AU646265B2 - Synthetic crystalline aluminosilicate for the catalytic conversion of hydrocarbons in petrochemical processes - Google Patents
Synthetic crystalline aluminosilicate for the catalytic conversion of hydrocarbons in petrochemical processes Download PDFInfo
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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
- 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
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- 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
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- 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
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7003—A-type
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
- C07C5/2775—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
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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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/36—Steaming
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The preparation of high-silicon zeolites of the pentasil family has hitherto been possible only with the addition of organic structure-controlling compounds to the synthesis mixture. These processes have, however, serious disadvantages which preclude environmentally sound production on a large industrial scale. Preparation processes in which it was possible to dispense with the use of organic substances lead only very slowly to the desired product, and the emergence of undesired secondary phases cannot be precluded. A process is to be developed in which the disadvantages of the known processes are avoided. The process is characterised in that the catalyst or catalyst component used is a synthetic crystalline aluminosilicate of the chemical composition 0-3M2O : Al2O3 : 15-40 SiO2 : 0-40 H2O, M being a metal cation, and the crystalline aluminosilicate showing in its X-ray diffractogram at least the X-ray reflections which correspond to the d values listed in Table 1, and the SiO2/Al2O3 molar ratio thereof at the crystallite surface being greater than or equal to the molar SiO2/Al2O3 ratio in the crystal interior, and the <29>silicon solid MAS nuclear magnetic resonance spectrum thereof showing absorption bands at about -100, -106, -112 and -116 ppm relative to tetramethylsilane as standard. The process is used for the catalytic conversion of hydrocarbons. Table 1 <IMAGE>
Description
A 4 COMMONWEALTH OF AUSTR A A PATENTS ACT 1952-69 COMPLETE SPECIFICATION
(ORIGINAL)
Class Ir Application Number: 80289/91 Lodged: 10th July 1991 Form it. Class Complete Specification Lodged: Accepted: Published: Priority Related Art Name of Applicant Address of Applicant 0oS4 o a a .0Actual Inventor o a aa a 0a« o 4 a"'"ddress for Service ae a t* as c o VEREINIGTE ALUMINIUM-WERKE LEUNA-WERKE AG AKTIENGESELLSCHAFT and Georg-von-Boeselager-strasse 25, D-5300 Thalmann-Platz, 4220 Leuna 3, Germany Bonn 1, and ARNO TISSLER, ROLAND THOME, KARL BECKER, HANS-DIETER NEUBAUER and HANS-HEINO JOHN WATERMARK PATENT TRADEMARK ATTORNEYS.
LOCKED BAG NO. 5, HAWTHORN, VICTORIA 3122, AUSTRALIA Complete Specification for the invention entitled: SYNTHETIC CRYSTALLINE ALUMINOSILICATE FOR THE CATALYTIC CONVERSION OF HYDROCARBONS IN PETROCHEMICAL PROCESSES STnh following statement is a full description of this invention, including the best method of performing it known to us It
I
SYNTHETIC CRYSTALLINE ALUMINOSILICATE FOR THE CATALYTIC CONVERSION OF HYDROCARBONS IN PETROCHEMICAL PROCESSES Description: The present invention concerns a synthetic crystalline aluminosilicate for the catalytic conversion of hydrocarbons or their derivatives at pressures in the region of 0.1-15 MPa, temperatures in the region of 523-823 K, raw material loadings of 0.5-8 in the presence of hydrogen or gases containing such, as formed catalysts i.e. as catalyst components.
The development and application of microfilter catalysts with form-selective properties has without doubt fundamentally shifted the impulse in the development of crude petroleum and petrochemical processing in the last decades. In particular this applies since the discovery of the silicon rich zeolites of the pentasil type containing middle-sized pores. This development was particularly stimulated due to external factors. Until just recently it was above all the drastic changes in the price of crude oil and the availability of crude oil, that sparked substantial activities in research and development in this field worldwide, so nowadays besides the continually operative factors of intensification and reduction of costs there is above all the increasing requirement of environmental protection and with it the associated environmental legislation.
i 20 In crude petroleum processing and crude petroleum chemistry it concerns particularly the new requirements relating to the quality of carburettor fuels with regard to the absence of lead, lowering of the benzene content and the presumably to be expected lowering of the vapour pressure, the replacement of the less environmentally friendly aromatic compoundalkylation and olefin hydration processes on the basis of concentrated liquid or mineral acids (sulphuric acid, hydrofluoric acid, phosphoric acid) in carriers as catalysts, the anticipated increased requirements for the limitation of the content of aromatic compounds and sulphur in diesel fuels.
Form selective catalysts on the basis of pentasil-zeolites offer new possibilities particularly for the solution of the two first-named problems. They achieve at the same time and independently of environmental protection requirements, new possibilities for the technically and economically more advantageous organisation of the processing of crude oil fractions. This applies to e.g. the processes of removal of 2 paraffins from distillates (kerosene, diesel fuel) and lubricants through the formselective splitting of the n-paraffins in the charging stock.
Pentasil-zeolites are characterised by an intra-crystalline system of channels with a cross-sectional diameter of about 5.5 A which extend in two directions and cross one another. The zone where crossing-over occurs have the very weakly defined character of a cage and are frequently the place where the reaction takes place. The shape of the pores and their sizes have, besides the acid strength of the acidic centre and its concentration, a crucial influence on the activity and the selectivity of the conversion of substances and mixtures of substances. A linear relationship exists between the 1 0 concentration of the acidic Br6nstedcentres and the number of the lattice aluminium atoms per elementary cell.
The size of the pore channels allows the entry and exit of unbranched or singlybranched aliphates and of single-ringed aromatic compounds up to a maximum of carbon atoms.
Accordingly, in principle only molecules of these particular substance classes are able to be chemically converted within the pore structure and to leave it again.
Herein lies the nature of the so-called reactant and product selectivity. Even within these substance classes differences, in part considerable, in the speed of the intracrystalline diffusion result from differences in the molecular sizes, whereby additional form selectivity effects arise xylene isomerisation). Reactions between molecules of these substance classes, for the transition stage (activated complex) of which a larger space is required than that which can be supplied from the crossing-over regions of the pentasil-zeolites, do not occur or only with a very small probability ("Transition stageform selectivity").
