Patent Application
20120296132
The present invention relates to a method for the production of styrene and ethylbenzene. More specifically, the invention relates to the alkylation of toluene with a carbon source (herein referred to as a C1 source) such as methanol and/or formaldehyde, to produce styrene and ethylbenzene.
Styrene is a monomer used in the manufacture of many plastics. Styrene is commonly produced by making ethylbenzene, which is then dehydrogenated to produce styrene. Ethylbenzene is typically formed by one or more aromatic conversion processes involving the alkylation of benzene.
Aromatic conversion processes, which are typically carried out utilizing a molecular sieve type catalyst, are well known in the chemical processing industry. Such aromatic conversion processes include the alkylation of aromatic compounds such as benzene with ethylene to produce alkyl aromatics such as ethylbenzene. Typically an alkylation reactor, which can produce a mixture of monoalkyl and polyalkyl benzenes, will be coupled with a transalkylation reactor for the conversion of polyalkyl benzenes to monoalkyl benzenes. The transalkylation process is operated under conditions to cause disproportionation of the polyalkylated aromatic fraction, which can produce a product having an enhanced ethylbenzene content and reduced polyalkylated content. When both alkylation and transalkylation processes are used, two separate reactors, each with its own catalyst, can be employed for each of the processes.
Ethylene is obtained predominantly from the thermal cracking of hydrocarbons, such as ethane, propane, butane, or naphtha. Ethylene can also be produced and recovered from various refinery processes. Thermal cracking and separation technologies for the production of relatively pure ethylene can account for a significant portion of the total ethylbenzene production costs.
Benzene can be obtained from the hydrodealkylation of toluene that involves heating a mixture of toluene with excess hydrogen to elevated temperatures (for example 500° C. to 600° C.) in the presence of a catalyst. Under these conditions, toluene can undergo dealkylation according to the chemical equation: C6H5CH3+H2→C6H6+CH4. This reaction requires energy input and as can be seen from the above equation, produces methane as a byproduct, which is typically separated and may be used as heating fuel for the process.
Another known process includes the alkylation of toluene to produce styrene and ethylbenzene. In this alkylation process, various aluminosilicate catalysts are utilized to react methanol and toluene to produce styrene and ethylbenzene. However, such processes have been characterized by having very low yields in addition to having very low selectivity to styrene and ethylbenzene.
Additionally, in a conventional process including the alkylation of toluene with methanol, a significant amount of hydrogen can form. The formation of a significant amount of hydrogen can be undesirable in the production of styrene by the alkylation of toluene with methanol. At least a portion of the hydrogen formed can hydrogenate the styrene to ethylbenzene.
Also, the aluminosilicate catalysts can be prepared using solutions of acetone and other highly flammable organic substances, which can be hazardous and require additional drying steps. For instance an aluminosilicate catalyst can include various promoters supported on a zeolitic substrate. These catalysts can be prepared by subjecting the zeolite to an ion-exchange in an aqueous solution followed by a promoter metal impregnation using acetone. This method requires an intermediate drying step after the ion-exchange to remove all water prior to the promoter metal impregnation with acetone. After the promoter metal impregnation the catalyst is subjected to a further drying step to remove all acetone. This intermediate drying step typically involves heating to at least 150° C., which results in increased costs.
In view of the above, it would be desirable to have a process of producing styrene and/or ethylbenzene that does not rely on thermal crackers and expensive separation technologies as a source of ethylene. It would further be desirable to avoid the process of converting toluene to benzene with its inherent expense and loss of a carbon atom to form methane. It would be desirable to produce styrene without the use of benzene and ethylene as feedstreams. It would also be desirable to produce styrene and/or ethylbenzene in one reactor without the need for separate reactors requiring additional separation steps. Furthermore, it is desirable to achieve a process having a high yield and selectivity to styrene and ethylbenzene. Even further, it is desirable to achieve a process having a high yield and selectivity to styrene such that the step of dehydrogenation of ethylbenzene to produce styrene can be reduced. It is further desirable to be able to produce a catalyst having the properties desired without involving flammable materials and/or intermediate drying steps.
