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WO2004067487A2 - Method for the production of non-aromatic hydrocarbons - Google Patents

Method for the production of non-aromatic hydrocarbons

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Publication number
WO2004067487A2
WO2004067487A2 PCT/EP2003/014308 EP0314308W WO2004067487A2 WO 2004067487 A2 WO2004067487 A2 WO 2004067487A2 EP 0314308 W EP0314308 W EP 0314308W WO 2004067487 A2 WO2004067487 A2 WO 2004067487A2
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WO
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Patent type
Prior art keywords
salt
method
gas
reducing
melt
Prior art date
Application number
PCT/EP2003/014308
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German (de)
French (fr)
Other versions
WO2004067487A3 (en )
Inventor
Rüdiger FORSTER
Peter Wasserscheid
Christiane Werth
Original Assignee
Ruhrgas Aktiengesellschaft
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing or organic materials, e.g. fatty oils, fatty acids
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/26Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02Boron or aluminium; Oxides or hydroxides thereof
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/08Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of gallium, indium or thallium
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06Halogens; Compounds thereof
    • C07C2527/08Halides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06Halogens; Compounds thereof
    • C07C2527/08Halides
    • C07C2527/10Chlorides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06Halogens; Compounds thereof
    • C07C2527/125Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06Halogens; Compounds thereof
    • C07C2527/125Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
    • C07C2527/126Aluminium chloride
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Bio-feedstock

Abstract

The invention relates to a method for the production of long-chain, branched-chain and/or cyclic hydrocarbons. A low molecular weight alkyl halide and a fused salt are firstly prepared. The fused salt contains an electrophilic compound and a reducing agent and is free from oxygen and oxygen compounds. The alkyl halide is then brought into contact with the fused salt such that long-chain, branched-chain and/or cyclic hydrocarbons are formed in the fused salt. The hydrocarbons formed in the fused salt are drawn off and can subsequently be separated from unreacted starting materials. By means of the above method, hydrogen can be produced during the reaction of the low molecular weight alkyl halide. The risk of oxidation of the alkane produced to give carbon monoxide or carbon dioxide is avoided by means of the reducing conditions in the fused salt. The product distribution can be controlled by means of suitable selection of the composition of the fused salt. Highly-branched hydrocarbons are produced with the preferred application of a sodium chloroaluminate fused salt.

Description

A method for producing non-aromatic hydrocarbons

The invention relates to a process for the homologation of lower alkanes or halogenated alkanes, that is, a method for manufacturing longer chain and / or branched and / or cyclic hydrocarbons from a lower alkane or haloalkane or a mixture of these substances.

The term "homologation" is to describe the production of any of longer and / or branched and / or cyclic hydrocarbons under this description. A lower alkane or haloalkane to be a preferably linear alkane or haloalkane with a carbon atom or a few linked carbon atoms, where the invention is preferably directed to the homologation of methane as a main component of natural gas.

As can be seen 987-1007 among others the article by Robert H. Crabtree, "Aspects of Methane Chemistry", Chem. Reviews, 1995, Vol. 95, pages that homologation of methane has an enormous economic impact. Almost 60% of the world's known gas reserves are off the consumer markets. The natural gas transportation by pipeline is economical only up to a distance of about 4000 to 6000. Therefore, an economically sensible use of these reserves without conversion of the energy carrier natural gas into a transportable form is not possible. It is therefore long been the attempt to convert natural gas into a liquid which can be transported with conventional tankers cost to consumer markets.

There are a number of so-called gas-to-liquid processes (GTL), in which natural gas, in particular its major component, methane is converted to a liquid. In an older method, the Fischer-Tropsch synthesis, is removed from the natural gas in a reforming step, firstly a synthesis gas, a mixture of CO and H 2 produced. The synthesis gas is then converted with the aid of catalysts in carbon hydrogens. Alternatively, can be produced from the synthesis gas, methanol, which is then converted to olefins or fuels according to the tanker transport in the vicinity of the consumer markets. An economic disadvantage of said prior method is based on its two-stage, and the increased installation costs associated therewith. In addition, the synthesis gas is an endothermic process with a low energy efficiency.

More recently, alternative, single-stage procedural (the aforementioned review article comp.) Have been developed reindeer, with the aid of a direct conversion of natural gas or methane to longer-chain or branched hydrocarbons is possible. The homologation of methane to ethane and longer chain or branched hydrocarbons, with the release of hydrogen is a highly endothermic process. The previous teaching assumes that reaches the homologation characterized in that initiates the lower alkane, for example at temperatures of 50-60 ° C, in a super acid solution which was a mild oxidizing agent added, alternatively, an oxidizing

can be used superacid (see FIG. at the abovementioned review article section F). When using oxygen-containing oxidizing agents, which is useful for economic reasons, the liberated during the reaction, hydrogen is oxidized to water. The formation of water results in conjunction with the superacid systems to problems in the maintenance of the required reaction conditions and / or in the regeneration of the catalyst. The object of the invention is to provide an alternative

to provide opportunity for the direct production of longer-chain and / or branched and / or cyclic hydrocarbons comprising at least one lower alkane or at least a lower haloalkane.

This object is inventively achieved by a method having the features of claim 1.

In the inventive method are first at least one lower haloalkane and a molten salt containing an electrophilic compound and a reducing agent is provided, wherein the molten salt is free from oxygen and / or oxygen compounds. The concept of "molten salt" is intended to both the classical salt melts (melting point> 100 ° C) and the so-called ionic liquids (lower melting point) (see article by Peter Wasserscheid and Wilhelm Keim. "Ionic Liquids - New" Solutions "for the include transition metal catalysis ", Angewandte Chemie, 2000, 112, pages 3926-3945). The electrophilic compound should be electrophilic within the meaning of the concept of Pearson. The reducing agent should be able to donate electrons such that can be formed in protic media hydrogen.

In the inventive method which is brought at least in such a lower haloalkane with the salt melt in contact, that the longer chain and / or branched and / or cyclic hydrocarbons are formed in the molten salt (possibly via several intermediate steps). The longer formed and / or branched and / or cyclic hydrocarbons are removed from the salt melt. Said novel process starts from the

Art path laid down the homologation under oxidizing conditions and performs the homologation by under reducing conditions. Hydrogen can be generated. Due to the reducing conditions, the risk of oxidation of the alkane or haloalkane is avoided to carbon monoxide or carbon dioxide. The required reaction energy is supplied in part by oxidation of the reducing agent. This is combined with a provision of the reducing agent in a molten salt with an electrophilic compound. Preferably a halogen methane as a haloalkane provided and the longer-chain and / or branched-chain and / or cyclic compounds have at least 2 carbon atoms, preferably 5 to 10 carbon atoms. In a preferred embodiment, as

Halogen methane methylene chloride provided. Methylene chloride is an important basic chemical in the chemical industry, easy to manufacture and accessible industrially, for example, by thermal chlorination of methane. In a further development of the invention, a lower haloalkane by at least one lower alkane, preferably methane, is brought into contact with the salt melt and reacts with one contained in the molten salt halogen and / or halide may be at least also be provided. By the provision of the at least one haloalkane in this manner, can be a process step, namely the production of the haloalkane be omitted, resulting in a more cost-effective process control are allowed. After the provision of at least one alkyl halide and before the formation of longer-chain and / or branched-chain and / or cyclic hydrocarbons, a preparation of the product mixture may be interposed.

In a preferred embodiment the at least one lower alkane containing up to 3 carbon atoms, and the longer-chain and / or branched and / or cyclic hydrocarbons, in comparison to the at least one lower alkane at least twice the number of carbon atoms. Preferably, the at least one lower alkane methane and the longer-chain and / or branched and / or cyclic hydrocarbons have at least 2 carbon atoms, preferably 5 - 10 carbon atoms.

In one embodiment, a lower alkane can be brought at least as a component of a gas mixture with the molten salt in contact. As a gas mixture of natural gas for example, can be used. The secured world reserves of conventional natural gas have increased steadily in recent years and amounted to the end of 1997 about 145 x 10 12 m 3. By using the available natural gas in large quantities, the inventive method can be performed particularly inexpensive.

Preferably, the electrophilic compound is a component of an acid salt melt containing the reducing agent. The molten salt preferably contains complex anions each having at least one central atom. At the at least one central atom of an alkyl ligand is preferably at least anlagerbar. The complex anions preferably comprise at least one central atom selected from a group comprising aluminum, tin, iron, zinc, copper, titanium, scandium, gallium, vanadium and zirconium, said complex anions

may contain halogen ligands.

Is preferably used as a molten salt Halogenoaluminat molten salt, especially an alkali and / or alkaline earth Halogenoaluminat molten salt used. a sodium or a sodium-Chloroaluminat- Bromoaluminat molten salt is particularly preferably used, which preferably consists of aluminum halide (as Lewis acid) and sodium halide in molar ratio 90:10 to 10:90, preferably about 70:30 to 30:70, is formed. Depending on the selected molar ratio can

. Sodium chloroaluminate salt melt in addition to the complex anion A1C1 4 ", the complex anions of the general formula Al n Cl 3n + 1 and A1 2 C1 6 contains the properties of chloroaluminate melts are studied in detail, in addition, these melts are relatively inexpensive to manufacture When. use of a sodium chloroaluminate salt melt arise advantageously highly-branched, non-recoverable by rectification of petroleum hydrocarbons whose octane number is partly considerably higher than that of the Isooktans. These are suitable, for example, as additives for fuels, in order to increase their antiknock or directly as a fuel. In the use of a sodium Bromoaluminat molten salt, however, preferred arise cyclic hydrocarbons, which serve as starting materials for a number of important chemical reac- tions. Thus, for example, cyclohexane in several subsequent steps to caprolactam, the starting compound of polyamide 6, implement.

In the inventive method a reducing agent is preferably provided which is less noble than hydrogen in the electrochemical voltage series.

In a preferred embodiment in providing the molten salt, the reducing agent is formed by an electrochemical reduction in the salt melt. In one embodiment, the reducing agent could be one of the ions of the molten salt forming salts simultaneously, which simplifies the deployment. For example, a complex anion of the melt itself could serve as a reducing agent, if it can change to a higher oxidation state. This is possible for example at a dimethyl tin dichloride containing melt.

In a preferred embodiment of the method according invention is used as a reducing agent is a metal, preferably the corresponding to that contained in the molten salt complex anion of metal or a metal alkyl compound is provided. In a Chloroaluminat- salt melt, this is preferably aluminum. Alternatively, gallium or a mixture of aluminum and gallium can be used as a reducing agent at a chloroaluminate salt melt. In a preferred embodiment, the at least bar a lower haloalkane in a salt melt at a temperature between 50 ° C and 650 ° C, preferably at a temperature between 130 ° C and 250 ° C, and at a pressure between 1 and 200, preferably between 1 and 50 bar, initiated. In a preferred embodiment of the invention, the haloalkane and / or spent reducing agent is consumed in the formation of longer-chain and / or branched and / or cyclic hydrocarbons in step c) continuously by supplying at least a lower haloalkane and / or a reducing agent is replaced, wherein the the is supplied to the reducing agent consumed replaced reducing agent or the salt melt formed in this by electrochemical reduction. Advantageously, it is possible to separate in step d) is derived, unreacted starting materials from the products and to provide these to the method available again. In this embodiment, it is possible to process according to the invention for producing longer-chain and / or branched and / or cyclic hydrocarbons can be operated continuously by the reactants are provided to the extent as it is consumed by the reaction and subsequently removed. This is particularly advantageous when the method for manufacturing longer chain and / or branched and / or cyclic hydrocarbons with a pressure of 1 to 200 bar, preferably 1 to 50 bar out. As the reducing agent used in the reaction may be provided by electrochemical reduction, there is no need to open a container filled with the Salzschmelεe reactor for feeding spent reducing agent.

Advantageous and / or preferred developments of the invention are characterized in the subclaims.

In the following the invention will be explained in more detail with reference to preferred embodiments.

Embodiment I In one equipped with a gas introduction means, an agitator and a gas discharge means autoclave under a protective gas, 21.34 g A1C1 3 (0.161 mol), 14.00 g of dry NaCl (0.240 mol) and about 0.05 g Al flakes are (0.002 mol) was weighed. From the weighed quantities a AlCl 3 / NaCl molar ratio of 40:60 results. The mixture is heated to 180 ° C and then stirred at the same temperature for 2 hours, being passed through a gas introduction means methylene chloride through the salt melt. The outgoing gas stream is analyzed. In addition to the starting material methylene chloride following components can be detected: methane, isobutane, neopentane, isopentane, 2-methyl butane, 2, 2-dimethylbutane, 2, 3-dimethylbutane, 2-methylpentane, 3-methylpentane, 2, 4-dimethyl pentane, 2, 2,3-trimethylbutane, 3, 3-dimethylpentane, 2-methylhexane, 2-methylhexane, and 2, 2, 3, 3 -Tetramethylbutan.

Embodiment II 62.32 g AlBr 3 and 10.31 g of NaBr are weighed out under protective gas, mixed and heated to 110 ° C. The solution is two times with 0.08 A electrolysed (two W electrodes), at the same time be passed through the melt 20 ml / min of methane. Subsequently, the melt is heated to 200 ° C and purged for 30 minutes with argon. The

Product gas Mixed is collected and contains 12% isobutane and 2-methylbutane, 88% cyclic alkanes, especially methylcyclohexane (24%), 1, 3 -Dimethylcyclohexan (cis and trans) (38%), 1, 2-dimethylcyclohexane (4%) , 1,3,5-trimethylcyclohexane (7%), 1, 1, 3-trimethylcyclohexane (5%),

1, 2, 4-trimethylcyclohexane (7%) (percentages are based on the total amount of hydrocarbon).

Embodiment III In an autoclave, 8.31 g of AlBr 3 (0.0312 mol) with 1.37 g of NaBr (0.0168 mol) and 1.00 g of aluminum flakes (0.0370 mol) are weighed. From the weighed quantities a AlBr 3 / NaBr molar ratio is of 70:30. It is condensed in 4.8 g of methylene chloride (0.0954 mol) and the solution is stirred for 2 hours at 110 ° C in an oil bath. Analysis of the hot gas expanded in a mouse gases gave the following composition: 4.4% methane, 93.6% ethane, 0.3% propane and butanes, pentanes, 0.7%, 0.4% and 0.02% higher hexanes hydrocarbons (C7 and higher). In addition, the gas mixture contained significant amounts of methyl bromide; Sales of methylene chloride was above 90%.

embodiment IV

Gallium as a reducing agent

8.67 g of A1C1 3 (0.0650 mol) and 2.63 g NaCl (0.0450 mol) and 2.58 g of Ga (0.0370) are filled with a magnetic stir bar in an autoclave. The weighed quantities result in a AlCl 3 / NaCl molar ratio of 60:40. There are condensed in 4.8 g of methylene chloride (0.0954 mol). The autoclave is placed for 2 hours at 130 ° C with stirring in an oil bath. The still hot gases are expanded in a gas mouse. The analysis of the gas mixture gave the following quantities of hydrocarbon: 6.5% methane, 0.1% ethane, 1.8% propane, 6.9% butane, 79.3% pentanes, hexanes 1.3%, and Octane (in the latter 30 % 2, 2, 3, 3 -Tetramethylbutan in the C8 fraction), 1% Heptane (of which 22.8% triptane) and nonanes and decanes 0.6%.

Embodiment V aluminum as a reducing agent 8.67g A1C1 3 (0.0650 mol) and 2.63 g NaCl (0.0450 mol) and 1.00 g of aluminum flakes (0.0370) are filled with a magnetic stir bar in an autoclave. The weighed quantities result in a AlCl 3 / NaCl molar ratio of 60:40. There are condensed in 4.8 g of methylene chloride (0.0954 mol). The autoclave is placed for 2 hours at 150 ° C with stirring in an oil bath. The still hot gases are expanded in a gas mouse. The analysis of the gas mixture gave the following quantities of hydrocarbon: 9.8% Cl, 54.3% C2, 0.9% C3, 1.4% C4, at least 6.9% C5 16.3% C6 and C7 5.5% (of which 18% triptane), 4.03% C8 (68% 2, 2, 3, 3-tetramethyl butane) and 0.5% C9. Sales of methylene chloride is about 80%.

Claims

claims
1. A method for manufacturing longer chain and / or branched and / or cyclic hydrocarbons, wherein: a) a lower haloalkane provided at least; b) a molten salt provided that includes an electrophilic compound and a reducing agent, wherein the molten salt is free from oxygen and / or oxygen compounds; c) which is brought at least in such a lower haloalkane with the salt melt in contact that are formed in the molten salt of the at least one lower haloalkane longer chain and / or branched and / or cyclic hydrocarbons; and d) the longer formed in step c) and / or branched and / or cyclic hydrocarbons are removed from the salt melt.
2. The method according to claim 1, characterized in that there is provided as a haloalkane halomethane, wherein the longer-chain and / or branched and / or cyclic hydrocarbons having at least 2 carbon atoms, preferably 5 to 10 carbon atoms.
3. The method according to claim 2, characterized in that there is provided as a halomethane methylene chloride.
4. The method according to claim 1, characterized in that is a lower haloalkane provided at least by at least one lower alkane with the
Molten salt is contacted and reacted with a molten salt contained in the halogen and / or a halide.
5. The method according to claim 4, characterized in that the at least one lower alkane containing up to 3 carbon atoms, and the longer and / or branched and / or cyclic hydrocarbons relative to the at least one lower alkane having at least twice the number of carbon atoms.
6. The method according to claim 4, characterized in that the at least one lower alkane methane and the longer-chain and / or branched and / or cyclic hydrocarbons at least 2 carbon atoms, preferably 5 to 10 carbon atoms.
7. A method according to any one of claims 4 - 6, characterized in that the contacting at least one lower alkane as a component of a gas mixture, for example in the form of natural gas, with the salt melt.
8. The method according to claim 1, characterized in that a salt melt is provided which contains complexing anions each having at least one central atom.
9. The method according to claim 8, characterized in that a salt melt is provided, wherein on the at least one central atom in each case at least one alkyl ligand is anlagerbar.
10. The method according to claim 9, characterized in that a salt melt is provided complexing
Anions with at least one central atom selected from a group comprising aluminum, tin, iron, zinc, copper, titanium, scandium, gallium, vanadium and zirconium comprises and includes with halogen ligand.
11. A method according to claim 10, characterized in that a Halogenoaluminat molten salt is used.
12. The method according to claim 11, characterized in that an alkali and / or alkaline earth Halogenoaluminat- is used molten salt of i) aluminum halide and ii) alkali and / or alkaline earth metal halide.
13. The method according to claim 12, characterized in that a sodium chloroaluminate salt melt of
Aluminum chloride and sodium chloride is about 70:30 to 30:70, is used in the molar ratio of 90:10 to 10:90, preferably.
14. The method according to claim 12, characterized in that a sodium chloroaluminate salt melt of aluminum chloride and sodium chloride in the molar ratio of 90:10 to 10:90, preferably about 70:30 to 30:70, is used.
15. The method according to any one of claims 1-14, characterized in that the reducing agent in the electrochemical series is less noble than hydrogen.
16. The method according to any one of claims 1 - 15, characterized in that the reducing agent is formed by an electrochemical reduction in the salt melt in providing the salt melt.
17. The method according to claim 15, characterized in that at least one of the ions of the molten salt forming salts also serves as a reducing agent.
18. The method according to claim 15, characterized in that a metal or metal-alkyl compound as a reducing agent.
19. The method according to claim 18, characterized in that the metal or the metal of the metal alkyl compound is a metal that forms which central atoms of complex anions of a molten salt-forming salt or at least one of a plurality of the molten salt-forming salts
20. The method according to claim 19, characterized in that an alkali and / or alkaline earth Halogenoaluminat- is provided salt melt, which contains aluminum as a reducing agent and / or gallium.
21. The method according to claim 20, characterized in that a sodium Bromoaluminat molten salt aluminum bromide and sodium bromide in the molar ratio of 90:10 to 10:90, preferably about 70:30 to 30:70, is provided.
22. The method according to claim 20, characterized in that a sodium chloroaluminate salt melt of aluminum chloride and sodium chloride in the molar ratio of 90:10 to 10:90, preferably about 70:30 to 30:70, is provided.
23. The method according to any one of claims 1 - 22 and characterized in that which is brought at least a lower haloalkane with the salt melt in contact by which is introduced at least a lower haloalkane in the salt melt.
24. The method according to any one of claims 1-23, characterized in that the at least one lower haloalkane with the molten salt at a temperature between 50 ° C and 650 ° C, preferably at a temperature between 130 ° C and 250 ° C, into contact is brought.
25. The method according to claim 24, characterized in that the a lower haloalkane with the salt melt is brought into contact bar at a pressure between 1 and 200 bar, preferably between 1 and 50 at least.
26. The method according to any one of claims 1 - 25, characterized in that the are in the formation of longer-chain and / or branched and / or cyclic hydrocarbons in step c) haloalkane and spent reducing agent consumed constantly replaced by a feed of haloalkane and reducing agent.
27. The method according to claim 26, characterized in that the reducing agent, the spent replacing reducing agent of the molten salt supplied to or formed in this by electrochemical reduction.
PCT/EP2003/014308 2003-01-28 2003-12-16 Method for the production of non-aromatic hydrocarbons WO2004067487A3 (en)

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US8436220B2 (en) 2011-06-10 2013-05-07 Marathon Gtf Technology, Ltd. Processes and systems for demethanization of brominated hydrocarbons
US8829256B2 (en) 2011-06-30 2014-09-09 Gtc Technology Us, Llc Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons
US8802908B2 (en) 2011-10-21 2014-08-12 Marathon Gtf Technology, Ltd. Processes and systems for separate, parallel methane and higher alkanes' bromination
US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems
US9441169B2 (en) 2013-03-15 2016-09-13 Ultraclean Fuel Pty Ltd Process for removing sulphur compounds from hydrocarbons

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