WO2010036252A1 - Procédé de préparation de perles de tamis moléculaire - Google Patents

Procédé de préparation de perles de tamis moléculaire Download PDF

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Publication number
WO2010036252A1
WO2010036252A1 PCT/US2008/077590 US2008077590W WO2010036252A1 WO 2010036252 A1 WO2010036252 A1 WO 2010036252A1 US 2008077590 W US2008077590 W US 2008077590W WO 2010036252 A1 WO2010036252 A1 WO 2010036252A1
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Prior art keywords
molecular sieve
beads
value
mole fraction
component
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PCT/US2008/077590
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English (en)
Inventor
Lance L. Jacobsen
Brian S. Konrad
David A. Lesch
Beckay J. Mezza
James G. Vassilakis
Cynthia R. Berinti-Vondrasek
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Uop Llc
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Application filed by Uop Llc filed Critical Uop Llc
Priority to KR1020117008382A priority Critical patent/KR20110081195A/ko
Priority to PCT/US2008/077590 priority patent/WO2010036252A1/fr
Priority to JP2011528995A priority patent/JP2012503589A/ja
Priority to CN2008801312709A priority patent/CN102164856A/zh
Priority to BRPI0823095-1A priority patent/BRPI0823095A2/pt
Priority to EP08823506A priority patent/EP2326593A4/fr
Publication of WO2010036252A1 publication Critical patent/WO2010036252A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing 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
    • 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
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/36—Steaming
    • 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
    • B01J2229/60—Synthesis on support
    • B01J2229/62—Synthesis on support in or on other molecular sieves
    • 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
    • B01J2229/60—Synthesis on support
    • B01J2229/64—Synthesis on support in or on refractory materials

