Method for the production of middle distillates by hydroisomerisation et hydrocracking of charges arising from the Fischer-Tropsch method
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C10G-047/10
C10G-047/12
출원번호
UP-0543494
(2004-01-16)
등록번호
US-7704378
(2010-05-20)
우선권정보
FR-03 00945(2003-01-27)
국제출원번호
PCT/FR2004/000101
(2004-01-16)
§371/§102 date
20050727
(20050727)
국제공개번호
WO04/076598
(2004-09-10)
발명자
/ 주소
Benazzi, Eric
Euzen, Patrick
출원인 / 주소
Institut Francais du Petrole
ENI S.p.A.
대리인 / 주소
Millen, White, Zelano & Branigan, P.C.
인용정보
피인용 횟수 :
2인용 특허 :
7
초록▼
The invention relates to a process for preparing middle distillates from a paraffinic feedstock produced by Fischer-Tropsch synthesis, using a hydrocracking/hydroisomerization catalyst which comprises at least one hydrodehydrogenating element chosen from the group formed by the noble elements of Gro
The invention relates to a process for preparing middle distillates from a paraffinic feedstock produced by Fischer-Tropsch synthesis, using a hydrocracking/hydroisomerization catalyst which comprises at least one hydrodehydrogenating element chosen from the group formed by the noble elements of Group VIII of the periodic table, a silica-alumina-based non-zeolitic support obtained from wherein the non-zeolitic silica-alumina based support was obtained from a process comprising starting from a mixture of a partially soluble alumina compound in an acid medium with a totally soluble silica compound or with a totally soluble combination of alumina and hydrated silica, the resultant moldable mixture is concentrated to form a moldable mixture, the resultant mixture is molded and the resultant molded article is subjected to a hydrothermal or thermal treatment.
대표청구항▼
The invention claimed is: 1. Process for preparing middle distillates from a paraffinic feedstock produced by Fischer-Tropsch synthesis, using a hydrocracking/hydroisomerization catalyst which comprises: at least one hydro-dehydrogenating element chosen from the group formed by the noble elements o
The invention claimed is: 1. Process for preparing middle distillates from a paraffinic feedstock produced by Fischer-Tropsch synthesis, using a hydrocracking/hydroisomerization catalyst which comprises: at least one hydro-dehydrogenating element chosen from the group formed by the noble elements of Group VIII of the periodic table. a non-zeolitic silica-alumina-based support containing a quantity greater than 5% by weight and lower than or equal to 95% by weight of silica (SiO2). an average pore diameter, measured by mercury porosimetry, comprised between 20 and 140 Å, a total pore volume, measured by mercury porosimetry, comprised between 0.1 ml/g and 0.6 ml/g, a total pore volume, measured by nitrogen porosimetry comprised between 0.1 ml/g and 0.6 ml/g, a BET specific surface comprised between 100 and 550 m2/g, a pore volume measured by mercury porosimetry, comprised in the pores with a diameter larger than 140 Å, smaller than 0.1 ml/g, a pore volume, measured by mercury porosimetry, comprised in the pores with a diameter larger than 160 Å, smaller than 0.1 ml/g, a pore volume, measured by mercury porosimetry, comprised in the pores with a diameter larger than 200 Å, smaller than 0.1 ml/g, a pore volume, measured by mercury porosimetry, comprised in the pores with a diameter larger than 500 Å, smaller than 0.01 ml/g, an X-ray diffraction diagram which contains at least the main lines characteristic of at least one of the transition aluminas comprised in the group made up of the alpha, rho, chi, eta, gamma, kappa, theta and delta aluminas, wherein the non-zeolitic based support was obtained from a process compromising starting from a mixture of a partially soluble alumina compound in an acid medium with a totally soluble silica compound or with a totally soluble combination to alumina and hydrated silica, the resultant mixture is concentrated to form a moldable mixture, the resultant moldable mixture is molded and the resultant molded article is subjected to a hydrothermal or thermal treatment. 2. A process according to claim 1 wherein in the catalyst the proportion of the octahedral AlVI atoms determined by analysis of the MAS NMR spectra of the 27Al solid is greater than 50%. 3. A process according to claim 1 wherein the catalyst comprises at least one doping element chosen from the group formed by phosphorus, boron and silicon and deposited on the catalyst. 