WO2016065035A1 - Réactions d'hydrocarbures à l'aide de supports en zéolite désagrégée formant catalyseurs - Google Patents

Réactions d'hydrocarbures à l'aide de supports en zéolite désagrégée formant catalyseurs Download PDF

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Publication number
WO2016065035A1
WO2016065035A1 PCT/US2015/056711 US2015056711W WO2016065035A1 WO 2016065035 A1 WO2016065035 A1 WO 2016065035A1 US 2015056711 W US2015056711 W US 2015056711W WO 2016065035 A1 WO2016065035 A1 WO 2016065035A1
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ssz
delaminated
catalyst
olefins
hydroprocessing
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PCT/US2015/056711
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English (en)
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Bi-Zeng Zhan
Stacey Ian Zones
Christopher M. LEW
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Chevron U.S.A. Inc.
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Priority claimed from US14/521,098 external-priority patent/US20160115397A1/en
Application filed by Chevron U.S.A. Inc. filed Critical Chevron U.S.A. Inc.
Publication of WO2016065035A1 publication Critical patent/WO2016065035A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or 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
    • 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • 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
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/86—Borosilicates; Aluminoborosilicates
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
    • 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
    • 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
    • C10G45/64—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 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other 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
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • 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
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • 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
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • 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
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/22—After treatment, characterised by the effect to be obtained to destroy the molecular sieve structure or part thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/38—Base treatment
    • 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
    • B01J35/50—

Definitions

  • the present invention relates to delaminated zeolites and their use as catalysts in the reactions of hydrocarbons. More specifically, the present invention relates to a delaminated SSZ-70 material and the use of delaminated SSZ-70 as a catalyst specifically in the hydroisomerization of hydrocarbons, alkylation of hydrocarbons or olefin oligomerization.
  • Zeolites are widely used as acidic catalysts for refining applications attributed to their unique and uniform pore structure with sizes in the sub-nanometer range.
  • the pore sizes of zeolites dictate the reaction in refining processes including hydroisomerization, hydrocracking, olefin alkylation and olefin oligomerization, and thus dictate reaction selectivity.
  • hydroprocessing products often experience varying degrees of continuous (over)cracking when they diffuse out of micrometer-scale zeolitic channels. Thus elimination of these types of side-reactions is significant for reaction efficiency and product quality improvement.
  • One of the solutions for preventing overcracking is reduction of acidic strength. But this approach reduces the catalyst activity at the same time.
  • delaminated SSZ-70 has been found to provide unexpected improvements in the catalysis of hydroprocessing hydrocarbons. It has been found that delaminated SSZ-70 offers a zeolite layer with a single unit cell of thickness in one dimension, allowing an elimination of mass transfer in comparison with regular SSZ-70 (non-delaminated). For example, an unexpected and significant improvement of isomerization selectivity has been achieved when using a catalyst comprising delaminated SSZ-70 compared to regular SSZ-70.
  • the delaminated SSZ-70 zeolite also exhibits features of maintaining zeolitic acidity strength and spatial constraint of internal zeolite framework. This provides opportunities to control novel chemistry by tailoring the location of acidic sites for desired chemical reactions.
  • delaminated SSZ-70 offers a zeolite layer with a single unit cell of thickness in one dimension, allowing an elimination of mass transfer in comparison with regular SSZ-70 (non-delaminated). It also provides the possibility of eliminating the spatial constraint on oligomerized product to meet some specific applications. For example, significant improvement of selectivity to larger molecules with boiling point in the range of base oil (e.g. 600 °F+) is believed possible in olefin oligomerization when using a delaminated SSZ-70 catalyst with acidic sites located on the external surface compared to regular SSZ-70.
  • delaminated SSZ-70 offers a zeolite layer with a single unit cell of thickness in one dimension, allowing an elimination of mass transfer in comparison with regular SSZ-70 (non-delaminated). This prevents coke formation inside zeolitic channels and improves catalyst stability.
  • the delaminated SSZ-70 zeolite also exhibits features of maintaining zeolite strength and spatial constraint of internal zeolitic framework. This provides opportunities to control novel chemistry by tailoring location of acidic sites for chemical reactions.
  • an improved alkylation process which comprises contacting a hydrocarbon feedstock comprising olefins and isoparaffins with a catalyst comprising delaminated SSZ-70 under alkylating reaction condition. Superior selectivity and catalyst stability is achieved for the reaction of olefins and isoparaffins. The resulting product is a high quality alkylate useful for gasoline or gasoline blending.
  • Figure 1 depicts acidic sites distribution on delaminated SSZ-70.
