PROCESS FOR THE PREPARATION OF AN AROMATIC HYDROCARBONS-CONTAINING MIXTURE

Abstract: A process for the preparation of an aromatic hydrocar­ bons-containing mixture by contacting a natural gas contain­ ing more than 50%w of methane and furthermore paraffins with at least three carbon atoms per molecule at a pressure higher than 20 bar and at elevated temperature with a catalyst comprising a crystalline silicate containing at least one of the metals aluminium and gallium, which silicate has the following properties after one hour's calcination in air at 500°C: a) an X-ray powder diffraction pattern in which the strongest lines are the lines given in Table A, and b) in the formula which represents the composition of the silicate, expressed as moles of the oxides, the SiO₂/Al₂O₃ molar ratio is 25-400 and/or the SiO₂/Ga₂O₃ molar ratio is 25-250. The invention further relates to a process for the preparation of middle distillates and gasoline in which the above-described process is employed as first step.

Description: PROCESS FOR THE PREPARATION OF AN AROMATIC RYDROCAR!3ONS-C0NThINING MIXTURE The invention relates to a process for the preparation of an aromatic hydrocarbons-containing mixture from wet natural gas and to aromatic hydrocarbona-containing mixtures thus obtained. Natural gas comprising a major part of methane and ethane map also contain considerable quantities of paraffins with at least three carbon atoms (hereinafter referred to as C3+ paraffins). When it is to be transported through gas pipelines or as liquefied natural gas, such C3+ paraffins present in this so-called "wet natural gas" should be removed. This can be accomplished step-wise, by adsorption and/or cooling, whereby first the wet gas is divided into what is called a "residual gas" (C1-C4) and a C5+ + fraction, followed by separation of the residual gas into what is called a "dry gas" (Cl/C2) and a C3/C4 fraction. A drawback to these physical separations is that they are rather cost lav and that they yield products which are not very desirable either for reasons of transport and storage (c3/c4) or because of their octane quality (C5+). The present invention results from an investigation into the possibility of catalytically converting C3+ paraffins present in residual or wet natural gas containing more than 50 Xw of methane, into an aromatic hydrocarbonscontaining mixture, instead of removing these paraffins by means of physical separation. The conversion can be carried out by using catalysts comprising a crystalline silicate containing at least one of the metals aluminium and gallium which silicate has a special structure. The crystalline silicates referred to are characterized in that, after one hour's calcination in air at 500-C, they have the following properties: a) an X-ray powder diffraction pattern in which the strongest lines are the lines given in Table A, TABLE A d(;) 11.1 + 0.1 10.0 + 0.1 3.84 + 0.07 3.72 + 0.06 b) and in the formula which represents the composition of the silicate, expressed as moles of the oxides, the Si02/A1203 molar ratio is 25-400 and/or the Si02/Ga203 molar ratio is 25-250. Gallium silicates can very suitably be used for converting C3/C4 paraffins in a stable operation into aromatic gasoline of high quality (low C11+ aromatics content). The conversion proceeds very selectively with only a minor quantity of C1/C2 paraffins being formed as by-products. Unlike gallium silicates, the use of aluminium silicates as catalysts resulted in the formation of a considerable quantity of C1/C2 paraffins as by-products. Since it was further found that conversion of pure C3/C4 paraffins at a high pressure ( > 20 bar) yielded a gasoline of low quality (high C11+ aromatics content), whilst conversion of highly diluted C3/C4 streams (such as residual or wet natural gas) at a low pressure ( < 10 bar) led to rapid deactivation of the catalyst, it had to be assumed that the favourable results obtained with crystalline gallium silicates could only be achieved if the conversion was carried out at a low pressure ( < 10 bar) and by using a feed which consisted substantially of C3/C4 paraffins () 50 %w). It has now been found that C3+ paraffins present in natural gas with a methane content higher than 50 Zw, which gas is subject to a pressure higher than 20 bar, can be converted in a stable operation into aromatic gasoline of high quality by using a catalyst comprising a crystalline gallium silicate. Since when natural gas is used as feedstock the occurence of considerable quantities of C1/C2 paraffins as by-product is no longer a drawback, the present conversion can also be carried out by using a catalyst comprising a crystalline aluminium or aluminium/gallium silicate or a physical mixture of aluminium - and/or gallium silicates. The present invention therefore relates to a process for the preparation of an aromatic hydrocarbons-containing mixture wherein a natural gas containing sore than 50 Zw of methane and furthermore pareffins with at least three carbon atoms per molecule is contacted at a Pressure higher than 20 bar and at elevated temperature with a catalyst comprising a crystalline silicate containing at least one of the metals aluminium and gallium which silicate has the following properties after one hour's calcination in air at 5000C: : a) an X-ray powder diffraction pattern in which the strongest lines are the lines given in Table A, and b) in the formula which represents the composition of the sili cate, expressed as moles of the oxides, the Si02/A1203 molar ratio is 25-400 and the SiO2/Ga203 molar ratio is 25-250. The conmlete X-ray powder diffraction pattern of a typical example of the emploved crystalline metal silicates after one hours calcination in air at5000C is given in Table B. TABLE B d(i) Rel. int. d(i) 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 it is preferred to use a crystalline silicate having a Si02/A1203 molar ratio of 25-250 and/or a Si02/Ga203 molar ratio of 60-220. When a catalyst comprising a crystalline gallium silicate or aluminium/gallium silicate is used, said catalyst is preferably subjected once or several times to a two-step treatment. hereinafter referred to as "redox treatment". which comprises a first steD in which the catalyst is contacted for at least 15 minutes, at a temperature of 350-700'C, with a hydrogen-containing reducing gas, and a second step in which the catalyst is contacted for at least 15 minutes, at a temperature of 350-700-C, with an oxygencontaining oxidizing gas. It is preferred to carry out the redox treatment not more than three times when the Si02/Ga203 molar ratio in the crystalline silicate is at most 110, and three to ten times when the molar ratio is from llO-130. When use is made of a crystalline silicate with a SiO2/Ga203 molar ratio higher than 130 but not higher than 220, it is preferred to subject the silicate first to a calcination treatment at a temperature of 600-1000tC, after which the redox treatment is carried out at least three and at most ten times. In the first step of the redox treatment the catalyst should be contacted for at least 15 minutes, at a temperature of 350-700-C with a hydrogen-containing reducing gas. In principle the first step of the redox treatment can be carried out in two ways. Firstly, the hydrogen-containing reducing gas can be supplied to the catalyst fros sn external source. In this case it is preferred to use a gas containing at least 20 Xv and in particular at least 40 Xv of hydrogen. In addition to hydrogen the gas used may very suitably contain either substantially nitrogen, or substantially carbon monoxide, or substantially C4- hydrocarbons. Suitable gases which, in addition to hydrogen, contain substantially carbon monoxide can be obtained as synthesis gas, by gasification starting from a heavy carbonaceous material such as coal, or bv steam reforming or partial oxidation starting from light hydrocarbons such as natural gas. Suitable gases which, in addition to hydrogen. contain substantially C4- hydrocarbons can be obtained as by-product in the catalytic conversion of hydrocarbons in the presence of hydrogen, such as cracking. isomerization and reforming. Secondly, the hydrogen-containing reducing gas can be allowed to form in situ by contacting the catalyst for at most five hours with a hydrocarbon or mixture of hydrocarbons. In this case the hvdrocarbon or mixture of hydrocarbons used can very suitably be the feedstock to be used in the process. In the second step of the redox treatment the catalyst should be contacted for at least 15 minutes, at a temperature of 350-700µC, with an oxygen-containing oxidizing gas. The gas used preferably contains at least 5 Xt and in particular at least 10 Xv of oxygen. The second step of the redox treatment can very suitably be carried out by using a gas which, in addition to oxygen, contains either substantially nitrogen, or substantially nitrogen, carbon monoxide and carbon dioxide. A suitable gas which, in addition to oxygen, contains substantially nitrogen, is air Suitable gases which, in addition to oxygen, contain substantially nitrogen, carbon monoxide and carbon dioxide, are exhaust gases obtained in the removal of coke from deactivated hydrocarbon conversion catalysts by means of an excess of air. It is preferred to carry out the two steps of the redox treatment at a temperature of 400-6500C and in particular at a temperature of 475-575-C. Furthermore, it is preferred to carry out the two steps of the redox treatment at the same temperature. The preparation of the crystalline metal silicates which are used in the process according to the invention can be carried out very suitably by starting from an aqueous mixture comprising the following compounds: one or more compounds of an alkali metal (M), one or more organic nitrogen compounds (RN) which contain an organic cation, or from which an organic cation is formed during the preparation of the silicate, one or more silicon compounds and one or more aluminium and/or gallium compounds. The preparation is carried out by maintaining the mixture at an elevated temperature until the silicate has formed, subsequently separating silicate crystals from the mother liquor and washing, drying and calcining the crystals. In the aqueous mixture from which the silicates are prepared the various compounds should be present in the following molar ratios, expressed - with the exception of the organic nitrogen compounds - as moles of the oxides: M20 : Si02 - 0.01-0.35, RN : Si02 - 0.02-1.0, Si02 : Al203 - 25-1000, and/or SiO2 : Ca20 = 25-400, and H20 : SiO2 " 5-65. In the preparation of the silicates the starting material may very suitably be a mixture in which a quaternary ammonium compound is present as organic nitrogen compound, a sodium compound as alkali metal compound and amorphous silica as silicon compound. The silicates prepared as described hereinbefore contain alkali metal ions. By using suitable exchange methods these can be replaced by other cations. such as hydrogen ions or ammonium ions The crystalline metal silicates which are used in the process according to the invention preferably have an alkali metal content of less than 0.05 Zw. In the process according to the invention the crystalline metal silicates can be used either alone or in combination with a binder material, such as refractory oxides, kaoline or bentonite. The process according to the invention is preferably carried out at a temperature of 400-700'C and in particular of 500-600-C, a pressure of 20-150 bar and in particular of 20-100 bar and a space velocity of 0.1-10 kg C3+.kg-1.h- and in particular of 0.2-5 kg C3+.kg-1.h-l. The process according to the invention can suitably be employed as an independent process in which, in addition to a dry natural gas, pn aromatic gasoline is obtained as product. The process according to the invention is of particular importance in that it can be combined with a recently developed process for the preparation of middle distillates from natural gas. In this process natural gas is converted into synthesis gas and subsequently the synthesis gas is converted into a paraffinic hydrocarbon mixture in the presence of a special cobalt-containing catalyst. Finally, at least the high-boiling fraction of the product prepared with said catalyst is subjected to a hydrocracking treatment in the presence of a catalyst comprising one or more noble metals from Group VIII supported on a carrier. The particular property of the special cobalt-containing catalysts used in this process is that they yield a product substantially consisting of unbranched paraffins of which a high-boiling fraction can be converted in high yield into middle distillates by means of hydrocracking. The cobalt-containing catalysts involved comprise silica, alumina or silica-alumina as a carrier and cobalt together with zirconium, titanium, chromium and/or ruthenium as catalytically active metals and have preferably been prepared by applying the metals involved to the carrier material by impregnation and/or kneading. In the process for the preparation of middle distillates described hereinbefore the starting material may be wet, residual or dry natural gas, at choice. However, if the natural gas available contains C3+ paraffins, it should preferably first be subjected to the process according to the invention, and for the following reason. Both in the conversion over the cobalt-containing catalyst and in the hydrocracking treatment a low-value paraffinic gasoline is formed as by-product. The process according to the invention yields a high-value aromatic gasoline. By mixing the aromatic gasoline (i.e. the aromatic hydrocarbons-containing mixture) obtained in the process according to the invention with paraffinic gasoline (i.e. z paraffinic hydrocarbons-containing mixture) obtained in the middle distillate synthesis, a gasoline can be composed which has an excellent quality. In the middle distillate synthesis