ZA200509837B - Process for improving the pour point of hydrocarbon charges resulting from the Fischer-Tropsch process, using a catalyst based on a mixture of zeolites - Google Patents
Process for improving the pour point of hydrocarbon charges resulting from the Fischer-Tropsch process, using a catalyst based on a mixture of zeolites Download PDFInfo
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- ZA200509837B ZA200509837B ZA200509837A ZA200509837A ZA200509837B ZA 200509837 B ZA200509837 B ZA 200509837B ZA 200509837 A ZA200509837 A ZA 200509837A ZA 200509837 A ZA200509837 A ZA 200509837A ZA 200509837 B ZA200509837 B ZA 200509837B
- Authority
- ZA
- South Africa
- Prior art keywords
- stage
- catalyst
- process according
- charge
- zeolites
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 104
- 238000000034 method Methods 0.000 title claims description 97
- 239000010457 zeolite Substances 0.000 title claims description 97
- 230000008569 process Effects 0.000 title claims description 74
- 239000000203 mixture Substances 0.000 title claims description 29
- 150000002430 hydrocarbons Chemical class 0.000 title description 18
- 229930195733 hydrocarbon Natural products 0.000 title description 16
- 239000004215 Carbon black (E152) Substances 0.000 title description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 52
- 229910021536 Zeolite Inorganic materials 0.000 claims description 50
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 44
- 239000001257 hydrogen Substances 0.000 claims description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims description 42
- 239000000047 product Substances 0.000 claims description 31
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- 238000009835 boiling Methods 0.000 claims description 28
- 230000003197 catalytic effect Effects 0.000 claims description 22
- 238000004821 distillation Methods 0.000 claims description 22
- 229910000510 noble metal Inorganic materials 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229910052697 platinum Inorganic materials 0.000 claims description 19
- 239000011159 matrix material Substances 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 230000000737 periodic effect Effects 0.000 claims description 10
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000003344 environmental pollutant Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000012263 liquid product Substances 0.000 claims description 3
- 231100000719 pollutant Toxicity 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 35
- 239000003921 oil Substances 0.000 description 34
- 229910052751 metal Inorganic materials 0.000 description 31
- 239000002184 metal Substances 0.000 description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000011282 treatment Methods 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000002808 molecular sieve Substances 0.000 description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000006317 isomerization reaction Methods 0.000 description 8
- 239000003350 kerosene Substances 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000002199 base oil Substances 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 235000010755 mineral Nutrition 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000007493 shaping process Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005336 cracking Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 230000001174 ascending effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 3
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 3
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 3
- 150000003057 platinum Chemical class 0.000 description 3
- 229910003446 platinum oxide Inorganic materials 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000011959 amorphous silica alumina Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241001269608 Enispa Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000008298 dragée Substances 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- KWUUWVQMAVOYKS-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe][Mo][Mo] KWUUWVQMAVOYKS-UHFFFAOYSA-N 0.000 description 1
- GXBKELQWVXYOPN-UHFFFAOYSA-N iron tungsten Chemical compound [W][Fe][W] GXBKELQWVXYOPN-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical class [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- -1 rings Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003568 thioethers Chemical group 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical class [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical class [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
-
- 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
- C10G2400/10—Lubricating oil
Description
ER wi
INSTITUT FRANGAIS DU PETROLE
AND
ENI SpA
PROCESS FOR IMPROVING THE POUR POINT OF HYDROCARBON CHARGES
RESULTING FROM THE FISCHER-TROPSCH PROCESS, USING A CATALYST
BASED ON A MIXTURE OF ZEOLITES invention of Eric BENAZZI and Emmanuelle GUILLON
ABSTRACT
The present invention relates to a process for improving the pour point of hydrocarbon charges resulting from the Fischer-Tropsch process, in particular for converting, with a good yield, charges having high pour points to at least one fraction having a low pour point and a high viscosity index for base oils. The process uses a catalyst comprising at least one zeolite (molecular sieve) chosen from the group comprising the zeolites of structural type TON (Theta-1, ZSM-22, ISI-1, NU-10 and KZ-2) and at least one ZBM-30 zeolite, at least one porous mineral matrix, at least one hydro-dehydrogenating element, preferably chosen from the elements of Group VIB and Group VIII of the periodic table.
Fig. 1 to be published.
The present invention relates to a process for improving the pour point of hydrocarbon charges resulting from the Fischer-Tropsch process, in particular for converting, at a good yield, charges having high pour points to at least one fraction having a low pour point and a high viscosity index for the oil bases, by passing over a catalytic hydrodewaxing catalyst comprising at least one zeolite (molecular sieve) chosen from the group formed by the zeolites of structural type TON (Theta-1, ZSM-22, I1SI-1, NU-10 and KZ-2) and at least one ZBM-30 zeolite preferably synthesized in the presence of a particular structuring agent such as triethylenetetramine, at least one porous mineral matrix, at least one hydro-dehydrogenating element, preferably chosen from the elements of Group VIB and Group VIII of the periodic table.
Prior art
High-quality lubricants are of fundamental importance for the satisfactory operation of modern machinery, cars and lorries. However, the quantity of untreated paraffins originating directly from petroleum, and having suitable properties for constituting good lubricants is very small compared with the growing demand in this sector.
The treatment of heavy petroleum fractions with high linear or slightly branched paraffins contents is necessary in order to obtain high-grade base oils with the best possible yields, by an operation aimed at eliminating the linear or very slightly branched paraffins, from charges which will then be used as base oils or as kerosene or jet fuel.
In fact paraffins with a high molecular weight, which are linear or very slightly branched and which are present in oils or in the kerosene or jet fuel lead to high pour points and therefore to solidification phenomena for low-temperature uses. In order to reduce the pour points, these linear, unbranched or very slightly branched paraffins must be entirely or partially eliminated.
This operation can be carried out by extraction using solvents such as propane or methyl ethyl ketone, which is called propane or methyl ethyl ketone (MEK) dewaxing.
However, these techniques are expensive, lengthy and not always easy to implement.
Another means is selective cracking of the longest linear paraffin chains which leads to the formation of compounds with a lower molecular weight, some of which can be eliminated by distillation.
Given their form selectivity, zeolites are among the most widely-used catalysts.
The idea underlying their use is that zeolitic structures exist, the pore openings of which are such that they allow the entry of the long linear or very slightly branched paraffins into their micropores, but exclude branched paraffins, naphthenes and aromatics. This phenomenon thus leads to a selective cracking of the linear or very slightly branched paraffins.
Catalysts based on zeolites having intermediate pore sizes such as ZSM-5,
ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 have been described for their use in these processes in particular in the patents US 3,894,938; US 4,176,050,
US 4,181,598; US 4,222,855; US 4,229,282 and US 4,247,388.
Mixtures of zeolites with large pores and these zeolites with intermediate pores which can be used in a dewaxing process are described in Patent W002088279.
Moreover, it was found that processes using these zeolites (ZSM-5, ZSM-11,
ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38) make it possible to obtain oils by cracking of charges containing quantities of linear or very slightly branched paraffins of less than 50% by weight. However, for charges containing higher quantities of these compounds it transpired that their cracking leads to the formation of large quantities of products with lower molecular weights, such as butane, propane, ethane and methane, which considerably reduces the yield of sought products.
To overcome these drawbacks, the applicant concentrated his research efforts on the development of a process for improving the pour point of hydrocarbon charges resulting from the Fischer-Tropsch process using catalysts comprising at least one zeolite (molecular sieve) chosen from the group formed by the zeolites of structural type TON (Theta-1, ZSM-22, ISI-1, NU-10 and KZ-2) and at least one zeolite chosen from the group comprising the zeolites (ZSM-48, EU-2, EU-11 and ZBM-30), at least one hydro- dehydrogenating element, preferably chosen from the elements of Group VIB and
Group VII of the periodic table. The applicant then discovered, surprisingly, that by using a catalyst comprising at least one zeolite of structural type TON and at least one
ZBM-30 zeolite preferably synthesized with a particular structuring agent such as triethylenetetramine it is possible to lower the pour point of the charge yet obtain a high viscosity index (V1) and maintain a good yield of desired products.