Together with this stands the most important catalytic property of the pentasilzeolite its very low tendency to carbonisation. Through this characteristic the use of its strongly acidic centre for the catalytic conversion of substances is technically advantageous, in that it allows very long usage periods between catalayst-regenerations.
The pentasil-zeolites, in accordance with their character as inorganic, crystalline solid acids, catalyse, in their protonated form, the following reaction types: SDehydration/hydration (Ethers and alkenes from alcohols, alcohols from alkenes) C-C-bonding reactions (oligomerisation of alkenes, condensations of compounds containing oxygen, and alkylation of aromatic compounds and iso-paraffins) C-C-splitting (cracking processes of paraffins and alkenes) 3 aromatisation (production of aromatic compounds from paraffins and alkenes) isomerisation (skeleton structure and double bonding isomerisations) The synthesis of silicon-rich zeolites of the pentasil family was first described by Argauer and Landolt (US Patent 3.702.886) in 1967.
The manufacture of these substances was only successful however with the addition of structure-guiding compounds to the synthesis mixture.
Mostly tetraalkylammonium compounds were used such as e.g.
tetrapropylammoniumbromide. In subsequent years the synthesis was successful with a multitude of organic substances such as secondary amines, alcohols, ethers, 1 0 heterocyclics and ketones.
All these synthesis variations have however a series of serious drawbacks which preclude manufacturing on a large industrial scale in a manner which protects the environment. The added substances are toxic and easily flammable. Since the synthesis must be carried out under hydrothermal conditions under high pressure, mostly in 1 5 autoclaves, an escape of these substances is never entirely to be ruled out.
Through this a high degree of potential danger exists for the work force and the nearby and wider vicinity of the place of production. The waste waters which result from the manufacturing process also contain these substances and must therefore be purified, at great costs, in order to preclude environmental contamination. In addition to this the organic constituents which are to be found in the lattice must be burnt out at high temperatures. They or possibly their derivatives or by-products pass thereby into the exhaust air. This burning out can additionally bring about damage to the lattice in the zeolite catalyst which interferes with its catalytic properties.
All these disadvantages have resulted in the situation that up till now large scale industrial manufacture of this useful catalyst has only been carried out in trials.
In recent years several manufacturing processes have been described in the patent literature in which it was possible to avoid the use of these organic substances 1 US 4. 257.885 The manufacturing processes described in these patents lead only very slowly (several days) and mostly incompletely to the desired product. Furthermore the apppearance of undesirable secondary phases cannot be ruled out.
In the meantime it is known that the acidity and the pore structure while indeed necessary requirements are not sufficient for the overall effectiveness of the catalyst components and of the entire catalyst.
4 In particular the long-term performance of these catalysts is largely determined by means of fine differences within the aluminosilicate structure. Thus it is known for example that the aluminium distribution over the cross-section of the crystal in pentasil-zeolites synthesised using organic template compounds is a different one compared with that seen when pentasil-zeolites are obtained using purely inorganic ingredients (see e.g. A. Tissler et al. Stud.Surf.Sci.Catal. 46 (1988) 399-408). In the first case one sees a concentration of aluminium in the periphery of the crystallite, in the latter an equal distribution dominates over the cross-section of the crystal. The use of an X-ray diffraction pattern to characterise a substance of this type with regard to its 1 0 usefulness for catalysis is consequently not sufficient and calls for a solution by means of more subtle methods.
The present invention deals with a synthetic aluminosilicate for the catalytic conversion of hydrocarbons in petrochemical processes. It distinguishes itself by having a high long term stability and can be produced through a purely inorganic synthesis 1 5 process- one which almost rules out the formation of secondary phases and which can be carried out in a short time.
Surprisingly it has been found that these synthetic aluninosilicates have even Sbetter physical-chemical properties than similar products which have been produced in i a different way and make them clearly distinguishable from those products.
These synthetic crystalline aluminosilicates have a chemical composition that can be described in molar ratios in the following manner: O-3M 2 0 A1 2 0 3 15-40SiO 2 0-40H 2 0, whereby M denotes an alkali cation. These cations can be exchanged with the help of a mineral acid, an ammonium compound, other proton carriers or with other cations.
In conjunction with the chemical composition shown above the aluminosilicates according to the invention show an X-ray diffraction pattern that contains at least those inter-lattice plane distances listed in Table 1.
In conjunction with the above chemical composition and the inter-lattice plane distances listed in Table 1 the aluminosilicates according to the invention show a largely homogeneous aluminium distribution over the cross-section of the crystal, i.e. the SiO 2 /A1 2 0 3 ratio at the crystallite surface is greater or the same as the SiO 2 /A1 2 0 3 ratio within the zeolite (see Figs. 4 and The aluminium concentration at the crystal periphery of a conventional comparable aluminosilicate is shown in Fig. 6.
In conjunction with the above chemical composition and the inter-lattice plane distances listed in Table 1 and the abovementioned equal distribution of aluminium over the cross-section of the crystal, the aluminosilicates according to the invention have absorption bands at approx. -100 -106, -112, -116 ppm relative to tetra-methylsilan as the standard in the 29-silicon-solid body-nuclear magnetic resonnance spectrum. With the aid of these the new aluminosilicates will be able to be differentiated from all similar aluminosilcates (Fig. 1 and 2).
The present invention concerns, then, a synthetic crystalline aluminosilicate and catalysts based on it for the catalytic conversion of hydrocarbons in petrochemical processes in the main. It can be produced in an economically advantageous and environmentally friendly manner and additionally is, in many cases, superior to similar 1 0 aluminosilicates manufactured with the aid of organic structure-guiding compounds with respect to its catalytic properties, in particular its activity.