described hereinbefore the conversion of the natural gas into synthesis gas is preferably carried out by steam reforming or partial oxidation. The conversion of the synthesis gas into a paraffinic hydrocarbon mixture is preferably carried out at a temperature of 175-275-C and a pressure of 10-75 bar in the presence of a catalyst comprising cobalt and zirconium on silica as carrier. The hydrocracking treatment is preferably carried out at a temperature of 250-350-C and a pressure of 10-75 bar in the presence of a catalyst comprising 0.2-1 %w platinum or palladium on silica-alumina as carrier. The invention is illustrated with the aid of the following Example. Example A crystalline gallium silicate (Silicate 1) was prepared by heating a mixture comprising NaOR, amorphous silica, (C3H7)4NOH and Ga(N03)3 in water for 24 hours in an autoclave under autogenous pressure at 150 C. After cooling of the reaction mixture the silicate formed was filtered off, washed with water until the pH of the wash water was about 8, and dried at 1200C. After one hour's calcination in air at 5000C Silicate 1 had the following properties: a) an X-ray powder diffraction pattern substantially correspond ing with that mentioned in Table B, and b) a Si02/Ga203 molar ratio of 70. Silicate 1A was prepared by boiling Silicate 1 with a 1.0 molar NH4NO3 solution, washing, drying at 1200C and calcining at 500 C. Silicate 1A was subjected three times to a redox treatment comprising a first step in which the silicate was contacted for 30 minutes, at a temperature of 5500C and a pressure of 1.5 bar, with an H2/N2 mixture having a 1:1 volume ratio, followed by a second step in which the silicate was contacted for 1 hour, at a temnerature of 5500C and a pressure of 1 5 bar, with air. Thus Silicate 1B was obtained from Silicate LA. Silicate 1B was tested in four experiments (Experiments 1-4) as catalyst employed in the preparation of an aromatic hydrocarbon mixture starting from n-butane and wet natural gas. The experiments were carried out in a reactor containing a fixed catalyst bed The conditions under which the experiments were carried out and the results are given in Table C. Of the experiments mentioned in Table C, only Experiment 4 is an experiment according to the invent ion. Comparative experiments 1-3 fall outside the scope of the invention. They have been included for comparison. Experiment 4 was carried out at a pressure higher than 20 bar using natural gas containing C3+ paraffins and having a methane content of over 50 Zw. In this experiment a high-quality gasoline was obtained in a stable operation. Experiments 1 and 2 were carried out using n-butane as feedstock. Experiment 2 was carried out at a pressure higher than 20 bar but it yielded a low-quality gasoline. tn Experiment 3 a suitable natural gas was used as feedstock, but it was carried out at a pressure below 20 bar. This experiment led to very rapid catalyst deactivation. TABLE C Experiments carried out using n-butane as feed, at 550 C and a space velocity of 2 kg.kg-1.h-1 Experiment 1 at 6 bar At run hour 2 : C5+ yield 42.7 %w with a C11+ aromatics content 8.9% *) At run hour 100: C5+ yield 41.9 %w with a C11+ aromatics content 9.4% Experiment 2 at 40 bar At run hour 2 : C5+ yield 39.9 %w with a C11+ aromatics content 18.5% Experiments carried out using wet natural gas, at 550 C and a space velocity of 1 kg C3+.kg-1.h-1 (Composition of the natural gas, in %w : C1 58.6; C2 13.6: C3 14.4; C4 9.2; C5+ 1.7; CO2 1.5; N2 1.0) Experiment 3 at 6 bar At run hour 2 : C5+ yield (calculated on C3+ in the feed) 46.7 %w with a C11+ aromatics content 10.5% At run 100 . C5+ yield 15.1 %w with a C11+ aromatics content 9.2% Experiment 4 at 40 bar At run hour 2 : C5+ yield 49.2%w with a C11+ aromatics content 9.8% At run hour 100: C5+ yield 46.2 %w with a C11+ aromatics content 9.7% %w C11+ aromatics *) C11+ aromatics content = x 100 %w C6+ aromatics

Claims: CLAIMS 1. A process for the preparation of an aromatic hydrocarbonscontaining mixture wherein a natural gas containing more than 50 %w of methane and furthermore paraffins with at least three carbon atoms per molecule is contacted at a pressure higher than 20 bar and at an elevated temperature with a catalyst comprising a crystalline silicate containing at least one of the metals aluminium and gallium, which silicate has the following properties after one hour's calcination in air at 5000C: a) an X-ray powder diffraction pattern in which the strongest lines are the lines given in Table A, and b) in the formula which represents the composition of the sili cate, expressed as moles of the oxides, the SiO2/A1203 molar ratio is 25-400 and/or the SiO2/Ga203 molar ratio is 25-250. 