The present invention proposes a catalytic process for reducing the pour point of charges resulting from the Fischer-Tropsch process based on said catalysts.
Object of the invention
More precisely the invention relates to a process for improving the pour point of a paraffinic charge produced by Fischer-Tropsch synthesis, in which the charge to be treated is brought into contact with a catalyst comprising at least one zeolite (molecular sieve) chosen from the group formed by the zeolites of structural type TON (Theta-1,
ZSM-22, I1SI-1, NU-10 and KZ-2) and at least one ZBM-30 zeolite (synthesized with a particular structuring agent such as triethylenetetramine), at least one hydro- dehydrogenating element, preferably chosen from the elements of Group VIB and
Group VIII of the periodic table, and at least one porous mineral matrix, the process is carried out at a temperature between 200 and 450°C, a pressure between 0.1 and 25
MPa and an hourly space velocity between 0.05 and 30 h, in the presence of hydrogen at a rate of 50 to 2000 normal litres of hydrogen per litre of charge.
The zeolites contained in the catalyst which can be used in the process according to the invention which are of structural type TON are described in the work "Atlas of Zeolite
Structure Types", W.M. Meier, D.H. Olson and Ch. Baerlocher, 4th Revised edition, 1996, Elsevier.
The synthesis of the ZBM-30 zeolite is described in the patent EP-A-46504.
Unexpectedly, said catalyst has a greater dewaxing activity and selectivity 5 (improvement of the pour point of charges resulting from the Fischer-Tropsch process) than the catalytic formulae based on zeolites (molecular sieve) known in the prior art.
Thus, this process makes it possible to convert a charge having a high pour point to a product having a lower pour point and makes it possible to obtain base oils having good low-temperature properties and a high viscosity index and gasoils of good quality.
The charges which can be treated according to the process of the invention are advantageously fractions having relatively high pour points, the value of which it is wished to reduce.
Typical charges which can be treated advantageously according to the invention generally have a pour point above 0°C. The products resulting from the treatment according to the process have pour points below 0°C and preferably below approximately -10°C.
The process according to the invention, under the conditions described above, allows, in particular, the production of products having a low pour point with good yieids, and a high viscosity index in the case of the heaviest fractions which are treated with a view to producing oil bases.
The process according to the invention uses a catalyst which comprises at least one zeolite chosen from the group comprising the zeolites of structural type TON and at least one ZBM-30 zeolite synthesized with a particular structuring agent such as triethylenetetramine, at least one hydro-dehydrogenating element, preferably chosen from the elements of Group VIB and Group Vill of the periodic table and at least one porous mineral matrix.
The zeolite of structural type TON included in the composition of the catalyst is chosen from the group comprising the zeolites Theta-1, ISI-1, NU-10, KZ-2 and ZSM-22 described in the work "Atlas of Zeolite Structure Types”, W.M. Meier, D.H. Olson and
Ch. Baerlocher, 4th Revised edition, 1996, Elsevier as well as in patents US 456477 and US 4902408 with respect to the ZSM-22 zeolite and in patents EP-65400 and EP- 77624 for the NU-10 zeolite.
The synthesis of the ZBM-30 zeolite is described in the patent EP-A-46504.
Preferably the zeolites NU-10 or ZSM-22 are used with ZBM-30. The ZBM-30 zeolite is preferably synthesized by the methods described in patent EP-A-46504 according to the procedure using the structuring agent triethylenetetramine.
The overall Si/Al ratio of the zeolites included in the composition of the catalysts of the process according to the invention as well as the chemical composition of the samples are determined by X-ray fluorescence and atomic absorption.
The Si/Al ratios of the zeolites described above are those obtained on synthesis according to the procedures described in the various documents cited or obtained after post-synthesis dealumination treatments well known to a person skilled in the art, such as, non-exhaustively, hydrothermal treatments followed or not followed by acid attacks or direct acid attacks by solutions of mineral or organic acids.
The zeolites included in the composition of the catalysts of the process according to the invention can be calcined and exchanged by at least one treatment with a solution of at least one ammonium salt so as to obtain the ammonium form of the zeolites which, once it is calcined, leads to the hydrogen form of said zeolites.
The zeolites included in the composition of the catalyst of the process according to the invention are at least partly, preferably practically totally, in the acid form, i.e. in the hydrogen form (H"). The Na/T atomic ratio is generally below 10% and preferably below 59% and even more preferably below 1%.
Moreover, the catalyst contains at least one hydro-dehydrogenating element, preferably chosen from the elements of Group VIB and Group VIII (i.e. metal or compound) of the periodic table and at least one porous mineral matrix.
In the case where the element is at least one metal of Group VIII, preferably when it is at least one noble metal and advantageously a noble metal chosen from the group comprising platinum and palladium, it can be introduced onto the zeolites for example by dry impregnation, by ion exchange or any other process known to a person skilled in the art, or it can be introduced onto the matrix.
According to a first variant, prior to their shaping at least one of the zeolites previously described is subjected to application of at least one metal of Group VII, preferably chosen from the group formed by platinum and palladium. The zeolites thus loaded with metals are mixed. Mixing of these zeolites which are then in the state of powder is carried out by any powder mixing techniques known to a person skilled in the art.
Once the metal-laden zeolite powders have been mixed, the mixture is shaped by any process known to a person skilled in the art. It can in particular be mixed with a matrix, generally amorphous, for example a moist powder of alumina gel. The mixture is then shaped, for example by extrusion through a die.
The shaping can be carried out with matrices other than alumina, for example : magnesia, amorphous silica-aluminas, natural clays (kaolin, bentonite, sepiolite, attapulgite), silica, titanium oxide, boron oxide, zirconia, aluminium phosphates, titanium phosphates, zirconium phosphates, charcoal and their mixtures. It is preferable to use matrices containing alumina, in all its forms known to a person skilled in the art, and even more preferably aluminas, for example gamma-alumina. Techniques other than extrusion, such as pelleting and dragée production, can be used.
Mixtures of alumina and silica, and mixtures of alumina and of silica-alumina, can also advantageously be used.
The catalysts obtained are shaped in the form of grains of various shapes and dimensions. They are generally used in the form of cylindrical or polylobate extrudates such as straight or twisted bilobates, trilobates, polylobates, but can optionally be produced and used in the form of crushed powders, tablets, rings, beads, coils.
After the shaping stage, the product obtained is subjected to a drying stage then to a calcination stage.
In the case where the hydrogenating metal belongs to Group VII, and is preferably platinum and/or palladium, it can also and advantageously be applied to the support after the shaping of the zeolites which are free of metals, using any process known to a person skilled in the art and allowing the application of the metal to the molecular sieve.
In this case the support is obtained in a manner analogous to that described previously.
In the remainder of the text, the term support will be used to describe the mixture of zeolites (free of metals), plus the matrix after shaping, drying and calcination, for example as obtained previously.
In order to apply the metal to the zeolite, it is possible to use the cation exchange technique with competition where the competitor is preferably ammonium nitrate, the competition ratio being at least equal to approximately 20 and advantageously approximately 30 to 200. In the case of platinum or palladium, a tetramine complex of platinum or a tetramine complex of palladium is customarily used: these latter will then be applied practically totally to the zeolites. This cation exchange technique can also be used in order to apply the metal directly to the molecular sieve powder, before its optional mixing with a matrix.