Table 1 d-values/inter-lattice plane distances Relative intensity 11.2 0.3 strong 10.2 0.3 strong 9.8 0.2 weak 3.85 0.1 very strong 3.83 0.1 strong 3.75 0.1 strong 3.73 0.1 strong 3.60 0.1 weak 3.06 0.05 weak 3.00 0.05 weak 2.01 0.02 weak 1.99 0.02 weak By this means the synthetic crystalline aluminosilicate according to the invention can be used in processes to some extent more sparingly with regard to the catalyst and with higher yields and selectivity.
The aluminosilicate according to the invention for the catalytic conversion of hydrocarbons or their derivatives can be used in petrochemical processes in formed catalysts at pressures between 0.5-15 MPa, temperatures in the region of 523-823 K, raw material loadings of 0.5 to 8 in the presence of hydrogen or gases containing hydrogen. It distinguishes itself in the majority of processes through its long term stability. The aluminosilicate according to the invention is ion-exchanged by means of an 3 5 ammonium compound or a mineral acid, if necessary converted to the active hydrogen form by means of subsequent calcination above 573 K and, by means of the addition of binding agents as well as, if necessary, a metal or metal oxide component, re-worked to the form of the finished catalyst.
Amorphous silica, pseudoboehmite and stratified silicate, or a combination of these substances, are favoured binding materials, if necessary with the addition of binding and auxilliary materials such as e.g. polyvinylalcohol.
The elements of the 4th to the 6th period of the Periodic Table of the Elements are suitable as metal or metal oxide components, in particular Zn, Mo, W, Pd, Ga or Pt or a combination of these.
1 0 Particularly advantageous properties are demonstrated by the aluminosilicate iaccording to the invention in processes for the removal of n-paraffins or singly i branched paraffins from hydrocarbon fractions, in the procedure for the treatment of j mixtures of C 8 -aromatic compounds, in the procedure for the alkylation of aromatic I compounds with lower alkenes, in the procedure for the alkylation of aromatic 1 5 compounds with alcohols, in the procedure for the splitting of high boiling point hydrocarbon fractions in the moving catalyst bed, in the procedure for the isomerisation of lower n-paraffins to iso-paraffins, in the procedure for the production of aromatic compounds from lower hydrocarbons, in the procedure for the production of liquid hydrocarbons from lower alkanes or alkenes and in the procedure for the conversion of 2 0 alcohols to liquid hydrocarbons, lower alkenes and to aromatic compounds.
Long chained un- or slightly-branched paraffins have higher melting points in i comparison with other hydrocarbons with the same number of C's. Small concentrations j of such wax-like components in substance mixtures whose serviceability is tied to the I paraffin content distillate fuel, lubricants), can negatively influence the flow 25 characteristics (pour point, freeze point, cloud point). Unlike narrow-pored zeolites erionite) whose form-selective cracking-properties stay confined to molecules of the petrol boiling range, pentasils having middle-sized pores are suited to selectively splitting paraffins with the properties of wax and thereby largely freeing the respective mixture of substances of them. The spectrum of possible charging stock is wide, ranging from jet fuel to distillation residues.
The synthetic crystalline aluminosilicate according to the invention for the removal of paraffins from hydrocarbon fractions is described in more detail in Example 4.
Initial materials for the xylene isomerisation contain all four of the C8isomers, i.e. ethylbenzene and the 3 xylene isomers m- and p-xylene. A function of the isomerisation contact consists of the readjustment of the balance of isomers (approx.
m-xylene and 25% each of o- and p-xylene) after a large portion of the p-xylene had been removed as product. Over and above that the catalyst must convert ethylbenzene to higher or lower boiling by-products that can be separated from the product stream.
This is necessary in order to avoid the concentration of ethylbenzene in the cycle. With regard to the activity, the limitation applies that the adjustment of the isomer balance must be ensured under conditions which enable at the same time a conversion of the ethylbenzene to the desired conversion level. The desired ethylbenzene conversion results from the optimisation of the overall isomerisation plant.
1 0 The process for the xylene isomerisation according to the invention will be further described in Example Pentasil-zeolites have proven themselves to be effective catalysts for the alkylation of aromatic compounds with lower alcohols or with olefins in the production of xylene from toluene and methanol as well as of ethylbenzene from benzene and ethene 1 5 (Mobil Badger Process). Over and above these there are also other variations out of the range of possible alkylation reactions with catalysts and these were therefore included on the basis not only of scientific but also of technical interest in the basic research and respectively in the applied research. It concerns in particular the following syntheses: p-ethyltoluene from toluene and ethene, 2 0 diethylbenzene from ethylbenzene and ethene, dimethylethylbenzene from xylene and ethene, cumene from benzene and propene, alkylbenzene from benzene and lower alcohols, diethylbenzene from ethylbenzene and ethanol, p-ethyltoluene from toluene and ethanol.
The manufacture of ethylbenzene as a precursor for styrene is a targeted selective heterogenoeusly catalytic gaseous phase reaction developed to the stage of a large scale industrial process on a pentasil-zeolite basis.
Substantial advantages compared with older processes homogeneous catalytic AICI3-(Friedel-Craft)-Processes Alkar-Process with BF 3 /Al 2 0 3 as catalyst are the following: S- no waste products which pollute the environment no corrosion problems problem-free regeneration of the catalyst by burning-off the coke 8 large extractability of the reaction heat at high temperature level small investment and operating costs (despite certain additional expenses for the benzene-recycling system and the product purification system).
i The synthetic crystalline aluminosilicate according to the invention for the 1 5 alkylation of aromatic compounds with lower alkenes will be further described in 1 Example 6.
Th. alkylation of toluene with methanol is a potential alternative to the process I of xylolisomerisation in view of the production of largely para- and orthoxylol as the t intermediate product for the manufacture of synthetic materials.
1 0 The synthetic crystalline aluminosilicate according to the invention for the alkylation of toluene with methanol is described further in Example 7.
Catalytic fluidised-bed-cracking processes occupy a key role in refinery operations. Their economy depends on the effectiveness of the catalyst which can be used for alkylation reactions for the manufacture of high-grade fuel (RON/MON) or else LPG- 1 5 products. In the main however the processes for the conversion of vacuum distillate are used but the trend is to develop the processes also for the use of distillation residues.
