preprints, 44 [2] , 199, 1998). Los heteropoliácidos del tipo peroxotungstofosfatos en sistemas bifásicos, con H202 como oxidante y agentes de transferencia de fase, son capaces de oxidar mercaptanos, dibenzotiofenos y alquil-dibenzotiofenos aunque son menos efectivos con los compuestos tiofénicos y benzotiofénicos (F. M. Collins et al. J. Mol . Catal . A : Chem . , 117, 397, 1997) . La utilización de catalizadores sólidos del tipo Ti- silicalitas en líquidos que contienen compuestos de azufre consigue bajos niveles de conversión a las correspondientes sulfonas (T. Kabe JP 11140462 A2 , 1999) . Si bien los catalizadores del tipo TS-1 y TS-2, basados en titanosilicatos microporosos con estructura zeolítica (M. Taramasso et al. Patente US-A- , 410, 501 , 1983), permiten la oxidación selectiva de distintos sulfuros con agua oxigenada (R. S. Reddy et al. J. Chem . Soc , Chem . Commun . , 84, 1992; V. Hulea et al. «J. Mol . Catal . A : Chem. , 111 , 325, 1996) , su pequeña apertura de poro imposibilita su uso en procesos en los que están involucradas moléculas más grandes como es el caso de los benzotiofenos, dibenzotiofenos, y sus respectivos homólogos alquil, di- alquil y tri-alquil sustituidos, principales componentes de la fracción diesel, y cuya oxidación es la más problemática .The use of organic peroxyacids, such as peroxyacetic acid, has been reported for the elimination of sulfides, disulfides and mercaptans present in liquid fuels, achieving 95% decreases in the sulfur content of some gasoline working temperatures between 2 and 100 ° C (SE Bonde et al. ACS Div. Pet. Chem. Preprints, 44 [2], 199, 1998). Heteropolyacids of the peroxotungstophosphate type in biphasic systems, with H 2 0 2 as oxidant and phase transfer agents, are capable of oxidizing mercaptans, dibenzothiophenes and alkyl dibenzothiophenes although they are less effective with the thiogenic and benzothiophene compounds (FM Collins et al. J. Mol. Catal. A: Chem., 117, 397, 1997). The use of solid catalysts of the type T-silicalites in liquids containing sulfur compounds achieves low levels of conversion to the corresponding sulfones (T. Kabe JP 11140462 A2, 1999). Although the catalysts of the TS-1 and TS-2 type, based on microporous titanosilicates with zeolitic structure (M. Taramasso et al. US-A-, 410, 501, 1983), allow selective oxidation of various sulfides with water oxygenated (RS Reddy et al. J. Chem. Soc, Chem. Commun., 84, 1992; V. Hulea et al. "J. Mol. Catal. A: Chem., 111, 325, 1996), its small opening of pore makes it impossible to use it in processes in which larger molecules are involved, such as benzothiophenes, dibenzothiophenes, and their respective substituted alkyl, di-alkyl and tri-alkyl homologs, main components of the diesel fraction, and whose oxidation It is the most problematic.
Recientemente, se ha llevado a cabo la oxidación de compuestos de azufre presentes en queroseno en un sistema bifásico, que comprende una fase hidrocarbonada y una fase acuosa, en presencia de un agente oxidante soluble en la fase acuosa (H202 acuoso) , añadiendo acetonitrilo como codisolvente y utilizando la zeolita Ti-Beta y el tamiz molecular mesoporoso Ti-HMS como catalizadores (A. Rabión
et al., Solicitud de patente FR-A-99 16559, 1999; V. Hulea et al., J. Catal . , 198, 179, 2001). La presencia de un medio bifásico obliga a introducir un proceso subsecuente de separación de las fases, así como a la recuperación del disolvente que se encuentra en una fase junto al H20 y a la mayor parte de los productos de oxidación de los compuestos de Azufre. En la solicitud de patente FR-A-99 16559, se indica específicamente que los catalizadores utilizados en el proceso, y más específicamente la zeolita Ti-Beta, debe contener el componente activo del catalizador (Ti) solamente en posiciones de red. Esto estaría de acuerdo con trabajos previos en los que este material se ha utilizado para reacciones de epoxidación de olefinas, y en los que se insiste en que el Ti activo se encuentra localizado en la red, siendo el Ti extrarred o Ti en posiciones no reticulares perjudicial para este proceso (J. C. van der Wall et al., J. Mol . Catal . A : Chem. , 124, 137, 1997).Recently, the oxidation of sulfur compounds present in kerosene has been carried out in a two-phase system, comprising a hydrocarbon phase and an aqueous phase, in the presence of a soluble oxidizing agent in the aqueous phase (aqueous H 2 0 2 ), adding acetonitrile as co-solvent and using the Ti-Beta zeolite and the Ti-HMS mesoporous molecular sieve as catalysts (A. Rabión et al., Patent Application FR-A-99 16559, 1999; V. Hulea et al., J. Catal. , 198, 179, 2001). The presence of a biphasic medium forces to introduce a subsequent phase separation process, as well as the recovery of the solvent that is in a phase next to H 2 0 and most of the oxidation products of the sulfur compounds . In patent application FR-A-99 16559, it is specifically indicated that the catalysts used in the process, and more specifically the zeolite Ti-Beta, must contain the active component of the catalyst (Ti) only in network positions. This would be in accordance with previous work in which this material has been used for epoxidation reactions of olefins, and in which it is insisted that the active Ti is located in the network, being the Ti extrarred or Ti in non-reticular positions Harmful to this process (JC van der Wall et al., J. Mol. Catal. A: Chem., 124, 137, 1997).
DESCRIPCIÓN DE LA INVENCIÓN La presente invención se refiere a un Procedimiento para la oxidación de compuestos de azufre seleccionados entre mercaptanos, compuestos tiofénicos y derivados de los mismos presentes en fracciones gasolina, queroseno y diesel que comprende someter dichos compuestos de azufre a una reacción de oxidación usando un agente oxidante seleccionado entre peróxidos y hidroperóxidos orgánicos, comprendiendo el procedimiento las etapas de preparar una fase líquida única, que comprende dicho agente antioxidante y una fracción de combustible seleccionada entre fracciones gasolina, queroseno y diesel, y contactar dicha fase líquida con un catalizador seleccionado entre catalizadores sólidos amorfos a los rayos X y macroporosos, que incorporan al menos Si y Ti .
El término "sólido amorfo" empleado aquí, se refiere a sólidos sin estructura ordenada o cristalina, de manera que, cuando se someten a rayos X a corta o larga distancia, no generan picos de difracción. La invención se basa en el hecho sorprendente que catalizadores basados en materiales amorfos del tipo sílice inorgánica conteniendo Ti, y preferentemente materiales amorfos del tipo sílice inorgánica conteniendo Ti y compuestos carbonados, permiten la oxidación de compuestos tiofénicos y sus derivados con excelentes conversiones por peso de catalizador, siendo estos catalizadores capaces de funcionar en un sistema monofásico en lugar del sistema bifásico descrito en la solicitud de patente . FR-A-99 16559 (1999) . El hecho de que permitan trabajar en un sistema monofásico en lugar del bifásico y sin necesidad de utilizar un codisolvente, como por ejemplo acetonitrilo, confiere una mayor flexibilidad Al procedimiento de la presente invención.DESCRIPTION OF THE INVENTION The present invention relates to a procedure for the oxidation of sulfur compounds selected from mercaptans, thiophene compounds and derivatives thereof present in gasoline, kerosene and diesel fractions comprising subjecting said sulfur compounds to an oxidation reaction. using an oxidizing agent selected from peroxides and organic hydroperoxides, the process comprising the steps of preparing a single liquid phase, comprising said antioxidant agent and a fraction of fuel selected from gasoline, kerosene and diesel fractions, and contacting said liquid phase with a catalyst selected from solid amorphous X-ray and macroporous catalysts, which incorporate at least Si and Ti. The term "amorphous solid" used herein refers to solids without an ordered or crystalline structure, so that, when subjected to short or long distance X-rays, they do not generate diffraction peaks. The invention is based on the surprising fact that catalysts based on amorphous materials of the inorganic silica type containing Ti, and preferably amorphous materials of the inorganic silica type containing Ti and carbon compounds, allow the oxidation of thiogenic compounds and their derivatives with excellent conversions by weight of catalyst, these catalysts being able to operate in a single phase system instead of the two phase system described in the patent application. FR-A-99 16559 (1999). The fact that they allow working in a single-phase system instead of the two-phase system and without using a co-solvent, such as acetonitrile, gives greater flexibility to the process of the present invention.