The application of the metal (or metals) of Group VIII is generally followed by calcination under air or oxygen, usually between 300 and 600°C for 0.5 to 10 hours, preferably between 350°C and 550°C for 1 to 4 hours. This can then be followed by reduction under hydrogen, generally at a temperature between 300 and 600°C for 1 to 10 hours, preferably operating between 350 and 550°C for 2 to 5 hours.
It is also possible to apply the platinum and/or palladium not directly to the molecular sieves, but to the matrix (for example the alumina binder) of the support, before or after the shaping stage, implementing an anion exchange with hexachloroplatinic acid,
hexachloropalladic acid and/or palladium chloride in the presence of a competing agent, for example hydrochloric acid. Generally, after the application of platinum and/or palladium, the catalyst is, as previously, subjected to calcination then reduced under hydrogen as indicated above.
The support of the catalytic dewaxing catalyst according to the present invention generally has the following contents of matrix and zeolites: - 5 to 95 wt.%, preferably 10 to 90 wt.%, more preferably from 15 to 85 wt.% and very preferably from 20 to 80 wt.% of zeolites such as at least one zeolite chosen from the group formed by the zeolites of structural type TON such as Theta-1, ZSM-22, ISI-1,
NU-10 and KZ-2 and at least one zeolite is a ZBM-30 zeolite, - 5 to 95%, preferably from 10 to 90%, more preferably from 15 to 85% and very preferably from 20 to 80 wt.% of at least one amorphous or poorly crystallized oxide- type porous mineral matrix.
The distribution between the two zeolites of each of the groups defined previously is such that the content of zeolite(s) chosen from the group formed by the zeolites of structural type TON (Theta-1, ZSM-22, ISI-1, NU-10 and KZ-2) can vary from 1% to 99%, preferably from 5 to 95% and even more preferably it can vary between 10 and 90% as a relative percentage of all of the zeolites included in the catalyst. Similarly, the content of ZBM-30 zeolite varies from 1% to 99%, preferably from 5 to 95% and even more preferably it varies between 10 and 90%, as a relative percentage of all of the zeolites introduced into the catalyst.
The content of noble metal(s) thus optionally introduced, expressed as a wt.% relative to the total mass of the catalyst, is generally below 5%, preferably below 3%, even more preferably below 2% and generally below 1 wt. %.
In the preferred case where the catalyst comprises a hydrogenating metal of Group VII preferably a noble metal and advantageously platinum and/or palladium, the catalyst is generally reduced in the reactor in the presence of hydrogen and in conditions well known to a person skilled in the art.
In the case where the hydrogenating metal is not a noble metal, any elements of Group
VIB and of Group VIII introduced into the catalyst according to the invention can be present totally or partially in metal form and/or oxide form and/or sulphide form.
Among the Group VIB elements, molybdenum and tungsten are preferred.
The sources of Group VIB element which can be used are well known to a person skilled in the art. For example, among the sources of molybdenum and tungsten, it is possible to use oxides and hydroxides, molybdic and tungstic acids and their salts, in particular the ammonium salts such as ammonium molybdate, ammonium heptamolybdate, ammonium tungstate, phosphomolybdic acid, phosphotungstic acid and their salts. Preferably ammonium oxides and salts are used, such as ammonium molybdate, ammonium heptamolybdate and ammonium tungstate.
The dewaxing catalyst according to the present invention can contain a non-noble metal of Group VIII and preferably cobalt and nickel. Advantageously, the following combinations of the non-noble elements of Groups VI and VIII are used: nickel- molybdenum, cobalt-molybdenum, iron-molybdenum, iron-tungsten, nickel-tungsten, cobalt-tungsten, the preferred combinations are: nickel-molybdenum, nickel-tungsten. It is also possible to use combinations of three metals for example nickel-cobait- molybdenum.
The sources of elements of Group VIII that can be used are well known to a person skilled in the art. For example, nitrates, sulphates, phosphates, halides will be used, for example chlorides, bromides and fluorides, carboxylates for example acetates and carbonates.
When the hydrogenating function is provided by a non-noble metal of Group Vil or a combination of a non-noble metal of Group VIII and a metal of Group VIB, - the composition of the support constituted by at least one matrix and zeolites described in the invention is the same as that described previously and,
- the catalyst's content by weight of at least one element chosen from the non-noble elements of Group VIB and Group Vil is between 0.1 and 60%, preferably between 1 and 50% and still more preferably between 2 and 40%.
Generally, in order to conclude the preparation of the catalyst, the moist solid is left to rest in a moist atmosphere at a temperature between 10 and 80°C, then the moist solid obtained is dried at a temperature between 60 and 150°C, and finally the solid obtained is calcined at a temperature between 150 and 800°C, generally between 250 and 600°C.
The catalysts of the present invention can optionally be subjected to a sulphurization treatment making it possible to convert, at least in part, the metallic species to sulphide before they are brought into contact with a charge to be treated. This activation treatment by sulphurizing is well known to a person skilled in the art and can be carried out by any method already described in the literature.
In the case of the non-noble metals, a standard sulphurizing treatment well known to a person skilled in the art consists of heating in the presence or under flow of a hydrogen/hydrogen sulphide mixture or also under pure hydrogen sulphide, at a temperature between 150 and 800°C, preferably between 250 and 600°C, generally in a crossed-bed reaction zone.
Charges
The hydrocarbon charges treated according to the process of the invention are charges produced by Fischer-Tropsch synthesis and advantageously fractions having relatively high pour points, whose value it is wished to reduce.
In general, at least a proportion of the compounds having a boiling point higher than or equal to 340°C is treated according to the invention.
In the Fischer-Tropsch process, synthesis gas (CO+H,) is converted catalytically to oxidized products and to essentially linear hydrocarbons in gaseous, liquid or solid form.
These products are generally free from heteroatomic impurities such as sulphur,
nitrogen or metals. They also have little if any content of aromatics, naphthenes and more generally cyclic compounds especially in the case of cobalt catalysts. In contrast, they may have a content of oxidized products that is not negligible which, expressed as oxygen by weight, is generally below approximately 5 wt.% and also a content of unsaturated compounds (olefinic products in general) generally below 10 wt.%.
However, these products, mainly consisting of normal paraffins, cannot be used as they are, in particular because their low-temperature properties are rather incompatible with the customary uses of petroleum fractions. For example, the pour point of a linear hydrocarbon containing 20 carbon atoms per molecule (boiling point equal to approximately 340°C, i.e. often included in the middle distillate cut) is approximately +37°C, which makes its use impossible, as the specification is -15°C for gasoil. The hydrocarbons resulting from the Fischer-Tropsch process, mostly comprising n- paraffins, must be converted to higher-grade products such as gasoil and kerosene, which are obtained, for example, after catalytic reactions of hydroisomerization.
Typical charges which can be treated advantageously according to the invention generally have a pour point above 0°C. The products resulting from the treatment according to the process have pour points below 0°C and preferably below approximately -10°C.
In the hydrocarbon charge which comes into contact with the catalyst based on ZBM-30 (from which oils and possibly distillates of high quality can be obtained) preferably at least 50 wt.% of the charge has a boiling point of at least 340°C, and even more preferably at least 60 wt.% and better still at least 80 wt.% of the charge has a boiling point of at least 340°C, preferably above at least 370°C and even more preferably above at least 380°C. This does not mean, for example, that the boiling point is 380°C and more, but 380°C or more.
The charge therefore consists mainly of normal paraffins.
Generally, charges which are suitable for the objective oils have an initial boiling point above at least 340°C and better still above at least 370°C and better still above at least 380°C.
The process according to the invention, under the conditions described below makes it possible, in particular, to produce products with a low pour point with good yields, and with a high viscosity index in the case of the heaviest fractions which are treated with the aim of producing base oils.
