Title of Invention

"PROCESS FOR PRODUCING LIGHT OLEFINS FROM AN OXYGENATE FEEDSTREAM"

Abstract Light olefins are produced from an oxygenate feedstream by ontacting the oxygenate feedstream in the presence of a methane diluent in a reaction zone containing a metal aluminium phosphate molecular sieve (ELAPO) catalyst at conditions selective for the conversion of at least a portion of the feedstock into light olefins producing a reactor effluent comprising water, methane, and light olefins. The water is preferably removed and the remaining reactor effluent is separated into a light fraction comprising methane and a light olefin stream. At least a portion of the light fraction is returned to be admixed with the feedstream as the diluent. This improved operation solves the problem caused by excessive water levels in the reaction zone which was found to adversely affect the activity of the catalyst.
Full Text The present invention relates to a process for production of light olefins having from 2 to 4 carbon atoms per molecule from an oxygenated feedstock.
BACKGROUND
Light olefins have traditionally been produced through the process of steam or catalytic cracking. Because of the limited availability and high cost of petroleum sources, the cost of producing light olefins from such petroleum sources has been steadily increasing. .Light olefins serve as feeds for the production of numerous chemicals. As the emerging economies of the developing nations move toward growth and expansion, the demand for light olefins will increase dramatically.
The search for alternative materials for light olefin production has led to the use of oxygenates such as alcohols, and more particularly to the use of methanol, ethanol, and higher-alcohols or their derivatives. These alcohols may be produced by fermentation or from synthesis gas. Synthesis gas can be produced from natural gas, petroleum liquids, and carbonaceous materials including coal, recycled plastics, municipal wastes, or any organic material. Thus, alcohol and alcohol derivatives may provide non-petroleum based routes for the production of olefin and other related hydrocarbons.
Molecular sieves such as the microporous crystalline zeolite and non-zeolitic catalysts, particularly silicoaluminophosphates (SAPO), are known to promote the conversion of oxygenates to hydrocarbon mixtures. This catalysts may be generally conducted in the presence of one or more diluents which may be present in the oxygenate feed in an amount between about 1 and about 99 molar percent, based on the total number of moles of all feed and diluent components fed to the reaction zone (or catalyst). Diluents include - but are not limited to -helium, argon, nitrogen, carbon monoxide, carbon dioxide, hydrogen, water, paraffins, hydrocarbons (such as methane and the like), aromatic compounds, or mixtures thereof. US-A-4,861,938 and US-A-4,677,242 particularly emphasize the use of a diluent combined with the feed to the reaction zone to maintain sufficient catalyst selectivity toward the production of light
olefin products, particularly ethylene. One such diluent which has been employed is steam.
US-A-4,543,435 discloses a process for converting an oxygenated feedstock comprising methanol, dimethyl ether or the like in an oxygenate conversion reactor into liquid hydrocarbons comprising C2-C4 olefins and C5+ hydrocarbons. The C2-C4 olefins are compressed to recover an ethylene-rich gas. The ethylene-rich gas is recycled to the oxygenate conversion reactor.
WO-A-93/13013 relates to an improved method for producing a silicon-alumino-phosphate catalyst which is more stable to deactivation by coking. The patent discloses that after a period of time, all such catalysts used to convert methanol to olefins (MTO) lose the active ability to convert methanol to hydrocarbons primarily because the microporous crystal structure is coked; that is, filled up with low volatility carbonaceous compounds which block the pore structure. The carbonaceous compounds can be removed by conventional methods such as combustion in air.
It has been found that high concentrations of water in the reaction mixture, which are generally required to maintain an appropriate level of dilution, have an adverse effect on the catalyst life and cause the catalyst to deactivate rapidly. Furthermore, water is a by-product of the reaction and its production increases the amount of water seen by the catalyst. Processes are sought which reduce the amount of water in the reaction mixture while maintaining the appropriate level of dilution. These and other disadvantages of the prior art are overcome by the present invention, however, and a new improved process for conversion of oxygenates to hydrocarbons is provided.
SUMMARY
In the present invention, a combination of water reduction steps are employed to reduce the amount of water at a critical point in the production of light olefins. It was discovered that the use of water or steam as a diluent in an oxygenate conversion process had a deleterious
effect on the metal aluminophosphate catalyst. By the process of the present invention, the water in the oxygenate conversion zone is significantly reduced and significant capital and operating cost savings are obtainable. By replacing steam with methane as a diluent and by obtaining the methane from the by-product of the oxygenate conversion reaction, the catalyst life and stability of the metal aluminosilicate catalyst in the oxygenate conversion zone can be improved. Methane, when used as a diluent, will not affect the activity of the catalyst. The availability of methane within the process reduces the treating requirements for preparing an external diluent stream to prevent exposing the catalyst to potentially harmful impurities. Although methane does not provide the thermal and separation advantages of a steam diluent, the use of methane as diluent significantly reduces the concentraiton of water in the reaction zone.
The invention provides a process for the production of light olefins having from 2 to 4 carbon atoms per molecule from an oxygenated feedstock. The oxygenated feedstock comprises at least one of the group consisting of an alcohol, an ether, an aldehyde, a ketone, and mixtures thereof. The process comprises passing the feedstock in the presence of a methane diluent to a reaction zone and therein contacting the feedstock with an metal