De acuerdo con la invención, también se ha observado que un catalizador basado en un material tipo "composite" formado por un compuesto o compuestos orgánicos carbonados unidos al componente inorgánico amorfo es más activo que el material inorgánico puro. El "composite" resultante es un material híbrido orgánico-inorgánico conteniendo Ti que no solamente produce buenos resultados cuando se trabaja con H202 y sin disolvente alguno, sino que además produce excelentes niveles de oxidación de los compuestos de azufre cuando se trabaja en una sola fase y se utiliza un hidroperóxido orgánico, como por ejemplo hidroperóxido de tert-butilo (TBHP) , como agente oxidante. De manera análoga, "composites" orgánico-inorgánicos basados en materiales amorfos conteniendo Si y Ti, y enlaces Si-C, son también más activos que el correspondiente componente
inorgánico tanto cuando se trabaja con H202 como agente oxidante, y un codisolvente, como por ejemplo acetonitrilo. La utilización de hidroperóxidos orgánicos como agentes oxidantes con los catalizadores de acuerdo con la presente invención permite llevar a cabo un proceso de oxidación selectiva de compuestos de azufre en combustibles líquidos en el que, además de eliminar etapas posteriores de separación de fases, se produce como subproducto derivado de la utilización del TBHP como agente oxigenante tert- butanol, compuesto que eleva el octanaje de gasolinas. El procedimiento de la presente solicitud, aún cuando también es aplicable para desulfurar fracciones del crudo no refinadas, es especialmente adecuado para la oxidación de los compuestos de Azufre remanentes en fracciones hidrotratadas del tipo gasolina, queroseno y diesel, y con contenidos de Azufre menores de 300 ppm.In accordance with the invention, it has also been found that a catalyst based on a "composite" type material formed of a carbon organic compound or compounds bonded to the amorphous inorganic component is more active than pure inorganic material. The resulting "composite" is an organic-inorganic hybrid material containing Ti that not only produces good results when working with H 2 0 2 and without any solvent, but also produces excellent levels of oxidation of sulfur compounds when working on a single phase and an organic hydroperoxide, such as tert-butyl hydroperoxide (TBHP), is used as the oxidizing agent. Similarly, organic-inorganic "composites" based on amorphous materials containing Si and Ti, and Si-C bonds, are also more active than the corresponding component inorganic both when working with H 2 0 2 as an oxidizing agent, and a cosolvent, such as acetonitrile. The use of organic hydroperoxides as oxidizing agents with the catalysts according to the present invention allows to carry out a process of selective oxidation of sulfur compounds in liquid fuels in which, in addition to eliminating subsequent stages of phase separation, it occurs as by-product derived from the use of TBHP as an oxygenating agent tert-butanol, a compound that increases the octane rating of gasoline. The process of the present application, even though it is also applicable to desulfurize unrefined crude oil fractions, is especially suitable for the oxidation of the sulfur compounds remaining in hydrotreated fractions of the gasoline, kerosene and diesel type, and with sulfur contents less than 300 ppm
En esta invención se reivindica un procedimiento de oxidación de mercaptanos, compuestos tiofénicos y sus derivados contenidos en fracciones gasolina, queroseno o diesel, o las correspondientes fracciones hidrotratadas, que comprende realizar una reacción de oxidación de dichos compuestos de azufre, en una fase o en dos fases, utilizando como catalizadores: materiales sólidos amorfos híbridos orgánico-inorgánicos macroporosos caracterizados por contener Si, Ti, y, preferentemente al mismo tiempo Si unido a carbono (enlaces Si-C) ; y usando como agentes oxidantes peróxidos orgánicos, como por ejemplo hidroperóxido de t-butilo, o peróxidos inorgánicos, como H202, sin ser estos ejemplos limitantes. Los materiales de la presente invención, contrariamente a los materiales mesoporosos puramente inorgánicos descritos en la solicitud de patente francesa FR-9916559, son amorfos a la difracción de Rayos X, y son macroporosos, facilitando todavía más la
difusión de moléculas de mayor tamaño.This invention claims an oxidation process of mercaptans, thiophene compounds and their derivatives contained in gasoline, kerosene or diesel fractions, or the corresponding hydrotreated fractions, which comprises carrying out an oxidation reaction of said sulfur compounds, in one phase or in two phases, using as catalysts: macroporous organic-inorganic hybrid amorphous solid materials characterized by containing Si, Ti, and, preferably at the same time Si bonded to carbon (Si-C bonds); and using organic peroxides as oxidizing agents, such as t-butyl hydroperoxide, or inorganic peroxides, such as H 2 0 2 , without these limiting examples. The materials of the present invention, contrary to the purely inorganic mesoporous materials described in French patent application FR-9916559, are amorphous to X-ray diffraction, and are macroporous, further facilitating the diffusion of larger molecules.
Según el procedimiento de la presente invención dichos materiales sólidos híbridos orgánico-inorgánico amorfos que comprenden al menos Si, Ti y silicio unido a carbono se obtienen mediante un procedimiento que comprende sililación durante la síntesis, o bien mediante un procedimiento que comprende la sililación del material inorgánico en una etapa postsíntesis .According to the process of the present invention said amorphous organic-inorganic hybrid solid materials comprising at least Si, Ti and silicon bonded to carbon are obtained by a process comprising silylation during synthesis, or by a method comprising silylation of the material inorganic in a post-synthesis stage.
Dichos "composites" orgánico-inorgánicos que comprenden al menos Si, Ti y silicio unido a carbono pueden consistir en sólidos silíceos inorgánicos amorfos químicamente combinados con Ti en proporciones entre 0.5 y 8% en peso de Ti en forma de óxido sobre el catalizador total, y que contienen silicio unido a carbono. Dicho material puede ser sintetizado en presencia de compuestos que contienen grupos Si-C, o bien se somete a una etapa de sililación postsíntesis creándose enlaces Si-C, y por consiguiente un material "composite" orgánico-inorgánico.Said organic-inorganic "composites" comprising at least Si, Ti and silicon bonded to carbon may consist of amorphous inorganic siliceous solids chemically combined with Ti in proportions between 0.5 and 8% by weight of Ti in the form of oxide on the total catalyst, and that contain silicon bonded to carbon. Said material can be synthesized in the presence of compounds containing Si-C groups, or it is subjected to a post-synthesis silylation step creating Si-C bonds, and therefore an organic-inorganic "composite" material.
Los agentes oxidantes pueden ser peróxidos orgánicos como por ejemplo hidroperóxido de t-butilo, hidroperóxido de etil-benceno o hidroperóxido de eumeno, o peróxidos inorgánicos, como por ejemplo peróxido de Hidrógeno (H202 acuoso) , perboratos, o el complejo urea - peróxido de Hidrógeno (H2N-NH2 - H202) , sin ser estos ejemplos limitantes. En nuestro proceso, el catalizador funciona en un sistema monofásico, desde el punto de vista de los componentes líquidos, y en cualquier caso sin la necesidad de utilizar un disolvente, como por ejemplo acetonitrilo, tal y como se describe en la solicitud de patente FR-A-99 16559 . Mediante esta oxidación selectiva, los compuestos de azufre presentes en fracciones de gasolina, queroseno y diesel se transforman en otros productos oxidados con diferente punto de ebullición y diferente polaridad, que
tienen un punto de ebullición por encima del corte de las fracciones en cuestión y/o que pueden ser más fácilmente extraídos por destilación o extracción siguiendo técnicas convencionales . Mediante el procedimiento de la presente invención se consiguen altas conversiones y selectividades en la oxidación de dichos compuestos de azufre. Nuestros catalizadores son también activos y selectivos cuando se desee trabajar en presencia de disolvente.The oxidizing agents may be organic peroxides such as, for example, t-butyl hydroperoxide, ethylbenzene hydroperoxide or ethane hydroperoxide, or inorganic peroxides, such as, for example, Hydrogen Peroxide (aqueous H 2 0 2 ), perborates, or the urea complex - Hydrogen peroxide (H 2 N-NH 2 - H 2 0 2 ), without these limiting examples. In our process, the catalyst works in a single-phase system, from the point of view of liquid components, and in any case without the need to use a solvent, such as acetonitrile, as described in the FR patent application -A-99 16559. Through this selective oxidation, the sulfur compounds present in gasoline, kerosene and diesel fractions are transformed into other oxidized products with different boiling point and different polarity, which they have a boiling point above the cut of the fractions in question and / or that can be more easily extracted by distillation or extraction following conventional techniques. Through the process of the present invention, high conversions and selectivities in the oxidation of said sulfur compounds are achieved. Our catalysts are also active and selective when you want to work in the presence of solvent.