  • the delaminated SSZ-70 contains Bronsted acidity on the internal and external surface of the micropore.
  • Figure 2 graphically depicts nCi 6 conversion with regard to reaction temperature for delaminated Al-SSZ-70 and Al-SSZ-70.
  • Figure 2 illustrates that the catalyst containing delaminated Al-SSZ-70 is less active than the Al-SSZ-70 because of lowered Al Bronsted acidic sites.
  • Figure 3 graphically depicts C7+ product yield for nCi 6 conversion when using delaminated SSZ-70 and Al-SSZ-70.
  • Figure 3 illustrates that the catalyst containing delaminated SSZ-70 significantly enhances the yield of C7+ products, indicating improved overcracking.
  • Figure 4 graphically depicts the significant improvement of hydroisomerization selectivity when using delaminated Al-SSZ-70.
  • Figure 4 illustrates that the catalyst containing delaminated Al-SSZ-70 significantly enhances the selectivity of isomerized C16 product by nearly 20%.
  • Figure 5 graphically depicts the selectivity of Ci 6 isomers for delaminated SSZ-70.
  • Figure 5 illustrates that the delaminated SSZ-70 inhibits further isomerization of methyl- pentadecane (MeC 15 ) isomers to dimethyl-tetradecane (DiMeCi4) products.
  • MeC 15 methyl- pentadecane
  • DIMeCi4 dimethyl-tetradecane
  • the present process relates to an improved hydrocracking process which allows one to achieve superior isomer selectivity or isoselectivity hereafter.
  • the process comprises contacting a hydrocarbon feed comprised of normal hydrocarbons under hydroprocessing conditions with a catalyst comprising delaminated SSZ-70. It has been found that delaminated SSZ-70 offers a zeolite layer with a single unit cell of thickness in one dimension, allowing an elimination of mass transfer in comparison with regular SSZ-70. The result is superior isoselectivity when used in a hydroprocessing process. It is important that the process involves hydrogen. Thermal cracking, for example, which would not involve hydrogen, would result in severe coking of the delaminated SSZ-70.
  • the present process relates to an improved olefin
  • oligomerization process which allows one to achieve superior selectivity.
  • the process comprises contacting a hydrocarbon feed comprised of straight and branched chain olefins under oligomerization conditions with a catalyst comprising delaminated SSZ-70. It has been found that delaminated SSZ-70 offers a zeolite layer with a single unit cell of thickness in one dimension, allowing for elimination of mass transfer in comparison with regular SSZ-70. The result is superior selectivity.
  • the present process relates to an improved alkylation process which allows one to achieve superior selectivity and catalyst stability.
  • the process comprises contacting a hydrocarbon feed comprised of isoparaffins and olefins under alkylation conditions with a catalyst comprising delaminated SSZ-70. It has been found that delaminated SSZ-70 offers a zeolite layer with a single unit cell of thickness in one dimension, allowing an elimination of mass transfer in comparison with regular SSZ-70. The result is superior selectivity in the alkylation reaction.
  • the delaminated SSZ-70 also exhibits features of maintaining zeolitic acidic strength and spatial constraint of the internal zeolitic framework. This provides one with the opportunity of controlling novel chemistry by tailoring the location of acidic sites.
  • Fig. 1 three scenarios are schematically provided of the controlled location of acidic sites that can be prepared with starting materials of delaminated SSZ-70 in either the Al- or B- form.
  • the molecular sieve SSZ-70 is known, as is the synthesis thereof.
  • U.S. Patent No. 7, 108,843, issued September 19, 2006, for example describes the molecular sieve SSZ-70 and a synthesis for preparing the molecular sieve.
  • the SSZ-70 is characterized in U.S. Patent No. 7,108,843 by its X-ray diffraction pattern before calcination, and by its X-ray diffraction pattern after calcination.
  • the delaminated SSZ-70 can be obtained by delaminating the SSZ-70 molecular sieve using conventional techniques of delamination. In one embodiment, the techniques described in U.S. 2012/0148487, published June 14, 2012, would be quite effective.
  • an aqueous mixture of chloride and fluoride anions e.g.,
  • alkylammoniumhalides and the SSZ-70 is prepared.
  • the aqueous mixture is maintained at a pH less than 12, e.g., about 9, and maintained at a temperature in the range of 5-150° C. for a length of time sufficient to effect the desired delamination.
  • the oxide product is then recovered, e.g., by acidification to a pH of about 2 followed by centrifugation.
  • a non-aqueous mixture of chloride and fluoride anions i.e., a mixture comprising an organic solvent
  • the organic solvent can be any suitable organic solvent which swells the starting material such as dimethyl formamide (DMF).
