PROCESS FOR THE PREPARATION OF CRYSTALLINE SILICATES, CRYSTALLINE SILICATES SO PREPARED AND PROCESS FOR CARRYING OUT CATALYTIC REACTIONS

Abstract: Process for the preparation of ZSM-5 type crystalline aluminium silicates. An aqueous mixture containing a com­ pound of an alkali metal (M), a quaternary alkyl ammonium compound (R₄NX), a silicon compound that after drying at 120°C and calcination at 500°C yields a product with an SiO₂ content of more than 90% by weight, and an aluminium com­ pound in which mixture the various compounds are present in the specific molar ratios, is maintained at elevated tempera­ ture until the crystalline silicate is formed which is separated, dried and calcined.

Description: PROCESS FOR THE PREPARATION OF CRYSTALLINE SILICATES, CRYSTALLINE SILICATES SO PREPARED AND PROCESS FOR CARRYING OUT CATALYTIC REACTIONS The invention relates to a process for the preparation of crystalline aluminium silicates having improved catalytic properties. Mixtures of carbon monoxide and hydrogen can be converted into aromatic hydrocarbon mixtures with the use of a mixture of two catalysts, one of which is capable of catalyzing the conversion of an X2/CO mixture into acyclic oxygen-containing hydrocarbons and the other being a crystalline aluminium silicate capable of catalyzing the conversion of acyclic oxygen-containing hydrocarbons into aromatic hydrocarbons. The said crystalline aluminium silicates are characterized in that they have the following properties after one hour's calcination in air at 5000C: a) thermally stable to a temperature above 6000C; b) an X-ray powder diffraction pattern containing the four lines stated in Table A as strongest lines, and c) in the formula representing the composition of the silicate expressed in moles of oxides, the SiO2/A1203 molar ratio (for brevity designated m in the present patent application) is more than 10. TABLE A d() Relative intensity 11.1 + 0.2 VS 10.0 + 0.2 VS 3.84 + 0.07 S 3.72 + o.o6 s where the letters used have the following meanings: VS = very strong; S = strong. The relevant silicates can be prepared from an aqueous mixture containing the following compounds: one or more compounds of an alkali metal (M), one or more quaternary alkyl ammonium compounds (R4NX), one or more silicon compounds with a high SiO content and one or more aluminium compounds. In the 2 present patent application by silicon compounds with a high SiO2 content are meant: silicon compounds that yield a product with an SiO content of more than 90% by weight after being 2 dried at 1200C and calcined at 5000C. The crystallized silicates are prepared by keeping the aqueous mixture at elevated temperature until the crystalline silicate is formed, separating it from the mother liquor and calcining it. In the aqueous mixture from which the silicates are prepared, the various compounds should be present in the following ratios, expressed in moles of oxides: Na20 : Si02 < 0.35 (R2N)2O : SiO2 < 0.40 SiO2: Al2O3 > 10 H20 : SiO2 < In an investigation by the Applicant into the use of the above-mentioned catalyst mixtures for the preparation of aromatic hydrocarbon mixtures starting from R2/CO mixtures with an H2/CO molar ratio below 1.0, it has been found that the C5 selectivity of said catalyst mixtures is greatly determined by the SiO2/A1203 molar ratio of the crystalline silicate component. It has been found that on introducing into the catalyst mixture a crystalline silicate prepared with the application of an Na2/SiO2 molar ratio of at most 0.04 in the aqueous base mixture usual for the preparation of said silicates, the C5 selectivity of the catalyst mixtures rises according as a crystalline silicate having a higher Si02/A1203 molar ratio is used therein and that + for obtaining a C5 selectivity of the catalyst mixtures that is acceptable for commercial use, the Si02/Al203 molar ratio of the crystalline silicate component must be more than 200. A drawback to the use of catalyst mixtures into which a crystalline silicate component is incorporated that is prepared with the application of the above-mentioned Na20/SiO2 molar ratio in the aqueous base mixture is that the activity of said catalyst mixtures decreases according as a crystalline silicate with a higher SiO2/A1203 molar ratio is used therein. Further investigation by the Applicant into said subject showed that said catalyst mixtures exhibit both a high activity and a high C5 selectivity if they contain a crystalline silicate component with an SiO2/A1203 molar ratio of more than 300 that is prepared with the application of an Na20/SiO2 molar ratio in the aqueous base mixture of o.o8-o.16. The preparation of crystalline aluminium silicates with an SiO2/Al203 molar ratio of more than 300 from an aqueous mixture in