2. A process as claimed in claim 1 wherein the crystalline silicate has a SiO2/A1203 molar ratio of 25-250 and/or a SiO2/Ga203 molar ratio of 60-220. 3. A process as claimed in claim 1 or 2 wherein the catalyst comprises a crystalline gallium silicate or an aluminium/gallium silicate which catalyst has been subjected at least once to a two ten redox treatment comprising a first step in which the catalyst is contacted for at least 15 minutes and at a temperature of 350-700-C with a hydrogencontaining reducing gas and a second step in which the catalyst is contacted for at least 15 minutes and at 350-7000C with an oxygen-containing oxidizing gas. 4. A process as claimed in claim 3 wherein the crystalline silicate has a SiO2/Ga203 molar ratio of at most 130 and the redox treatment is carried out not more than three times when the molar ratio is at most 110 and three to ten times when the molar ratio is from 110-130. 5. A process as claimed in claim 3 or 4 wherein the first step of the redox treatment is carried out using a hydrogencontaining reducing gas which is formed in situ by contacting the catalyst for at most five hours with hydrocarbons. 6. A process as claimed in any of claims 3-5 wherein the two steps of the redox treatment are carried out at a temperature from 400-650*C, and preferably from 475-5750C. 7. A process as claimed in any of the preceding claims wherein the crystalline metal silicates have been prepared bv maintaining an aqueous mixture comprising the following compounds: one or more compounds of an alkali metal (M), one or more organic nitrogen compounds (RN) which contain an organic cation, or from which an organic cation is formed during the preparation of the silicate, one or more silicon compounds and one or more aluminium and/or gallium compounds, in which mixture the various compounds are present in the following molar ratios: N20 : SiO2 - 0.01-0.35, RN : Si02 - 0.02-1.0, Si02 : A1203 - 25-1090, and/or Si02 : Ga203 - 25-400, and H20 : Si02 - 3-65, at an elevated temperature until the silicate has formed, subsequently separating silicate crystals from the mother liquor and calcination. 8. A process as claimed in claim 7 wherein the aqueous mixture contains a quaternary ammonium compound as organic nitrogen compound, a sodium compound as alkali metal compound and amorphous silica as silicon compound. 9. A process as claimed in any of the preceding claims which is carried out at a temperature of 400-700-C, a pressure of 20-150 bar and a space velocity of 0.1-10 kg C3+.kg-1.h-l. 10. A process substantially as described hereinbefore with reference to the Example. 11. Aromatic hydrocarbons-containing mixtures and dry natural gas, prepared by a process as claimed in any of the preceding claims. 12. A process for the preparation of middle distillates and gasoline which comprises as first step a process as claimed in any of claims 1-10 in which a natural gas comprising C3+ paraffins is converted into a dry natural gas and an aromatic hydrocarbons-containing mixture, which dry natural gas is converted in a second step into synthesis gas which is converted in a third step into a paraffinic hydrocarbonscontaining mixture in the presence of catalyst comprising silica, alumina, or silica-alumina as carrier and cobalt together with zirconium, titanium, chromium and/or ruthenium as catalytically active metals, at least the high-boiling fraction of the product obtained from the third step is subjected in a fourth step to a hydrocracking treatment in the presence of a catalyst comprising one or more noble metals from Group VIII supported on a carrier, and a gasoline is prepared by mixing at least part of the aromatic hydrocarbonscontaining mixture obtained in the first step with at least part of the paraffinic hydrocarbons-containing mixture obtained in the third step andl or in the fourth step. 13. A process as claimed in claim12 wherein the second step is carried out by steam reforming or partial oxidation, the third step is carried out at a temperature of 175-275'C and a pressure of 10-75 bar in the presence of a catalyst comprising cobalt and zirconium on silica as carrier, and the fourth step is carried out at a temperature of 250-350-C and a pressure of 10-75 bar in the presence of a catalyst comprising 0.2-1 Zw of platinum or palladium on silica-alumina as carrier. 14. Middle distillates and gasoline prepared by a process according to claim 12 or 13.

Inventors: KIEFFER, EDUARD PHILIP, SIE, SWAN TIONG
Applicants: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1986
Main classification: C07C2
IPC codes: C10L1, C07C2, B01J29