En el procedimiento de la presente invención, la oxidación de los compuestos de azufre presentes en los combustibles líquidos se lleva a cabo poniendo en contacto una mezcla reactiva que contiene la fracción de combustible y el peróxido orgánico o inorgánico, en una sola fase y, preferentemente, en ausencia de disolvente, con el catalizador sólido de sílice amorfa con Ti anclado, o el co-gel de sílice y titanio, o preferentemente el material sólido híbrido orgánico-inorgánico conteniendo especies Si- C, o una mezcla de ellos a una temperatura comprendida entre 10 y 120 °C durante tiempos de reacción que pueden variar entre 2 minutos y 24 horas dependiendo del catalizador y de las condiciones de reacción empleadas. La relación en peso de la fracción de combustible a catalizador está comprendida entre 5 y 600, y preferentemente entre 10 y 300, estando la relación en peso entre la fracción de combustible y agente oxidante comprendida entre 300 y 10, y preferentemente entre 200 y 20. La incorporación de titanio en los materiales silíceos amorfos puede realizarse mediante síntesis directa de un cogel de sílice y titanio, o a través del anclaje de compuestos de titanio sobre la superficie de los materiales, dando lugar a especies de Ti aisladas tras un proceso de calcinación.In the process of the present invention, the oxidation of the sulfur compounds present in the liquid fuels is carried out by contacting a reactive mixture containing the fuel fraction and the organic or inorganic peroxide, in a single phase and, preferably , in the absence of solvent, with the solid amorphous silica catalyst with anchored Ti, or the silica-titanium co-gel, or preferably the organic-inorganic hybrid solid material containing Si-C species, or a mixture thereof at a temperature between 10 and 120 ° C during reaction times that can vary between 2 minutes and 24 hours depending on the catalyst and the reaction conditions employed. The weight ratio of the fuel fraction to catalyst is between 5 and 600, and preferably between 10 and 300, the weight ratio being between the fuel fraction and oxidizing agent between 300 and 10, and preferably between 200 and 20 The incorporation of titanium in the amorphous siliceous materials can be carried out by direct synthesis of a silica and titanium cogel, or through the anchoring of titanium compounds on the surface of the materials, giving rise to isolated Ti species after a calcination process. .
Los catalizadores sólidos amorfos pueden basarse en
sílices amorfas tales como las comercializadas con los nombres CAB-O-SIL (un sílice amorfa coloidal aglomerada en forma de cadena, comercializada por Cabot Corporation, EE.UU.) y AEROSIL (una sílice amorfa pirogénica comercializada por Degussa-Hüls AG, Frankfurt a.M., Alemania) .Solid amorphous catalysts can be based on amorphous silicas such as those marketed under the names CAB-O-SIL (a chain-shaped colloidal amorphous silica, marketed by Cabot Corporation, USA) and AEROSIL (a pyrogenic amorphous silica marketed by Degussa-Hüls AG, Frankfurt aM, Germany).
Como ejemplos de catalizadores sólidos amorfos idóneos, se describen a continuación los formados por Ti- aerosil y Ti-aerosil conteniendo grupos Si-C, y cógeles de silicio y titanio y dichos cógeles conteniendo grupos Si-C. Estos últimos se comparan con cógeles reportados por otros grupos de investigación (J. L. Fierro y col., Chem . Commun . , 855, 2000; y A. Baiker y col., Catal . Lett . , 75, 131, 2001) . En una realización particular del procedimiento de la presente invención el catalizador de oxidación de compuestos de azufre puede ser un "composite" orgánico- inorgánico que consiste en sólidos silíceos inorgánicos amorfos, químicamente combinados con Ti en proporciones entre 0.2 y 8% en peso de Ti en forma de óxido sobre el catalizador total, y que contienen silicio unido a carbono. Dichos sólidos silíceos inorgánicos amorfos comprenden al menos 80% de sílice, y son de manera preferida sílices pirogénicas seleccionadas entre cab-o-sil y Aerosil con superficies específicas entre 40 y 450 rr^.g"1 y tamaño de partícula entre aproximadamente 0.007 y 0.05 micrones . Otros sólidos silíceos inorgánicos amorfos preferidos son cógeles de silicio y titanio. Estos catalizadores son sólidos amorfos que contienen al menos Si y Ti, pudiendo contener también otros elementos seleccionados entre V, B,As examples of suitable amorphous solid catalysts, those formed by Thi-aerosil and Ti-aerosil containing Si-C groups, and silicon and titanium cogels and said cogels containing Si-C groups are described below. The latter are compared with cogels reported by other research groups (JL Fierro et al., Chem. Commun., 855, 2000; and A. Baiker et al., Catal. Lett., 75, 131, 2001). In a particular embodiment of the process of the present invention the sulfur compound oxidation catalyst may be an organic-inorganic composite consisting of amorphous inorganic siliceous solids, chemically combined with Ti in proportions between 0.2 and 8% by weight of Ti in oxide form on the total catalyst, and containing silicon bonded to carbon. Said amorphous inorganic siliceous solids comprise at least 80% silica, and are preferably pyrogenic silicas selected between cab-o-sil and Aerosil with specific surfaces between 40 and 450 rr ^ .g "1 and particle size between about 0.007 and 0.05 microns Other preferred amorphous inorganic siliceous solids are silicon and titanium cogels These catalysts are amorphous solids containing at least Si and Ti, and may also contain other elements selected from V, B,
Zr, Mo y mezclas de ellos en un porcentaje en peso total y en forma de óxidos inferior al 8%. Además estos catalizadores pueden contener cantidades entre 0.01 y 4% en
peso de promotores del grupo de los metales alcalinos, alcalinotérreos o mezclas de ellos, en forma de óxidos.Zr, Mo and mixtures thereof in a percentage by total weight and in the form of oxides less than 8%. In addition, these catalysts may contain amounts between 0.01 and 4% in weight of promoters of the group of alkali metals, alkaline earth metals or mixtures thereof, in the form of oxides.
Estos catalizadores se someten, en una etapa durante la síntesis, o bien en una etapa postsíntesis, a un proceso de sililación dando lugar a la formación de especies que contienen enlaces Si-C, conformando el "composite" orgánico-inorgánico que se usa en el procedimiento de oxidación de compuestos de azufre de la presente invención. Un procedimiento preferido, para preparar catalizadores de Ti-Si02 aptos para la oxidación de compuestos de azufre de la fracción gasolina, consiste en tratar una sílice amorfa, por ejemplo del tipo aerosil con un compuesto de Ti, óxidos, oxihidróxidos, alcóxidos, haluros o cualquiera de sus sales, y preferentemente tetraetóxido, tetrapropóxido o tetrabutóxido de Ti.These catalysts are subjected, in a stage during synthesis, or in a post-synthesis stage, to a silylation process resulting in the formation of species containing Si-C bonds, forming the organic-inorganic "composite" used in the sulfur compound oxidation process of the present invention. A preferred method, for preparing Ti-Si0 2 catalysts suitable for the oxidation of sulfur compounds of the gasoline fraction, is to treat an amorphous silica, for example of the aerosol type with a compound of Ti, oxides, oxyhydroxides, alkoxides, halides or any of its salts, and preferably tetraethoxide, tetrapropoxide or tetrabutoxide of Ti.
Otro procedimiento preferido para preparar catalizadores amorfos del tipo reinvindicado en la presente patente conlleva la formación de un cogel de silicio y titanio, mediante la interacción de una fuente adecuada de titanio, por ejemplo alcóxidos de Ti y preferentemente tetraetóxido, tetrapropóxido o tetrabutóxido de Ti (IV), con la correspondiente fuente de silicio, tetraetilortosilicato, entre otras. Durante la preparación de estos cógeles o en una etapa post-síntesis pueden someterse a un proceso de sililación dando lugar a la formación de enlaces silicio-carbono. También se pueden preparar cógeles de silicio y titanio, por ejemplo, siguiendo los procedimientos descritos en J. L. Fierro y col., Chem . Commun . , 855, 2000, y por A. Baiker y col., Catal . Lett . , 75_, 131, 2001. En esta memoria hemos incluido ejemplos de la preparación de éstos últimos catalizadores (J. L. Fierro y col., Chem . Commun . , 855, 2000) para poder efectuar una comparación con nuestros materiales amorfos
conteniendo titanio, y especialmente con nuestros materiales amorfos conteniendo silicio, titanio y compuestos carbonados .Another preferred method for preparing amorphous catalysts of the type reinvindicated in the present patent involves the formation of a silicon and titanium cogel, by the interaction of a suitable source of titanium, for example Ti alkoxides and preferably Ti tetraethoxide, tetrapropoxide or tetrabutoxide ( IV), with the corresponding source of silicon, tetraethylorthosilicate, among others. During the preparation of these cogels or in a post-synthesis stage they can undergo a silylation process resulting in the formation of silicon-carbon bonds. Silicon and titanium cogels can also be prepared, for example, by following the procedures described in JL Fierro et al., Chem. Commun. , 855, 2000, and by A. Baiker et al., Catal. Lett. , 75_, 131, 2001. In this report we have included examples of the preparation of the latter catalysts (JL Fierro et al., Chem. Commun., 855, 2000) in order to make a comparison with our amorphous materials containing titanium, and especially with our amorphous materials containing silicon, titanium and carbon compounds.
