PROCESS FOR THE PREPARATION OF HYDROCARBONS

Abstract: A hydrocarbon mixture is prepared by contacting a mixture of H₂ and CO with a mixture of two catalysts, of which one is capable of catalysing the conversion of the H₂/CO mixture into oxygen-containing compounds and the other one of which is a crystalline aluminium silicate with a SiO₂/Al₂O₃ molar ratio between 100 and 250, which silicate after calcination during 1 hour in air at 500 °C shows an X-ray diffraction pattern with the four strongest lines at d(Å) 11.1 ± 0.2; 10.0 ± 0.2; 3.84 ± 0.07 and 3.72 ± 0.06. The silicate is prepared from an aqueous mixture containing one or more alkali metal (M) compounds, one or more Al compounds, one or more Si compounds which after drying and calcina­ tion yield a product of more than 90 %w SiO₂ and one or more quaternary alkylammonium halides (R₄NX), the va­ rious compounds being present in the following molar ratios, expressed, except the quaternary alkylammonium halides, in moles of their oxides:

Description: FOR THE PREPARATION OF The invention relates to a process for the preparation of a hydrocarbon mixture from a mixture of carbon monoxide and hydrogen. Mixtures of carbon monoxide and hydrogen can be converted into hydrocarbon mixtures by using a mixture of two catalysts, one of which is capable of catalysing the conversion of a mixture into oxygen-containing organic compounds and the other is a crystalline aluminium silicate which is characterized in that, after one hour's calcination in air at 500 OC, it has the following prsperties: : a) an X-ray powder diffraction pattern in which the strongest lines are the four lines mentioned in Table A TABLE A d( ) 11.1 + 0.2 10.0 i 0.2 3.84 + 0.07 3.72 t 0.06, and b) in the formula representing the composition of the silicates expressed in moles of the oxides the SiO2/A12O3 molar ratio is higher than 10. far the crystalline aluminium silicates used in the catalyst mixtures were prepared starting from an aqueous mixture comprising the following compounds: one or more quaternary alkylammonium compounds wherein the alkyl groups contain 2-4 carbon atans, one or mLre silicon compounds, one or more aluminium compounds and one or itore compounds of an alkali metal (M), if desired. The silicon compounds used in the prepratin of the crystalline silicates may be divided into two classes on the basis of the SiO2 contents of the products obtained fran these compounds after drying at 120 C and calcination at 500 CC, viz. silicon compounds yielding a product having a SiO2 content of more than 90 %w and silicon ccmpounds yielding a product having a SiO2 content of at most 90 %w. For the sake of brevity the silicon compounds used in the preparation of the crystalns silicates will on account of the afore-mentioned division hereinafter be referred to as "silicon compounds having a high or low SiO2 content, respectively". Examples of silicon compounds having a high SiO2 content are arrzFbcus solid silicas, silica sols, silica gels and kieselguhr. An example of a silicon compound having a low SiO2 content is water glass. The preparation of the crystalline silicates is carried ot by maintair the aqueous mixture at an elevated temperature until the silicate has formed and subsequently separating the silicate crystals fran the mother-liquor and washing, drying and calcining the crystals. It was found that quaternary alkylammonium halides (R4NX) are excellently suited for use as organic reaction components in the preparation of the present crystalline aluminium silicates. With the use of R4NX-type compounds there exists a relation between the R4N+/SiO2 molar ratio in the aqueous base mixture from which the silicate is prepared and the stability of the catalyst mixture composed by using the silicate. With R4NX-type catponds it was seen that, as higher R4NX/SiO2 molar ratios were used, the stability of the catalyst mixtures increased at first and then, after a maximum value had been reached, decreased. The R4NX/SiO2 molar ratio used in the aqueous mixture should lie between 0.02 and 0.40. In the preparation of the silicates by using an R4NX-type compound the aqueous mixture from which they are prepared must include one or more compounds of an alkali metal (M), notably in a concentration expressed as M2O/SiO2 molar ratio lying between 0.01 and. 0.35. ?or the preparation of the silicates ty using an R4NX-type cotocand only silican ozopounds with a high SiO2 content are eligible. Quaternary alkylammonium halides (R4NX) are produced on a technical scale by reacting a trialkylamine (R3N) with an alkyl halide (RX) in a solvent at an elevated temperature. On the assumption that the preparation of the present silicates could possibly be ca=ied'ut in an even cheaper way if the R4NX cctpnd was not added to the aqueous mixture per se, but was allowed to be formed in situ fran an R3N canpnnd and an RX compound during the silicate preparation, a number of experiments were carried out and the silicates Prepared were tested as catalyst components. The results of these experiments were disappointing. Although in this way crystalline aluminium silicates could be prepared which, after one hour's calcination in air at 500 C, bad the properties mentioned under a) and b), the catalyst mixtures composed by using these silicates showed an unacceptably low stability in the conversion of H2/CO mixtures. The stability of the aluminium silicates obtained with R4NX in the aqueous mixture, was found to be dependent on the SiO2/Al2O3 molar ratio. Optional stabilities were obtained in silicates having a SiO2/A1203 molar ratio between 100 and 250. Such silicates are prepared when in the aqueous base mixture silicon and aluminium compounds are present in such quantities that their molar ratio, expressed in moles of the axides is SiO2: :Al2O3=100-350 The, present ineention therefore relates to a process for the preparation of a hydrocarbon mixture in which a mixture of carbon monoxide and hydrogen is contacted with a mixture of two catalysts, one of which is capable of catalysing the conversion of a H2/CO mixture into oxygen-containing organic compounds and the other is a crystalline aluminium silicate which after one hour's calcination in air at 500 C has the ft11o g properties: : a) an X-ray powder diffraction pattern in which the strongest lines are the four lines mentioned in Table A, and b) in the formula which represents the composition of the silicate expressed in moles of the oxides the SiO2/Al2O3 molar ratio is between 100 and 250, which silicate has been prepared by maintaining an aqueous mixture comprising the following compounds: one or more compounds of an alkali natal (M), one or more silicon compounds having a high SiO2 content, one Qr more aluminium ccmpcnnrds and one or more quaternary alkylammonium halides (R4NX) whose alkyl groups contain 2-4 carbon atoms, in which mixture the various compounds are present in the following molar ratios expressed - with the exception of the quaternary alkylammonium hades - in moles of the oxides: : O : SiO2 = 0.01 - 0,35, R4EX : SiO2 = 0.02 - 0.40, SiO2 : Al2O3 = 100 - 350, and : SiO2 = 5 - 100 at an elevated temperature until the crystalline silicate has formed and subsequently separating the latter fran the other liquor and calcination. In the process according to the invention the starting material is a H2/CO mixture. Such a mixture can very suitably be prepared by gasiing heavy carbonaceous materials, such as coal, or by catalytic steam reforming of light hydrocarbons, such as matane. The process -according to the invention is preferably carried out at a temperature of 200-500 C and in particular of 300-450 OC, a pressure of 1-150 bar and in particular of 5-100 bar and a space velocity of 50-5000 and in particular 300-3000 Nl gas per litre catalyst per hour. In the process according to the invention a mixture of two catalysts is used, one of which is capable of catalysing the conversion of a H2/CO mixture into oxygen-containing organic compounds. Preference is given to the use of catalysts capable of converting a H2/CO mixture into substantially methanol and/or dimethylether. Very suitable compositions are zinc-containing compositions which, in addition to zinc, contain one or more of the metals chromium, topper and aluminium. Examples of suitable metal combinations are zinc-chromium, zinc-chromium-copper and zinc-aluminium-copper. Preference is given to the use of catalysts which, in addition to zinc, contain chromium, in particular catalysts in which the atanic percentage of zinc calculated on the sum of zinc and chromium is at least 60 % and in particular 60-80 %. The above-mentioned zinc-containing compositions are generally prepared by calcination of one or more precipitates obtained by adding a basic reacting substance to one or more aquequs solutions containing salts of the metals involved. From the zinc-containing compositions thus prepared the present catalyst mixtures can be obtained by mechanically mixing particles of the zinc containing catpositions with the crystalline silicate. Another very attractive method of preparing these catalyst mixtures is spray-drying. Spray-drying is a method which has been applied on a commercial scale for may years for preparing small globular particles starting from a solid material or a mixture of solids. The process is carried out by atanizing a dispersion in water of the material to be spray-dried through a nozzle or fran a rotating dise into hot gas. The process is excellently suited to effect a very intimate contact between different materials. The preparation of the present catalyst mixtures by spray-drying is carried out by dispersing the crystalline silicate in water together with one or more precipitates in which zinc and one or more metals chosen from chromium, copper and aluminium are present and which precipitates have been obtained by adding a basic reacting substance to one or more aqueous solutions of salts of the metals involved and using the dispersion thus obtained to prepare the desired catalyst mixture by spray-drying. In view of fonn, size and strength of the catalyst particles prepared by spray-drying they are very suitable for use in a fluidized state. As regards the ratio of the two catalysts in the catalyst mixtures used in the process according to the invention per part by weight of the crystalline aluminium silicate catalyst these mixtures preferably contain 2.5-12.5 pbw of the catalyst having activity for the conversion of a H2/CO mixture. The crystalline aluminium silicates used as catalyst components in the process according to the invention are defined among other things with the aid of the X-ray powder diffraction pattern which they display after one hours calcination in air at 500 OC. In this pattern the strotigest lines should be the four lines mentioned in Table A. The complete X-ray powder diffraction pattern of a typical example of the present crystalline aluminium silicates after one hour's calcination in air at 500 C is given in Table B. TABLE B d( ) Rel. int. d( ) Rel. int. 11.1 100 3.84 (D) 57 10.0 (D) 70 3.72 (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 In the process according to the invention a catalyst mixture is used the silicate component of which has been prepared by using a quaternary alkylammonium halide R4NX whose alkyl groups contain 2-4 carbon atans. In the preparation of the silicate preference is given to the use of a compound R4NX wherein the alkyl groups are sirtilar and contain three or four carbon atoms. The cceçound R4NX is preferably used in the form of a bromide. In the aqueous base mixture from which the silicate component is prepared the R4NX/SiO2 molar ratio is 0.02-0.40. The crystalline aluminium silicates used in the catalyst mixtures have a SiO2/Al2O3 molar' ratio between 100 and 250. In the preparation of the crystalline silicates the starting material may very suitably be a base mixture in which the alkali metal compound present is a sodium compound and the silicon compound artrphous silica. The silicates prepared as described hereilibefore contain alkali metal ions. By using appropriate exchange methods those can be replaced by other cations, such as hydrogen ions or armanium ions. The crystalline aluminium silicates used in the present catalyst mixtures preferably have an alkali metal content lower than 0.05 %w. The process according to the invention in which a hydrocarbon mixture is prepared from a H2/CO mixture can very suitably be carried out as an independent process in which. the caversion of the H2/CO mixture is effected in a single step. Unconverted synthesis gas may optionally be recirculated. The process according to the iiwention may also be used very suitably as part of a multi-step process for the conversion of H2/CO mixtures into hydrocarbon mixtures. In that case two possibilities offer, viz. a) the process is carried out as the first step of a two-step process in which h and CO present in the reaction product of the first step are contacted in a second step, together with other components from that reaction product if desired, with other components from that reaction product if desired, with a catalyst containing one or more metal components with activity for the conversion of H2/CO mixture into paraffinic hydrocarbons, which metal components have been chosen from the group formed by cobalt, nickel and ruthenium. b) The process is carried out as the first step of a three-step process in which the first two steps are carried out as described under a) and in which in the second step the catalyst used is a zirconium, titanium or chromium-promoted cobalt catalyst supported on silica as the carrier, which catalyst has been prepared by impregnation and/or kneading. In this three-step process advantage is taken of the fact that the high-boiling part of the reaction product of the second step can be converted in a high yield into middle distillates by using a catalytic hydrotreatment. The three-step process mentioned under b) involves carrying out an additional catalytic hydrotreatment as the third step, foiing the two-step process as mentioned under a). As the feed for the catalytic hydrotreatment at least the part of the reaction product of the second step is chosen whose initial boiling point lies above the final boiling point of the heaviest middle distillate desired as final product. The hydrotreatment, which is characterized by a very low hydrogen consumption, yields middle distillates of a considerably lower pour point than those obtained in the direct conversion of a H2/CO mixture according to Fischer-Tropsch. Very suitable catalysts for carrying out the catalytic hydrotreatment are those containing one or more noble metals form Group VIII supported on a carrier. The invention is now illustrated with the aid of the following example. EXAMPLE 15 Crystalline aluminium silicates (silicates 1-15) were prepared from mixtures of Na0H, amorphous silica, NaAlO2 and (C3H7)4NOH or (C3H7)4NBr in water. In addition one crystalline aluminium silicate (silicate 16) was prepared from a mixture of NaOH, amorphous silica, NaA102, (C3H7)3N and C3H7Br in water. Finally one crystalline aluminium silicate (silicate 17) was prepared fran a mixture of water glass, Al2(SO4)3, H2SO4 and (C3b)4NBr in water. The preparation of the silicates was carried out by maintaining the mixtures in an autoclave under autogenous pressure with stirring at 150 C for 24 hours. After cooling of the reaction mixtures the silicates were filtered off, washed with water until the pH of the wash water was about 8, dried at 120 C and calcined in air during one hour at 500 OC. Silicates 1-17 had the following properties: a) an X-ray powder diffraction pattern substantiAlly correscoflang to that mentioned in Table B, and b) values for the SiO2/Al2O3 molar ratios as listed in Table C. TABLE C Silicate No. SiO2/Al2O3 molar ratio 1 490 2 515 3 196 4 203 5 195 6 180 7 221 8 183 9 171 - 10 170 11 167 12 495 13 405 14 59 15 73 16 164 17 173 ± anrorphous silica used in the preparation of silicates 1-16 after drying at 120 C and calcination at 500 C yield a product 99.97 %w of which consisted of SiO2. The water glass used in the preparation of silicate 17 after drying at 120 C and calcination at 500 C yielded a product 78 %w of which consisted of SiO2. The molar composition of the aqueous mixtures used to prepare silicates 1-15 may be rendered as follows: w Na2O.x (C3H7)4NOH.y (C3H7)4NBr.z Al2O3.25 SiO2.450 H2O were w, x, y and z have the values given in Table D. TABLE D Silicate No. w x y z 1 1 W 3 - 0.044 2 1 9 - 0.037 3 1 1 - 0.125 4 1 3 - 0.125 5 1 9 - 0.095 6 1 15 - 0.071 7 3 3 - 0.075 8 3 9 - 0.058 9 4 - 15 0.125 10 4 - 9 0.125 11 4 - - 3 0.125 12 4 - 9 0.042 13 2 - 1 0.063 14 4 - 3 0.333 15 2 - 7 0.333 The molar compositions of the aqueous mixtures fran which silicates 16 and 17 are prepared may be rendered as follows: For silicate 16: 4 Na20.9 (C3H7)3N.9 C3H7Br.0.125 Al2O3.25 SiO2.450 H2O For silicate 17: 1.2 Na2O.6.0 Na2SO4.2.5 (C3H7)4NBr.0.14 Al2O3.25 SiO2. 