The present invention in its many embodiments relates to a process of making styrene. In an embodiment of the present invention, a process is provided for making styrene including reacting toluene with a C1 source in the presence of a catalyst and a co-feed including at least one oxidizing agent in a first reactor to form a product stream including ethylbenzene and styrene. Optionally, the process can include re-oxidizing the de-oxidized oxidizing agent and recycling the re-oxidized oxidizing agent to the first reactor.
In an embodiment, either by itself or in combination with any other embodiment, the co-feed can be selected from the group of oxygen, air, nitrobenzene, quinones, anthracene, nitrous oxide, and combinations thereof. The co-feed can be added to the catalyst prior to the toluene and the C1 source. Optionally, the co-feed is simultaneously fed to the reactor with the toluene and the C1 source. The co-feed can be present in amounts of C1 source:co-feed molar ratio ranging from 100:1 to 1:1. Optionally, the co-feed is present in the first reactor of at least 30 mol % of the total feed stream, wherein the total feed stream comprises toluene, the C1 source and the co-feed.
In an embodiment, either by itself or in combination with any other embodiment, the C1 source is selected from the group of methanol, formaldehyde, formalin, trioxane, methylformcel, paraformaldehyde, methylal, and combinations thereof. The C1 source can include formaldehyde produced by the oxidation of methanol with an oxygen feed in a preliminary reactor, and the co-feed can include oxygen. The oxygen feed and the co-feed are provided from a common source. Optionally, the C1 source includes formaldehyde produced by the dehydrogenation or oxidation of methanol, and the co-feed is selected from the group of oxygen, air, nitrobenzene, quinones, anthracene, and combinations thereof.
In an embodiment, either by itself or in combination with any other embodiment, the catalyst includes at least one promoter on a support material. The promoter can be selected from the group of Co, Mn, Ti, Zr, V, Nb, K, Cs, Ga, B, P, Rb, Ag, Na, Cu, Mg, Fe, Mo, Ce, and combinations thereof. Optionally, the promoter is selected from the group of Ce, Cu, P, Cs, B, Co, Ga, and combinations thereof. The support material can include a zeolite. The catalyst can include B and Cs supported on a zeolite.
Another embodiment of the present invention includes a method of making styrene. The method includes contacting a catalyst with a co-feed including at least one oxidizing agent in a first reactor to obtain a treated catalyst; contacting the treated catalyst with a reactant feed stream including toluene and a C1 source; and reacting the toluene with the C1 source in the presence of the treated catalyst to form a product stream including ethylbenzene and styrene and, optionally, the oxidizing agent, wherein the oxidizing agent is de-oxidized. The C1 source is selected from the group of methanol, formaldehyde, formalin, trioxane, methylformcel, paraformaldehyde, methylal, dimethyl ether, and combinations thereof. Optionally, the method includes re-oxidizing the de-oxidized oxidizing agent and recycling the re-oxidized oxidizing agent to the first reactor.
In an embodiment, either by itself or in combination with any other embodiment, the co-feed is selected from the group of oxygen, air, nitrobenzene, quinones, anthracene, nitrous oxide, and combinations thereof. The catalyst can include at least one promoter supported on a zeolite. The promoter can be selected from the group of Co, Mn, Ti, Zr, V, Nb, K, Cs, Ga, B, P, Rb, Ag, Na, Cu, Mg, Fe, Mo, Ce, and combinations thereof
In yet another embodiment of the present invention, a process is provided for producing styrene including reacting toluene with a C1 source in the presence of a catalyst and a co-feed including at least one oxidizing agent in a first reactor to form a product stream including ethylbenzene and styrene and, optionally, at least one de-oxidized oxidizing agent. The C1 source is selected from the group of methanol, formaldehyde, formalin, trioxane, methylformcel, paraformaldehyde, methylal, dimethyl ether, and combinations thereof. The catalyst includes boron and cesium supported on an X-type zeolite, and the co-feed is selected from the group of oxygen, air, nitrobenzene, quinones, anthracene, nitrous oxide, and combinations thereof
The various embodiments of the present invention can be joined in combination with other embodiments of the invention and the listed embodiments herein are not meant to limit the invention. All combinations of embodiments of the invention are enabled, even if not given in a particular example herein.
