NL8103532A - Prepn. of new aluminium-contg. silica-rich iron silicate cpds. - catalysts esp. for making aromatic cpds. from aliphatic oxygen cpds. - Google Patents

Abstract

The prepn. is claimed of new crystalline Fe silicates of defined X-ray powder pattern and of compsn. (expressed as oxide molar ratios) in which SiO2/Fe2O3 is 75-300, SiO2/Al2O3 is below 2000 and Fe2O3/Al2O3 is above 1. Prepn. is by heating an aq. mixt. of one or more of each of: an alkali metal (M) cpd., an amine R1R2R3N (R1 is alkyl; R2 and R3 are H or alkyl), a cpd. of high SiO2 content, an Fe(III) cpd. and an Al(III) cpd. Equiv. molar ratios in the mixt. are: M2O/SiO2, 0.01-0.35; R1R2R3N/SiO2, 0.04-2.0; SiO2/Fe2O3, 50-400; SiO2/Al2O3, 50-4000; and H2O/SiO2, 5-65. The silicate formed is sepd. and calcined. The silicates are useful as catalysts, esp. for conversion of acyclic O cpds. to aromatics. Activity and stability are high. With catalysts for O cpds. prodn. from synthesis gas, they give aromatics from synthesis gas. Other uses are as adsorption, extn. and drying agents and ion exchangers.

Description

It <0

K 5582 NET

PROCESS FOR THE PREPARATION OF CRYSTALLINE SILICATES

The invention relates to a process for the preparation of crystalline iron silicates with improved catalytic properties.

Mixtures of carbon monoxide and hydrogen can be converted into aromatic hydrocarbon mixtures using a mixture of two catalysts, one of which has the ability to catalyze the conversion of an H 2 / CO mixture into oxygen-containing organic compounds and the other one crystalline iron silicate has the ability to catalyze the conversion of oxygenated organic compounds to aromatic hydrocarbons. Said crystalline iron silicates are characterized in that after calcining in air at 500 ° C for one hour, they have the following properties: a) thermally stable to a temperature of at least 600 ° C, b) an X-ray powder diffraction pattern which shows the four lines listed in Table A as strongest 20 lines contains: 8103532 * ί »-2-

Table A

Relative d (A) intensity

11.1 +0.2 ZS

10.0 + 0.2 ZS

3.84 + 0.07 S

3.72 + 0.06 S

in which the letters used have the following meaning: ZS = very strong; S = strong, and c) in the formula which represents the composition of the silicate expressed in moles of the oxides, the SiO 2 / Fe 2 O 3 mole is. ratio 75-300.

In this patent application, a crystalline silicate with thermal stability of at least t ° C is understood to mean a silicate of which the X-ray powder diffraction pattern does not substantially change when heated to a temperature of t ° C.

The crystalline silicates used in the catalyst mixtures can be prepared starting from an aqueous mixture containing the following compounds: one or more compounds of an alkali metal (M), one or more amines of the general formula R 1 R 2 R 3 N wherein R 1 an alkyl group and R2 and R3 represent an alkyl group or a hydrogen atom, one or more silicon compounds with a high SiO2 content and eSn or more compounds in which iron is in trivalent form. In this patent application, silicon compounds with a high 8103532 * *> -3-

Understand SiO £ content; silicon compounds which, after drying at 120 ° C and calcining at 500 ° C, yield a product with an S102 content of more than 90% by weight. The crystalline silicates are prepared by keeping the mixture at an elevated temperature until the crystalline silicate is formed, separating it from the mother liquor and calcining. In the aqueous mixture from which the silicates are prepared, the various compounds must be present in the following molar ratios, with the exception of the amines expressed in moles of the oxides: Μ £ θ: SiO2 * 0.01-0.35, R 1 R 2 R 3 N: SiO 2 - 0.04-2.0, SiO 2: Fe 2 O 3 * 50-400, and H 2 O: SiO 2 * 5-65.