  • DMF dimethyl formamide
  • the delaminated product can then be recovered from the mixture. Generally, acidification is used to recover the product. Sonication prior to recovery need not be employed, but sonification can be employed in the process if desired.
  • the chloride and fluoride anions can be obtained from any source of the anions. Any compound which will provide the anions in aqueous solution can be used. The cation is generally not important. Providing the fluoride and chloride anions is important.
  • Bromide anions can also be present, but both fluoride and chloride anions must be present.
  • the cations can be any cation, with the use of alkylammonium cations being suitable in one embodiment.
  • the alkyl group of such a cation can be any length, and in one embodiment ranges from 1-20 carbons. Tetrabutylammonium cations in particular have been found useful.
  • the molar ratio of chloride to fluoride anions can be 100 or less, generally from 100: 1 to 1 : 100. In one embodiment, the ratio can range from 50: 1 to 1 :50. It is the combination of the fluoride and chloride anions which has been discovered to be important.
  • the pH used in the synthesis when an aqueous mixture is used is lower than that generally used in delamination synthesis.
  • the pH is generally 12 or less, but can be any pH which does not transform the silica in the zeolite to create an amorphous silica phase.
  • a pH of 12 or less generally accomplishes this task and thereby allows one to obtain a delaminated layered zeolite precursor material substantially without an amorphous phase.
  • the pH is 11 or less, and even 10 or less, with a pH of about 9 or less also being quite advantageous.
  • a pH of approximately 9 is typically used in fluoride- mediated synthesis of zeolites.
  • the temperature used in the process for either the aqueous or non-aqueous mixture can range widely. In general a temperature for the aqueous solution of from 5-150° C. is suitable. In another embodiment, the temperature can range from 50-100° C.
  • the length of time the zeolite is allowed to swell, and delaminate, in the aqueous solution can vary greatly. Generally, the time can vary from 30 minutes to one month. In one embodiment, the time ranges from 2 hours to 50 hours. In another embodiment, the time can range from 5 to 20 hours prior to collection of the product.
  • the delaminated oxide product is collected using conventional techniques such as centrifugation.
  • An acid treatment step can be employed prior to centrifugation, and may be conveniently conducted by contacting the swollen or partially delaminated layered zeolite precursor material with a strong acid, e.g., a mineral acid such as hydrochloric acid or nitric acid, at low pH, e.g., pH 2. Collection of the resulting oxide material product can be performed by centrifugation.
  • the present process comprises contacting the hydroprocessing catalyst, i.e., a catalyst comprising delaminated SSZ-70, with a hydrocarbon feed under hydrocracking conditions.
  • a catalyst comprising delaminated SSZ-70 means.
  • the catalyst can comprise pure delaminated SSZ-70 or is in mixture with any suitable conventional catalyst, and can be present in the catalyst in an amount as small as 2 parts by weight.
  • the catalyst will comprise at least 2 parts by weight of the delaminated SSZ-70.
  • the hydrocarbon feed for the process comprises a substantial amount of C 4 to C20 normal hydrocarbons. Slightly branched hydrocarbons can also be in the feed.
  • the hydrocarbon feed is a hydrotreated VGO.
  • the hydroprocessing reaction is carried out in the presence of hydrogen.
  • hydrogen is added to give a hydrogen to hydrocarbon ratio (H 2 /HC) of between about 500 and about 30,000 SCF/bbl (standard cubic feet per barrel) (0.089 to 5.34 SCM/liter (standard cubic meters/liter)), preferably about 3,000 to about 10,000 SCF/bbl (0.534 to 1.78 SCM/liter).
  • H 2 /HC hydrogen to hydrocarbon ratio
  • the delaminated SSZ-70 catalyst preferably contains one or more metals.
  • each metal employed is selected from the group consisting of elements from Group VI and Groups VIII through X of the periodic Table, and mixtures thereof.
  • each metal is selected from the group consisting of nickel (Ni), palladium (Pd), platinum (Pt), cobalt (Co), iron (Fe), chromium (Cr), molybdenum (Mo), tungsten (W), and mixtures thereof.
  • the delaminated SSZ-70 catalyst contains at least one Group VI metal and at least one metal selected from Groups VIII through X of the periodic table.
  • Exemplary metal combinations include Ni/Mo/W, Ni/Mo, Ni/W, Co/Mo, Co/W, Co/W/Mo and Ni/Co/W/Mo.
  • Modifying agents can be added to the metal-containing solution before impregnation. See U.S. Pat. No. 8,637,419 for a further discussion of hydroprocessing catalyst preparation conditions with modifying agents, which patent is expressly incorporated by reference herein in their entirety.