which the Na2O/SiO2 molar ratio has the above-mentioned high value, is novel. The present patent application therefore relates to a novel process for the preparation of crystalline aluminium silicates that after one hour's calcination in air have the properties stated under a) and b) and a value of more than 300 for m as meant under c), in which an aqueow mixture containing the following compounds: one or more compounds of an alkali metal (M), one or more quaternary alkyl ammonium compounds (R4NX), one or more silicon compounds with a high SiO2 content and one or more aluminium compounds, in which mixture the various compounds are present in the following ratios, expressed in moles of oxides: M20 : SiO2 = 0.08 - 0.16 (R4N)20 : SiO2 = 0.01 H2O: SiO2 = 5 - 65, and Sing : Al203 > 400, is maintained at elevated temperature until the crystalline silicate is formed which is subsequently separated from the mother liquor, dried and calcined. The silicates prepared according to the invention are inter alia defined with reference to the X-ray powder diffraction pattern. This pattern should contain the four lines stated in Table A as strongest lines. The complete X-ray powder diffraction pattern of a typical example of a silicate prepared according to the invention is stated in Table B: : TABLE B d(A) Relative intensity d(2) Relative intensity 11.1 100 )4.oo 3 10.0 70 3.84 57 8.93 1 3.72 31 7.99 1 3.64 10 7.42 1 3.44 5 6.68 7 3.34 3 6.35 11 3.30 5 5.97 18 3.25 2 5.70 7 3.05 5 5.56 10 2.98 12 5.35 2 2.96 3 )+.98 6 2.86 2 4.60 h 2.73 2 h.35 5 2.60 2 4.25 7 2.48 3 4.07 2 2.40 2 The silicates can be prepared both at atmospheric pressure and at elevated pressure. If use is made of reaction temperatures lying above the boiling point of the mixture it is preferred to work under autogenous pressure in an autoclave. The silicates are preferably prepared by maintaining the mixture for at least four hours at a temperature between 90 and 300 C and in particular between 125 and 1750C. After formation of the silicates the crystals are separated from the mother liquor, for example by means of filtration, decantation and centrifuging. The crystal mass is subsequently washed with water and finally dried and calcined. Examples of suitable compounds which can be used in the preparation of the silicates according to the invention are nitrates, carbonates, hydroxides and oxides of alkali metals; quaternary alkyl ammonium bromides and hydroxides; amorphous solid silicas, silicasols, silica gels and silicic acid; aluminium hydroxide, sodium aluminate, aluminium sulphate and gamma-alumina. In the preparation of the silicates according to the invention it is preferred to start from an aqueous mixture in which M is present in a sodium compound and RhNX is a tetrapropyl ammonium compound. Silicates prepared according to the invention can inter alia be used as adsorbent and extractant means, drying agent, ion-exchanger and as catalyst or catalyst carrier in the operation of various catalytic processes, in particular the catalytic preparation of aromatic hydrocarbons from acyclic organic compounds. If the intention is to use the silicates prepared according to the invention as catalyst or catalysts carrier, it is preferred to reduce the alkali metal content of these silicates previously to less than 0.1% by weight and in particular to less than 0.01% by weight. The reduction of the alkali metal content of the silicates can very suitably be carried out by contacting the silicates once or several times with an aqueous solution containing ammonium ions. From the NH'4 silicates thus obtained the R+ silicates can be prepared by calcination. When the crystalline aluminium silicates are used as catalyst they can be combined, if desired, with a binder material, such as bentonite or kaolin. As explained in the foregoing an important application of the silicates prepared according to the invention is their use in catalyst mixtures for the preparation of an aromatic hydrocarbon mixture from an H2/CO mixture having an H2/CO molar ratio below 1.0. Such H2/CO mixtures can very suitably be prepared by steam gasification of coal at a temperature between 900 and 15000C and a pressure between 10 and 50 bar. The preparation of the aromatic hydrocarbon mixture from an H2/CO mixture with an H2/CO molar ratio below 1.0 with the use of a catalyst mixture containing a crystalline aluminium silicate prepared according to the invention, is preferably carried out at a temperature of 200-5000C and in particular of 300-4500C, a pressure of 1-150 bar and in particular of 5-100 bar and a space velocity of 50-5000 and in particular of 300-3000 Nl of gas/l of catalyst/h. The two catalysts present in the catalyst mixture used in the preparation of an aromatic hydrocarbon