Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/90—Regeneration or reactivation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
  • B01J29/7042—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J38/00—Regeneration or reactivation of catalysts, in general
  • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
  • B01J38/12—Treating with free oxygen-containing gas
• • 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
  • C10G11/10—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with stationary catalyst bed
• • 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
  • C10G11/182—Regeneration
• • 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/42—Catalytic treatment
  • C10G3/44—Catalytic treatment characterised by the catalyst used
  • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
  • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
• • 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
• • 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/62—Catalyst regeneration
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
  • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/42—Addition of matrix or binder particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/64—Pore diameter
  • B01J35/647—2-50 nm
• • 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
  • C10G2300/1011—Biomass
  • C10G2300/1014—Biomass of vegetal origin
• • 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
  • C10G2300/1011—Biomass
  • C10G2300/1018—Biomass of animal origin
• • 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
  • C10G2400/02—Gasoline
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

• the invention relates to a process for the preparation of C2-C8 hydrocarbons by cracking catalytically one or more hydrocarbons which have been obtained from natural fat or a derivative thereof.
• Cracking is a refining process involving decomposition and recombination of organic compounds, especially hydrocarbons, affected by heat, pressure and optionally a catalyst, to form molecules suitable for different petrochemicals such as motor fuels. If the cracking is carried out by heat alone, it is called thermal cracking. If a catalyst is used, it is called catalytic cracking.
• Catalytic cracking is carried out by either the fixed, moving or fluid bed technique.
• the feed In the fixed bed technique, the feed is contacted with a fixed layer of catalyst.
• the feed In the moving bed technique, the feed is contacted with a stirred layer of loose catalyst.
• the feed In the fluidized technique, the feed is contacted with small particles of catalyst which are suspended in upwards flowing gas to be handled like a liquid and circulated through pipes and valves between reaction and regeneration vessels.
• catalytic cracking The main purpose of catalytic cracking is to convert heavy distillate into compounds of lower molecular weight in the boiling range of gasoline and middle distillate. An increase in gasoline yield and a raise of the octane number is the primary object.
• the temperature typically ranges from 480 to 510 0 C while the catalyst is regenerated at about 600 to 700 0 C.
• Conventional operating pressures range from 150 to 200 kPa.
• fatty acids and their triglycerides can be hydrogenated with conventional desulphuhzation catalysts to give diesel fuel having good ignition properties.
• hydrogenation is in this publication meant the reation of hydrogen with any organic compound.
• the fatty acid may be a tall oil fatty acid and the triglyceride may be obtained from plant oils such as rapeseed, sunflower and palm oil.
• Fl 100248 discloses the hydrogenation of fatty acids or their triglycerides, based on plant oils such as rapeseed oil, tall oil, sunflower oil palm oil or soybean oil, into n-paraffins, followed by isomerisation of the n-paraffins into paraffins having good cold properties.
• the above documents relate to the preparation of diesel fuel from fatty acids. Effective processes have not been presented for converting natural fat or a derivative thereof into hydrocarbons in the boiling range of gasoline having a high octane number.
• An objective of the invention is therefore to provide a process for the preparation of C2-C8 hydrocarbons from natural fat or derivatives thereof.
• a further object of the invention is to obtain process for the effective conversion into C2-C8 hydrocarbons with as little coke as possible produced.
• Still another object of the invention is to find a catalyst which in addition to above good process properties is also easy to regenerate for further use.
• the invention relates to a process for the preparation of C2- Cs hydrocarbons by cracking catalytically one or more hydrocarbons which have been obtained from natural fat or a derivative thereof.
• the above-mentioned goals of the invention have now been achieved by carrying out the cracking at a temperature between 250 and 450 0 C using a catalyst based on a zeolite and a mesoporous inorganic oxide.
• the temperature of most known catalytic cracking processes typically ranges from 480 to 510 0 C, while the catalyst is regenerated at about 700°C.
• a catalyst comprising a zeolite and a mesoporous inorganic oxide for cracking hydrocarbons from natural fats
• a much lower temperature may be used; only 250 to 450 0 C.
• Such low temperatures give more C2-C8 hydrocarbon product and less decomposed hydrocarbon in the form of coke.
• the regeneration temperature is also very low; just from 0 to 50°C higher than the cracking temperature. See below.
• the starting material i.e. the precursor of the hydrocarbon to be catalytically cracked
• fat is meant one or more solid or liquid glyceryl esters of one or more higher fatty acids.