In accordance with an embodiment of the current invention, toluene is reacted with a carbon source capable of coupling with toluene to form ethylbenzene or styrene, which can be referred to as a C1 source, in the presence of a co-feed to produce styrene and ethylbenzene. In an embodiment, the C1 source includes methanol or formaldehyde or a mixture of the two. In an embodiment, the co-feed includes an oxidant. In an alternative embodiment, toluene is reacted with one or more of the following: formalin, trioxane, methylformcel, paraformaldehyde and methylal. In a further embodiment, the C1 source is selected from the group of methanol, formaldehyde, formalin (37-50% H2CO in solution of water and methanol), trioxane (1,3,5-trioxane), methylformcel (55% H2CO in methanol), paraformaldehyde and methylal (dimethoxymethane), dimethyl ether, and combinations thereof
Formaldehyde can be produced either by the oxidation or dehydrogenation of methanol.
In an embodiment, formaldehyde is produced by the dehydrogenation of methanol to produce formaldehyde and hydrogen gas. This reaction step produces a dry formaldehyde stream that may be preferred, as it would not require the separation of the water prior to the reaction of the formaldehyde with toluene. The dehydrogenation process is described in the equation below:
CH3OH→CH2O+H2
Formaldehyde can also be produced by the oxidation of methanol to produce formaldehyde and water. The oxidation of methanol is described in the equation below:
2 CH3OH +O2→2 CH2O+2 H2O
In the case of using a separate process to obtain formaldehyde, a separation unit may then be used in order to separate the formaldehyde from the hydrogen gas or water from the formaldehyde and unreacted methanol prior to reacting the formaldehyde with toluene for the production of styrene. This separation would inhibit the hydrogenation of the formaldehyde back to methanol. Purified formaldehyde could then be sent to a styrene reactor and the unreacted methanol could be recycled.
Although the reaction has a 1:1 molar ratio of toluene and the C1 source, the ratio of the C1 source and toluene feedstreams is not limited within the present invention and can vary depending on operating conditions and the efficiency of the reaction system. If excess toluene or C1 source is fed to the reaction zone, the unreacted portion can be subsequently separated and recycled back into the process. In one embodiment the ratio of toluene:C1 source can range from between 100:1 to 1:100. In alternate embodiments the ratio of toluene:C1 source can range from 50:1 to 1:50; from 20:1 to 1:20; from 10:1 to 1:10; from 5:1 to 1:5; from 2:1 to 1:2. In a specific embodiment, the ratio of toluene:C1 source can range from 2:1 to 5:1.
In an embodiment, the reactants (toluene and the C1 source) are combined with a co-feed. In an embodiment, the co-feed includes an oxidant. In another embodiment, the co-feed includes an oxidizing agent selected from the group of oxygen, air, nitrobenzene, quinones, anthracene, nitrous oxide, and combinations thereof. The co-feed may be combined with nitrogen prior to combining the co-feed with the reactants. The co-feed may be combined with the reactants in any desired amounts. In an embodiment, the process of the present invention contains a reactant:co-feed molar ratio of at least 1:1. In another embodiment, the process of the present invention contains a reactant:co-feed molar ratio ranging from 100:1 to 1:1. In an embodiment, the co-feed is added in amounts of at least 0.5 molar equivalent in relation to the C1 source. In another embodiment, the co-feed is added in amounts ranging from 0.05 to 0.9 molar equivalent in relation to the C1 source.