1000 O. Silicates 1-17 were used to prepare silicates 18-34, respectively, by boiling silicates 1-17 with a 1.0 molar NH4NO3 solution, washing with water, boiling again with a 1.0 molar NH4NO3 solution and washing, drying at 120 C and calcination at 500 OC, Subsequently 17 catalyst mixtures (catalyst mixtures A-Q) were prepared by mixing a ZnO-Cr2O3 carposition with each one of silicates 18-34. The ataxic Zn percentage of the ZnO-Cr2O3 composition, based on the sum of Zn and Cr, was 70 %. Catalyst mixtures A-Q contained 10 pbw of the ZnO-Cr2O3 composition per pbw silicate. Catalyst mixtures A-Q 'were tested for the production of a hydrocarbon mixture fran a H2/CO mixture. Catalysts A-Q were tested in a 50 ml reactor containing a fixed catalyst bed of 10 g in weight. In 17 experiments (Experiments 1-17) a H2/CO mixture having a H2/CO molar ratio of 0.5 was passed aver each one of catalyst mixtures A-Q at a temperature of 375 OC, a pressure of 60 bar and a space velocity of 850 Nl.kg N1.. The results of these experiments are listed in Table E. TABLE E Exp. Catalyst Silicate Conversion of Stability expressed C3+ selectivity C5+ selectivity No. mixture No. synthesis as difference averaged over averaged over No. gas after between conversion 200 hours, %w 200 hours, %w 10 hours, %w after 10 and 200 hours 1 A 18 52 9 93 75 2 B 19 54 4 93 74 3 C 20 60 13 93 72 4 D 21 58 10 94 71 5 E 22 61 4 94 72 6 F 23 62 3 94 70 7 G 24 62 7 85 60 8 H 25 63 6 93 71 9 I 26 66 10 95 72 10 J 27 65 < 1 94 74 11 K 28 64 < 1 94 73 12 L 29 62 2 96 80 13 M 30 61 3 97 78 14 N 31 71 4 93 69 15 O 32 68 4 94 71 16 P 33 58 8 93 71 17 Q 34 64 8 93 72 Of Experiments 1-17 given in Table E only Experiments 10 and 11 are experiments according to the invention. Experiments 1-9 and 12-17 fall outside the scope of the invention. They have been included in the patent application for comparison. In Experiments 1-8 catalyst mixtures were used which contained silicates prepared by using a tetra alkylammonium hydroxide (R4NOH) compound. In Experiment 9 the catalyst mixture used contained a silicate which inded had been prepared by using an R4ux-type compound, but in a quantity corresponding to an R4NX/SiO2 molar ratio higher than 0.40. In Experiment 16 a catalyst mixture was used which contained a silicate prepared by using a mixture of an R3N-type compound with an RX-type compound in a 1:1 molar ratio, instead of an R4NX-type compound. In Experiment 17 a catalyst mixture was used which contained a silicate prepared by using a silicon wund with a low Sio2 content. In Experiments 12-15 catalyst mixtures containing a silicate prepared by using R4NX were used, but the SiO2/Al2O3 molar ratios of the silicates are beyond the range according to the invention. As regards the results given in Table E the following may be remarked: a) Comparison of the results of Experiments 1 and 2, 3-6 and 7 and 8 in relation with each other shows that the stability of the catalyst mixtures increases as higher R4NOH/SiO2 molar ratios are used in the preparation of the silicate. This holds good both for the silicates Prepared by using a M2O/SiO2 molar ratio of 0.04 (Experiments 1-6) and for silicates prepared by using a M2O/SiO2 molar ratio of 0.12 (Experiments 7 and 8). b) Ccmparisan of the results of Experiments 5 and 8 (both carried out by using a catalyst mixture in which the silicates had comparable SiO2ZA12O3 molar ratios and had been prepared by using the same high R4NOH/SiO2 molar ratio) shows that in combination with the high R4NOH/SiO2 molar ratio used an increase of the M2O/SiO2 molar ratio leads to a decrease in stability. c) Comparison of the results of Experiments 10 and 11, 4 and 5 and 7 and 8 (carried out by using catalyst mixtures in which the silicates had comparable SiO2/A12O3 molar ratios) shows that replacing R4NOH by R4NX results in very considerable stability enhancement. Furthermore, catalyst mixtures prepared by using R4NX have hither activities and higher selectivities. Caparison of the results of Experiments 9 and 6 shows that the stability-promoting effect Produced by replacing R4NOH by R4NX is absent when R4NX/SiO2 molar ratios higher than 0.40 are used. d) Comparison of the results of Experiments 10 and 11 with those of Experiments 12-15 sbows that crystalline aluminium silicates prepared by using R4NX-type compounds having either a SiO2SA1203 molar ratio below 100 or a SiO2/Al2O3 molar ratio above 250, have a decreased stability. e) Comparison of the results of Experiments 10 and 17 shows that use of silicates obtained from silicon compounds having a low SiO2 content has a detrimental effect an the stability of the catalyst mixtures. f) The results of Experiments 10 and 16 show that the stability of a catalyst containing a silicate, is disadvantageously influenced when in the silicate preparation a combination of and RX is used instead of R4NX.