Definitions

  • This invention relates to a process for preparing molecular sieve beads comprising an amorphous component and optionally a crystalline molecular sieve component.
  • the process comprises taking a reaction mixture comprising sources of the framework element(s) of a molecular sieve and optionally molecular sieve particles at reaction conditions and adding to it reactive sources of the framework element(s) at a rate and for a time to form beads.
  • Molecular sieve beads are used in many catalyst and adsorbent applications. However, methods used to produce beads have certain drawbacks. For example when spray- drying is used, a binder needs to be used to afford good strength which in turn dilutes the molecular sieve concentration.
  • Pellet formation techniques also usually employ a binder and further have a minimum size limitation.
  • catalyst particles are formed by depositing a layer onto an inner core.
  • US 4,283,583 discloses a coated zeolite catalyst consisting of an inert core and an outer coating comprising an active catalytic zeolite material. The catalyst is prepared by wetting the inner core partially drying and then contacting the core with a zeolite powder.
  • US 4,482,774 discloses a composite zeolite having a crystalline silica polymorph as the core material and a modified silica overlayer which has substantially the same crystalline structure.
  • the overlayer is formed by adding preformed particles of the silica core into a crystallization gel at crystallization conditions thereby crystallizing the zeolite onto the core.
  • US 4,088,605 discloses growing a substantially aluminum free shell onto an aluminum containing zeolite.
  • US 5,895,769 discloses depositing a polycrystalline zeolite onto a porous substrate.
  • US 5,935,889 discloses preparing catalyst particles by coating core particles with an atomized slurry containing a coating material.
  • US 6,013,851 discloses a core zeolite having deposited thereon a surface layer where the surface layer has a higher Si/Al ratio than the core.
  • Applicants have developed a unique process for preparing molecular sieve beads in which molecular sieve seeds or particles are slurried in a solution containing reactive sources of the framework elements of the molecular sieve. To this slurry there are added sources of the framework elements at a rate and for a time to form a gel and agglomerate the gel and particles into beads.
  • the beads can be isolated and comprise a crystalline molecular sieve component and an amorphous component which is a precursor to a molecular sieve.
  • a process for producing a bead composition comprising an amorphous and a crystalline molecular sieve component, the crystalline component having a three dimensional framework and a framework composition represented by an empirical formula of:
  • Another embodiment of the invention is isolating the beads, slurrying the beads in a reaction mixture and adding to the mixture nutrient(s) at a rate to maintain the nutrient(s) concentration between the saturation limit and critical supersaturation limit to grow a molecular sieve layer on the beads.
  • Yet another embodiment is the product obtained from any of the processes described above.
  • a further embodiment of the invention is the use of the molecular sieve beads described above in a hydrocarbon conversion process.
  • One embodiment of the present invention is a process for preparing a bead composition which comprises at least an amorphous component.
  • the amorphous component is a precursor to a molecular sieve.
  • Other components of the beads can be a molecular sieve component and crystalline alumina.
  • the process involves forming a reaction mixture comprising reactive sources of the elements of the molecular sieve component and optionally seeds of the molecular sieve component.
  • the molecular sieve component can be any molecular sieve which has a three dimensional framework and which have crystallographically uniform pores. These sieves are classified as either zeolitic or non- zeolitic molecular sieves.
  • Zeolites are alumino-silicate compositions in which the framework structure is composed of SiO 2 and AlO 2 tetrahedral oxides.
  • Non- zeolitic molecular sieves are those which contain elements other than aluminum and silicon. Examples include silicoalumino phosphates and aluminophosphate molecular sieves.
  • the zeolitic and non- zeolitic molecular sieves which can be prepared using the process of the present invention have a three dimensional framework structure and a framework composition represented by the general empirical formula:
  • El is an element capable of forming a three-dimensional framework (tetrahedral) oxide unit as described below, and P, Al and Si are also framework elements present as tetrahedral oxide units.
  • the mole fraction of El is represented by "w” and has a value from zero to 0.5
  • "x” is the mole fraction of Al and has a value from 0 to 0.5
  • "y” is the mole fraction of P and has a value from 0 to 0.5
  • "z” is the mole fraction of Si and has a value from 0 to 1
  • "El” is characterized by an electronic orbital configuration selected from the group consisting of d°, d 1 , d 2 , d 5 , d 6 , d 7 , or d 10 where the small crystal field stabilization energy of the metal ligand "-O-E1" favors tetrahedral coordination of element El with O 2 ⁇ , as discussed in "Inorganic Chemistry” J. E. Huheey, Harper Row, p.
  • x has a value from 0 to 0.5.
  • zeolites include but are not limited to zeolite A, zeolite X, mordenite, silicalite, zeolite beta, zeolite Y, zeolite L, ZSM- 12, UZM-4 and UZM-5. UZM-4 and UZM-5 are described in US 6,419,895 Bl and US 6,613,302 Bl respectively which are incorporated in their entirety by reference.
  • x is zero, the zeolite is silicalite. In the case where "x" in formula (1) is greater than zero one obtains formula (3)
