CN1288225C - FCC process incorporating crystalline microporous oxide catalysts having increased lewis acidity - Google Patents
FCC process incorporating crystalline microporous oxide catalysts having increased lewis acidity Download PDFInfo
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- CN1288225C CN1288225C CN 01814855 CN01814855A CN1288225C CN 1288225 C CN1288225 C CN 1288225C CN 01814855 CN01814855 CN 01814855 CN 01814855 A CN01814855 A CN 01814855A CN 1288225 C CN1288225 C CN 1288225C
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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
- 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
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- 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
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- 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
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
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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
- 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
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract
A catalyst component, a catalyst, and a process for making the component and catalyst are disclosed herein. Also disclosed herein is a fluid catalytic cracking process for converting petroleum feedstocks to lower boiling products wherein the feedstock is contacted with the catalyst. The catalyst component is a crystalline microporous oxide catalyst to which a compound for promoting dehydrogenation and increasing Lewis acidity is effectively added. This catalyst component can be included in an inorganic oxide matrix material and used as a catalyst. Preferably, the compound for promoting dehydrogenation and increasing Lewis acidity is effectively added to a non-framework portion of the crystalline microporous oxide.
Description
Background
The present invention relates to catalyst component, composition and preparation and use method for compositions, said composition comprises crystalline microporous oxide, and described crystalline microporous oxide contains and can promote dehydrogenation and increase lewis acidity and do not increase the promoter metal compounds of the unit cell dimension of crystalline microporous oxide.
For many years, crystalline microporous oxide such as zeolite material have commercial use always in various industry.These materials have value because of it especially as the fluid separation ability of molecular sieve and because of its ability as catalyzer.
Crystalline microporous oxide is particularly useful as the catalyzer that the big paraffin molecules of hydrocarbon mixture can be changed into littler, more undersaturated molecule such as alkene and aromatics.Method for transformation commonly used comprises fluid catalystic cracking and hydrocracking.For this conversion process being maximized many structure propertiess such as aperture, pore volume, lewis acidity and the Bronsted acidity of necessary equilibrium catalyst.If the structure properties of conversion catalyst is balance suitably not, then to change into the transformation efficiency of product low for hydrocarbon mixture, and product quality is poor, or the rapid inactivation of conversion catalyst.
Useful especially is to obtain the high crystalline microporous oxide catalysts of catalytic activity by the skeleton of equilibrium catalyst and the Bronsted acidity and the lewis acidity of non-skeleton part.By the skeleton of balance crystalline structure and the composition of non-skeleton part, can optimize catalytic activity effectively.Under the situation of cracking catalyst, the alkene of bigger paraffin molecules can be formed reaction and more effectively connect with the micromolecular scission reaction that forms in the end product.
General introduction
A kind of embodiment of the present invention comprises catalyzer, this catalyzer comprise (i) substrate material and (ii) introduce substrate material or with substrate material bonded crystalline microporous oxide.Crystalline microporous oxide comprises non-skeleton part and has certain unit cell dimension.Non-skeleton portion branch comprises the promoter metal compounds of the non-skeleton part of only introducing crystalline microporous oxide.Promoter metal compounds does not increase the unit cell dimension of crystalline microporous oxide in fact.
In the another embodiment of catalyzer, crystalline microporous oxide comprises the Y zeolite of introducing substrate material.Y zeolite comprises non-skeleton part, and its unit cell dimension is greater than about 24.30 , and comprises the aluminum oxide of the non-skeleton part of only introducing crystalline microporous oxide, so that aluminum oxide can increase lewis acidity, but does not increase the unit cell dimension of zeolite in fact.
In the another embodiment of catalyzer, crystalline microporous oxide comprises non-skeleton part, described non-skeleton portion branch comprises the promoter metal compounds that can increase lewis acidity and only introduce the non-skeleton part of crystalline microporous oxide, so that promoter metal compounds does not increase the unit cell dimension of crystalline microporous oxide in fact.
The embodiment of described catalyzer can be used for FCC apparatus, isomerization unit or hydroeracking unit by catalyzer is contacted with suitable raw material.
Another embodiment of the present invention comprises the method for preparing catalyzer.This method comprises that (a) contacts crystalline microporous oxide with the promotor precursor that comprises the promoter metal that can form promoter metal compounds, and described crystalline microporous oxide comprises non-skeleton part and has certain unit cell dimension; (b) with the mixture heating up to 150 of step (a) ℃ to 550 ℃; The promoter metal compounds that wherein will comprise described promoter metal is only introduced the non-skeleton part of crystalline microporous oxide, and wherein promoter metal compounds does not increase the unit cell dimension of crystalline microporous oxide in fact.
Another embodiment of the present invention is a kind of method that comprises following steps: (a) crystalline microporous oxide is contacted with the promotor precursor, crystalline microporous oxide comprises non-skeleton part and has certain product born of the same parents size, and the promotor precursor comprises the promoter metal that can form promoter metal compounds; (b), form the promoter metal compounds that comprises described promoter metal oxide form thus with described promotor precursors decompose; (c) described promoter metal compounds only is distributed in the non-skeleton part of described crystalline microporous oxide; Wherein promoter metal compounds does not increase the unit cell dimension of crystalline microporous oxide in fact.
Another embodiment of the present invention is a kind of method that comprises following steps: the zeolite that (a) will comprise non-skeleton part and have certain unit cell dimension is calcined; (b) zeolite is contacted with the promotor precursor that comprises the promoter metal that can form promoter metal compounds, wherein said promoter metal is selected from magnesium, chromium, iron, lanthanum, gallium, manganese and aluminium, and wherein said promotor precursor is selected from aluminium acetylacetonate, aluminum isopropylate, hexafluoroacetylacetone aluminium, dichloro two hydrated aluminums (aluminum dichlorohydrol), aluminum ethylate, three [2,2,6,6-tetramethyl--3,5-heptadione root closes] aluminium-III[Al (TMHD)
3], aluminum acetate, aluminum nitrate, Tripropoxyaluminum, magnesium acetylacetonate, chromium acetylacetonate, ferric acetyl acetonade, methyl ethyl diketone gallium, manganese acetylacetonate and lanthanon acetylacetonate; (c) with the mixture heating up to 150 of step (b) ℃ to 550 ℃; (d) product of step (b) is introduced substrate material, the promoter metal compounds that wherein will comprise described promoter metal is only introduced the non-skeleton part of zeolite, and wherein promoter metal compounds can not increase the unit cell dimension of zeolite basically.