Turning now to the Figures,
As shown in
In the first separation unit (30), the de-oxidized, or reduced, oxidizing agents (35), (other than oxygen), can be separated from the product stream (28) and sent to an oxidation reactor (34), wherein the de-oxidized oxidizing agents are re-oxidized and recycled to the first reactor (24) as a co-feed stream (36).
As illustrated in
Looking now at
As shown in
The toluene (26) and formaldehyde (22) react in the presence of the co-feed to produce a product stream (28), which can include styrene, ethylbenzene, unreacted toluene, and unreacted formaldehyde and methanol. The product stream (28) of the first reactor (24) is sent to a first separation unit (30). In an embodiment, the first separation unit (30) includes one or more distillation units where the components of the product stream (28) may be separated and routed as shown in
The operating conditions of the reactors and separators as illustrated in
Additionally, the operating conditions of the first reactor can vary depending on the co-feed fed into the first reactor. In at least one embodiment, wherein the co-feed includes an oxidant, the reactor conditions thermodynamically favor the reduction of the oxidant.
Turning now to
Looking now at
The operating conditions of the reactors and separators as illustrated in
Additionally, the operating conditions of the first reactor can vary depending on the co-feed fed into the first reactor. In at least one embodiment, wherein the co-feed includes an oxidizing agent, the reactor conditions thermodynamically favor the reduction of the oxidizing agent.
Improvement in side chain alkylation selectivity may be achieved by treating a molecular sieve zeolite catalyst with chemical compounds to inhibit the external acidic sites and minimize aromatic alkylation on the ring positions. Another means of improvement of side chain alkylation selectivity can be to inhibit overly basic sites, such as for example with the addition of a boron compound. Another means of improvement of side chain alkylation selectivity can be to impose restrictions on the catalyst structure to facilitate side chain alkylation. In one embodiment the catalyst used in an embodiment of the present invention is a basic or neutral catalyst.
The catalytic reaction systems suitable for this invention can include one or more of the zeolite or amorphous materials modified for side chain alkylation selectivity. A non-limiting example can be a zeolite promoted with one or more of the following: Co, Mn, Ti, Zr, V, Nb, K, Cs, Ga, B, P, Rb, Ag, Na, Cu, Mg, Fe, Mo, Ce, or combinations thereof. In an embodiment, the zeolite can be promoted with one or more of Ce, Cu, P, Cs, B, Co, or Ga, or combinations thereof. The promoter can exchange with an element within the zeolite or amorphous material and/or be attached to the zeolite or amorphous material in an occluded manner. In an embodiment the amount of promoter is determined by the amount needed to yield less than 0.5 mol % of ring alkylated products such as xylenes from a coupling reaction of toluene and a C 1 source.
In an embodiment, the catalyst contains greater than 0.1 wt % of at least one promoter based on the total weight of the catalyst. In another embodiment, the catalyst contains up to 5 wt % of at least one promoter. In a further embodiment, the catalyst contains from 0.1 to 3 wt % of at least one promoter. In an embodiment, the at least one promoter is boron.
Zeolite materials suitable for this invention may include silicate-based zeolites and crystalline compounds such as faujasite, mordenite, chabazite, offretite, clinoptilolite, erionite, sihealite, and the like. Silicate-based zeolites are made of alternating SiO4− and MO4− tetrahedra, where M is an element selected from the Groups 1 through 16 of the Periodic Table (new IUPAC). These types of zeolites have 4-, 6-, 8-, 10-, or 12-membered oxygen ring channels. An example of zeolites of this invention can include faujasites. Other suitable zeolite materials include zeolite A, zeolite L, zeolite beta, zeolite X, zeolite Y, ZSM-5, MCM-22, and MCM-41. In a more specific embodiment, the zeolite is an X-type zeolite.
In an embodiment, the zeolite materials suitable for this invention are characterized by silica to alumina ratio (Si/Al) ranging from 1.0 to 200, optionally from 1.0 to 100, optionally from 1.0 to 50, optionally from 1.0 to 10.