An investigation by the Applicant concerning the use of the above-mentioned catalyst mixtures for the preparation of aromatic hydrocarbon mixtures from H2 / CO mixtures has shown that the presence of aluminum in the crystalline iron silicates has a large influence on the stability of the catalyst mixtures. It has been found that the catalyst mixtures have an exceptionally high stability, If the crystalline iron silicate contained therein contains such an amount of aluminum that in the formula which represents the composition of the silicate expressed in moles of the oxides, the SiO2 / Al2 O3 mole. ratio is less than 2000. In this patent application, the term "crystalline iron silicates" refers both to crystalline silicates which, as trivalent metal, contain only iron, and to crystalline silicates which, as trivalent 8103532 ί * -1 + - metal, besides iron, contain aluminum, raits in the formula containing the composition of the silicate expressed in moles of the oxides represents the Fe 2 O 3 / Al 2 O 3 mole. ratio is more than 1.0.

The aluminum-containing crystalline iron silicates are prepared starting from an aqueous mixture containing one or more aluminum compounds in addition to the aforementioned compounds. The aluminum compounds should be present in the aqueous mixture in an amount such that the SiO 2 / Al 2 O 3 mole. ratio is 50-4000. The preparation of the above-mentioned aluminum-containing crystalline iron silicates, starting from an aqueous mixture containing one or more amines of the general formula R1R2R3N and one or more silicon compounds with a high SiO2 content, is new.

The present patent application therefore relates to a process for the preparation of 20 crystalline iron silicates, which are characterized in that after an hour of calcination in air at 500 ° C they have the following properties: a) thermally stable to a temperature of at least 600 ° C, 25 b ) an X-ray powder diffraction pattern containing the four lines listed in Table A as the strongest lines, and c) in the formula representing the composition of the silicate expressed in moles of the oxides, the SiO 2 / Fe 2 O 3 mole is. ratio 75-300, the SiO2 / Al2 O3 mol. ratio less than 2000 and the Fe2 O3 / Al2 O3 mol. ratio more than 1.0.

8103532 * fc -5-

The preparation is carried out by an aqueous mixture containing the following compounds: one or more compounds of an alkali metal (M), one or more amines of the general formula 5, one or more silicon compounds with a high SiO2 content, one or more compounds in which trivalent iron is present and one or more aluminum compounds, in which mixture the various compounds are present in the following molar ratios, with the exception of the amines expressed in moles of the oxides: M2O: SiO2 - 0, 01-0.35, R1R2R3N: Si02 - 0.04-2.0,

Si02 ϊ Fe2O3 * 50-400, 15 Si02: AI2O3 350-4000, and H20 ϊ Si02 * 5-65, keep at elevated temperature until the crystalline silicate is formed and then separate it from the mother liquor and calcining. The M20 / S102 is preferably mol. ratio in the aqueous mixture less than 0.12.

The silicates prepared according to the invention have been defined, inter alia, on the basis of the X-ray powder diffraction pattern that they show in air at 500 ° C after one hour of calcination. This should include the four lines listed in Table A as the strongest lines. The complete X-ray powder diffraction pattern of a typical example of a silicate prepared according to the invention is shown in Table B.

8103532 -6- - 4

Table B

d (A) Rel. int. d (A) Rel. int.

11.1 100 3.84 (D) 57 10.0 (D) 70 3.70 (D) 31 8.93 1 3.63 16 7.99 1 3.47 1 7.42 2 3.43 5 6.68 7 3.34 2 6.35 11 3.30 5 5.97 17 3.25 1 5.70 7 3.05 8 5.56 10 2.98 11 5.35 2 2.96 3 4.98 (D) 6 2.86 2 4, 60 4 2 ', 73 2 4.35 5 2.60 2 4.25 7 2.48 3 4.07 2 2.40 2 4.00 4 (D) = doublet

The preparation of the silicates can be carried out both at atmospheric pressure and at elevated pressure. If reaction temperatures above the boiling point of the mixture are used, it is preferred to work in an autoclave under autogenous pressure. The silicates are preferably prepared by keeping the mixture at a temperature between 90 and 300 ° C and in particular at a temperature between 125 and 175 ° C for at least four hours. After the formation of the silicates, the crystals are separated from the mother liquor, for example by filtration, decantation or centrifugation. The crystal mass is then washed with water and finally dried and calcined.