aluminium phosphate (ELAPO) molecular sieve catalyst selective for the conversion of at least a portion of the feedstock into light olefins to produce a reactor effluent comprising methane and light olefins. The reactor effluent is passed to a separation zone to provide a light hydrocarbon fraction comprising methane and a product fraction comprising light olefins. At least a portion of the light hydrocarbon fraction is recycled to the reaction zone as the methane diluent.
The preferred ELAPO molecular siee catalyst for use in the reaction zone is SAPO catalyst such as SAPO-34 or SAPO-17 and the light olefins produced inlcude ethylene, propylene, and butylene.
In another embodiment, the invention relates to a process for the production of light olefins comprising ethylene and propylene from an oxygenated feedstock comprising at least one of methanol and dimethyl ether. The process comprises passing the oxygenated feedstock in the present of a diluent comprising methane to a reaction zone. The reaction zone contains a SAPO catalyst selective for the conversion of at least a portion of the oxygenaed feedstock into
light olefins to produce a reactor effluent comprising water, methane, and light olefins. At least a portion of the water from the reactor effluent is removed to provide a de-watered reactor effluent. The de-watered reactor effluent is passed to a separation zone to provide a light hydrocarbon fraction which is essentially free of ethylene and a light olefin stream. At least a portion of the light hydrocarbon stream is returned to the reaction zone to provide the diluent. The light olefin stream is recovered. The light olefin stream may be further separated into essentially pure ethylene and propylene. Ethylene and propylene are preferably produced at purities of at least 99.9 mol %.
In a further embodiment, the invention is a process for the production of light olefins comprising ethylene and propylene from a feedstock. The feedstock comprises at least one methanol and dimethyl ether. The process comprises admixing the feedstock with a methane diluent to provide a feed admixture. The feed admixture is passed to a feed/effluent exchanger to heat the feed admixture providing a heated feedstream. The heated feedstream is cooled providing a cooled feedstream and the cooled feedstream is passed to a reaction zone. The reaction zone contains a SAPO catalyst selective for the conversion of at least a portion of the cooled feedstream into light olefins. A reactor effluent stream comprising methane, light olefins, and water is produced in the reaction zone. At least a portion of the methane is separated from the reactor effluent and the portion of the methane is returned to be admixed with the feedstock as the diluent.
According to the present invention there is provided a process for the production of light olefins having from 2 to 4 carbon atoms per molecule from an oxygenated feedstock comprising at least one of the group consisting of methanol, dimethyl ether and mixtures thereof, said process comprising the steps of:
a) passing the feedstock to a reaction zone and therein contacting said
feedstock in the presence of a methane diluent with metal aluminium phosphate
(ELAPO) molecular sieve catalyst at a reaction temperature of 350°C to 525°C and a
pressure of 101.3 to 506.5 kPa for the conversion of at least a portion of said
feedstock into said light olefins and water to produce a reactor effluent comprising
methane and said light olefins;
b) passing said reactor effluent to a separation zone to provide a light
hydrocarbon fraction comprising methane and a product fraction comprising light
olefins; and
c) recycling at least a portion of said light hydrocarbon fraction to said reaction
zone as said diluent.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
The attached figure is a schematic process flow diagram illustrating the process of the instant invention employing a methane recycle.
DETAILED DESCRIPTION
In accordance with the process of the present invention, an oxygenate feed is catalytically converted to hydrocarbons containing aliphatic moities such as - but not limited to -
methane, ethane, ethylene, propane, propylene, butylene, and limited amounts of other higher aliphatics by contacting the oxygenate feed with a preselected catalyst. The oxygenate feed comprises hydrocarbons containing aliphatic moieties such as - but not limited to - alcohols, halides, mercaptans, sulfides, amines, ethers and carbonyl compounds or mixtures thereof. The aliphatic moiety preferably contains from 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. Representative oxygenates include - but are not limited to - methanol, isopropanol, n-propanol, ethanol, fuel alcohols, dimethyl ether, diethyl ether, methyl mercaptan, methyl sulfide, methyl amine, ethyl mercaptan, ethylchloride, formaldehyde, dimethylketone, acetic acid, n-alkylamines, n-alkylhalides, and n-alkyl-sulfides having alkyl groups of 1 to 10 carbon atoms or mixtures thereof. In a preferred embodiment, methanol is used as the oxygenate feed. In a more preferred embodiment, dimethyl ether is used as the oxygenate feed. The term "oxygenate feed" as employed hi the present invention and described herein designates only the organic material used as the feed. The total charge of feed to the reaction zone may contain additional compounds such as diluents.