En el proceso para la oxidación de mercaptanos, compuestos tiofénicos y sus derivados de las fracciones gasolina, queroseno y diesel de la presente invención la etapa de oxidación se puede llevar a cabo en un reactor discontinuo, un reactor continuo de tanque agitado (CSTR) , en un reactor continuo de lecho fijo, en un reactor de lecho fluidizado, o un reactor de lecho ebullente, utilizando peróxidos orgánicos o inorgánicos como agentes oxidantes, en una única fase orgánica y en ausencia de disolvente. En el caso de un reactor discontinuo la relación en peso de la fracción de combustible a catalizador está convenientemente comprendida entre 5 y 600, y preferentemente entre 10 y 300, estando la relación en peso entre la fracción de combustible y agente oxidante preferentemente comprendida entre 300 y 10, y preferentemente entre 200 y 20. La temperatura del proceso puede estar comprendida entre 10 y 120°C, y preferentemente entre 20 y 80°C; y el tiempo de reacción oscila habitualmente entre 2 minutos y 24 horas.In the process for the oxidation of mercaptans, thiophene compounds and their derivatives of the gasoline, kerosene and diesel fractions of the present invention the oxidation step can be carried out in a batch reactor, a continuous stirred tank reactor (CSTR), in a continuous fixed bed reactor, in a fluidized bed reactor, or a boiling bed reactor, using organic or inorganic peroxides as oxidizing agents, in a single organic phase and in the absence of solvent. In the case of a discontinuous reactor, the weight ratio of the fuel fraction to catalyst is conveniently between 5 and 600, and preferably between 10 and 300, the weight ratio being between the fraction of fuel and oxidizing agent preferably between 300 and 10, and preferably between 200 and 20. The process temperature may be between 10 and 120 ° C, and preferably between 20 and 80 ° C; and the reaction time usually ranges from 2 minutes to 24 hours.
Los productos de la reacción de oxidación pueden separarse por destilación, extracción con disolvente adecuado, o por adsorción en una columna de adsorción que permite adsorber selectivamente los compuestos más polares (sulfóxidos y sulfonas) formados durante la etapa de oxidación de los compuestos de azufre; pudiendo el resto no reaccionado ser reciclado total o parcialmente al reactor. También con los mismos sistemas descritos más arriba y trabajando en una única fase líquida y en ausencia de disolvente el procedimiento de la presente invención se puede llevar a cabo utilizando el complejo H202-Urea como
agente oxidante .The products of the oxidation reaction can be separated by distillation, extraction with suitable solvent, or by adsorption on an adsorption column that allows selectively adsorbing the more polar compounds (sulfoxides and sulfones) formed during the oxidation stage of the sulfur compounds; the unreacted remainder being able to be totally or partially recycled to the reactor. Also with the same systems described above and working in a single liquid phase and in the absence of solvent the process of the present invention can be carried out using the H 2 0 2 -Urea complex as oxidizing agent .
Finalmente, el procedimiento de la presente invención puede también operar en presencia de un disolvente, como por ejemplo acetonitrilo, especialmente adecuada para las oxidaciones catalíticas con tamices moleculares conteniendo Ti en una publicación previa (A. Corma et al., J. Catal . , 161, 11, 1996) , y H202 en disolución acuosa (preferentemente al 35% en peso) .Finally, the process of the present invention can also operate in the presence of a solvent, such as acetonitrile, especially suitable for catalytic oxidations with molecular sieves containing Ti in a previous publication (A. Corma et al., J. Catal., 161, 11, 1996), and H 2 0 2 in aqueous solution (preferably 35% by weight).
BREVE DESCRIPCIÓN DE LAS FIGURAS Como parte integrante de la presente memoria descriptiva, se adjunta una figura que muestra los espectros UV-Visble de reflectancia difusa de varias muestras cuyas características se describirán con más detalle en unos ejemplos. MODOS DE REALIZAR LA INVENCIÓNBRIEF DESCRIPTION OF THE FIGURES As an integral part of the present specification, a figure is attached showing the UV-Visible spectra of diffuse reflectance of several samples whose characteristics will be described in more detail in some examples. MODES OF CARRYING OUT THE INVENTION
Los siguientes ejemplos ilustran la preparación de materiales empleables de acuerdo con la presente invención y la aplicación de los mismos a la reacción de oxidación selectiva de mercaptanos, compuestos tiofénicos y sus derivados contenidos en fracciones de gasolina gasolina y/o diesel simulados, y un corte de diesel de bajo contenido en S (Low S Diesel - LSD) , cuyas composiciones son las siguientes :
The following examples illustrate the preparation of employable materials according to the present invention and the application thereof to the reaction of selective oxidation of mercaptans, thiophene compounds and their derivatives contained in simulated gasoline and / or diesel gasoline fractions, and a cut of diesel of low content in S (Low S Diesel - LSD), whose compositions are the following:
Gasolina sintética >>>>>> ComposiciónSynthetic gasoline >>>>>> Composition
S en Mezcla (ppm) = 240S in Mix (ppm) = 240
Diesel simulado >>>>>> ComposiciónSimulated Diesel >>>>>> Composition
S en Mezcla (ppm) = 240
Corte de Diesel (Lo S Diesel) - Bajo en S >>>>>>S in Mix (ppm) = 240 Diesel Cut (Lo S Diesel) - Low in S >>>>>>
ComposiciónComposition
S en Mezcla (ppm) 240S in Mix (ppm) 240
EJEMPLOSEXAMPLES
Ejemplo 1: Preparación de un material del tipo Si02 amorfa conteniendo Ti en su composición.Example 1: Preparation of a material of the amorphous Si0 2 type containing Ti in its composition.
A una sílice amorfa (Aerosil) de superficie específica de aproximadamente 400 m^g"1 (60-200 mesh) se le ancla un compuesto de Titanio sobre la superficie, según el siguiente procedimiento: 5 g de Si02 se deshidratan a 300 °C y 10"3 mm de Hg durante 2 horas, adicionándose una disolución que contiene 0.079 g de dicloruro de titanoceno en 45 g de cloroformo anhidro. La suspensión resultante se agita a temperatura ambiente durante 1 hora bajo atmósfera de Ar. A esta suspensión se le adiciona una disolución que contiene 0.063 g de trietilamina en 10 g de cloroformo. Se observa desprendimiento de gases blancos y el color de la disolución cambia de rojo-anaranjado a amarillo-anaranjado.To a specific surface amorphous silica (Aerosil) of approximately 400 m ^ g "1 (60-200 mesh) a Titanium compound is anchored on the surface, according to the following procedure: 5 g of Si0 2 is dehydrated at 300 ° C and 10 "3 mm Hg for 2 hours, adding a solution containing 0.079 g of titanocene dichloride in 45 g of anhydrous chloroform. The resulting suspension is stirred at room temperature for 1 hour under Ar. To this suspension is added a solution containing 0.063 g of triethylamine in 10 g of chloroform. White gas evolution is observed and the color of the solution changes from red-orange to yellow-orange.
Se prolonga la agitación durante 1 hora. El sólido se recupera por filtración y el exceso de reactivos se elimina
por lavado exhaustivo con diclorometano y secado a 60 °C durante 12 horas . El contenido en Ti del material amorfo determinado por análisis químico es del 2.23 % en peso, expresado como Ti02, mostrándose su espectro de UV-Visible en la Figura 1. El sólido obtenido presenta una superficie específica de 328 m2-g_1.Stirring is prolonged for 1 hour. The solid is recovered by filtration and the excess reagents are removed by thorough washing with dichloromethane and drying at 60 ° C for 12 hours. The Ti content of the amorphous material determined by chemical analysis is 2.23% by weight, expressed as Ti0 2 , showing its UV-Visible spectrum in Figure 1. The solid obtained has a specific surface area of 328 m 2 -g _1 .
Ejemplo 2: Preparación de un material composite orgánico- inorgánico amorfo . 2.0 g de la muestra obtenida en el ejemplo 1 se deshidratan a 100 °C y 10~3 Tor durante 2 horas. La muestra se enfría, y a temperatura ambiente se adiciona una disolución de 1.88g de hexametildisilazano (CH3)3Si-NH- Si(CH3)3) en 30g de tolueno. La mezcla resultante se refluye a 120°C durante 90 minutos y se lava con tolueno. El producto final se seca a 60 °C.Example 2: Preparation of an amorphous organic-inorganic composite material. 2.0 g of the sample obtained in example 1 are dehydrated at 100 ° C and 10 ~ 3 Tor for 2 hours. The sample is cooled, and at room temperature a solution of 1.88g of hexamethyldisilazane (CH 3 ) 3 Si-NH-Si (CH 3 ) 3 ) in 30g of toluene is added. The resulting mixture is refluxed at 120 ° C for 90 minutes and washed with toluene. The final product is dried at 60 ° C.
