NZ543189A

NZ543189A - Process for the simultaneous conversion of methane and organic oxygenate to C2 to C10 hydrocarbons

Info

Publication number: NZ543189A
Application number: NZ543189A
Authority: NZ
Inventors: Vasant Ramchandra Choudhary; Kartick Chandra Mondal; Shafeek Abdul Rashid Mulla
Original assignee: Council Scient Ind Res
Priority date: 2003-03-31
Filing date: 2003-03-31
Publication date: 2009-02-28

Abstract

Disclosed is a process for the simultaneous conversion of methane and organic oxygenate(s), represented by a general formula: CnH2n+1OCmH2m+1 wherein, C, H and O are carbon, hydrogen and oxygen elements, respectively; n is an integer having a value between 1 and 4; and m is an integer having a value between zero and 4, to C2-C10 hydrocarbons and hydrogen, the process comprises: i. contacting a gaseous feed comprising methane and at least one organic oxygenate with a methane to organic oxygenate mole ratio above 0.5, with a bifunctional pentasil zeolite catalyst essentially comprising at least one metallic element selected from the group consisting of Ga, In, Zn, Fe, Mo, Ag, Au, noble metals and rare earth elements, having strong acidic and dehydrogenation sites, such that the ratio of moles of methane converted to moles of organic oxygenate in the feed is at least 0.05, to obtain a product stream; ii. subjecting the product stream obtained in step (i) to condensation to condense normally liquid products containing liquid hydrocarbons and water therefrom, and separating the condensed liquid products from gaseous products in the product stream, to obtain liquid hydrocarbons and water and a gaseous product stream; iii. separating hydrogen from the gaseous product stream obtained in step (ii); and iv. recycling the gaseous product stream after separation of hydrogen in step (iii) to step (i), with or without the separation of normally gaseous C2+ hydrocarbons.