Operating conditions
The operating conditions under which the process of catalytic dewaxing of the invention is carried out are the following: - the reaction temperature is between 200 and 450°C and preferably between 200 and 420°C, advantageously 250-410°C; - the pressure is between 0.1 and 25 MPa and preferably between approximately 1 and 20 MPa; - the hourly space velocity (HSV expressed as volume of charge injected per unit volume of catalyst per hour) is between approximately 0.05 and approximately 30 and preferably between approximately 0.1 and approximately 20 h™' and even more preferably between approximately 0.1 and approximately 10 h'.
The contact between the charge and the catalyst is carried out in the presence of hydrogen. The level of hydrogen used is expressed in litres of hydrogen per litre of charge and is between 50 and approximately 2000 litres of hydrogen per litre of charge and preferably between 100 and 1500 litres of hydrogen per litre of charge.
In a preferred first embodiment, the catalytic dewaxing process according to the invention can be preceded by a hydroisomerization-hydroconversion stage in the presence of a catalyst containing at least one noble metal applied to an amorphous acid support.
This hydroisomerization-hydroconversion stage is optionally preceded by a hydrorefining stage for removing the (oxidized) heteroatoms, and this hydrorefining stage can be followed by an intermediate separation.
This stage of hydroisomerization-hydroconversion may be preceded by a hydrorefining stage for removing the (oxidized) heteroatoms, and this hydrorefining stage can be followed by an intermediate separation.
The stage of hydroisomerization-hydroconversion takes place in the presence of hydrogen and in the presence of a bifunctional catalyst comprising an amorphous acidic support (preferably an amorphous silica-alumina) and a hydro-dehydrogenating metal function provided by at least one noble metal of Group VIII.
The support is called amorphous, i.e. having no molecular sieve, and in particular zeolite, as well as the catalyst. The amorphous acid support is advantageously an amorphous silica-alumina but other supports can be used. When it is a silica-alumina, the catalyst generally does not contain added halogen, other than that which could be introduced for the impregnation, of the noble metal for example. The silica-alumina can be obtained by any synthesis technique known to a person skilled in the art, such as the techniques of co-precipitation, co-gelation, etc.
During the hydroisomerization-hydroconversion stage, the molecules of the charge to be treated, for example n-paraffins, in the presence of a bifunctional catalyst, undergo an isomerization then optionally hydrocracking in order to lead respectively to the formation of isoparaffins and lighter cracking products such as gasoils and kerosene.
The conversion of the products having boiling points greater than or equal to the initial boiling point of the charge, which is at least 340°C, or even 370°C or better still at least 380°C, to products with boiling points below the initial boiling point of the charge ° generally varies between 5 and 90%, preferably between 5 and 80% but is generally preferably below 80% and better still below 60%.
The characteristics of the hydroisomerization-hydroconversion catalyst are, in more detail:
The preferred support used for preparation of the catalyst for pretreatment by hydroisomerization-hydroconversion described within the scope of this patent is composed of silica SiO, and alumina Al,O;. The silica content of the support, expressed as percentage by weight, is generally between 1 and 95%, advantageously between 5 and 95% and preferably between 10 and 80% and still more preferably between 20 and 70% and between 22 and 45%. This silica content is measured exactly using X-ray fluorescence.
For this particular type of reaction, the metal function is provided by a noble metal of
Group VIII of the periodic table of the elements and more particularly platinum and/or palladium.
The noble metal content, expressed as a wt.% of metal relative to the catalyst, is between 0.05 and 10 and more preferentially between 0.1 and 5.
The preparation and shaping of the support, and in particular of the silica-alumina, are carried out by the usual methods well known to a person skilled in the art.
Advantageously, prior to the impregnation of the metal, the support can undergo calcination such as for example a heat treatment at 300-750°C (600°C preferred) for 0.25-10 hours (2 hours preferred) under 0-30 vol.% of water vapour (for silica-alumina 7.5% preferred).
The noble metal salt is introduced by one of the usual methods used to apply the metal (preferably platinum and/or palladium, platinum being especially preferred) to the surface of a support. One of the preferred methods is dry impregnation, which consists of the introduction of the metal salt into a volume of solution which is equal to the pore volume of the catalyst mass to be impregnated. Before the reduction operation, the catalyst can undergo calcination, for example a treatment under dry air at 300-750°C (520°C preferred) for 0.25-10 hours (2 hours preferred).
Before use in the hydroisomerization-conversion reaction, the metal contained in the catalyst must be reduced. One of the preferred methods for carrying out the metal reduction is treatment under hydrogen at a temperature between 150°C and 650°C and a total pressure between 0.1 and 25 MPa. For example, a reduction consists of a 2-hour plateau at 150°C then a rise in temperature to 450°C at a rate of 1°C/minute then a 2- hour plateau at 450°C: throughout this reduction stage, the hydrogen flow rate is 1000 litres of hydrogen per litre of catalyst. It should also be noted that any ex situ reduction method is suitable.
The operating conditions under which the hydroisomerization-hydroconversion stage is carried out are described below.
Pressure will be maintained between 2 and 25 MPa and preferably 3 to 20 MPa and advantageously 2 to 18 MPa, the hourly space velocity will be between 0.1 h'!and 10 i 10! preferably between 0.2 and 10 h™' and advantageously between 0.5 and 5.0 h”'. The hydrogen flow rate is between 100 and 2000 litres of hydrogen per litre of charge and preferentially between 150 and 1500 litres of hydrogen per litre of charge.
The temperature used in this stage is between 200 and 450°C and preferentially from 250°C to 450°C, advantageously from 300 to 450°C, and even more advantageously above 340°C, for example between 320-450°C. in the case where a hydrorefining stage precedes the hydroisomerization- hydroconversion stage, the two stages of hydrorefining and hydroisomerization- conversion can be carried out on two types of catalysts in (two or more) different reactors, and/or on at least two catalyst beds installed in one and the same reactor.
The use of the catalyst described above in the hydroisomerization-hydroconversion stage has the effect of increasing the degree of isomerization of the heavy fraction (340°C+, or 370°C+ and better still 380°C+) and reducing its pour point. More generally, it is found that the treatment of the hydroisomerization-hydroconversion stage then makes it possible to obtain better yields of dewaxed oil fraction which will be obtained in the catalytic dewaxing stage and to obtain the desired viscosimetric properties (viscosity and viscosity index V1).
In a one embodiment variant, all of the effluent from the hydroisomerization-conversion stage can be treated in the dewaxing process according to the invention. This variant, with passage of all of the effluent from the hydroisomerization-hydroconversion stage through the stage of catalytic dewaxing, is economically beneficial, since a single distillation unit is used at the end of the process. Moreover, in the final distillation (after catalytic dewaxing or subsequent treatments) a very-low-temperature gasoil is obtained. in one variant, the effluent from the hydroisomerization-hydroconversion stage can undergo separation of at least a proportion (and preferably of at least a major part) of light gases comprising hydrogen and possibly also hydrocarbon compounds with a maximum of 4 carbon atoms. The hydrogen can be separated beforehand.
Advantageously, in another embodiment variant, the effluent from the hydroisomerization-hydroconversion stage is distilled in order to separate the light gases and also separate at least one residue containing compounds having a boiling point above at least 340°C. This is preferably an atmospheric distillation.
Distillation can advantageously be carried out to obtain several fractions (gasoline, kerosene, gasoil for example), having a boiling point of at most 340°C and a fraction (called residue) having an initial boiling point above at least 340°C and better still above 350°C and preferably of at least 370°C or 380°C.
This fraction (residue) is then treated in the catalytic dewaxing stage, i.e. without undergoing vacuum distillation. But in another variant vacuum distillation can be used.