Another embodiment of the present invention is a kind of method that comprises the steps: the crystalline microporous oxide after (a) will calcining contacts with the promotor precursor that comprises the promoter metal that can form promoter metal compounds, and described crystalline microporous oxide comprises non-skeleton part and has certain unit cell dimension; (b) described promoter metal compounds is activated, wherein said promoter metal compounds is only introduced the non-skeleton part of crystalline microporous oxide, and wherein promoter metal compounds can not increase the unit cell dimension of crystalline microporous oxide basically.
Another embodiment of the present invention is a kind of method that comprises the steps: (a) calcining crystalline microporous oxide, crystalline microporous oxide comprise non-skeleton part and have certain unit cell dimension; (b) contact is selected from the aluminum alkyls of trimethyl aluminium, triethyl aluminum, tri-tert aluminium and triisobutyl aluminium; (c) product of step (b) is handled to form promoter metal compounds with oxygen carrier, wherein promoter metal compounds can not increase the unit cell dimension of crystalline microporous oxide basically.
Other embodiment of the present invention comprises the product by method preparation of the present invention.Substrate material can be introduced or do not introduced to these products, but the preferred substrate material of introducing uses in process unit then.
Describe in detail
Can promote dehydrogenation and increase the lewis acidity of crystalline microporous oxide and do not increase the promoter metal compounds of its unit cell dimension by introducing effectively, can improve for example catalytic activity of zeolite of crystalline microporous oxide.Although crystalline microporous oxide can be used alone as catalyzer, preferably crystalline microporous oxide is introduced substrate material, preferred inorganic oxide.The catalyst component or the on-catalytic component that in substrate material, also can have other.
Crystalline microporous oxide of the present invention can be used for the elementary product catalytic pyrolysis of catalytic cracking reaction is become refined products, as petroleum naphtha that is used as fuel and the alkene that is used as chemical feedstocks.Crystalline microporous oxide is preferably selected from crystalloid aluminosilicate zeolite (below be called zeolite), tectosilicate, the aluminophosphates (ALPOs) of positive tetrahedron and the silicoaluminophosphates (SAPOs) of positive tetrahedron.More preferably crystalline microporous oxide is a zeolite.
Suitable zeolite comprises natural and synthetic zeolite.Suitable natural zeolite comprises sarcolite, chabazite, dachiardite, clinoptilolite, faujusite, heulandite, levyne, erionite, cancrinite, scolecite, offretite, mordenite and ferrierite.Suitable synthetic zeolite is X zeolite, Y zeolite, L zeolite, ZK-4 zeolite, ZK-5 zeolite, E zeolite, H zeolite, J zeolite, M zeolite, Q zeolite, T zeolite, Z zeolite, α and β zeolite, ZSM type zeolite and omega zeolite.Preferred faujusite, preferred especially unit cell dimension more than or equal to 24.30 , more preferably greater than or equal Y zeolite and the X zeolite of about 24.40 .Aluminium in the zeolite and silicon components can replace with other skeleton component.For example, aluminum portions can replace with boron, gallium, titanium or the trivalent metal composition heavier than aluminium.Germanium can be used for replacing the silicon part.
In the catalyst product of making, crystalline microporous oxide is preferably included in the inorganic oxide matrix material that catalyst component is bonded together, and is enough to bear between particle and the collision of wall of reactor so that final catalyst is very hard.The inorganic oxide matrix material can be made by inorganic oxide sol or gel, thereby this inorganic oxide sol or gel are dried with catalyst component " bonding " together.Preferred inorganic oxide matrix material comprises the oxide compound of silicon and aluminium.The inorganic oxide matrix material also can comprise active porous inorganic oxide catalyst component and inert catalyst component.The all components of preferred catalyst keeps together by being attached on the inorganic oxide matrix material.
Active porous inorganic oxide catalyst component is generally too big and can not enter the formation that the hydrocarbon molecule of crystalline microporous oxide comes the elementary product of catalysis by the cracking volume.The active porous inorganic oxide catalyst component that can introduce cracking catalyst is the porous inorganic oxide preferably, compares with the blank thing of acceptable heat, and the hydrocarbon cracking that described porous inorganic oxide will be a large amount of relatively becomes more low-molecular-weight hydrocarbon.The silicon-dioxide of low surface area (for example quartzy) is one type the blank thing of acceptable heat.(little activity test ASTM#D3907-8) can be measured the cracking degree with any for example MAT in the various ASTM tests.Preferably be disclosed in Greensfelder, B.S. waits the people, Industrial and Engineering Chemistry, pp.2573-83, those compounds of Nov.1949.Preferred compound is aluminum oxide, silica-alumina and silica-alumina-zirconium white.
The inert catalyst component can increase density, intensity usually and serve as the holder of protectiveness.Can introduce the cracking activity of the inert catalyst component of cracking catalyst of the present invention does not preferably want obviously greater than the blank thing of acceptable heat.The clay of kaolin and other and Alpha-alumina, titanium dioxide, zirconium white, quartz and silicon-dioxide are the examples of suitable inert component.
Preferably discontinuous aluminum oxide is introduced the inorganic oxide matrix material mutually.Can use aluminum oxyhydroxide class-gama-alumina, boehmite, diaspore and transitional alumina for example Alpha-alumina, beta-alumina, gama-alumina, δ-aluminum oxide, ε-aluminum oxide, κ-aluminum oxide, ρ-aluminum oxide.Preferred alumina type is for example gibbsite, bayerite, promise gibbsite or doyelite of three aluminium hydroxides.
In one embodiment of the present invention, the crystalline microporous oxide catalysts component comprises the compound that can promote dehydrogenation and increase lewis acidity, and this compound is called promoter metal compounds in this article.The distribution of promoter metal compounds in crystalline microporous oxide can not cause any substantive the increasing of crystalline microporous oxide unit cell dimension, and the unit cell dimension of crystalline microporous oxide material is substantially the same.