There is a multitude of FCC-catalysts available on the market which are tailor-made for various user requirements which deal sometimes with the initial substances and at other times with the end products. These days Y-zeolites, often ultrastable, are used above all.
2 0 Their acidity is brought about by ion-exchange or ammonium-exchange and subsequent thermal treatment. The zeolite with a particle size of approx. 11 m is built into a matrix which consists of e.g. SiO 2 -A1 2 0 3 The zeolite portion amounts to 5 25% by mass.
Since 1983 pentasil zeolites have been added to FCC-catalysts. Experiments showed that with the addition of of 5 SE-exchanged pentasil to the de-aluminiumised SE-exchanged Y-zeolite, which brought a high fuel yield, an increase of the olefin yield from 6 to 12% by weight (C 3 or from 9 to 18% by weight (C 4 was achieved.
The addition of pentasil-zeolite results in the removal of the low octane paraffin fraction, and the formation of C 3
C
4 -olefins which form the initial product for the alkylation whereby petrol yield losses, assuming free alkylation capacity, can be in part compensated for.
The synthetic crystalline aluminosilicate according to the invention for the splitting of high boiling point hydrocarbon fractions is described further in Example 8.
A synthetic crystalline aluminosilicate according to the invention for the isomerisation of lower n-paraffins with the aim of improving the front octane rating of carburettor fuels is described further in Example 9.
The reforming process is the main source of aromatic hydrocarbons from crude oil. It is however only able to convert hydrocarbons with at least 6 carbon atoms in the molecule into aromatic compounds. Paraffins and olefins with five and fewer carbon atoms are not changed into aromatic compounds in the reforming process.
For the most diverse reasons the use of lighter hydrocarbons (C2-C5), in particular liquid petroleum gas, for the production of high-grade fluid products has gained increasing importance over recent years. The fundamental possibility of the dehydrocyclodimerisation of Cs-Cs-akanes on catalysts with an acidic and dehydrogenating function was known at least since the work of Csicsery. The disadvantage of these catalysts lay however in the shortness of the working periods in between regenerations. Form selective zeolites which vastly slow down the formation of coke should be better suited for this.
The synthetic crystalline aluminosilicate according to the invention for the production of aromatic compounds from lower hydrocarbons is described further in Example 10 Methanol can be converted to higher hydrocarbons on pentasil-zeolites.
According to catalyst modification and the manner of the process for the conversion, either a qualitatively high-grade fuel for carburettor motors, aromatic compounds for further processing e.g. in the synthetic materials industry, or preferably alkenes, can be produced. Since methanol can be produced by familiar techniques from crude oil G: coal it is possible to get high-grade hydrocarbons from this raw material.
The synthetic crystalline aluminosilicate according to the invention for the production of liquid hydrocarbons or lower alkenes from methanol is described further in Example 11.
Manufacture of catalysts from the powders of synthetic crystalline S. aluminosilicates produced in Examples 1+2+3 Catalyst 1 A synthetic crystalline aluminosilicate of type B is ion exchanged several times with a hydrous solution of an ammonium salt and subsequently, in a ratio of aluminosilicate to 30% inorganic binder, in this case aluminium oxide in the form of pseudo-boehmite with the addition of 3 by nass of HN0 3 mixed in a kneader and formed into extrusions of 3 mm diameter and activated at temperatures of 673 K.
Reference catalyst 2 A synthetic zeolite of type C according to Example 10a on page 19 in "Synthesis of High-Silica Aluminosilicate Zeolites" published as Stud. Surf. Sci. Catal., 3 (1987), published by P. A. Jacobs and A. Martens, with tetrapropylammoniumbromide as structure guiding compound is repeatedly ion-exchanged in a hydrous solution of an ammonium salt and subsequently, in a ratio of 70% aluminosilicate to 30% inorganic binder, in this case aluminium oxide in the form of pseudo-boehmite with the addition of 1 0 3% by mass of HNO 3 mixed in a kneader and formed into extrusions of 3 mm diameter and activated at temperatures of 673 K.
Catalyst 3 A synthetic crystalline aluminosilicate of Type A is ion exchanged several times with a hydrous solution of an ammonium salt and subsequently, in a ratio of aluminosilicate to 30% inorganic binder (see Catalyst mixed and formed into extrusions of 3mm diameter. Subsequently the catalyst casting is coated with 3 by weight molybdenun oxide by means of soaking in a ammoniacal solution of MoO 3 and activated at temperatures of 673 K.
Reference catalyst 4 A synthetic zeolite of type C according to Example 10a on page 19 in "Synthesis of High-Silica Aluminosilicate Zeolites" published as Stud. Surf. Sci. Catal., 3 (1987), published by P. A. Jacobs and A. Martens, with tetrapropylammoniumL.:r.'ide as structure guiding compound is ion exchanged several times in a hydrous solution of an ammonium salt and subsequently, in a ratio of 70 aluminosilicate to 30 inorganic binder (see Catalyst mixed and formed into extrusions of 3 mm diameter.
Subsequently the catalyst casting is coated with 3 by weight molybdenum oxide by means of soaking in an ammoniacal solution of MoO 3 and activated at temperatures of 673
K.
Catalyst A synthetic crystalline aluminosilicate of Type B is ion exchanged several times with a hydrous solution of an ammonium salt and subsequently, in a ratio of aluminosilicate to 30 inorganic binder (see Catalyst mixed and formed into extrusions of 3mm diameter. Subsequently the catalyst is coated with 2 by weight j 11 gallium oxide by means of soaking in a solution of a gallium salt and activated at temperatures of 673 K.
Catalyst 6 A synthetic zeolite of type C according to Example 10a on page 19 in "Synthesis of High-Silica Aluminosilicate Zeolites" published as Stud. Surf. Sci. Catal., 2 (1987), published by P. A. Jacobs and A. Martens, with tetrapropylammoniumbromide as structure guiding compound is ion exchanged several times in a hydrous solution of an ammonium salt and subsequently, in a ratio of 70% aluminosilicate to 30 inorganic binder (see Catalyst mixed and formed into extrusions of 3 mm diameter.