Este sólido presenta una superficie específica de 268 ir^-g"1, además el espectro de 29Si-MAS-RMN presenta una banda de resonancia a 14 ppm asignada a la presencia de enlaces Si-C.This solid has a specific surface area of 268 ir ^ -g "1 , in addition the spectrum of 29 Si-MAS-NMR has a resonance band at 14 ppm assigned to the presence of Si-C bonds.
Ejemplo 3: Preparación de un material amorfo basado en un cogel del tipo Ti02-Si02-Example 3: Preparation of an amorphous material based on a tiger type Ti0 2 -Si0 2 -
37.4 g de tetraetilortosilicato (TEOS) se hidrolizan en 15 g de una solución acuosa 0.1N de HCl y 15 g de agua, a temperatura ambiente durante una hora y 45 minutos con agitación constante. A continuación se adiciona una solución de 1.02 g de tetrabutóxido de Ti en 82.5 g de iso- propanol, y se deja la mezcla agitando en las mismas condiciones por aproximadamente 15 minutos. A la mezcla resultante (pH = 2.3-2.5) se añaden a continuación 2.82 g de hidróxido de tetrapropilamonio (TPAOH) y la mezcla que comienza a gelificar (pH = 7.5-8) se continúa agitando por
2 horas. El sólido obtenido se seca a 100 °C en estufa, siendo el contenido en Ti del material amorfo determinado por análisis químico es del 2.32% en peso, expresado como Ti02, mostrándose su espectro de UV-Visible en la Figura 1. Posteriormente se calcina en atmósfera de aire a 500 °C durante 5 horas. El sólido obtenido presenta una superficie específica de 686 rr^-g"1.37.4 g of tetraethylorthosilicate (TEOS) are hydrolyzed in 15 g of a 0.1N aqueous solution of HCl and 15 g of water, at room temperature for one hour and 45 minutes with constant stirring. A solution of 1.02 g of Ti tetrabutoxide in 82.5 g of isopropanol is then added, and the mixture is allowed to stir under the same conditions for approximately 15 minutes. To the resulting mixture (pH = 2.3-2.5), 2.82 g of tetrapropylammonium hydroxide (TPAOH) are then added and the mixture that begins to gel (pH = 7.5-8) is further stirred by 2 hours. The solid obtained is dried at 100 ° C in an oven, the Ti content of the amorphous material determined by chemical analysis is 2.32% by weight, expressed as Ti0 2 , showing its UV-Visible spectrum in Figure 1. Subsequently calcined in an air atmosphere at 500 ° C for 5 hours. The solid obtained has a specific surface area of 686 rr ^ -g "1 .
Ejemplo 4: Preparación de un material composite orgánico- inorgánico amorfo.Example 4: Preparation of an amorphous organic-inorganic composite material.
2.0 g de la muestra obtenida en el ejemplo 3 se deshidratan a 100 °C y 10~3 Tor durante 2 horas. La muestra se enfría, y a temperatura ambiente se adiciona una disolución de 1.88g de hexametildisilazano (CH3)3Si-NH- Si(CH3)3) en 30g de tolueno. La mezcla resultante se refluye a 120 °C durante 90 minutos y se lava con tolueno. El producto final se seca a 60 °C.2.0 g of the sample obtained in example 3 are dehydrated at 100 ° C and 10 ~ 3 Tor for 2 hours. The sample is cooled, and at room temperature a solution of 1.88g of hexamethyldisilazane (CH 3 ) 3 Si-NH-Si (CH 3 ) 3 ) in 30g of toluene is added. The resulting mixture is refluxed at 120 ° C for 90 minutes and washed with toluene. The final product is dried at 60 ° C.
Este sólido presenta una superficie específica de 505 rr^-g-1, además el espectro de 29Si-MAS-RMN presenta una banda de resonancia a 14 ppm asignada a la presencia de enlaces Si-C.This solid has a specific surface area of 505 rr ^ -g -1 , in addition the spectrum of 29 Si-MAS-NMR has a resonance band at 14 ppm assigned to the presence of Si-C bonds.
Ejemplo 5: Preparación de un material amorfo basado en un cogel del tipo Ti02-Si02, según la metodología empleada por J. L. Fierro y col. (Cheai. Co-πnnu-n., 855, 2000).Example 5: Preparation of an amorphous material based on a tiger type Ti0 2 -Si0 2 , according to the methodology used by JL Fierro et al. (Cheai. Co-πnnu-n., 855, 2000).
37.4 g de tetraetilortosilicato (TEOS) se hidrolizan en 4.04 g de agua y 3.22 g de una solución acuosa 0.1N de HCl, a temperatura ambiente durante 90 minutos con agitación constante. A continuación se adicionan 1.02 g de tetrabutóxido de Ti, y se sigue agitando la mezcla en las mismas condiciones por 45 minutos. A la mezcla resultante se le añaden 8.5 g de una solución 1M de hidróxido de amonio (NH4OH) y la mezcla que gelifica instantáneamente se
continúa agitando por aproximadamente 15 minutos hasta homogeinización. El gel así obtenido se deja envejecer por 48 horas con recipiente cerrado. El sólido obtenido se lava primero con etanol y luego con hexano, se seca a 100 °C en estufa, siendo el contenido en Ti del material amorfo determinado por análisis químico es del 2.16% en peso, expresado como Ti02, mostrándose su espectro de UV-Visible en la Figura 1. Posteriormente se calcina en atmósfera de aire a 500 °C durante 3 horas. El sólido obtenido presenta una superficie específica de 854 m2-g-1.37.4 g of tetraethylorthosilicate (TEOS) are hydrolyzed in 4.04 g of water and 3.22 g of a 0.1N aqueous solution of HCl, at room temperature for 90 minutes with constant stirring. Then 1.02 g of Ti tetrabutoxide are added, and the mixture is stirred under the same conditions for 45 minutes. To the resulting mixture is added 8.5 g of a 1M solution of ammonium hydroxide (NH 4 OH) and the mixture that instantly gels Continue stirring for approximately 15 minutes until homogenization. The gel thus obtained is allowed to age for 48 hours with a closed container. The solid obtained is washed first with ethanol and then with hexane, dried at 100 ° C in an oven, the Ti content of the amorphous material determined by chemical analysis is 2.16% by weight, expressed as Ti0 2 , showing its spectrum of UV-Visible in Figure 1. Subsequently it is calcined in an air atmosphere at 500 ° C for 3 hours. The solid obtained has a specific surface area of 854 m 2 -g -1 .
Ejemplo 6: Preparación de un material composite orgánico- inorgánico amorfo.Example 6: Preparation of an amorphous organic-inorganic composite material.
2.0 g de la muestra obtenida en el ejemplo 5 se deshidratan a 100 °C y 10~3 Tor durante 2 horas. La muestra se enfría, y a temperatura ambiente se adiciona una disolución de 1.88g de hexametildisilazano (CH3)3Si-NH- Si(CH3)3) en 30g de tolueno. La mezcla resultante se refluye a 120CC durante 90 minutos y se lava con tolueno. El producto final se seca a 60 °C.2.0 g of the sample obtained in example 5 are dehydrated at 100 ° C and 10 ~ 3 Tor for 2 hours. The sample is cooled, and at room temperature a solution of 1.88g of hexamethyldisilazane (CH 3 ) 3 Si-NH-Si (CH 3 ) 3 ) in 30g of toluene is added. The resulting mixture was refluxed at 120 C C for 90 minutes and washed with toluene. The final product is dried at 60 ° C.
Este sólido presenta una superficie específica de 509 π^-g"1, además el espectro de 29Si-MAS-RMN presenta una banda de resonancia a 14 ppm asignada a la presencia de enlaces Si-C.This solid has a specific surface area of 509 π ^ -g "1 , in addition the spectrum of 29 Si-MAS-NMR has a resonance band at 14 ppm assigned to the presence of Si-C bonds.
Ejemplo 7: En este ejemplo se compara la actividad para la oxidación selectiva de compuestos de Azufre presentes en Gasolina sintética con H202 al 35% en peso como agente oxidante y en ausencia de disolvente, utilizando catalizadores basados en materiales silíceos amorfos conteniendo Ti según Ejemplos 1, 3 y 5, y según Ejemplos 2, 4 y 6.Example 7: In this example, the activity for the selective oxidation of sulfur compounds present in synthetic gasoline with 35% H 2 0 2 by weight as an oxidizing agent and in the absence of solvent is compared, using catalysts based on amorphous silica materials containing Ti according to Examples 1, 3 and 5, and according to Examples 2, 4 and 6.