Generally, in this text the term "middle distillates" refers to the fraction or fractions with an initial boiling point of at least 150°C and final boiling point up to before the residue, i.e. generally up to 340°C, 350°C or preferably below 370°C or 380°C.
The effluent from the hydroisomerization-hydroconversion stage can undergo, before or after distillation, other treatments such as for example extraction of at least a proportion of the aromatic compounds.
In general, at least a proportion of the effluent from the hydroisomerization- hydroconversion stage, said effluent possibly having undergone the separations and/or treatments described above, is then subjected to the catalytic dewaxing process according to the invention.
It should be noted that compounds boiling above at least 340°C are always subjected to the catalytic dewaxing.
The effluent leaving the catalytic hydrodewaxing process according to the invention is advantageously sent to the distillation line, which preferably combines atmospheric distillation and vacuum distillation, with the aim of separating the conversion products with a boiling point below 340°C and preferably below 370°C, (and in particular including those formed during the catalytic hydrodewaxing) stage, and of separating the fraction which constitutes the base oil and whose initial boiling point is above at least 340°C and preferably above or equal to 370°C.
Moreover, this vacuum distillation section makes it possible to separate the different grades of oil.
Preferably, before being distilled, the effluent leaving the catalytic hydrodewaxing stage is, at least partly and preferably in its entirety, sent over a hydrofinishing catalyst in the presence of hydrogen so as to effect deep hydrogenation of any aromatic compounds still present which impair the stability of the oils and distillates. However, the acidity of the catalyst must be weak enough not to lead to the formation of cracked product with boiling point below 340°C so as not to degrade the final yields in particular of oils.
The catalyst used in this hydrofinishing stage contains at least one metal of Group Vili and/or at least one element of Group VIB of the periodic table. The strong metal functions: platinum andlor palladium, or nickel-tungsten and nickel-molybdenum combinations, will be advantageously used in order to carry out deep hydrogenation of the aromatics.
These metals are deposited and dispersed on an amorphous or crystalline oxide-type support, such as for example aluminas, silicas, and silica-aluminas.
The hydrofinishing (HDF) catalyst can also contain at least one element of Group Vil A of the periodic table of the elements. Preferably these catalysts contain fluorine and/or chlorine.
The contents of metals by weight are between 10 and 30% in the case of the non-noble metals and below 2%, preferably between 0.1 and 1.5%, and still more preferably between 0.1 and 1.0% in the case of the noble metals.
The total halogen quantity is between 0.02 and 30 wt.%, advantageously between 0.01 and 15%, or even more advantageously between 0.01 and 10%, preferably between 0.01 and 5%.
Among the catalysts which can be used in this hydrofinishing stage, leading to excellent performance, and in particular for obtaining medicinal oils, there can be mentioned catalysts containing at least one noble metal of Group VII (platinum and palladium for example) and at least one halogen (chlorine and/or fluorine), the combination of chlorine and fluorine being preferred.
The operating conditions under which the hydrofinishing stage optionally following the catalytic dewaxing process according to the invention is carried out are as follows: - the reaction temperature is between 180 and 400°C and preferably between 210 and 350°C, advantageously 230-320°C; - the pressure is between 0.1 and 25 MPa and preferably between 1.0 and 20 MPa; - the hourly space velocity (HSV expressed as volume of charge injected per unit volume of catalyst per hour) is between approximately 0.05 and approximately 100 and preferably between approximately 0.1 and approximately 30 h'.
The contact between the charge and the catalyst is carried out in the presence of hydrogen. The amount of hydrogen used, expressed in litres of hydrogen per litre of charge, is between 50 and approximately 2000 litres of hydrogen per litre of charge and preferably between 100 and 1500 litres of hydrogen per litre of charge.
Advantageously, the temperature of the hydrofinishing stage (HDF) is below the temperature of the catalytic hydrodewaxing (CHDW) stage. The difference Tcrow-Tror is generally between 20 and 200°C, and preferably between 30 and 100°C. The effluent leaving HDF is then sent to the distillation line.
In the first preferred embodiment of the process according to the invention including a preliminary hydroconversion/hydroisomerization stage, the base oils obtained have a pour point below -10°C, a VI above 95, preferably above 110 and still more preferably above 120, a viscosity of at least 3.0 cSt at 100°C, an ASTM colour below 1 and a UV stability such that the increase in ASTM colour is between 0 and 4 and preferably between 0.5 and 2.5.
Another advantage of this embodiment of the process according to the invention is that it is possible to achieve very low aromatics contents, below 2 wt.%, preferably below 1 wt.% and better still below 0.05 wt.% and even to go as far as the production of medicinal-grade white oils having aromatics contents below 0.01 wt.%. These oils have
UV absorbance values at 275, 295 and 300 nanometres below 0.8, 0.4 and 0.3 respectively (ASTM process D2008) and a Saybolt colour between 0 and 30.
Particularly interestingly, therefore, the process according to the invention also makes it possible to obtain medicinal white oils. Medical white oils are mineral oils obtained by thorough refining of petroleum; their quality is subject to various regulations that are intended to guarantee their harmlessness for pharmaceutical applications, they are non- toxic and are characterized by their density and their viscosity. Medicinal white oils essentially comprise saturated hydrocarbons, they are chemically inert and their aromatic hydrocarbons content is low. Particular attention is given to aromatic compounds and in particular to 6 polycyclic aromatic hydrocarbons (PAH) which are toxic and present at concentrations of one part per billion by weight of aromatic compounds in white oil. The total aromatics content can be monitored using the ASTM process D2008; this UV absorption test at 275, 292 and 300 nanometres makes it possible to monitor an absorbance below 0.8, 0.4 and 0.3 respectively (i.e. the white oils have aromatics contents below 0.01 wt.%). The measurements are effected with concentrations of 1 g of oil per litre, in a 1 cm cell. The white oils on the market vary in viscosity and according to the crude from which they were obtained, which can be paraffinic or naphthenic, and these two parameters will lead to differences both in the physicochemical properties of the white oils in question and in their chemical composition.
In a second preferred embodiment, the dewaxing process of the present invention is used advantageously in the following sequence of stages: - the charge to be treated is separated (D1) into at least one light fraction 3 with a boiling point below 380°C, and at least one heavy fraction 4 (residue), - said light fraction 3, hydrogenated if necessary in a hydrotreatment (HDT) stage, is subjected to hydroisomerization (HISM), - said heavy fraction 4 is subjected to a hydrocracking (HCK) stage in the presence of hydrogen, and is then subjected to distillation (D2) to produce at least one light fraction (13) and at least one heavy fraction (10), - the mixture resulting from hydroisomerization (HISM) is fractionated (D3) at the same time as at least a proportion of the light fraction 13 obtained from distillation D2 to obtain middle distillates having excellent low-temperature properties, and/or a high cetane number and/or reduced emission of pollutants, - the heavy fraction from D2 is subjected to a dewaxing (DWX) stage to obtain, after separation of the volatile products that formed, an isomerized liquid product that can be used as a high-grade lubricant base, and the dewaxing process is the process according to the invention.
This especially preferred form of sequence including the process according to the present invention is shown schematically by the diagram in Fig. 1.
A liquid stream 1 consisting of a mixture of linear hydrocarbons from a Fischer-Tropsch synthesis process, also containing unsaturated products (linear olefins), in an amount up to 10 wt.%, preferably from 2 to 5 wt.%, and oxidized products (especially alcohols)
in an amount up to 10 wt.%, preferably from 2 to 7 wt.%, is separated in a distillation column D1 into a light fraction 3 with a boiling point below 380°C, preferably between 260 and 360°C and a heavy fraction 4, which constitutes the distillation residue. The distillation in D1 is preferably carried out in a single stage (flash) and can be followed by differential offtake of two fractions directly from the Fischer-Tropsch synthesis reactor.
Preferably, the mass ratio between the two fractions 3 and 4 is in the range from 0.5to 2.0, even more preferably from 0.8 to 1.5.
Light fraction 3 will be the feed for a hydroisomerization (HISM) unit. However, especially In the case where heteroatoms or unsaturated groups, and oxidized compounds in particular, are present and could constitute a problem for the proper functioning of the catalyst in this stage, said fraction 3 will preferably feed a hydrogenation (HDT) unit in which it comes into contact with hydrogen (line 2) in the presence of a suitable catalyst, in conditions such as to minimize or even eliminate the hydrocracking reaction.
The hydrogenation unit (HDT) can be effected by the usual methods and comprises preferentially a reactor under pressure containing a fixed bed of catalyst chosen for meeting the aforementioned specifications. Typical hydrogenation catalysts meeting the above specifications comprise a hydrogenating metal, such as nickel, platinum or palladium supported on an inert or acidic solid such as alumina, silica, silica-alumina, zeolite or molecular sieve. Occurrence of a hydroisomerization reaction and partial hydrocracking during hydrogenation is not excluded, but is generally limited to conversion of less than 15 wt.% of the total feed fraction. The small fraction of volatile compounds (150°C-) and water that may be formed, can if necessary be separated by means of a distillation operation.
The light fraction, hydrogenated or not, on a second occasion, is then subjected to a stage of hydroisomerization (HISM) by means of line 6, in which it will react, still in the presence of hydrogen, in the usual conditions making it possible to achieve deep isomerization and partial rupture of the linear hydrocarbon chains. The appropriate conditions for isomerization are extensively reported in the state of the art as well as an extensive list of suitable catalysts.
A portion normally less than 50%, preferably between 0 and 25%, of said light fraction can if necessary be taken by means of line 7, before the isomerization stage and mixed again with said heavy fraction from line 4 to be sent to hydrocracking.
In said isomerization stage, typically the hydrocarbon mixture is supplemented with hydrogen (line 5) in an amount between 150 and 1500 normal litres per litre of liquid and passes over a fixed bed of a suitable catalyst, preferentially based on noble metal, at an hourly space velocity between 0.1 and 10 h! and a temperature between 300 and 450°C and a pressure between 1 and 10 MPa.
The isomerized mixture is introduced via line 14 into a fractionating column D3 with light fraction 13 from column D2 of distillation of the heavy fraction sent for hydrocracking. In accordance with the embodiment, a middle distillate is obtained at the outlet of column
D3, and is if necessary taken off at two different levels to separate the kerosene (line 17) from the gasoil (line 18), having excellent low-temperature properties, a high cetane number, preferably above 50 and reduced emission of pollutants.
Smaller amounts of low molecular weight products are also obtained at the outlet of the distillation and fractionating column D3, in particular, via line 15, a gaseous fraction C1-
C5, relatively of little significance, normally via line 16, a light hydrocarbon fraction, preferably having a boiling point below 150°C (naphtha).
According to a particularly advantageous aspect of this embodiment of the present invention, the amount of these volatile fractions is reduced significantly in comparison with the similar methods of the prior art, preferably to less than 20 wt.%, more preferably to less than 15 wt.% relative to the initial feed of line 1.
The fraction (line 4) of hydrocarbons with high boiling point and with low content of oxidized and unsaturated compounds is supplemented with the necessary amount of hydrogen (line 8) and provides the feed for a hydrocracking (HCK) unit, employing the usual techniques. The product obtained will feed, via line 9, a device for distillation and fractionation, which operates in a preferred manner to obtain separation of the hydrocarbon mixture essentially into two fractions. A light fraction, having a boiling point below 380°C, preferably below 350°C and containing less than 10 wt.% of volatile compounds (150°C-), consisting of a product having a high concentration of iso- paraffins, which will feed, via line 13, the stage for fractionation of the light fraction isomerized in HISM. This combining of the two streams, which come from the stages carried out on the initial feed and in different, but complementary conditions, makes it possible advantageously to obtain kerosene and gasoil fractions with the excellent properties mentioned previously. In this case, a portion, preferably less than 50 wt. %, of the mixture obtained from distillation D2 is fed via line 19 to the inlet of the isomerization stage (HISM) for further enhancement of the grade and distribution of the isomerized fractions and for controlling the relative amount of gasoil and kerosene produced.
The residual fraction from distillation D2 consists of a mixture of high boiling point hydrocarbons surprisingly having a reduced content of waxes, relative to the products obtained with other catalysts of the prior art in similar conditions. Said residue can also be used "as is" for special uses, but will preferably feed (line 10) a stage of catalytic dewaxing (DWX) prior to its use as lubricant base. According to a preferred embodiment, the latter is partly recycled to the hydrocracking stage (HCK) via line 12 in order to control the productivity of the process or vary the degree of isomerization according to the production requirements.
Said dewaxing stage (DWX) is carried out according to the process of the present invention in the presence of a catalyst that is appropriate to the required objective. The partially isomerized mixture will further react in the presence of hydrogen and a suitable solid catalyst as described previously, in the conditions of the process according to the invention.
Advantageously, as the amounts of linear paraffins have been reduced, the dewaxing stage according to the process of the present embodiment can be carried out in particularly favourable conditions of contact time and yield of lubricant base.
At the end of this dewaxing stage, the volatile products that formed are separated (generally less than 3 wt.%), and an isomerized liquid product is recovered (line 11), with excellent low-temperature properties and a high viscosity, having an initial boiling point above 350°C, preferably above 360°C and having an optimum composition for use as a high-grade lubricant base.
The examples given below illustrate the invention though without limiting its scope.
Example 1: Preparation of a dewaxing catalyst C1 according to the invention
Catalyst C1 contains a ZSM-22 zeolite and a ZBM-30 zeolite. This catalyst is obtained in accordance with the procedure described below.
The ZSM-22 zeolite is obtained by the synthetic procedure described in the article in
Applied Catalysis, 1989, 48, page 137 and the ZBM-30 zeolite is synthesized according to BASF patent EP-A-46504 with the organic structuring agent triethylenetetramine.
The raw ZSM-22 and ZBM-30 zeolites as synthesized are calcined at 550°C under a stream of dry air for 12 hours. Then the ZSM-22 solid obtained is subjected to 4 successive ion exchanges in a solution of NH4sNO; 10N, at approximately 100°C for 4 hours for each exchange.
The H-ZSM-22 zeolite in acidic form thus obtained has a Si/Al ratio equal to 30 and a
Na/Al ratio equal to 0.003. The H-ZBM-30 zeolite (acidic form) thus obtained has a Si/Al ratio of 45 and a Na/Al ratio below 0.001.
Then 30 grams of H-ZSM-22 zeolite in the form of powder is mixed with 70 grams of H- 7ZBM-30 zeolite. Then the mixture of the two zeolites is kneaded with a type SB3 alumina gel (supplied by the company Condéa) previously peptized with an aqueous solution containing 68 wt.% nitric acid and kneaded for 15 minutes. The kneaded paste (alumina gel + zeolites) is then extruded through a 1.4 mm diameter die. The extrudates thus obtained are calcined at 500°C for 2 hours in air. The content by weight of ZSM-22 zeolite in the support extrudates is 24% and that of the H-ZBM-30 zeolite is 56% giving a total content of zeolites of 80 wt.%.
Then the support extrudates undergo a stage of dry impregnation with an aqueous solution of the platinum salt Pt(NH;)42+.20H-, then calcined in dry air at 550°C. The platinum content by weight in the catalyst C1 thus obtained is 0.48%.