1 0 Subsequently the catalyst is coated with 2 by weight gallium oxide by means of soaking with a solution of a gallium salt and activated at temperatures of 673 K.
Catalyst 7 A synthetic crystalline aluminosilicate of Type A is ion exchanged several times with a hydrous solution of an ammonium salt and subsequently, in a ratio of 70 aluminosilicate to 30% inorganic binder (see Catalyst mixed and formed into extrusions of 3mm diameter. Subsequently the catalyst is soaked with a zinc nitrate solution (2 by weight) and activated in the current of hydrogen at 40 bar H 2 pressure and 673 K.
Catalyst 8 2 0 A synthetic zeolite of type C according to Example 10a on page 19 in "Synthesis of High-Silica Aluminosilicate Zeolites" published as Stud. Surf. Sci. Catal., 3. (1987), published by P. A. Jacobs and A. Martens, with tetrapropylammoniumbromide as structure guiding compound is ion exchanged several times in a hydrous solution of an ammonium salt and subsequently, in a ratio of 70% aluminosilicate to 30 inorganic binder (see Catalyst mixed and formed into extrusions of 3 mm diameter.
Subsequently the catalyst is soaked with a zinc nitrate solution (2 by weight) and activated in the current of hydrogen at 40 bar H 2 pressure and 673 K.
Examples 1. Manufacture of an aluminosilicate of Type A: 3 0 A reaction starting mixture of solutions of Na-waterglass aluminium sulphate, sodium sulphate and sulphuric acid with the molar ratios Si0 2 /Al 2 0 3 OH-/SiO 2 0.14
H
2 0/SiO 2 12 is heated to a reaction temperature of 185°C in a stirring autoclave and treated hydrothermally for 24 hours. The solid product is filtered and dried at 1100C.
The dry substance consists of phase-pure aluminosilicate with an X-ray diffraction pattern with at least the d-values listed in the Table 1.
The chemical composition of the product expressed in molar ratios is: 1.1 Na 2 O: Al 203 31SiO 2 6H 2 0 The aluminium distribution over the crystal cross-section of the product is shown in Fig. 4.
The retained portions of the single absorption bands of the 29-silicon-solid 1 0 body-MAS-nuclear magnetic resonance spectra (Fig. which are a measure for the various silicon tetrahedra coordinates lie at: Si(4SiOAI)% Si(3Si1AI) Si(25i2AI) -112 and -116 ppm -106 ppm -100 ppm 23 2 1 5 2. Aluminosilicate of type B A reaction starting mixture of solutions of Na-waterglass aluminium sulphate, sodium sulphate and sulphuric acid with the molar ratios SiO 2 /Al203 OH-/SiO 2 0.14
H
2 0/SiO 2 is heated to a reaction temperature of 185 C in a stirring autoclave and treated hydrothermally for 24 hours. Ths solid product is filtered and dried at 110 C.
The dry substance consists of phase-pure aluminosilicate with an X-ray diffraction pattern with at least the d-values listed in the Table 1.
2 5 The chemical composition of the product expressed in molar ratios is: 1.1 Na20: A1 2 0 3 23SiO 2 7H 2 0 The aluminium distribution over the crystal cross-section of the product is shown in Fig. The retained portions of the single absorption bands of the 29-silicon-solid body-MAS-nuclear magnetic resonance spectra (Fig. which are a measure for the various silicon tetrahedral coordinates lie at: Ii
I
13 Si(4SiOAl)% Si(3Si1AI) Si(2Si2AI) -112 and -116 ppm -106 ppm -100 ppm 71 26 3 3. Manufacture of a conventional reference aluminosilicate of Type C A reaction starting mixture of pyrogenic silica, tetrapropylammoniumbromide, glycerol, ammonia, sodium hydroxide, aluminium nitrate and water with the molar ratios SiO 2 /A1 2 0 72 Na 2 O/SiO 2 0.2 TPA/SiO 2 1.25 Glycerol/SiO 2 19.86
NH
3 /SiO 2 0.2
H
2 0/SiO 2 146 is heated up in a non-moving autoclave to a reaction temperature of 423 K and is treated 1 5 hydrothermally for 72 hours. The solid product is filtered and dried at 383 K. The product has a SiO 2
/A
2 0 3 O-ratio of The aluminium distribution over the crystal cross-section of the conventional reference catalyst is shown in Fig. 6. Furthermore this product shows no absorption bands in the 29-silicon-solid body-MAS-nuclear magnetic resonance spectrum at -100 ppm (see Fig. 3).
Example 4 A Diesel fuel uith a density of 0.865 kg/I, a nitrogen content of 142 mg NH 3 /l and a BPS-point Beginning of the Paraffin Separation) of 30C under a pressure of MPa and with a loading of 2 (v/vh) and a gas product ratio (GPR) of 1000 1 at 663 K starting temperature is converted once on the catalyst 7 and then on the conventional reference catalyst 8.
The results of the catalytic paraffin removal are listed in the Table below.
Results Initial product Catal. 7 Catal. 8 Density (kg/I) 0.865 0.859 0.858 BPS 30C -15/-25 -15/-25 AT/d 0.17 0.48 AT/d was averaged over a test period of 30 days.
1111 The catalyst 7 according to the invention has a much lower fouling rate (AT/d) and thereby a higher stability at about the same initial activity, compared with catalyst 8.
Example A mixture of C-8-aromatic compounds at a pressure of 1.0 MPa, a temperature of 633 K, a loading of 2.0 and a gas product ratio (GPR) of 1000:1 is converted once on the catalyst 3 and on the other hand on the conventional reference catalyst 4.
The results of the C-8-aromatic compound conversion are listed in the Table below.
