GB2120249A - Process for the production of methyl or ethyl mono-halide - Google Patents
Process for the production of methyl or ethyl mono-halide Download PDFInfo
- Publication number
- GB2120249A GB2120249A GB08313007A GB8313007A GB2120249A GB 2120249 A GB2120249 A GB 2120249A GB 08313007 A GB08313007 A GB 08313007A GB 8313007 A GB8313007 A GB 8313007A GB 2120249 A GB2120249 A GB 2120249A
- Authority
- GB
- United Kingdom
- Prior art keywords
- reaction
- process according
- halogen
- methane
- alkane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 title claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 21
- 150000002367 halogens Chemical class 0.000 claims abstract description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 17
- 239000000460 chlorine Substances 0.000 claims abstract description 17
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000005670 electromagnetic radiation Effects 0.000 claims abstract description 13
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 230000000977 initiatory effect Effects 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 229940050176 methyl chloride Drugs 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011491 glass wool Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 229910052573 porcelain Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 14
- 239000000376 reactant Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Alkyl monohalides wherein the alkyl substituent is methyl or ethyl are selectively produced by reacting a halogen with methane or ethane in the absence of a catalyst and at a temperature below 300 DEG C, provided that in the absence of electromagnetic radiation the temperature is greater than the thermal initiation temperature. In a preferred embodiment methyl monochloride is selectively produced by reacting methane with chlorine.
Description
SPECIFICATION
Process for the production of an alkyl mono-halide wherein the alkyl substituent is methyl or ethyl
The present invention relates to a process for the production of an alkyl mono-halide wherein the alkyl substituent is methyl or ethyl.
Methyl mono-halides, being functional derivatives of methane, are potentially important intermediates in the production, for example of methanol. Converting methane to methyl mono-halides and thence to methanol offers an alternative to converting it first to synthesis gas (carbon monoxide + hydrogen) and thereafter to methanol. Similarly, ethyl monohalides, being functional derivatives of ethane, are potentially important intermediates in the production, for example of ethanol. Converting ethane to ethyl mono-halides and thence to ethanol offers an alternative to converting it first to ethylene and thereafter to ethanol.It is known to produce such alkyl mono-halides by reacting methane or ethane with a halogen, but this is conventionally carried out at elevated temperatures at which the selectivity to the desired alkyl mono-halides is low, there being generally formed in addition to the alkyl monohalide a variety of halogenated alkane derivatives.
Thus in the case of chlorine as the halogen for example the reaction is usually carried out at temperatures near 450"C at which temperature in addition to methyl chloride substantial amounts of methylene dichloride, chloroform and carbon tetrachloride are also obtained.
It has now been found unexpectedly that alkyl mono-halides wherein the alkyl substituent is methyl or ethyl can be obtained in high selectivities and with high conversions of alkane or halogen in the absence of a catalyst under relatively mild conditions.
Accordingly, the present invention provides a process for the selective production of an alkyl mono-halide wherein the alkyl substituent is methyl or ethyl which process comprises reacting a halogen with an alkane which is methane or ethane in the absence of a catalyst and at a temperature below 300 C, provided that in the absence of electromagnetic radiation the temperature is greater than the thermal initiation temperature.
Both methane and ethane are abundantly available in hydrocarbon reservoirs. Methane may also be obtained by the biological conversion of organic materials and by the methanation or in-situ gasification of coal. Halogens and in particular chlorine are readily available on an industrial scale. Suitably the halogen may be either chlorine or bromine and is preferably chlorine.
The reaction is carried out in the absence of a catalyst. However, it is preferred to react the halogen with the alkane in the presence of an inert material.
The inert material may be any material which does not react in a chemical sense with or remove alkane or halogen from the system. Alternatively, the inert material may be any material which becomes inert after an initial stabilisation period in the presence of the reactant gases. During the stabilisation period reaction between the reactant gases and the material may occur but thereafter the material is essentially chemically inert to the reactants. The presence of an inert material facilitates the transfer of heat during the reaction. Suitable inert materials include glass wool, alumina, silica, clay, porcelain and the internal surface of the vessel in which the reaction is carried out.
Energy is required to effect initiation af the reaction of the alkane with a halogen. Any suitable form of energy may be used but it is preferred to use thermal energy, electromagnetic radiation energy or chemical energy. Any combination of these forms of energy may be used if so desired. The nature and quantity of energy required will depend on the particular halogen employed. In the case of chlorine for example, the reaction with methane may suitably be initiated either by visible light, or in the dark by thermal energy at temperatures above about 1800C.