Example 2: Use of catalyst C1 for improving the pour point of a charge resulting from the Fischer-Tropsch process
Catalyst C1, preparation of which is described in example 1, is used for improving the pour point of a charge consisting of paraffins obtained from Fischer-Tropsch synthesis : for the purpose of obtaining oils. With this aim and within the non-exhaustive scope of this example, the Fischer-Tropsch paraffins obtained from the paraffin production unit are distilled to obtain a 370°C+ cut. The main characteristics of the charge thus obtained are as follows: initial point 356°C 5% point 370°C 10% point 383°C 30% point 399°C 50% point 424°C 80% point 509°C 90% point 568°C 95% point 631°C pour point + 88°C density (20/4) 0.789
The catalytic testing unit comprises a fixed-bed reactor, with ascending circulation of the charge ("up-flow"), in which 80 ml of catalyst C1 is placed. The catalyst is then subjected to an atmosphere of pure hydrogen at a pressure of 10 MPa to effect reduction of the platinum oxide to metallic platinum then the charge is finally injected.
The total pressure is 10 MPa, the hydrogen flow rate is 1000 litres of gaseous hydrogen per litre of charge injected, the hourly space velocity is 1.1 h"' and the reaction temperature is 340°C. After reaction, the effluents are fractionated into light products (P1-150°C gasoline), middle distillates (150-370°C) and residue (370°C).
The following table shows the yields for the various fractions and the characteristics of the oils obtained directly with the charge and with the effluents hydroisomerized on catalyst C1 (according to the invention) then dewaxed catalytically.
According to the
Raw conversion to | 58.8 el
Distribution by fractions
Yield PI-370°C (wt.%)
Oil grade (fraction 370°C+)
It can be seen very clearly that the charge treated with the catalyst (C1) according to the invention leads to an oil fraction (370°C+) whose pour point is much lower than that of the charge yet it still has a high viscosity index.
Example 3: Preparation’ of pretreatment catalyst C2 and of hydrodewaxing catalyst C3 according to the invention
The catalyst for the pretreatment stage C2 is prepared from a silica-alumina support used in the form of extrudates. It contains 40 wt.% of silica SiO, and 60 wt.% of alumina
Al,O;. Before the noble metal is added, the silica-alumina has a surface area of 332 m?/g and its total pore volume is 0.82 ml/g.
Catalyst C2 is obtained after impregnation of the noble metal on the support. The platinum salt ClgH,Pt is dissolved in a volume of solution corresponding to the total pore volume to be impregnated. The solid is then calcined for 2 hours in air at 500°C. The platinum content is 0.48 wt.%. Measured on the catalyst, the BET surface area is equal to 310 m*/g. The dispersion of the platinum measured by H,/O, titration is 75%.
The hydrodewaxing catalyst C3 comprises a ZSM-22 zeolite and a ZBM-30 zeolite. This catalyst is obtained in accordance with the procedure described below.
The ZSM-22 zeolite is obtained by the synthetic procedure described in the article in
Applied Catalysis, 1989, 48, page 137 and the ZBM-30 zeolite is synthesized according to BASF patent EP-A-46504 with the organic structuring agent triethylenetetramine.
The raw ZSM-22 and ZBM-30 zeolites as synthesized are calcined at 550°C under a stream of dry air for 12 hours. Then the ZSM-22 solid obtained is subjected to 4 successive ion exchanges in a solution of NHsNO3 10N, at approximately 100°C for 4 hours for each exchange.
The H-ZSM-22 zeolite in acidic form thus obtained has a Si/Al ratio equal to 30 and a
Na/Al ratio equal to 0.003. The H-ZBM-30 zeolite (acidic form) thus obtained has a Si/Al ratio of 45 and a Na/Al ratio below 0.001.
Then 30 grams of H-ZSM-22 zeolite in the form of powder is mixed with 70 grams of H-
ZBM-30 zeolite. Then the mixture of the two zeolites is kneaded with a type SB3 alumina ge! (supplied by the company Condéa) previously peptized with an aqueous solution containing 68 wt.% nitric acid and kneaded for 15 minutes. The kneaded paste (alumina gel + zeolites) is then extruded through a 1.4 mm diameter die. The extrudates thus obtained are calcined at 500°C for 2 hours in air. The content by weight of ZSM-22 zeolite in the support extrudates is 24% and that of the H-ZBM-30 zeolite is 56% giving a total content of zeolites of 80 wt.%.
Then the support extrudates undergo a stage of dry impregnation with an aqueous solution of the platinum salt Pt(NH;)42+.20H-, then calcined in dry air at 550°C. The platinum content by weight in the catalyst C2 thus obtained is 0.51%.
Example 4: Use of catalyst C3 for improving the pour point of a paraffinic Fischer-
Tropsch charge pretreated on catalyst C2 (for converting hydroisomerization)
Catalyst (C2), the preparation of which is described in Example 3, is used for pretreating a charge of paraffins obtained from Fischer-Tropsch synthesis for the purpose of obtaining oils. The paraffinic charge used in this example is the same as that used and described in Example 2.
The catalytic testing unit comprises a fixed-bed reactor, with ascending circulation of the charge ("up-flow"), in which 80 ml of catalyst C2 is placed. The catalyst is then subjected to an atmosphere of pure hydrogen at a pressure of 10 MPa to effect reduction of the platinum oxide to metallic platinum then the charge is finally injected.
The total pressure is 10 MPa, the hydrogen flow rate is 1000 litres of gaseous hydrogen per litre of charge injected, the hourly space velocity is 1.0 h! and the reaction temperature is 350°C. After reaction, the effluents are fractionated into light products (P1-150°C gasoline), middle distillates (150-370°C) and residue (370°C).
The residue (3707°C) is then treated, in order to lower its pour point, in a second reactor with ascending circulation of the charge ("up-flow"), in which 80 ml of catalyst C3 is placed. The catalyst is then subjected to an atmosphere of pure hydrogen at a pressure of 10 MPa to effect reduction of the platinum oxide to metallic platinum then the charge is finally injected. The total pressure is 10 MPa, the hydrogen flow rate is 1000 litres of gaseous hydrogen per litre of charge injected, the hourly space velocity is 1.0 h! and the reaction temperature is 330°C. After reaction, the effluents are fractionated into light products (Pi-150°C gasoline), middle distillates (150-370°C) and oil fraction (370°C).
The characteristics of the oil obtained are measured.
The following table shows the yields for the various fractions and the characteristics of the oils obtained directly with the charge and with the effluents pretreated on catalyst C2 then dewaxed on catalyst C3 according to the invention.
Hydroisomerized Effluent effluent hydroisomerized and dewaxed catalytically on C3
Raw conversion to] 40.5 28.7
Ee A
Distribution by fractions
Yield PI-370°C (wt.%)
Oil grade (fraction 370°C+) *Yields in the catalytic dewaxing stage
It can be seen very clearly that carrying out a stage of pretreatment of the charge on the hydroisomerization-conversion catalyst C2 followed by treatment on catalyst C3 (according to the invention) makes it possible to achieve pour points that are far lower than those obtained with just the pretreatment catalyst C2 or the catalyst C1 (see the table in Example 2). Moreover, we can also see that the use of a pretreatment stage, upstream from catalyst C3 according to the invention, makes it possible to obtain a yield of oil fraction 370°C+ having a pour point of -24°C at a yield of 42.4 wt.% whereas the catalyst C1 (according to the invention) used does not permit the production of an oil fraction with such a low pour point (it is only -13°C) and the yield of this oil fraction is lower 41.2% (cf. table in Example 2). Finally, the viscosity index and the VI of the oil fraction obtained with the pretreatment stage C2 and catalyst C3 according to the invention are higher than in the absence of the pretreatment stage (cf. table in Example
Claims (13)
1. Process for improving the pour point of a charge resulting from the Fischer-Tropsch process in which the charge to be treated is brought into contact with a catalyst containing at least one zeolite chosen from the group comprising the zeolites of structural type TON (Theta-1, ZSM-22, ISI-1, NU-10 and KZ-2) and at least one ZBM-30 zeolite synthesized in the presence of triethylenetetramine, at least one hydro-dehydrogenating element and at least one porous mineral matrix.