The present catalyst is adaptable to use in the various physical forms in which catalysts are commonly used. The catalyst of the invention may be used as a particulate material in a contact bed or as a coating material on structures having a high surface area. If desired, the catalyst can be deposited with various catalyst binder and/or support materials.
A catalyst including a substrate that supports a promoting metal or a combination of metals can be used to catalyze the reaction of hydrocarbons. The method of preparing the catalyst, pretreatment of the catalyst, and reaction conditions can influence the conversion, selectivity, and yield of the reactions.
The various elements that make up the catalyst can be derived from any suitable source, such as in their elemental form, or in compounds or coordination complexes of an organic or inorganic nature, such as carbonates, oxides, hydroxides, nitrates, acetates, chlorides, phosphates, sulfides and sulfonates. The elements and/or compounds can be prepared by any suitable method, known in the art, for the preparation of such materials.
The term “substrate” as used herein is not meant to indicate that this component is necessarily inactive, while the other metals and/or promoters are the active species. On the contrary, the substrate can be an active part of the catalyst. The term “substrate” would merely imply that the substrate makes up a significant quantity, generally 10% or more by weight, of the entire catalyst. The promoters individually can range from 0.01% to 60% by weight of the catalyst, optionally from 0.01% to 50. If more than one promoter is combined, they together generally can range from 0.01% up to 70% by weight of the catalyst. The elements of the catalyst composition can be provided from any suitable source, such as in its elemental form, as a salt, as a coordination compound, etc.
The addition of a support material to improve the catalyst physical properties is possible within the present invention. Binder material, extrusion aids or other additives can be added to the catalyst composition or the final catalyst composition can be added to a structured material that provides a support structure. For example, the final catalyst composition can include an alumina or aluminate framework as a support. Upon calcination these elements can be altered, such as through oxidation which would increase the relative content of oxygen within the final catalyst structure. The combination of the catalyst of the present invention combined with additional elements such as a binder, extrusion aid, structured material, or other additives, and their respective calcination products, are included within the scope of the invention.
In one embodiment, the catalyst can be prepared by combining a substrate with at least one promoter element. Embodiments of a substrate can be a molecular sieve, from either natural or synthetic sources. Zeolites and zeolite-like materials can be an effective substrate. Alternate molecular sieves also contemplated are zeolite-like materials such as the crystalline silicoaluminophosphates (SAPO) and the aluminophosphates (ALPO).
The present invention is not limited by the method of catalyst preparation, and all suitable methods should be considered to fall within the scope herein. Particularly effective techniques are those utilized for the preparation of solid catalysts. Conventional methods include co-precipitation from an aqueous, an organic or a combination solution-dispersion, impregnation, dry mixing, wet mixing or the like, alone or in various combinations. In general, any method can be used which provides compositions of matter containing the prescribed components in effective amounts. According to an embodiment the substrate is charged with promoter via an incipient wetness impregnation. Other impregnation techniques such as by soaking, pore volume impregnation, or percolation can optionally be used. Alternate methods such as ion exchange, wash coat, precipitation, and gel formation can also be used. Various methods and procedures for catalyst preparation are listed in the technical report Manual of Methods and Procedures for Catalyst Characterization by J. Haber, J. H. Block and B. Dolmon, published in the International Union of Pure and Applied Chemistry, Volume 67, Nos 8/9, pp. 1257-1306, 1995, incorporated herein in its entirety.
The promoter elements can be added to or incorporated into the substrate in any appropriate form. In an embodiment, the promoter elements are added to the substrate by mechanical mixing, by impregnation in the form of solutions or suspensions in an appropriate liquid, or by ion exchange. In a more specific embodiment, the promoter elements are added to the substrate by impregnation in the form of solutions or suspensions in a liquid selected from the group of acetone, anhydrous (or dry) acetone, methanol, and aqueous solutions.