As examples of suitable compounds which can be used in the preparation of the silicates according to the invention, mention can be made of nitrates, carbonates, hydroxides and oxides of alkali metals; amorphous solid silicas, silica sols, silica gels and silica; oxides, hydroxides, normal salts and complex salts of trivalent iron; linear and branched alkyl amines. The silicates according to the invention are preferably started from an aqueous mixture in which M is present in a sodium compound and R1R2R3N is a linear primary alkylamine with 3-5 carbon atoms in the alkyl group, in particular n-butylamine.

The following can be noted with regard to aluminum which must be present in the aqueous mixture during the preparation of the crystalline iron silicates according to the invention. The high SiO 2 silicon compounds which are economically suitable for the industrial scale preparation of crystalline iron silicates according to the invention usually contain a small amount of aluminum as an impurity. This aluminum is found at least in part in the prepared iron silicate.

This means that crystalline iron silicates are obtained from these silicon compounds, the formula which shows the composition of the silicate expressed in moles of the oxides additionally containing S102 and Fe3 O3k Al2O3.

8103532 € Ψ -8-

The SiO 2 / Al 2 O 3 mol. however, the ratio is generally considerably more than 2000. For example, starting from silicon compounds with a usual aluminum contamination of 50-100 gpm, crystalline iron silicates are obtained with an S102 / Al2O3 mol. ratio of 5000-20000. Regarding the inclusion of aluminum in the aqueous mixtures that make up the crystalline. iron silicates according to the invention are prepared, in principle two possibilities are available. It is possible to start from an aqueous mixture containing a silicon compound which is so contaminated with aluminum that a crystalline iron silicate is obtained that has the desired SiO2 / Al2O3 mol.

15 ratio of less than 2000 possession. For example, starting from silicon compounds with a high aluminum contamination of about 1000 gpm, crystalline iron silicates with an S102 / Al2O3 mol are obtained. ratio of 500-1000.

One or more aluminum compounds can also be included in the aqueous mixture in an amount such that, taking into account the amount of aluminum already present in the silicon compound used, a crystalline silicate is obtained which has the desired Si0.2 / Al2 O3 mol. ratio of less than 2000 possession. Examples of suitable aluminum compounds which can be incorporated into the aqueous mixture 30 in the preparation of the crystalline iron silicates of the invention are: aluminum hydroxide, aluminum sulfate, sodium aluminate and amorphous alumina.

8103532 •% -9-

Silicates prepared according to the invention can be used, inter alia, as an adsorbent and extraction agent, as a drying agent, as an ion exchanger and as a catalyst or catalyst support in carrying out various catalytic processes, in particular the catalytic preparation of aromatic hydrocarbons from acyclic organic compounds. - things. If it is intended to use the silicates prepared according to the invention as a catalyst or catalyst support, it is preferable to reduce the alkali metal content of these silicates in advance to less than 0.1% by weight and in particular to less than 0.01 wt%. The reduction of the alkali metal content of the silicates can very suitably be carried out by contacting it once or several times with an aqueous solution containing ammonium ions. From the NH4 + silicates obtained in this way, the phosphyl silicates can be prepared by calcination. When used as a catalyst, the crystalline iron silicates can optionally be combined with a binder material such as bentonite or kaolin.

As set forth above, 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 H 2 / CO mixture.

H 2 / CO mixtures can be prepared by steam gasification of a carbonaceous material. Examples of such materials are brown coal, anthracite, coke, crude oil and fractions thereof, as well as oils obtained from tar sand and bituminous slate. The steam gasification is preferably carried out at a temperature between 900 and 1500 ° C and a pressure between 10 and 50 bar. The preparation of the aromatic hydrocarbon mixture is preferably started from an H2 / CO mixture with a 5 H2 / CO mol. ratio between 0.25 and 1.0.