At lowertemperatures, in the absence of electromagnetic radiation, thermal initiation of the reaction does not occur to any appreciable extent. It is believed that the energy input is required to dissociate the halogen molecule into free radicals which are active in the reaction steps, though it is not intended to be bound in any way by this theory.
In order to sustain a continuous reaction or high yields in a batch process further quantities of initiation energy must be supplied. The additional energy may be supplied either continuously or intermittently. However, it is preferred to introduce either electromagnetic energy or thermal energy continuously in order to sustain a continuous reaction. Sufficient thermal energy may be available in the form of exothermic heat released from the reaction of halogen with the alkane.
The proportions of halogen and alkane in the feed to the reactor may be varied over a wide range.
Preferably the molar ratio of alkane to halogen in the feed is in the range 10:1 to 1:10. Gas hourly space velocities (GHSVs) for the feed may also be varied over a wide range. Suitably the GHSVs may be in the range from 1 to 10,000 preferably 30 to 2000. The units for GHSV are cc(total gaseous reactants)/hour/ gram (inert material).
In order to achieve high selectivitiesto alkyl mono-halidesthe reaction temperature must be controlled. In the absence of electromagnetic radiation the temperature must be controlled at a value greater than the thermal initiation temperature. The reaction temperature must be selected with reference to the reactants. In the case of the reaction of methane with chlorine for example the reaction temperature in the absence of electromagnetic radiation may suitably be greater than about 1 80 C, preferably in the range 180 to 280"C. In the case of the reaction of ethane with chlorine in the absence of electromagnetic radiation lower temperatures may be employed, for example greater than about 70"C.
Using electromagnetic radiation the process can be operated at temperatures below 1 80 C.
The process may be operated at subatmospheric, atmospheric or superatmospheric pressures. Operation at atmospheric or superatmospheric pressure is preferred.
The reaction may be carried out batchwise or continuously, preferably continuously.
It is preferred to recycle unreacted alkane and halogen to the reaction.
It is preferred to utilise the process of the invention to produce methyl chloride or bromide by reacting methane with chlorine or bromine respectively.
The invention will now be illustrated by reference to the following Examples.
Example 1
A mixture of methane and chlorine (mole ratio 1:1) was passed over alumina in a continuous flow reactor (GHSV 1780 cc of gaseous reactants/hour/ gram of alumina) which was heated by means of an electric furnace. All light was excluded from the gaseous reaction mixture whilst in the feed lines, the heated zone where the temperature of the alumina bed was 270 C, and the product lines. The product stream was analysed by gas chromatography.
The composition of the product stream, excluding unreacted reactants and hydrogen chloride was methyl chloride (91% v/v) and methylene chloride (9% v/v) and the methane conversion was 36%.
Comparison Test
Example 1 was repeated except thatthe tempera- ture of the alumina bed was 66"C.
The composition of the product gas stream was essentially the same as the reaction feed stream with less than 0.1% conversion of methane to chlorinated products.
This Example is presented for comparison only and demonstrates that no reaction is obtained at lower temperatures in the absence of light.
Example 2
A mixture of methane and chlorine (mole ratio 1:2) was passed over glass wool in a continuous flow reactor (total gas flow 120 cc/min) which was heated by means of an electric furnace. All light was excluded from the gaseous reaction mixture whilst in the feed lines, the heated zone where the temperature of the glass wool was 234"C, and the product lines. The product gas stream was analysed by gas chromatography.
The composition of the product stream, excluding unreacted reactants and hydrogen chloride was methyl chloride (95% v/v) and methylene chloride (5% v/v) and the methane conversion was 15%.
Example 3
A mixture of methane and chlorine (mole ratio 1:4) was passed through an empty Pyrex (RTM) continuous flow reactor (total gas flow 62 cc/min) which was heated by means of an electric furnace. All light was excluded from the gaseous reaction mixture in the feed line and the heated zone where the temperature of the furnace was 184"C. Light was not excluded from the product line or from that part of the reactorwherethe reaction mixture left the heated zone. The product gas stream was analysed by gas chromatography.
The composition of the product stream, excluding unreacted reactants and hydrogen chloride was methyl chloride (86% v/v) and methylene chloride (14% v/v) and the methane conversion was 50%.
Example 4
A mixture of methane and chlorine (mole ratio 1:1) was passed over alumina in a continuous flow reactor (GHSV 211 cc of gaseous reactants/hour/ gram of alumina) which was heated by a Pyrex (RTM) glass electricfurnace. No precautions were taken to exclude light from the gaseous reaction mixture whilst in the feed lines, the heated zone where the temperature of the alumina bed was 200"C, and the product lines. The product gas stream was analysed by gas chromatography.
The composition of the product gas stream, excluding unreacted reactants and hydrogen chloride was methyl chloride (82% v/v) and methylene chloride (18% v/v) and the methane conversion was 52%.
Example 5
A mixture of ethane and chlorine (mole ratio 1:1) was passed over alumina in a continuous flow reactor (GHSV 150 cc of gaseous reactants/hour/ gram of alumina) which was heated by means of an electric furnace. All light was excluded from the gaseous reaction mixture whilst in the feed lines, the heated zone where the temperature of the alumina bed was 185"C, and the product lines. The product gas stream was analysed by gas chromatography.
The composition of the product stream, excluding unreacted reactants and hydrogen chloride was ethyl chloride (88% v/v) and 1,2-dichloroethane (12% v/v) and the conversion of ethane was 65%.
Claims (10)
1. A process for the selective production of an alkyl monohalide wherein the alkyl substituent is methyl or ethyl which process comprises reacting a halogen with an alkane which is methane or ethane, in the absence of a catalyst and at a temperature below 300"C, provided that in the absence of electromagnetic radiation the temperature is greater than the thermal initiation temperature.
2. A process according to claim 1 wherein the halogen is chlorine, the alkane is methane and the product is methyl chloride.
3. A process according to either claim 1 or claim 2 wherein the halogen is reacted with the alkane in the presence of a chemically inert material.
4. A process according to claim 3 wherein the inert material is either glass wool, alumina, silica, clay or porcelain.
5. A process according to any one of the previous claims wherein the reaction is initiated by thermal energy, electromagnetic radiation energy, chemical energy or a combination thereof.
6. A process according to claim 5 wherein further quantities of initiation energy are supplied during the reaction.
7. A process according to claim 6 wherein electromagnetic radiation energy or thermal energy is supplied continuously to the reaction.
8. A process according to anyone of the preceding claims wherein the alkane is methane, the halogen is chlorine and the reaction temperature in the absence of electromagnetic radiation is greater than about 1800C.
9. A process according to claim 8 wherein the reaction temperature is in the range 180 to 280"C.
10. A process according to any one of claims 1 to 7 wherein the alkane is ethane, the halogen is chlorine and the reaction temperature in the absence of electromagnetic radiation is greater than about 70"C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08313007A GB2120249B (en) | 1982-05-15 | 1983-05-11 | Process for the production of methyl or ethyl mono-halide |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8214202 | 1982-05-15 | ||
| GB08313007A GB2120249B (en) | 1982-05-15 | 1983-05-11 | Process for the production of methyl or ethyl mono-halide |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8313007D0 GB8313007D0 (en) | 1983-06-15 |
| GB2120249A true GB2120249A (en) | 1983-11-30 |
| GB2120249B GB2120249B (en) | 1985-11-27 |
Family
ID=26282847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08313007A Expired GB2120249B (en) | 1982-05-15 | 1983-05-11 | Process for the production of methyl or ethyl mono-halide |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2120249B (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7244867B2 (en) | 2004-04-16 | 2007-07-17 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| US7579510B2 (en) | 2006-02-03 | 2009-08-25 | Grt, Inc. | Continuous process for converting natural gas to liquid hydrocarbons |
| US7674941B2 (en) | 2004-04-16 | 2010-03-09 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| US7838708B2 (en) | 2001-06-20 | 2010-11-23 | Grt, Inc. | Hydrocarbon conversion process improvements |
| US7847139B2 (en) | 2003-07-15 | 2010-12-07 | Grt, Inc. | Hydrocarbon synthesis |
| US7883568B2 (en) | 2006-02-03 | 2011-02-08 | Grt, Inc. | Separation of light gases from halogens |
| US7964764B2 (en) | 2003-07-15 | 2011-06-21 | Grt, Inc. | Hydrocarbon synthesis |
| US7998438B2 (en) | 2007-05-24 | 2011-08-16 | Grt, Inc. | Zone reactor incorporating reversible hydrogen halide capture and release |
| US8008535B2 (en) | 2004-04-16 | 2011-08-30 | Marathon Gtf Technology, Ltd. | Process for converting gaseous alkanes to olefins and liquid hydrocarbons |
| US8173851B2 (en) | 2004-04-16 | 2012-05-08 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| US8198495B2 (en) | 2010-03-02 | 2012-06-12 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8273929B2 (en) | 2008-07-18 | 2012-09-25 | Grt, Inc. | Continuous process for converting natural gas to liquid hydrocarbons |
| US8282810B2 (en) | 2008-06-13 | 2012-10-09 | Marathon Gtf Technology, Ltd. | Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery |
| US8367884B2 (en) | 2010-03-02 | 2013-02-05 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8436220B2 (en) | 2011-06-10 | 2013-05-07 | Marathon Gtf Technology, Ltd. | Processes and systems for demethanization of brominated hydrocarbons |
| US8642822B2 (en) | 2004-04-16 | 2014-02-04 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor |
| US8802908B2 (en) | 2011-10-21 | 2014-08-12 | Marathon Gtf Technology, Ltd. | Processes and systems for separate, parallel methane and higher alkanes' bromination |
| US8815050B2 (en) | 2011-03-22 | 2014-08-26 | Marathon Gtf Technology, Ltd. | Processes and systems for drying liquid bromine |
| 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 |
| 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 |
| US9206093B2 (en) | 2004-04-16 | 2015-12-08 | Gtc Technology Us, Llc | Process for converting gaseous alkanes to liquid hydrocarbons |
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-
1983
- 1983-05-11 GB GB08313007A patent/GB2120249B/en not_active Expired
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7838708B2 (en) | 2001-06-20 | 2010-11-23 | Grt, Inc. | Hydrocarbon conversion process improvements |
| US8415512B2 (en) | 2001-06-20 | 2013-04-09 | Grt, Inc. | Hydrocarbon conversion process improvements |
| US7964764B2 (en) | 2003-07-15 | 2011-06-21 | Grt, Inc. | Hydrocarbon synthesis |
| US7847139B2 (en) | 2003-07-15 | 2010-12-07 | Grt, Inc. | Hydrocarbon synthesis |
| US8232441B2 (en) | 2004-04-16 | 2012-07-31 | Marathon Gtf Technology, Ltd. | Process for converting gaseous alkanes to liquid hydrocarbons |
| US8173851B2 (en) | 2004-04-16 | 2012-05-08 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| US7348464B2 (en) | 2004-04-16 | 2008-03-25 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| US7880041B2 (en) | 2004-04-16 | 2011-02-01 | Marathon Gtf Technology, Ltd. | Process for converting gaseous alkanes to liquid hydrocarbons |
| US9206093B2 (en) | 2004-04-16 | 2015-12-08 | Gtc Technology Us, Llc | Process for converting gaseous alkanes to liquid hydrocarbons |
| US7560607B2 (en) | 2004-04-16 | 2009-07-14 | Marathon Gtf Technology, Ltd. | Process for converting gaseous alkanes to liquid hydrocarbons |
| US8642822B2 (en) | 2004-04-16 | 2014-02-04 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor |
| US8008535B2 (en) | 2004-04-16 | 2011-08-30 | Marathon Gtf Technology, Ltd. | Process for converting gaseous alkanes to olefins and liquid hydrocarbons |
| US7244867B2 (en) | 2004-04-16 | 2007-07-17 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| US7674941B2 (en) | 2004-04-16 | 2010-03-09 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| US8053616B2 (en) | 2006-02-03 | 2011-11-08 | Grt, Inc. | Continuous process for converting natural gas to liquid hydrocarbons |
| US7883568B2 (en) | 2006-02-03 | 2011-02-08 | Grt, Inc. | Separation of light gases from halogens |
| US7579510B2 (en) | 2006-02-03 | 2009-08-25 | Grt, Inc. | Continuous process for converting natural gas to liquid hydrocarbons |
| US8921625B2 (en) | 2007-02-05 | 2014-12-30 | Reaction35, LLC | Continuous process for converting natural gas to liquid hydrocarbons |
| US7998438B2 (en) | 2007-05-24 | 2011-08-16 | Grt, Inc. | Zone reactor incorporating reversible hydrogen halide capture and release |
| US8282810B2 (en) | 2008-06-13 | 2012-10-09 | Marathon Gtf Technology, Ltd. | Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery |
| US8273929B2 (en) | 2008-07-18 | 2012-09-25 | Grt, Inc. | Continuous process for converting natural gas to liquid hydrocarbons |
| US8415517B2 (en) | 2008-07-18 | 2013-04-09 | Grt, Inc. | Continuous process for converting natural gas to liquid hydrocarbons |
| US8198495B2 (en) | 2010-03-02 | 2012-06-12 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US9133078B2 (en) | 2010-03-02 | 2015-09-15 | Gtc Technology Us, Llc | Processes and systems for the staged synthesis of alkyl bromides |
| US8367884B2 (en) | 2010-03-02 | 2013-02-05 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8815050B2 (en) | 2011-03-22 | 2014-08-26 | Marathon Gtf Technology, Ltd. | Processes and systems for drying liquid bromine |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2120249B (en) | 1985-11-27 |
| GB8313007D0 (en) | 1983-06-15 |
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| PCNP | Patent ceased through non-payment of renewal fee |