EP0319538A1 - Modification de zeolites - Google Patents

Modification de zeolites

Info

Publication number
EP0319538A1
EP0319538A1 EP19870905261 EP87905261A EP0319538A1 EP 0319538 A1 EP0319538 A1 EP 0319538A1 EP 19870905261 EP19870905261 EP 19870905261 EP 87905261 A EP87905261 A EP 87905261A EP 0319538 A1 EP0319538 A1 EP 0319538A1
Authority
EP
European Patent Office
Prior art keywords
zeolite
aluminium
solvent
sicl
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19870905261
Other languages
German (de)
English (en)
Inventor
Lovat Victor Charles Imperial College Of Rees
Edward Fook Tin Imperial College Of Lee
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3I Research Exploitation Ltd
Original Assignee
Research Corp Ltd
3I Research Exploitation Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB868620434A external-priority patent/GB8620434D0/en
Priority claimed from GB878709566A external-priority patent/GB8709566D0/en
Application filed by Research Corp Ltd, 3I Research Exploitation Ltd filed Critical Research Corp Ltd
Publication of EP0319538A1 publication Critical patent/EP0319538A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • C01B33/28—Base exchange silicates, e.g. zeolites
    • C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
    • C01B33/2884—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures the aluminium or the silicon in the network being partly replaced
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/1009—Compounds containing boron and oxygen having molecular-sieve properties
    • 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
    • C01B39/026—After-treatment
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • 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
    • B01J2229/34—Reaction with organic or organometallic compounds
    • 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