The preparation of the aromatic hydrocarbon mixture from an H2 / CO mixture using a catalyst mixture containing a crystalline iron silicate prepared according to the invention is preferably carried out at a temperature of 200-500 ° C and in particular of 300-450 ° C C, a pressure of 1-150 bar and in particular of 5-100 bar and a spatial throughput of 50-5000 and in particular of 300-3000 N1 gas / 1 catalyst / hour. Both. catalysts present in the catalyst mixture used in the preparation of the aromatic hydrocarbon mixture from an H 2 / CO mixture will further be referred to as catalysts X and Y for brevity. Catalyst X is the catalyst which has the ability to convert a H 2 / CO mixture in oxygen-containing organic compounds and catalyst Y is the crystalline iron silicate prepared according to the invention. Catalysts which are preferably used are catalysts which are capable of converting an H 2 / CO mixture into mainly methanol and / or dimethyl ether.

If an attempt is made to prepare a product consisting essentially of hydrocarbons boiling in the gasoline range, catalyst X can very suitably be used with a catalyst containing zinc together with chromium. When using a solid catalyst, preferably 8103532 is chosen. 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%.

If the aim is to prepare a high calorific fuel gas in addition to hydrocarbons boiling in the gasoline range, catalyst X can very suitably be used with catalyst containing zinc together with copper. Preferably, a catalyst mixture is used, i.e. that per volume part of catalyst Y, 1-5 volume *. parts of catalyst X contains

The above-described conversion using a mixture of a crystalline iron silicate prepared according to the invention and a catalyst which has the ability to catalyze the conversion of an H 2 / CO mixture into oxygen-containing organic compounds can very suitably be used as the first step of a two-step process for the conversion of H 2 / CO mixtures into 20 hydrocarbon mixtures. In this case, carbon monoxide and hydrogen present in the reaction product of the first step, optionally together with other components of this reaction product, are contacted in a second step with a catalyst containing έ§η or more metal components with catalytic activity for the conversion of an H2 / CO mixture into paraffinic hydrocarbons, which metal components are selected from the group consisting of cobalt, nickel and ruthenium, with care being taken to ensure that the feed for the second step is an H2 / CO mol. ratio of 1.75-2.25.

The above-described conversion using a mixture of a crystalline iron silicate 8103532 <rw -12- prepared according to the invention and a catalyst which has the ability to catalyze the conversion of an H2 / CO mixture into oxygen-containing organic compounds, may furthermore be very suitable are used as the first step of a three-step process for the preparation of, for example, middle distillates with an H2 / CO mixture.

In this case, carbon monoxide and hydrogen contained in the reaction product of the first step, XO optionally together with other components of this reaction product, are contacted in a second step with a cobalt catalyst containing zirconium, titanium or chromium as promoter, whereby Care should be taken to ensure that the feed f χ5 for the second step is an H2 / CO mol. ratio of 1.75-2.25. An example of a suitable catalyst for use in the second step is a catalyst containing 10-40 wt. parts of cobalt and 0.25-5 wt. parts of zircon, titanium or chromium per 20 100 wt. parts of silica prepared by impregnating a silica support with one or more aqueous solutions of cobalt and zirconium, titanium or chromium salts, followed by drying the composition, calcining at 350-700 ° C and reducing at 200-350 ° C. Of the reaction product of the second step, at least the part whose initial boiling point is above the final boiling point of the heaviest intermediate distillate desired as end product, is subjected to a catalytic hydrotreatment in a third step.

The invention is now illustrated by the following example.

. 10 8103532 f <-13-

Example

Three crystalline iron silicates (silica tea X-3) were prepared from aqueous mixtures of NaOH, C4H9NH2, amorphous silica I (for silicates 2 and 3) or amorphous silica II (for the silicate 1) and optionally amorphous alumina (for the silicate 3). Two crystalline aluminum silicates (silicates 4 and 5) were further prepared from aqueous mixtures of NaOH, C4H9NH4 amorphous silica I and amorphous alumina.