  • the molecular sieve seeds which are an optional component, are prepared by means known in the art and basically involves preparing a reaction mixture containing reactive sources of El, Al, Si and P along with one or more templating/structure directing agent and water and reacting it at a temperature and for time, usually under autogenous pressure, to crystallize the molecular sieve.
  • Tempolating agents which can be used are well known in the art and include but are not limited to alkali metals, alkaline earth metals and organic compounds.
  • the organic compounds are any of those well known in the art and include but are not limited to amines such as piperidine, tripropylamine, dipropylamine, diethanolamine, triethanolamine, cyclohexylamine and quaternary ammonium compounds such as the halide or hydroxide compound of tetramethyl ammonium, tetrabutyl ammonium, tetraethylammonium, tetrapropylammonium, ethyltrimethylammonium, diethyldimethylammonium, etc.
  • amines such as piperidine, tripropylamine, dipropylamine, diethanolamine, triethanolamine, cyclohexylamine and quaternary ammonium compounds such as the halide or hydroxide compound of tetramethyl ammonium, tetrabutyl ammonium, tetraethylammonium, tetrapropylammonium, ethyltrimethyl
  • sources of aluminum include without limitation aluminum alkoxide, pseudoboehmite, gibbsite, colloidal alumina, alumina sol, sodium aluminate, aluminum trichloride and aluminum chlorohydrate.
  • preferred aluminum sources are pseudoboehmite, sodium aluminate and aluminum alkoxides such as aluminum isoproxide.
  • Silicon sources include without limitation silica sol, colloidal silica, fumed silica, silica gel, silicon alkoxides, silicic acid and alkali metal silicate such as sodium silicate.
  • Phosphorus sources include without limitation phosphoric acid and organic phosphates such as triethylphosphate.
  • the sources of the element(s) "El” can be any form which permits the formation in situ of a reactive form of the element, i.e., reactive to form a framework oxide unit of element "El".
  • Compounds of element(s) "El” which may be employed include oxides, hydroxides, alkoxides, nitrates, sulfates, halides, carboxylates, and mixtures thereof.
  • Representative compounds which may be employed include without limitation: carboxylates of arsenic and beryllium; cobalt chloride hexahydrate, alpha cobaltous iodide; cobaltous sulfate; cobalt acetate; cobaltous bromide; cobaltous chloride; boron alkoxides; chromium acetate; gallium alkoxides; zinc acetate; zinc bromide; zinc formate; zinc iodide; zinc sulfate heptahydrate; germanium dioxide; iron (II) acetate; lithium acetate; magnesium acetate; magnesium bromide; magnesium chloride; magnesium iodide; magnesium nitrate; magnesium sulfate; manganese acetate; manganese bromide; manganese sulfate; titanium tetrachloride; titanium carboxylates; titanium acetate; zinc acetate; tin chloride; and the like.
  • the resultant reaction mixture is now reacted at a temperature of 70 to 200 0 C and a time of 1 hour to 144 hours usually under autogenous pressure thereby crystallizing the desired molecular sieve.
  • the molecular sieve particles are isolated by conventional techniques such as filtration, centrifugation, etc. and dried to give a powder.
  • This molecular sieve powder can now be used as seeds or particles which are optional components in preparing a reaction mixture for carrying out the process of the invention.
  • the reaction mixture will comprise reactive sources of El, Al, P and Si corresponding to equation (1).
  • the reaction mixture will also optionally contain sources of the templating agent and acid or base in order to adjust the pH to the desired range.
  • nutrient(s) sources of the desired framework element(s), hereinafter referred to as nutrient(s).
  • nutrient sources of the desired framework element(s), hereinafter referred to as nutrient(s).
  • the nutrient or combination of nutrients which are added are any of those which can form a molecular sieve. These combinations include without limitation: 1) silicon source; 2) aluminum and silicon sources; 3) aluminum, phosphorus and silicon sources; 4) aluminum and phosphorus sources; 5) El and silicon sources; 6) El, aluminum and phosphorus sources; and 7) El, aluminum, silicon and phosphorus sources.
  • additional templating agent/structure directing agent may need to be added. This can be done by adding the desired source of the agent with one of the nutrients or as a separate stream.
  • the initial reaction mixture can contain an excess of the desired templating agent.
  • nutrients can be added by any convenient means. These means include preparing solutions of the nutrients, preparing solid suspensions or slurries, adding solids directly and adding neat nutrients.
  • one nutrient can be added by one method, while other nutrient(s) can be added by another method.
  • additional acid or base may need to be added to arrive at the desired pH. For example when sodium silicate is used as the nutrient or source of silicon, acid may need to be added to neutralize the sodium hydroxide which may be generated.
  • more than one nutrient e.g. Si and Al, they can be added simultaneously or sequentially.
  • each nutrient is fed into the reactor containing the reaction mixture using individual ports or injectors.
  • the individual nutrients can be fed into a holding tank, mixed and then fed as one stream into the reactor containing the seed slurry. The latter method is preferred.
  • the nutrients can be added continuously or intermittently. If intermittently, the addition can be at regular intervals or at irregular intervals.