• fat is genus for, among others butter, tallow, blubber, lard, oil, etc.
• the natural fat used in the invention is selected from the glycerides (mono, di and tri) of C10-C26 fatty acids.
• the starting material is typically an animal or plant fat selected from: the lauric- myristic acid group (Ci2-Ci 4 ) including milk fats, as well as coconut oil, palmseed oil, babassu oil, muscat butter oil, laurel seed oil; from the palmitic acid group (Ci 6 ) including earth animal fats, as well as palm oil and stillingia tallow; the stearic acid group (Ci 8 ) including fats of earth animals, as well as cocoa butter, shea butter and Borneo tallow; the oleic and linoleic acid group (unsatd.
• Cis including whale and fish oils as well as tall oil (fatty acid fraction), olive oil, peanut oil, sesame oil, maize oil, sunflower oil, poppyseed oil, cottonseed oil and soy oil; the linolenic acid group (unsatd. Cis) including whale and fish oils as well as linseed oil, perilla oil and hemp oil; the erucic acid group (unsatd. C22) including whale and fish oils as well as rapeseed oil and mustard seed oil; the eleostearic acid group (conjug. unsatd. Cis) including whale and fish oils as well as Chinese wood oil; and fats with substituated fatty acids (hcinoleic acid, Cis) such as castor oil.
• tall oil fatty acid fraction
• olive oil peanut oil, sesame oil, maize oil, sunflower oil, poppyseed oil, cottonseed oil and soy oil
• the linolenic acid group unsatd. Cis
• the erucic acid group unsat
• the derivative of the natural fat is typically the fatty acid component of the above listed fats, or a corresponding fatty alcohol.
• the raw material of the claimed process i.e. the object of the catalytic cracking, is generally one or more hydrocarbons which have been obtained by removing oxygen from the natural fat or derivative thereof.
• the oxygen has been removed from the natural fat or derivative thereof by hydrolyzation and decarboxylation, or, most preferably, by hydrogenation.
• such hydrogenation is typically carried out at a temperature of 330-450 0 C, a pressure of 3-15 MPa and an LHSV of 0.5-5.0 hr "1 in the present of a hydrogenation catalyst.
• Catalysts suitable for the hydrogenation are commercial hydroprocessing catalysts including cobalt-molybdenum catalysts, nickel-molybdenum catalysts, or other transition metal based catalysts used for hydroprocessing [e.g. American Cyanamide HDS-20 or Shell S-424].
• the catalyst is the NiMo/AI 2 O3 or COMO/AI2O3 catalysts mentioned in Fl 1090248, see page 3, lines 30 and 31 , of the document.
• the hydrogenation has been carried still further to remove unwanted double bonds from the hydrocarbon chain, or combined with isomerisation of the formed hydrocarbon.
• the cracking is carried out by feeding said one or more hydrocarbons from natural fat or a derivative thereof in liquid form through a reactor containing said catalyst based on a zeolite and a mesoporous inorganic oxide.
• the reactor contains the catalyst as a fixed-bed, moving-bed or fluidized bed. However, it is preferable, that the reactor contains the catalyst as a fixed bed, trough which the hydrocarbon feed is led. In one embodiment, said one or several hydrocarbons are fed to the top of the reactor and the product is recovered from the bottom of the reactor.
• the catalytic cracking is preferably carried out at a temperature between 250 and 399°C, most preferably between 320 and 380 0 C.
• the pressure is preferably 0.01-5.0 MPa, most preferably 0.2-2.0 MPa.
• a catalyst which is based on a zeolite and a mesoporous inorganic oxide.
• This definition includes e.g. catalysts which have been prepared by mixing and optionally reacting a zeolite with a mesoporpus inorganic oxide, carrying out a zeolite synthesis in the presence of a mesoporous inorganic oxide, carrying out a mesoporous inorganic oxide synthesis in the presence of a zeolite, or carrying out a zeolite synthesis and an mesoporous inorganic oxide synthesis simultaneously in the same vessel.
• the zeolite may be added to the reaction mixture of the mesoporous inorganic oxide synthesis at any stage, and vice versa.
• the definition also includes mixtures of such catalysts.
• the catalyst based on a zeolite and a mesoporous inorganic oxide has been prepared by synthesizing the mesoporous inorganic oxide in the presence of the zeolite.
• the zeolite may be added at any stage of synthesizing the mesoporous inorganic oxide.
• the catalyst based on a zeolite and a mesoporous inorganic oxide preferably contains 4-80%, preferably 20-70%, of added dry zeolite, based on the total dry weight of the zeolite and the mesoporous inorganic oxide.