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number 543189 543189 WO 2004/087624 PCT/IN2003/000120 PROCESS FOR THE SIMULTANEOUS CONVERSION OF METHANE AND ORGANIC OXYGENATE TO C2 TO CM HYDROCARBONS Field of the invention This invention relates to a process for the production of C2 - C10 hydrocarbons and hydrogen simultaneously from methane and organic oxygenate(s). This invention particularly relates to a process for the production of C2 - Cjq hydrocarbons, particularly gasoline range C; - C10 hydrocarbons and hydrogen by the catalytic non-oxidative conversion of methane, simultaneously with the conversion of organic oxygenate(s), such as aliphatic alcohols and ethers, to gasoline range hydrocarbons using a Afunctional pentasil zeolite catalyst, having strong acidic and dehydrogenation functions. The process of this invention is useful in petroleum and petrochemical industries for production of Co - Ciq hydrocarbons; particularly gasoline range hydrocarbons, from natural gas, particularly that produced during the oil production in remote places, and also from methane produced in the number of petroleum refining and petrochemical processes. Backgrouud of the invention Methane is the major constituent of natural gas and also of biogas. World reserves of natural gas are constantly being upgraded and more and more natural gas is currently being discovered than oil. Because of the problems associated with transportation of a very large volume of gas, most of the natural gas produced along with oil, particularly, at remote places, and the methane produced in petroleum refining and petrochemical process are flared and hence wasted. Both methane and CO2 are green house gases, responsible for global warming. Ilence, in future the flaring of natural gas produced during the oil production and methane produced in the petroleum refining and petrochemical processes would not be allowed and hence the methane or natural gas is to be converted to useful value-added and easily transportable product like liquid hydrocarbons of gasoline range. The conversion of methane directly to higher hydrocarbons and aromatics is extremely difficult. If technologies are made available for the conversion of the natural gas or methane to easily transportable less volatile value added products such as aromatic hydrocarbons, a far reaching economic impact can be achieved which will also lead to exploration of more gas-rich field and also natural gas hydrates increasing the natural gas reserves. Gasoline and aromatic hydrocarbons are an important commodity in the petroleum and petrochemical industries. The most commercially important aromatics are benzene, toluene, ethyl benzene and xylenes. Aromatics are currently produced by catalytic reforming of various petroleum feed stocks and catalytic cracking of naphtha. Aromatics can also be 1 543189 WO 2004/087624 PCT/!IN2003/0(M >120 produced by catalytic conversion of alcohols (particularly methanol), olefins or lower alkalies (particularly propane, butanes or LPG). The catalyst used in these processes (methanol-to-gasoline Mobil's MTG process. olefms-to-gasoline-aftd-distiUate or MOGD or M2 forming, both developed by Mobil Oil, and LPG-to~aromatics conversion process or Cyciar Process developed by UOP) belong to the pentasil zeolite family, particularly that having ZSM-5 structure. An oxidative activation of methane for converting it directly to C2 -hydrocarbons, ethane and ethylene, is known in the prior art and It is described in a book {F„ E. Wolf "Methane Conversion by Oxidative Process: Fundamental and Engineering Aspects" Van NosLrand Trrnhold Catalysis Series, New York, (1992)} and also in a mimber or review articles {J. R. Aderson, Appl. Catal,, 47 (1989) 177; J. S. Lee et. al., Catal. Rev. -Sci. Eng., 30 (1988) 249; G. J. Hutchings et al. Cliem. Soc, Rev,. IB (1989) 25: J. H. Lunsford, Catal. Today 6 (1990) 235; J. H, Lunsford, Angew. Chem. ML Ed. Engl, 34 (1995)970}. According to a recent U.S. Pat, No. 5,336,825 (1984) of Choudhary V. R. and coworkers, methane can be converted to gasoline range hydrocarbons comprising aromatic hydrocarbons by carrying out the conversion of methane in the following two steps- Step (i): Catalytic oxidative conversion of methane to ethylene and minor amounts of C3 and €4 olefins in presence of free oxygen using a basic solid catalyst at a temperature preferably between 600°C and 850°C Step (ii): catalytic conversion of ethylene and higher olefins formed in the step (i) to liquid hydrocarbons of gasoline range over an acidic solid catalyst containing high silica pentasil. zeolite, using product stream of the step (I) as the feed. In the other multistep processes as described in Eur, Pat. Appln. BP 516,507 (1992) and Fr. Appl. 91/6,195 (1991), a methane rich fraction of natural gas is selectively oxidized, mixed with a Qh- hydrocarbon rich natural gas fraction, pyrolized and then the mixture is aromatized with, a catalyst based on zeolite and gallium. Ail the prior art teach the process for the oxidative activation of methane involves the following undesirable highly exothermic methane combustion reactions: Hence, these processes are hazardous in nature. Moreover, in these processes, undesirable carbon oxides, CO and CO?., are formed thus reducing the product selectivity and also creating environmental pollution problems and global warming by the release of CO2 in the atmosphere. CR, +202 CO> + 2H20 CR)+1.502 -»CO + 2HoO (1) (2) WO 2fl04/087<524 PCT/I N200Mti>0120 High temperature non-.oxidative conversion of methane to C2+ hydrocarbons is known in the prior art. It has been known for a long time that methane and natural gas can be pyrolytically converted to benzene at temperatures above 899CC (1659°F), preferably above 120G°C. A paper on "High Temperature Synthesis of Aromatics Hydrocarbons from Methane" published in Science 153 (1966) 1393 disclosed that aromatic hydrocarbons can be prepared from methane by contact with silica at 100Q°C. The yield of hydrocarbons was in the range of 4.8-7.2% based on the methane used in the single pass at a gas space velocity of 1224 h"1. More recent, a non-oxidative activation of methane by dehydrogenase coupling of methane over active carbon at temperature > 1100°C has been reported by H. Yagita et. al. [H. Yagita et. al.. in Environmental Catalysis. G, Centi et. aL Eds. SCI Publication. Rome, 1995. page 639-642). U.S. Pat. No. 4,814,533 (1989) discloses a continuous catalytic process for the production of higher molecular weight hydrocarbons rich in ethylene or aromatics or both, from lower molecular weight hydrocarbons or methane in which a lower molecular weight hydrocarbon containing gas is contacted in a reaction zom with a higher molecular weight hydrocarbon synthesis catalyst at a temperature greater than 1000°C. A recent Japanese Patent, Jpn. Kckai Tokkyo Koho JP. 07,1-55,600 (1995), discloses a process for the preparation of reaction media for aromatization and preparation of aromatics from methane at high temperature. The reaction media., which is prepared by thermal