The preparation was carried out by heating the aqueous mixtures in an autoclave under stirring and under autogenous pressure for 120 hours at 150 ° C. After cooling the reaction mixtures, the resulting silicates were filtered off, washed with water until the pH of the wash water was about 8 and dried at 120 ° C. After an hour of calcination In air at 500 ° C, the silicates 1-5 had the following properties: a) thermally stable to a temperature of at least 800 ° C, 20 b) an X-ray powder diffraction pattern substantially corresponding to that stated in Table B, and c) a value for the SiO 2 / Fe 2 O 3 and SIO 2 / Al 2 O 3 mol. ratio as stated in table C.

Table C

Silicate Si02 / Fe203 Si02 / Al203

No. mole, elev. mole, elev.

1 108 10000 2 115 2570 3 130 560 4 - 540 5 - 300 8103532 ♦ -14- V w

The amorphous silica I used in the preparation of the silicates 2-5 contained 280 ppm of aluminum and after drying at 120 ° C and calcining at 500 ° C gave a product consisting of 99.9 wt.% SiO 2. The amorphous silica II used in the preparation of silicate 1 contained 70 gpm aluminum and after drying at 120 ° C and calcining at 500 ° C gave a product consisting of 99.97 wt% SiO 2.

The molar composition of the aqueous mixtures from which the silicates 1 to 5 were prepared can be shown as follows: 1.0 Na 2 O 10 C4H9NH 4 X Fe 2 O 3 y Al 2 O 3 25 SiO 2 450 H 2 O wherein x and y have the values listed in Table D. .

Table P

Silicate No. x y 1 0.20 0.002 2 0.20 0.008 3 0.20 0.041 4 - 0.041 5 - 0.075 15 From the silicates 1-5, resp. the silicates 6-10 are prepared by boiling the silicates 1-5 with 1.0 molar NH4NO3 solution, washing with water, boiling again with 1.0 molar NH4NO3 solution and washing, drying at 120 ° C and calci-20 down at 500 ° C. Five catalyst mixtures (Catalyst mixtures A-E) were then prepared by mixing a ZnO-Cr 2 O 3 composition 8103532-15 with each of the silicates 6-10. The atomic Zn primal percentage of the ZnO-Cr203 composition based on the sum of Zn and Cr was 70%. The catalyst mesela all contain per wt. part silicate, 10 wt. parts 5 of the ΖηΟ-θΓ £ θ3 composition.

Catalyst mixtures A-E were tested for the preparation of an aromatic hydrocarbon mixture from an H2 / CO mixture. The test took place in a 50 ml reactor. which contained a fixed catalyst bed with a volume of 7.5 ml. In several experiments, an H2 / CO mixture was mixed with an H2 / CO mol. ratio of 0.5 at a temperature of 375 ° C, a pressure of 60 bar and a spatial flow rate of 15 1000 Nl. l “1 hour” * passed over each of the catalyst mixtures A-E. In all cases, a product was obtained whose C5 + fraction consisted of more than 30% by weight of aromatics. The other results of the experiments are shown in Table E.

8103532 -16- * V

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Of the silicates listed in Table G, only the crystalline iron silicate 3 was prepared according to the invention. The crystalline iron silicates 1 and 2 and the crystalline aluminum silicates 5, 4 and 5 are outside the scope of the invention.

They are included in this patent application for comparison. Of the experiments listed in Table E, alien experiment 3 was conducted using a catalyst containing a crystalline iron silicate prepared according to the invention.

Experiments 1, 2, 4 and 5 are outside the scope of the invention. They are included in the patent application for comparison.