  • the delaminated SSZ-70 catalyst contains a Group VIII metal compound.
  • Group VIII metal compound as used herein, is meant the metal itself or a compound thereof.
  • the Group VIII noble metals and their compounds, platinum, palladium, and iridium, or combinations thereof can be used. Rhenium and tin may also be used in conjunction with the noble metal.
  • the most preferred metal is platinum.
  • the amount of Group VIII metal present in the conversion catalyst should be within the normal range of use in hydroprocessing catalysts, from about 0.05 to 2.0 weight percent, preferably 0.2 to 0.8 weight percent.
  • the catalyst is quite useful in an isomerization/dewaxing process.
  • the catalyst can be used to dewax hydrocarbonaceous feeds by selectively isomerizing straight chain paraffins.
  • the viscosity index of the dewaxed product is improved (compared to the waxy feed) when the waxy feed is contacted with the delaminated SSZ-70 under isomerization dewaxing conditions.
  • the catalytic isomerization dewaxing conditions are dependent in large measure on the feed used and upon the desired pour point.
  • Hydrogen is preferably present in the reaction zone during the catalytic isomerization dewaxing process.
  • the hydrogen feed ratio is typically between about 500 and about 30,000 SCF/bbl (standard cubic feet per barrel) (0.089 to 5.34 SCM/liter (standard cubic meters/liter)), preferably about 1000 to about 20,000 SCF/bbl (0.178 to 3.56 SCM/liter).
  • Typical feedstocks include light gas oil, heavy gas oils and reduced crudes boiling above about 350° F. (177° C).
  • a typical isomerization dewaxing process can comprise the catalytic dewaxing of a hydrocarbon oil feedstock boiling above about 350° F. (177° C.) containing straight chain and slightly branched chain hydrocarbons by contacting the hydrocarbon oil feedstock in the presence of added hydrogen gas at a hydrogen pressure of about 15-3000 psi (0.103- 20.7 Mpa) with a catalyst comprising delaminated SSZ-70 and at least one Group VIII metal.
  • the delaminated SSZ-70 catalyst may optionally contain a hydrogenation component of the type commonly employed in dewaxing catalysts. See, for example, U.S. Pat. No. 5,316,753 for examples of these hydrogenation components.
  • the hydrogenation component is present in an effective amount to provide an effective hydrodewaxing and hydroisomerization catalyst preferably in the range of from about 0.05 to 5% by weight.
  • the catalyst may be run in such a mode to increase isomerization dewaxing at the expense of cracking reactions.
  • the feed may be hydrocracked, followed by isomerization dewaxing.
  • This type of two stage process and typical hydrocracking conditions are described in U.S. Pat. No. 4,921,495, issued May 1, 1990 to Miller, which is incorporated herein by reference in its entirety.
  • the catalyst comprising delaminated SSZ-70 can be used to oligomerize straight and branched chain olefins having from about 2 to 21 and preferably 2- 5 carbon atoms.
  • the oligomers which are the products of the process are medium to heavy olefins which are useful for fuels and lube oil. It can also useful as feedstocks for chemicals and surfactants.
  • the oligomerization process comprises contacting the olefin feedstock in the liquid phase with a catalyst comprising the delaminated SSZ-70.
  • the delaminated SSZ-70 can be in the hydrogen form.
  • the delaminated SSZ-70 can be a delaminated Al-SSZ-70 material or a delaminated B-SSZ-70 material.
  • the delaminated SSZ-70 containing catalyst can contain transition metals, which are introduced through any conventional methods such as impregnation or ion exchange with their corresponding metal salts or oxides.
  • the delaminated SSZ- 70 catalyst comprises a noble metal selected from the group of nickel (Ni), palladium (Pd), platinum (Pt), ruthenium (Ru), rhodium (Rh), iron (Fe), gold (Au), silver (Ag) and mixtures thereof.
  • the delaminated SSZ-70 catalyst contains at least one metal selected from Groups VI through VIII of the Periodic Table.
  • the deactivated catalyst can be regenerated by hydrogenation or hydrocracking of coke or heavy hydrocarbons deposited on its surface under hydrogenation and
  • the delaminated SSZ-70 can be used to oligomerize olefin feeds comprising olefins containing from 2 to 8 carbon atoms, preferably the olefin feeds are alpha-olefins, especially linear alpha-olefins.
  • Ethylene is especially preferred but other suitable olefins include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1- octene, and mixtures thereof.
  • the olefin feed can be a mixture of olefins or a single olefin such as ethylene.
  • the delaminated SSZ-70 comprising catalyst can be contacted with the olefin feed in any convenient manner. Sometimes a suitable solvent such as paraffins or aromatics can be added to co-process with olefin feeds.
  • the oligomerization process can be conducted as a batch, continuous, semi-bath or multi-step process. It can be conducted in fixed-bed reactor process with up and down flow. Inert gas or refinery light hydrocarbon gas stream can be added to the process. The process can be conducted using suitable equipment in the art.
  • the reaction conditions for oligomerizing the olefin feed can vary broadly, depending on the desired product, and the olefins employed. They include the temperature and pressure sufficient to produce the desired oligomerized product. Generally, the reaction temperatures will be in the range of from 0° C. to 500° C, preferably from 25° C. to 400° C, and more preferably from 50° C. to 350° C. Generally, the pressure is at least 200 psi, preferably the pressure is greater than 500 psi.
  • the olefin product generally comprises a mixture of alpha-olefins containing from 4 to 54 carbon atoms, preferably from 8 to 50.
  • the olefin product contains only trace amounts of vinylidene, branched and isomerized olefins. When proper conditions and catalyst are employed, the olefin product contains less than 1000 ppm polymerized olefin.
  • a typical product distribution for the process is shown below.
  • the product distribution is due to a geometric product distribution [see Alpha Olefin Handbook by Lappin et al, page 28].
  • C 4 to C 8 content 34%.
  • Cio to Ci 6 weight content 25%.
  • Ci8 to C5 4 weight content 33%.
  • the olefin products of this invention have established utility in a wide variety of applications such as, for example, fuels, lube oils, surfactants and monomers for use in the preparation of polymers.
  • the catalyst comprising delaminated SSZ-70 is useful in a process for the alkylation of olefins with isoparaffins for making alkylate.
  • the process comprises contacting C2 to Ci6 olefins and C 4 -Cio isoparaffins under olefin alkylation conditions, and in the presence of a catalyst comprising the delaminated SSZ-70.
  • the delaminated SSZ-70 can also be used for removing benzene from gasoline by alkylating the benzene with olefins.
  • the delaminated SSZ-70 zeolite can be in any form, but is preferred predominantly in its hydrogen ion form. It is preferred that, after calcination, at least 80% of the cation sites are occupied by hydrogen ions and/or rare earth ions.
  • alkylation feedstocks which may be alkylated by the present process of the invention include various streams in a petroleum refinery, a gas-to-liquid conversion plant, a coal-to-liquid conversion plant, or in naphtha crackers, middle distillate cracker or wax crackers, FCC off-gas, FCC light naphtha, coker off-gas, coker naphtha, hydrocracker naphtha, and the like.
  • Such streams generally contain isoparaffin(s) and/or olefin(s).
  • Such streams can be fed to the reactor of a hydrocarbon conversion system of the present invention via one or more feed dryer units.
  • Examples of separate olefin containing streams include FCC off-gas, coker gas, olefin metathesis unit off-gas, polyolefin gasoline unit off-gas, methanol to olefin unit off- gas, FCC light naphtha, coker light naphtha, Fischer-Tropsch unit condensate, and cracked naphtha.
  • Some olefin containing streams may contain two or more olefins selected from ethylene, propylene, butylenes, pentenes, and up to Ci 6 olefins.
  • the olefin containing stream can be a fairly pure olefinic hydrocarbon cut or can be a mixture of hydrocarbons having different chain lengths thus a wide boiling range.
  • the olefinic hydrocarbon can be terminal olefin (an alpha olefin) or can be an internal olefin (having an internal double bond).
  • the olefinic hydrocarbon chain can be either straight chain or branched or a mixture of both.
  • the olefinic feed may comprise a mixture of mostly linear olefins from C2 to about C ⁇ .
  • the olefins may be mostly, but not entirely, alpha olefins.
  • the olefinic feed can comprise 50% of a single alpha olefin species.
  • the olefinic feed can comprise at least 20% of alpha olefin species.
  • olefins in the feed may also undergo oligomerization when contacted with delaminated SSZ-70 catalyst in the hydrocarbon conversion zone.
  • Delaminated SSZ-70 catalyzed olefin oligomerization may take place under the same or similar conditions as the olefin-isoparaffin alkylation process. As a result, in an
  • both olefin oligomerization and olefin-isoparaffin alkylation may take place in a single reaction zone of the hydrocarbon conversion process.
  • an oligomeric olefin produced may be subsequently alkylated by an isoparaffin to provide a distillate, and/or lubricant component or base oil product.
  • Examples of isoparaffin containing streams include, but are not limited to, FCC naphtha, hydrocracker naphtha, coker naphtha, Fisher-Tropsch unit condensate, and cracked naphtha.
  • Such streams can comprise a mixture of two or more isoparaffins.
  • the feed for a delaminated SSZ-70 catalyzed process can comprise isobutane, which may be obtained, for example, from a hydrocracking unit, or may be purchased.
  • Suitable olefins for the alkylation of an aromatic hydrocarbon are those containing 2 to 16, preferably 2 to 4, carbon atoms, such as ethylene, propylene, butene-1, trans-butene-2 and cis-butene-2, or mixtures thereof. There may be instances where pentenes are desirable.
  • the preferred olefins are butenes. Longer chain alpha olefins may be used as well.
  • reaction conditions are as follows. It is preferred that the molar ratio of isoparaffins to olefins be greater than four-to-one to prevent rapid catalyst fouling.
  • the reaction temperature may range from 100° F. to 600° F., preferably 250° F. to 450° F.
  • the reaction pressure should be sufficient to maintain at least a partial liquid phase in order to retard catalyst fouling. This is typically 50 psig to 1000 psig depending on the feedstock and reaction temperature.
  • Contact time may range from 10 seconds to 10 hours, but is usually from 5 minutes to an hour.
  • the weight hourly space velocity (WHSV), in terms of grams (pounds) of isoparaffins and olefins per gram (pound) of catalyst per hour, is generally within the range of about 0.5 to 50.
  • the delaminated SSZ-70 catalyst comprises a noble metal selected from the group consisting of nickel (Ni), palladium (Pd), platinum (Pt), ruthenium (Ru), rhodium (Rh), iron (Fe), gold (Au), silver (Ag) and mixtures thereof.
  • the delaminated SSZ-70 catalyst contains at least one metal selected from Groups 6 through 8 of the periodic table.
  • the deactivated catalyst can be regenerated by hydrogenation or hydrocracking of coke or heavy hydrocarbons deposited on its surface under hydrogenation and
  • the temperature was increased to 160°C with a ramp time of 8 h and a stir rate of 150 rpm.
  • the reaction mixture was synthesized for 120h.
  • the final solids were filtered and washed with deionized water to a conductivity of ⁇ 50 ⁇ 8/ ⁇ .
  • the temperature was increased to 160°C with a ramp time of 8 h and a stir rate of 70 rpm.
  • the reaction mixture was synthesized for 116 h.
  • the final solids were filtered and washed with deionized water to a conductivity of 26 ⁇ 8/ ⁇ .
  • tetrabutylammonium fluoride trihydrate tetrabutylammonium fluoride trihydrate
  • 8.5 g tetrabutylammonium chloride were added to the flask.
  • the contents of the flask were stirred in a 95°C oil bath for 48 h.
  • the contents of the flask were then poured into a 500 mL wide-mouth bottle and sonicated in an ice bath for 2 h using a sonicator made by Sonics and Materials Inc. (Vibracell VC 750, 35% power) operating under pulse mode (4 s on and 1 s off).
  • the delaminated solution was divided into four equal parts and poured into four 250 mL centrifuge bottles.
  • a comparative catalyst was prepared per the following procedure: 90 parts by weight pseudo boehmite alumina powder (obtained from Sasol), and 10 parts by weight of Al-SSZ-70 zeolite were mixed well.
  • the SSZ-70 zeolite employed had the following properties: a S1O2/AI2O 3 mole ratio of about 80.
  • a diluted ⁇ 3 acid aqueous solution (1 wt.%) was added to the mix powder to form an extrudable paste.
  • the paste was extruded in 1/16 inch asymmetric quadrilobe shape, and dried at 250°F (121°C) overnight.
  • the dried extrudates were calcined at 850°F (454°C) for 1 hour with purging excess dry air and cooled down to room temperature.
  • Impregnation of Pt metal was done using an aqueous solution containing 3.3% Pt salt in concentrations equal to the target metal loadings of 0.5 wt.% Pt based on the bulk dry weight of the finished catalyst.
  • the total volume of the solution matched the 103% water pore volume of the above calcined base extrudate sample (incipient wetness method).
  • the metal solution was added to the base extrudates of base-A (base case) gradually while tumbling the extrudates. When the solution addition was completed, the soaked extrudates were aged for 2 hours. Then the extrudates were dried at 250°F (121°C) overnight. The dried extrudates were calcined at 662°F (350°C) for 1 hour with purging excess dry air, and cooled down to room temperature. The performance of this catalyst was evaluated with nC16 pure compound.