• the specific surface area of the catalyst is generally from 300 to 1400 m 2 /g, preferably from 400 to 1200 m 2 /g.
• the catalyst based on a zeolite and a mesoporous inorganic oxide is mechanically, thermally and hydrothermally stable and can easily be handled and regenerated in a cracking process.
• the catalyst based on a zeolite and a mesoporous inorganic oxide is typically a mesoporous molecular sieve material matrix containing zeolite structures.
• the characteristic features of the catalyst used for the claimed cracking is measurable by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, specific surface area measurement by N 2 absorption (BET), 27 AI-NMR, and acidity measurements using ammonia-TPD and pyridine-FTIR.
• the catalyst typically has acid sites on its surface.
• the catalyst based on a zeolite and a mesoporous inorganic oxide is generally based on one or more inorganic oxides such as silicon oxide SiO 2 and aluminium oxide AI 2 O3.
• the silicon atoms may be replaced by metal atoms. These include, but are not limited to, metals selected from the group consisting of aluminium, titanium, vanadium, zirconium, gallium, boron, manganese, zinc, copper, gold, lanthanum, chromium molybdenum, nickel, cobalt, iron, tungsten, palladium, platinum and combinations thereof.
• the replacement is carried out by contacting the zeolite or a precursor thereof and/or the mesoporous inorganic oxide or a precursor thereof with a source of the metal.
• the modifying metal is aluminium
• the aluminium source may be selected from aluminium sulphate (AI 2 (SO 4 )3-18H 2 O, hydrated aluminium hydroxides, aluminates, aluminium isopropoxide and alumina.
• the preferred aluminium content is between 0.01 and 10% by weight, most preferably between 0.5 and 5.0% by weight, based on the weight of the catalyst based on a zeolite and a mesoporous inorganic oxide.
• the aluminium makes the catalyst acidic and more suitable for catalytic cracking.
• the zeolite is preferably selected from the group consisting of medium pore
• zeolites such as MFI-framework zeolite (ZSM-5), MTT-frame- work zeolite (ZSM-23), TON-framework zeolite (ZSM-22, theta-1 ), AEL-framework zeolite (SAPO-11 ), MWW-framework zeolite (MCM-22, PSH-3, ITQ-1 ), FER- framework zeolite (ZSM-35), MEL-framework zeolite (ZSM-11 ), and larger pore (12-member ring) zeolites such as BEA-framework zeolite (zeolite ⁇ ), FAU-frame- work zeolite (zeolite X, zeolite Y, ZSM-20, SAPO-37) and MOR-framework zeolite
• SAPO-5 an several other zeolites like clinoptilolite, ZSM-34, ZSM-48, SSZ-32,
• zeolites selected from the group consisting of medium pore (10-member ring) zeolites such as MFl- framework zeolite, MTT- framework zeolite, TON- framework zeolite, AEF- framework zeolite, MWW- framework zeolite, FER- framework zeolite, larger pore (12- member ring) zeolites such as BEA- framework zeolite, FAU- framework zeolite and MOR- framework zeolite, and precursors and mixtures thereof.
• medium pore (10-member ring) zeolites such as MFl- framework zeolite, MTT- framework zeolite, TON- framework zeolite, AEF- framework zeolite, MWW- framework zeolite, FER- framework zeolite, larger pore (12- member ring) zeolites such as BEA- framework zeolite, FAU- framework zeolite and MOR- framework zeolite, and precursors and mixtures thereof
• zeolite groups are ZSM-5, ZSM-23, ZSM-22, SAPO-11 , MCM-22, ferhehte, beta, Y- and X-zeolites and mordenite. Most advantageous are the MFI-framework zeolite, MTT-framework zeolite, TON-framework zeolite, MWW-framework zeolite and precursors and mixtures thereof.
• the average pore diameter of the zeolite is from 0.2 to 2.0 nm, preferably from 0.3 to 0.7 nm.
• the particle size of the zeolite is typically from 0.001 ⁇ m to 3.0 ⁇ m.
• the other component of the catalyst used in the invention is the mesoporous inorganic oxide. It typically includes aluminium oxide AI2O3, silicon oxide SiO2, or combinations thereof.
• the volume of the mesopores preferably constitutes at least 80%, preferably at least 90%, as measured by N 2 porosimetry, of the combined volume of mesopores and micropores.