100 mg de uno de los materiales descritos en los
ejemplos 1 a 6 se introducen en un reactor de vidrio a 80 °C que contiene 15000 mg de Gasolina sintética y 120 mg de peróxido de hidrógeno (Sol. al 35% en peso) . La mezcla de reacción se agita y se toma muestra a las 7 horas de reacción. Las muestras son analizadas mediante GC con detector especial de S, siendo las composiciones iniciales y finales en contenido de compuestos de azufre no oxidados para las mezclas de reacción y las conversiones obtenidas las siguientes :100 mg of one of the materials described in the Examples 1 to 6 are introduced into a 80 ° C glass reactor containing 15,000 mg of synthetic Gasoline and 120 mg of hydrogen peroxide (35% sol. by weight). The reaction mixture is stirred and sample is taken at 7 hours of reaction. The samples are analyzed by GC with special S detector, the initial and final compositions being in the content of non-oxidized sulfur compounds for the reaction mixtures and the conversions obtained the following:
Ejemplo 8: En este ejemplo se compara la actividad para la oxidación selectiva de compuestos de Azufre presentes en Gasolina sintética con TBHP como agente oxidante y en una sola fase líquida, en ausencia de disolvente, utilizando catalizadores basados en materiales silíceos amorfos conteniendo Ti según Ejemplos 1, 3 y 5, y según Ejemplos 2, 4 y 6.Example 8: In this example, the activity for the selective oxidation of sulfur compounds present in synthetic Gasoline with TBHP as an oxidizing agent and in a single liquid phase, in the absence of solvent, is compared using catalysts based on amorphous silica materials containing Ti according to Examples 1, 3 and 5, and according to Examples 2, 4 and 6.
100 mg de uno de los materiales descritos en los ejemplos 1 a 6 se introducen en un reactor de vidrio a 80 °C que contiene 15000 mg de Gasolina sintética y 80 mg de hidroperóxido de tert-butilo (TBHP, Sol. 80% en peso). La mezcla de reacción se agita y se toma muestra a las 7 horas de reacción. Las muestras son analizadas mediante GC con detector especial de S, siendo las composiciones iniciales y finales en contenido de compuestos de azufre no oxidados
para las mezclas de reacción y las conversiones obtenidas las siguientes:100 mg of one of the materials described in Examples 1 to 6 are placed in a 80 ° C glass reactor containing 15,000 mg of synthetic Gasoline and 80 mg of tert-butyl hydroperoxide (TBHP, Sol. 80% by weight ). The reaction mixture is stirred and sample is taken at 7 hours of reaction. The samples are analyzed by GC with a special S detector, the initial and final compositions being contained in non-oxidized sulfur compounds for the reaction mixtures and the conversions obtained the following:
Ejemplo 9: En este ejemplo se compara la actividad catalítica para la oxidación selectiva de compuestos de Azufre presentes en Diesel Simulado de los catalizadores basados en materiales silíceos amorfos conteniendo Ti según Ejemplos 1, 3 y 5, y según Ejemplos 2, 4 y 6, utilizando H202 al 35% en peso como agente oxidante y en ausencia de disolvente.Example 9: In this example, the catalytic activity for the selective oxidation of sulfur compounds present in Simulated Diesel is compared to catalysts based on amorphous siliceous materials containing Ti according to Examples 1, 3 and 5, and according to Examples 2, 4 and 6, using H 2 0 2 at 35% by weight as oxidizing agent and in the absence of solvent.
50 mg de uno de los materiales amorfos descritos (ejemplos 1 y 2) se introducen en un reactor de vidrio a 80 °C que contiene 120 mg de peróxido de hidrógeno (H202, Sol. al 35% en peso) y 15000 mg de Diesel Simulado. La mezcla de reacción se agita y se toma muestra a las 7 horas de reacción. Las muestras son analizadas mediante GC con detector especial de S, siendo las composiciones iniciales y finales en contenido de compuestos de azufre no oxidados para las mezclas de reacción y las conversiones obtenidas para cada uno de los catalizadores ensayados las siguientes :
50 mg of one of the amorphous materials described (examples 1 and 2) are introduced into a glass reactor at 80 ° C containing 120 mg of hydrogen peroxide (H 2 0 2 , Sol. 35% by weight) and 15000 mg of Simulated Diesel. The reaction mixture is stirred and sample is taken at 7 hours of reaction. The samples are analyzed by GC with a special S detector, the initial and final compositions being in the content of non-oxidized sulfur compounds for the reaction mixtures and the conversions obtained for each of the catalysts tested the following:
Ejemplo 10: En este ejemplo se compara la actividad catalítica para la oxidación selectiva de compuestos de Azufre presentes en Diesel Simulado de los catalizadores basados en materiales silíceos amorfos conteniendo Ti según Ejemplos 1, 3 y 5, y según Ejemplos 2, 4 y 6, utilizando TBHP como agente oxidante y en ausencia de disolvente.Example 10: In this example, the catalytic activity for the selective oxidation of sulfur compounds present in Simulated Diesel is compared to catalysts based on amorphous siliceous materials containing Ti according to Examples 1, 3 and 5, and according to Examples 2, 4 and 6, using TBHP as an oxidizing agent and in the absence of solvent.
30 mg de uno de los materiales amorfos descritos (ejemplos 1 a 6) se introducen en un reactor de vidrio a 80 °C que contiene 80 mg de hidroperóxido de t-butilo (TBHP, Sol. al 80% en peso) y 15000 mg de Diesel Simulado. La mezcla de reacción se agita y se toma muestra a las 7 horas de reacción. Las muestras son analizadas mediante GC con detector especial de S, siendo las composiciones iniciales y finales en contenido de compuestos de azufre no oxidados para las mezclas de reacción y las conversiones obtenidas para cada uno de los catalizadores ensayados las siguientes :
30 mg of one of the amorphous materials described (examples 1 to 6) are introduced into a 80 ° C glass reactor containing 80 mg of t-butyl hydroperoxide (TBHP, Sol. 80% by weight) and 15000 mg of Simulated Diesel. The reaction mixture is stirred and sample is taken at 7 hours of reaction. The samples are analyzed by GC with a special S detector, the initial and final compositions being in the content of non-oxidized sulfur compounds for the reaction mixtures and the conversions obtained for each of the catalysts tested the following:
Ejemplo 11: En este ejemplo se compara la actividad catalítica para la oxidación selectiva de compuestos de Azufre presentes en Diesel (Low S Diesel) de los catalizadores basados en materiales silíceos amorfos conteniendo Ti según Ejemplos 1, 3 y 5, y según Ejemplos 2, 4 y 6, utilizando H202 al 35% en peso como agente oxidante y en ausencia de disolvente. 30 mg de uno de los materiales amorfos descritosExample 11: In this example, the catalytic activity for the selective oxidation of sulfur compounds present in Diesel (Low S Diesel) of the catalysts based on amorphous siliceous materials containing Ti according to Examples 1, 3 and 5, and according to Examples 2, is compared. 4 and 6, using H 2 0 2 at 35% by weight as oxidizing agent and in the absence of solvent. 30 mg of one of the amorphous materials described
(ejemplos 1 a 6) se introducen en un reactor de vidrio a(Examples 1 to 6) are introduced into a glass reactor at
80 °C que contiene 120 mg de peróxido de hidrógeno (H202,80 ° C containing 120 mg of hydrogen peroxide (H 2 0 2 ,
Sol. al 35% en peso) y 9000 mg de una fracción Diesel. La mezcla de reacción se agita y se toma muestra a las 7 horas de reacción. Las muestras son analizadas mediante GC con detector especial de S, siendo las composiciones iniciales y finales en contenido de compuestos de azufre no oxidados para las mezclas de reacción y las conversiones obtenidas para cada uno de los catalizadores ensayados las siguientes:
Sol. 35% by weight) and 9000 mg of a Diesel fraction. The reaction mixture is stirred and sample is taken at 7 hours of reaction. The samples are analyzed by GC with a special S detector, the initial and final compositions being in the content of non-oxidized sulfur compounds for the reaction mixtures and the conversions obtained for each of the catalysts tested the following:
Ejemplo 12: En este ejemplo se compara la actividad catalítica para la oxidación selectiva de compuestos de Azufre presentes en Diesel (Low S Diesel) de los catalizadores basados en materiales silíceos amorfos conteniendo Ti según Ejemplos 1, 3 y 5, y según Ejemplos 2, 4 y 6, utilizando TBHP como agente oxidante y en ausencia de disolvente. 30 mg de uno de los materiales amorfos descritos (ejemplos 1 a 6) se introducen en un reactor de vidrio a 80 °C que contiene 80 mg de hidroperóxido de t-butilo (TBHP, Sol. al 80% en peso) y 9000 mg de una fracción Diesel. La mezcla de reacción se agita y se toma muestra a las 7 horas de reacción. Las muestras son analizadas mediante GC con detector especial de S, siendo las composiciones iniciales y finales en contenido de compuestos de azufre no oxidados para las mezclas de reacción y las conversiones obtenidas para cada uno de los catalizadores ensayados las siguientes:
Example 12: In this example, the catalytic activity for the selective oxidation of sulfur compounds present in Diesel (Low S Diesel) of the catalysts based on amorphous siliceous materials containing Ti according to Examples 1, 3 and 5, and according to Examples 2, is compared. 4 and 6, using TBHP as an oxidizing agent and in the absence of solvent. 30 mg of one of the amorphous materials described (examples 1 to 6) are introduced into a 80 ° C glass reactor containing 80 mg of t-butyl hydroperoxide (TBHP, Sol. 80% by weight) and 9000 mg of a diesel fraction. The reaction mixture is stirred and sample is taken at 7 hours of reaction. The samples are analyzed by GC with a special S detector, the initial and final compositions being in the content of non-oxidized sulfur compounds for the reaction mixtures and the conversions obtained for each of the catalysts tested the following:
Claims
1. Procedimiento para la oxidación de compuestos de azufre seleccionados entre mercaptanos, compuestos tiofénicos y derivados de los mismos presentes en fracciones gasolina, queroseno y diesel que comprende someter dichos compuestos de azufre a una reacción de oxidación usando un agente oxidante seleccionado entre peróxidos y hidroperóxidos orgánicos, caracterizado porque el procedimiento comprende las etapas de preparar una fase líquida única, que comprende dicho agente antioxidante y una fracción de combustible seleccionada entre fracciones gasolina, queroseno y diesel, y contactar dicha fase líquida con un catalizador seleccionado entre catalizadores sólidos amorfos a los rayos X y macroporosos, que incorporan al menos Si y Ti .1. Process for the oxidation of sulfur compounds selected from mercaptans, thiophene compounds and derivatives thereof present in gasoline, kerosene and diesel fractions comprising subjecting said sulfur compounds to an oxidation reaction using an oxidizing agent selected from peroxides and hydroperoxides organic, characterized in that the process comprises the steps of preparing a single liquid phase, comprising said antioxidant agent and a fuel fraction selected from gasoline, kerosene and diesel fractions, and contacting said liquid phase with a catalyst selected from amorphous solid catalysts to the X-rays and macroporous, which incorporate at least Si and Ti.