In another more specific embodiment, the promoter is added to the substrate by ion exchange. Ion exchange may be performed by conventional ion exchange methods in which sodium, hydrogen, or other inorganic cations that may be typically present in a substrate are at least partially replaced via a fluid solution. In an embodiment, the fluid solution can include any medium that will solubilize the cation without adversely affecting the substrate. In an embodiment, the ion exchange is performed by heating a solution containing any promoter selected from the group of, Co, Mn, Ti, Zr, V, Nb, K, Cs, Ga, B, P, Rb, Ag, Na, Cu, Mg, Fe, Mo, Ce, and any combinations thereof in which the promoter(s) is (are) solubilized in the solution, which may be heated, and contacting the solution with the substrate. In another embodiment, the ion exchange includes heating a solution containing any one selected from the group of Ce, Cu, P, Cs, B, Co, Ga, and any combinations thereof In an embodiment, the solution is heated to temperatures ranging from 50 to 120° C. In another embodiment, the solution is heated to temperatures ranging from 80 to 100° C.
The solution for use in the ion exchange method may include any fluid medium. A non-fluid ion exchange is also possible and within the scope of the present invention. In an embodiment, the solution for use in the ion exchange method includes an aqueous medium or an organic medium. In a more specific embodiment, the solution for use in the ion exchange method includes water.
The promoters may be incorporated into the substrate in any order or arrangement. In an embodiment, all of the promoters are simultaneously incorporated into the substrate. In more specific embodiment, each promoter is in an aqueous solution for ion-exchange with and/or impregnation to the substrate. In another embodiment, each promoter is in a separate aqueous solution, wherein each solution is simultaneously contacted with the substrate for ion-exchange with and/or impregnation to the substrate. In a further embodiment, each promoter is in a separate aqueous solution, wherein each solution is separately contacted with the substrate for ion-exchange with and/or impregnation to the substrate.
In an embodiment, the at least one promoter includes boron. In an embodiment, the catalyst contains greater than 0.1 wt % boron based on the total weight of the catalyst. In another embodiment, the catalyst contains from 0.1 to 3 wt % boron, optionally from 0.1 to 1 wt % boron.
The boron promoter can be added to the catalyst by contacting the substrate, impregnation, or any other method, with any known boron source. In an embodiment, the boron source is selected from the group of boric acid, boron phosphate, methoxyboroxine, methylboroxine, and trimethoxyboroxine and combinations thereof. In another embodiment, the boron source contains boroxines. In a further embodiment, the boron source is selected from the group of methoxyboroxine, methylboroxine, and trimethoxyboroxine and combinations thereof
In an embodiment, a substrate may be previously treated with a boron source prior to an addition of at least one promoter, wherein the at least one promoter includes boron. In another embodiment, a boron treated zeolite may be combined with at least one promoter, wherein the at least one promoter includes boron. In a further embodiment, boron may be added to the catalyst system by adding at least one promoter containing boron as a co-feed with toluene and methanol. In an even further embodiment, boron may be added to the catalyst system by adding boroxines as a co-feed with toluene and methanol. The boroxines can include, methoxyboroxine, methylboroxine, and trimethoxyboroxine, and combinations thereof. The boron treated zeolite further combined with at least one promoter including boron may be used in preparing a supported catalyst such as extrudates and tablets.
In an embodiment, the at least one promoter includes phosphorus. In an embodiment, the catalyst contains greater than 0.1 wt % phosphorus based on the total weight of the catalyst. In another embodiment, the catalyst contains from 0.1 to 3 wt % phosphorus, optionally from 0.1 to 1 wt % phosphorus.
The phosphorus promoter can be added to the catalyst by contacting the substrate, impregnation, or any other method, with any known phosphorus source.
When slurries, precipitates or the like are prepared, they may be dried, usually at a temperature sufficient to volatilize the water or other carrier, such as from 100° C. to 250° C., with or without vacuum. Irrespective of how the components are combined and irrespective of the source of the components, the dried composition is generally calcined in the presence of an oxygen-containing gas, usually at temperatures between about 300° C. and about 900° C. for from 1 to 24 hours. The calcination can be in an oxygen-containing atmosphere, or alternately in a reducing or inert atmosphere.