• the mesoporous material of the catalyst comprising a zeolite and a mesoporous inorganic oxide is selected from the group consisting of aluminosilicates of type M41 S (including hexagonal MCM-41 , cubic MCM-48 and plate-like MCM-50), MSA-1 , MSA-2, MSA-3, MAS-8, and mixtures thereof.
• the average pore diameter of the mesoporous material is by definition from 2 to 50 nm, preferably from 2 to 30 nm and most preferably from 2 to 20 nm.
• the pore volume of the mesoporous material from 0.2 cm 3 /g to 2.4 cm 3 /g.
• the catalyst comprising a zeolite and a mesoporous inorganic oxide can be prepared e.g. by mixing together and, optionally, reacting the zeolite and the mesoporous inorganic oxide, preparing the zeolite in the presence of a mesoporous inorganic oxide, preparing the mesoporous inorganic oxide in the presence of the zeolite, or preparing both the zeolite and the inorganic oxide simultaneously in the same vessel.
• the catalyst has been prepared by synthesizing hydrothermally the mesoporous inorganic oxide in the presence of the zeolite.
• the zeolite may be added at any stage of preparing the mesoporous inorganic oxide (For example, US 20060128555 adds the zeolite before the mesoporous inorganic oxide precursor and the mesopore forming compound (templating agent), whereas WO 2006/070073 adds the zeolite after adding the mesoporous inorganic oxide precursor and a first mesopore forming compound, but before adding a second mesopore forming compound).
• the mesopore forming compound is typically a compound which mixes and forms hydrogen bonds with the inorganic oxide or its precursor.
• the zeolite, the inorganic oxide precursor, the water and the mesopore forming compound are heated to a temperature of about 100 to about 200 0 C in order to form a composite containing mesopores. After the heating, the mesopore forming compound is removed from the composite by calcining and/or extraction.
• the catalyst based upon the zeolite and the mesoporous inorganic oxide may be mixed with a binder or other additive in order to enlarge its activity zone and/or enable its forming into an optimal shape (e.g. extrudates, pellets, rings, etc).
• a binder or other additive e.g. silica, silica gel and/or alumina.
• the catalyst may also be peptized, e.g. by using acetic acid and Boehmite.
• C 2 -C 8 -hydrocarbons are prepared by cracking catalytically one or more hydrocarbons which have been obtained from natural fat or a derivative thereof.
• the catalytic cracking is carried out at a temperature between 250 and 450 0 C using a catalyst as described above which is based on a zeolite and a mesoporous inorganic oxide.
• the cracking is carried out in cycles, whereby, most advantageously, the cracking cycles last for 6 to 18 hours. Under such conditions, low coke product is produced.
• the catalyst based on a zeolite and a mesoporous inorganic oxide is regenerated. This preferably takes place by flushing the catalyst with hot gas, preferably every 10 to 50 hours, most preferably every 15 to 30 hours.
• the regeneration temperature is typically 0 to 50°C higher, preferably 10 to 30 0 C higher, than the cracking temperature.
• the regeneration typically takes place by flushing with a gas selected from hydrogen, nitrogen, steam, helium, argon, a lower alkane (Ci-C 5 ), and mixtures thereof. Regeneration may also be carried out occasionally by burning deposited coke, preferably after several regenerations with hot gas.
• the burning of the deposited coke is carried out by introducing air or oxygen to a bed of the catalyst.
• the coke burning usually takes place at a temperature of 450 to 550°C.
• Test equipment consists of feed vessel and pump (Neste technology), mass flow controllers (Brooks) for nitrogen and air, gas/liquid mixer, pre-heater for product mixture, reactor and furnace, pressure controller (Kammer), gas/liquid separator and sample collector. Nitrogen was used as internal standard for mass balance calculation and simultaneously as carrier for gaseous product. The gas/liquid mixture was fed to a heated pre-heater whose temperature was set to 300 0 C.
• In-situ regeneration option was also available wherein air was introduced into the reactor at a temperature of 500 0 C. The state of regeneration was measured with an on-line CO/CO2-analyser type Siemens Ultramat 22P.
• On-line sampling and analysis were automated with a timer to take and collect 9- 10 gas and liquid samples during a day.
• the pressure of the gaseous sample line was adjusted into constant pressure and the concentration of hydrocarbons (Ci - C 7 ) and perma nent gases (H 2 , O 2 , N 2 , CO and CO 2 ) were analysed simultaneously. Permanent gases were separated with HayeSepQ and molecular sieve connected in series and hydrocarbons with a capillary column. Gas sample quantification was achieved with external calibration. A separation column was used for liquid on-line samples, which was of the type DB-1. The identified compounds ranged from methane up to boiling point 221 °C. Fraction analyses on off-line samples were carried out with a DB-1 column.