  • the addition is carried out at a temperature from ambient temperature to 80 0 C. At temperatures of ambient to 80 0 C, (and preferably at ambient temperatures) it is preferred to carry out the addition continuously until the nutrient(s) concentration is above the critical supersaturation concentration at which point beads are formed. Addition can be continued until beads with a desired particle size are obtained. If no seeds are added and the addition is carried out below the crystallization temperature of the molecular sieves and preferably at ambient temperature, then the beads will be substantially 100% amorphous. These beads will be referred to as first bead compositions. As stated the initial reaction mixture can also contain molecular sieve seeds having the same composition which would result from the reactive sources in the mixture.
  • the beads produced at the end of the addition process would have a mixture of amorphous component and crystalline molecular sieve component.
  • the amount of seed material present at the start of the process can vary widely from 0.1 to 20 wt.% of the reaction mixture. Seeds can also be optionally added periodically during the addition of nutrient(s) to obtain larger beads and control the particle size distribution. These beads will be referred to as second bead compositions.
  • the reaction mixture either with or without seeds, can also be heated to a reaction temperature which is at or above the crystallization temperature of the desired molecular sieve. This temperature is generally from 70 to 200°C.
  • the nutrient(s) it is preferred to pulse the addition of the nutrient(s) until their concentrations go above the critical supersaturation limit. At this point crystallization begins and beads are formed. Again seeds can be periodically added during the process in order to grow larger beads and/or control bead size. Further, after the nutrient(s) addition is complete, the mixture can be maintained at the reaction temperate for a time of 1 hour to 144 hours to further crystallize the molecular sieve component. It has also been found that when aluminum is one of the framework elements, the beads formed at or above the crystallization temperature will also contain crystalline alumina in an amount from 0 to 60 wt.% of the beads. These beads will be referred to as third bead compositions.
  • the first or second bead compositions can be further processed by taking the ending reaction mixture and heating it up to the crystallization temperature and holding the mixture there to crystallize at least a portion of the amorphous component.
  • the temperature will vary from 70 0 C to 200 0 C and the time will vary from 1 hour to 144 hours.
  • the beads can have a composition which can vary from 100% amorphous to 100% crystalline molecular sieve component.
  • the amorphous content can be from 0% to 100wt.%, preferably from 0 to 50 wt.%, depending on the application, and most preferably from 0 to 20 wt.%.
  • the crystalline molecular sieve component can likewise be present from 0wt.% to 100wt.%, but preferably from 15 to 100 wt.% and most preferably from 80 to 100 wt.%. If crystalline alumina is also present, then it is present in an amount from greater than 0 to 60 wt%, but usually from 5 to 15 wt%.
  • the first, second and third bead compositions can be used for example, as supports for catalytic metals, as catalysts and as adsorbents, although not all compositions can be used for all applications. However, a preferred use is as cores onto which is deposited one or more layers of molecular sieves or other inorganic oxides. A layer of a particular molecular sieve can be grown or deposited onto the above beads using the basic process described above.
  • a reaction mixture is prepared from the beads, sources of El, Al, P and Si, additional base or acid and templating agent.
  • the ending reaction mixture can act as the starting reaction mixture of this specific process.
  • the beads can be isolated and then slurried in a mixture comprising the desired sources of elements, templating agents, etc.
  • the layer can comprise the same elements or different elements (at least one) as the core elements. Additionally, the molecular sieve layer can have the same or different structure.
  • the reaction conditions for this process include a temperature of 70 0 C to 200 0 C and autogenous pressure. Under these conditions the amorphous component (if any) will begin to crystallize. Nutrient(s) are next added either continuously or intermittently. When added continuously, the nutrient(s) concentration is kept below the critical supersaturation but above the saturation concentration. In this regime, the molecular sieve crystals on the outer surface of the beads will begin to grow thereby forming a layer of the molecular sieve. The nutrient(s) addition rate is controlled such that it is essentially the same as the crystal growth rate. The crystal growth rate is determined empirically using analytical techniques such as Scanning Electron Microscopy (SEM).
  • SEM Scanning Electron Microscopy
  • Another way to control the continuous addition rate is to measure and keep the concentration of each nutrient between the saturation concentration and the critical supersaturation concentration.
  • the continuous addition is carried out for a time until the layer is of the desired thickness.
  • the continuous addition is carried out as described when the structure of the molecular sieve bead is the same as the layer.
  • the two molecular sieves can have different compositions, e.g. S APO-34 and ALPO-34.
  • molecular sieve seed crystals can be added intermittently throughout the process.
  • the molecular sieve which crystallizes does not have to have the same structure as the bead molecular sieve.
  • a period of pulsed or intermittent addition is followed by a period of continuous addition as described above in order to grow the molecular sieve crystals which have formed a layer on the beads.
  • molecular sieve seeds can also be added.
  • the addition pulse can last from 1 second to 5 minutes with the time between pulses being from 10 seconds to 3 hours.
