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    • 专利摘要:
    Incorporation into a fixed bed reactor for an exothermic reaction having a catalyst supported on a support having a thermal conductivity typically less than 30 W / mk within the limits of reaction temperature control and heat dissipating particles having a thermal conductivity of at least minus 50 W / mk less than 30 W / mk within the reaction temperature control limits help to control the reactor bed temperature.
    公开号:BR112018004651B1
    申请号:R112018004651-5
    申请日:2016-09-08
    公开日:2021-02-23
    发明作者:Vasily Simanzhenkov；Shahin Goodarznia；Kamal Serhal
    申请人:Nova Chemicals (International) S.A；
    IPC主号:
    专利说明:

    TECHNICAL FIELD
    [001] The present invention relates to the use of a heat sink diluent in fixed reactors to try to reduce the risk of an uncontrolled reaction. Many chemical reactions are exothermic, and particularly hydrocarbon treatments in fixed beds. A problem may arise if the reactor starts to get too hot. As the reactor heats up, the reaction rate increases by adding more heat to the reactor, increasing the reaction rate further. In many cases, for safety reasons it is necessary to have “neutralization systems” designed inside the reactor to stop a reactor quickly. TECHNICAL FUNDAMENTALS
    [002] United States patent 6,013,741 issued on January 11, 2000 to Ohtani et al., Assigned to Mitsui teaches the design of a reactor to allow the rapid introduction of a neutralizing gas into a fluidized bed reactor to quickly stop a reaction in the event of an equipment failure.
    [003] US patent 8,435,920 issued on May 7, 2013 to White et al., Assigned to Eltron Research & Development, Inc. refers to Col. 1 lines 45 to 66 for Lyon that teaches the use of catalysts for metal oxide in the partial oxidation of hydrocarbon foods. The reference does not refer to the use of inert metal thinners in a reactor bed.
    [004] There are several United States Patents issued to Petro-Tex Chemical Corporation issued in the late 1960s that disclose the use of various ferrites in a steam cracking unit to produce olefins from paraffins. Patents include United States Patents 3,420,911 and 3,420,912 in the names of Woskow et al. Patents teach the introduction of ferrites such as zinc, cadmium and manganese ferrites (ie, oxides mixed with iron oxide). Ferrites are not inert and release oxygen to react with the hydrocarbon stream. Ferrites are introduced into a dehydrogenation zone at a temperature of about 250 ° C to about 750 ° C at pressures less than 100 psi (689.476 kPa) for less than 2 seconds, typically from 0.005 to 0, 9 seconds. The reaction appears to occur in the presence of steam that can tend to shift the balance in the "wrong" direction. In addition, the reaction does not occur in the presence of a catalyst.
    [005] U.S. Patent 2,267,767, issued December 30, 1941 to Thomas, assigned to Universal Oil teaches the use of non-porous metallic substrates as supports for catalysts for the treatment of hydrocarbons. The metal substrates are treated with non-aqueous solutions of a metal alkoxide and an ortho alkyl silicate. The substrate appears to be a component for the reaction. Metal oxides can be alumina, zirconia, thorium, vanadium, magnesia and other metal oxides that are active in cracking and / or reforming reactions.
    [006] U.S. Patent 2,478,194 issued August 9, 1949 issued to Houdry Process Corporation teaches a catalyst and support in a composite form comprising a metallic component such as iron or steel. The metallic component can take various shapes such as an "I", a cross, or even the shape of a child's overalls. The catalytic component is then applied to the metal support to form the catalyst. The metallic component provides an oxidation promoter, not an inert heatsink.
    [007] The fixed bed reactor is the most used equipment in the refining and petrochemical industry. In commercial reactors the ratio of reactor diameter to effective particle diameter is at least 50: 1 generally greater than 500: 1. Catalyst supports generally have a low thermal conductivity. Under these conditions, there is a low heat transfer from the inside of the bed fixed to the reactor wall where the heat can be dissipated. These conditions can lead to localized hot spots that can be the center for an uncontrolled reaction, particularly for exothermic reactions.
    [008] The present invention seeks to provide a fixed catalyst bed and a metallic diluent having a thermal conductivity greater than 30 W / mK (watts / meter Kelvin) within the reaction temperature control limits to allow heat transfer within the bed and also outside the bed. DESCRIPTION OF THE INVENTION
    [009] In one embodiment, the present invention provides a process for conducting an exothermic reaction in the presence of a fixed bed comprising supported catalyst, the improvement comprising incorporation in the bed of 5 to 90% by weight based on the total weight of the catalyst bed of one or more inert non-catalytic heat dissipating particles having a melting point of at least 30 ° C above the upper temperature control limit for the reaction, a particle size within 1 mm to 15 mm and a higher thermal conductivity than 50 W / mK (watts / meter Kelvin) within the reaction temperature control limits.
    [010] In another embodiment, the particles are metals, alloys and compounds having a thermal conductivity greater than 150 W / mK (watts / meter Kelvin) within the reaction temperature control limits.
    [011] In another embodiment, the inert heat dissipating particles comprise silver, copper, gold, steel, stainless steel, molybdenum and tungsten.
    [012] In another embodiment, the reaction involves one or more of cracking, isomerization, oxidative coupling, oxidative dehydrogenation, hydrogen transfer, polymerization and desulfurization of a hydrocarbon or any other exothermic reaction.
    [013] In another mode, the particles are metallic.
    [014] In another embodiment, the particles have a size of 0.5 mm to 75 mm.
    [015] In another embodiment, the process is the oxidative coupling of one or more C1-4 hydrocarbons.
    [016] In another embodiment, the process is oxidative dehydrogenation of one or more C2-4 hydrocarbons.
    [017] In another mode, the process is conducted using a mixed ethane and oxygen feed in a volumetric ratio of 70:30 to 95: 5 at an upper temperature control limit of less than 420 ° C at a spatial speed hourly gas of not less than 280 h-1 and a pressure of 80 to 1,000 kPa (about 0.8 to 10 atmospheres).
    [018] In another mode, the process has an ethane conversion of not less than 90%.
    [019] In another embodiment, the hourly space velocity of the process gas is not less than 280 h-1 (preferably, at least 1,000 h-1).
    [020] In another mode, the upper temperature control limit is less than 400 ° C.
    [021] In another modality, the catalyst has the empirical formula MogVhTeiNbjPdkOl, where g, h, i, j, k are the relative atomic quantities of the elements Mo, V, Te, Nb, Pd and O, respectively, and when g = 1, h ranges from 0.01 to 1.0, i ranges from 0.01 to 1.0, j ranges from 0.01 to 1, 0.001 <k <0.10 and l is dependent on the oxidation status of other elements.
    [022] In another modality, the catalyst has the empirical formula VxMoyNbzTemMenOp in which Me is a metal selected from the group consisting of Ta, Ti, W, Hf, Zr, Sb and mixtures thereof; and x is 0.1 to 3 since when Me is absent, x is greater than 0.5; y is 0.5 to 1.5; z is 0.001 to 3; m is 0.001 to 5; n is 0 to 2; and p is a number to satisfy the valence state of the mixed oxide catalyst.
    [023] In another embodiment, the crystalline phase of the catalyst has the formula Mo1,0V0,22-035Te0,10-0,20Nb0,15-0,19Od, preferably Mo1,0V0,22-033Te0,10-0,16Nb0 , 15-0,18Od where d is a number to satisfy the oxide valence (as determined by PIXE).
    [024] In another embodiment, the crystalline phase of the catalyst, the amount of the phase having the formula (TeO) 0.39 (Mo3.52V1.06Nb0.42) O14 is above 75% by weight as determined by XRD.
    [025] In another embodiment, the crystalline phase of the catalyst, the amount of the phase having the formula (TeO) 0.39 (Mo3.52V1.06Nb0.42) O14 is above 85% by weight as determined by XRD. BRIEF DESCRIPTION OF THE DRAWINGS
    [026] Figure 1 is a schematic diagram of the fixed bed reactor used to conduct the experiments. BEST MODE FOR CARRYING OUT THE INVENTION Number ranges
    [027] Except in operational examples or where otherwise indicated, all numbers or expressions referring to the quantities of ingredients, reaction conditions, etc. used in the specification and claims are to be understood as modified in all cases by the term "about". Consequently, unless otherwise indicated, the numerical parameters presented in the following specification and appended claims are approximations that may vary depending on the properties that the present invention wishes to obtain. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter must at least be interpreted in light of the number of significant digits reported and applying usual rounding techniques.
    [028] Nevertheless, the numerical ranges and parameters that define the broad scope of the invention are approximations, the numerical values presented in the specific examples are reported as accurately as possible. Any numerical values, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective test measurements.
    [029] Also, it should be understood that any numerical range mentioned here is intended to include all the sub-ranges included in them. For example, a range from “1 to 10” is intended to include all sub-ranges between and including the minimum quoted value of 1 and the maximum quoted value of 10; that is, having a minimum value equal to or greater than 1 and a maximum value equal to or less than 10. As the numerical ranges disclosed are continuous, they include all values between the minimum and maximum values. Unless expressly stated otherwise, the various numerical ranges specified in this application are approximations.
    [030] All compositional ranges expressed here are limited in total to and do not exceed 100 percent (percent by volume or percent by weight) in practice. Where multiple components can be present in a composition, the sum of the maximum quantities of each component can exceed 100 percent, with the understanding that, and as that person skilled in the art readily understands, that the quantities of the components actually used will be at the maximum 100 percent. The Catalyst
    [031] The present invention is suitable for use with any fixed bed reactor where there is a desire to have better control over the heat flow within the fixed bed and also the transfer of heat into or out of the bed. Since, the inert non-catalytic heat dissipating particles present in the bed have a thermal conductivity greater than 50, in some modalities 100, in other modalities 150, still other modalities 200, W / mK (watts / meter Kelvin) within the limits reaction temperature control and inert non-catalytic heat dissipating particles can transfer heat directly to the reactor walls, improving cooling homogeneity (or heating if the wall is heated) and reducing hot spots in the fixed bed.
    [032] The reactions may comprise one or more of oxidative cracking, isomerization, oxidative coupling, oxidative dehydrogenation, hydrogen transfer, polymerization, and desulfurization of a hydrocarbon or any other exothermic reaction. In some embodiments, the reaction is oxidative dehydrogenation of a C2-4 alkane or oxidative coupling of a C1-4 alkane. These last two reactions are cause for concern, as the feed comprises a hydrocarbon and oxygen. If the oxygen to hydrocarbon ratio exceeds the lower flammable limit (explosive) and the reaction temperature of the bed exceeds the ignition temperature of the mixture, there is a certainty of an undesired result.
    [033] In some methods of carrying out such reactions, the reagent stream is diluted with steam or an inert gas such as nitrogen to keep the reaction mixture below the lower (explosive) flammability limit. This type of method tends to reduce conversion by passing the reagents and the product stream needs to be separated, typically using some type of unit as a C2 divider that is energy intensive and producing greenhouse gas.
    [034] Another approach is to operate such reactions above the lower (explosive) flammability limit, but at a temperature below the auto-ignition temperature of the feed. In such a method of operation it is essential to have a uniform temperature within the bed (that is, without hot spots) and to have good control over the removal of heat from the fixed bed.
    [035] There are several catalysts that can be used for oxidative dehydrogenation.
    [036] In some embodiments, the catalyst may have the composition MoaVbNbcSbdXe. X is nothing or Li, Sc, Na, Ser, Mg, Ca, Sr, Ba, Ti, Zr, Hf, Y, Ta, Cr, Fe, Co, Ni, Ce, La, Zn, Cd, Hg, Al, T1, Pb, As, Bi, Te, U, Mn and / or W; a is 0.5 to 0.9, b is 0.1 to 0.4, c is 0.001 to 0.2, d is 0.001 to 0.1, and is 0.001 to 0.1 when X is an element.
    [037] In some embodiments, the catalyst has the formula: MoaVvTaxTeyOz where, a is 1.0, v is about 0.01 to about 1.0, x is about 0.01 to about 1.0 , y is about 0.01 to about 1.0, and z is the number of oxygen atoms needed to make the catalyst electronically neutral. The catalyst can be supported on typical supports including porous silicon dioxide, ignited silicon dioxide, kieselgur, silica gel, porous and non-porous aluminum oxide, titanium dioxide, zirconium dioxide, thorium dioxide, lanthanum oxide, oxide magnesium, calcium oxide, barium oxide, tin oxide, cerium dioxide, zinc oxide, boron oxide, boron nitride, boron carbide, boron phosphate, zirconium phosphate, aluminum silicate, silicon nitride or silicon carbide, but also glass or metal metal oxide networks. In some embodiments, titanium oxide.
    [038] In some modalities, the catalyst may have the formula: VxMoyNbzTemMenOp in which Me is a metal selected from the group consisting of Ta, Ti, W, Hf, Zr, Sb and mixtures thereof; and x is 0.1 to 3 since when Me is absent, x is greater than 0.5; y is 0.5 to 1.5; z is 0.001 to 3; m is 0.001 to 5; n is 0 to 2; and p is a number to satisfy the valence state of the mixed oxide catalyst.
    [039] In some examples, the catalyst may have the empirical formula (measured by PIXE): Mo1,0V0,22-033Te0,10-0,16Nb0,15-0,18Od where d is a number to satisfy the valence of oxide.
    [040] In some embodiments, the catalyst may have the empirical formula MogVhTeiNbjPdkOl, where g, h, i, j, k are the relative atomic quantities of the elements Mo, V, Te, Nb, Pd and O, respectively, and when g = 1, h ranges from 0.01 to 1.0, i ranges from 0.01 to 1.0, j ranges from 0.01 to 1, 0.001 <k <0.10 and l is dependent on the oxidation status of other elements. The addition of small amounts of Pd to the catalyst provides an increase in activity while maintaining high selectivity for ethylene.
    [041] In one embodiment of this catalyst containing Pd, the relative atomic quantity of the vanadium element, indicated by the subscript h, ranges from 0.1 to 0.5. In another embodiment of the catalyst, h ranges from 0.2 to 0.4. In another embodiment of the then catalyst, h ranges from 0.25 to 0.35.
    [042] In a modality of this catalyst containing Pd, the relative atomic quantity of the element tellurium, indicated by the subscript i, ranges from 0.05 to 0.4. In another embodiment of the catalyst, i ranges from 0.08 to 0.3. In another embodiment of the catalyst, i ranges from 0.10 to 0.25.
    [043] In one embodiment of this catalyst containing Pd, the relative atomic quantity of the niobium element, indicated by the subscript j, ranges from 0.05 to 0.4. In another embodiment of the catalyst, it already ranges from 0.08 to 0.3. In another embodiment of the catalyst, it already ranges from 0.10 to 0.25.
    [044] Hydrothermal synthesis for the preparation of mixed metal oxide catalysts is known in the art, its advantages over conventional preparation methods such as solid-state reaction and drying are covered in Watanabe, et al., “New Synthesis Route For Mo- V-Nb-Te Mixed Metal Oxides For Propane Ammoxidation ”. Applied Catalysis A: General, 194-195, pages 479-485 (2,000).
    [045] Generally, a hydrothermal synthesis step is used for the preparation of the catalyst before the addition of the Pd compound. Compounds containing elements Mo, V, Nb and Te and a solvent are mixed to form a first mixture. The first mixture is then heated in a closed container for 24 to 240 hours. A useful solvent for hydrothermal synthesis of the first mixture is water. Any water suitable for use in chemical syntheses can be used, and includes, without limitation, distilled water, deionized water). The amount of solvent used is not critical to the present invention.
    [046] Preparation of the mixture is not limited to the addition of all the compounds of Mo, V, Nb and Te at the same time before the heat treatment in a first closed container. For example, the compounds of Mo and Te can be added first, followed by the compound of V and eventually the compound of Nb. For yet another example, the process can be reversed in which the compounds of Te and Nb are combined followed by the addition of a mixture of the compounds of Mo and V. Other addition sequences would be apparent to a person skilled in the art. Sequence and time of addition are not limited by these examples.
    [047] In one embodiment of the invention, the first mixture is heated to a temperature of 100 oC to 200 oC. In another embodiment of the invention, the first mixture is heated to a temperature of 130 oC to 190 oC. In another embodiment of the invention, the first mixture is heated to a temperature of 160 oC to 185 oC.
    [048] After hydrothermal synthesis of the first four components of the catalyst, the first insoluble material is recovered from the first closed container. At this point, the first insoluble material can be dried before a first calcination in order to remove any residual solvent. Any method known in the art can be used for optional drying of the first insoluble material, including, but not limited to, air drying, vacuum drying, lyophilization, and oven drying.
    [049] In another embodiment of the invention, the first insoluble material can be subjected to peroxide washing before optional drying and before a first calcination. The peroxide washing treatment can take place at atmospheric pressure and room temperature (for example, from 15 ° C to 30 ° C) at about 80 ° C, in some cases from 35 ° C to 75 ° C in other cases from 40 ° C to 65 ° C and the peroxide has a concentration of 10 to 30% by weight, in some cases from 15 to 25% by weight, and a time of 1 to 10 hours, in some cases from 2 to 8 hours, in other cases from 4 to 6 hours.
    [050] The first insoluble material is treated with the equivalent of 1.3 to 3.5 mL of a 30% by weight solution of H2O2 per gram of precursor. The treatment must be in a suspension (for example, the precursor is at least partially suspended) to provide the same distribution of H2O2 and to control the increase in temperature. For post-treatment of calcination with H2O2 there is a late violent reaction with H2O2. The process of the present invention is an instant reaction that is more controlled and safer.
    [051] Methods for calcination are well known in the art. The first calcination of the first insoluble material is carried out in a second closed container with an inert atmosphere. The second closed container for calcination can be a quartz tube. The inert atmosphere can include any material that does not interact with or react with the first insoluble material. Examples include, without limitation, nitrogen, argon, xenon, helium or mixtures thereof. The preferred embodiment of the present invention comprises an inert atmosphere comprising nitrogen gas.
    [052] Calcination methods for the preparation of mixed metal oxide catalysts vary in the art. Variables include time, temperature range, heating speed, the use of multiple temperature stages, and the use of an oxidizer or inert atmosphere. For the present invention, the heating speed is not fundamental and can vary between 0.1 oC / minute to about 10 oC / minute. Also, the inert gas can be statically present or can be passed over the catalyst at flow rates where the loss of catalyst is minimized, that is, removed from the bed.
    [053] In an embodiment of the invention, the time for the first calcination varies from 1 hour to 24 hours. In another embodiment of the invention, the time for the first calcination varies from 3 hours to 15 hours. In the preferred embodiment of the invention, the time for the first calcination varies from 4 hours to 12 hours.
    [054] In one embodiment of the invention, the first calcination takes place in an inert atmosphere at a temperature of 500 ° C to 700 ° C. In another embodiment of the invention, the first calcination takes place in an inert atmosphere at a temperature of 550 ° C to 650 ° C. In the preferred embodiment of the invention, the first calcination takes place in an inert atmosphere at a temperature of 580 ° C to 620 ° C. The resulting calcined product is suitable as an oxidative dehydrogenation catalyst.
    [055] In some embodiments after the first calcination, the first calcination product is mixed with a Pd component to form a second mixture. For these aspects of the invention the addition of a Pd component to the catalyst is only effective in increasing the activity of the catalyst, without significantly decreasing selectivity, depending on the method for addition and the nature of the Pd compound used. The addition of the Pd compound must be carried out after the first calcination of the first insoluble material containing the four components Mo, V, Te and Nb. In one embodiment of the invention the Pd compound, in the form of an aqueous solution, is added dropwise to the first calcination product until saturation and the mixture forms a paste. In another embodiment of the invention, the Pd component and the first calcination product are mixed in an aqueous solution to form a suspension. In one embodiment of the invention, the aqueous solution is water. Any water suitable for use in chemical syntheses can be used, and includes, without limitation, distilled water and deionized water. The amount of solvent used is not critical to the present invention.
    [056] The amount of Pd component added, either in a dropwise form or in a suspension, will correspond approximately with 0.044 mmolPd / gODH catalyst to produce a final relative atomic amount of Pd, represented by the subscript and in the formula MoaVbTecNbdPdeOf, between 0.001 and 0.1.
    [057] The nature of the Pd compound used must be free of halogens. A useful Pd component is tetra-amine nitrate, chemically represented by the formula [(NH3) 4Pd] (NO3) 2.
    [058] Prior to the second calcination of the second mixture, the product can be dried using any method known in the art including, but not limited to, air drying, vacuum drying, lyophilization, and oven drying.
    [059] The second calcination is carried out under conditions and follows the same limitations as those applicable to the first calcination. The resulting second insoluble material is recovered from the second closed container and can be used directly as a catalyst for ODH, using conditions where only the atmospheric components exposed to the catalyst are oxygen and ethane. The oxygen and ethane ratios and the temperature used for the ODH process are such that the upper explosive limit is not triggered. The ability to perform ODH using this catalyst whereby there is no dilution of the reagents with nitrogen or other inert gas or water confers a commercial advantage as the expensive downstream processes for removing excess oxygen or any undesirable by-products are not necessary or limited in nature.
    [060] In some embodiments, the catalyst may have the formula: MoaVbNbcTeeOd where: a is 0.75 to 1.25, preferably 0.90 to 1.10; b is 0.1 to 0.5, preferably 0.25 to 0.4; c is 0.1 to 0.5, preferably 0.1 to 0.35; and is 0.1 to 0.35, preferably 0.1 to 0.3; and d is a number to satisfy the valence state of the mixed oxide catalyst.
    [061] The MoVNbTeMeO type catalysts above are heterogeneous. They have an amorphous phase and a crystalline phase. The structure and content of the crystalline phase can be influenced by treating the catalyst with hydrogen peroxide prior to final calcination (i.e., catalyst precursor treatment). After such a treatment, the crystalline phase of the catalyst has the formula: Mo1.0V0.25-035Te0.10-0.20Nb0,15-0,19Od where d is a number to satisfy the oxide valence. In some embodiments, at least 75% by weight of the crystalline phase has the preceding formula as determined by XRD. In other embodiments, at least 85% by weight of the crystalline phase has the preceding formula as determined by XRD. The support
    [062] The catalyst support for the fixed bed can be a ceramic precursor formed from oxides, dioxides, nitrides, carbides selected from the group consisting of silicon dioxide, fused silicon dioxide, aluminum oxide, titanium dioxide, dioxide zirconium, thorium dioxide, lanthanum oxide, magnesium oxide, calcium oxide, barium oxide, tin oxide, cerium dioxide, zinc oxide, boron oxide, boron carbide, yttrium oxide, aluminum silicate , silicon nitride, silicon carbide and mixtures thereof. Typically, the thermal conductivity of the support is less than 50 W / mk, preferably less than 30 W / mk within the reaction temperature control limits.
    [063] In one embodiment, the support for the fixed bed may have a low surface area of less than 20 m2 / g, alternatively, less than 15 m2 / g, alternatively, less than 3.0 m2 / g for the oxidative dehydrogenation catalyst. Such a support can be prepared by compression molding. At higher pressures, the interstices within the ceramic precursor are collapsing compressed. Depending on the pressure exerted on the support precursor, the surface area of the support can be about 20 to 10 m2 / g.
    [064] The low surface area support can be of any conventional shape such as sphere, rings, saddles, etc.
    [065] It is important that the support is dried before use (ie, before adding the catalyst). Generally, the support can be heated to a temperature of at least 200 ° C for up to 24 hours, typically to a temperature of 500 ° C to 800 ° C for about 2 to 20 hours, preferably 4 to 10 hours. The resulting support will be free of adsorbed water and should have a hydroxyl surface content of about 0.1 to 5 mmol / g of support, preferably from 0.5 to 3 mmol / g.
    [066] The amount of hydroxyl groups on silica can be determined according to the method disclosed by J. B. Peri and A. L. Hensley, Jr., in J. Phys. Chem., 72 (8), 2926, 1968, the entire contents of which are hereby incorporated by reference.
    [067] The dry support for the fixed bed catalyst can then be compressed in the necessary form by compression molding. Depending on the particle size of the support, it can be combined with an inert binder to maintain the shape of the compressed part. Uploads
    [068] Typically, the catalyst loading on the support for the fixed bed catalyst provides from 1 to 30% by weight, typically from 5 to 20% by weight, preferably from 8 to 15% by weight of said catalyst and from 99 to 70% by weight, typically 80 to 95% by weight, preferably 85 to 92% by weight, respectively, of said support. The heat dissipating particles are different from the support.
    [069] The catalyst can be added to the support in any number of ways. For example, the catalyst can be deposited from an aqueous suspension on one of the surfaces of the low surface area support by impregnation, wash coating, brushing or spraying. The catalyst can also be co-precipitated from a suspension with the ceramic precursor (for example, alumina) to form the catalyst supported on the low surface area. The Heat Dissipative Particles for the Fixed Bed
    [070] The heat dissipating particles for the fixed bed comprise one or more inert non-catalytic particles having a melting point of at least 30, in some embodiments at least 250, in other embodiments at least 500 ° C above the control limit higher temperature for the reaction, a particle size in the range of 0.5 to 75 mm, in some modalities 0.5 to 15, in other modalities in the range of 0.5 to 8, desirably in the range of 0.5 to 5 mm and a thermal conductivity greater than 30 W / mK (watts / meter Kelvin) within the reaction temperature control limits. In some embodiments, the particles are alloys and metal compounds having a thermal conductivity greater than 50 W / mK (watts / meter Kelvin) within the reaction temperature control limits. Some suitable metals include silver, copper, gold, aluminum, steel, stainless steel, molybdenum and tungsten.
    [071] Heat dissipating particles can typically have a particle size of about 1 to 15 mm. In some embodiments, the particle size can be from about 1 mm to about 8 mm. The heat dissipating particles can be added to the fixed bed in an amount of 5 to 95% by weight, in some embodiments 30 to 70% by weight, in other embodiments 45 to 60% by weight based on the total weight of the fixed bed. The Processes
    [072] The present invention can be used with any fixed bed exothermic reaction. In some embodiments, the fixed bed reactor is a tubular reactor and in another embodiment, the fixed bed reactor comprises multiple tubes within an enclosure (for example, a shell and tube heat exchanger construction). In another embodiment, the fixed bed reactor may comprise several series and / or parallel shells. The reactions may involve one or more of cracking, isomerization, dehydrogenation including oxidative dehydrogenation, hydrogen transfer including oxidative coupling and desulfurization of a hydrocarbon.
    [073] Typically, these reactions are conducted at temperatures from about 200 ° C to about 850 ° C at pressures of about 80 to 21,000 kPa (about 12 to 3,000 psi) in the presence of a catalyst. The hydrocarbon stream can contain a wide range of compounds including C1-20 aliphatic or aromatic hydrocarbons.
    [074] In some embodiments, the reactions are oxidative coupling of aliphatic hydrocarbons, typically C1-4 aliphatic hydrocarbons, particularly methane, and oxidative dehydrogenation of C2-4 aliphatic hydrocarbons. Such reactions can be conducted using a mixed hydrocarbon feed, in some modalities methane or ethane and oxygen in a volumetric ratio of 70:30 to 95: 5 at a temperature less than 420 ° C at an hourly space velocity of no gas. less than 280 h-1, in some embodiments not less than 1,000 h-1, in some embodiments no less than 2,000 h-1 and a pressure of 80 to 1,000 kPa (0.8 to 1.2 atmosphere). Typically, the process can have an overall conversion of about 50 to about 100%, typically about 75 to 98% and a selectivity for ethylene of not less than 90%, in some cases not less than 95%, in other modalities no less than 98%. In some cases, the upper temperature control limit is less than about 400 ° C, in some embodiments less than 385 ° C.
    [075] The resulting product stream is treated to separate ethylene from the rest of the product stream which may also contain co-products such as acetic acid, and unreacted feed that is recycled back to the reactor.
    [076] In addition, the product stream should have a low content of carbon dioxide, and carbon monoxide, and acetic acid, usually cumulatively in a range of less than 10, preferably less than 2% by weight.
    [077] There are up to four concurrent reactions for oxidative dehydrogenation. Reaction 1 C2H6 + 0.5 O2 θ C2H4 + H2O (ΔH1 = -105 kJ / Mol C2H6) Reaction 2 C2H6 + 2.5 O2 θ 2CO + 3H2O (ΔH2 = -862 kJ / Mol C2H6) Reaction 3 C2H6 + 3, 5 O2 θ 2CO2 + 3H2O (ΔH3 = -1430 kJ / Mol C2H6) Reaction 4 C2H6 + 1.5 O2 θ C2H2O2 + H2O (ΔH4 = -591 kJ / Mol C2H6)
    [078] From a temperature / heat control point of view, if a catalyst preferably leads to reaction 1, there is a lower potential for thermal uncontrolling.
    [079] Food and products may need to be separated from the product chain. Some processes may use so-called diluted ethylene chains. For example, if the product stream does not contain much ethane, for example, less than about 15 vol%. the stream can be fed directly without further purification to a polymerization reactor such as a gas phase, suspension or solution reactor.
    [080] The most common separation technique would be to use a cryogenic C2 divider. Other known ethylene / ethane separation techniques can also be used including adsorption (oil, ionic liquids and zeolite).
    [081] The present invention will now be illustrated by the following non-limiting examples.
    [082] In the examples, the catalysts were prepared by a hydrothermal process as described above.
    [083] The catalyst had the empirical formula: (Mo1.00V0.36Te0.12Nb0.12) O4.57 as determined by XRD.
    [084] For the comparative example, the catalyst was not treated with hydrogen peroxide. For example 1, the sample comprises a mixture of five catalyst samples treated with peroxide. The catalyst for the comparative example has a slightly higher propensity to oxidize the feed to CO2.
    [085] In the examples, the fixed bed reactor unit used is shown schematically in Figure 1. The reactor was a fixed bed stainless steel tube reactor having an outside diameter of 2 mm (% ”) and a length of 117 cm (46 inches). The reactor is in an electric oven sealed with ceramic insulating material. There are 7 thermocouples in the reactor indicated in numbers from 1 to 7. Thermocouples are used to monitor the temperature in this zone of the reactor. Thermocouples 3 and 4 are also used to control the heating of the reactor bed. The power flows from the top to the bottom of the reactor. At the entrance there is a ceramic cup 8 to prevent drafts in the reactor. Below the ceramic cup is a layer of quartz wool 9. Below the layer of quartz wool is a layer of catalytically inert quartz powder. Below the quartz powder is the fixed bed 10 comprising catalyst and diluent. Below the fixed bed is a layer of quartz powder 11, a layer of quartz wool 12 and a ceramic cup 13. At the outlet of the bed was a gas analyzer to determine the composition of the product stream. The fixed bed comprised 28.83 g of catalyst and 3.85 g of diluent (32.86 g of% by weight of diluent 11.7% by weight of total bed). The GHSV was 2,685 h-1 and the pressure was ambient.
    [086] For the examples, the bed temperature was taken as an average of the temperatures of thermocouples 2, 3 and 4. The supply current was considered to have the same temperature as the bed. A stoichiometric reactor block was conducted using the temperature conditions above using Aspen Plus simulation to calculate the global heat release from the reactions. Comparative Example
    [087] The heat dissipating particles in this example were quartz particles having an average particle size of 568 micrometers. The reaction temperature (bed temperature) increased to 355 ° C and then there was an uncontrolled thermal reaction. The overall conversion to ethylene was 19% and the selectivity for ethylene was 93%. The calculated heat rate of the reactions was calculated to be a heat release of -26.28 kJ / h. At this point there was a rapid drop in oxygen content in the product stream and a rapid, uncontrolled thermal reaction began. The reaction was quenched with nitrogen. Example 1
    [088] The heat dissipating particles were 316 Stainless Steel particles having an average particle size of 568 micrometers. The weight% of diluent was the same as for Example 1. As steel is denser than quartz this resulted in a lower volume% of diluent in the bed. It is believed that these conditions tend to lead to thermal uncontrollability. The reactor was operated to maintain an overall conversion of 19% with a selectivity for ethylene of 89%. The calculated global heat of reaction was -31.13 kJ / h. The bed temperature increased to 372 ° C. No uncontrolled reactions were observed. The stainless steel thinner allowed better heat release through the reactor walls to control the reaction.
    [089] Example 1 shows that the bed temperature did not rise above 372 ° C, while in the comparative example the bed temperature approached 355 ° followed by an uncontrolled thermal reaction. Example 1 shows the dissipation of the reaction heat. INDUSTRIAL APPLICABILITY
    [090] The present invention helps to control / dissipate the heat generated from the oxidative dehydrogenation reaction.
    权利要求:
    Claims (3)
    [0001]
    1. Process for conducting oxidative dehydrogenation, CHARACTERIZED by the fact that it comprises: providing a mixed feed of ethane and oxygen in a volume ratio of 70:30 to 95: 5; and lead to oxidative dehydrogenation of the mixed feed at a temperature of less than 400 ° C at an hourly gas space velocity of not less than 280 h-1, at a pressure of 0.8 to 102 atmospheres (80 to 1,000 kPa) , an ethane conversion of not less than 90%, and in the presence of a fixed bed comprising a mixed metal oxide catalyst having a crystalline phase of the formula: Mo1.0V0.25-0.35Te0.10-0, 20Nb0,15-0,19Od where d is a number to satisfy the oxide valence; wherein said mixed oxide catalyst is supported on one or more of porous silicon dioxide, ignited silicon dioxide, kieselgur, silica gel, porous or non-porous aluminum oxide, titanium dioxide, zirconium dioxide, thorium dioxide, lanthanum oxide, magnesium oxide, calcium oxide, barium oxide, tin oxide, cerium dioxide, zinc oxide, boron oxide, boron nitride, boron carbide, boron phosphate, zirconium phosphate, silicate aluminum, silicon nitride or silicon carbide; wherein said fixed bed further comprises one or more inert non-catalytic heat dissipating particles comprising silver, copper, gold, steel, stainless steel, molybdenum and tungsten in an amount of 5 to 90% by weight based on the weight of the bed fixed; and wherein said particles have a melting point of at least 30 ° C above an upper temperature control limit for said oxidative dehydrogenation, a particle size of 0.5 mm to 5 mm and a thermal conductivity greater than 150 W / mK (watts / meter Kelvin) within the reaction temperature control limits.
    [0002]
    2. Process for conducting oxidative dehydrogenation, CHARACTERIZED by the fact that it comprises: providing a mixed feed of ethane and oxygen in a volumetric ratio of 70:30 to 95: 5; and lead to oxidative dehydrogenation of the mixed feed at a temperature of less than 400 ° C, at an hourly space gas velocity of not less than 280 h-1, at a pressure of 0.8 to 102 atmospheres (80 to 1,000 kPa ), an ethane conversion of not less than 90%, and in the presence of a fixed bed comprising a mixed metal oxide catalyst; where the fixed bed mixed metal oxide catalyst has a crystalline phase of the formula: Mo1,0V0,25-0,35Te0,10-0,20Nb0,15-0,19Od where d is a number to satisfy the valence of oxide; wherein in a crystalline phase of said mixed metal oxide catalyst the amount of a crystalline phase having the formula (TeO) 0.39 (Mo3.52V1.06Nb0.42) O14 is above 75% by weight as determined by XRD ; wherein said mixed oxide catalyst is supported on one or more of porous silicon dioxide, ignited silicon dioxide, kieselgur, silica gel, porous or non-porous aluminum oxide, titanium dioxide, zirconium dioxide, thorium dioxide, lanthanum oxide, magnesium oxide, calcium oxide, barium oxide, tin oxide, cerium dioxide, zinc oxide, boron oxide, boron nitride, boron carbide, boron phosphate, zirconium phosphate, silicate aluminum, silicon nitride or silicon carbide; wherein said fixed bed further comprises one or more inert non-catalytic heat dissipating particles comprising silver, copper, gold, steel, stainless steel, molybdenum and tungsten in an amount of 5 to 90% by weight based on the weight of the bed fixed; and wherein said particles have a melting point of at least 30 ° C above an upper temperature control limit for said oxidative dehydrogenation, a particle size of 0.5 mm to 5 mm and a thermal conductivity greater than 150 W / mK (watts / meter Kelvin) within the reaction temperature control limits.
    [0003]
    3. Process for conducting oxidative dehydrogenation, CHARACTERIZED by the fact that it comprises: providing a mixed feed of ethane and oxygen in a volumetric ratio of 70:30 to 95: 5; and lead to oxidative dehydrogenation of the mixed feed at a temperature of less than 400 ° C at an hourly gas space velocity of not less than 280 h-1, at a pressure of 0.8 to 102 atmospheres (80 to 1,000 kPa) , an ethane conversion of not less than 90%, and in the presence of a fixed bed comprising a meta mistol oxide catalyst; where the fixed bed mixed metal oxide catalyst has a crystalline phase of the formula: Mo1,0V0,25-0,35Te0,10-0,20Nb0,15-0,19Od where d is a number to satisfy the valence of oxide; wherein in the crystalline phase of the catalyst the amount of said crystalline phase having the formula (TeO) 0.39 (Mo3.52V1.06Nb0.42) O14 is above 85% by weight as determined by XRD; wherein said mixed oxide catalyst is supported on one or more of porous silicon dioxide, ignited silicon dioxide, kieselgur, silica gel, porous or non-porous aluminum oxide, titanium dioxide, zirconium dioxide, thorium dioxide, lanthanum oxide, magnesium oxide, calcium oxide, barium oxide, tin oxide, cerium dioxide, zinc oxide, boron oxide, boron nitride, boron carbide, boron phosphate, zirconium phosphate, silicate aluminum, silicon nitride or silicon carbide; wherein said fixed bed further comprises one or more inert non-catalytic heat dissipating particles comprising silver, copper, gold, steel, stainless steel, molybdenum and tungsten in an amount of 5 to 90% by weight based on the weight of the bed fixed; and wherein said particles have a melting point of at least 30 ° C above an upper temperature control limit for said oxidative dehydrogenation, a particle size of 0.5 mm to 5 mm and a thermal conductivity greater than 150 W / mK (watts / meter Kelvin) within the reaction temperature control limits.
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    同族专利:
    公开号 | 公开日
    US20180272303A1|2018-09-27|
    MX2018002766A|2018-04-13|
    US20200254414A1|2020-08-13|
    CA2904477A1|2017-03-14|
    JP6828022B2|2021-02-10|
    US11110423B2|2021-09-07|
    BR112018004651A2|2018-09-25|
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    WO2017046680A1|2017-03-23|
    JP2018529515A|2018-10-11|
    TW201716542A|2017-05-16|
    KR20180052637A|2018-05-18|
    CN107949433A|2018-04-20|
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    法律状态:
    2020-03-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-12-29| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-02-23| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/09/2016, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    CA2904477|2015-09-14|
    CA2904477A|CA2904477A1|2015-09-14|2015-09-14|Heat dissipating diluent in fixed bed reactors|
    PCT/IB2016/055365|WO2017046680A1|2015-09-14|2016-09-08|Heat dissipating diluent in fixed bed reactors|
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