A diluent is required to maintain the selectivity of the catalyst to produce light olefins, particularly ethylene and propylene. The use of steam as the diluent provides certain equipment cost and thermal efficiency advantages. The phase change between steam and liquid water can be employed to advantage in transferring heat between the feedstock and the reactor effluent, and the separation of the diluent from the product requires simple condensation of the water to separate the water from the hydrocarbons. Ratios of 1 mole of feed to 4 moles of water have been disclosed. It was found that these high levels of water combined with the water produced as a by-product of the reaction resulted hi the rapid loss of catalyst activity. Laboratory and pilot plant testing showed that catalyst activity is significantly reduced by combination of a steam diluent and the by-product water levels. The use of methane, a by-product of the conversion reaction, significantly reduces the amount of water in the reaction zone. Preferably the ratio of moles of feed to moles of methane diluent will range from 1:1 to 1:5. To illustrate the major differences in thermal efficiency between a steam diluent and a methane diluent flow scheme, the steam diluent scheme requires a feed heater following a feed/effluent exchanger to raise the combined feedstock to the reaction temperature. When methane is employed, the combined feedstock must be cooled to reach the reaction temperature. The cooling of the
combined feedstocks may be accomplished by the direct cooling of the combined feedstock after the feed/effluent exchanger or by the use of a cooler on the reactor effluent stream to reduce the temperature of the reactor effluent prior to the feed/effluent exchanger. The cooling of the reactor feed may be accomplished by generating steam to remove the process heat. It is preferred that at least a portion of the process heat be removed from the combined feedstock prior to entering the reactor. This cooling step also serves as a trim cooler to maintain the temperature of the cooled reactor effluent at a temperature which permits the cooled reactor effluent to be water-scrubbed to remove catalyst fines. If the cooled reactor effluent is too hot, the water-scrubbing step will not be effective and catalyst fines will be introduced to the reactor effluent compressor.
The water concentration in the reaction zone may be reduced further by the use of a feedstock comprising dimethyl ether (DME) rather than methanol. The ratio of methyl groups to oxygen in DME is twice that of methanol resulting in the production of half the production of water for the same amount of light olefin produced.
The process of the present invention is preferably conducted in the vapor phase such that the oxygenate feed is contacted in a vapor phase in a reaction zone with the ELAPO molecular sieve catalyst at effective process conditions to produce olefin hydrocarbons, i.e., an effective temperature pressure, Weight Hourly Space Velocity (WHSV) and an effective amount of methane diluent, correlated to produce olefin hydrocarbons. The process is affected for a period of time sufficient to produce the desired light olefin products. In general, the residence time employed to produce the desired product can vary from seconds to a number of hours. It will be readily appreciated that the residence time will be determined to a significant extent by the reaction temperature, the ELAPO molecular sieve selected, the WHSV, the phase (liquid or vapor) and process design characteristics selected. The feedstock flow rate affects olefin production. Increasing the feedstock flow rate (expressed as WHSV) enhances the formation of olefin production relative to paraffin production. However, the enhanced olefin production relative to paraffin production is offset by a diminished conversion of oxygenate to hydrocarbons.
The process is effectively carried out over a wide range of pressures, including autogenous pressures. At pressures between 0.1 kPa (0.001 atmospheres) and 101.3 mPa (1000 atmospheres) the formation of light olefin products will be affected although the optimum amount of product will not necessarily form at all pressures. The preferred pressure is between 1 kPa (0.01 atmospheres) to 10.1 mPa (100 atmospheres). The pressures referred to herein for the process are exclusive of the inert diluent, if any, that is present and refer to the partial pressure of the feedstock as it relates to oxygenate compounds and/or mixtures thereof. At the lower and upper end of the pressure range and beyond, the selectivities, conversions and/or rates to light olefin products may not occur at the optimum, although light olefin such as ethylene may still be formed.
The temperature which may be employed in the process may vary over a wide range depending, at least in part, on the selected molecular sieve catalyst. In general, the process can be conducted at an effective temperature between 200 °C (392 °F) and 700 °C (1292 °F). At the lower end of the temperature range, and thus, generally at a lower rate of reaction, the formation of the desired light olefin products may become markedly slow. At the upper end of the temperature range and beyond, the process may not form an optimum amount of light olefin products.