2. Procedimiento de acuerdo con la reivindicación 1 caracterizado porque comprende el agente antioxidante es H202.2. Method according to claim 1 characterized in that it comprises the antioxidant agent is H 2 0 2 .
3. Procedimiento de acuerdo con la reivindicación 1 o 2, caracterizado porque el catalizador es al menos un composite orgánico-inorgánico basado en un material silíceo inorgánico amorfo que contiene al menos Si, Ti y silicio unido a carbono.3. Method according to claim 1 or 2, characterized in that the catalyst is at least one organic-inorganic composite based on an amorphous inorganic siliceous material containing at least Si, Ti and carbon bonded silicon.
4. Procedimiento según una cualquiera de las reivindicaciones 1 a 3, caracterizado porque la fase líquida comprende un disolvente.4. Method according to any one of claims 1 to 3, characterized in that the liquid phase comprises a solvent.
5. Procedimiento según una cualquiera de las reivindicaciones 3 y 4, caracterizado porque dicho composite orgánico-inorgánico ha sido obtenido mediante un proceso en el que un reactivo que contiene grupos Si-C ha sido adicionado durante la etapa de síntesis.5. Method according to any one of claims 3 and 4, characterized in that said composite Organic-inorganic has been obtained by a process in which a reagent containing Si-C groups has been added during the synthesis stage.
6. Procedimiento según una cualquiera de las reivindicaciones 3 y 4, caracterizado porque dicho composite orgánico-inorgánico basado en un material silíceo inorgánico amorfo que contiene al menos Si, Ti y silicio unido a carbono, ha sido obtenido mediante un proceso que comprende una etapa de sililación postsíntesis.Method according to any one of claims 3 and 4, characterized in that said organic-inorganic composite based on an amorphous inorganic siliceous material containing at least Si, Ti and silicon bonded to carbon, has been obtained by a process comprising a step of postsynthesis silylation.
7. Procedimiento según una cualquiera de las reivindicaciones 1 a 6, caracterizado porque el catalizador es un material silíceo inorgánico amorfo químicamente combinado con Ti en una proporción entre 0,2 y 8% en peso en forma de óxido sobre el peso total del catalizador.Method according to any one of claims 1 to 6, characterized in that the catalyst is an amorphous inorganic siliceous material chemically combined with Ti in a proportion between 0.2 and 8% by weight in the form of oxide over the total weight of the catalyst.
8. Procedimiento según la reivindicación 7, caracterizado porque dicho sólido silíceo inorgánico amorfo contienen Si unido a C, formando un composite orgánico- inorgánico.Method according to claim 7, characterized in that said amorphous inorganic siliceous solid contains Si bound to C, forming an organic-inorganic composite.
9. Procedimiento según la reivindicación 7, caracterizado porque dicho sólido silíceo inorgánico amorfo comprende al menos 80% en peso de sílice.9. Method according to claim 7, characterized in that said amorphous inorganic siliceous solid comprises at least 80% by weight of silica.
10. según la reivindicación 9, caracterizado porque dicho sólido silíceo inorgánico amorfo es una sílice pirogénica seleccionada entre cab-o-sil y Aerosil con superficies específicas entre 40 y 450 m2.g_1 y un tamaño de partícula entre aproximadamente 0,007 y 0,05 mieras. 10. according to claim 9, characterized in that said amorphous inorganic siliceous solid is a pyrogenic silica selected from cab-o-sil and Aerosil with specific surfaces between 40 and 450 m 2 .g _1 and a particle size between about 0.007 and 0, 05 microns
11. Procedimiento según la reivindicación 9, caracterizado porque dicho sólido silíceo inorgánico amorfo es un óxido inorgánico sintético de sílice.11. Method according to claim 9, characterized in that said amorphous inorganic siliceous solid is a synthetic inorganic silica oxide.
12. Procedimiento según la reivindicación 11, caracterizado porque dicho óxido inorgánico sintético de sílice es gel de sílice.12. Method according to claim 11, characterized in that said synthetic silica inorganic oxide is silica gel.
13. Procedimiento según la reivindicación 7, caracterizado porque dicho sólido silíceo contiene además de Si y Ti, al menos otro elemento seleccionado entre V, B,13. Method according to claim 7, characterized in that said siliceous solid contains in addition to Si and Ti, at least one other element selected from V, B,
Zr, Mo y mezclas de los mismos en una proporción referida al peso total y en forma de óxidos inferior al 8%.Zr, Mo and mixtures thereof in a proportion referred to the total weight and in the form of oxides of less than 8%.
14. Procedimiento según una cualquiera de las reivindicaciones 7 a 13, caracterizado porque dicho sólido silíceo comprende una cantidad entre 0.01 y 4% en peso de un promotor seleccionados del grupo de los metales alcalinos, alcalinotérreos y mezclas de ellos, en forma de óxidos.14. Method according to any one of claims 7 to 13, characterized in that said siliceous solid comprises an amount between 0.01 and 4% by weight of a promoter selected from the group of alkali metals, alkaline earth metals and mixtures thereof, in the form of oxides.
15. Procedimiento según una cualquiera de las reivindicaciones 1, 3 y 7 a 14, caracterizado porque el agente oxidante hidroperóxido orgánico está seleccionado entre hidroperóxido de tert-butilo, hidroperóxido de etil- benceno y hidroperóxido de eumeno.15. Process according to any one of claims 1, 3 and 7 to 14, characterized in that the oxidizing agent organic hydroperoxide is selected from tert-butyl hydroperoxide, ethylbenzene hydroperoxide and eumene hydroperoxide.
16. Procedimiento según una cualquiera de las reivindicaciones 2, 4 y 7 a 14, caracterizado porque el agente oxidante es un complejo H202 - Urea.16. Process according to any one of claims 2, 4 and 7 to 14, characterized in that the oxidizing agent is an H 2 0 2 -Urea complex.
17. Procedimiento según una cualquier de las reivindicaciones 2, 4 y 7 a 14, caracterizado porque el agente oxidante es un perborato .17. Method according to any one of claims 2, 4 and 7 to 14, characterized in that the oxidizing agent is a perborate.