4. A process according to claim 1 in which the catalyst has a cationic impurities content of less than 0.1% by weight. 5. A process according to claim 1 in which the catalyst has an anionic impurities content of less than 0.5% by weight. 6. A process according to claim 1 wherein an X-ray diffraction diagram of the non-zeolitic silica-alumina support contains at least the main lines characteristic of at least one of the transition aluminas comprised in the group made up of the eta, theta, delta and gamma aluminas. 7. A process according to claim 1 using wherein an X-ray diffraction diagram of the non-zeolitic silica alumina support contains at least the main lines characteristic of at least one of the transition aluminas comprised in the group made up of the eta and gamma aluminas. 8. A process according to claim 1 using a catalyst such that: the ratio between the volume V2, measured by mercury porosimetry, comprised between the Daverage−30 Å and the Daverage+30 Å, over the total mercury volume is 0.6. the volume V3, measured by mercury porosimetry, comprised in the pores with diameters greater than Daverage+30 Å, is less than 0.1 ml/g. the volume V6, measured by mercury porosimetry, comprised in the pores with diameters greater than Daverage+15 Å, is less than 0.2 ml/g. 9. A process according to claim 1, such that the average pore diameter of the catalyst is comprised between 40 and 120 Å. 10. A process according to claim 1, such that the compacted filling density of the catalyst is greater than 0.85 g/cm3. 11. A process according to claim 1, such that the acidity of the catalyst support measured by IR monitoring of the thermo-desorption of the pyridine is such that the B/L ratio (ratio of the number of Bronsted sites/number of Lewis sites) is comprised between 0.05 and 1. 12. Process for producing middle distillates from a paraffinic feedstock produced by Fischer-Tropsch synthesis comprising the following successive stages: separation of a single “heavy” fraction with an initial boiling point comprised between 120 and 200° C. a) hydrotreatment of at least part of said heavy fraction, b) fractionation into at least three fractions: at least one intermediate fraction having an initial boiling point T1 comprised between 120 and 200° C., and a final boiling point T2 greater than 300° C. and less than 410° C., at least one light fraction boiling below the intermediate fraction, at least one heavy fraction boiling above the intermediate fraction, c) passage of at least part of said intermediate fraction into a process according to claim 1 on a hydroisomerization/hydrocracking non-zeolitic catalyst, d) passage into a process according to claim 1 on a hydroisomerization/hydrocracking non-zeolitic catalyst, of at least part of said heavy fraction, e) distillation of the hydrocracked/hydroisomerized fractions in order to obtain middle distillates, and recycling of the residual fraction boiling above said middle distillates into Stage (e) on the catalyst treating the heavy fraction. 13. A process for producing middle distillates from a paraffinic feedstock produced by Fischer-Tropsch synthesis comprising the following successive stages: a) separation of at least one light fraction from the feedstock in order to obtain a single “heavy” fraction with an initial boiling point comprised between 120 and 200° C. b) optional hydrotreatment of said heavy fraction, optionally followed by a stage c) of removal of at least part of the water, d) passage into a process according to claim 1 of at least part of said fraction optionally hydrotreated, the conversion on the hydroisomerization/hydrocracking catalyst of the products with boiling points above or equal to 370° C., into products with boiling points below 370° C. is greater than 80% by weight. e) distillation of the hydrocracked/hydroisomerized fraction in order to obtain middle distillates, and recycling into Stage (d) of the residual fraction boiling above said middle distillates. 