Claims: CLAIMS 1. A process for the preparation of a hydrocarbon mixture, characterized in that a mixture of carbon monoxide and hydrogen is contacted with a mixture of two catalysts, one of which is capable of catalysing the conversion of a H2/CO mixture into oxygen-containing organic compounds, and the other is a crystalline aluminium silicate which after one hour's calcination in air at 500 C has the following properties: a) an X-ray powder diffraction pattern in which the strongest lines are the four linas mentioned in Table A VIABLE A d( ) 11.1 # 0.2 10.0 + 0.2 3.84 i 0.07 3.72 + 0.06, and b) in the formula which represents the oompositian of the silicate expressed in moles of the oxides the SiO2/A1203 molar ratio is between 100 and 250, which silicate has been prepared by maintaining an aqueous mixture comprising one or more compounds of an alkali metal (M), one or more aluminium compounds, one or more silica catccunds which after drying at 120 C and calcination at 500 C yield a product having an SiO2 content of more than 90 bw, and one or more quaternary alkylammonium halides (R4NX) wherein the alkyl groups contain 2-4 carban atans, in which mixture the various copounds are present in the following molar ratios expressed - with the exception of the quaternary alkylammonium halides - in moles of the oxides M2O : SiO2 = 0..01 - 0.35, R4NX : SiO2 = 0.02 - 0.40, SiO2 : Al2O3 = 100 - 350, and H2O: SiO2 = 5-100 at an elevated temperature until the crystalline silicate has formed followed by separating the latter from the mother-liquor and calcination. 2. A process as claimed in clam 1, characterized in that it is carried out at a temperature of 200-500 OC, a pressure of 1-150 bar and a space velocity of 50-5000 Nl.1-1.h-1. 3. A process as claimed in clam 1 or 2, characterized in that the catalyst present in the catalyst mixture which is capable of catalysing the conversion of a H2/CO mixture into oxygencontaining organic compounds is a zinc-containing composition which, in addition to zinc, comprises one or more of the chrsmium, copper and aluminium 4. A process as claimed in claim 3, characterized in that the catalyst mixture has been prepared by spray-drying. 5. A process as claimed in any one of claims 1-4, characterized in that per pbw of the crystalline silicate catalyst the catalyst mixture contains 2.5-12.5 pbw of the catalyst having activity for the conversion of a H2/CO mixture. 6. A process as claimed in any one of claims 1-5, characterized in that in the preparation of the crystalline silicate an R4NX compound is used in which the alkyl groups are- similar and contain three or four carbon atoms. 7. A process as claimed in any one of claims 1-6, charatterized in that in the preparation of the crystalline silicate the compound R4NX is used as a bromide. 8. A process as claimed in any one of claims 1-7,-characerized in that the crystalline silicate has an alkali metal content lower than 0.05 bw. 9. A process as claimed in any one of claims 1-8, characterized in that it is used as the first step of a two-step process, that H2 and CO present in the reaction product of the first step, together with other components of that reaction product, if desired, are contacted in the second step with a catalyst catprising one or more metal components having activity for the conversion of a H2/CO mixture into paraffinic hydrocarbons, which metal components have been chosen fran the groups formed by cobalt, nickel and ruthenium. 10. A process as claimed in any one of claims 1-8, characterized in that it is carried out as the first step of a three-step process, that the first two-steps are carried out as stated in claim 16, that in the second step use is made of a zirconium, titanium or chromium-promoted cobalt catalyst supported on silica as the carrier, Which catalyst has been prepared by impregnaticn and/or kneading and that a middle distillate is prepared by separating fran the reaction product of the second step at least the part whose initial boiling point laes above the final boiling point of the heaviest middle distillate desired as end product and subjecting it in the third step to a catalytic hydrotreatment.

Inventors: POST, MARTIN FRANCISCUS MARIA
Applicants: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1983
Main classification: C07C1
IPC codes: B01J21, B01J35, C07C67, C07C1, B01J23, C07C9, B01J37, C10G2, B01J29