MXPA06002543A - Process for preparing branched chain hydrocarbons - Google Patents

Abstract

The present invention relates to a process for the production of branched chain hydrocarbons from methanol and/or dimethyl ether, which process comprises contacting, in a reactor, methanol and/or dimethyl ether with a catalyst comprising indium halide.

Description

PROCESS TO PREPARE RAMIFIED CHAIN HYDROCARBONS FIELD OF THE INVENTION The present invention relates to a process for preparing branched chain hydrocarbons, in particular to a process for preparing a branched chain hydrocarbon product comprising triptan.

BACKGROUND OF THE INVENTION Branched chain hydrocarbons can be synthesized by several routes. In particular, mixtures of branched chain hydrocarbons can be formed by homologation of methanol and / or dimethyl ether in the presence of a zinc aluro catalyst, as described, for example, in GB 1,547,955, US 2,492,984, US 3,969. .427, US 4,059,646, US 4,059,647, US 4,249,031 and WO 02/70440. For example, U.S. Pat. No. 4,249,031, describes a process for preparing a hydrocarbon mixture by contacting one or more oxygen-containing organic compounds, such as methanol, with one or more zinc halides. For example, U.S. Pat. No. 4,059,647, describes a process for producing triptan (2,2,3-trimethylbutane) comprising contacting methanol, dimethyl ether or mixtures thereof with zinc iodide.

Triptan is a branched chain hydrocarbon of high octane number, which can be used in unleaded aviation naphtha and unleaded naphtha for engines (see, for example, WO 98/22556 and WO 99/49003).

SUMMARY OF THE INVENTION The inventors have now discovered an alternative and / or improved process for producing branched chain hydrocarbons from methanol and / or dimethyl ether. According to a first aspect, the present invention provides a process for producing branched chain hydrocarbons from methanol and / or dimethyl ether. The process comprises contacting, in a reactor, methanol and / or dimethyl ether with a catalyst comprising indium halide.

DETAILED DESCRIPTION OF THE INVENTION In the present invention, the reaction of methanol and / or dimethyl ether yields reaction products comprising branched chain hydrocarbons. Preferably, the indium halide is one or more of Inx and / or lnX3, where X is a halide selected from Cl, Br and i, and combinations thereof. More preferably, the indium halide is InX3, and, even more so preferably it is Inl3, although other indium compounds may be present in the reactor. The indium halide can be introduced into a reactor in the form of a compound comprising indium and also at least one halogen atom. Preferably, the indium halide is introduced into the reactor as InX and / or InX3, preferably, InX3, where X is a halide selected from Cl, Br and I, and combinations thereof.

Even more preferably, the indium halide is introduced to the reactor as Inl3. The indium halide can be introduced to the reactor in the form of an anhydrous salt or it can be added in the form of a solid hydrate. Alternatively, or additionally, the indium halide can be formed in situ in the reactor, for example, by reaction of an appropriate indium source with a halide source in the reactor. Suitable indium sources include, for example, indium compounds such as, for example, oxides, hydroxides, acetates, alkoxides, nitrates and sulfates. Suitable halide sources include hydrogen halides and alkyl halides, for example, methyl halides. In addition to the indium halide, the reactor may also contain zinc halide, such as for example zinc iodide.

However, preferably, no zinc compounds are present in the reactor.

In addition to the methanol and / or dimethyl ether reagents, additional delivery components can also be introduced into the reactor. Additional supply components that are suitable include hydrocarbons, halogenated hydrocarbons and oxygenated hydrocarbons, especially olefins, dienes, alcohols and ethers. The additional delivery components may be straight chain, branched chain or cyclic compounds (including heterocyclic compounds and aromatic compounds). In general, any additional supply component can be incorporated into the products of the reaction in the reactor. Some additional delivery components may act as initiators and / or promoters - for the reaction to produce branched chain hydrocarbons.

Therefore, in a preferred embodiment, the reactor also contains one or more compounds that can act as initiators for the reaction to produce branched chain hydrocarbons. Suitable initiators are preferably one or more compounds (having at least 2 carbon atoms) which are selected from alcohols, ethers, olefins and dienes. Preferred initiator compounds are olefins, alcohols and ethers, preferably with 2 to 8 carbon atoms. The initiator compounds that are especially preferred are 2-methyl-2-butene, ethanol and MTBE. In a further preferred embodiment, one or more promoters that are selected from one or more of hydrogen halides and alkyl halides with 1 to 8 carbon atoms are also present in the reactor. Methyl halides and / or hydrogen halides are preferred. Preferably, the halide of the promoter is the same element as the halide of the indium halide catalyst. Additional supply components, including compounds that can act as initiators and / or promoters, can be introduced into the reactor as fresh compounds or mixtures of compounds, although they can also be formed in the reactor in the reaction to produce hydrocarbons. For example, the olefins and dienes that can be formed in the reaction can act as initiators.As a further example, alkyl halides that can be formed, such as for example methyl iodide, can act as promoters. Therefore, in a preferred embodiment, as an alternative to any additional "fresh" supply component that is introduced into the reactor or in addition thereto, the additional supply components, and especially the initiators and / or promoters, can be introduced into the reactor as components of a stream of proper recycling. Suitable recycle streams can be obtained, for example, by recycling a portion of a stream of product from the reactor, preferably by recycling at least a portion of a by-product stream that is formed after separating the branched-chain hydrocarbons that are desired , as for example the triptan, and any other useful product coming from this product stream of the reactor. As for the additional supply components in general, all initiators and / or promoters that are introduced into the reactor can be incorporated into the reaction products. During the reaction of methanol and / or dimethyl ether to produce branched-chain hydrocarbons, water is formed. Optionally, additional water can also be introduced into the reactor. It has been found that catalysts comprising indium halide can produce branched chain hydrocarbons from methanol. The process can be a process in both gas and liquid phase. However, with advantage, the process is operated substantially in the liquid phase. Therefore, in a second aspect, the present invention provides a process for producing branched chain hydrocarbons from methanol and / or dimethyl ether.

The process comprises contacting in a reactor, in a liquid phase reaction composition, methanol and / or dimethyl ether with a catalyst comprising indium halide. In a preferred embodiment of said second aspect of the present invention, the liquid reaction composition also comprises at least one additional delivery component, and even more preferably comprises at least one initiator and / or at least one promoter, wherein said additional supply components, initiators and promoters are as defined herein. The process of the second aspect of the present invention allows branched chain hydrocarbons to be formed in a liquid phase reaction at relatively low temperatures, such as, for example, between 100 ° C and 300 ° C. In a third aspect, the present invention also provides a continuous or semi-continuous process for producing branched chain hydrocarbons from methanol and / or dimethyl ether. Said process comprises contacting in a reactor, in a liquid phase reaction composition, methanol and / or dimethyl ether with a catalyst comprising indium halide, at a temperature of at least 100 ° C, to give a mixture of product that comprises (i) methanol and / or dimethyl ether and (ii) a hydrocarbon reaction product comprising branched chain hydrocarbons, and wherein in said process the catalyst is maintained in the reactor in an active form and in an effective concentration. The catalyst comprising indium halide can be maintained in the reactor in an active form and in an effective concentration by recycling to the reactor one or more promoter compounds as defined above, such as, for example, hydrogen iodide and / or methyl iodide, one or several stage (s) of recovery of .product downstream. In a preferred embodiment of the third aspect of the present invention, the liquid reaction composition also comprises at least one different additional delivery component, and more preferably comprises at least one initiator, wherein said delivery components and initiators additional are as defined here. Said other additional supply component has preferably been recycled from one or more downstream product recovery stage (s). Preferably, the processes of the present invention are carried out substantially in liquid phase to give a product mixture comprising methanol and / or ether dimethyl in a first liquid phase and the hydrocarbon reaction product comprising branched chain hydrocarbons in a second liquid phase. However, it may be necessary to cool the product mixture to form the first and second liquid phases. Then, the hydrocarbon reaction product is usually separated from the mixture. The first liquid phase is typically a hydrophilic phase comprising at least one of water, methanol and dimethyl ether. The first liquid phase may also comprise the catalyst comprising indium halide. The catalyst may be completely dissolved or may also be present in a solid phase and the catalyst may be partially dissolved in the first liquid phase. The first liquid phase and the entire solid phase can be retained in the reactor. As an alternative, they can be extracted and processed to recover the water before recycling it. Alternatively or in addition, the catalyst can be recovered from the first phase, and optionally, can be regenerated to reuse it. The precipitation of a solid phase comprising undissolved catalyst components during the reaction can cause problems during the operation of a continuous process. In general, it is preferred to remove said precipitated solids, for example, by filtration. The precipitation of solids is a particular problem when they are used zinc halides, such as zinc iodide, as catalysts. It has been found that the formation of said precipitates can be avoided or at least significantly reduced by using the indium halide catalysts of the present invention. The second liquid phase, if present, is typically a hydrophobic phase comprising the branched chain hydrocarbon product. In the second phase, other by-product hydrocarbon compounds may also be present. Examples of possible by-product hydrocarbon compounds include unbranched paraffinic and olefinic hydrocarbons, and aromatic hydrocarbons. The hydrophobic phase is generally less dense than the hydrophilic phase. The hydrophobic phase can also comprise, dissolved therein, one or more of methanol, dimethyl ether, methyl halide (for example iodide) and water. Preferably, a mixture of methanol and dimethyl ether is used in the present invention. It has the advantage that the reaction between dimethyl ether and methanol produces less water than that produced in the reaction of methanol alone. If methanol is used in the downstream stages of the total process to produce branched-chain hydrocarbons, for example in the purification of gaseous effluents or to contribute to separations, then there may be a limit to the amount of methanol that can be replaced by dimethyl ether in the process if methanol and / or dimethyl ether are recycled from processes downstream of the reactor. It has also been found that the processes for producing branched chain hydrocarbons according to the present invention give a more advantageous distribution of products than the analogous reactions with zinc halide. In particular, it has been discovered that significant amounts of triptan can be formed, and that with respect to the amount of triptan that is formed, compared to a reaction using a zinc halide catalyst, during the reaction with an indium halide catalyst less "heavy" products are formed (typically those greater than Cs) and correspondingly more "light" products (such as compounds with C4 and C6). Therefore, the reaction products which are branched chain hydrocarbons preferably comprise at least 10% by weight, for example, 10-60% by weight, preferably, 20-50% by weight of tryptan. In the processes of the present invention, usually methanol and / or dimethyl ether are contacted with the indium halide catalyst at a temperature of at least 100 ° C.

Preferably, the methanol and / or the dimethyl ether are contacted with the indium halide at a temperature between 100 and 300 ° C, preferably 100-250 ° C, more preferably between 150 and 250 ° C. The reaction time of the processes of the present invention is usually 0.1-6 hours, for example, 0.3-3 hours. Lower temperatures tend to require longer reaction times. Times or reaction temperatures are usually lower for dimethyl ether than for methanol. The times can be the reaction times in a semicontinuous reaction, or the residence time (which includes the average residence time) for continuous processes. The conversion of methanol or dimethyl ether in the reaction of the processes of the present invention can be monitored by periodic sampling in the reaction (for a semi-continuous or continuous process) or in the reaction effluent for a continuous process, and subsequent analysis by an appropriate technique for example liquid gas chromatography or mass spectroscopy. The reaction of the processes of the present invention can be carried out at ambient pressure, but is usually carried out under high pressure such as for example at 1-100 barg, preferably at 5-100 barg, such as at 50-lOObarg. The pressure can be autogenous, or it can be provided 3 also by the presence of an inert gas that is added, such as nitrogen or argon, and / or preferably by the presence of added hydrogen, as further described below. The ratio between methanol and / or dimethyl ether and water to each other and to the indium halide catalyst that is employed in the reaction can vary widely. As methanol, dimethyl ether and water may be present in one or more liquid phases in the reactor and in the vapor phase, and the indium halide may be present in liquid or solid phase, it is convenient to express the concentrations of methanol, ether dimethyl, • water and catalyst components as relative parts by weight in the reactor excluding all components or hydrocarbon phase. For example, for a total (excluding hydrocarbon components or phase) of 100 parts by weight of methanol, dimethyl ether, water and catalyst, the catalyst is preferably present in more than 50 parts and less than 99 parts, more preferably in more than 70 parts and less than 95 parts and even more preferably more than 80 parts and less than 90 parts. Water is preferably present in less than 50 parts and more than 0, more preferably less than 25 parts and even more preferably less than 10 parts. The remaining methanol and dimethyl ether will be necessary to form 100 parts in weight. The hydrocarbon components / phase will be added to this. The ratio of methanol to dimethyl ether can vary between being all dimethyl ether and all methanol. If preferred, the composition can be selected to maximize the solubility of the catalyst in the liquid phase (s) at the reaction temperature but the operation of the invention is not limited to compositions in the reactor where a solid phase is not present . Preferably, the process is carried out in the substantial absence of added water, especially with methanol as reagent. Since water is a byproduct of the process, it can be removed from the reactor appropriately as the reaction proceeds to maintain a steady state concentration during the process. It is also possible to remove the water coming from the reactor using techniques such as, for example, by means of desiccants, for example magnesium silicate or molecular sieves, for example zeolites such as 3A or 13X, usually in a non-acidic form, ie in metallic form where the metal it may be an alkali metal, for example, Na or K. It may be useful to recycle part of the product water that is separated as a wash stream to remove all of the catalyst dissolved in the second liquid phase.

The reaction of the present invention can be carried out in the presence of hydrogen. The hydrogen can be introduced into the reactor as fresh feed and / or as a component in a recycle stream. Therefore, the hydrogen can be introduced into the reactor as a separate feed stream, or together with the catalyst and / or one of the other reactants. Alternatively or in addition, the reaction may also be carried out in the presence of a hydrogenation catalyst, which may be soluble or insoluble. The catalyst usually comprises a group VIII metal (CAS notation, as defined in the Periodic Table of the Elements in Advanced Inorganic Chemistry, 5th Edition by Cotton and Wilkinson), for example, Ni ', Rb, Pd, Os, Ir, Pt, and Ru. Preferred examples include catalysts consisting essentially of ruthenium, nickel and / or palladium, or comprising them. Preferably, a Ru catalyst is employed, optionally, in the presence of Re. Preferably, the metal of group VIII is on an inert support, such as for example activated carbon, for example, carbon, or alumina, silica or silica / alumina. The amounts of the group VIII metal in the catalyst on a support can be between 0.01-30% by weight (expressed as metal): for example, a Ni 'catalyst on a support can comprise between 0.01-10% or between 10-30% by weight of Ni.

Preferred catalysts include Ru, Ni or Pd on carbon, Ru on alumina and Ru and Re (in relative amounts by weight of 2-6: 1) on C. The catalyst that is most preferred is Ru / C, for example, where the amount of Ru in the catalyst is between 0.01-10% by weight. The reaction of the present invention can be carried out in the presence of carbon monoxide. The carbon monoxide can be introduced into the reactor as fresh feed and / or as a component in a recycle stream. Therefore, the carbon monoxide can be introduced to the reactor as a separate feed stream, or together with the catalyst and / or one of the other reagents. If both hydrogen and carbon monoxide are introduced into the reactor, it is especially desired to use synthesis gas as the source of both. The presence of carbon monoxide in the reactor will lead to the production of branched chain esters, as described, for example, in U.S. Pat. 4,166,189, the contents of which are incorporated herein by reference. To produce branched chain esters, preferably carbon monoxide will be present in the reactor at a molar ratio of carbon monoxide to methanol of at least 0.25: 1, more preferably at least 10: 1.

The production of branched chain esters including carbon monoxide in the reactor can be further improved by including one or more initiators and / or one or more promoters, as described above, especially by introducing one or more olefins into the reactor. In contrast to the above, if it is desired to introduce hydrogen into the reactor but avoid or reduce the production of branched chain esters, it is desirable to use feed streams containing hydrogen with only a low content of carbon monoxide, such as streams with a molar ratio of hydrogen to all of the carbon monoxide present of at least 5: 1, and preferably hydrogen in the substantial absence of carbon monoxide. The invention will be further described with respect to a process for producing triptan as a branched chain hydrocarbon reaction product which is desired, it being understood that other branched chain hydrocarbons can be produced by the present invention. In a continuous or semi-continuous process for producing triptan, the methanol and / or the dimethyl ether fed to the reactor can be introduced continuously or semi-continuously, preferably continuously.

In one embodiment, the second liquid phase, if present, is separated from the first liquid phase, and recovered from the reactor. The second liquid phase, if present, generally comprises the triptan product that is desired. The second liquid phase may also comprise tryptene, which may be converted to the triptan product that is desired. Triptane is useful in the production of naphtha for engines and aviation, especially lead-free naphtha for engines and lead-free aviation naphtha. The second phase will also comprise other hydrocarbon compounds, such as other branched chain hydrocarbons, some or all of which may also be useful in the production of naphtha for engines and aviation. In addition, some of the other hydrocarbon compounds, especially byproduct compounds, may be useful for other uses, in addition to the production of naphtha for engines and aviation. Typically useful compounds may include, for example, branched chain C4 to C8 alkanes (other than triptan) and branched chain C4 to Cs alkenes, such as, for example, iso-butene, iso-pentene and 2,3-dimethylbutene. Additional useful compounds may include, for example, aromatic compounds, such as, for example, methyl substituted benzene compounds, in particular tetramethylbenzenes and pentamethylbenzenes, for example, they could be separated and used subsequently to produce xylenes, in particular p-xylene, which is useful as a supply for the manufacture of PTA. Therefore, the processes of the present invention may further comprise the step of recovering a second liquid phase from the reactor and recovering therefrom a hydrocarbon product containing triptan. The recovered product containing triptan can be used as naphtha for engines or aviation, or as an additive thereto, preferably, a naphtha without lead for engines or aviation. Preferably the second liquid phase can be purified, for example by distillation, to improve its triptan concentration. Optionally, at least one additive for naphtha for engines or aviation can be added to the hydrocarbons recovered from the second recovered liquid phase. In the processes of the present invention, a vapor phase will also be present in the reactor. Said vapor phase may comprise at least one of hydrogen, steam, hydrocarbons (including triptan), methanol and / or dimethyl ether. In one embodiment, the water is separated from the process by extracting at least part of the vapor phase from the reactor. The steam can be condensed and purified, for example, by distillation, to improve its triptan concentration. The vapor phase can be purified by condensation and distillation to provide a product with clean water to discard it, a hydrocarbon product comprising triptan and a recycle stream containing unreacted feed components. In a preferred embodiment, the processes of the present invention can be carried out in an adiabatic reactor or a reactor with cooling coils for extracting heat, which can extract up to 20% of the heat of reaction. In one embodiment of a preferred continuous process, the reactor is provided with a feed admission through which, when in use, the recycled gas mixture, the methanol and / or the dimethyl ether are passed through and fresh. the recycled methanol. During use, methanol and / or dimethyl ether react in the reactor in the presence of a catalyst comprising indium halide to produce a mixture comprising water, hydrocarbons (including triptan) and unreacted methanol. Preferably, the reactor contains a liquid hydrophilic phase comprising the indium halide catalyst, a second hydrophobic liquid phase comprising hydrocarbons, and a vapor phase comprising water and triptan. The water is removed from the reactor by extracting the vapor phase from the reactor. The triptan product can be recovered from the reactor from the vapor phase and / or from the liquid phase (s) that are extracted from the reactor. All the catalyst components (halide and optionally indium) that are removed from the reactor as process streams that are extracted for product recovery are recycled to the reactor to maintain in said reactor an effective concentration of the catalyst comprising indium halide. The methanol and / or the dimethyl ether present in the recovered vapor phase can be recycled to the reactor. Reactors and processes that are suitable are further described, for example, in WO 02/070440, the contents of which are incorporated herein by reference. Although the hydrocarbon reaction product comprising triptan will be used as a mixture component for a naphtha, it is preferably distilled beforehand to concentrate the triptan fraction, and any triptene fraction. Preferably, before using it as a blending component for a naphtha, the hydrocarbon reaction product is hydrogenated to convert all of the triptene and / or the other alkenes to triptan and / or other alkanes. There are several preferred ways where the processes of the present invention can be used, part of which are described below.

(A) The process of the present invention may include reacting methanol and / or dimethyl ether and the indium halide, to form a mixture of methanol and / or dimethyl ether and a hydrocarbon reaction product comprising triptan. Then, the hydrocarbon reaction product can be separated from the methanol and / or the dimethyl ether, the indium halide or both, for example, by separating it as a different liquid phase or by distillation. Then, the hydrocarbon reaction product can be hydrogenated separately with hydrogen on a hydrogenation catalyst as described above, for example, at a pressure of 1-10 bar and at a temperature of 10~100 ° C, preferably 10-500 ° C. Hydrogenation converts all of the triptene (and other alkenes) to triptan (and other alkanes). (B) As an alternative, instead of separating the hydrocarbon reaction product before hydrogenating the product, the hydrogenation can be carried out before separation. After hydrogenation of triptan and other alkanes, these can be separated by distillation of methanol or dimethyl ether, which can be recycled for reuse. (C) In another alternative, the reaction of the methanol and / or the dimethyl ether with the indium halide can be carried out at least in part in the presence of hydrogen, both in the presence and absence of the hydrogenation catalyst. At the desired conversion point, the hydrocarbon reaction product can be separated from the indium halide, and optionally methanol and / or dimethyl ether, preferably followed by hydrogenation on the catalyst especially if no hydrogenation catalyst was used in the reaction step with indium halide. If desired, the hydrogenation catalyst can be used in both steps. If the hydrocarbon reaction product does not contain triptene, then the hydrocarbon reaction product is preferably separated from the indium halide, and optionally methanol and / or dimethyl ether without further hydrogenation. In said three alternatives (A) to (C), the indium halide catalyst is separated from the coproduct water in a vapor phase which is retained in a liquid or solid phase. The invention will now be illustrated with respect to the following examples: Comparative experiment A Znl2 (9.35g), methanol (1.88g) and ethanol were weighed (0.17g) in a 15ml glass ACE ™ pressure tube.

The contents were then stirred with a spatula and agitated to dissolve most of the Znl2. Some heat came off. 2 Once the tube and contents were cooled, 0.07 g of methyl iodide was added and the tube was sealed. The tube was placed in a steel mesh and placed in an oven at 200 ° C for 2 hours. When cooled, the tube contained two liquid layers plus a large amount of whitish precipitate. The upper organic phase was crystalline and an aliquot was extracted for analysis by gas chromatography (GC). Said aliquot was diluted in CDCl3 before the GC analysis. The liquid layer at the bottom had a dark brown / red color. The GC analysis showed that the organic phase contained a range of branched chain hydrocarbons, which included iso-butane, iso-pentane, 2-methyl-2-butene, 2,3-dimethylbutane, triptan and triptene. In terms of hydrocarbons present (ie, excluding methanol, CDCl 3, dimethyl ether and methyl iodide) the organic phase contained 20.1% by weight of triptan, 1.1% by weight of 2-methyl-2-butene, 2, 8% by weight of tryptene and 4.9% by weight of hexamethylbenzene.

Example 1 The method of Comparative Experiment A was repeated except that an equivalent molar amount of Inl3 was used instead of Znl2. Inl3 (14.38g), methanol (1.87g) and ethanol (0.17g) were weighed in an ACE ™ pressure tube of 15ml glass Then the contents were stirred with a spatula and stirred to dissolve the Inl3, all of which dissolved. Some heat came off. Once the tube was cooled and the contents were added 0.08 g of methyl iodide, and the tube was sealed. The tube was placed in a steel mesh and placed in an oven at 200 ° C for 2 hours. Upon cooling, the tube contained two liquid layers and a negligible amount of precipitate. The upper organic phase was crystalline and an aliquot was extracted to be analyzed by GC. Said aliquot was diluted in CDC13 before the GC analysis. The GC analysis showed that the organic phase contained a range of branched chain hydrocarbons, which included significant amounts of iso-butane, iso-pentane, 2,3-dimethylbutane and triptan. In terms of the distribution of hydrocarbon products, it was observed that the branched chain hydrocarbon products that were produced in Example 1 were predominantly alkanes. In comparison, Comparative Experiment A showed a significantly greater amount of alkene products. More specifically, in terms of hydrocarbons present (i.e. excluding methanol, CDC13, dimethyl ether and methyl iodide.) The organic phase contained 26.4% by weight of triptan and 0.4% by weight of hexamethylbenzene. The organic phase contained negligible amounts of 2-methyl-2-butene and triptene. Example 1 also showed a greater amount of iso-pentane and 2,3-dimethylbutane products compared to Comparative Experiment A (with respect to both the triptan and the total "weights", where the "weighers" are compounds with 8 or more carbon atoms, such as for example tetramethylbenzenes, pentamethylbenzene and hexamethylbenzene). Although Example 1 showed a higher amount of pentamethylbenzene and tetramethylbenzenes compared to Comparative Experiment A, with respect to the amount of triptan that was produced, the production of total "weights" was also lower. Therefore, Example 1 shows that the use of indium iodide as a catalyst instead of zinc iodide allows obtaining a significant triptan production, and without significant precipitation. Further, when comparing the distribution of products with Comparative Experiment A, (Example 1) tends to a higher amount of branched chain alkanes compared to branched chain olefins, and with a lower production of "heavy" in comparison with the production of "light" (where "light" in general are compounds with 6 or less carbon atoms).

Example 2 The method of Example 1 was repeated except that in the reaction MTBE was used instead of ethanol. Lnl3 (14.80g), methanol (1.92g) and MTBE (0.20g) were weighed in a 15ml glass ACE ™ pressure tube. Then the contents were stirred with a spatula and stirred to dissolve the lnl3, all of which dissolved. Some heat came off. Once the tube was cooled and the contents were added 0.09g of methyl iodide, and the tube was sealed. The tube was placed in a steel mesh and placed in an oven at 200 ° C for 2 hours. Upon cooling, the tube contained two liquid layers and a negligible amount of precipitate. The upper organic phase was crystalline and an aliquot was extracted to be analyzed by GC. Said aliquot was diluted in CDCl3 before the GC analysis. The GC analysis showed that the organic phase contained a range of branched chain hydrocarbons, which included significant amounts of iso-butane, iso-pentane, 2,3-dimethylbutane and triptan. In terms of the distribution of hydrocarbon products, it was observed that the branched chain hydrocarbon products that were produced in Example 2 were predominantly alkanes. In comparison, Comparative Experiment A showed a significantly greater amount of alkene products. More specifically, in terms of hydrocarbons present (ie excluding methanol, CDC13, dimethyl ether and methyl iodide) the organic phase contained 25.3% by weight of triptane and 0.1% by weight of hexamethylbenzene. The organic phase contained negligible amounts of 2-methyl-2-butene and triptene. Compared with Comparative Experiment A, Example 2 also showed a larger amount of iso-pentane and 2,3-dimethylbutane products (with respect to both the triptan and the total "weights"). Although Example 2 showed a higher amount of pentamethylbenzene and tetramethylbenzenes compared to Comparative Experiment A, with respect to the amount of triptan that was produced, the production of total "weights" was also lower. Therefore, Example 2 shows that the use of indium iodide as a catalyst instead of zinc iodide allows a significant triptan production to be obtained, and without significant precipitation. Further, when comparing the product distribution with Comparative Experiment A, (Example 2) tends towards a higher amount of branched chain alkanes in comparison with branched-chain olefins, and with a lower production of "heavy" compared to the production of "light". Comparative Experiment B Znl2 (2.33g), methanol (1.87g) and ethanol (0.17g) were weighed into a 15ml glass ACE ™ pressure tube. The contents were then stirred with a spatula and shaken to dissolve Znl2, all of which dissolved. Some heat came off. Once the tube and contents were cooled, methyl iodide (0.40 g) and 2-methyl-2-butene (0.005 g) were added and the tube was sealed. The tube was placed in a steel mesh and placed in an oven at 200 ° C for 2 hours. When cooled, the tube contained only one liquid layer, which had a red / brown color. There was no organic phase. Therefore, at this concentration, the zinc iodide catalyst showed no activity, or only had a negligible amount.

Example 3 The method of Comparative Experiment B was repeated except that in addition to Znl2 Inl3 was added to the reaction. Inl3 (3.63g), Znl2 (2.33g), methanol (1.87g) and ethanol (0.17g) were weighed into an ACE ™ glass pressure tube of 15ml. Then the contents were stirred with a spatula and stirred to dissolve the Inl3 and Znl2, all of which dissolved. Some heat came off. Once the tube and contents were cooled, methyl iodide (0.40g) and 2-methyl-2-butene were added. (0.005g) and the tube was sealed. The tube was placed in a steel mesh and placed in an oven at 200 ° C for 2 hours. Upon cooling, the tube contained two liquid layers and a small amount of whitish precipitate. The upper organic phase was crystalline and an aliquot was extracted for GC analysis. Said aliquot was diluted in CDC13 before the GC analysis. The GC analysis showed that the organic phase contained a range of branched chain hydrocarbons, which included iso-butane, 2-methyl-2-butene, iso-pentane, pentane, 2,3-dimethylbutane, triptane and triptene. In terms of the distribution of hydrocarbon products, it was observed that the branched chain hydrocarbon products that were produced in Example 3 were predominantly alkanes. More specifically, in terms of hydrocarbons present (ie excluding methanol, CDCl 3, dimethyl ether and methyl iodide) the organic phase contained 26.4% by weight of triptan and 8.7% by weight of hexamethylbenzene. The organic phase contained only small amounts of 2-methyl-2-butene (0.1% by weight) and negligible amounts of triptene. In addition, only small amounts of pentamethylbenzene and tetramethylbenzenes were present. This example shows that a mixture of indium halide and zinc halide catalyst can be used. Comparative experiment C Znl2 (9, 30g) and methanol (2.01g) in a 15ml glass ACE ™ pressure tube. The contents were then stirred with a spatula and shaken to dissolve Znl2, most of which dissolved. Some heat came off. Once the tube was cooled and the contents were added methyl iodide (0.40 g) and 2 methyl-2-butene (0.005 g) and the tube was sealed. The tube was placed in a steel mesh and placed in an oven at 200 ° C for 2 hours. Upon cooling, the tube contained two liquid layers and a large amount of a whitish precipitate. The lower layer had a dark red / brown color. The tube was cooled in water and ice and cyclohexane was added to the upper organic phase as an internal standard, the contents of the tube were shaken and then allowed to settle. An aliquot (50μl) of the upper organic phase was extracted for analysis by gas chromatography (GC). Bliss aliquot was diluted in CDCl3 (250μl) before analysis by CG. The GC analysis showed that the organic phase contained a range of branched chain hydrocarbons, which included substantial amounts of triptan and triptene. The detailed distribution of the hydrocarbon products present (ie, excluding methanol, CDCl 3, dimethyl ether and methyl iodide) is given in Table 2.

Example 4 The method of Comparative Experiment C was repeated except that in the reaction Inl3 was used instead of Znl2. Inl3 (14.47g) and methanol (2.00g) were weighed into a 15ml glass ACE ™ pressure tube. Then the contents were stirred with a spatula and shaken to dissolve the Inl3, most of which dissolved. Some heat was released. Once the tube was cooled and the contents were added, methyl iodide (0.40 g) and 2-methyl-2-butene were added. (0.005g) and the tube was sealed. The tube was placed in a steel mesh and placed in an oven at 200 ° C for 2 hours. Upon cooling, the tube contained two liquid layers and a negligible amount of precipitate. On one side of Also, some small, colorless crystals were observed on the liquid layers. The lower layer had a dark red / brown color. The tube was cooled in water and ice and cyclohexane was added to the upper organic phase as an internal standard, the contents of the tube were shaken and then allowed to settle. An aliquot (50μl) of the upper organic phase was extracted for analysis by gas chromatography (GC). Said aliquot was diluted in CDC13 (250μl) before the GC analysis. The CG analysis showed that the organic phase contained a range of branched chain hydrocarbons, which included substantial amounts of triptan. The detailed distribution of the hydrocarbon products present (i.e. excluding methanol, dimethyl ether, CDC13, cyclohexane and methyl iodide) is given in Table 2. It was observed that the total volume of the organic phase in Example 4 was approximately 50% less than that of Comparative Experiment C (also supported by the relative peak sizes of the CG of the internal cyclohexane standard). In terms of the distribution of hydrocarbon products, it was observed that the branched chain hydrocarbon products that were produced in Example 4 were predominantly alkanes, while the Experiment Comparative C produced significant amounts of triptene and 2-methyl-2-butene. More specifically, the organic phase in Comparative Experiment C contained 18.87% by weight of triptan, 3.79% by weight of tryptene, 56.21% by weight of different "heavies" of hexamethylbenzene, and 6.51% by weight. % hexamethylbenzene. In contrast, the organic phase in Example 4 contained 29.95% by weight of triptan. Only 27.77% by weight of different "heavies" of hexamethylbenzene, and 6.10% of hexamethylbenzene, Example 4 showed a greater amount of iso-pentane and 2,3-dimethylbutane products with respect to both the triptan and the " "heavy" totals compared to Comparative Experiment C. Example 4 also showed a higher amount of pentamethylbenzene and tetramethylbenzenes compared to Comparative Experiment C, but the amount of triptan that was produced with respect to the production of "heavy" totals was significantly better than for Example 4. Therefore, Example 4 showed that the use of indium iodide as a catalyst instead of zinc iodide allows to obtain a significant triptan production, and without significant precipitation. In addition to the product distribution, when compared to Comparative Experiment C, it tends towards a higher amount of branched chain alkanes compared to chain olefins branched, and with a lower production of "heavy" in comparison with the production of "light". A summary of the loading compositions for the different experiments is given in Table 1.

Table 1 Load compositions for methanol homologation reactions fifteen twenty Table 2 Product distribution for Comparative Experiment C and Example 4 * .Excuding HMB. ** Normalized to the hydrocarbons produced (excludes CDCl 3, MCI, MeOH, DME and cyclohexane).

Claims (17)

NOVELTY OF THE INVENTION Having described the invention as antecedent, the content of the following claims is claimed as property: CLAIMS

1. A process for producing branched chain hydrocarbons from methanol and / or dimethyl ether CHARACTERIZED BECAUSE said process comprises contacting in a reactor methanol and / or dimethyl ether with a catalyst comprising indium halide.

2. A process as claimed in claim 1, wherein the indium halide is one or more of InX and / or InX3, where X is a halide selected from Cl, Br and I, and combinations thereof.

3. A process as claimed in claim 1 or claim 2, CHARACTERIZED BECAUSE the reactor also contains zinc halide in addition to the indium halide.

4. A process as claimed in any preceding claim, CHARACTERIZED BECAUSE in addition to the reagents methanol and / or dimethyl ether, additional supply components selected from hydrocarbons, halogenated hydrocarbons and oxygenated hydrocarbons may also be introduced into the reactor.

5. A process as claimed in claim 4, CHARACTERIZED BECAUSE the additional supply components are selected from olefins, dienes, alcohols and ethers.

6. A process as claimed in claim 4, CHARACTERIZED BECAUSE the additional delivery components act as initiators and / or promoters for the reaction to produce branched chain hydrocarbons.

7. A process as claimed in claim 6, CHARACTERIZED BECAUSE the reactor contains one or more compounds that act as reaction initiators, which are selected from alcohols, ethers, olefins and dienes and having at least 2 carbon atoms .

8. A process as claimed in claim 6, CHARACTERIZED BECAUSE in the reactor there are present one or more promoters that are selected from one or more of hydrogen halides and alkyl halides with 1 to 8 carbon atoms.

9. A process as claimed in any of the preceding claims, CHARACTERIZED BECAUSE said process is operated substantially in liquid phase.

10. A process as claimed in any of the preceding claims, CHARACTERIZED BECAUSE methanol and / or dimethyl ether are contacted with the indium halide at a temperature between 100 and 300 ° C.

11. A process as claimed in any of the preceding claims, CHARACTERIZED BECAUSE the reaction is carried out at a pressure within the range between 1-100 barg.

12. A process as claimed in any of the preceding claims, CHARACTERIZED BECAUSE the reaction is carried out in the presence of hydrogen.

13. A process as claimed in any of the preceding claims, CHARACTERIZED BECAUSE the reaction is carried out in the presence of a hydrogenation catalyst.

14. A process as claimed in any of the preceding claims, CHARACTERIZED BECAUSE the reaction is carried out in the presence of carbon monoxide.

15. A process as claimed in claim 1, CHARACTERIZED BECAUSE said process is a continuous or semi-continuous process for producing branched chain hydrocarbons from methanol and / or dimethyl ether comprising contacting in a reactor, in a composition of reaction in liquid phase, methanol and / or dimethyl ether with a catalyst comprising indium halide, and at a temperature of at least 100 ° C, to give a product mixture comprising (i) methanol and / or dimethyl ether and (ii) a hydrocarbon reaction product that it comprises branched chain hydrocarbons, and where in said process the catalyst is maintained in the reactor in an active form and in an effective concentration.

16. A process as claimed in claim 15, CHARACTERIZED BECAUSE the catalyst comprising indium halide is maintained in the reactor in an active form and in an effective concentration by recycling to the reactor one or more promoter compounds of a? several stage (s) of product recovery downstream.

17. A process as claimed in claim 16, CHARACTERIZED BECAUSE the liquid reaction composition also comprises at least one additional additional supply component, wherein said other additional supply component has preferably been recycled from one or more downstream product recovery step (s).