14. A process for producing middle distillates from a paraffinic feedstock produced by Fischer-Tropsch synthesis comprising the following successive stages: a) Fractionation (Stage a) of the feedstock into at least 3 fractions: at least one intermediate fraction having an initial boiling point T1 comprised between 120 and 200° C., and a final boiling point T2 greater than 300° C. and less than 410° C., at least one light fraction boiling below the intermediate fraction, at least one heavy fraction boiling above the intermediate fraction, b) Hydrotreatment (Stage b) of at least part of said intermediate fraction, then passage (Stage d) into a process of treatment of at least part of the hydrotreated fraction on a hydroisomerization/hydrocracking catalyst, f) Passage (Stage f) into a process of treatment of at least part of said heavy fraction on a hydroisomerization/hydrocracking catalyst, with conversion of the products with boiling points above or equal to 370° C., to products with boiling points below 370° C., greater than 80% by weight. e and g) Distillation (Stages e and g) of at least part of the hydrocracked/hydroisomerized fractions in order to obtain middle distillates, and at least one of said treatment processes is the process according to claim 1. 15. A process for producing middle distillates from a paraffinic feedstock produced by Fischer-Tropsch synthesis comprising the following successive stages: a) optional fractionation of the feedstock into at least one heavy fraction with an initial boiling point comprised between 120 and 200° C., and at least one light fraction boiling below said heavy fraction, b) optional hydrotreatment of at least part of the feedstock or the heavy fraction, optionally followed by a Stage c) c) elimination of at least part of the water, d) passage of at least part of the optionally hydrotreated effluent or fraction into a treatment process on a first hydroisomerization/hydrocracking catalyst containing at least one noble metal of Group VIII, e) distillation of the hydroisomerized/hydrocracked effluent in order to obtain middle distillates (kerosene, diesel oil) and a residual fraction boiling above the middle distillates, f) on a second hydroisomerization/hydrocracking catalyst containing at least one noble metal of Group VIII, passage into a treatment process of at least part of said residual heavy fraction and/or part of said middle distillates and distillation of the resultant effluent in order to obtain middle distillates, and at least one of said treatment processes is the process according to claim 1. 16. A process for producing middle distillates from a paraffinic feedstock produced by Fischer-Tropsch synthesis comprising the following successive stages: a) separation of the feedstock into at least one fraction with a low boiling temperature (B) richer in oxygenated compounds, and at least one fraction with a high boiling temperature (A) less rich in oxygenated compounds; b) subjection of said fraction (B) to a hydrogenating treatment under conditions so as to avoid any substantial variation in its average molecular weight in order to obtain hydrogenated mixture of substantially non-oxygenated hydrocarbons; c) recombination of at least part of said hydrogenated mixture according to Stage (b) with said fraction (A) in order to form a mixture (C) of linear hydrocarbons with a reduced content of oxygenated hydrocarbons and subjection of said mixture (C) to a hydrocracking treatment in the presence of a hydroisomerization/hydrocracking catalyst, in order to convert at least 40% of said fraction with a high boiling point to a fraction of hydrocarbons which can be distilled at a temperature below 370° C.; d) separation of at least one fraction of hydrocarbons from the product obtained in Stage (c), the distillation temperature of which is within the range of the middle distillates; process in which the hydrocracking process of Stage c) is the process according to claim 1. 17. A process according to claim 1, in which the hydrocracking/hydroisomerization catalyst is based on platinum/palladium. 18. Process according to claim 1, in which the hydrocracking/hydroisomerization catalyst contains from 0.05 to 10% of noble metal of Group VIII. 19. A process according to claim 8, wherein the silica content of the silica-alumina-based, non-zeolitic support is between 10 and 50% by weight, the average pore diameter is 50-100 Å, the pore volume measured by mercury porosimetry, comprised in the pores with a diameter larger than 140 Å is less than 0.03 ml/g, the pore volume measured by mercury porosimetry, comprised in the pores with a diameter larger than 160 Å is less than 0.025 ml/g, a pore volume measured by mercury porosimetry, comprised in the pores with a diameter larger than 200 Å is less than 0.025 ml/g. 20. A process according to claim 1, wherein the at least one hydro-dehydrogenating element is platinum. 