  • Continuous addition is usually carried out for a time from 1 hour to 144 hours.
  • the intermittent and continuous additions can be repeated a number of times, but at least two times, provided that the last step is a continuous addition.
  • shear can be applied by mechanical means, hydraulic means etc. Specific methods of applying shear include but are not limited to stirrers, impellers, ultrasound, opposed jets, etc.
  • the amount of shear is controlled such that excessive agglomeration does not occur but in the case of forming a layer the shear is not so great as to break away the layer from the beads.
  • the layered molecular sieve beads or fourth bead composition have uses in various processes including but not limited to adsorption, catalyst or catalyst supports in hydrocarbon conversion processes.
  • Hydrocarbon conversion processes are well known in the art and include ring-opening, cracking, hydrocracking, alkylation of both aromatics and isoparaffms, isomerization, polymerization, reforming, dewaxing, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydration, dehydration, hydrotreating, hydrodenitrogenation, hydrodesulfurization, methanation and syngas shift process.
  • Specific reaction conditions and the types of feeds which can be used in these processes are set forth in US 4,310,440 and US 4,440,871 which are incorporated by reference.
  • Hydrocracking conditions typically include a temperature in the range of 400° to 1200 0 F (204-649 0 C), preferably between 600° and 950 0 F (316-510 0 C).
  • Reaction pressures are in the range of atmospheric to 3,500 psig (24,132 kPa), preferably between 200 and 3000 psig (1379 - 20,685 kPa).
  • Contact times usually correspond to liquid hourly space velocities (LHSV) in the range of 0.1 hr 1 to 15 hr "1 , preferably between 0.2 and 3 hr "1 .
  • Hydrogen circulation rates are in the range of 1,000 to 50,000 standard cubic feet (scf) per barrel of charge (178-8,888 std. mVm 3 ), preferably between 2,000 and 30,000 scf per barrel of charge (355-5,333 std. mVm 1 ).
  • Suitable hydrotreating conditions are generally within the broad ranges of hydrocracking conditions set out above.
  • reaction zone effluent is normally removed from the catalyst bed, subjected to partial condensation and vapor-liquid separation and then fractionated to recover the various components thereof.
  • the hydrogen, and if desired some or all of the unconverted heavier materials, are recycled to the reactor.
  • a two-stage flow may be employed with the unconverted material being passed into a second reactor.
  • Catalysts of the subject invention may be used in just one stage of such a process or may be used in both reactor stages.
  • Catalytic cracking processes are preferably carried out using feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residua, etc. with gasoline being the principal desired product.
  • Alkylation of aromatics usually involves reacting an aromatic, especially benzene, with a monoolefin (C 2 to C] 2 ) to produce a linear alkyl substituted aromatic.
  • the process is carried out at an aromatic: olefin (e.g., benzene:olefin) ratio of between 5: 1 and 30: 1 , a LHSV of 0.3 to 6 hf ', a temperature of 100° to 250 0 C and pressures of 200 to 1000 psig (1379 kPa to 6895 kPa).
  • aromatic: olefin e.g., benzene:olefin
  • Alkylation of isoparaffins with olefins to produce alkylates suitable as motor fuel components is carried out at temperatures of -30° to 40 0 C, pressures from atmospheric to 6,894 kPa (1,000 psig) and a weight hourly space velocity (WHSV) of 0.1 to 120 hf '. Details on paraffin alkylation may be found in US 5,157,196 and US 5,157,197, which are incorporated by reference.
  • An especially preferred bead composition is a fourth bead composition in which the bead core contains zeolite Y prepared with or without seeds and the layer is also zeolite Y.
  • These zeolite Y bead compositions are particularly useful in cracking or hydrocracking and particularly fluidized catalytic cracking (FCC).
  • FCC units and processes are well known in the art and are carried out under the catalytic cracking conditions set forth above.
  • the catalyst is a moving bed of catalyst particles. Examples of patents which describe FCC include US 3,838,036 and US 4,064,038 which are incorporated by reference in their entirety.
  • the product was filtered, washed and then dried at room temperature. The mother liquor was retained for recycle. The solids were washed, screened and elutriated to retain the beads that were between 20 and 150 ⁇ m. The yield was 130.5g of sized beads. [0047] 80 g of the sized beads were added back to the reactor with 70 g of zeolite Y seeds and 416.4 g of recycled mother liquor and the same procedure was repeated. This procedure was then repeated again resulting in 3 coatings on the initial beads. The final yield was 94.5 g of sized beads. The beads were ammonium ion exchanged in an elutriation column with 3.5 L of 10% ammonium nitrate solution at 75°C.
  • the exchanged beads were steamed at 600 0 C for 2hrs in 50% steam then re-exchanged.
  • X-ray diffraction analysis showed the product to be 38.7% Y zeolite with small amounts of gibbsite crystalline impurities.
  • chemical analysis of the sized product showed the Si/Al 2 ratio to be 2.7.
  • the feeds were shut off, and the solids were filtered from the mother liquor to give 42 grams of beads, which were found to have a molecular sieve component and an amorphous component.
  • the mean particle diameter was typically 50 microns, with a particle size distribution from 1 to 150 microns.
  • the beads were ammonium ion exchanged with 10% ammonium nitrate solution at 75°C.
  • the exchanged beads were steamed at 600 0 C for 2hrs in 50% steam then re-exchanged.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Catalysts (AREA)