The selection of a particular catalyst for use in the conversion process where an aliphatic hetero compounds are converted into light olefins, can be based on any of the ELAPO molecular sieves but it is preferred that the molecular sieve have relatively small pores. The preferred small pore molecular sieve are defined as having pores at least a portion, preferably a major portion, of which have an average effective diameter characterized such that the adsorption capacity (as measured by the standard McBain-Bakr gravimetric adsorption method using given adsorbate molecules) shows adsorption of oxygen (average kinetic diameter of about 0.346 ran) and negligible adsorption of isobutane (average kinetic diameter of about 0.5 ran). More preferably the average effective diameter is characterized by adsorption of xenon (average kinetic diameter of about 0.4 ran) and negligible adsorption of isobutane and most preferably by adsorption of n-hexane (average kinetic diameter of about 0.43 nm) and negligible adsorption of isobutane. Negligible adsorption of a given adsorbate is adsorption of less than three percent by
weight of the molecular sieve and adsorption of the adsorbate is over three percent by weight of the adsorbate based on the weight of the molecular sieves in the catalyst. Certain of the molecular sieves useful in the catalyst used in the present invention have pores with an average effective diameter of less than 5 Angstroms. The average effective diameter of the pores of preferred molecular sieves is determined by measurements described in D. W. Breck, ZEOLITE MOLECULAR SIEVES by John Wiley & Sons, New York (1974), hereby incorporated by reference in its entirety. The term effective diameter is used to denote that occasionally the pores are irregularly shaped, e.g., elliptical, and thus the pore dimensions are characterized by the molecules that can be adsorbed rather than the actual dimensions. Preferably, the small pore catalysts have a substantially uniform pore structure, e.g., substantially uniformly sized and shaped pore. Suitable catalyst may be chosen from among non-zeolitic molecular sieves known as ELAPO materials.
Non-zeolitic molecular sieves (i.e. ELAPO materials) include molecular sieves which have the proper effective pore size and are embraced by an empirical chemical composition, on an anhydrous basis, expressed by the empirical formula:
where EL is an element selected from the group consisting of silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and mixtures thereof, x is the mole fraction of EL and is at least 0.005, y is the mole fraction of Al and is at least 0.01, z is the mole fraction of P and is at least 0.01 and x + y + z = 1. When EL is a mixture of elements, x represents the total amount of the element mixture present. Preferred elements (EL) are silicon, magnesium and cobalt with silicon being especially preferred.
The preparation of various ELAPOs are well known in the art and may be found in US-A-5,191,141 (ELAPO); US-A-4,554,143 (FeAPO); US-A-4,440,871 (SAPO); US-A-US-A-4,853,197 (MAPO, MnAPO, ZnAPO, CoAPO); US-A-4,793,984 (CAPO), US-A-4,752,651 and US- A-4, 310,440 all of which are incorporated by reference. Generally, the ELAPO molecular sieves are synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of EL, aluminum, phosphorus and a templating agent. Reactive
sources of EL are the metal salts such as the chloride and nitrate salts. When EL is silicon, a preferred source is fumed, colloidal or precipitated silica. Preferred reactive sources of aluminum and phosphorus are pseudo-boehmite alumina and phosphoric acid. Preferred templating agents are amines and quaternary ammonium compounds. An especially preferred templating agent is tetraethylammonium hydroxide (TEAOH).
The reaction mixture is placed in a sealed pressure vessel, optionally lined with an inert plastic material such as polytetrafluoroethylene and heated preferably under autogenous pressure at a temperature between 50 to 250 °C and preferably between 100 and 200 °C for a time sufficient to produce crystals of the ELAPO molecular sieve. Typically the time varies from 2 hours to 30 days and preferably from 4 hours to 20 days. The desired product is recovered by any convenient method such as centrifugation or filtration.
It is known that the particle size of the ELAPO molecular sieve can be reduced by stirring the reaction mixture at high speeds (see examples) and by using TEAOH as the templating agent. It is preferred that the ELAPO molecular sieves are composed of particles at least 50% of which have a particle size less than 1.0 µm and no more than 10% of the ELAPO particles have a particle size greater than 2.0 µm.
The ELAPOs which are synthesized using the process described above will usually contain some of the organic templating agent in its pores. In order for the ELAPOs to be active catalyst, the templating agent in the pores must be removed by heating the ELAPO powder in an oxygen containing atmosphere at a temperature of 200 to 700 °C until the template is removed, usually a few hours.
A preferred embodiment of the invention is one in which the metal (EL) content varies from 0.005 to 0.05 mole fraction. If EL is more than one element, then the total concentration of all the metals is between about 0.005 and 0.05 mole fraction. An especially preferred embodiment is one in which EL is silicon (usually referred to as SAPO). The SAPOs which can be used in the instant invention are any of those described in US-A-4,440,871; US— A-5,126,308, and US-A-5,191,141. Of the specific crystallographic structures described in the