Definitions

  • This invention relates to a process for the chemical modification of zeolite structures.
  • Zeilites are crystalline hydrated aluminium silicates which have the general chemical formula:
  • M is a cation of valency n and x is greater than or equal to 2.0. Structurally they have a porous framework based on an extended three-dimensional framework of SiO 4 and AlO 4 tetrahedra linked together through common oxygen atoms.
  • the value of x in the above formula for zeolite Y is approximately 5.0 and the resulting framework is not sufficently stable to withstand the high temperatures (800oC) involved in the regenerator unit of cracking plants where coke is burnt off.
  • “coke” is meant the deposits of carbon and low hydrogen content hydrocarbons that build up in petroleum cracking).
  • the SiO 2 /Al 2 O 3 ratio has to be increased.
  • H + ammonium
  • the net result is the production of a partially crystalline material along with some amorphous material and the introduction of some mesopores into the system.
  • the resulting material is an excellent selective catalyst.
  • the other methods which can be used to increase the silicon to aluminium ratio are (a) extraction of aluminium by EDTA (ethylenediaminetetraacetic acid) (b) acid treatment and (c) use of silicon tetrachloride vapour.
  • EP-A-82211 describes the use of an aqueous solution of a fluorosilicate to replace aluminium with silicon in the framework.
  • the use of the SiCl, vapour, as described for example in EP-A-62123 and EP-A-72397, has some useful effects.
  • the vacancies in the framework, produced by the extraction of aluminium are healed by silicon atoms from the tetrachloride, and, the aluminium removed from the framework is converted to its volatile trichloride effecting removal from the system.
  • EP-A-210018 describes another process for the modification of zeolite framework structures which involves treatment of the zeolite with a molten salt medium which contains a reactive component which has a "radius ratio" of less than 0.6, the "radius ratio” being defined as the ratio of the crystal ionic radius of the central atom of the reactive component to that of the the oxygen anion 0 2- .
  • the method is applicable to porous crystalline minerals which have pores large enough to sorb normal hexane.
  • Examples of the components which have the required radius ratio are: the trichlorides of aluminium, boron, iron, phosphorus and gallium, and the tetrachlorides of titanium and tin, the Si 4+ ion being also mentioned.
  • the method may be used to insert aluminium into high silicon zeolite frameworks or otherwise alter the framework without substantial alteration of its structure.
  • An object of the present invention is to provide an improved method for the modification of zeolite framework structures.
  • a method for the modification of the framework structure of a zeolite comprising treating the zeolite with a solution in an organic solvent of a compound of an element capable of structural replacement of aluminium in the framework.
  • the compound is preferably a metal halide of the aluminium- replacing element, examples being: BCl 3 , BBr 3 , SnCl 4 , SnBr 4 , Snl 4 , SiCl 4 , Sil 4 , TiCl 4 , GeCl 4 , GaCl 4 ,
  • organometallic compounds of the selected element may also be suitable, for example, beryllium diphenyl.
  • the zeolite may be, for example, Erionite, Beta, ZSM-5, ZSM-11 (Trade Marks), Mordenite, Chabazite, and Offretite.
  • the selection of the solvent is not critical. Solvents, and solvent mixtures, of small molecular size, such as carbon tetrachloride and ethanol, are suitable but the reaction may be accelerated by the use of a solvent of a molecular size which is too large to enter the channels of the zeolite, one particularly preferred solvent for this purpose being tetraethoxysilane [C 2 H 5 O) 4 Sil.
  • the temperature of the treatment is not of critical importance but would normally be carried out at the reflux temperature of the solvent in order to minimise the treatment time.
  • the method of the invention may include a pretreatment step in which the zeolite is treated with acid to effect a desired degree of dealumination, prior to treatment with the solvent solution compound of the aluminium-replacing element. Since the degree of dealumination with acid is restricted only by the need to maintain the integrity of the zeolitic structure, the use of the acid pretreatment step enables the production of zeolites with very high silicon to aluminium ratios.
  • NaY zeolite was calcined in a muffle furnace at 600oC for a few hours. The zeolite was then cooled to 80-100oC in a desiccator and 25ml of carbon tetrachloride (CCl 4 ) was then added with continuous stirring to form a slurry. various amounts (0.10 to 0.77ml) of silicon tetrachloride (SiCl 4 ) were added to several separate samples of the slurry which were then refluxed at a fixed temperature (58-59°C; 76-77°C) for a period of three hours. The final slurry was then centrifuged to separate the solid and liquid phases.
  • CCl 4 carbon tetrachloride
  • SiCl 4 silicon tetrachloride
  • the calcined zeolite was allowed to cool and treated with sodium chloride solution (1-5M at pH 8-9) repeatedly. The final product was well washed until chloride-free, filtered and dried at 100°C.
  • Example 2 The same procedure as described in Example 1 was used except that 15ml of CCl 4 and 0.3ml SiCl 4 were refluxed with NaY zeolite with different water content at 59°C for 20 minutes. The results are given in Table II below.
  • CCl 4 and 10ml SiCl 4 were refluxed with zeolites with different cationic forms at 58-60oC for one hour.
  • Samples S0.50/57, S1.0/57 and S1.5/57 were mixed with 15ml SiCl 4 and refluxed at 57oC for 30 minutes to produce sample SS0.5/1.5.
  • Example 1 Using the procedure described in Example 1, 15ml of SiCl 4 were refluxed with zeolite produced from Example 1 (Sample Nos. CS0.10/58 + CS0.20/58 + CS0.10/76) at 57°C for 30 minutes. Four cycles were carried out.
  • Table VI reports the results of infra-red characterisation studies and Table VII the results of X-ray diffraction studies, confirming the increase of the Si/Al ratio of the zeolite Y framework.
  • Table VIII below reports the products (in sodium form) resulting from the dealumination of sodium Y zeolites by SiCl 4 in the solvent tetraethoxysilane [( C2 H 5 O) 4 Si] (TES).
  • the methods used were as follows:
  • Table IX reports the product (in sodium form) resulting from the dealumination of sodium Y zeolite by a SiCl 4 /CCl 4 /
  • Table X reports the products (in sodium form) resulting from the dealumination of sodium Y zeolites by SiCl 4 /ethanol solutions.
  • Al/u.c.; ZY[D]) was calcined at 600oC for a few hours and allowed to cool in a desiccator. 20 ml of SiCl 4 were added to the zeolite and stirred for 5 minutes. Five successive portions of CCl 4 of approximately 20ml were added to the zeolite slurry and the CCl 4 was discarded after centrifuging the slurry. 80ml of ethanol were then added and refluxed for one hour. Approximately 50ml of the slurry was withdrawn after 30 minutes and the rest after one hour.
  • the method was the same as Method (i) above except that the contact time of the zeolite and SiCl 4 was increased to 15 minutes.
  • SiCl 4 were added to the zeolite and stirred for 5 minutes.
  • ZY[H] sodium Y zeolite
  • the method was the same as Method (vi) except that 1ml of SICl 4 and 14ml of CCl 4 were used in the first refux.
  • the method was the same as Method (vi) except that 10 grams of sodium Y zeolite (ZY[G]), 80ml of SiCl 4 and 100ml of ethanol were used.
  • Table XI reports the products resulting from the dealumination of sodium Y zeolites followed by treatment with various mixtures including SiCl 4 as a component.
  • the dealuminated zeolite is made by treatment of sodium Y zeolite with hydrochloric acid. Dealumination does not occur when the pH of the acid is greater than 2.30, while complete dealumination occurs at pH less than 0.46. It appears that four hydrogen atoms are required to remove one aluminium atom. This acid dealumination results in a structure which is less crystalline than the initial zeolite (due to accumulated defects In the structure ) and is not thermally stable. However, treatment with SiCl 4 -containing mixtures allows insertion of silicon into the zeolite matrix and gives a product of reasonable thermal stability.
  • the treatment with SiCl 4 was by three different methods.