mixture from an H2/CO mixture having an H2/CO molar ratio below 1.0 will for brevity hereinafter be designated catalysts X and Y. Catalyst X is the one having the capacity of catalyzing the conversion of an H2/CO mixture into acyclic oxygen-containing hydrocarbons and catalyst Y is the crystalline aluminium silicate prepared according to the invention. As catalyst X it is preferred to use catalysts capable of converting an H2/CO mixture into substantially methanol and/or dimethyl ether. If the aim is to prepare a product mainly consisting of hydrocarbons boiling in the gasoline range, as catalyst X use can very suitably be made of a catalyst containing zinc together with chromium. When such a catalyst is used, preference is given to a catalyst in which the atomic percentage of zinc, based on the sum of zinc and chromium, is at least 60% and in particular 60-80%. Further, it is preferred to use mixtures containing 1-5 volume parts of catalyst X per volume part of catalyst Y. The above conversion with the use of a mixture of a crystalline aluminium silicate prepared according to the invention and a catalyst capable of catalyzing the conversion of an H2/CO mixture into acyclic oxygen-containing hydrocarbons, can also very suitably be used as the first stage in a two-stage process for the conversion of an H2/CO mixture with an X2/CO molar ratio below 1.0 into an aromatic hydrocarbon mixture. In this case at least the C2 fraction of the reaction product of the first stage is contacted in a second stage with a catalyst containing one or more metal components with catalytic activity for the conversion of an H2/CO mixture into acyclic hydrocarbons, which metal components are chosen from the group consisting of cobalt, nickel and ruthenium, with the proviso that if the feed for the second stage has an H2/CO molar ratio of less than 1.5, water is added to said feed and that in the second stage a bi-functional catalyst combination is used containing, in addition to the metal components having catalytic activity for the conversion of an H2/CO mixture into acyclic hydrocarbons, also one or more metal components with catalytic activity for the conversion of an H20/CO mixture into an H2/CO mixture. The invention is now illustrated with reference to the following Example. EXAMPLE Six crystalline aluminium silicates (silicates 1-6) were prepared by heating mixtures of NaOH, amorphous silica, (C3H7)4NOH and NaA102 in water at 1500C for 24 hours in an autoclave. After the reaction mixtures had been cooled the silicates obtained were filtered off, washed with water until the pH of the washing water was about 8, dried at 1200C and calcined at 5000C. The silicates 1-6 had the following properties: a) thermally stable to a temperature above 8000C; b) an X-ray powder diffraction pattern mainly corresponding with that stated in Table B, and c) a value for m as stated in Table C. TABLE C Silicate No. m 1 290 2 285 3 4 700 5 330 6 310 After drying at 1200C and calcining at 5000C the amorphous silica used in the preparation of silicates 1-6 yielded a product containing 99.97% by weight of SiO2. The molar composition of the aqueous mixtures from which silicates 1-6 were prepared can be represented as follows: 25 SiO2 . x Al203 . y Na2O . '4.5E(C3H7)'4N20 . 450 H20 where x and y have the values stated in Table D. The Na20/SiO2 molar ratios used in the aqueous mixtures are also stated in Table D: TABLE D Silicate No. x y Na20/SiO2 molar molar ratio 1 0.063 1.0 2 0.039 3.0 0.12 3 0.042 1.0 4 o.o15 3.0 0.12 5 0.056 1.0 6 0.031 3.0 0.12 From silicates 1-6 silicates I-VI were respectively prepared by boiling the materials calcined at 5000C with 1.0 molar NHhNO 3 solution, washing with water, reboiling with a 1.0 molar NH4N03 solution, washing and drying at 1200C and calcining at 5000C. Subsequently, six catalyst mixtures (A-F) were prepared by mixing a ZnO-Cr203 composition with each of the silicates I-VI. The atomic Zn-percentage of ZnO-Cr203 composition, based on the sum of Zn and Cr, was 70%. All the catalyst mixtures contained per volume part of silicate, 10 parts by weight of the ZnO-Cr203 composition. The catalyst mixtures A-F were tested for the preparation of an aromatic hydrocarbon mixture from an H /CO mixture. The test was 2 carried out in a 50 ml reactor containing a fixed catalyst bed having a volume of 7.5 ml. In six experiments an H2/CO mixture with an H2/CO molar ratio of 0.5 was passed over each of the catalyst mixtures A-F at a temperature of 3750C, a pressure of 60 bar and a space velocity of 1000 Nl.l .h . In all the cases a product was obtained, the C5 fraction of which contained more than 50% by weight of aromatics. The remaining results of the experiments are stated in Table E: TABLE E Exp. Cat. Silicate