Results Raw material Catal. 3 Catal. 4 non-aromat. 1.09 0.45 0.71 benzene 14.39 5.32 toluene 0.71 6.62 5.04 ethylbenzene 23.75 2.79 12.24 para-xylene 9.73 17.89 16.01 meta-xylon 47.57 40.38 38.12 ortho-xylene 16.44 16.29 15.27 C9 1 aromatics 0.71 1.35 7.29 Sxylenes 73.74 74.5 69.4 The catalyst 3 according to the invention shows a much higher ethylbenzene conversion and at the same time better xylene selectivity (fewer C9+-aromatic compounds) than the reference catalyst 4.
Example 6 A mixture of benzene and ethene in the ratio of 1 2.6 at 673 K 693 K with a loading of 6.5 h' 1 (benzene ethene) is converted once on the catalyst I and then on the conventional reference catalyst II.
The results of the alkylation reaction are listed in the Table below.
Li I I I f- Ir -rir r ix-,~ll_ ~i i i- -illl-i-~l~a Results Catal. I Catal. II conversion benzol 28 26 conversion ethene 81 72 selectivity of benzen to ethylbenzen+diethylbenzen 95 92 selectivity of ethene to ethylbenzen diethylbenzen 90 1 0 portion of para-di-ethylin diethylbenzenes 85 The catalyst I according to the invention shows, at a somewhat higher activity, a comparable selectivity to ethylbenzene and diethylbenzene but over and above that however a markedly improved selectivity to para-diethylbenzene as compared with the reference catalyst II.
Example 7 A mixture of toluene and methanol in a ratio of 2 :1 at 623 K and a loading of 4 h -1 (toluene methanol) is converted once on the catalyst I and then on the other hand on the conventional reference catalyst II.
2 0 The results of the alkylation reaction are listed in the Table below.
Results Catal. I Catal. II methanol conversion 100 toluene conversion 30 17 benzene 1 toluene 51 61 metha-xylene 8 4 para-xylene 11 3.9 ortho-xylene 7 ,Cs-aromatic compounds 26 1 1 3 0 The catalyst I according to the invention shows a clearly higher activity and a slightly improved para-selectivity as compared with the reference catalyst II.
Ls Catalyst I and Catalyst II respectively are added by weight) to a conventional commercially available moving-bed catalyst based on a Y-zeolite. After a steam treatment of the catalysts at 1023 K over 17 hours a hydrogenated vacuum distillate at 748 K and a loading of 10 h "1is directed over the mixed catalysts.
The results of the cracking experiments are listed in the Table below.
Results conv. catal. I with catal. I with 5 catal. II methane ethane 1 0 ethene propane propene n-butane i-butane
.C
4 Cs-C2 (petrol) 50.2 48.5 48.20 coke 8.4 5.8 8.1 The catalyst according to the invention produces, similarly to the reference catalyst, a somewhat higher gas yield however a somewhat better benzine output and a markedly lower coke component. The iso-butane portion rises sharply which produces a marked improvement in the motor octane rating. Likewise the components of the C3 and
C
4 -olefins are increased which results in an improvement in the research octane rating.
Example 9 A n-hexane/waterglass mixture in a ratio of 1 10, at a temperature of 573 K and 4 MPa and a loading of 1 h' 1 is converted once on the catalyst 7 and as a comparison converted on the conventional reference catalyst 8.
The results of the reaction are listed in the Table below: Results Catalyst 7 Catalyst 8 3 0 n-hexane conversion 48 hexaneisomer/ Crackprod. 1.3 1.2 The catalyst 7 according to the invention shows a markedly higher activity and a slightly better hexaneisomer/ Crackproduct ratio than the conventional reference catalyst.
VA. I Example N-pentane, at a pressure of 0.1 MPa and a loading of 1 h-1 at a temperature of 773 K is converted first on the catalyst 5 and then converted on the conventional reference catalyst 6.
The results of the aromatisation reaction are listed in the Table below: Results Catalyst 5 Catalyst 6 Liquid product 45 39.2 Gases 54.1 60.3 Carbon 0.9 Aromatic compounds 44.5 38.5 The catalyst according to the invention, in comparison with the conventional catalyst 6, shows an improved aromatic compound yield.
Example 11 Methanol, at a pressure of 0.1 MPa, a temperature of 573 K and a loading of 1 5 lh-1 is converted first on the catalyst 1 and then on the conventional catalyst 2.
The results of the reaction are listed in the Table below: Results Catalyst 1 Catalyst 2 conversion 99 70 Olefins 33 23 2 0 Aromatic compounds 1 2 15 The catalyst 1 according to the invention shows a markedly higher activity and an improved olefin yield as compared with the conventional reference catalyst.
Claims (19)
1. Synthetic crystalline aluminosilicate with the chemical composition 02 3M 2 0 A1 2 0 3 15 40Si0 2 0 4H 2 0, whereby M represents a metal-cation, that has in its X-ray diffraction pattern at least the X-ray reflexes which belong to the d- values listed in Table 1, and whose SiO 2 /A1 2 C -molar ratio at the crystal surface is greater or equal to the SiO 2 /A1 2 0 3 -molar ratio within the crystal, characterised in that the aluminosilicate whose 29-silicon-solid body-MAS-nuclear magnetic resonance spectrum absorption bands are at approx. -100, -106, -112 and -116 ppm relative to the standard tetra-methyl silane, is used for catalytic conversion in petrochemical processes.
2. Synthetic crystalline aluminosilicate according to claim 1, characterised in that the aluminosilicate is used as a component in a catalyst for the removal of n- paraffins or singly branched paraffins from hydrocarbon fractions with the aim of improving the low temperature behaviour of fuels and respectively of producing precursors of lubricants at pressures in the region of 1.0 to 15 MPa and temperatures ofls K to 723 K.
3. Synthetic crystalline aluminosilicate according to one of the previous claims, characterised in that aluminosilicate is used as catalyst-component for the processing of mixtures of C -aromatic compounds at pressures in the region of 0.5 5.0 MPa and temperatures in the region of 523 K to 773 K with the aim of producing ortho- and/or para-xylene.