18. Procedimiento según una cualquiera de las reivindicaciones 1 a 17, caracterizado porque la reacción de oxidación se lleva a cabo en un reactor seleccionado entre un reactor discontinuo, un reactor CSTR, un reactor continuo de lecho fijo, un reactor de lecho fluidizado y un reactor de lecho ebullente.18. Method according to any one of claims 1 to 17, characterized in that the oxidation reaction is carried out in a reactor selected from a discontinuous reactor, a CSTR reactor, a continuous fixed bed reactor, a fluidized bed reactor and a boiling bed reactor.
19. Procedimiento según la reivindicación 18, caracterizado porque dicha oxidación se lleva a cabo en un reactor discontinuo, con una relación en peso de la fracción de combustible a catalizador comprendida entre 5 y 600, y una relación en peso entre la fracción de combustible y agente oxidante comprendida entre 300 y 10.19. Method according to claim 18, characterized in that said oxidation is carried out in a batch reactor, with a weight ratio of the fuel fraction to catalyst comprised between 5 and 600, and a weight ratio between the fuel fraction and oxidizing agent between 300 and 10.
20. Procedimiento según la reivindicación 19, caracterizado porque dicha relación en peso de la fracción de combustible a catalizador está comprendida entre 10 y 300.20. Method according to claim 19, characterized in that said weight ratio of the fuel fraction to catalyst is between 10 and 300.
21. Procedimiento según la reivindicación 19, caracterizado porque dicha relación en peso de la fracción de combustible y agente oxidante está comprendida entre 200 y 20.21. Method according to claim 19, characterized in that said weight ratio of the fuel fraction and oxidizing agent is between 200 and 20.
22. Procedimiento según una cualquiera de las reivindicaciones 1 a 21, caracterizado porque la reacción de oxidación se lleva a cabo a una temperatura comprendida entre 10 y 120°C.22. Method according to any one of claims 1 to 21, characterized in that the oxidation reaction is carried out at a temperature between 10 and 120 ° C.
23. Procedimiento según la reivindicación 22, caracterizado porque dicha reacción de oxidación se lleva a cabo a una temperatura comprendida entre 20 y 80 °C.23. Method according to claim 22, characterized in that said oxidation reaction is carried out out at a temperature between 20 and 80 ° C.
24. Procedimiento según una cualquiera de las reivindicaciones 1 a 23, caracterizado porque la reacción de oxidación se produce en un tiempo de reacción entre 2 minutos y 24 horas.24. Method according to any one of claims 1 to 23, characterized in that the oxidation reaction occurs in a reaction time between 2 minutes and 24 hours.
25. Procedimiento según una cualquiera de las reivindicaciones 1 a 24, caracterizado porque comprende una separación de los productos oxidados resultantes de la reacción de oxidación mediante una etapa seleccionada entre destilación, extracción y combinaciones de las mismas, con un disolvente, y un reciclado al menos parcial de productos que no han reaccionado en el reactor.25. A method according to any one of claims 1 to 24, characterized in that it comprises a separation of the oxidized products resulting from the oxidation reaction by a step selected from distillation, extraction and combinations thereof, with a solvent, and a recycling at less partial of products that have not reacted in the reactor.
26. Procedimiento según las reivindicaciones 1 a 24, caracterizado porque comprende una etapa de separación de los productos oxidados resultantes de la reacción de oxidación mediante una columna de adsorción que permite adsorber selectivamente los compuestos más polares formados durante la etapa de oxidación de los compuestos de azufre; y un reciclado al menos parcial de productos que no han reaccionado en el reactor. 26. A method according to claims 1 to 24, characterized in that it comprises a step of separating the oxidized products resulting from the oxidation reaction by means of an adsorption column that allows selectively adsorbing the more polar compounds formed during the oxidation stage of the compounds of sulfur; and at least partial recycling of products that have not reacted in the reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2003254517A AU2003254517A1 (en) | 2002-08-07 | 2003-07-31 | Method of oxidising mercaptans, thiophenic compounds and derivatives thereof in petrol, kerosene and diesel fractions |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ESP200201943 | 2002-08-07 | ||
| ES200201943A ES2200707B1 (en) | 2002-08-07 | 2002-08-07 | PROCESS FOR OXIDATION OF MERCAPTANS, THIOPHENIC COMPOUNDS AND THEIR DERIVATIVES, IN THE GASOLINE, CHEROSENE AND DIESEL FRACTIONS. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004015030A1 true WO2004015030A1 (en) | 2004-02-19 |
Family
ID=31502898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/ES2003/000399 WO2004015030A1 (en) | 2002-08-07 | 2003-07-31 | Method of oxidising mercaptans, thiophenic compounds and derivatives thereof in petrol, kerosene and diesel fractions |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU2003254517A1 (en) |
| ES (1) | ES2200707B1 (en) |
| WO (1) | WO2004015030A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009007490A1 (en) * | 2007-07-10 | 2009-01-15 | Consejo Superior De Investigaciones Científicas | Method for elimination of sulphur from liquid fuels |
| CN101012390B (en) * | 2007-02-02 | 2010-09-29 | 清华大学 | Method of realizing oil desulfuration by TiO2 catalyzed oxidation |
| US9005433B2 (en) | 2011-07-27 | 2015-04-14 | Saudi Arabian Oil Company | Integrated process for in-situ organic peroxide production and oxidative heteroatom conversion |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001048119A1 (en) * | 1999-12-28 | 2001-07-05 | Elf Antar France | Method for desulphurizing thiopene derivatives contained in fuels |
| WO2002031086A1 (en) * | 2000-10-11 | 2002-04-18 | Consejo Superior De Investigaciones Cientificas | Process and catalysts for eliminating sulfur compounds from the gasoline fraction |
| WO2002083819A1 (en) * | 2001-04-12 | 2002-10-24 | Consejo Superior De Investigaciones Cientificas | Method and catalysts for the elimination of sulfur compounds from the diesel fraction |
| WO2003044129A1 (en) * | 2001-11-20 | 2003-05-30 | Consejo Superior De Investigaciones Cientificas | Method of oxidising sulphur compounds present in gasoline, kerosene and diesel fractions |
-
2002
- 2002-08-07 ES ES200201943A patent/ES2200707B1/en not_active Expired - Fee Related
-
2003
- 2003-07-31 AU AU2003254517A patent/AU2003254517A1/en not_active Abandoned
- 2003-07-31 WO PCT/ES2003/000399 patent/WO2004015030A1/en not_active Application Discontinuation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001048119A1 (en) * | 1999-12-28 | 2001-07-05 | Elf Antar France | Method for desulphurizing thiopene derivatives contained in fuels |
| WO2002031086A1 (en) * | 2000-10-11 | 2002-04-18 | Consejo Superior De Investigaciones Cientificas | Process and catalysts for eliminating sulfur compounds from the gasoline fraction |
| WO2002083819A1 (en) * | 2001-04-12 | 2002-10-24 | Consejo Superior De Investigaciones Cientificas | Method and catalysts for the elimination of sulfur compounds from the diesel fraction |
| WO2003044129A1 (en) * | 2001-11-20 | 2003-05-30 | Consejo Superior De Investigaciones Cientificas | Method of oxidising sulphur compounds present in gasoline, kerosene and diesel fractions |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012390B (en) * | 2007-02-02 | 2010-09-29 | 清华大学 | Method of realizing oil desulfuration by TiO2 catalyzed oxidation |
| WO2009007490A1 (en) * | 2007-07-10 | 2009-01-15 | Consejo Superior De Investigaciones Científicas | Method for elimination of sulphur from liquid fuels |
| ES2311408A1 (en) * | 2007-07-10 | 2009-02-01 | Consejo Superior De Investigaciones Cientificas | Method for elimination of sulphur from liquid fuels |
| US9005433B2 (en) | 2011-07-27 | 2015-04-14 | Saudi Arabian Oil Company | Integrated process for in-situ organic peroxide production and oxidative heteroatom conversion |
| US9540572B2 (en) | 2011-07-27 | 2017-01-10 | Saudi Arabian Oil Company | Integrated system for in-situ organic peroxide production and oxidative heteroatom conversion |
| US9637690B2 (en) | 2011-07-27 | 2017-05-02 | Saudi Arabian Oil Company | Integrated system for in-situ organic peroxide production and oxidative heteroatom conversion and hydrotreating |
| US9909074B2 (en) | 2011-07-27 | 2018-03-06 | Saudi Arabian Oil Company | Integrated process for in-situ organic peroxide production and oxidative heteroatom conversion |
| US10508246B2 (en) | 2011-07-27 | 2019-12-17 | Saudi Arabian Oil Company | Integrated process for in-situ organic peroxide production and oxidative heteroatom conversion |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2003254517A1 (en) | 2004-02-25 |
| ES2200707B1 (en) | 2005-05-01 |
| AU2003254517A8 (en) | 2004-02-25 |
| ES2200707A1 (en) | 2004-03-01 |
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