The prepared catalyst can be ground, pressed, sieved, shaped and/or otherwise processed into a form suitable for loading into a reactor. The reactor can be any type known in the art, such as a fixed bed, fluidized bed, or swing bed reactor. Optionally an inert material can be used to support the catalyst bed and to place the catalyst within the bed. Depending on the catalyst, a pretreatment of the catalyst may, or may not, be necessary. For the pretreatment, the reactor can be heated to elevated temperatures, such as 200° C. to 900° C. with an air flow, such as 100 mL/min, and held at these conditions for a length of time, such as 1 to 3 hours. Then, the reactor can be brought to the operating temperature of the reactor, for example 300° C. to 550° C., or optionally down to any desired temperature, for instance down to ambient temperature to remain under a purge until it is ready to be put in service. The reactor can be kept under an inert purge, such as under a nitrogen or helium purge.
Embodiments of reactors that can be used with the present invention can include, by non-limiting examples: fixed bed reactors; fluid bed reactors; and entrained bed reactors. Reactors capable of the elevated temperature as described herein, and capable of enabling contact of the reactants with the catalyst, can be considered within the scope of the present invention. Embodiments of the particular reactor system may be determined based on the particular design conditions and throughput, as by one of ordinary skill in the art, and are not meant to be limiting on the scope of the present invention. An example of a suitable reactor can be a fluid bed reactor having catalyst regeneration capabilities. This type of reactor system employing a riser can be modified as needed, for example by insulating or heating the riser if thermal input is needed, or by jacketing the riser with cooling water if thermal dissipation is required. These designs can also be used to replace catalyst while the process is in operation, by withdrawing catalyst from the regeneration vessel from an exit line or adding new catalyst into the system while in operation.
In another embodiment, the one or more reactors may include one or more catalyst beds. In the event of multiple beds, an inert material layer can separate each bed. The inert material can include any type of inert substance. In an embodiment, a reactor includes between 1 and 25 catalyst beds. In a further embodiment, a reactor includes between 2 and 10 catalyst beds. In a further embodiment, a reactor includes between 2 and 5 catalyst beds. In addition, the co-feed, the C1 source and/or toluene may be injected into a catalyst bed, an inert material layer, or both. In a further embodiment, at least a portion of the C1 source and at least a portion of the co-feed are injected into a catalyst bed(s) and at least a portion of the toluene feed is injected into an inert material layer(s).
In an alternate embodiment, the entire C1 source is injected into a catalyst bed(s), all of the toluene feed is injected into an inert material layer(s) and all of the co-feed is injected into one of: the catalyst bed(s), the inert material layer(s), or any combination thereof. In another embodiment, at least a portion of the toluene feed is injected into a catalyst bed(s), at least a portion of the co-feed is injected into a catalyst bed(s), and at least a portion the C1 source is injected into an inert material layer(s). In a further embodiment, all of the toluene feed and all of the co-feed are injected into a catalyst bed(s) and the entire C1 source is injected into an inert material layer(s).
The toluene and C1 source coupling reaction may have a toluene conversion percent greater than 0.01 mol %. In an embodiment the toluene and C1 source coupling reaction is capable of having a toluene conversion percent in the range of from 0.05 mol % to 40 mol %. In a further embodiment the toluene and C1 source coupling reaction is capable of having a toluene conversion in the range of from 2 mol % to 40 mol %, optionally from 5 mol % to 35 mol %, optionally from 10 mol % to 30 mol %.