With the results listed in Table E, the following can be noted: a) The results of Experiments 1 and 2 show that catalyst mixtures containing a crystalline iron silicate with a low Al content (SiO 2 / Al 2 O 3 molar ratio> 2000), 20 show a high initial activity and a very high selectivity. The stability of these catalyst mixtures is still eligible for improvement.

b) The result of experiment 3 shows that by increasing the Al content of the crystalline iron silicate to a SiO 2 / Al 2 O 3 mol. ratio <2000, a very strong improvement in stability occurs, while retaining the high initial activity and the very high selectivity.

c) The catalyst mixture used in Experiment 4 contained a crystalline aluminum silicate of which the SiO 2 / Al 2 O 3 mol. ratio was chosen to correspond to 8103532-18 that of the crystalline iron silicate in the catalyst mixture used in Experiment 3. The results of experiment 4 show that this catalyst mixture has a low initial activity and a very low stability.

d) The catalyst mixture used in experiment 5 contained a crystalline aluminum silicate of which the SiO 2 / Al 2 O 3 mol. ratio was chosen so that an initial activity similar to that of the catalyst mixture used in Experiment 3 could be achieved with this catalyst mixture. The results of experiment 5 show that the catalyst mixture used still has a very low stability. Comparison of the results of experiments 5 and 4 shows that reduction of the SiO 2 / Al 2 O 3 mole. The crystalline aluminum-20 silicate ratio results in a significant decrease in the C5 + selectivity of the catalyst mixture.

8103532

Claims (11)

1. Process for the preparation of crystalline iron silicates which, after an hour of calcination in air at 500 ° C, have the following proper properties: listed four lines as strongest lines. Table A Relative d (A) intensite.it 11.1 + 0.2 ZS 10.0 +0.2 ZS 3.84 + 0.07 S 3.72 + 0.06 S 10 in which the letters used have the following meaning ZS = very strong; S = strong and * /. 8103532 sr - -20 -20---c))))) c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c ratio 75-300, the SiO2 / Al2 O3 mol. ratio less than 2000 and the Fe2 O3 / Al2 O3 mol. ratio more than 1.0, characterized in that an aqueous mixture containing the following compounds: one or more compounds of an alkali metal (M), one or more amines of the general formula R 1 R 2 R 3 N wherein R 1 is an alkyl group and R2 and R3 represent an alkyl group or a hydrogen atom, one or more silicon compounds which, after drying at 120 ° C and calcining at 500 ° C, yield a product with an SiO2 content of more than 90% by weight, one or more compounds in which iron in trivalent form and one or more aluminum compounds, in which mixture the compounds are present in the following 20 molar ratios, with the exception of the amines expressed in moles of the oxygen: M2O: SiO2 = 0.01-0.35, RXR2R3N SiO 2 = 0.04-2.0, SiO 2: Fe 2 O 5 * 50-400, SiO 2: Al 2 O 3 = 50-4000, and H 2 O: SiO 2 = 5-65, are kept at an elevated temperature until the crystalline silicate is formed and then separated from the mother liquor and calcined. 2. Process according to claim 1, characterized in that in the aqueous mixture the M20 / SiO2 mol. ratio is less than 0.12. 8103532 -21- Process according to Claim 1 or 2, characterized in that the alkali metal compound used is a sodium compound exi as the compound RiB-2, 3, n-butylamine. Method according to any one of claims 1-3, characterized in that the aqueous mixture is kept at a temperature between 90 and 300 ° C for at least 4 hours. 5. A method according to any one of claims 1-4, characterized in that the required amount of aluminum is introduced into the aqueous mixture by using a highly aluminum-contaminated silicon compound and / or by adding a separate aluminum compound. Crystalline iron silicates prepared according to a method as described in any one of claims 1-5. 7. Process for carrying out catalytic processes, characterized in that a catalyst is used which contains a crystalline iron silicate according to claim 6. 8. Process according to claim 7, characterized in that an aromatic hydrocarbon mixture is prepared by contacting an H2 / CO mixture with a mixture of two catalysts, one of which has the ability to convert an H2 / CO mixture into oxygen containing to catalyze organic compounds and the other is the crystalline iron silicate. 8103532 *> 5 -V -22- 9. Process according to claim 8, characterized in that as a catalyst, which has the ability to catalyze the conversion of an H2 / CO mixture into oxygen-containing organic compounds, a composition is used which contains zinc together with chromium or copper. A method according to claim 8 or 9, characterized in that the H2 / CO mixture is an H2 / CO mol. ratio has between 0.25 and 1.0. Hydrocarbon mixtures prepared by a method as described in any one of claims 8-10. 8103532