• the test run was started by adjusting the set point of pressure with a controller and increasing the pressure with nitrogen flow. Simultaneously a feed line was pre- filled through a 3-way valve and the reactor temperature was set to the test value. After the reaction conditions were reached, the test was started by directing the feed flow into the reactor using a 3-way valve. Sampling timer and analysing sequences were started at the same time. During and at the end of the experiment the amounts of liquid product collected to the vials were weighted. The experiment was finished by stopping the feed flow and flushing the reactor with nitrogen flow until all liquid came out. After that the heating of the pre-heater and the reactor furnace were turned off and reactor was cooled under nitrogen flow.
• In-situ regeneration was carried out introducing air into the reactor at 500 0 C under ambient pressure. The regeneration was continued over night for at least 12 hours and the state of regeneration was measured with an on-line CO/CO 2 -analyser. After regeneration, the gas flow was changed to nitrogen and the reactor was cooled into ambient temperature.
• Argon was fed through a mass flow controller and used as an internal standard, and as a carrier gas for the reactant and products.
• the reactant was pumped with a HPLC-pump to the reactor through a stainless steel line which was kept hot with heating tapes. Also, the body of the pump was heated with a circulating water jacket.
• the feed vessel was placed on a scale to monitor the exact feed rate.
• nitrogen was added to the product stream using a mass flow controller in order to increase the flow rate, and thus to decrease the propensity for the thermal reactions prior to the analysis of the product stream.
• the product diluted with nitrogen was lead from the reactor through a heated line to a Tescom-back- pressure valve.
• the product stream was cooled in a small "pipe and shell-type" heat exchanger with circulating water from a thermostated bath.
• a small gas-liquid-separator was used to separate the gaseous products from heavy condensable liquids. Gases were analyzed on-line and liquid samples were collected in vials.
• the gaseous product stream collected from the gas-liquid separator was analysed on-line by GCs.
• the product was introduced through a heated stainless steel line to the analysis system.
• the analysis system consisted of two HP-5890 gas chromatographs, one for the analysis of heavy hydrocarbons (>C 7 ) and permanent gases, and the other for the analysis of light hydrocarbons (CrC 7 ) and when necessary also oxygenates.
• the gas chromatographs were equipped with three FID:s, one TCD, five pneumatic valves and six wide-bore capillary or packed columns.
• the liquid feed was first pumped via a 3-way valve to an outlet test line to certify that the feed line is filled with the feed. Thereafter, the following actions were taken:
• the duration of the run is 5 hours.
• the liquid flow is stopped, the oven is allowed to cool overnight, and the gas flows are left running.
• the liquid trap is emptied and the amount of liquid product is weighed.
• the gas flows are stopped, the pressure is released and the catalyst is collected and stored for later analyses.
• the catalyst is regenerated in situ and used in further experiments.
• the gas-liquid separator is cleaned, and it always contains minor amounts of liquid product.
• the Tescom pressure regulator was cleaned after each catalyst sample (in runs 0506-0639). It should be noted that after the reaction-regeneration sequence, the pressure regulator typically contained a significant amount of liquid product. This amount could not be accurately weighed, but the amount was estimated by captivating the liquid on a pre-weighed paper, and by weighing the "wet" paper. In a typical run of 5 hours with a feed rate of 4,3- 6,0 g/h it can accounts as much as approx. 5-10% meaning that a mass balance of approx. 90% is excellent.
• the mass balance is not likely to remain at approx. 80% max, and if the feed rate is high, such as 18 g/h, the effect of this accumulation is less significant.
• the maintenance tasks also include flushing the reactor lines with argon after the reaction-regeneration cycles upon change of the catalysts.
• the on-line GC lines and valves were cleaned with elongated flow of inert gas after each catalyst sample, that is, after reaction-regeneration cycles.
• the in situ regeneration of the catalysts was carried out as follows: 1 ) The catalyst is cooled to room temperature under argon-flow.
• Example 20a The preparation of the catalyst comprising a zeolite and a mesoporous inorganic oxide used by the invention is described in example 20a of WO patent application 2006/070073. Before the test reactions, the catalyst is pressed to plates, crushed and sieved to desired particle size. Example 2.
• the preparation of the catalyst comprising a zeolite and a mesoporous inorganic oxide used by the invention is described in example 20b of WO patent application 2006/070073. Before the test reaction, the catalyst material is pressed to plates, crushed and sieved to desired particle size.
• the catalyst material thereof was mixed with silica gel (Ludox-AS40).
• the catalyst to silica gel weight ratio is 1 :1.
• the formed gel mixture is baked on a plate and dried at 115°C overnight.
• the material is calcined at 500 0 C for 2 hours. Then, the catalyst is crushed and sieved to desired particle size.
• the catalyst comprising a zeolite and a mesoporous inorganic oxide, before pressing, crushing and sieving, as described in example 2, is peptized by using 2.5 wt-% acetic acid and boehmite (Catapal B).
• the amount catalyst was 10 g and amount of boehmite was 4 g that were carefully mixed.
• the acetic acid was drop wise added to the mixture to get a formable paste.
• the paste is baked on the plate and dried at 120 0 C overnight.
• the catalyst material is calcined at 500°C for 2 hours. Then, the catalyst is crushed and sieved to desired particle size.
• Example 5
• the method of preparation of catalyst material 6 used in the present invention is described in example 8 in WO patent application 2006/070073.
• the catalyst material is mixed with silica gel (Ludox-AS40).
• the weight ratio of catalyst to silica gel (Ludox-AS40) is 1 :1.
• the formed gel mixture is baked on a plate and dried at 115°C overnight.
• the material is calcined at 500 0 C for 2 hours. Then, the catalyst is crushed and sieved to desired particle size.
• inventive catalyst material is described in example 6 in WO patent application 2006/070073.
• the mesoporous catalyst material is mixed with silica gel (Ludox-AS40).
• the ratio of mesoporous material to silica gel (Ludox-AS40).
• solutions A, B and C are prepared.
• Solution A was prepared by mixing fumed silica with distilled water with continuous stirring (r.m.p. 196) for 20 minutes.
• Solution B was prepared by adding tetramethylammonium silicate to sodium silicate with continuous stirring (r.m.p 180) and the mixture was stirred for 20 minutes.
• Solution C was prepared by dissolving tetradecyl thmethyl ammonium bromide in distilled water with vigorous stirring (r.m.p. 336) for 20 minutes.
• Solution B was added to Solution A slowly (in 15 min) with vigorous stirring (r. m. p.
• zeolite nucleis with code TON were prepared.
• Reagents used in the synthesis of TON structure zeolite nucleis were Ludox AS 40, aluminium sulphate, potassium hydroxide, 1 , 6 - diamino hexane and distilled water.
• Three different solutions A, B and C were made for TON zeolite nuclei preparation.
• Solution A was prepared by adding Ludox AS40 silica to distilled water.
• Solution B was prepared by dissolving aluminium sulphate and potassium hydroxide in Solution B was added to Solution A and the obtained gel mixture stirred for 20 minutes.
• Solution C was prepared by dissolving 1 ,6-diaminohexane in distilled water and stirring for 20 minutes.
• Solution C was added to the gel mixture (A+B) and stirred for 15 minutes.
• the synthesis was carried out at 160 0 C for 48 h. After the completion of the synthesis the product was filtered, washed with distilled water, dried and calcined and TON zeolite nuclei were obtained.
• the TON zeolite nuclei precursor prepared above was added to the gel solutions (A +B +C) under vigorous stirring (r.m.p. 340) for 20 min.
• the homogenisation of the dispersed TON was carried out by further stirring (r.m.p. 340) of the gel for 35 minutes.
• the gel was introduced in Teflon cups which were then inserted in an autoclave. The synthesis was carried out for 96 h at 100 0 C.
• the mesoporous catalyst material is then transformed to the proton form by ammonium ion exchange and calcination procedures to replace the sodium ions of materials with protons
• the catalyst material is pressed to plates, crushed and sieved to desired particle size.
• Y-zeolite TOSOH Corporation HSZ395HUA
• silica gel Lidox-AS40
• the weight ratio of Y-zeolite to silica gel is 1 :1.
• the formed gel mixture is baked on a plate and dried at 115°C overnight.
• the material is calcined at 500 0 C for 2 hours.
• the catalyst is crushed and sieved to desired particle size.
• Mesoporous silica alumina tablets were purchased from Nikki Chemicals. This catalyst is crushed and sieved to the desired particle size, and tested in paraffin cracking.

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• 2008
  • 2008-04-25 FI FI20085366A patent/FI20085366L/sv not_active Application Discontinuation
• 2009
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