Abstract

L’invention porte sur un procédé de préparation de perles de diverses compositions. Le procédé met en jeu la préparation d'un mélange réactionnel de sources d'éléments de squelette d'un tamis moléculaire. Le mélange réactionnel peut facultativement contenir des germes de tamis moléculaire. Des sources supplémentaires des éléments de squelette sont ajoutées pour donner une concentration au-dessus de la limite de sursaturation critique, permettant ainsi de former des perles. En fonction de la composition du mélange réactionnel et des conditions réactionnelles, on peut obtenir des perles qui sont sensiblement amorphes à des perles qui constituent un tamis moléculaire sensiblement cristallin. Ces perles à leur tour peuvent subir un nouveau traitement pour déposer une couche de tamis moléculaire sur les perles.
PCT/US2008/077590 2008-09-25 2008-09-25 Procédé de préparation de perles de tamis moléculaire WO2010036252A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
KR1020117008382A KR20110081195A (ko) 2008-09-25 2008-09-25 분자체 비드의 제조 방법
PCT/US2008/077590 WO2010036252A1 (fr) 2008-09-25 2008-09-25 Procédé de préparation de perles de tamis moléculaire
JP2011528995A JP2012503589A (ja) 2008-09-25 2008-09-25 モレキュラーシーブビーズの調製方法
CN2008801312709A CN102164856A (zh) 2008-09-25 2008-09-25 一种制备分子筛珠的方法
BRPI0823095-1A BRPI0823095A2 (pt) 2008-09-25 2008-09-25 Processos para reproduzir uma composição de contas, para preparar uma conta de peneira molecular, composição de contas, e, processo de conversão de hidrocarboneto
EP08823506A EP2326593A4 (fr) 2008-09-25 2008-09-25 Procédé de préparation de perles de tamis moléculaire

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PCT/US2008/077590 WO2010036252A1 (fr) 2008-09-25 2008-09-25 Procédé de préparation de perles de tamis moléculaire

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WO (1) WO2010036252A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2867167A4 (fr) * 2012-06-29 2016-03-23 Uop Llc Tamis moléculaires de métallophosphate, procédé de préparation et utilisation
EP2867166A4 (fr) * 2012-06-29 2016-03-23 Uop Llc Tamis moléculaires de métallophosphate, procédé de préparation et utilisation
CN107418288A (zh) * 2017-07-14 2017-12-01 湖南沃特邦恩新材料有限公司 一种可净化空气的涂料添加剂及其制备方法及应用

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US4427577A (en) * 1980-12-12 1984-01-24 Exxon Research & Engineering Co. Composite zeolite
US6022513A (en) * 1996-10-31 2000-02-08 Pecoraro; Theresa A. Aluminophosphates and their method of preparation
US7442365B1 (en) * 2004-06-14 2008-10-28 Uop Llc Process for preparing molecular sieve beads

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US4818509A (en) * 1984-03-23 1989-04-04 Mobil Oil Corporation Continuous process for manufacturing crystalline zeolites in continuously stirred backmixed crystallizers
US5370859A (en) * 1990-05-08 1994-12-06 Unisearch Limited Growing sodium type X zeolite crystals
US6585952B1 (en) * 2000-05-25 2003-07-01 Board Of Trustees Operating Michigan State University Ultrastable hexagonal, cubic and wormhole aluminosilicate mesostructures
US7320782B1 (en) * 2004-06-14 2008-01-22 Uop Llc Process for preparing a layered molecular sieve composition
US7112316B1 (en) * 2005-08-08 2006-09-26 Uop Llc Process for preparing molecular sieves via continuous addition of nutrients
EP2067528A1 (fr) * 2007-11-29 2009-06-10 Uop Llc Procédé de préparation d'une composition de tamis moléculaire en couche

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Publication number Priority date Publication date Assignee Title
US4427577A (en) * 1980-12-12 1984-01-24 Exxon Research & Engineering Co. Composite zeolite
US6022513A (en) * 1996-10-31 2000-02-08 Pecoraro; Theresa A. Aluminophosphates and their method of preparation
US7442365B1 (en) * 2004-06-14 2008-10-28 Uop Llc Process for preparing molecular sieve beads

Non-Patent Citations (2)

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Title
See also references of EP2326593A4 *
VALENTIN VALTCHEV ET AL., MICROPOROUS AND MESOPOROUS MATERIALS, vol. 43, 2001, pages 41 - 49, XP004317682 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2867167A4 (fr) * 2012-06-29 2016-03-23 Uop Llc Tamis moléculaires de métallophosphate, procédé de préparation et utilisation
EP2867166A4 (fr) * 2012-06-29 2016-03-23 Uop Llc Tamis moléculaires de métallophosphate, procédé de préparation et utilisation
CN107418288A (zh) * 2017-07-14 2017-12-01 湖南沃特邦恩新材料有限公司 一种可净化空气的涂料添加剂及其制备方法及应用

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JP2012503589A (ja) 2012-02-09
BRPI0823095A2 (pt) 2015-06-16
EP2326593A1 (fr) 2011-06-01
CN102164856A (zh) 2011-08-24
EP2326593A4 (fr) 2012-09-12

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