Abstract

Procédé de modification de la structure d'une zéolite, consistant à traiter la zéolite avec une solution dans un solvant organique d'un composé d'un élément pouvant effectuer le remplacement structural de l'aluminium dans la structure, cet élément remplaçant l'aluminium étant sélectionné, par exemple, parmi le bore, l'étain, le silicium, le titane, le germanium, le gallium, le phosphore, le béryllium et le magnésium, de préférence sous la forme d'halogénures ou de composés organométalliques desdits éléments. Des composés représentatifs sont BCl3, BBr3, SnCl4, SnBr4, SnI4, SiCl4, SiI4, TiCl4, GeCl4, GaCl4, PCl5, BeCl2, MgCl2, et le biphénylbéryllium. Dans une forme préférée du procédé, on fait réagir la zéolite avec du tétrachlorure de silicium dans du tétrachlorure de carbone au reflux. Il est toutefois possible de réduire la durée de la réaction par l'utilisation d'un solvant, par exemple du tétraéthoxysilane, possédant une taille moléculaire qui l'empêche de pénétrer dans les canaux de la zéolite.
EP19870905261 1986-08-22 1987-08-21 Modification de zeolites Withdrawn EP0319538A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB868620434A GB8620434D0 (en) 1986-08-22 1986-08-22 Zeolites
GB8620434 1986-08-22
GB878709566A GB8709566D0 (en) 1987-04-23 1987-04-23 Zeolites
GB8709566 1987-04-23

Publications (1)

Publication Number Publication Date
EP0319538A1 true EP0319538A1 (fr) 1989-06-14

Family

ID=26291206

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19870905261 Withdrawn EP0319538A1 (fr) 1986-08-22 1987-08-21 Modification de zeolites

Country Status (3)

Country Link
EP (1) EP0319538A1 (fr)
JP (1) JPH02500434A (fr)
WO (1) WO1988001254A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10787618B2 (en) 2018-01-23 2020-09-29 Saudi Arabian Oil Company Modified USY-zeolite catalyst for reforming hydrocarbons

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EP0325053A1 (fr) * 1987-12-29 1989-07-26 Mobil Oil Corporation Titanosilicate ayant la structure d'une zéolite bêta et contenant un métal noble ainsi que son application comme catalyseur d'aromatisation
US5145816A (en) * 1990-12-10 1992-09-08 Mobil Oil Corporation Method for functionalizing synthetic mesoporous crystalline material
GB9008038D0 (en) * 1990-04-09 1990-06-06 Univ Manchester Gallium zeolites
FR2694549A1 (fr) * 1992-08-06 1994-02-11 Atochem Elf Sa Procédé de préparation de zéolites bêta au titane et zéolites bêta nouvelles.
WO1999003579A1 (fr) * 1997-07-14 1999-01-28 Northwestern University Catalyseur de reduction des oxydes d'azote
US5968473A (en) 1998-12-18 1999-10-19 Uop Llc Stannosilicate molecular sieves
KR100816651B1 (ko) * 2006-03-31 2008-03-27 테크노세미켐 주식회사 제올라이트를 함유하는 구리 화학 기계적 연마 조성물
JP2011042577A (ja) * 2010-12-03 2011-03-03 Tosoh Corp 新規ｍｏｒ型メタロアルミノシリケート
CN102874840B (zh) * 2011-07-11 2014-08-20 中国石油化工股份有限公司 一种zsm-5沸石的改性处理方法
RU2634702C2 (ru) * 2011-07-27 2017-11-03 Джонсон Мэтти Паблик Лимитед Компани Низкофосфористые хабазиты
CN102557066B (zh) * 2011-12-30 2013-11-06 大连理工大学 一种正硅酸乙酯改性硅硼分子筛，其制备方法及应用
CN108726535B (zh) * 2018-06-11 2021-06-29 山东多友科技有限公司 一种具有多级孔的磷改性zsm-5分子筛的制备方法
US11305264B2 (en) * 2019-09-12 2022-04-19 Saudi Arabian Oil Company Manufacturing hydrocracking catalyst
US11332678B2 (en) 2020-07-23 2022-05-17 Saudi Arabian Oil Company Processing of paraffinic naphtha with modified USY zeolite dehydrogenation catalyst
US11274068B2 (en) 2020-07-23 2022-03-15 Saudi Arabian Oil Company Process for interconversion of olefins with modified beta zeolite
US11154845B1 (en) 2020-07-28 2021-10-26 Saudi Arabian Oil Company Hydrocracking catalysts containing USY and beta zeolites for hydrocarbon oil and method for hydrocracking hydrocarbon oil with hydrocracking catalysts
US11420192B2 (en) 2020-07-28 2022-08-23 Saudi Arabian Oil Company Hydrocracking catalysts containing rare earth containing post-modified USY zeolite, method for preparing hydrocracking catalysts, and methods for hydrocracking hydrocarbon oil with hydrocracking catalysts
US11142703B1 (en) 2020-08-05 2021-10-12 Saudi Arabian Oil Company Fluid catalytic cracking with catalyst system containing modified beta zeolite additive
US11618858B1 (en) 2021-12-06 2023-04-04 Saudi Arabian Oil Company Hydrodearylation catalysts for aromatic bottoms oil, method for producing hydrodearylation catalysts, and method for hydrodearylating aromatic bottoms oil with hydrodearylation catalysts

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
US10787618B2 (en) 2018-01-23 2020-09-29 Saudi Arabian Oil Company Modified USY-zeolite catalyst for reforming hydrocarbons

Also Published As

Publication number Publication date
WO1988001254A1 (fr) 1988-02-25
JPH02500434A (ja) 1990-02-15

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