Promoter metal compounds preferably be in can promote paraffinic hydrocarbons and cyclanes compound in the hydrocarbon incoming flow effectively dehydrogenation to form the chemical state of alkenes compounds.For example, aluminum oxide (Al
2O
3) comprise suitable promoter metal (aluminium).The oxide compound of aluminium is to be in a kind of like this effective chemical attitude.
Crystalline microporous oxide comprises skeleton part and non-skeleton part.The number of the effective metal cation-bit of the non-skeleton part by increasing crystalline microporous oxide increases the lewis acidity of crystalline microporous oxide and does not increase unit cell dimension.Normally, when the skeleton portion timesharing of material being introduced material, unit cell dimension will increase.When promoter metal compounds of the present invention being introduced in the crystalline microporous oxide material of the present invention, it is identical that unit cell dimension keeps basically.Therefore, preferably promoter species is only introduced the non-skeleton part of crystalline microporous oxide material.Referring to W.O.Haag, " utilize the katalysis-Science and Technology of zeolite ", Zeolites andRelated Microporous Materials, J.Weitkamp, H.G.Karge, H.Pfeifer and W.Holderich edit, Vol.84, Elsevier Science B.V., 1994, wherein pp.1375-1394 has discussed the mutual relationship of lewis acidity position, at this document is incorporated herein by reference.In this article, metallic cation is meant metal ion or metal ion oxygenates ionic species.
A kind of embodiment of the present invention is the method for preparing active catalytic components.Other embodiment is the active catalytic components and the final catalyst product that comprises substrate material by this method preparation.
A kind of embodiment of the inventive method comprises by mixing or other appropriate means, crystalline microporous oxide is contacted with the promotor precursor that can form promoter metal compounds.In this article, mix being meant, might not need any mechanical stirring each component merging.The promotor precursor is contacted the non-skeleton part that makes the promotor precursor be dispensed into crystalline microporous oxide with crystalline microporous oxide.Preferably the decomposition by the promotor precursor activates promoter metal compounds then, the promoter metal compounds of the non-skeleton that produces remaining organic moiety and absorption or be distributed to product attitude microporous oxide in partly.In order to increase effective number of the non-skeleton acidic site of metallic cation, promoter metal compounds by liquid phase or gas-phase reaction for example the gas phase transmission be adsorbed onto on the crystalline microporous oxide.
The time that the promotor precursor contacts with crystalline microporous oxide, should be enough to make crystalline microporous oxide to keep the promoter metal oxide compound by the generation of promotor precursors decompose of 40 to 60% weight, preferred about 50% weight.Measure reserving degree by the weight of measuring crystalline microporous oxide/promotor precursor mixture in the activation/heating steps process.With crystalline microporous oxide and promotor precursor with crystalline microporous oxide: the promotor precursor is that mix 100: 15 to 100: 200, preferred 100: 15 to 100: 100 weight ratio.For example, with in zeolite and the embodiment that aluminium acetylacetonate contacts, aluminium acetylacetonate is about 15.7% Al because of decomposition/reaction produces a kind of
2O
3Suppose after decomposition/reaction, from the Al of aluminium acetylacetonate
2O
3In about 55% weight be distributed to the non-skeleton part of zeolite and kept here by zeolite, in order to make 15 gram Al
2O
3Be distributed on the 100 gram zeolites and (increase 15%Al
2O
3), 100 gram zeolites should be mixed with about 175 gram aluminium acetylacetonates:
15g Al
2O
3/ (0.157 Al
2O
3/ aluminium acetylacetonate * 0.55 (percentage ratio of decomposition)))=173.4 restrains aluminium acetylacetonate.
By being contacted with suitable oxygen-containing gas with the burning organic moiety, organic moiety removes remaining organic moiety.Also can use other proper method well known in the art.
Promoter metal compounds is polyvalent metal compounds preferably.Preferred polyvalent metal compounds is the compound that contains divalence or trivalent metal, is preferably selected from magnesium, chromium, iron, lanthanum, gallium, manganese and aluminium.
The preferred promoter precursor is stable in gas phase, and preferably its boiling point less than about 550 ℃, be more preferably less than about 500 ℃.The example of preferred promotor precursor includes but not limited to aluminium acetylacetonate, aluminum isopropylate, hexafluoroacetylacetone aluminium, dichloro two hydrated aluminums, aluminum ethylate, three [2,2,6,6-tetramethyl--3,5-heptadione root closes] aluminium-III[Al (TMHD)
3], aluminum alkyls for example trimethyl aluminium, triethyl aluminum and triisobutyl aluminium, aluminum acetate, aluminum nitrate, Tripropoxyaluminum, methyl ethyl diketone gallium, manganese acetylacetonate, magnesium acetylacetonate, chromium acetylacetonate, ferric acetyl acetonade and lanthanon Acetyl Acetone thing.
In a kind of specific embodiment, preferably by means commonly known in the art crystalline microporous oxide is calcined, then it is contacted with the promotor precursor, described promotor precursor includes but not limited to aluminium acetylacetonate, aluminum isopropylate, hexafluoroacetylacetone aluminium, dichloro two hydrated aluminums, aluminum ethylate, three [2,2,6,6-tetramethyl--3,5-heptadione root closes] aluminium-III[Al (TMHD)
3], aluminum acetate, aluminum nitrate, Tripropoxyaluminum, magnesium acetylacetonate, chromium acetylacetonate, ferric acetyl acetonade, manganese acetylacetonate, methyl ethyl diketone gallium and lanthanon Acetyl Acetone thing, its activation back forms promoter metal compounds.
By the mixture heating up of crystalline microporous oxide/promotor precursor is come the active cocatalyst metallic compound to about 150 ℃ to about 550 ℃.Heating steps becomes remaining organic moiety with the promotor precursors decompose and can be dispensed into the promoter metal compounds of the non-skeleton part of crystalline microporous oxide.The activatory crystalline microporous oxide catalysts component of Sheng Chenging can be mixed with suitable substrate material and as catalyzer then.In this embodiment, preferred promotor precursor comprises that in one embodiment crystalline microporous oxide is a zeolite, preferred Y zeolite, and the promotor precursor is an aluminium acetylacetonate, generates the aluminum oxide promoter metal compounds of aluminum oxide.