C + selectivity Conversion of No. mix No. ater 10 hours, the syngas after No. % by wt 10 hours, % by vol. 1 A I 65 65 2 B II 64 66 3 C III 75 40 4 D IV 80 56 5 E V 75 48 6 F VI 77 58 Of the silicates stated in Table D only silicates k and 6 were prepared according to the invention. Silicates 1, 2, 3 and 5 fall outside the scope of the invention. They are included in the patent application for comparison. Of the experiments stated in Table E, only experiments 4 and 6 were carried out with the use of a catalyst mixture containing a crystalline aluminium silicate prepared according to the invention. Experiments 1, 2, 3 and 5 fall outside the scope of the invention. They are included in the patent application for comparison. It is apparent from the results stated in Table E that in the conversion of an H2/CO mixture with an H2/CO molar ratio below 1.0 into an aromatic hydrocarbon mixture with the use of a catalyst mixture containing a crystalline aluminium silicate with an SiO2/A1203 molar ratio of less than 300, the activity of the catalyst mixture is independent of the Na2O/SiO2 molar ratio in the base mixture from which the relevant silicate was prepared. Further, it appears from the results that when use is made of a catalyst mixture containing a crystalline aluminium silicate having an SiO2/A1203 molar ratio of more than 300, the activity of the catalyst mixture for said conversion is greatly dependent on said molar ratio in the base mixture and that by a correct choice of said molar ratio, catalyst mixtures can be prepared having a high activity in addition to a very high C5+ selectivity.

Claims: C L A I M S 1. A process for the preparation of crystalline aluminium silicates having the following properties after one hour's calcination in air at 5000C: a) thermalzystable to a temperature above 6000C; b) an X-ray powder diffraction pattern containing the four lines stated in Table A as strongest lines. TABLE A d(i) Relative intensity 11.1 + 0.2 VS 10.0 + 0.2 VS 3.84 + 0.07 S 3.72 + 0.06 S where the letters used have the following meanings: VS = very strong; S = strong, and c) in the formula representing the composition of the silicate expressed in moles of oxides, the SiO2/A1 203 molar ratio (m) is more than 300, characterized in that an aqueous mixture containing the following compounds: one or more compounds of an alkali metal (M), one or more quaternary alkyl ammonium compounds (R4NX), one or more silicon compounds that after drying at 1200C and calcination at 5000C yield a product with an SiO2 content of more than 90% by weight, and one or more aluminium compounds in which mixture the various oompounds are present in the following molar ratios, expressed in moles of oxides: M20 : Si02 = 0.08 - 0.16 (R4N)20 : SiO2 = 0.01 H20 : SiO2 ¯ 5-65, and SiO2 : Al2O3 > '4oo, is maintained at elevated temperature until the crystalline silicate is formed which is subsequently separated from the mother liquor, dried and calcined. 2. A process as claimed in claim 1, characterized in that as R4NX compound a tetrapropyl ammonium compound and as alkali metal compound a sodium compound is used. 3. A process as claimed in claim 1 or 2, characterized in that the mixture is kept at a temperature between 90 and 3000C for at least four hours. h. A process as claimed in claim 3, characterized in that the mixture is kept at a temperature between 125 and 1750C. 5. A process for the preparation of crystalline aluminium silicates, mainly as described in the foregoing and in particular with reference to the preparation of silicates 4 and 6 in the Example. 6. Crystalline aluminium silicates prepared by a process as described in any one or more of claims 1-5. 7. Crystalline aluminium silicates as claimed in claim 6, characterized in that the alkali metal content thereof is reduced to less than 0.1% by weight. 8. Crystalline aluminium silicates as claimed in claim 7, characterized in that the alkali metal content is reduced to less than 0.01% by weight. 9. A process for carrying out catalytic reactions, characterized in that use is made of a catalyst containing a crystalline aluminium silicate as claimed in any one of claims 6-8. 10. A process as claimed in claim 9, characterized in that an aromatic hydrocarbon mixture is prepared by contacting an H2/CO mixture having an H2/CO molar ratio below 1.0 with a mixture of two catalysts, one of which being capable of catalyzing the conversion of an H2/CO mixture into acyclic oxygen-containing hydrocarbons and the other being the crystalline alumium silicate.

Inventors: BOERSMA, MICHAEL ADRIAAN MARIA, POST, MARTIN FRANCISCUS MARIA
Applicants: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1981
Main classification: C01B33
IPC codes: B01J29, C07C1, C01B39, B01J31, C07C15, C07C67