In an embodiment the toluene and C1 source coupling reaction is capable of selectivity to styrene greater than 1 mol %. In another embodiment, the toluene and C1 source coupling reaction is capable of selectivity to styrene in the range of from 1 mol % to 99 mol %. In an embodiment the toluene to a C1 source coupling reaction is capable of selectivity to ethylbenzene greater than 1 mol %. In another embodiment, the toluene and C1 source coupling reaction is capable of selectivity to ethylbenzene in the range of from 1 mol % to 99 mol %. In an embodiment the toluene and C1 source coupling reaction is capable of yielding less than 0.5 mol % of ring alkylated products such as xylenes.
The term “conversion” refers to the percentage of reactant (e.g. toluene) that undergoes a chemical reaction.
XTol=conversion of toluene (mol %)=(Tolin−Tolout)/Tolin×100
XMeOH=conversion of methanol to styrene+ethylbenzene (mol %)=(MeOHin−MeOHout)/MeOHin×100
The term “molecular sieve” refers to a material having a fixed, open-network structure, usually crystalline, that may be used to separate hydrocarbons or other mixtures by selective occlusion of one or more of the constituents, or may be used as a catalyst in a catalytic conversion process.
Use of the term “optionally” with respect to any element of a claim is intended to mean that the subject element is required, or alternatively, is not required. Both alternatives are intended to be within the scope of the claim. Use of broader terms such as comprises, includes, having, etc. should be understood to provide support for narrower terms such as consisting of, consisting essentially of, comprised substantially of, etc.
The term “selectivity” refers to the relative activity of a catalyst in reference to a particular compound in a mixture. Selectivity is quantified as the proportion of a particular product relative to all other products.
SSty=selectivity of toluene to styrene (mol %)=Styout/Tolconverted×100
SBz=selectivity of toluene to benzene (mol %)=Benzeneout/Tolconverted×100
SEB=selectivity of toluene to ethylbenzene (mol %)=EBout/Tolconverted×100
SXyl=selectivity of toluene to xylenes (mol %)=Xylenesout/Tolconverted×100
SSty+EB (MEOH)=selectivity of methanol to styrene+ethylbenzene (mol %)=(Styout+EBout)/MeOHconverted×100
The term “zeolite” refers to a molecular sieve containing an aluminosilicate lattice, usually in association with some aluminum, boron, gallium, iron, and/or titanium, for example. In the following discussion and throughout this disclosure, the terms molecular sieve and zeolite will be used more or less interchangeably. One skilled in the art will recognize that the teachings relating to zeolites are also applicable to the more general class of materials called molecular sieves.
The various embodiments of the present invention can be joined in combination with other embodiments of the invention and the listed embodiments herein are not meant to limit the invention. All combinations of various embodiments of the invention are enabled, even if not given in a particular example herein.
While illustrative embodiments have been depicted and described, modifications thereof can be made by one skilled in the art without departing from the spirit and scope of the disclosure. Where numerical ranges or limitations are expressly stated, such express ranges or limitations should be understood to include iterative ranges or limitations of like magnitude falling within the expressly stated ranges or limitations (e.g., from about 1 to about 10 includes, 2, 3, 4, etc.; greater than 0.10 includes 0.11, 0.12, 0.13, etc.).
Depending on the context, all references herein to the “invention” may in some cases refer to certain specific embodiments only. In other cases it may refer to subject matter recited in one or more, but not necessarily all, of the claims. While the foregoing is directed to embodiments, versions and examples of the present invention, which are included to enable a person of ordinary skill in the art to make and use the inventions when the information in this patent is combined with available information and technology, the inventions are not limited to only these particular embodiments, versions and examples. Also, it is within the scope of this disclosure that the embodiments disclosed herein are usable and combinable with every other embodiment disclosed herein, and consequently, this disclosure is enabling for any and all combinations of the embodiments disclosed herein. Other and further embodiments, versions and examples of the invention may be devised without departing from the basic scope thereof and the scope thereof is determined by the claims that follow.
This application claims priority to U.S. Provisional Patent No. 61/488,783 filed on May 22, 2011.
| Number | Date | Country | |
|---|---|---|---|
| 61488783 | May 2011 | US |