decomposition of cyelohexaae at 1050°C, was fed with methane at 1050*0 for 2 h to give benzene in 54.7% selectivity at 30.9% conversion. Because of the requirement of a high temperature for the conversion of methane and also due to the extensive coke formation at the .high reaction temperature, the above processes based on the non-axidative conversion of methane are difficult to practice and hence uneconomical. Catalytic aromatization of methane in the absence of O2 using zeolite catalyst is also known in the prior art. U.S. Pat. No. 4,727,206. GB Patent 8531687 and European Patent Application No. 0 228 267 Al disclosed the aromatization of methane by contacting with gallium loaded zeolite containing group VIIB metal or metal compound as a catalyst at a temperature from 600°C to 800T., preferably from 650°C to 775°C.S in the absence of oxygen, However, the conversion of methane into aromatics and the yield of the aromatics reported in the examples of these patents, are very low. At a weight hourly space velocity of 1,0 and absolute pressure of 7.0 3 543189 WO 2004/087624 PCT/IN2003/000120 bar, methane conversion at 675°C, 700°C and 750°C was 3.6 wt.%, 4.9 wt. % and 8.3 wt. %, respectively and aromatics yield was 2.0 wt. %. 2.53 wt. % and 2.95 wt, %, respectively. Because of the very low aromatics yield even at a temperature as high as 750°C, this process cannot be economically practiced. A U.S. Pat. No. 5,026,937 (1991) discloses a process for the aromatization of methane using a catalyst comprising about 0.1 to about 2 wt. % gallium containing ZSM zeolite and phosphorus-containing alumina, at a gas hourly space velocity of 400-7500 h"1 at relatively low temperature conditions. As per the illustrated example of this process, when the catalyst was contacted with a stream of 100 mole % methane at a flow rate of 1.4 h1 LIISV (liquid hourly space velocity) at 750°C and at atmospheric pressure, the overall methane conversion was 3.5 mole % in the single pass, the selectivity to C2+ hydrocarbons was 72%, and the selectivity to coke was 28%. Because of the very low methane conversion even at 750°C and low space velocity and also due to the very high selectivity to coke, this process is not economical. Because of the extensive coke formation, this process is also difficult to practice on a commercial basis. Although aromatization of methane at a temperature below 700°C is desirable for making the conversion of methane-to-aromatics process commercially more feasible, the aromatization of methane alone at the low temperatures is not at all thermodynamically possible. At a temperature below 700°C, the conversion of methane to benzene proceeds according to following reaction, 6CH4 -> C6Hfi + 9H2 (3) and involves a very large free energy change, AGr. The value of AGr, which is greater than 35 kcal per mole of benzene formed at or below 700°C, is much larger than zero. This high thermodynamic barrier does not allow the formation of benzene from methane at the lower temperatures. Hence, for the conversion of methane to aromatics at or below 700°C. it is necessary to find ways for overcoming the thermodynamic barrier and especially for the non-oxidative conversion of methane, which is the most inert of all of the hydrocarbons, at lower temperatures. A number of US patents 3, 928,483 (1975), 3,931,349 (1976), and 4,05,576 (1977), 4,046,825 (1977), and 4.138,440(1979), assigned to Mobil oil corporation disclosed process for the production of gasoline from methanol, other alcohol and ether, using shape selective ZSM-5 zeolite catalyst. A commercial plant based on Mobil's methanol-to-gasolme (MTG) process, involving production of methanol from methane via syngas route: methane steam reforming to syngas and syngas conversion to methanol, was also successfully operated in 4 WO 2004/087624 543189 PCMN2003/000120 New Zealand in 1985. However, the process economics was then not favourable to sustain the gasoline production. Since the commercial plant could not be operated economically, it was shut-down [Ref. J. Haggin, Methane-to-Gasoline Plant Adds to New Zealand Liquid Fuel Resources, Chemical & Engineering News page 22, June 22, 1987; J. H. Lunsford, The Catalytic Conversion of Methane to Higher Hydrocarbons. Catal. Today, vol. 6 page 235, (1990)]. It is therefore of the great challenge to inventors to develop not only technically feasible but also economically feasible process for the conversion of methane to higher hydrocarbons by finding a novel way for non-oxidative activating chemically inert methane, particularly at lower temperatures, below 700SC. Objects of the invention The main object of the present invention is therefore to provide a novel process for non-oxidative activation of methane at low temperature (below 700°C) and to convert methane to higher hydrocarbons. Another object of the invention is to provide a process for conversion of methane to higher hydrocarbons at temperature below 700°C, overcoming the thermodynamic barrier. It is a further or alternative object of the invention to provide a process which overcomes or ameliorates at least one of the abovementioned disadvantages of the prior art. The above objects of the invention are each to be read with the alternative object of to at least provide a useful choice. Summary of tlie invention The process of the present invention has been developed on the basis of our findings that in the presence of a Afunctional zeolite catalyst having dehydrogenation and acidic properties and in the presence of an aliphatic alcohol and / or ether with methane to alcohol or ether ratio above 0.5, the conversion of methane into higher hydrocarbons takes place at a temperature below 700°C, overcoming the thermodynamic barrier. The moles of methane converted per mole of alcohol or ether converted is found to be as high as 2.6 under the particular set of conditions. The conversion of methane in the process of the present invention can be explained by the alkylation reactions between methane and the alcohol or ether over the bifunctional zeolite (Ga-modified ZSM-5 zeolite), involving the activation of methane in the presence of alcohol or ether as follows: IT Z" H* T WO 2004/087624 543189 PCT/IN2003/000120 + h 27h* +CH3OR -» z~[ch30< ] r (5) .(where R=H or CH3) © ' + h -5 +8 z"[ch30 r (6) h ztch3+ + ch3or ^ zr [ch3—< f -► CH3CH2OR + Z"H+ (7) ch2or (ID The activation of methane is expected to result from a combined effect of the Ga-oxide species and zeolite protons or acid-base pairs (Z~ H*). The formation of methyl cations is then facilitated in the presence of oxonium cation (I), ultimately leading to the Because of fee involvement of high free energy change, AGr >35 kcal/mole of benzene, according to reaction 3, the direct formation of benzene from methane below 700°C is not possible thermodynamically. The thermodynamic barrier is, however, drastically reduced or even eliminated because of the addition of an aliphatic alcohol or ether in the feed; the value of AGr approaches to zero or even becomes negative, depending upon the additive and its concentration relative to that of methane and the temperature. Summary of the invention It has now been found by the present inventors due to exclusive research work that, by adding at least one aliphatic alcohol or ether or both to methane in the presence of a bifunctional pentasil zeolite catalyst, having strong dehydrogWiation and acid sites, the thermodynamic barrier for the aromatization of methane is overcome and the non-oxidative activation of methane, leading to its conversion to higher hydrocarbons, occurs below 700°C temperature. In one aspect, the present invention provides a process for the simultaneous conversion of methane and organic oxygenate(s), represented by a general formula: CnH2n+iOCmH2m+L wherein, C, H and O are carbon, hydrogen and oxygen elements, respectively; n is an integer having a value between 1 and 4; and m is an integer having a value between zero and 4, to C2-C10 hydrocarbons and hydrogen, the process comprises: formation of penta coordinated carbocations (H). 6 ^ 2 8 JAN 2009 n r ^ c l \/ C H 543189 WO 2004/087624 PCT/EN2003/O00120 i. contacting a gaseous feed comprising methane and at least one organic oxygenate with a methane to organic oxygenate mole ratio above 0.5, with a bifimctional pentasil zeolite catalyst essentially comprising at least one metallic element selected from the group consisting of Ga, In, Zn, Fe, Mo, Ag, Au, noble metals and rare earth elements, having strong acidic and dehydrogenation sites, such that the ratio of moles of methane converted to moles of organic oxygenate in the feed is at least 0.05, to obtain a product stream; ii. subjecting the product stream obtained in step (i) to condensation to condense normally liquid products containing liquid hydrocarbons and water therefrom, and separating the condensed liquid products from gaseous products in the product stream, to obtain liquid hydrocarbons and water and a gaseous product stream; iii. separating hydrogen from the gaseous product stream obtained in step (ii); and iv. recycling the gaseous product stream after separation of hydrogen in step (iii) to step (i), with or without the separation of normally gaseous C2+ hydrocarbons. In one embodiment, the invention provides a process for the simultaneous conversion of methane and organic oxygenate(s), represented by a general formula: CnH2n+lOCmH2M+l wherein, C, H and O are carbon, hydrogen and oxygen elements, respectively; n is an integer having a value between 1 and 4; and m is an integer having a value between zero and 4, to C2-Cio hydrocarbons and hydrogen, the process comprises: INTELLECTUAL PR0P1RTY OFFICE OF NX 2 8 m 2009 RECEIVE'D 6A WO 2004/087624 543189 PCT/IN20O3/OOO12O I) contacting with, a Afunctional pentasil zeolite catalyst essentially comprising at least one metallic element, selected from a group consisting of Ga, In, Zn, Fe, Mo, Ag, Au, noble metals and rare earth elements, having strong acidic and dehydrogenation sites, a gaseous feed comprising methane and at least one organic oxygenate, with ox without an inert gas, with a methane to organic oxygenate mole ratio above 0.5, at a gas hourly space velocity in the range from 100 cm3g_1h"1 to 10,000 cm3g"1h"1, at a temperature below 700°C and at a pressure of at least 1 atm, such that the ratio of moles of methane converted to moles of organic oxygenate in the feed is at least 0.05; ii) condensing the normally liquid products from the products stream obtained from step-i and separating liquid hydrocarbons and water from condensed liquid products; iii) separating hydrogen from the gaseous products obtained from step-ii; and iv) recycling to step-i the gas stream obtained from step-iii, with or without the separation of normally gaseous C2+ hydrocarbons. In the another embodiment of the invention, the zeolite catalyst is selected from Ga-and/or In-modified ZSM-5 type zeolites, such as Ga and/or In-impregnated H-ZSM-5, Ga-and/or In-exchanged ZSM-5, H-gaUoaluminosilicate of ZSM-5 type structure and H-gallosilicate of ZSM-5 type structure. In the another embodiment of the invention, the organic oxygenate is selected from a group of organic oxygenates, such as methanol, ethanol, dimethyl ether and diethyl ether. In the another embodiment of the invention, the organic oxygenate is methanol or ethanol. In the another embodiment of the invention, the methane to organic oxygenate mole ratio in the gaseous feed is between 1 and 25. In the another embodiment of the invention, the gas hourly space velocity of the gaseous feed is between 500 cm3g"1h"1 and 5000 cm3g"1h"1. In the other embodiment of the invention, the temperature employed in step-i is between 350°C and 650°C. In the another embodiment of the invention, the ratio of inert gas to methane in the feed in step-i is between zero to 1. In the another embodiment of the invention, the reaction in step-i is carried out in a single or multiple fixed-bed reactor or fluid bed reactor or moving bed reactor. In another aspect, the present invention provides a product produced by the process as defined in the previous aspect The main finding of this invention is that methane can be activated non-oxidatively and converted to higher hydrocarbons along with the conversion of an organic oxygenate, 543189 WO 2004/087624 PCT/IN2003/000120 such as aliphatic alcohol or ethers, to aromatics at a low temperature (below 700°C), using bifunctional pentasil zeolite catalyst having strong acidic and dehydrogenation functions. Other finding of this invention is that the moles of methane conversion per mole of oxygenate converted could be above 1.0, as high as 2.6 depending upon the process conditions. DETAILED DESCRIPTION OF THE INVENTION The present invention provides a process for the simultaneous conversion of methane and organic oxygenate(s), represented by a general formula: CnH2n+iOCmH2m+i wherein, C, H and 0 are carbon, hydrogen and oxygen elements, respectively; n is an integer having a value between 1 and 4; and m is an integer having a value between zero and 4, to C2-C10 hydrocarbons and hydrogen, the process comprises: i) contacting with a bifunctional pentasil zeolite catalyst essentially comprising at least one metallic element, selected from a group consisting of Ga, In, Zn, Fe, Mo, Ag, Au, noble metals and rare earth elements, having strong acidic and dehydrogenation sites, a gaseous feed comprising methane and at least one organic oxygenate, with or without an inert gas, with a organic oxygenate to methane to organic oxygenate mole ratio above 0.5, at a gas hourly space velocity in the range from 100 cm3g~1h~1 to -t _-j 10.000 cm g" h , at a temperature below 700°C and at a pressure of at least 1 atm, such that the ratio of moles of methane converted to moles of organic oxygenate in the feed is at least 0.05; ii) condensing the normally liquid products from the products stream obtained from step-i and separating liquid hydrocarbons and water from condensed liquid products; iii) separating hydrogen from the gaseous products obtained from step-ii; and iv) recycling to step-i the gas stream obtained from step-iii, with or without the separation of normally gaseous C2+ hydrocarbons. The bifunctional pentasil zeolite which may be employed in the process of the present invention may have ZSM-5, ZSM-8 or ZSM-11 type crystal structure consisting of a large number of 5-membered oxygen-rings, i.e., pentasil rings, which are more stable as compared to other 0-rings. The zeolite with ZSM-5 type structure is the more preferred catalyst. The ZSM-5, ZSM-8 and ZSM-11 type zeolite structures are all well known in the prior art and have unique shape-selective behavior. Zeolite ZSM-5 is described in greater detail in U.S. Pat No. 3,702,886. ZSM-11 zeolite is described in U.S. Pat. No. 3,709,979. ZSM-8 zeolite is described in Netherlands Patent 7,014,807 and U.S. Pat. No. 3,700,585. ZSM-5/ZSM-11 intermediate zeolite structures are described in U.S. Pat. No. 4,229,424. The 8 543189 WO 2004/087624 PCT/IN2003/000120 term "Zeolite" used herein is not only for microporous crystalline aluminosilicate but also for microporous crystalline galloaluminosilicates and gallosilicates. The bifunctional pentasil zeolite catalyst used may be preferably selected from the group consisting of Ga and/or In-modified ZSM-5 type zeolites such as Ga and/or In-impregnated H-ZSM-5, Ga and/or In-exchanged H-ZSM-5, H-gallosilicate of ZSM-5 type structure and H-galloaluminosilicate of ZSM-5 type structure. These zeolites can also be prepared by methods known in the prior art. The bifunctional ZSM-5 type pentasil zeolite used in the process of present invention contains tetrahedral aluminium and/or gallium, which are present in the zeolite framework or lattice, and octahedral gallium or indium, which is not present in the zeolite framework but present in the zeolite channels in a close vicinity of the zeolitic protonic acid sites, which are attributed to Hie presence of tetrahedral aluminium and gallium in the zeolite. The tetrahedral or framework Al and/or, Ga is responsible for the acid function of zeolite and octahedral or non-framework Ga and/ or In is responsible for the dehydrogenation function of the zeolite. The most effective and efficient bifunctional pentasil zeolite which can be used in the process of the present invention is H-galloalummosilicate of ZSM-5 type structure having framework (tetrahedral) Si/Al and Si/Ga mole ratio of about 10-100 and 15-150, respectively, and non-framework (octahedral) Ga of about 0.5-5.0 wt. %. These pentasil H-galloaluminosilicate zeolite can be prepared by procedures known in the prior art. When pentasil H-galloaluminosilicate zeolites are used, the density of strong acid sites can be controlled by the framework Af/Si mole ratio, the higher the Al/Si ratio, the higher is the density of strong acid sites. The highly dispersed non-framework gallium oxide species can be obtained by the degalliation of the zeolite by its pre-treatment with H.sub.2 and steam. The zeolite containing strong acid sites with high density and also highly-dispersed non-framework gallium oxide species in close proximity of the zeolite acid site is preferred for the process of the present invention. The catalyst may or may not contain any binder such as alumina, silica or clay material. The catalyst can be used in the form of pellets, extrudates and particles of different shapes and sizes. The examples of the organic oxygenate are methanol, ethanol, propanols, butanois. dimethyl ether, diethyl ether, dipropvl ether, dibutyl ether, methyl ethyl ether, methyl propyl ethers, methyl butyl ether and the like. The preferred organic oxygenate in the feed may be selected from methanol, ethanol, dimethyl ether and diethyl ether and more preferably from methanol and ethanol. 9 543189 WO 2004/087624 PCT'I?f20O3/OOO12O In the process of this invention, the preferred mole ratio of methane to organic oxygenate in the feed ranges from about 1.0 to about 25; the preferred gas hourly space velocity of the feed ranges from about 500 cm3 g^lr1 to about 5,000 cm':'g "h"1; the preferred temperature ranges from 350°C to 650°C; and the preferred ratio of inert gas to methane in the feed is between zero to 1.0. Products of fee process of this invention are mainly water, and 0^ and Cio aromatics with smaller amounts of ethylene, ethane, propylene, propane and C4 hydrocarbons and traces of C5+ aliphatic hydrocarbons. Water is formed by dehydration of said organic oxygenate, The presence of oxygenate in the feed is essential in the process of this inventions. In absence of said organic oxygenate methane is not converted in tire process of this invention. The role of the bifunctional pentasil zeolite catalyst is to activate both methane and said oxygenate and convert then into the products. The carbon deposited on the catalyst of the process of this invention can be removed by oxidizing it by an oxygen containing gas. In the process of this invention, the feed comprising methane and said one or more organic oxygenates may be contacted with the catalyst in a single or multiple fixed bed reactors, fluid bed reactor or moving bed reactor, known in the prior art. in the process of this invention, the normally gaseous products from the normally liquid products are separated from each other by known prior art method. Also, the water from the liquid products and the hydrogen jk»m the gaseous products are asperated by method known in the prior art. Terms used in this specification have following meanings. Framework Si means Si present in the lattice of the zeolite. Framework Al or Ga means the Tetrahedral Al or Ga present in the lattice of the zeolite. Non-framework Ga means octahedral Ga present in the zeolite channels. Gas hourly space velocity, (GHSV) means volume of feed gases, measured at 0.°.C and 1 aim pressure, passed over a unit mass of catalyst per hour. Conversion, %, means weight percent of a particular reactant converted to all the products. Product Selectivity, %=[(percent of reactant or reactants converted to a particular product -r percent of reactant or reactants converted to all products)] X 100. When nitrogen is used in the feed of the invented proeess, the methane conversion (%} was obtained from the CH4/N2. mole ratios in the feed and products as follows: Methane conversion (%) = 100 x [(CH+ZN^sd - (CH^/Ns^fo&rets] {(CI-Lj/Nz^eed] Conversion given in the examples is per pass conversion. The present invention is described with reference to the examples given below which are provided to illustrate the invention only and, therefore, should not be construed to limit the scope of the invention. 10 543189 WO 2004/087624 PCT/IN2003/000120 EXAMPLE 1 This example illustrates the catalytic process of the present invention for the low temperature non-oxidative conversion of methane and thereby converting it directly to higher hydrocarbons or aromatics using methanol as an additive in the feed comprising methane, and using ZSM-5 type H-galloaluminosilicate zeolite having bulk Si/Ga=24.3, bulk Si/Al=40.3, framework Si/Ga=49.9, framework Si/Al=40.3, Na/(Al+Ga)-0,03, non-framework Ga~0.32 mmol g~', crystal morphology or shape^spherical-hexagonal, crystal size=5.5 ±1.5 um and strong acid sites measured in terms of pyridine chemisorbed at 400°C = 0.46 mmol g"1. All the ratio are mole ratios. The zeolite was prepared by process described in European Patent Application EP 0124271 and in the reference: Choudhary et.al. J. Catal. 158 (1996) 23. A conventional tubular quartz reactor of 12 mm internal diameter packed with the zeolite catalyst of 30-52 mesh size particles and kept in the tubular electrical furnace such that the catalyst is in a constant temperature zone of the furnace, was used for illustrating the process. The catalytic process is carried out by passing continuously a mixture of methane and N2 with or without methanol additive in the feed over the zeolite catalyst at the process conditions given in Table 1. The reactor or reaction temperature was measured by Chromel-Alumel thermocouple located axially in the catalyst bed. The reaction gaseous products after the removal of water and normally liquid hydrocarbons formed in. the reaction by condensation at 2°C, the liquid hydrocarbons and the feed were analyzed by an on-line gas ehromatograph with thermal conductivity and flame ionized detectors and computing integrator, using a 3 mm x 3 m Poropak-Q column for separating Q - Ci hydrocarbons and using a 3 mm x 5 m column containing 5 % Benton-34 - 5 % dinonyphthalate on chromosorb-W for separating aromatic hydrocarbons. Conversion data were obtained from the feed and product composition, as follows: conversion (%)-{(moles of reactant in the feed - moles of reactant in the products) + (moles of reactant in the feed hydrocarbons)} xl 00. The results are presented in Table 1. The results in the Table 1 clearly show that, in the absence of methanol (experiment no. 2), the conversion of methane in the process is zero and hence there is no conversion of methane at 600°C and consequently below (SOOT. But when methanol is added to the feed (experiment no. 1), the thermodynamic barrier is overcome and the methane from the feed is activated even at 540°C and thereby it is converted to higher hydrocarbons or aromatics with a high ratio of methane converted per mole of methanol converted. The methanol additive from the feed is completely converted to hydrocarbons, water and hydrogen. There was no formation of carbon dioxide in the reaction. 11 543189 WO 2004/087624 PCT/IN2003/000120 Table 1: Results of the conversion of methane to C2+ hydrocarbons and hydrogen in the presence and absence of methanol in the feed. Experiment no.: 1 2 Reaction conditions Methanol/Methane mole ratio in feed 0.15 0.0 N2 /Methane mole ratio in feed 0.08 0.08 Feed gas space velocity (cm?g~,h~1) 1090 1090 Temperature (°C) 540 600 Pressure (atm) 1.3 1.3 Conversion of methane (%) 10.1 0.0 Conversion of methanol (%) 100 - Methane converted/ methanol converted (mol/mol) ratio 0.70 - Distribution of hvdrocarbons in the hydrocarbon products (\vt.%) Methane 81.4 100 Ethylene 0.46 0.0 Ethane 0.17 0.0 C3 hydrocarbons 0.52 0.0 C4 hydrocarbons 0.05 0.0 Cs+ aliphatics 0.02 0.0 Benzene 1.29 0.0 Toluene 5.99 0.0 Cs aromatics 7.16 0.0 C9 aromatics 2.84 0.0 C10 aromatics 0.14 0.0 H2 produced 7.5 0.0 (mmol.g 'h ') 12 543189 WO 2004/087624 PCT/"iN20fl3/0«>120 EXAMPLES - 2 to 9 These examples illustrate the influence of process conditions, such as methane'methanol mole ratio in the feed, reaction temperature and gas hourly space velocity, GHSV, on the conversion of methane and methanol present in the feed and also on the methane converted per mole of methanol converted in the process of this invention. The catalytic process of this invention was carried out by the reactor and procedures described in EXAMPLE -1 and using the catalyst of Example-1, at the different process conditions, given in Tables 2 and 3. The results are presented in Tables 2 and 3. Table 2: Results of the simultaneous conversion of methane and methanol over the catalyst of Exaraplel at different process conditions Example No. o * 4 5 Catalyst used Catalyst Example I of Catalyst of Example 1 Catalyst of Example 1 Catalyst of Example 1 Organic oxygenate used Methanol Methanol Methanol Methanol Reaction conditions Methane/methanol mole ratio in feed n-i « 24.0 11.9 6.8 N? /methane mole ratio in feed 0.083 0.084 0.082 0.080 GHSV (cmY'lf1) 1080 1080 1080 '1070 Temperature (°C) 560 532 558 540 Pressure (atm) 1.3 1.3 1.2 1.3 Conversion of methane (%) 10.8 10.6 9.2 10.9 Conversion of methanol (%) 100 100 100 100 Methane converted/ methanol converted (mol/mol) ratio 2.6 2.5 LI 0.74 13 543189 WO 2004/087624 PCT'I?f2803/000120 Table 3: Results of the simultaneous conversion of methane and methanol over the catalyst of Example 1 at different process conditions Example No. 6 n j 8 9 Catalyst used Catalyst Example 1 of Catalyst of Example 1 Catalyst of Example 1 Catalyst of Example 1 Organic oxygenate used Methanol Methanol Methanol Methanol Reaction conditions Metlraae/methanol mole ratio in feed 6.9 7.0 6,8 6.9 N> /methane mole ratio in feed 0.081 0.084 0.05 0.0 GHSV (cin3g-1h-1) 2700 540 550 1795 Temperature PC) 545 470 530 585 Pressure (aim) 1.4 1:2 1.3 1.2 Con version of methane (%) 9.8 4.7 10.6 11.8 Conversion of methanol to i hydrocarbons {%) 100 100 100 100 Methane converted./ methanol converted (mol/mol) ratio 0.71 0.3 0.72 0.82 EXAMPLES - 10 to 13 These examples illustrates the use of the ethanol instead of methanol as an organic oxygenate additive to the feed comprising methane in the process of this invention. The catalytic process of this invention was carried out by the procedure described in the EXAMPLE-1 and using the same catalyst and reactor described in EXAMPLE-1, except 14 543189 WO 2004/087624 PCT/IN2003/000120 at ethanol is used instead of methanol and process conditions arc different, as given in Table 4. The results are presented in Table 4. Table 4: Results of the simultaneous conversion of methane and ethanol over the catalyst of Example 1 at different process conditions Example No. 10 11 12 13 Catalyst used Catalyst Example 1 of Catalyst of Example 1 Catalyst of Example 1 Catalyst of Example I Organic oxygenate used Ethanol Ethanol Ethanol Ethanol Reaction conditions Methane/ethanol mole ratio in feed 9.8 9.7 9.8 9.6 N? /methane mole ratio in feed 0.082 0.084 0.083 0.081 GHSV (emV lh_1) 1040 1040 1040 1050 Temperature (°C) 615 480 580 560 Pressure (atm.) 1.3 1.3 1.3 1.2 Conversion of methane (%) 15.3 2.2 13.2 5.1 Conversion of ethanol to hydrocarbons (%) 100 100 100 100 Methane converted/ ethanol converted (mol/mol) ratio 1.5 0.21 1.3 0.5 EXAMPLES - 14 to 17 These examples illustrates the use of the diethyl ether instead of methanol as an organic oxygenate additive to the feed comprising methane in the process of this invention. The catalytic process of this invention was carried out by the procedure described in the EXAMPLE-! and using the same catalyst and reactor described in EXAMPLE-1, except 15 543189 WO 2004/087624 PCT/IN2003/000120 then diethyl ether is used instead of methanol and process conditions are different, as given in Table 5. The results are presented in Table 5, Table 5: Results of the simultaneous conversion of methane and diethyl ether over the catalyst of Examplel at different process conditions Example No. 14 15 16 17 Catalyst used Catalyst of Example 1 Catalyst of Example 1 Catalyst of Example 1 Catalyst of Example 1 Organic oxygenate used Diethyl ether Diethyl ether Diethyl ether Diethyl ether Reaction conditions Methane/diethyl ether mole ratio in feed 17.5 17.4 17.5 17.3 N? /methane mole ratio in feed 0.08 0.08 0.08 0.08 GHSV (ctnYV) 1090 1090 1095 1100 Temperature (°C) 633 560 610 650 .Pressure (atm.) 1.3 1.2 1.3 1.2 Conversion of methane (%) 14.3 3.7 12.8 8.5 Conversion of diethyl ether to hydrocarbons (%) 100 100 100 100 Methane converted/ diethyl ether converted (mol/mol) ratio 1.61 0.42 1.44 1.0 EXAMPLES -IS to 21 These examples further illustrate the process of this invention, using, Ga/H-ZSM-5 zeolite catalyst (with Si/Al = 35, Ga-loading: 1.0 wt.%, strong acid sites measured in terms of pyridine chemisorbed at 400°C = 0.28 mmol.g-1). The preparation and characterization of the zeolite catalyst are given elsewhere [ref. Choudhary, et.al. Microporous Mesoporous Material 37 (2000) 1-8] The process over the catalyst was carried out using the reactor and procedures similar to that used in Example 1 at the process conditions given in Table 6. The results are presented in Table 6. 16 543189 WO 2004/087624 PCT/IN2003/00012(1 Table 6: Results of the simultaneous conversion of methane and methanol over the Ga/H~ZSM-5 catalyst at different process conditions Example No, 18 19 20 21 Organic oxygenate used Methanol Methanol Methanol Methanol j Reaction conditions Methane/metkanol mole ratio in feed 6,9 6.8 6.8 6.8 j i : Nj /methane mole ratio in feed 0.08 o.os 0.08 0.08 GHSV (cmV'h"1) 1080 1090 1100 < 1040 Temperature (°C) 560 610 580 530 Pressure (atm.) 1,2 1.3 1.3 1.4 Conversion of methane (%) 10.3 8,7 9.5 8.0 Conversion of methanol to hydrocarbons (%) 100 100 100 100 Methane converted/ methanol converted (mol/mol) ratio 0.7 0.6 0.65 0.56 EXAMPLES - 22 and 23 These examples further illustrate the process of this invention using In/II-ZSM-5 (with Si/Al = 20, In-loading 0.11 mmolg"1 and strong acid sites measured in terms of pyridine chemisorbed at 400°C ~ 0.32 mmol.g4) zeolite catalyst. The catalyst was prepared and characterized by the methods similar to that used for the Ga/H-ZSM-5 zeolite catalyst used in Examples- 18 to 21, except that instead of gallium nitrate, Indium nitrate was used in the catalyst preparation. 17 543189 WO 2004/087624 PCT/I?f2003/000120 The process over the catalyst was carried out using the reactor and procedures similar to that used in EXAMPLE 1 at the process conditions green in Table 7. The results are presented in Table 7. Table 7: Results of the simultaneous conversion of methane utul methanol over the ln/li-ZSM- 5 catalyst at different process conditions Example No. 22 23 Organic oxygenate used Methanol Methanol Reaction conditions Methane/methanol mole ratio in feed 6.8 - ^ Ni/methane mole ratio in feed 0.085 0.084 GHSV (cm3g"'h~5) 1090 1080 Temperature C'C) 503 530 Pressure (atm.) 1.3 1.4 Conversion of methane (%) 6.7 9.0 Conversion of methanol to hydrocarbons (%) 100 100 Methane converted/ methanol converted (mol/mol) ratio 0.46 1.1 EXAMPLES-24 to 27 These examples illustrate the use of H-gallosilicate (ZSM-5 type) (bulk Si/'Ga ~ 30.1, concentration of non-framework Ga = 1.5 wt.% and strong acid sites measured in terms of the pyridine chemisorbed at 400°C ~ 0.25), preparation of which described by Choudhary et. a3 [ref, Choudhary et.al. Appl,Catal.A: Gen 162 (1997) 239-248], in the process of this invention. Tlie process over the catalyst was carried out using the reactor and procedures similar to that used in EXAMPLE 1 at the process conditions given in Table 8. The results are presented in Table 8. 18 543189 WO 2004/087624 PC 171N2003/H00120 Table 8: Results of the simultaneous conversion of methane and methanol or dimethyl ether over the H-gallosilicate (ZSM-5 type) zeolite catalyst at different process conditions Example No. 24 25 26 Organic oxygenate used Methanol Methanol Methanol Reaction conditions Methane/methanol mole ratio in feed 6.82 6.81 6.B N?/methane mole ratio in feed 0.084 0.082 0.083 GHSV (cm3g"!ir;) 1075 1090 1080 Temperature (°C) 607 635 555 Pressure (atm.) 1.3 1.3 1.3 Conversion of methane (%) 9.5 7.5 5.2 Conversion of methanol to hydrocarbons (%) 100 100 100 Methane converted/ methanol converted (mol/mol) ratio 0.65 0.51 0.35 EXAMPLES 28 to 30 These examples further illustrate the process of this invention, using Pt. Zn.Ga/II-ZSM-5 zeolite catalyst (with Si/Al = 20, loading of Pt, Zn and Ga = 0.1, 1.5 and 0.7 wt.%, respectively, and strong acid sites measured in terras of the pyridine chemisorbed at 400°C = 0.33 mmol.g"1). The process over the catalyst was carried out using the reactor and procedures similar to that described in EXAMPLE 1 at the process conditions given in Table 9. The results are presented in Table 9. The catalyst was prepared by impregnating 0.05 mmol of H^PtClg, 2.3 mmoles of Zinc nitrate and 1.0 mmoles of gallium nitrate from their aqueous solution on 10 g H-ZSM-5 19 543189 WO 2004/087624 PCT/IN2003/00012(1 zeolites (with Si/Al = 20 and Ka/AI < 0.03), drying and then calcining the impregnated zeolite at 60GC'C for 2 h. Table 9: Results of the simultaneous conversion of methaae and methanol or ethanol or dimethyl ether over the Pt.Zn.Ga/H-ZSM-5 catalyst at different process conditions Example No. 28 29 30 Organic oxygenate used Methanol Ethanol Diethyl ether Reaction conditions Methane/oxygenate mole ratio in feed 24.0 9.9 10.2 N? /methane mole ratio in reed 0.082 0.0 0.083 j GHSV (cmY'h !) 1100 1010 1070 Temperature (°C) 570 581 575 Pressure (atm.) 1.3 1.3 1,3 Conversion of methane (%) 11.0 13.3 13.5 Conversion of oxygenate to hydrocarbons (%) 100 100 100 Methane converted/ oxygenate 2.6 1.4 1.5 All the above examples illustrated that methane can be converted simultaneously -with the conversion of methanol, ethanol, n-butanol, diethyl ether or dimethyl ether over bifunctional pentasil (ZSM-5) zeolite catalyst at a temperature much lower than 700°C. with the ratio of the methane converted to the oxygenate converted ill the range from 0.2 to 2.5, depending upon tlie catalyst and process conditions employed in the process of this invention. Novel features and advantages of the process of this invention over the prior art processes for methane conversion or methanol-to-gasoline conversion are as follows: i) Because of the high thermodynamic barrier, the direct conversion of methane to aromatics or higher hydrocarbons at or below 700°C temperature in the absence of oxygen or other oxidizing agent is not possible thermodynamieally. By the process of the present invention, the thermodynamic barrier is overcome and methane can be converted non-oxidatively below 700°C temperature to higher hydrocarbons simultaneously with the aromatization of organic oxygenate, such as methanol, dimethyl ether, ethanol, diethyl ether and the like. 20 </div>