4. Synthetic crystalline aluminosiliscate according to one of the previous claims, characterised in that the aluminosilicate is used for the alkylation of aromatic compounds with lower alkenes, especially benzene with ethene or propene, with the aim of producing ethylbenzene or cumene at pressures in the region of 1.0 to 5.0 MPa and temperatures of 623 K 773 K. I I V 4W b 19 Synthetic crystalline aluminosilicate according to one of previous claims, characterised in that the aluminosilicate is used as catalyst-component for the alkylation of aromatic compounds with alcohols especially for the alklyation of toluene with methanol to form xylene at pressures in the region of 0.1 0.5 MPa and temperatures in the region of 523 K to 773 K.
6. Synthetic crystalline aluminosilicate according to one or more of the previous claims, characterised in that the aluminosilicate is used as a component of catalysts for the splitting of high boiling point hydrocarbon fractions in the moving catalyst bed with the aim of improving the octane rating of the cracked gasoline.
7. Synthetic crystalline aluminosilicate according to one or more of the previous claims, characterised in that the aluminosilicate is used as a component of catalysts for the isomerisation of lower n-paraffins to iso-paraffins at pressures in the region of to 5 MPa and temperatures in the region of 473 K to 773 K.
8. Synthetic crystalline aluminosilicate according to one or more of the previous claims, characterised in that the aluminosilicate is used as a component of catalysts for the production of aromatic compounds from lower hydrocarbons at pressures of 0.5 to MPa and temperatures in the region of 773 K to 873 K.
9. Synthetic crystalline aluminosilicates according to one or more of the previous claims, characterised in that the aluminosilicate is used as a component of catalysts for the production of liquid hydrocarbons or lower alkanes or alkenes from methanol at pressures in the region of 0.5 to 5.0 MPa and temperatures in the region of 523 K to 823 K. WATERMARK THE ATRIUM 290 BURWOC HAWTHORN AUSTRAUA A, H-I.S-F-UT--eay--1U T- JU VEREINIGTE ALUMINIUM-WERKE AKTIENGESELLSCHAFT and LEUNA-WERKE AG. SPATENT TRADEMARK ATTORNEYS )D ROAD VICTORIA 3122 I rti r t t i: n preceding I 8 pages apy true 0 M&aa utrjoinally lodged, IAS/ML i 19 Aw" sllflar I- Process for catalytic conversion of hydrocarbons and their derivatives in petrochemical processes by use of synthetic crystalline aluminosilicates in moulded catalysts, characterised in that the catalytic conversion is carried out at pressures in the region of 0.1-15 MPa, at temperatures in the region of 473 K to 873 K and under catalyst loads of 0.5 to 10 g/h educt per g catalyst, in that for catalytic conversion for splitting of higher-boiling hydrocarbon fractions in a moving catalyst bed, for removal of n-paraffins and singly branched paraffins from hydrocarbon fractions, from Ca aromatic mixtures for producing ortho- and/or para-xylenes, for alkylation of aromatics with lower alkenes, for alkylation of aromatics with alcohols, for isomerising lower n-paraffins to iso-paraffins, for producing aromatics from lower hydrocarbons, and from methanol for producing liquid hydrocarbons or lower alkanes and alkenes, a synthetic crystalline aluminosilicate having the chemical composition 0-3 M 2 0:Al2:
15-40 SiO 2 0-40 H 2 0, whereby M signifies a metal cation, is used as a catalyst or as catalyst-components, which exhibits at least the x-ray diffractions belonging to the d-values (A) 11.2 strong 10.2 strong 9.8 weak 3.85 very strong 3.83 strong 3.75 strong 3.73 strong 3.60 weak 3.06 weak 3.00 weak 2.01 weak 1.99 weak a greater or similar Si/A1 molar ratio on the crystalline surface compared to the crystallite interior, @0*0. 0 0 I iIII 21 and absorption bands of the 29-silicon solid MAS nuclear resonance spectrum relative to the tetramethylsilane standard at ca. -100, -106, -112 and -116 ppm. 11. Process as claimed in Claim 10, characterised in that the catalytic splitting of higher-boiling hydrocarbons such as vacuum distillates and hydrogenated gas oils is carried out at a temperature between 723 K and 773 K and under a catalyst load of g/h educt per g. 12. Process as claimed in Claim 10, characterised in that the catalytic conversion for removal of n-paraffins and singly branched paraffins from hydrocarbon fractions is carried out at pressures in the region of 1.0 to 1.5 MPa and at temperatures of 523 K and 873 K. 13. Process as claimed in Claims 10 or 12, characterised in that a gas oil is dewaxed at a temperature between 663 K and 723 K and at a catalyst load of 2 g/h gas oil per g catalyst. 4 4 14. Process as claimed in Claim 10, characterised in that the catalytic conversion 't of Ca aromatic mixtures for producing ortho- and/or para-xylenes is carried out at pressures in the region of 0.5 to 5.0 MPa and at temperatures of 523 K to 773 K. o Process as claimed in Claims 10 or 14, characterised in that a Ca aromatic mixture for isomerising xylenes is catalytically converted at a temperature between 623 K and 773 K at a catalytic load of 2 g/h educt per catalyst. 1 6. Process as claimed in Claim 10, characterised in that the catalytic conversion for alkylating aromatics with lower alkenes is carried out at pressures in the region of to 5.0 MPa and at temperatures of 623 K and 773 K.
17. Process as claimed in Claims 10 or 16, characterised in that benzene is converted with ethene to ethylbenzene. 22
18. Process as claimed in Claims 10, 16 or 17, characterised in that [some original text missing] is [catalytically] converted to ethylbenzene.
19. Process as claimed in Claims 10 or 16, characterised in that benzene is converted with propene to cumene. Process as claimed in Claim 10, characterised in that the catalytic conversion for alkylation of aromatics with alcohols is carried out at pressures in the region of 0.1 to 0.5 MPa and at temperatures in the region of 523 K to 773K.
21. Process as claimed in Claims 10 or 20, characterised in that toluene is converted with methanol to xylene.
22. Process as claimed in Claims 10, 20 or 21, characterised in that for alkylation of toluene with methanol a mixture in a molar ratio of toluene methanol of 2 1 is converted at a temperature between 573 K and 673 K and at a catalyst load of 4 g/h educt per catalyst.