2 Process according to claim 1 in which the hydro-dehydrogenating element is chosen from the elements of Group VIB and Group VIII of the periodic table.
3 Process according to claim 2 in which the hydro-dehydrogenating element of Group VIB is molybdenum and/or tungsten.
4 Process according to one of the claims 2 to 3 in which the hydro-dehydrogenating element of Group Vil is a Group Vill noble metal.
5. Process according to claim 4 in which the hydro-dehydrogenating element of Group Vil is platinum and/or palladium. :
6. Process according to one of the claims 1 to 5 in which the charges treated have at least 50 vol.% of compounds boiling above 340°C.
7 Process according to one of the claims 1 to 6 in which the operating conditions are as follows: - the reaction temperature is between 200 and 450°C, . the pressure is between 0.1 and 25 MPa. - the hourly space velocity (HSV expressed as volume of charge injected per unit volume of catalyst per hour) is between approximately 0.05 and approximately 30 ht.
8. Process according to one of the claims 1 to 7 in which the charge undergoes a stage of hydroisomerization-hydroconversion before it is treated.
9. Process according to claim 8 in which the effluent from the stage of hydroisomerization-conversion is sent in its entirety to the dewaxing stage.
10. Process according to one of the claims 8 and 9 in which the stage of hydroisomerization-hydroconversion is preceded by a hydrorefining stage.
11. Process according to claim 10 in which the hydrorefining stage is followed by an intermediate separation.
12. Process according to one of the claims 1 to 11 in which the effluent leaving the catalytic hydrodewaxing stage is sent at least partially over a hydrofinishing catalyst.
13. Process in which the following stages are carried out: - the charge to be treated is separated (D1) into at least one light fraction 3 with a boiling point below 380°C, and at least one heavy fraction 4 (residue), - said light fraction 3 hydrogenated if necessary in a hydrotreatment (HDT) stage is subjected to hydroisomerization (HISM), . said heavy fraction 4 is subjected to a stage of hydrocracking (HCK) in the presence of hydrogen, and is then subjected to distillation (D2) to produce at least one light fraction (13) and at least one heavy fraction (10), - the mixture obtained from hydroisomerization (HISM) is fractionated (D3) at the same time as at least a proportion of the light fraction 13 coming from distillation D2 to obtain middle distillates having excellent low-temperature properties, and/or a high cetane number and/or reduced emission of pollutants, _ the heavy fraction leaving D2 is subjected to a stage of dewaxing (DWX) to obtain, after separation of the volatile products that have formed, an isomerized liquid product that can be used as a high-grade lubricant base,
and the dewaxing process is the process according to one of the claims 1 to 7.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0308153A FR2857020B1 (en) | 2003-07-03 | 2003-07-03 | METHOD FOR IMPROVING THE FLOW POINT OF HYDROCARBON LOADS FROM THE FISCHER-TROPSCH PROCESS USING A CATALYST BASED ON A ZEOLITH MIXTURE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ZA200509837B true ZA200509837B (en) | 2007-02-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| ZA200509837A ZA200509837B (en) | 2003-07-03 | 2005-12-05 | Process for improving the pour point of hydrocarbon charges resulting from the Fischer-Tropsch process, using a catalyst based on a mixture of zeolites |
Country Status (6)
| Country | Link |
|---|---|
| DE (1) | DE112004001058B4 (en) |
| FR (1) | FR2857020B1 (en) |
| IT (1) | ITMI20041313A1 (en) |
| RU (1) | RU2346977C2 (en) |
| WO (1) | WO2005012461A1 (en) |
| ZA (1) | ZA200509837B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108816279A (en) * | 2018-05-23 | 2018-11-16 | 中国中化股份有限公司 | A kind of preparation method of n-alkane catalyst for hydroisomerizing |
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| US8940253B2 (en) | 2012-03-29 | 2015-01-27 | Uop Llc | Process and apparatus for producing diesel from a hydrocarbon stream |
| US8871082B2 (en) * | 2012-03-29 | 2014-10-28 | Uop Llc | Process and apparatus for producing diesel from a hydrocarbon stream |
| CA2877172A1 (en) * | 2012-06-28 | 2014-01-03 | Shell Internationale Research Maatschappij B.V. | Process to prepare a gas oil fraction and a residual base oil |
| RU2490307C1 (en) * | 2012-10-01 | 2013-08-20 | Андрей Владиславович Курочкин | Oil processing method |
| RU2515938C1 (en) * | 2013-04-24 | 2014-05-20 | Андрей Владиславович Курочкин | Oil refining method |
| WO2015080611A1 (en) | 2013-11-26 | 2015-06-04 | Infra XTL Technology Limited | Catalyst for direct production of isoparaffin-rich synthetic oil and method for preparing catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3031557C2 (en) * | 1980-08-21 | 1986-05-22 | Basf Ag, 6700 Ludwigshafen | Crystalline borosilicate zeolite ZBM-30 and process for its preparation |
| FR2805762B1 (en) * | 2000-03-02 | 2004-01-16 | Inst Francais Du Petrole | ZEOLITE ZSM-48 CATALYST AND METHOD FOR IMPROVING THE FLOW POINT OF PARAFFINIC LOADS |
| FR2808028B1 (en) * | 2000-04-21 | 2003-09-05 | Inst Francais Du Petrole | FLEXIBLE PROCESS FOR PRODUCING OIL BASES WITH A ZSM-48 ZEOLITE |
| FR2818285B1 (en) * | 2000-12-15 | 2004-12-17 | Inst Francais Du Petrole | IMPROVED FLEXIBLE PROCESS FOR PRODUCING OIL BASES AND DISTILLATES BY A HYDROISOMERIZATION CONVERSION ON A LOW-DISPERSE CATALYST FOLLOWED BY CATALYTIC DEPAINTING |
| FR2818284B1 (en) * | 2000-12-15 | 2006-08-04 | Inst Francais Du Petrole | IMPROVED FLEXIBLE PROCESS FOR THE PRODUCTION OF OIL BASES AND MEDIUM DISTILLATES WITH CONVERSION-HYDROISOMERIZATION FOLLOWED BY CATALYTIC DEPARAFFINING |
-
2003
- 2003-07-03 FR FR0308153A patent/FR2857020B1/en not_active Expired - Lifetime
-
2004
- 2004-06-30 IT ITMI20041313 patent/ITMI20041313A1/en unknown
- 2004-07-02 WO PCT/FR2004/001715 patent/WO2005012461A1/en active Search and Examination
- 2004-07-02 RU RU2006103076/04A patent/RU2346977C2/en not_active IP Right Cessation
- 2004-07-02 DE DE112004001058T patent/DE112004001058B4/en not_active Expired - Fee Related
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108816279A (en) * | 2018-05-23 | 2018-11-16 | 中国中化股份有限公司 | A kind of preparation method of n-alkane catalyst for hydroisomerizing |
| CN108816279B (en) * | 2018-05-23 | 2021-03-16 | 中国中化股份有限公司 | Preparation method of normal paraffin hydroisomerization catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2857020A1 (en) | 2005-01-07 |
| DE112004001058T5 (en) | 2006-04-27 |
| WO2005012461A1 (en) | 2005-02-10 |
| FR2857020B1 (en) | 2007-08-17 |
| RU2346977C2 (en) | 2009-02-20 |
| ITMI20041313A1 (en) | 2004-09-30 |
| RU2006103076A (en) | 2006-06-10 |
| DE112004001058B4 (en) | 2009-04-23 |
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