Claims

<div class="application article clearfix printTableText" id="claims"> WO 2004/087624 543189 PCT/IN2003/000120 ii) In the process of the present invention, the catalyst used for the low temperature non-oxidation conversion is a bifunctional pentasil zeolite having both strong acid dehydrogenation properties, which facilitate the conversion of methane to higher hydrocarbon at low temperatures and at non-oxidative conditions. iii) By the process of this invention, the methane present in the feed can be converted to higher hydrocarbons or aromatics with a high mole ratio of the methane converted to the methanol converted. Methane converted per mole of methanol consumed in process is as high as 2.5 or more. Hence, the present process drastically enhances the economics of the prior art Methanol—To-Gasoline (MTG) conversion process. iv) By the process of this invention, methane which is the most inert hydrocarbon and which is difficult to activate for direct conversion to higher hydrocarbons can be converted to higher hydrocarbon or aromatics at low temperatures, below 700°C. v) Unlike the prior art processes, involving oxidative activation of methane, the process of this invention does not produce undesirable carbon dioxide, which is a green house gas, responsible for global wanning. Hence, the present process is environmentally The organic oxygenates, particularly methanol, dimethyl ether, ethanol or butanol added in the feed of this invention can be produced from natural gas and/or renewable resources; for example, methanol and dimethyl ether can be produced firom natural gas or methane or biogas (obtained from renewable sources) and ethanol or butanol can be produced by fermentation using renewable natural resources. Throughout this specification, unless the context requires otherwise, the words "comprise", "comprising" and the like, are to be construed in an inclusive sense as opposed to an exclusive sense, that is to say, in the sense of "including, but not limited to". The reference to any prior art in this specification is not, and should not be taken as, an acknowledgment or any form of suggestion that that prior art forms part of the common general knowledge in New Zealand. friendly. 2 8 JAN 2009 21 WO 2004/087624 543189 PCT/IN2003/000120 We claim:

1. A process for the simultaneous conversion of methane and organic oxygenate(s)3 represented by a general formula: CnH^iOQnH^i wherein, C, H and O are carbon, hydrogen and oxygen elements, respectively; n is an integer having a value between 1 and 4; and m is an integer having a value between zero and 4, to C2-C10 hydrocarbons and hydrogen, the process comprises: i. contacting a gaseous feed comprising methane and at least one organic oxygenate with a methane to organic oxygenate mole ratio above 0.5, with a bifunctional pentasil zeolite catalyst essentially comprising at least one metallic element . selected from the group consisting of Ga, In, Zn, Fe, Mo, Ag, Au, noble metals and rare earth elements, having strong acidic and dehydrogenation sites, such that the ratio of moles of methane converted to moles of organic oxygenate in the feed is at least 0.05, to obtain a product stream; ii. subjecting the product stream obtained in step (i) to condensation to condense normally liquid products containing liquid hydrocarbons and water therefrom, and separating the condensed liquid products from gaseous products in the product stream, to obtain liquid hydrocarbons and water and a gaseous product stream; iii. separating hydrogen from the gaseous product stream obtained in step (ii); and iv. recycling the gaseous product stream after separation of hydrogen in step (iii) to step (i), with or without the separation of normally gaseous C2+ hydrocarbons.

2. A process as claimed in claim 1 wherein the contacting in step (i) is carried out at a gas hourly space velocity in the range from 100 cm3g_1h"1 to 10,000 cmVV1, at a temperature below 700°C and at a pressure of at least 1 atm,

3. A process as claimed in claim 2 wherein the gas hourly space velocity of the gaseous feed is between 500 cm3g"1h"1 and 5000 cm3g"1h"1.

4. A process as claimed in claim 2 wherein the temperature employed in step (i) is between 350°C and 650°C.

5. A process as claimed in any one of claims 1 to 4 wherein the zeolite catalyst comprises a ZSM - 5 catalyst modified by Ga and/or In.

6. A process as claimed in claim 5 wherein the Ga and/or In modified ZSM-5 catalyst is selected from the group consisting of Ga and/or In-impregnated H-ZSM-5, Ga-and/or In-exchanged ZSM-5, H-galloaluminosilicate of ZSM-5 type structure and H-gallosilicate of ZSM-5 type structure. IHITELLECTUAL PROPERTY i 22 1 OFFICE OF N.Z. J 1 28 JAM 2009 \ In cr e 1 \1 F D! WO 2004/087624 543189 PCT/IN2003/000120

7. A process as claimed in any one of claims 1 to 6 wherein the organic oxygenate is selected from the group consisting of methanol, ethanol, dimethyl ether and diethyl ether.

8. A process as claimed in claim 7 wherein the organic oxygenate is selected from methanol and ethanol.

9. A process as claimed in any one of claims 1 to 8 wherein the methane to organic oxygenate mole ratio in the gaseous feed is between 1 and 25.

10. A process as claimed in any one of claims 1 to 9 wherein the contacting in step (i) is carried out in the presence of an inert gas.

11. A process as claimed in claim 10 wherein the ratio of inert gas to methane in the feed in step (i) is up to 1.

12. A process as claimed in any one of claims 1 to 11 wherein the contacting in step (i) is carried out in a single or multiple fixed-bed reactor or fluid bed reactor or moving bed reactor.

13. A process as claimed in any one of claims 1 to 12 wherein the moles of methane conversion per mole of oxygenate converted is between 1.0 to 2.6.

14. A product produced by the process as defined in any one of claims 1 to 13.

15. A process as claimed in claim 1 substantially as hereinbefore described with particular reference to any one of the examples.

16. A product as claimed in claim 14 substantially as hereinbefore described with particular reference to any one of the examples. INTELLECTUAL WQSW j OFFICE OP NA 2 8 JAN 2009 RECEIVED 23 </div>