In another kind of specific embodiment, preferably, then it is contacted with the promotor precursor that comprises aluminum alkyls by means commonly known in the art with the crystalline microporous oxide calcining.Suitable aluminum alkyls includes but not limited to trimethyl aluminium, triethyl aluminum, tri-tert aluminium, triisobutyl aluminium.In this embodiment, contact the active cocatalyst metallic compound by mixture and oxygen carrier with crystalline microporous oxide/promotor precursor.Suitable oxygen carrier includes but not limited to air, oxygen, water and alcohols for example methyl alcohol, ethanol, Virahol and butanols.Oxygen carrier and aluminum alkyls reaction come the active cocatalyst metallic compound by the organic moiety that forms aluminum oxide and remnants thus.Reactions steps becomes the promotor precursors decompose can be distributed in the non-skeleton part of crystalline microporous oxide and enters the promoter metal compounds of remaining organic moiety, if desired, can the organic moiety of remnants be removed according to top description.The activatory crystalline microporous oxide catalysts component of Sheng Chenging can be mixed with suitable substrate material and as catalyzer then.The preferred promoter metal comprises aluminium, and crystalline microporous oxide comprises zeolite.
The method of earlier paragraphs is obtained, comprise the crystalline microporous oxide material and be incorporated into the product of promoter metal compounds of the non-skeleton part of crystalline microporous oxide material, join in the aforesaid inorganic oxide matrix material to form catalyzer, be preferably formed fresh free of contamination catalyzer.Then this catalyzer is sent in the process unit with as described below and carries out suitable application.
Although other catalyst component and material can be introduced catalyzer, substrate material can constitute the surplus of finished catalyst composition.About 40% weight that the preferred substrate material accounts for catalyzer is to about 90% weight, more preferably from about 50% weight is to about 80% weight, according to total restatement of catalyzer.Microporous oxide, clay and the carbon monoxide oxidation promotor of other type are introduced catalyzer also within the scope of the invention.Catalyzer of the present invention is preferably freshly prepd in being sent to cracking technology the time, and just, catalyzer is substantially free of the metal that can pollute catalyzer in catalytic cracking process.Described metal includes but not limited to nickel, vanadium, sodium and iron.
Catalyzer of the present invention can be used for various oil and chemical process, particularly wherein needs those processes of paraffin dehydrogenation.For example, they can be used for the reaction in catalysis fluid catalystic cracking, hydrocracking and the isomerization.Promoter metal compounds is adsorbed onto on the crystalline microporous oxide part of catalyzer in the mode that can promote paraffinic hydrocarbons and naphthenic hydrocarbon dehydrogenation.Result as paraffinic hydrocarbons contacts with crystalline microporous oxide preferably becomes alkene with bigger paraffin conversion.Preferably alkene is changed into littler paraffin molecules, olefin hydrocarbon molecules and aromatics molecule with the ratio that fuel Products needs then.
Fluid catalystic cracking is used to high boiling oil oils is changed into more valuable low-boiling products, comprises gasoline and intermediate oil for example kerosene, aviation kerosene and heated oil.The charging commonly used of catalytic cracking unit has higher boiling point and comprises residual oil itself, perhaps the mixture of residual oil and other high boiling fraction.The most frequently used charging is a gas oil, its initial boiling point usually above about 230 ℃, more generally be higher than about 350 ℃, terminal point is the highest to be about 620 ℃.Gas oil commonly used comprises straight run (normal pressure) gas oil, vacuum gas oil and coker gas oil.As those of ordinary skill in the art understands, owing in the petroleum hydrocarbon cut, have so much dissimilar compound, so be difficult to accurately define described hydrocarbon-fraction by initial boiling point.Hydrocarbon-fraction in this boiling range comprises gas oil, thermal oil, residual oil, turning oil, topped oil and whole crude, tar sand oils, shale oil, synthol, the heavy hydrocarbon fractions that derives from coking, tar, wood pitch, petroleum pitch and derives from any hydrotreated feed in the aforementioned substances.
Fluidized bed catalytic cracker comprises reactor usually, and raw material contacts therein with the hot fine catalyst that heats in revivifier.Conveyer line connects two containers to remove catalyst particle to and fro.Cracking reaction is preferably carried out under the following conditions: temperature be about 450 ℃ to about 680 ℃, more preferably from about 480 ℃ to about 560 ℃, pressure be about 5 to 60psig, more preferably from about 5 to 40psig, duration of contact (catalyzer contacts with charging) for the ratio of about 0.5 to 15 second, more preferably from about 1 to 6 second, catalyzer and oils be about 0.5 to 10, more preferably from about 2 to 8.
In the cracking reaction process, form low-boiling products, and some hydrocarbons and nonvolatile sedimentation of coke are to catalyst particle.By stripping catalyst, preferably remove hydrocarbons with the steam stripped catalyzer.Nonvolatile coke is made up of height condensed aromatic hydrocarbon usually.Along with hydrocarbons and coke build-up on catalyzer, cracking catalyst active and the catalyst selectivity that generates the gasoline adulterant reduce.Remove most hydrocarbons by stripping, and remove coke, can recover most of initial activity of catalyst particle by suitable oxidation regeneration.Therefore, catalyst particle is sent to stripper, is sent to revivifier then.
By with oxygen-containing gas for example the deposits of coke on the air combustion catalyst surface realize the regeneration of catalyzer.Catalyst temperature in the regenerative process is about 560 ℃ to about 760 ℃.Granules of catalyst after the regeneration is returned to reactor by conveyer line then, and because its heat can maintain reactor the required temperature of cracking reaction.Combustion of coke is thermopositive reaction; Therefore, in utilizing the conventional fluidized bed catalytic cracker of conventional charging, do not need to add other fuel.In implementation process of the present invention used raw material mainly because of the content of its lower aromatics and because of the duration of contact in reactor or conveyer line shorter relatively, may not with enough sedimentation of coke to the catalyst particle in revivifier, to reach required temperature.Therefore, may need to use other fuel so that the higher temperature in the revivifier to be provided, the heat of getting back to the catalyst particle of reactor like this is enough to keep cracking reaction.The suitable non-limitative example of adding fuel comprises the C that derives from catalytic cracking process itself
2Gas, Sweet natural gas and torch oil.Preferred C
2Gas.