  • a new isomerization-improved catalyst base was prepared per the following procedure: 90 parts by weight pseudo boehmite alumina powder (obtained from Sasol), and 10 parts by weight of delaminated Al-SSZ-70 zeolite were mixed well. A diluted HN0 3 acid aqueous solution (1 wt.%) was added to the mix powder to form an extrudable paste. The paste was extruded in 1/16 inch asymmetric quadrilobe shape, and dried at 250°F (121°C) overnight. The dried extrudates were calcined at 850°F (454°C) for 1 hour with purging excess dry air and cooled down to room temperature.
  • Impregnation of Pt was done using an aqueous solution containing 3.3 wt.% Pt salt in concentrations equal to the target metal loadings of 0.5 wt.% Pt based on the bulk dry weight of the finished catalyst.
  • the total volume of the solution matched the 103% water pore volume of the above calcined base extrudate sample (incipient wetness method).
  • the metal solution was added to the base extrudates of base-B gradually while tumbling the extrudates. When the solution addition was completed, the soaked extrudates were aged for 2 hours. Then the extrudates were dried at 250°F (121°C) overnight. The dried extrudates were calcined at 662°F (350°C) for 1 hour with purging excess dry air, and cooled down to room temperature. The performance of this catalyst was evaluated with nC16 pure compound.
  • a new isomerization-improved catalyst base was prepared per the following procedure: 25 parts by weight pseudo boehmite alumina powder (obtained from Sasol), 73 parts by weight of silica-alumina powder (obtained from Sasol), and 2 parts by weight of delaminated Al-SSZ-70 zeolite were mixed well.
  • a diluted HNO 3 acid aqueous solution (1 wt.%) was added to the mix powder to form an extrudable paste.
  • the paste was extruded in 1/16 inch asymmetric quadrilobe shape, and dried at 250°F (121°C) overnight.
  • the dried extrudates were calcined at 850°F (454°C) for 1 hour with purging excess dry air and cooled down to room temperature.
  • Impregnation of Pt was done using an aqueous solution containing 3.3 wt.% Pt salt in concentrations equal to the target metal loadings of 0.5 wt.% Pt based on the bulk dry weight of the finished catalyst.
  • the total volume of the solution matched the 103% water pore volume of the above calcined base extrudate sample (incipient wetness method).
  • the metal solution was added to the base extrudates of base-C gradually while tumbling the extrudates. When the solution addition was completed, the soaked extrudates were aged for 2 hours. Then the extrudates were dried at 250°F (121°C) overnight.
  • a new isomerization-improved catalyst base was prepared per the following procedure: 25 parts by weight pseudo boehmite alumina powder (obtained from Sasol), 72 parts by weight of silica-alumina powder (obtained from Sasol), and 3 parts by weight of delaminated B-SSZ-70 zeolite were mixed well. A diluted HNO 3 acid aqueous solution (1 wt.%) was added to the mix powder to form an extrudable paste. The paste was extruded in 1/16 inch asymmetric quadrilobe shape, and dried at 250°F (121°C) overnight. The dried extrudates were calcined at 850°F (454°C) for 1 hour with purging excess dry air and cooled down to room temperature.
  • Impregnation of Pt was done using an aqueous solution containing 3.3 wt.% Pt salt in concentrations equal to the target metal loadings of 0.5 wt.% Pt based on the bulk dry weight of the finished catalyst.
  • the total volume of the solution matched the 103% water pore volume of the above calcined base extrudate of base-D (incipient wetness method).
  • the metal solution was added to the base extrudates gradually while tumbling the extrudates. When the solution addition was completed, the soaked extrudates were aged for 2 hours. Then the extrudates were dried at 250°F (121°C) overnight. The dried extrudates were calcined at 662°F (350°C) for 1 hour with purging excess dry air, and cooled down to room temperature.
  • Bronsted acidity determined by isopropylamine-temperature-programmed desorption (IPam TPD) adapted from the published descriptions by T.J. Gricus Kofke, R.K. Gorte, W.E. Farneth, J. Catal. 1 14, 34-45, 1988; T.J. Gricus Kifke, R.J. Gorte, G.T.
  • IPam TPD isopropylamine-temperature-programmed desorption
  • Table 1 Properties of calcined catalyst bases containing Al-SSZ-70 and delaminated Al-
  • the high external surface area of the support of the new catalyst base-B in comparison with the base case catalyst support of catalyst base-A is contributed to the high external surface area of delaminated Al-SSZ-70.
  • the delaminated SSZ-70-containing catalyst base-B showed a lower micropore volume. Delaminated SSZ-70 showed less Bronsted acidic density than its original precursor.
  • Table 2 Properties of calcined catalyst bases containing delaminated Al-SSZ-70 and delaminated B-SSZ-70
  • the catalyst-B containing 10% delaminated SSZ-70 significantly increased the yield of C7+.
  • the delaminated SSZ-70 significantly enhances the selectivity of isomerized CI 6 products, by nearly 20%, while also further inhibiting isomerization of MeC15 isomers to DiMeC14 products.
  • This demonstrates the superior isoselectivity of the delaminated SSZ-70 catalyst.
  • a NiW-based hydroprocessing catalyst containing USY zeolite as a base case catalyst for VGO hydroprocessing was prepared per the following procedure: 67 parts by weight silica-alumina powder (obtained from Sasol), 25 parts by weight pseudo boehmite alumina powder (obtained from Sasol), and 8 parts by weight of zeolite Y (from Tosoh) were mixed well. A diluted HNO 3 acid aqueous solution (1 wt.%) was added to the mix powder to form an extrudable paste. The paste was extruded in 1/16" asymmetric quadrilobe shape, and dried at 250°F (121°C) overnight. The dried extrudates were calcined at 1 100°F (593°C) for 1 hour with purging excess dry air, and cooled down to room temperature.
  • Impregnation of Ni and W was done using a solution containing tungsten and nickel metal salts in concentrations equal to the target metal loadings of 4 wt.% NiO and 28 wt.% WO 3 based on the bulk dry weight of the finished catalyst.
  • Organic citric acid in an amount equal to 10 wt.% of the bulk dry weight of the finished catalyst, was added to the Ni/W solution. See U.S. Pat. No. 8,637,419 for a further discussion of hydroprocessing catalyst preparation conditions with modifying agents, which patent is expressly incorporated by reference herein in their entirety.
  • the solution was heated to above 120°F (49°C) to ensure a completed dissolved (clear) solution.
  • the total volume of the metal solution matched the 103% water pore volume of the base extrudates (incipient wetness method).
  • the metal solution was added to the base extrudates gradually while tumbling the extrudates. When the solution addition was completed, the soaked extrudates were aged for 2 hours. Then the extrudates were dried at 400°F (205°C) for 2 hour with purging excess dry air, and cooled down to room temperature.
  • Impregnation of Ni and W was prepared in the same way as described above for the hydroprocessing catalyst containing USY zeolite. The impregnation was done using a solution containing tungsten and nickel metal salts in concentrations equal to the target metal loadings of 4 wt.% NiO and 28 wt.% WO 3 based on the bulk dry weight of the finished catalyst. Citric acid, in an amount equal to 10 wt.% of the bulk dry weight of the finished catalyst, was added to the Ni/W solution. See U.S. Pat. No. 8,637,419 for a further discussion of hydroprocessing catalyst preparation conditions with modifying agents, which patent is expressly incorporated by reference herein in their entirety.
  • the solution was heated to above 120°F (49°C) to ensure a completed dissolved (clear) solution.
  • the total volume of the metal solution matched the 103% water pore volume of the extrudates of catalyst base-C (incipient wetness method).
  • the metal solution was added to the base extrudates gradually while tumbling the extrudates. When the solution addition was completed, the soaked extrudates were aged for 2 hours. Then the extrudates were dried at 400°F (205°C) for 2 hour with purging excess dry air, and cooled down to room
  • VGO feed for hydroprocessing test
  • the hydroprocessing process conditions were 1900 psia hydrogen partial pressure, 1.5 LHSV, 5000 SCF/B hydrogen oil ratio, ⁇ 60wt% per pass
  • Results in Table 4 show that delaminated SSZ-70 improves cloud point and pour point more than 10°C for diesel and unconverted oil products in comparison with the catalyst containing USY zeolite because of its enhanced isomerization activity.

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Abstract

L'invention concerne des procédés améliorés utilisant un catalyseur comprenant du SSZ-70 désagrégé. Les procédés permettent d'obtenir une isosélectivité supérieure. Dans un procédé, le procédé consiste à mettre en contact une charge constituée d'hydrocarbures normaux dans des conditions d'hydrotraitement avec un catalyseur comprenant du SSZ-70 désagrégé. Dans un autre procédé, le procédé consiste à mettre en contact une charge d'hydrocarbures comprenant des oléfines à chaîne linéaire et ramifiée dans des conditions d'oligomérisation avec un catalyseur comprenant du SSZ-70 désagrégé. Dans un procédé, le procédé consiste à mettre en contact une charge d'hydrocarbures comprenant des oléfines et des isoparaffines avec un catalyseur comprenant du SSZ-70 désagrégé dans des conditions de réaction d'alkylation.
PCT/US2015/056711 2014-10-22 2015-10-21 Réactions d'hydrocarbures à l'aide de supports en zéolite désagrégée formant catalyseurs WO2016065035A1 (fr)

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