21. A process according to claim 20, wherein the non-zeolitic silica-alumina based support was obtained from a process comprising starting from a mixture of a partially soluble alumina compound in an acid medium with a totally soluble silica compound the resultant mixture is concentrated to form a moldable mixture, the resultant moldable mixture is molded and the resultant molded article is subjected to a hydrothermal or thermal treatment. 22. A process according to claim 20, wherein the non-zeolitic silica-alumina based support was obtained from a process comprising starting from a mixture of a totally soluble combination of alumina and hydrated silica, the resultant mixture is concentrated to form a moldable mixture, the resultant moldable mixture is molded and the resultant molded article is subjected to a hydrothermal or thermal treatment. 23. A process according to claim 1,wherein the silica-alumina has the following characteristics: a composition of 70% Al2O3-30% SiO2: a BET surface of 242 m2/g, a total pore volume, measured by nitrogen adsorption, of 0.46 ml/g, an average pore diameter, measured by mercury porosimetry, of 67 {acute over (Å)}, a ratio between the volume V2, measured by mercury porosimetry, comprised between the Daverage+30 {acute over (Å)} and the Daverage+30 {acute over (Å)}, over the total mercury volume of 0.9, a volume V3 measured by mercury porosimetry, comprised in the pores with diameters greater than Daverage+30 {acute over (Å)}, of 0.023 ml/g, a volume V6, measured by mercury porosimetry, comprised in the pores with diameters greater than Daverage+15 {acute over (Å)}, of 0.029 ml/g, a ratio between the adsorption surface and the BET surface of 0.83, a pore volume, measured by mercury porosimetry, comprised in the pores with a diameter greater than 140 {acute over (Å)} of 0.0 13 ml/g, a pore volume, measured by mercury porosimetry, comprised in the pores with a diameter greater than 160 {acute over (Å)} of 0.011 ml/g, a pore volume, measured by mercury porosimetry, comprised in the pores with a diameter greater than 200 {acute over (Å)} of 0.062 ml/g, a pore volume, measured by mercury porosimetry, comprised in the pores with a diameter greater than 500 {acute over (Å)} of 0.001 ml/g, a corresponding X-ray diffraction diagram containing at least the main characteristic gamma lines and containing the peaks at a d comprised between 1.39 and 1.40 {acute over (Å)}, and at a d comprised between 1.97 and 2 {acute over (Å)}, a B/L ratio of 0.12, a compacted filling density of the catalyst of 1.08 g/cm3, an atomic sodium content of 200 +/−20 ppm, an atomic sulphur content of 800 ppm, a corresponding MAS NMR spectra of the solid of 27Al of the catalysts having two multiplets of distinct peaks, a first type of aluminium, the maximum of which resonates towards 10 ppm extends between −100 and 20 ppm, whereby it is essentially of AlVI type (octahedral), and a second type of minority aluminium, the maximum of which resonates towards 60 ppm extends between 20 and 100 ppm, wherein this multiplet can be decomposed into at least two species, the predominant species of this multiplet coffesponding to the atoms of AlVI type (tetrahedral), and wherein the proportion of the octahedral AlVI atoms is 70%, and wherein the catalyst contains two silica-alumina zones, said zones have Si/Al ratios less than or greater than the overall Si/Al ratio determined by X-ray fluorescence, and one of the zones has an Si/Al ratio determined by MET of 0.22 and the other zone has an Si/Al ratio determined by MET of 5.8. 24. A process according to claim 1, wherein the silica-alumina has the following characteristics: a composition of 50.12% Al2O3-49.88% SiO2, a BET surface of 254 m2/g, a total pore volume, measured by nitrogen adsorption, of 0.43 ml/g, an average pore diameter, measured by mercury porosimetry, of 65 {acute over (Å)}, a ratio between the volume V2, measured by mercury porosimetry, comprised between the Daverage−30 {acute over (Å)} and the Daverage+30 {acute over (Å)}, over the total mercury volume of 0.91, a volume V3 measured by mercury porosimetry, comprised in the pores with diameters greater than Daverage+30 {acute over (Å)}, of 0.03 ml/g, a volume V6, measured by mercury porosimetry, comprised in the pores with diameters greater than Daverage+15 {acute over (Å)}, of 0.047 ml/g, a ratio between the adsorption surface and the BET surface of 0.76, a pore volume, measured by mercury porosimetry, comprised in the pores with a diameter greater than 140 {acute over (Å)} of 0.015 ml/g, a pore volume, measured by mercury porosimetry, comprised in the pores with a diameter greater than 160 {acute over (Å)} of 0.013 ml/g, a pore volume, measured by mercury porosimetry, comprised in the pores with a diameter greater than 200 {acute over (Å)} of 0.011 ml/g, a pore volume, measured by mercury porosimetry, comprised in the pores with a diameter greater than 500 {acute over (Å)} of 0.001 ml/g, a corresponding X-ray diffraction diagram containing at least the main lines characteristic of gamma alumina and the peaks at a d comprised between 1.39 and 1.40 {acute over (Å)}, and at a d comprised between 1.97 and 2.00 {acute over (Å)}, a B/L ratio of 0.12, a compacted filling density of the catalyst of 1.05 g/cm3, an atomic sodium content of 310 +/−20 ppm, an atomic sulphur content of 1600 ppm, a corresponding MAS NMR spectra of the solid of 27A1 of the catalysts having two multiplets of distinct peaks, a first type of aluminium, the maximum of which resonates towards 10 ppm extends between −100 and 20 ppm, whereby it is essentially of AlVI type (octahedral), and a second type of minority aluminium, the maximum of which resonates towards 60 ppm extends between 20 and 110 ppm, wherein this multiplet can be decomposed into at least two species, the predominant species of this multiplet coffesponding to the atoms of AlIV type (tetrahedral), and wherein the proportion of the octahedral AlVI atoms is 67%, and wherein the catalyst contains two silica-alumina zones, said zones having Si/Al ratios less than or greater than the overall Si/Al ratio determined by X-ray fluorescence, and one of the zones has an Si/Al ratio determined by MET of 0.25 and the other zone has an Si/Al ratio determined by MET of 5.8. 25. A process according to claim 1, wherein the silica-alumina has the following characteristics: a composition of 47.7% Al2O3-52.3% SiO2, a BET surface of 282 m2/g, a total pore volume, measured by nitrogen adsorption, of 0.41 ml/g, an average pore diameter, measured by mercury porosimetry, of 59 {acute over (Å)}, a ratio between the volume V2, measured by mercury porosimetry, comprised between the Daverage−30 {acute over (Å)} and the Daverage+30{acute over (Å)}, over the total mercury volume of 0.90, a volume V3 measured by mercury porosimetry, comprised in the pores with diameters greater than Daverage+30 {acute over (Å)}, of 0.035 ml/g, a volume V6, measured by mercury porosimetry, comprised in the pores with diameters greater than Daverage+15 {acute over (Å)}, of 0.04 ml/g, a ratio between the surface adsorption and the BET surface of 0.75, a pore volume, measured by mercury porosimetry, comprised in the pores with a diameter greater than 140 {acute over (Å)} of 0.011 ml/g, a pore volume, measured by mercury porosimetry, comprised in the pores with a diameter greater than 160 {acute over (Å)} of 0.01 ml/g, a pore volume, measured by mercury porosimetry, comprised in the pores with a diameter greater than 200 {acute over (Å)} of 0.009 ml/g, a pore volume, measured by mercury porosimetry, comprised in the pores with a diameter greater than 500 {acute over (Å)} of 0.001 ml/g, a corresponding X-ray diffraction diagram containing the main lines characteristic of gamma alumina and the peaks at a d comprised between 1.39 and 1.40 {acute over (Å)} , and at a d comprised between 1.97 and 2.00 {acute over (Å)}, a B/L ratio of 0.13, a compacted filling density of the catalyst of 1.07 g/cm3, an atomic sodium content of 300+/−20 ppm, an atomic sulphur content of 1500 ppm, a corresponding MAS NMR spectra of the solid of 27Al of the catalysts having two multiplets of distinct peaks, a first type of aluminium, the maximum of which resonates towards 10 ppm extends between −100 and 20 ppm, whereby it is essentially of 27 AlVI type (octahedral), and a second type of minority aluminium, the maximum of which resonates towards 60 ppm extends between 20 and 110 ppm, wherein this multiplet can be decomposed into at least two species, the predominant species of this multiplet coffesponding to the atoms of AlIV type (tetrahedral), and wherein the proportion of the octahedral AlVI atoms is 67%, and wherein the catalyst contains two silica-alumina zones, said zones having Si/Al ratios less than or greater than the overall Si/Al ratio determined by X-ray fluorescence, and one of the zones has an Si/Al ratio determined by MET of 0.25 and the other zone has an Si/Al ratio determined by MET of 6.
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