Isomerization is the another kind of method that wherein can use catalyzer of the present invention.Can carry out isomerized hydro carbons by method of the present invention and comprise and contain 4-20, preferred 4-12, the more preferably from about paraffinic hydrocarbons and the olefinic hydro carbons of 4-6 carbon atom usually, and aromatics dimethylbenzene for example.Preferred charging is made up of the paraffinic hydrocarbons that with butane, pentane, hexane, heptane etc. is representative.Isomerisation conditions comprises: temperature is about 80 ℃ to about 350 ℃, preferred about 100 ℃ to 260 ℃; Pressure be about 0 to 1000psig, preferred about 0 to 300psig; Liquid hourly space velocity is about 0.1 to 20, preferred about 0.1 to 2; Hydrogen gas rate in standard cubic feet per barrel is about 1000 to 5000, preferred about 1500 to 2500.Service temperature and catalyst activity and air speed is interrelated, handle thereby under the catalyst deactivation rate of maximum stream time of the catalyzer that can guarantee regeneration period, provide the reasonable raw material rapid processing.
Catalyzer of the present invention also can be used for hydrocracked, treated.Hydrocracking has improved the total refining yield of premium blending compound.In fixed-bed reactor, hydrocracking can utilize low-quality relatively gas-oil feed (otherwise this gas oil will be impregnated in distillate fuel) and with its conversion in the presence of hydrogen and suitable catalyzer.Usually raw material mixed, is heated to about 140 ℃ to 400 ℃ with hydrogen, be forced into about 1200 to 3500psi, be fed to first step reactor then, the raw material reaction of about 40 to 50% weight disinthibites cracking reaction and makes the nitrogen of product quality reduction and the compound of sulphur to remove in this reactor.The logistics cooling that to flow out from first step reactor, liquefy and pass separator, in this separator, take out butane and light gas.Bottom fraction is sent to second stage reactor and carries out cracking with higher temperature and pressure, wherein generate other gasoline blending compound and isocrackate.
With reference to the following embodiment that is used to illustrate embodiment of the present invention, can further understand the present invention.
Embodiment 1
The three kinds of enterprising column criterion MAT test of independent commercially available crystalline microporous oxide (for example little activity tests, ASTM#D3907-8): USY is (available from W.R.Grace, the Z14USY of Davison Division, or derive from LZY 82 or the LZY 84 of UOP), LZ-210 is (available from Katalystiks, Inc.) and the Y (CREY of incinerating rare earth exchanged, available from W.R.Grace, Davison Division).Before carrying out MAT test, with crystalline microporous oxide and substrate material (Ludox is available from DuPont) mix be incorporated in 1400 with steam treatment 16 hours with the generation cracking catalyst.
Each catalyzer of testing comprises 20% weight zeolite and 80% weight substrate material.The result is illustrated in as in the following table 1.
Table 1
| MAT result | USY | LZ-210 | CREY |
| Transformation efficiency (% weight, 400 -) H 2(% weight) C (% weight) surface-area (m 2/ g) pore volume (cm 3/ g) unit cell dimension () | 42.5 0.0113 1.480 200 0.439 24.21 | 47.7 0.0186 1.891 189 0.023 24.24 | 64.1 0.0064 1.760 130 0.254 24.51 |
Embodiment 2
According to A.Dyer, An Introduction to Zeolite Molecular Sieves, the 6th chapter, " as the zeolite of ion-exchanger ", John Wiley ﹠amp; Sons, the method for carrying out cationic exchange in zeolite described in 1998 is carried out metal ion exchanged with the crystalline microporous oxide of embodiment 1, at this these chapters and sections is incorporated herein by reference.After crystalline microporous oxide carries out ion-exchange, it is mixed with substrate material and use steam treatment, carry out the MAT test of standard then according to the description among the embodiment 1.The results are shown in the table 2.
Table 2
| MAT result | USY +Al 2O 3 | LZ-210 +Al 2O 3 | CREY +Al 2O 3 |
| Transformation efficiency (% weight, 400 -) H 2(% weight) C (% weight) surface-area (m 2/ g) pore volume (cm 3/ g) unit cell dimension () | 29.8 0.0047 1.119 194 0.346 24.25 | 38.5 0.0055 1.737 172 0.314 24.22 | 51.1 0.0056 1.516 161 0.318 24.36 |
The result shows: compare with the non-commutative crystalline microporous oxide of embodiment 1, the crystalline microporous oxide of metal ion exchanged significantly reduces the transformation efficiency of product.This shows that the metal ion exchanged step causes the loss of the non-skeleton effective metal cation-bit partly of crystalline microporous oxide, because the balance between Bronsted position and the Louis position is unfavorable for required activity.
Embodiment 3
MAT three kinds of independent enterprising column criterions of commercially available crystalline microporous oxide tests: utilize the CREY (RECREY) of the method for Dyer with the prepared rare earth exchanged of a part of the CREY of rare-earth ion solution switching implementation example 1; Method NH according to Dyer
4 +About 4% weight Na of exchange CREY
+The Y (HCREY) of prepared hydrogen incinerating rare earth exchanged; With according to R.Szostak, " modified zeolite " (the 5th chapter), Introduction to ZeoliteScience and Practice, Vol.58, H.Van Bekkum, E.M.Flanigan and J.C.Jansen edit, Elsevier, the method of describing among 1991 the reference 6-13 is by calcining NH
4The Y (USCREY) of the prepared overstable incinerating rare earth exchanged of CREY.Before carrying out the MAT test, with zeolite and substrate material (10% weight zeolite; 30% weight SiO
2, for available from Unimin Specialty Minerals, the IMSIL-A-8 of Inc.; 60% weight SiO
2-Al
2O
3, from deriving from W.R.Grace, the gel of Davison Division makes, and this gel drying also provides 25% weight Al when washing
2O
3, SiO
2-Al
2O
3) mix to generate cracking catalyst.The results are shown in the table 3.
Table 3
| MAT result | RECREY | HCREY | USCREY |
| Transformation efficiency (% weight, 430 -) C (% weight) 650 +product (% weight) surface-area (m 2/ g) unit cell dimension () | 45.3 1.34 32.4 101 24.49 | 50.1 1.39 27.4 129 24.45 | 44.0 1.33 32.7 113 - |
Embodiment 4
In independent container, each crystalline microporous oxide of embodiment 3 is mixed (ratio of zeolite and aluminium acetylacetonate was near 1: 1.4, and the decomposition temperature of aluminium acetylacetonate is higher than 320 ℃ a little) with aluminium acetylacetonate.Each container is all placed baking oven and is heated to 150 ℃, kept 1 hour, purge baking oven with the nitrogen amount that is enough to wash out the degradation production that decomposes of methyl ethyl diketone that may be inflammable then.Behind the purging, with baking oven for heating to 500 ℃ and kept cooling then 1 hour.Then baking oven was heated 2 hours at 500 ℃ in air.Weight meter according to product can calculate the result as adition process, about 45% weight estimate that from the aluminium acetylacetonate amount available aluminum oxide is retained in the zeolite.The zeolite that will contain the aluminum oxide of adding according to the description among the embodiment 3 is made catalyzer then, and tests under the MAT of standard condition then.The results are shown in the table 4.
Table 4
| MAT result | RECREY +Al 2O 3 | HCREY +Al 2O 3 | USCREY +Al 2O 3 |
| Transformation efficiency (% weight, 430 -) | 55.2 | 58.2 | 60.8 |
| C (% weight) 650 +product (% weight) surface-area (m 2/ g) unit cell dimension () | 1.63 22.6 118 - | 1.57 19.3 81 24.43 | 1.65 17.4 143 24.46 |
The result shows: compare with the crystalline microporous oxide that does not add metal of embodiment 3, the crystalline microporous oxide that contains the metallic compound that can promote dehydrogenation and lewis acidity of interpolation obviously raises to the transformation efficiency of gasoline product.This shows that the adding metallic compound has increased the number of the non-skeleton effective metal cation-bit partly of crystalline microporous oxide.In other words, the adding of metallic compound causes the lewis acidity position obviously to increase.This point be also illustrated in by the acidic site number of the every gram catalyzer of direct mensuration as in the following table 5.
If after carrying out steam treatment according to the description among the embodiment 3, with pyridine adsorption to catalyzer, heating under vacuum to 250 ℃ is to inhale any pyridine in nonacid position from more weak acidolysis then, infrared spectra can be used for measuring the relative quantity that is adsorbed onto the pyridine on the Bronsted acidity position with pyridinium ion, and with the amount of coordination pyridine adsorption to the strong lewis acid position.When the catalyzer after the desorb is carried out described Infrared spectroscopy, can on three kinds of catalyzer, observe the following band intensity of the pyridine of absorption.
Three kinds of different materials are arranged: 1) RECREY, the zeolite of the rare earth exchanged of FAU structure-type in table 5.This is the raw material of two samples in back in this table.2) aluminum oxide-I of RECREY+ adding, it is the sample that has added aluminum oxide with method teaching herein in RECREY, described aluminum oxide is the aluminum oxide that effectively adds.3) aluminum oxide-II of RECREY+ adding, it is the sample that has added aluminum oxide in RECREY, the adding mode of described aluminum oxide can not effectively increase Lewis acid.
People such as R.J.Gorte [Journal of Catalysis 148,213-223, (1994), and reference wherein] and people [Journal of Catalysis 148 such as G.L.Price, 228-236, (1994)] Jiao Dao method is used for quantitatively determining total acidity, be characterized by the amount of the amount of strong acidic site (intensity is enough to make Tri N-Propyl Amine resolve into propylene and ammonia when thermal desorption) and slightly acidic position (this acidity keeps amine because of itself and Tri N-Propyl Amine 50 ℃ of interactions, but when temperature raises with the desorb Tri N-Propyl Amine).This mensuration can be measured Bronsted and lewis acidity position simultaneously.Tart is measured with the milligramequivalent of every gram material and is represented (1 mmole amine is counted and the reaction of 1 mmole acidic site).
Table 5
| The Al that RECREY adds 2O 3 | The Al that RECREY+ adds 2O 3 | RECREY+ | |
| Total Al 2O 3(% weight) strongly-acid, the MEQV/G slightly acidic, the MEQV/G total acidic, MEQV/G | 19.7 0.46 2.64 3.10 | 30.5 0.38 2.99 3.37 | 27.0 0.40 2.59 2.99 |
Table 5 explanation: only under the situation that adds aluminum oxide effectively (I), slightly acidic just increases together together with total acidic.The amount of simple increase aluminum oxide that shows another embodiment (II) differs increases acidity surely.
According to the description among the embodiment 3, aforesaid each zeolite sample is used to prepare catalyzer, then with embodiment 3 described identical conditions under with these composite catalysts with steam treatment so that its inactivation.
Part with every kind of catalyst sample is pressed into thin disk then.Each disk is weighed and measure its diameter and thickness.Then each disk is placed vacuum chamber and heating to remove all water or the gas of other absorption.Then it is cooled to 50 ℃ and contact in short time with the pyridine steam.Then sample is kept in a vacuum a few hours and measured its infrared spectra, particularly at 1400cm
-1To 1600cm
-1Between infrared spectra.Then sample is heated to 250 ℃ and keep a few hours, measures its infrared spectra once more.The temperature of this rising and high vacuum are removed the pyridine of all physical adsorptions.
On the material before the pyridine adsorption, measure 1400cm
-1To 1600cm
-1Between infrared spectra, from the spectrum of the sample that contains pyridine, deduct this spectrum.The spectrum that obtains is because the acidic site results of interaction of pyridine and catalyzer.
In this SPECTRAL REGION, 1540cm
-1To 1550cm
-1The peak at place is owing to carrying out the coordinate pyridine with proton from the Bronsted acidity position.1440cm
-1To 1460cm
-1Between the peak receive position (Lewis acid) interactional pyridine owing to the electron pair on the nitrogen and solid electronics.At this SPECTRAL REGION 1440cm
-1To 1660cm
-1In, 1480cm
-1To 1500cm
-1Between other bands of a spectrum are the results that are adsorbed onto the bands of a spectrum combination of the pyridine on Bronsted and the Louis position.
For the composite catalyst that the zeolite of crossing with steam treatment, usefulness is shown in Table 5 is made, table 6 has been listed because of there being the observed band intensity of Bronsted and Louis position on the catalyzer.
Table 6
| The reason of band intensity: (absolute units/gram) | RECREY I | RECREY+ADA II | RECREY+ADA |
| Lewis acidity position, Bronsted position | 22 55 | 33 104 | 33 60 |
These results show that effective adding of this metallic compound has increased the lewis acidity of active catalyst really.
Now describe the present invention fully, it should be appreciated by those skilled in the art, in claims wide parameter area required for protection, can carry out the present invention.
Claims (17)
1, a kind of fluid catalystic cracking method, this method comprises:
Under the fluid catalystic cracking condition raw material is contacted with freshly prepd catalyzer, this freshly prepd catalyzer comprises:
(i) substrate material
The crystalline microporous oxide of (ii) introducing substrate material or combining with described substrate material, described crystalline microporous oxide comprises non-skeleton part and has certain unit cell dimension, described non-skeleton portion branch comprises the promoter metal compounds of the non-skeleton part of only introducing crystalline microporous oxide, and wherein promoter metal compounds can not increase the unit cell dimension of crystalline microporous oxide in fact.
2, the described method of claim 1, wherein promoter metal compounds is a polyvalent metal compounds.
3, the described method of claim 1, wherein promoter metal compounds is an aluminum compound.
4, the described method of claim 1, wherein crystalline microporous oxide is a zeolite.
5, the described method of claim 4, wherein crystalline microporous oxide is X or Y zeolite.
6, the described method of claim 5, wherein crystalline microporous oxide is the Y zeolite that unit cell dimension is equal to or greater than 24.30 .
7, the described method of claim 5, wherein crystalline microporous oxide is the Y zeolite that unit cell dimension is equal to or greater than 24.40 .
8, the described method of claim 1, wherein said crystalline microporous oxide is selected from zeolite, tectosilicate, tetrahedral aluminophosphates and tetrahedral silicoaluminophosphates.
9, the described method of claim 1, wherein said crystalline microporous oxide is a zeolite, and wherein said promoter metal compounds is an aluminum oxide.
10, the described method of claim 1, wherein said promoter metal compounds is a metal oxide, the metal of wherein said metal oxide is selected from magnesium, chromium, iron, lanthanum, gallium, manganese and aluminium.
11, a kind of fluid catalystic cracking method, this method comprises:
Under the fluid catalystic cracking condition raw material is contacted with freshly prepd catalyzer, this freshly prepd catalyzer comprises:
(i) substrate material
(ii) introduce the Y zeolite of described substrate material, described Y zeolite comprises non-skeleton part and has unit cell dimension greater than about 24.30 , described non-skeleton portion branch comprises the aluminum oxide of the non-skeleton part of only introducing crystalline microporous oxide, and wherein aluminum oxide has increased lewis acidity and do not increased the unit cell dimension of zeolite in fact.
12, a kind of fluid catalystic cracking method, this method comprises:
Under the fluid catalystic cracking condition raw material is contacted with freshly prepd catalyzer, this freshly prepd catalyzer comprises:
(i) substrate material
(ii) introduce the crystalline microporous oxide of described substrate material, described crystalline microporous oxide comprises non-skeleton part and has certain unit cell dimension, described non-skeleton portion branch comprises can increase lewis acidity, only introduce the promoter metal compounds of the non-skeleton part of crystalline microporous oxide, and wherein promoter metal compounds does not increase the unit cell dimension of crystalline microporous oxide in fact.
13, the described method of claim 12, wherein said crystalline microporous oxide is selected from zeolite, tectosilicate, tetrahedral aluminophosphates and tetrahedral silicoaluminophosphates.
14, the described method of claim 12, wherein said crystalline microporous oxide is a zeolite, and wherein said promoter metal compounds is an aluminum oxide.
15, the described method of claim 12, wherein said promoter metal compounds is a metal oxide, the metal of wherein said metal oxide is selected from magnesium, chromium, iron, lanthanum, gallium, manganese and aluminium.
16, the described method of claim 14, its mesolite is the Y zeolite that unit cell dimension is equal to or greater than 24.30 .
17, the described method of claim 14, its mesolite is the Y zeolite that unit cell dimension is equal to or greater than 24.40 .
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/653,136 US6673734B1 (en) | 1994-10-03 | 2000-08-31 | Crystalline microporous oxide catalysts having increased Lewis acidity and methods for the preparation thereof |
| US09/653,135 US6482313B1 (en) | 1994-10-03 | 2000-08-31 | FCC process incorporating crystalline microporous oxide catalysts having increased Lewis acidity |
| US09/653,135 | 2000-08-31 | ||
| US09/653,136 | 2000-08-31 |
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| CN1288225C true CN1288225C (en) | 2006-12-06 |
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| AU2001285090B2 (en) * | 2000-08-31 | 2005-11-10 | Exxonmobil Research And Engineering Company | Crystalline microporous oxide catalysts having increased lewis acidity and methods for the preparation thereof |
| JP5399705B2 (en) * | 2006-08-31 | 2014-01-29 | Ｊｘ日鉱日石エネルギー株式会社 | Fluid catalytic cracking method |
| JP5390857B2 (en) * | 2006-08-31 | 2014-01-15 | Ｊｘ日鉱日石エネルギー株式会社 | Fluid catalytic cracking method |
| BRPI0803718A2 (en) * | 2008-08-29 | 2010-06-15 | Petroleo Brasileiro Sa | method for the production of light olefins in catalytic cracking units with energy deficiency |
| RU2548362C2 (en) | 2009-06-25 | 2015-04-20 | Чайна Петролеум & Кемикал Корпорейшн | Catalyst for catalytic cracking and method of increasing catalyst selectivity (versions) |
| EP2463028A1 (en) * | 2010-12-11 | 2012-06-13 | Umicore Ag & Co. Kg | Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic removal of nitrogen oxides |
| US8945373B2 (en) * | 2011-12-22 | 2015-02-03 | Iogen Corporation | Method for producing renewable fuels |
| CN106179391B (en) * | 2015-04-30 | 2019-01-25 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN106179387B (en) * | 2015-04-30 | 2019-01-25 | 中国石油化工股份有限公司 | The preparation method of Hydrobon catalyst composition |
| CN106179378B (en) * | 2015-04-30 | 2018-12-21 | 中国石油化工股份有限公司 | The preparation method of hydrotreating catalyst |
| CN106179379B (en) * | 2015-04-30 | 2018-11-06 | 中国石油化工股份有限公司 | A kind of preparation method of hydrotreating catalyst |
| CN106179388B (en) * | 2015-04-30 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of preparation method of hydrotreating catalyst |
| CN106179383B (en) * | 2015-04-30 | 2018-11-06 | 中国石油化工股份有限公司 | The preparation method of hydrotreating catalyst |
| CN106179465B (en) * | 2015-04-30 | 2018-12-21 | 中国石油化工股份有限公司 | The preparation method of hydrocracking catalyst |
| CN106179384B (en) * | 2015-04-30 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrobon catalyst |
| CN106179385B (en) * | 2015-04-30 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrobon catalyst |
| CN106179381B (en) * | 2015-04-30 | 2019-03-19 | 中国石油化工股份有限公司 | The preparation method of Hydrobon catalyst |
| CN106179382B (en) * | 2015-04-30 | 2019-02-22 | 中国石油化工股份有限公司 | A kind of preparation method of body phase hydrotreating catalyst |
| CN106179390B (en) * | 2015-04-30 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and preparation method thereof |
| CN106179464B (en) * | 2015-04-30 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocracking catalyst |
| CN106179389B (en) * | 2015-04-30 | 2019-01-25 | 中国石油化工股份有限公司 | Hydrobon catalyst and preparation method thereof |
| CN106179466B (en) * | 2015-04-30 | 2019-01-25 | 中国石油化工股份有限公司 | The preparation method of hydrocracking catalyst |
| CN106179377B (en) * | 2015-04-30 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrobon catalyst composition |
| CN106179386B (en) * | 2015-04-30 | 2018-10-12 | 中国石油化工股份有限公司 | The preparation method of Hydrobon catalyst |
| CN106179461B (en) * | 2015-04-30 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocracking catalyst |
| JP6203910B2 (en) * | 2016-06-28 | 2017-09-27 | 住友化学株式会社 | Insulating porous layer for non-aqueous electrolyte secondary battery and laminated separator for non-aqueous electrolyte secondary battery |
| CN107837819B (en) * | 2017-11-20 | 2020-07-24 | 运城学院 | MnY catalyst for indoor formaldehyde catalytic removal and preparation method thereof |
| CN109061778B (en) * | 2018-09-12 | 2020-04-24 | 江西泰华光电科技股份有限公司 | Mobile phone lens processing method |
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| US3644220A (en) * | 1969-11-13 | 1972-02-22 | Exxon Research Engineering Co | Metal halide containing zeolites and method for their preparation |
| US4259175A (en) * | 1978-10-10 | 1981-03-31 | Union Oil Company Of California | Process for reducing sox emissions from catalytic cracking units |
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| CA1161019A (en) * | 1980-08-05 | 1984-01-24 | Brent J. Bertus | Cracking catalyst restoration with aluminum compounds |
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| NL8103069A (en) * | 1980-10-28 | 1982-05-17 | Grace W R & Co | METHOD FOR PREPARING CATALYTIC CRACKING CATALYSTS |
| US4357265A (en) * | 1980-10-28 | 1982-11-02 | W. R. Grace & Co. | Catalytic cracking catalyst |
| EP0130251B1 (en) * | 1983-07-04 | 1987-09-16 | Mobil Oil Corporation | Process for converting propane to aromatics over zinc-gallium zeolite |
| EP0134331B1 (en) * | 1983-08-15 | 1987-07-22 | Mobil Oil Corporation | Treatment of zeolites |
| JPS60197240A (en) * | 1984-03-21 | 1985-10-05 | Shokubai Kasei Kogyo Kk | Preparation of catalyst composition for catalitic cracking of hydrocarbon |
| GB8708961D0 (en) * | 1987-04-14 | 1987-05-20 | Shell Int Research | Preparation of modified zeolites |
| US5159128A (en) * | 1990-08-31 | 1992-10-27 | Shell Oil Company | Process for cracking paraffins to olefins |
| US5294332A (en) * | 1992-11-23 | 1994-03-15 | Amoco Corporation | FCC catalyst and process |
| BR9400475A (en) * | 1994-02-09 | 1995-09-19 | Petroleo Brasileiro Sa | Preparation process of modified zeolite and modified zeolite |
| US6482313B1 (en) * | 1994-10-03 | 2002-11-19 | Exxonmobil Research And Engineering Company | FCC process incorporating crystalline microporous oxide catalysts having increased Lewis acidity |
| CA2177293C (en) * | 1995-06-23 | 2003-12-09 | William Lee Schuette | Crystalline microporous oxide having increased lewis acidity and fluid catalytic cracking process using same |
| AU2001285090B2 (en) * | 2000-08-31 | 2005-11-10 | Exxonmobil Research And Engineering Company | Crystalline microporous oxide catalysts having increased lewis acidity and methods for the preparation thereof |
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| TW583021B (en) | 2004-04-11 |
| CA2419668A1 (en) | 2002-03-07 |
| CN1449306A (en) | 2003-10-15 |
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| AU2001285090B2 (en) | 2005-11-10 |
| JP2004507347A (en) | 2004-03-11 |
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