23. Process as claimed in Claim 10, characterised in that the catalytic conversion for isomerizing lower n-paraffins to iso-paraffins is carried out at pressures in the region of 0.5 to 5 MPa and at temperatures in the region of 473 K to 773 K. S24. Process as claimed in Claims 10 or 23, characterised in that the n-paraffins are isomerized at a temperature between 523 K and 623 K and at a catalyst load of 1 g/h S educt per g catalyst. C t
25. Process as claimed in Claim 10, characterised in that the catalytic conversion Sfor producing aromatics from lower hydrocarbons is carried out at pressures in the region of 0.1 to 5.0 MPa and at temperatures in the region of 773 K to 873 K.
26. Process as claimed in Claims 10 or 25, characterised in that for production of aromatics hydrocarbons with a lower molecular weight are converted at a temperature between 773 K and 873 K and at a catalyst load of 1 g/h educt per catalyst. 23
27. Process as claimed in Claim 10, characterised in that the catalytic conversion of methanol for producing liquid hydrocarbons or lower alkanes and alkenes is carried out at pressures in the region of 0.1 to 5.0 MPa and at temperatures in the region of 573 K to 873 K.
28. Process as claimed in Claims 10 or 27, characterised in that methanol is converted catalytically to liquid hydrocarbons of C 4 to C 12 or lower alkenes <C6 at a temperature between 523 K and 773 K and at a catalyst load of 1 g/h educt per g catalyst. DATED this 1st day of December, 1993. VEREINIGTE ALUMINIUM-WERKE AKTIENGESELLSCHAFT and LEUNA-WERKE AG WATERMARK PATENT TRADEMARK ATTORNEYS THE ATRIUM 290 BURWOOD ROAD SHAWTHORN VICTORIA 3122 AUSTRAUA IAS/JZ (Doc.33) AU8028991.WPC
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DE4022140A DE4022140C2 (en) | 1990-07-11 | 1990-07-11 | Use of a synthetic, crystalline aluminosilicate |
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DE3919400A1 (en) * | 1989-06-14 | 1991-01-10 | Vaw Ver Aluminium Werke Ag | METHOD FOR PRODUCING HIGHLY SEQUINED ALUMINOSILICATES |
CN101332433B (en) * | 2007-06-27 | 2011-07-20 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and use thereof |
RU2453359C1 (en) * | 2011-04-25 | 2012-06-20 | Вера Борисовна Обухова | Method of cleaning hydrocarbon fractions from sulphur-containing compounds |
US8889940B2 (en) * | 2011-11-01 | 2014-11-18 | Uop Llc | Catalyst and process for hydrocarbon conversion |
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EP0136680A2 (en) * | 1983-09-30 | 1985-04-10 | Union Carbide Corporation | Novel fatty ethenoid acylaminoorganosilicon compounds and their use as a coupling agent |
EP0170751A1 (en) * | 1984-08-10 | 1986-02-12 | Tonen Corporation | Novel crystalline aluminosilicate, process for the preparation thereof, and process for the conversion of organic materials using the same |
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US3702886A (en) * | 1969-10-10 | 1972-11-14 | Mobil Oil Corp | Crystalline zeolite zsm-5 and method of preparing the same |
US4257885A (en) * | 1976-02-04 | 1981-03-24 | Union Carbide Corporation | Novel zeolite compositions and processes for preparing and using same |
FR2552418B1 (en) * | 1983-09-28 | 1985-10-25 | Rhone Poulenc Spec Chim | PROCESS FOR MANUFACTURING ZSM-5 TYPE ZEOLITE |
JPH01157584A (en) * | 1987-09-25 | 1989-06-20 | Lion Corp | Lasing material |
DE3922181A1 (en) * | 1989-07-06 | 1991-01-17 | Vaw Ver Aluminium Werke Ag | SYNTHETIC CRYSTALLINE ALUMOSILICATE AND METHOD FOR THE PRODUCTION THEREOF |
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- 1991-07-10 JP JP3169554A patent/JP3061897B2/en not_active Expired - Fee Related
- 1991-07-11 DE DE91111557T patent/DE59101269D1/en not_active Expired - Fee Related
- 1991-07-11 EP EP91111557A patent/EP0473907B1/en not_active Expired - Lifetime
- 1991-07-11 ES ES91111557T patent/ES2055491T3/en not_active Expired - Lifetime
- 1991-07-11 AT AT91111557T patent/ATE103506T1/en not_active IP Right Cessation
- 1991-07-11 DK DK91111557.4T patent/DK0473907T3/en active
-
1994
- 1994-09-15 RU RU9494033348A patent/RU2083281C1/en active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0136680A2 (en) * | 1983-09-30 | 1985-04-10 | Union Carbide Corporation | Novel fatty ethenoid acylaminoorganosilicon compounds and their use as a coupling agent |
EP0170751A1 (en) * | 1984-08-10 | 1986-02-12 | Tonen Corporation | Novel crystalline aluminosilicate, process for the preparation thereof, and process for the conversion of organic materials using the same |
Also Published As
Publication number | Publication date |
---|---|
CA2046438A1 (en) | 1992-01-09 |
RU2094419C1 (en) | 1997-10-27 |
RU94033348A (en) | 1996-07-10 |
AU8028991A (en) | 1992-01-16 |
NO911325L (en) | 1992-01-13 |
JP3061897B2 (en) | 2000-07-10 |
EP0473907A3 (en) | 1992-04-08 |
EP0473907A2 (en) | 1992-03-11 |
EP0473907B1 (en) | 1994-03-30 |
RU2083281C1 (en) | 1997-07-10 |
NO911325D0 (en) | 1991-04-04 |
DE59101269D1 (en) | 1994-05-05 |
DK0473907T3 (en) | 1994-11-07 |
JPH0748573A (en) | 1995-02-21 |
ES2055491T3 (en) | 1994-08-16 |
DE4042655C2 (en) | 1996-12-19 |
ATE103506T1 (en) | 1994-04-15 |
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MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |