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
  • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
  • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
  • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
  • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
  • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
  • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
• • 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
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
• • 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
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
  • C10G11/04—Oxides
  • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
• • 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
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
  • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1022—Fischer-Tropsch products
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/1048—Middle distillates
  • C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4006—Temperature
• • 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
  • C10G2400/06—Gasoil

Definitions

• the invention relates to a process to prepare a gas oil, in combination with a gasoline, by catalytic cracking of a Fischer-Tropsch product.
• Background of the invention It is known that paraffinic products boiling in the gas oil range can be prepared from a Fischer-Tropsch derived synthesis product.
• step (b) contacting the heavier fraction with a catalyst system comprising a catalyst, which catalyst comprises an acidic matrix and a large pore molecular sieve in a riser reactor at a temperature of between 450 and 650 °C at a contact time of between 1 and 10 seconds and at a catalyst to oil ratio of between 2 and 20 kg/kg, (c) isolating from the product of step (b) a second gas oil fraction; (d) combining the first gas oil fraction with the second gas oil.
• a catalyst system comprising a catalyst, which catalyst comprises an acidic matrix and a large pore molecular sieve in a riser reactor at a temperature of between 450 and 650 °C at a contact time of between 1 and 10 seconds and at a catalyst to oil ratio of between 2 and 20 kg/kg
• the first gas oil fraction, obtained in step (a) will improve the cetane number of the second gas oil obtained by catalytically cracking a Fischer-Tropsch synthesis product.
• a relatively heavy Fischer-Tropsch product is used as feed to the catalytic cracking step (b) .
• the enrichment of the catalytically cracked gas oil fraction with paraffins, as obtained in step (a) increases the cetane number to the level that makes the gas oil suitable as a diesel fuel blend component.
• Another advantage is that use can be made of well-known processes known for fluid catalytic cracking (FCC) , step (b) .
• FCC fluid catalytic cracking
• the Fischer-Tropsch synthesis product may in principle be any reaction product as obtained when performing the well know Fischer-Tropsch synthesis reaction.
• a relatively heavy Fischer-Tropsch product in step (b) .
• This heavy feed preferably has at least 30 wt%, preferably at least 50 wt%, and more preferably at least 55 wt% of compounds having at least 30 carbon atoms.
• the weight ratio of compounds having at least 60 or more carbon atoms and compounds having at least 30 carbon atoms of the Fischer-Tropsch product is at least 0.2, preferably at least 0.4 and more preferably at least 0.55.
• the Fischer-Tropsch product comprises a C20+ fraction having an ASF-alpha value (Anderson-Schulz-Flory chain growth factor) of at least 0.925, preferably at least 0.935, more preferably at least 0.945, even more preferably at least 0.955.
• the initial boiling point of the Fischer-Tropsch product used in step (b) may suitably range from below 200 up to 450 °C.
• the initial boiling point is between 300 and 450 °C in case all compounds having a boiling point in the gas oil range are separated from the Fischer-Tropsch synthesis product before the Fischer- Tropsch synthesis product is used in step (b) .
• the relatively heavy Fischer-Tropsch synthesis product can be obtained by any process, which yields a relatively heavy Fischer-Tropsch product. Not all Fischer-Tropsch processes yield such a heavy product.
• Preferred processes are the cobalt catalysed Fischer- Tropsch processes.
• An example of a suitable Fischer- Tropsch process is described in O-A-9934917 and in AU-A-698391. These processes may yield a Fischer-Tropsch product as described above.
• a preferred catalyst to be used to obtain the relatively heavy Fischer-Tropsch product is suitably a cobalt-containing catalyst as obtainable by (aa) mixing (1) titania or a titania precursor, (2) a liquid, and (3) a cobalt compound, which is at least partially insoluble in the amount of liquid used, to form a mixture; (bb) shaping and drying of the mixture thus obtained; and (cc) calcination of the composition thus obtained.
• Preferably at least 50 weight percent of the cobalt compound is insoluble in the amount of liquid used, more preferably at least 70 weight percent, and even more preferably at least 80 weight percent, and most preferably at least 90 weight percent.
• the cobalt compound is metallic cobalt powder, cobalt hydroxide or an cobalt oxide, more preferably Co (OH) 2 or C03O .
• the cobalt compound is used in an amount of up to 60 weight percent of the amount of refractory oxide, more preferably between 10 and 40 wt percent.
• the catalyst comprises at least one promoter metal, preferably manganese, vanadium, rhenium, ruthenium, zirconium, titanium or chromium, most preferably manganese.
• the promoter metal (s) is preferably used in such an amount that the atomic ratio of cobalt and promoter metal is at least 4, more preferably at least 5.
• At least one promoter metal compound is present in step (aa) .
• the cobalt compound is obtained by precipitation, optionally followed by calcination.
• the cobalt compound and at least one of the compounds of promoter metal are obtained by co-precipitation, more preferably by co-precipitation at constant pH.
• the cobalt compound is precipitated in the presence of at least a part of the titania or the titania precursor, preferably in the presence of all titania or titania precursor.
• the mixing in step (aa) is performed by kneading or mulling. The thus obtained mixture is subsequently shaped by pelletising, extrusion, granulating or crushing, preferably by extrusion.
• the mixture obtained has a solids content in the range of from 30 to 90% by weight, preferably of from 50 to 80% by weight.
• the mixture formed in step (aa) is a slurry and the slurry thus-obtained is shaped and dried by spray-drying.
• the slurry obtained has a solids content in the range of from 1 to 30% by weight, more preferably of from 5 to 20% by weight.
• the calcination is carried out at a temperature between 400 and 750 °C, more preferably between 500 and 650 °C. Further details are described in O-A-9934917.
• the Fischer-Tropsch process is typically carried out at a temperature in the range from 125 to 350 °C, preferably 175 to 275 °C.
• the pressure is typically in the range from 5 to 150 bar abs., preferably from 5 to 80 bar abs., in particular from 5 to 70 bar abs.
• Hydrogen (H2) and carbon monoxide (synthesis gas) is typically fed to the process at a molar ratio in the range from 0.5 to 2.5.
• the gas hourly space velocity (GHSV) of the synthesis gas in the process of the present invention may vary within wide ranges and is typically in the range from 400 to 10000 Nl/l/h, for example from 400 to 4000 Nl/l/h.
• GHSV is well known in the art, and relates to the volume of synthesis gas in Nl, i.e. litres at STP conditions (0 °C and 1 bar abs) , which is contacted in one hour with one litre of catalyst particles, i.e. excluding interparticular void spaces. In the case of a fixed catalyst bed, the GHSV may also be expressed as per litre of catalyst bed, i.e. including interparticular void space.
• the Fischer-Tropsch synthesis can be performed in a slurry reactor or preferably in a fixed bed. Further details are described in WO-A-9934917.
• Synthesis gas may be obtained by well known processes like partial oxidation and steam reforming and combinations of these processes starting with a (hydro) carbon feedstock.
• feedstocks are natural gas, associated gas, refinery off-gas, residual fractions of crude oil, coal, pet coke and biomass, for example wood.
• Partial oxidation may be catalysed or non- catalyzed.
• Steam reforming may be for example conventional steam reforming, autothermal (ATR) reforming and convective steam reforming.
• suitable partial oxidation processes are the Shell Gasification Process and the Shell Coal Gasification Process.
• the Fischer-Tropsch product will contain no or very little sulphur and nitrogen containing compounds .
• the Fischer-Tropsch product can advantageously be directly used in step (a) without having to hydrotreat the feed to remove olefins and/or oxygenates.
• the catalyst system used in step (b) will at least comprise of a catalyst comprising of a matrix and a large pore molecular sieve.
• suitable large pore molecular sieves are of the faujasite (FAU) type as for example Zeolite Y, Ultra Stable Zeolite Y and Zeolite X.
• the matrix is preferably an acidic matrix.
• the acidic matrix will suitably comprise amorphous alumina and preferably more than 10 wt% of the catalyst is amorphous alumina.
• the matrix may further comprise, for example, aluminium phosphate, clay and silica and mixtures thereof.
• Amorphous alumina may also be used as a binder to provide the matrix with enough binding function to properly bind the molecular sieve.
• suitable catalysts are commercially available catalysts used in fluid catalytic cracking processes which catalysts comprise a Zeolite Y as the molecular sieve and at least alumina in the matrix. The temperature at which feed and catalyst contact is between 450 and 650 °C.
• the temperature is above 475 °C and even more preferably above 500 °C.
• Good gasoline yields are seen at temperatures above 600 °C.
• higher temperatures than 600 °C will give rise to thermal cracking reactions and the formation of non-desirable gaseous products like for example methane and ethane.
• the temperature is more preferably below 600 °C.
• the process may be performed in various types of reactors. Because the coke make is relatively small, as compared to an FCC process operating on a petroleum-derived feed, it is possible to conduct the process in a fixed bed reactor. In order to be able to regenerate the catalyst more simply, preference is nevertheless given to either a fluidised bed reactor or a riser reactor.
• the preferred contact time is between 1 and 10 seconds and more preferred between 2 and 7 seconds.
• the catalyst to oil ratio is preferably between 2 and 20 kg/kg. It has been found that good results may be obtained at low catalyst to oil ratios of below 15 and even below 10 kg/kg. This is advantageous because this means a higher productivity per catalyst resulting in, e.g. smaller equipment, less catalyst inventory, less energy requirement and/or higher productivity.
• the catalyst system may advantageously also comprise of a medium pore size molecular sieve such to also obtain a high yield of propylene and other lower olefins next to the gasoline fraction. It has also been found that the yield to gas oil increases when such medium pore molecular sieves are present.
• Preferred medium pore size molecular sieves are zeolite beta, Erionite, Ferrierite, ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23 or ZSM-57.
• the weight fraction of medium pore crystals on the total of molecular sieves present in this process is preferably between 2 and 20 wt%.
• the medium pore molecular sieve and the large pore molecular sieve may be combined in one catalyst particle or be present in different catalyst particles.
• the large and medium pore molecular sieves are present in different catalyst particles for practical reasons. For example, the operator can thus add the two catalyst components of the catalyst system at different addition rates to the process. This could be required because of different deactivation rates of the two catalysts.
• a suitable matrix is alumina.
• the molecular sieve may be dealu inated by for example steaming or other known techniques. It has been found that the combination of the large pore molecular sieve, more preferably of the FAU type, in combination with the medium pore size molecular sieve, results in a high selectivity to the lower olefins .
• Applicants have found that, by performing the process according the invention with a large pore molecular sieve, more preferably of the FAU type, in combination with the medium pore size molecular sieve, as described above, not only lower olefin yield improves, but also the yield to the iso and normal pentenes and hexenes increases.
• these pentenes and hexenes are preferably oligomerised to compounds boiling in the gas oil range. This is preferred for at least two reasons, namely that the ultimate yield to gas oil increases and also because low octane contributing compounds are removed from the gasoline. Oligomerisation is a well known process and is for example exemplified in US-A-20020111521.
• a second gas oil fraction is isolated from the product of step (b) from the main gasoline product. Isolation of said fractions is suitably performed by means of distillation.
• a gasoline or gasoline fraction is a fraction boiling for more than 90 wt% between 25 and 215 °C, preferably boiling for more than 95 wt% in said boiling range.
• a gas oil or gas oil fraction is a fraction boiling for more than 90 wt% between 200 and 370 °C, preferably boiling for more than 90 wt% between 215 and 350 °C.
• the first and second gas oil fraction may separately or in a mixture be subjected to an additional catalytic dewaxing step in order to reduce the pour point to an acceptable level if required.
• Such a treatment is not only advantageous for reducing the pour point but will also decrease the content of any aromatic compounds formed in step (a) .
• the pour point is preferably below -10 °C and even more preferably below -15 °C.
• Catalytic gas oil dewaxing may suitably be performed using a catalyst comprising a binder, a molecular sieve and a hydrogenation metal component.
• the binder may be any binder, suitably alumina, silica-alumina or silica.
• the molecular sieve is preferably a zeolite or a silica- aluminophosphate (SAPO) material.
• SAPO silica- aluminophosphate
• the zeolites preferably have a pore diameter of between 0.35 and 0.8 nm.
• Suitable intermediate pore size zeolites are mordenite, Zeolite Beta, ZSM-5, ZSM-12, ZSM-22, ZSM-23, MCM-68, SSZ-32, ZSM-35 and ZSM-48.
• Preferred silica-aluminophosphate (SAPO) materials are SAPO-11.
• the hydrogenation component is preferably a Group VIII metal, more preferably nickel, cobalt, platinum or palladium. Most preferably the noble metal Group VIII metals are used.
• Catalytic dewaxing conditions are known in the art and typically involve operating temperatures in the range of from 200 to 500 °C, suitably from 250 to 400 °C, hydrogen partial pressures in the range of from 10 to 200 bar, preferably from 15 to 100 bar, weight hourly space velocities (WHSV) in the range of from 0.1 to 10 kg of oil per litre of catalyst per hour (kg/l/hr) , suitably from 0.2 to 5 kg/l/hr, more suitably from 0.5 to 3 kg/l/hr and hydrogen to oil ratios in the range of from 100 to 2,000 litres of hydrogen per litre of oil.
• WHSV weight hourly space velocities
• Examples of suitable dewaxing processes and catalysts are described in WO-A-200029511 and EP-B-832171.
• Examples A-D A Fischer-Tropsch product having the properties as listed in Table 1 was contacted with a hot regenerated catalyst at different temperatures and contact times at a catalyst to oil ratio of 4 kg/kg.
• the catalyst was a commercial FCC catalyst comprising an alumina matrix and Ultra Stable Zeolite Y, which had been obtained from a commercially operating FCC unit.
• the Zeolite Y content was 10 wt%.
• the operating conditions are presented in Table 3.
• Examples 1-4 A Fischer-Tropsch product having the properties as listed in Table 2 was contacted with a hot regenerated catalyst at different temperatures and contact times as in Examples A-D.
• the Fischer-Tropsch product was obtained according to Example VII using the catalyst of Example III of WO-A-9934917.
• the operating conditions are presented in Table 3. Table 2
• the feed in Table 5 can be obtained from the feed in Table 2, by removing 22 wt% of the gas oil and lighter fraction of Table 1.
• the yields are presented in Table 6.
• the gas oil yields are higher than the yields in Examples 2-4, but considerably lower than the sum. of the gas oil yields from Examples 2-4 and the 9 wt% (on total feed) gas oil that can be recovered from the fraction of Table 1, and blended with the gas oil fractions obtained in Examples 2-4, according to the invention.
• Example 8 Example 6 was repeated except that part of the catalyst was exchanged for a 25 wt% ZSM-5 containing catalyst.
• the content of ZSM-5 based catalyst on the whole catalyst charge was 20 wt% (as calculated on the total catalyst weight).
• the gasoline yield was 47.99 wt%, and the middle distillate yield 9.27 wt% on total product.
• the content of normal and iso-pentenes was 54.61 wt% in the gasoline fraction.
• Example 9 Example 2 was repeated except that part of the catalyst was exchanged for a 25 wt% ZSM-5 containing catalyst.
• the content of ZSM-5 based catalyst on the whole catalyst charge was 20 wt% (as calculated on the total catalyst weight) .
• Table 7 The results are presented in Table 7.
• Example 10 Example 3 was repeated except that part of the catalyst was exchanged for a 25 wt% ZSM-5 containing catalyst.
• the content of ZSM-5 based catalyst on the whole catalyst charge was 20 wt% (as calculated on the total catalyst weight) .
• the results are presented in Table 7.
• Examples 8-10 show that the addition of ZSM-5 increases gas oil yields.

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• Organic Chemistry (AREA)
• Crystallography & Structural Chemistry (AREA)
• Catalysts (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2005
  • 2005-05-25 US US11/597,441 patent/US20070227946A1/en not_active Abandoned
  • 2005-05-25 RU RU2006146060/04A patent/RU2388791C2/ru not_active IP Right Cessation
  • 2005-05-25 WO PCT/EP2005/052391 patent/WO2005118747A1/en active Application Filing
  • 2005-05-25 JP JP2007513930A patent/JP4955541B2/ja not_active Expired - Fee Related
  • 2005-05-25 BR BRPI0510476-9A patent/BRPI0510476A/pt not_active IP Right Cessation
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