'871 patent, the SAPO-34, (i.e., structure type 34), is preferred. The SAPO-34 structure is characterized in that it adsorbs xenon but dues not adsorb isobutane, indicating that it has a pore opening of about 4.2 A. Another SAPO, SAPO-17, as exemplified in Examples 25 and 26 of the '871 patent, is also preferred. The SAPO-17 structure is characterized in that it adsorbs oxygen, hexane, and water but does not adsorb isobutane, indicating that it has a pore opening of greater than 4.3 A and less than 5.0 A.
The preferred ELAPO molecular sieve may be, and preferably is, incorporated into solid catalyst particles in which the molecular sieve is present in an amount effective to promote the desired hydrocarbon conversion. In one aspect, the solid catalyst particles comprise a catalytically effective amount of the ELAPO molecular sieve and at least one matrix material, preferably selected from the group consisting of binder materials, filler materials, and mixtures thereof to provide a desired property or properties, e.g., desired catalyst dilution, mechanical strength, and the like to the solid particles. Such matrix materials are often, to some extent, porous in nature and may or may not be effective to promote the desired hydrocarbon conversion. The matrix materials may promote conversion of the feedstream and often provide reduced selectivity to the desired product or products relative to the catalyst. Filler and binder materials include, for example, synthetic and naturally occurring substances such as metal oxides, clays, silicas, aluminas, silica-aluminas, silica-magnesias, silica-zirconias, silica-thorias, silica-berylias, silica-titanias, silica-alumina-thorias, silica-alumina-zirconias, aluminophosphates, mixtures of these and the like.
If matrix materials, e.g., binder and/or filler materials, are included in the catalyst composition, the non-zeolitic molecular sieves preferably comprise about 1 % to 99%, more preferably about 5% to about 90% and still more preferably about 10% to about 80%, by weight of the total composition. The preparation of solid particles comprising catalyst and matrix materials is conventional and well known in the art and, therefore, need not be discussed in detail herein.
DESCRIPTION OF THE DRAWINGS
The process of the present invention is hereinafter described with reference to the drawing which illustrates various aspects of the process.
With reference to the drawing, an oxygenated feedstock comprising at least one of the group consisting of an alcohol, an ether, an aldehyde, a ketone, and mixtures thereof in line 10 is admixed with a methane diluent 52 and the admixture is passed via line 12 to a first heat exchanger 100 to preheat the feedstock/diluent admixture by cross exchange and to provide a preheated feedstream mixture 14. The preheated feedstream mixture 14 is passed to a second heat exchanger 101 wherein the preheated feedstream mixture is exchanged with a reactor effluent stream 20 to provide a heated feedstream 16 and a cooled reactor effluent stream 22. The heated feedstream 16 is passed to a reactor cooler 102 to cool the reactor feedstream 18 to reaction conditions including a reaction temperature ranging from 350 °C to 525 °C and a pressure of 101.3 to 506.5 kPa (1 to 5 atmospheres). The reactor feedstream mixture is passed to a reaction zone 103 containing a SAPO catalyst selective for the conversion of at least a portion of the reactor feedstream 18 into C2-C4 olefins and to produce a reactor effluent stream 20. The reactor effluent stream 20 is cooled in heat exchanger 112 and the resulting cooled stream 20' comprising methane, water, and light olefins is passed to the second heat exchanger 101 to provide cooled reactor effluent stream 22. In an alternate embodiment, the reactor effluent stream 20 can be passed to a steam generator 112 to cool the reactor effluent by removing a portion of the process heat and providing a first cooled reactor effluent in line 20'. The first cooled reactor effluent 20' is passed to the second heat exchanger 101, further cooling the reactor effluent and providing the cooled reactor effluent stream 22. The cooled reactor effluent stream 22 is passed to a water scrubber zone 104 wherein the cooled reactor effluent stream 22 is contacted with a water wash stream 24 to remove any catalyst fines from the cooled reactor effluent stream 22 in an aqueous stream 28. It is necessary to remove catalyst fines from the cooled effluent stream prior to further compressing the cooled reactor effluent stream in preparation for the separation of the individual components. The aqueous stream 28 is withdrawn for further treatment (not shown). A water scrubbed stream 26 is withdrawn from the water scrubber zone 104 and passed to reactor effluent compressor 105 to raise the pressure of
the water scrubbed stream 26 and to provide a compressed effluent stream 30. The compressed effluent stream 30 is cross exchanged with the feedstock/diluent admixture 12 in the first heat exchanger 100 to preheat the admixture 12 and to first cool the compressed effluent stream 30 to provide a first cooled compressed effluent stream 32. This permits the recovery of low grade heat in exchanger 100. The first cooled compressed effluent stream 32 is further cooled in condenser 106 to condense at least a portion of the water in the effluent stream 32 and to provide a condensed effluent stream 34. The condensed effluent stream 34 is passed to a flash zone 107 to separate the condensed effluent stream 34 into a hydrocarbon stream 38 and a second aqueous stream 36. The second aqueous stream 36 is passed to an off-site water treatment zone (not shown). The hydrocarbon stream 38 comprising the light olefins and methane is passed to compressor 108 to provide a compressed hydrocarbon stream 40. Preferably, the compressed hydrocarbon stream 40 will be at a pressure of from 2000 to 4000 kPa, and more preferably stream 40 will be at a pressure ranging from 3000 to 4000 kPa. The compressed hydrocarbon stream 40 is passed to a water removal zone 109 containing a desiccant to reduce the amount of water in the hydrocarbon stream to less than about 1 ppm-vol and to provide a dry hydrocarbon stream 42. The dry hydrocarbon stream 42 is passed to an acid gas removal zone 110, containing an adsorbent selective for the removal of acid gases such as CO2 from the dry hydrocarbon stream 42 and to provide an acid gas reduced stream 44. The acid gas reduced stream 44 is passed to a demethanizer 111 wherein the methane is recovered in an overhead stream 46 and the light olefins comprising C2-C4 are recovered in a bottoms stream 48. It is preferred that the overhead stream 46, which comprises a light hydrocarbon fraction, comprises from about 75 to about 99.9 mol % methane; thus, it is essentially all methane and is essentially free of ethylene. The ethylene content of the overhead stream is preferably less than 5 mol % and more preferably the ethylene content of the overhead stream is less than 1 mol %. The bottom stream 48 is passed to further fractionation (not shown) for recovery of essentially pure ethylene and propylene at purities greater than about 99 mol % and more preferably at purities greater than 99.9 mol %. At least a portion of the overhead stream 46 and 52 is returned to be admixed with the feedstock 10 as the diluent and a portion of the overhead stream 46 is withdrawn in line 50 typically to be used as a fuel stream. Preferably the molar ratio of the diluent in the feed admixture will range from 1.8 to 2.3.
EXAMPLES EXAMPLE I
A series of runs to determine the effect of accelerated hydrothermal aging on the catalyst of the present invention was carried out. A 40 gram sample of SAPO-34 catalyst was placed in a 2.2 cm (7/8 inch) I.D. tubular monel reactor forming a catalyst bed therein. The reactor was fitted with stainless steel sintered frits at the bottom of the catalyst bed and on the reactor outlet above the catalyst bed. An air purge flowing up from the bottom to the top of the catalyst bed was established to fluidize the catalyst bed. The pressure was increased to 793 kPa (100 psig) and the temperature was raised from room temperature to 460 °C. When the temperature stabilized, the air flow was replaced with water at a rate of 90 grams/hour. The steaming of the catalyst in this manner continued for a series of specified times ranging from 5 hours to 200 hours. At the end of the specified time, the water flow was replaced with air and the reactor was cooled to about 100 °C and depressurized.
Portions of the fresh and hydrothermally aged catalyst of approximately 10 grams each were separately loaded into a 2.2 cm (7/8 inch) I.D., porcelain-lined stainless steel reactor. The catalyst sample was pre-treated with flowing nitrogen at 435 °C for about 1 hour to dry the catalyst and raise the temperature of the catalyst bed. The nitrogen was replaced with a mixture of methanol and water containing about 80 wt% methanol at a feed rate of about 12.5 grams per hour and at a pressure of about 138 kPa (5 psig). The time, or on-stream time, from the start of the reaction to the point at which the conversion of methanol (and DME) dropped to 99% was recorded. The performance of the catalysts were monitored using an on-line GC measuring the composition of the reactor effluent. The results of these accelerated hydrothermal aging tests are shown in Table 1. The hydrothermal aging of the SAPO-34 catalyst showed a progressive loss in catalyst activity ranging from about 4.8 hours for fresh catalyst to about 3.5 hours for a catalyst sample after 100 hours of steaming.
TABLE 1
HYDROTHERMAL AGING TESTS OF SAPO-34 HOURS ON STREAM AT >99% CONVERSION
(Table Removed)
EXAMPLE II
The evaluation of the effect of the accelerated hydrothermal aging on conversion for the fresh catalyst and the 100 steaming hour samples of Example I was continued. The conversion was recorded as a function of time from the introduction of the feed. The effect of the continued hydrothermal aging of the catalyst is shown in Table 2. For the fresh catalyst and the 100 hour aged catalyst, the conversion dropped to about 20% after on-stream times ranging from 5 to 6.3 hours, with the steamed catalyst exhibiting a more pronounced reduction in conversion at an earlier on-stream time than the feed catalyst. Although the accelerated hydrothermal testing showed that steaming the catalyst results in the permanent loss of catalyst activity, this steaming was evaluated at levels well beyond water levels which would normally be encountered when methane is employed as a diluent. The use of a methane diluent sharply reduces the effective hydrothermal aging rate of this SAPO-34 catalyst.
TABLE 2
EFFECT OF STEAMING ON MTO CATALYST
CONVERSION. % FRESH CATALYST 100 HOURS AGING
(Table Removed)



We claim:
1. A process for the production of light olefins having from 2 to 4 carbon atoms per molecule from an oxygenated feedstock comprising at least one of the group consisting of methanol, dimethyl ether and mixtures thereof, said process comprising the steps of:
a) passing the feedstock to a reaction zone and therein contacting said
feedstock in the presence of a methane diluent with metal aluminium phosphate
(ELAPO) molecular sieve catalyst at a reaction temperature of 350°C to 525°C and a
pressure of 101.3 to 506.5 kPa for the conversion of at least a portion of said
feedstock into said light olefms and water to produce a reactor effluent comprising
methane and said light olefms;
b) passing said reactor effluent to a separation zone to provide a light
hydrocarbon fraction comprising methane and a product fraction comprising light
olefins; and
c) recycling at least a portion of said light hydrocarbon fraction to said
reaction zone as said diluent.

2. The process as claimed in claim 1 further comprising removing at least a
portion of said water from said reactor effluent prior to passing said reactor effluent to
said separation zone.
3. The process as claimed in claim 1 or 2 wherein said ELAPO molecular sieve
is an empirical composition on anhydrous basis by the formula:
(Formula Removed)
where EL is metal selected from the group consisting of silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium, and mixtures thereof, x is the mole fraction of EL and is between 0.005 and 0.98, inclusive, y is the mole fraction of
Aluminium (Al) and Z is the mole fraction of phosphorus (P) and y and z are each between 0.01 and 0.985, inclusive.
4. The process as claimed in claim 1 or 2 wherein said ELAPO molecular sieve
catalyst is selected from the group consisting of silicoaluminium phosphate-34
(SAPO-34), silicoaluminium phosphate-17 (SAPO-17), and mixtures thereof.
5. The process as claimed in claim 1 or 2 wherein said light hydrocarbon fraction
comprises from about 75 to about 99.9 mol-% methane.
6. The process as claimed in claim 1 or 2 wherein said oxygenated feedstock
comprises at least one of methanol and dimethyl ether.
7. The process as claimed in claim 1 or 2 where the ratio of moles of feedstock to
methane diluent is from 1:1 to 1:5.
8. A process for the production of light olefins having from 2 to 4 carbon atoms
per molecule from an oxygenated feedstock, substantially as hereinbefore described
with reference to the accompanying drawings.

Documents:

1089-del-1998-abstract.pdf

1089-del-1998-claims.pdf

1089-del-1998-correspondence-others.pdf

1089-del-1998-correspondence-po.pdf

1089-del-1998-description (complete).pdf

1089-del-1998-drawings.pdf

1089-del-1998-form-1.pdf

1089-del-1998-form-19.pdf

1089-del-1998-form-2.pdf

1089-del-1998-form-3.pdf

1089-del-1998-form-4.pdf

1089-del-1998-gpa.pdf

1089-del-1998-petition-138.pdf


Patent Number 230863
Indian Patent Application Number 1089/DEL/1998
PG Journal Number 13/2009
Publication Date 27-Mar-2009
Grant Date 28-Feb-2009
Date of Filing 27-Apr-1998
Name of Patentee UOP
Applicant Address 25 EAST ALGONQUIN ROAD,DES PLAINES, ILLINOIS,U.S.A.
Inventors:
# Inventor's Name Inventor's Address
1 ROBERT C. MULVANEY III 1712 S. FERNANDEZ AVE. ,ARLINGTON HEIGHTS, ILLINOIS 60005
2 TERRY L. MARKER 29W 220 CALUMET, WARRENVILLE, ILLINOIS 60555
PCT International Classification Number C07C 1/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA