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    • 专利摘要:
    POROUS CERAMIC BODY; CATALYST; PROCESS; PROCESS FOR PREPARING A 1, 2-DIOL, A 1,2-DIOL ETHER, A 1,2-CARBONATE OR AN ALKANOLAMINE This is a carrier that has at least three shoulders, a first end, a second end, a wall between the ends and a non-uniform transition radius at the intersection of an end and the wall. It also reveals a catalyst that comprises the carrier, silver and promoters deposited on the carrier and useful for the epoxidation of olefins. It also reveals a method for producing the carrier, a method for producing the catalyst and a process for epoxidizing an olefin with catalyst.
    公开号:BR112013016091B1
    申请号:R112013016091-8
    申请日:2011-12-12
    公开日:2020-11-10
    发明作者:John David Covey；Michael A. Richard
    申请人:Saint-Gobain Ceramics & Plastics, Inc；
    IPC主号:
    专利说明:

    CROSS REFERENCE TO RELATED ORDER
    This claim claims the benefit of Provisional Application No. US 61 / 428,009 filed on December 29, 2010. BACKGROUND OF THE INVENTION
    This invention relates to porous ceramic bodies having an outlined shape which is particularly suitable for use as a carrier for catalytically active material. The combination of carrier and active material can - function as a catalyst when randomly disposed in a reactor tube that is useful in the manufacture of 15 chemicals such as ethylene oxide. Ethylene oxide, to be abbreviated in this document as EO, is an important industrial chemical used as a raw material for the production of such chemical substances as ethylene glycol, ethylene glycol ethers, alkanol amines and detergents. One method of making ethylene oxide is by partially catalyzing oxidation of ethylene with oxygen. These are ongoing efforts to develop catalysts that can improve the operating efficiency of such ethylene oxide manufacturing processes. Some of the desirable properties of an ethylene oxide catalyst include good selectivity, good activity and long catalyst life. It is also important that the catalyst as placed in the reactor tubes results in as little pressure drop across the EO reactor as possible as possible. Achieving an improvement in pressure drop with higher packing density would improve the stability of an EO catalyst in existing EO installations and allow the design of new, more efficient EO 5 installations.
    Typical catalysts used to produce EO comprise silver and other metals and promoters in a carrier, typically an alpha alumina carrier. These silver catalysts are described in many 10 OS and foreign patents, including, among others, US 4,242,235; OS 4,740,493; US 4,766,105; US 7,507,844; US 7,507,845; US 7,560,577; US 7,560,411; US 7,714,152; US 2008/0081920; US 2008/0306289; US 2009/0131695 and US 2009/0198076. The shape of the catalyst takes on the shape of the carrier. The shape of a carrier can be characterized by describing one or more of the following features: length, outside diameter, inside diameter; the ratio of length to diameter; radius of an exterior wall; radius of an end surface; shape when viewed from one end; and shape when viewed from the side. The most common commercially available carrier is a small cylinder pellet shape with a hole in the center of the pellet. See, for example, US 7,259,129, the disclosure of which is hereby incorporated by reference.
    In the '129 Patent, the support material has specific physical properties and is preferably formed in a formatted agglomerate of the support material which has a geometric configuration or structure of a hollow cylinder with a relatively small internal diameter. In contrast, 30 US 4,441,990 discloses hollow formatted catalytic extrudates that can be used in catalytically promoted processes that include hydrocarbon processing operations. The shapes include essentially rectangular shaped tubes, and triangular shaped tubes in the section cut. One modality is characterized by having bulbous protrusions around the outer periphery. Wall thicknesses of about 3.18 mm, 2.54 mm or even 1.02 mm (1/8 inch, 1/10 inch or even 1/25 inch) or less are declared. US 2009/0227820 discloses 10 a geometrically formatted refractory solid carrier in which at least one carrier wall thickness is less than 2.5 mm. US 6,518,220 discloses formatted catalysts. for heterogeneously catalyzed reactions in the form of hollow cylinders or annular tablets whose ends are rounded both to the extreme margin and the margin of the central hole so that they have no right-angle margins. A modification of such a catalyst shape comprises a pellet where the rounded edges are only on the outer edge of the pellet, and the inner edge of the central orifice does not comprise rounded edges. US 6,325,919 discloses catalyst carriers composed of an inorganic refractory oxide that has a rotationally symmetrical shape that has a hollow portion, such as the shape of a donut. An outer peripheral surface 25 and the inner peripheral surface that separate the hollow portion are connected by curved surfaces, and the height of the carrier along the rotational symmetry axis is less than the outer diameter of the carrier. EP 1,184,077 discloses a porous refractory carrier in the form of an angular extrudate with rounded edges. WO 03/013725 discloses particles with three elongated shaped shoulders. US 2,408,164 discloses a catalyst of various shapes including planar, cylindrical with a central opening and a plurality of parallel grooves 5 on the outer periphery, cylindrical with several parallel passages formed therein. US 4,645,754 discloses catalysts made from a carrier that is in the form of Intalox supports or Berl supports. Other formats that have been mentioned in the patent technique 10 include spheres, tablets, rings, spirals, pyramids, cylinders, prisms, cuboids, cubes, etc. See, for example: Published Patent Applications US 2008/0015393, 2008/0255374, 2009/0041751, 2009/0227820; US patents 5,155,242 and 7,547,795; and International Publication WO 15 2004/014549.
    However, there remains a need for improved catalysts that perform better in the reactor than is currently available. The present invention provides carriers and catalysts that allow for such an improvement. SUMMARY
    A carrier of the present invention provides improved performance * in a reactor by combining a cross-sectional configuration with multiple shoulders with non-uniform rounding at the intersections of the ends and the carrier wall. A catalyst of the present invention is an innovative combination of catalyst components and a carrier of this invention.
    In one embodiment, this invention is a porous ceramic body 30 comprising a first end, a second end and a wall disposed at the ends. The wall comprises at least three shoulders formed in the length of the wall. The first end and the wall intersect in a first circumferential line that has a non-uniform transition radius.
    In another embodiment, the invention is a catalyst that includes silver and promoters useful for an epoxidation of ethylene deposited in a specifically shaped porous ceramic body that has a first end, a second end and a wall disposed between the ends. The wall comprises at least three shoulders formed in the length of the wall. The first end and the wall itself. intersect on a first circumferential line that has a non-uniform transition radius.
    According to another aspect of the invention, a method is provided to produce the catalyst of this invention. Suitably, the method involves a carrier of this invention and impregnating the carrier with a solution containing silver so that the amount of silver metal in the carrier exceeds 8% by weight of the catalyst weight.
    Preferred amounts of silver are between 10 and 30% by weight of the catalyst weight. The silver-impregnated formatted carrier * then receives heat treatment to supply the catalyst, for example, in a temperature range of 100 ° C to 500 ° C, preferably 150 ° C to 320 ° C.
    In accordance with yet another aspect of the invention, a stuffed catalyst bed is provided which is formed from catalyst particles comprising sustained silver 30 in a carrier of this invention, whose catalyst bed has a silver charge of at least 50 kg silver / mJ of the catalyst bed.
    According to yet another aspect of the invention, the catalyst made by the method described above, or by the catalyst bed 5 described above, is used in a process to produce ethylene oxide upon contact with the catalyst, under conditions of epoxidation process with a supply chain comprising ethylene and oxygen.
    In addition, the invention provides a method of using ethylene oxide for the production of ethylene glycol, an ethylene glycol ether or a 1,2-alkanolamine comprising converting ethylene oxide into ethylene glycol, ethylene glycol ether or 1,2-alkanolamine, wherein the ethylene oxide was obtained by the process for preparing the ethylene oxide according to this invention. BRIEF DESCRIPTION OF THE DRAWINGS
    Figure 1 is a perspective view of a first embodiment of a carrier of this invention;
    Figure 2 is an end view of a second embodiment of a carrier of this invention;
    Figure 3 is a side view of the carrier shown in Figure 2;
    Figures 4A and 4B show an end view and a perspective view of a third embodiment of a carrier of this invention;
    Figures 5A and 5B show an end view and a perspective view of a fourth embodiment of a carrier of this invention;
    Figures 6A and 6B show an end view and a perspective view of a fifth embodiment of a carrier of this invention;
    Figure 7 reveals a carrier in the shape of a conventional ring and is labeled Prior Art; and
    Figures 8A to 8J show cross-sectional views of ten carriers of this invention. DETAILED DESCRIPTION
    As used in this document, the expressions "porous ceramic body", "carrier" and "support" are used interchangeably. The word "catalyst" refers to a carrier that includes a catalytically active material deposited on the carrier. Because the thickness of the catalytically active material is very small in relation to the width of the carrier, the apparent shape of the carrier and the shape of the catalyst are essentially identical.
    A "porous ceramic body" can refer to a body similar to an elongated rod that has a cross-sectional shape with multiple shoulders - that is, when viewed from either end, the faces of the end of the porous body have a shape with multiple shoulders and the body has a certain height that can also be described as its length. Examples of carriers with multiple shoulder shapes are shown, for example, in Figures 25 8A to 8J. One embodiment of a porous ceramic body with multiple shoulders is a hollow shaped carrier with four shoulders. The expression "shape with four shoulders" refers to the cross-sectional view of the carrier which has four extensions formatted in a non-triangular way, for example, in a semicircular way, on the circumference of the same.
    Perspective views of hollow shaped carriers with four shoulders are shown, for example, in Figures 1 and 5B. The expression "shape object with four shoulders" refers to a cross-section that has at least one passage through it, with extensions formatted in a non-triangular way, for example, in a semicircular way, on the circumference of the same.
    Porous ceramic bodies used as carriers for catalytically active material have numerous 10 chemical and physical characteristics that collectively and individually influence the selectivity, longevity, efficiency and durability of the catalyst when disposed in a reactor. chemical. The chemical and physical characteristics of the porous body can also impact the fabricability of the carrier and the catalyst. Several patents and technical articles have focused on improving the catalyst by modifying characteristics such as the carrier surface area, pore size distribution and morphology, which can be referred to in this document as the 20 micro physical characteristics of the carrier. In other publications, the carrier's macro physical characteristics, such as length, outside diameter and inside diameter, have been described. In still other publications, the relationships between the macro physical characteristics of the carrier and the inner diameter of the reactor tube have been described. The inventor of the invention claimed in the present document observed the total performance of the catalyst, which includes: preparation of the carrier and preparation of the catalyst; selectivity and longevity of the catalyst; pressure drop 30 inside the reactor; and the carrier's resistance to friction and breakage, can all be favorably influenced by formatting the carrier to include multiple shoulders and rounded corners that have a non-uniform transition radius. The combination of rounded corners and multiple 5 bosses can be used to increase the packing density of the catalyst in the reactor in relation to conventional carrier rings with non-rounded corners. An increase in the packing density can be significant because the amount of silver per unit volume of the reactor increases as the packing density of the carrier increases. Increasing the amount of silver per unit volume of the reactor can improve the productivity of the reactor which can be referred to in this document as the yield. Furthermore, the combination of rounded corners 15 and multiple shoulders can also cooperate with the provision of less tortuous passages for the flow of fluids through the catalyst bed in the reactor, in relation to a bed of carrier rings with non-rounded corners, which avoids a significant increase in the pressure drop despite the increase in the packing density of the catalyst. The combination of rounded corners and multiple shoulders also eliminates the portions of the catalyst that are most readily rubbing during the procedures used to manufacture the catalyst.
    Minimizing both the pressure drop in the reactor and the amount of particles in friction while increasing the packing density of the catalyst allows the potential impact of the micro physical characteristics of the carrier to be more fully utilized, resulting, 30 in this way , in improved selectivity and longevity which collectively improves the economic performance of the reactor. In addition to features that improve the selectivity and longevity of the catalyst, the carrier should also have sufficient mechanical strength to prevent breakage 5 during the catalyst manufacturing process and the catalyst loading process in the reactor. In some embodiments, the carrier has at least one passage arranged across the length of the carrier. In some modalities, the carrier can have 2 to 4 passes.
    In some modalities, the carrier may have a ticket for each shoulder. If the carrier has an even number of lugs, the carrier can have an even number of passes. Similarly, if the carrier has an odd number of rebounds, the carrier may have an odd number of passes. In addition, the number of rebounds and the number of passes need not be identical. The passages can be arranged symmetrically or asymmetrically around the central geometric axis of the carrier which, by definition, extends from the first end of the carrier to its second end and is located in the center of the carrier. One of the advantages of a hollow shaped carrier with multiple shoulders is that the carrier can have good mechanical strength, which can be quantified by measuring the resistance to lateral crushing of the carrier (SCS) and its resistance to crushing volume (BCS), despite the presence of a passage through the catalyst. The use of multiple passages may be preferable to the use of a single pass which has the same surface area in cross section as the combined multiplicity of passages, because the multiple passages provide a smaller wall thickness and thus minimize the impact of limitations diffusion through the carrier. In addition, the multi-pass catalyst may also be easier to manufacture than the single-opening catalyst. In a 5 modality and as shown in Figure 4A, the carrier has a shape with three shoulders in which the shoulders are truncated on the outer portion of the shoulders and the number of passes is equal to the number of shoulders.
    Features and characteristics of the carriers and the 10 catalysts of this invention and the methods for making them will now be described.
    A carrier with four shoulders 20 is shown in Figure 1 which can also be described in the present document as a carrier with four shoulders that includes the first 15 end 22, the second end 24 and the wall 26. Carrier 20 includes the first shoulder 28A , the second boss 28B, the third boss 28C and the fourth boss 28D. The intersection of the first end 22 and the wall 26 forms the first circumferential line 30 which is denoted 20 by the dotted line in Figure 1. The first circumferential line is defined with a series of continuous points around the carrier where the surface of the first end 22 makes the transition to the surface of the wall 26. The transition radii from the first end 25 to the wall are non-uniform along the circumferential line because the transition from the first end to the wall has been more rounded in some places and not rounded or slightly rounded elsewhere, thereby creating the non-uniform transition radius along the circumferential line. The largest transition rays are at the apex 32 of each of the shoulders and the smallest transition rays are at nadir 34 in the valleys 35 formed between two shoulders. Between one of the largest transition rays and one of the smallest adjacent transition rays, the transition rays vary along the circumferential line. The carrier 20 includes the first pass 36, the second pass 38 and the third pass 40. Each pass extends completely through the carrier, thus allowing fluids, including 10 fluids used in the process of preparing the catalyst and gases used in a reactor tube, flow into and through the carrier from one end of the carrier to the opposite end of the carrier. The first passage 36 is circular. The second passage 38 has an oval shape and the longest geometric axis 15 42 of the oval passage aligns with the tips of the shoulders 28B and 28D. Third pass 28C is a six-sided polygon. The radius of the shoulder 28B is identified by the arrow 44 and the radius of the valley between the shoulders 28A and 28D is identified by the arrow 46. Although not shown in Figure 1, the second end 24 crosses the wall 26 in a second circumferential line that is defined as a continuous series of points around the "carrier where the surface of the second end 24 transitions to the surface of the wall 26.
    To determine the transition radius for the leading edge of a carrier shoulder, an optical comparator can be used to illuminate the carrier, thereby creating an image that can be measured. However, to determine the minimum transition radius in a carrier valley, the carrier can be cut transversely to expose the valley and the radius can be measured using an optical comparator.
    As used in this document, a carrier is considered to have a non-uniform transition radius if a greater transitional radius of the carrier at the intersection of the wall and end is at least three times greater than the smaller carrier transition radii at the intersection. intersection of the same wall and end. For example, if the largest transition radius on the leading edge of a shoulder on carrier 10 is 6.0 mm, then the smallest transition radius in an adjacent valley should be 2.0 mm or less.
    Although the location of the passages through the porous ceramic body may not be critical in some applications, providing a plurality of passages symmetrically spaced around the end of the body, so that the distances from a passage to the surface closest to the wall is minimized and standardized, it can facilitate the preparation of the catalyst by minimizing the amount of time required to diffuse the liquid used in the catalyst preparation process 20 in and through the carrier. The format of all passages can be identical or, as shown in Figure 1, the passages can be of different formats.
    Figures 2 and 3 show an end view and a side view, respectively, of a four-shoulder catalyst containing a passage through it. The passage has an inner diameter B. The catalyst contains four round shoulders. D refers to the diameter of the general catalyst. R refers to the radius of the individual round boss 30. H refers to the height of the catalyst. In one embodiment, the present invention can be a catalyst comprising silver and promoters useful for the epoxidation of olefins deposited on a carrier with a multiple bead format that has between 3 and 8 bumps with a geometric configuration in which the ratio of D divided by R is between 3 and 8, and the ratio of H to D is between 0.5 and 3. It has been found to be particularly advantageous to use a formatted catalyst in which the ratio of H to D is in the range of from 0.8 to 1.5. In Figure 2, the diameter of the general catalyst is approximately four times the radius of the individual shoulders (R). The range of R is about 0.1 millimeter on the bottom and almost infinite or "flat" on the top. Preferably, R is about 1 to 20 millimeters; more preferably about 1 to 10 millimeters. The diameter D of the general catalyst is preferably between 2 and 50 millimeters; more preferably between about 4 and 20 millimeters. The range for H is about 2 to 50 millimeters; preferably about 4 to 20 millimeters; preferably the ratio of H to D is about 1 to 1. The diameter (hole size) of hole B ranges from 0.5 to about 5 millimeters, preferably between about 1 and about 4 millimeters. The hole size can be between about 0.1 to 0.9 times the diameter (D) of the catalyst; preferably between about 0.2 and 0.6 times the diameter of the catalyst. Although only one hole is in Figure 3, it is contemplated that one or more passages can be used. In a preferred mode, there is a ticket for each shoulder.
    Figures 4A and 4B show an end view and a perspective view, respectively, of a carrier with three shoulders having three passages.
    In Figure 5A and 5B, an end view and a perspective view, respectively, of a carrier with four shoulders having a single passage are shown.
    Figures 6A and 6B show an end view and a perspective view, respectively, of another four-shoulder carrier that has a single pass.
    Figure 7 is a perspective view of a carrier of the prior art that has no shoulders and the carrier corners are not rounded.
    Figures 8A to 8J show cross-sectional views of several carriers with multiple shoulders that have at least three shoulders and between one and five passages. The shape designated as A has four truncated shoulders and two oval shaped passages. The format called B has four shoulders and a gradual rounded intersection of the shoulders. The shape called C has four semicircular shoulders. The shape designated by D has 20 five semicircular shoulders. The format called E has four shoulders and a gradual rounded intersection of the shoulders. The format called F has four truncated shoulders and three passages. The format designated by G has four extended shoulders. The shape designated 25 by H has four extended semicircular shoulders. The format designated by I has five shoulders and a rounded intersection of the shoulders. The shape designated by J has four semicircular shoulders including a rounded intersection of the shoulders.
    A typical prior art preparation of an alpha alumina carrier involves mixing alpha alumina powder (s) with a combination of bonding agents, extrusion aids, water, fluxes, other alumina materials and, optionally, firing materials for supply a 5 malleable mixture manually. Detailed descriptions of processes that can be used to produce suitable mixtures can be found in US 6,831,037 and US 7,825,062. A suitable blend can then be extruded through an appropriately fused formatted die 10 to provide an extrudate that has three or more shoulders formed in that of the extrudate and parallel to the central geometric axis of extrusion. The extrudate can then be cut into a plurality of individual carrier precursors not subjected to the flame action commonly known as 15 dry clay (greenware). The extrudate can be cut by a fast moving blade that cuts through the extrudate essentially perpendicular to the direction of the extrusion. The resulting carrier precursors have a first end, a second end and the wall 20 that extends between the first end and the second end. The ends are essentially parallel to each other and perpendicular to the wall. The first end and the wall intersect at a right angle that inherently defines a uniform and small transition radius. The transition radius defines a circumferential line that has a uniform transition radius. Similarly, the second end and the wall intersect at a right angle that inherently defines a uniform and small transition radius that is equal to the transition radius at the intersection of the first end and the wall. A plurality of carrier precursors can then be agitated in a container, such as a rotating tube, which allows the precursors to contact each other and / or the sides of the container. During the agitation process, the carrier precursors come into contact with each other and the main edges of the shoulders are compressed, thereby rounding the edges of the shoulders. Due to the precursor's multiple shoulder design, the main margin of the precursor is compressed a large amount and the valleys between the shoulders are not compressed or are little compressed. Consequently, the main edges of the shoulders have the longest transition radius and the valleys between the shoulders have the shortest transition radius. Between the main margin of a shoulder and the valley, the transition radius of the precursor may be greater than the smallest transition radius but less than the largest transition radius. The amount of compression of the leading edge, and thus the transition radius of the leading edge, can be controlled by adjusting factors such as the length of time the precursor is agitated and the speed with which the container is rotated. The precursors that have a non-uniform transition radius are then dried to remove water and subjected to flame action at high temperatures to form the carrier body.
    High temperatures (greater than 1,200 ° C) are necessary to properly bond the alpha alumina particles to each other and to provide a carrier that has the desired surface area. Instead of using an extrusion process to form the carriers of this invention, a suitable mixture can be arranged in a cavity and the carrier can be formed by pressing the mixture into the desired shape. The carriers that were formed by the press can be manufactured with the desired roundness at the end of the carrier with the 5 interfaces of the wall and therefore do not need to be agitated in order to assign the desired non-uniform transition radius at the intersections of the ends and the wall carrier.
    A carrier of this invention can be produced from any porous refractory material that is relatively inert in the presence of ethylene oxidation feeds, products and reaction conditions and provided that such material has the desired chemical and physical properties. In general, the material comprises an inorganic material, in particular an oxide, which may include, for example, alumina, silicon carbide, carbon, silica, zirconia, magnesia, silica-alumina, silica-magnesia, silica-titania, alumina-titania, alumina-magnesia, alumina-zirconia, thorium, silica-titania-zirconia and various clays. The preferred porous refractory material comprises alumina preferably of a high purity of at least 90% by weight of alumina and, more preferably, at least 98% by weight of alumina. Often, the refractory material comprises a maximum of 99.9% by weight, more often a maximum of 99.5% by weight of alumina. Among the various forms of alumina available, alpha-alumina is the most preferred. After being subjected to the action of flames, the micro physical characteristics of the carrier can have an average pore diameter 30 of 0.3 to 15 pm, preferably 1 to 10 pm; and a pore size distribution of a single mode, bimodal or multimodal as determined by mercury intrusion at a pressure of 3.0 x 108 Pa using a Micrometrics Autopore 9200 model (130 ° contact angle, mercury with a voltage surface area of 0.473 N / m, and correction for applied mercury compression). The following are some of the many pore carrier pore distribution options. Firstly, the carrier can have a surface area of at least 1 rrr / g and a pore size distribution so that pores with diameters in the range from 0.2 to 10 pm represent at least 70% of the total pore volume and such pores together provide a pore volume of at least 0.27 ml / g, relative to the carrier weight. Second, a carrier can have an average pore diameter of more than 0.5 pm, and a pore size distribution in which at least 80% of the total pore volume is contained in pores with diameters in the range from 0, 1 to 10 pm and at least 80% of the pore volume contained in the pores with diameters in the range from 0.1 to 10 pm is contained in pores with diameters in the range from 0.3 to 10 pm. Third, a carrier that has at least two peaks of log pore volume distribution differentiates in a pore diameter range of 0.01 to 100 pm and at least one peak of the above peaks is present in a pore diameter range of 0 , 01 to 1.0 pm in the pore size distribution measured by mercury intrusion, where each peak is a maximum value of the differential log pore volume distribution of 0.2 cm3 / g or greater. Fourth, a carrier that has a bimodal pore size distribution, with a first pore mode that has an average diameter in the range of about 0.01 pm to about 5 pm, and a second pore mode that has an average diameter in the range of about 5 pm to about 30 pm. Fifth, a carrier that has a pore volume of less than 1 micron in diameter of less than 0.20 ml / g, 5 a pore volume of more than 5 micron in diameter of less than 0.20 ml / g, and a pore volume between 1 micron in diameter and 5 microns in diameter at least 40% of a total pore volume. In addition, the carrier's surface area, as measured by the 10 BET method, can be in the range from 0.03 m "/ g to 10 m2 / g, preferably from 0.05 rrr / g to 5 rrr / g plus preferably from 0.1 m2 / g to 3 nr / g. Suitably, the surface area is at least 0.5 m2 / g. The BET method of measuring the surface area has been described in detail by Brunauer, Emmet and Teller in J. Am. Chem. Soc. 60 (1938) 309 to 316, which is hereby incorporated by reference.
    In addition to the carrier having a specific geometric configuration, incorporated into the carrier is at least a catalytically effective amount of silver and, optionally, one or more promoters and, optionally, one or more co-motors. Thus, the catalyst of the invention comprises a carrier, a catalytically effective amount of silver and, optionally, one or more promoters and, optionally, one or more co-motors.
    In general, a catalyst of the present invention can be prepared by impregnating a carrier of this invention with silver and, optionally, one or more promoters, such as, for example, rare earth metals, magnesium, rhenium and 30 alkali metals (lithium, sodium, potassium, rubidium and cesium), or compounds thereof, and, optionally, one or more copromotors, such as, for example, sulfur, molybdenum, tungsten and chromium, or compounds thereof. Among the promoter components that can be incorporated into the carrier, rhenium and alkali metals, in particular, the higher alkali metals, such as potassium, rubidium and cesium, are preferred. Most preferred among the higher alkali metals is cesium, which can be used alone or in a mixture together with, for example, potassium 10 and / or lithium. Any rhenium promoter can be used without an alkali promoter present or an alkali promoter can be used without a rhenium promoter or a rhenium promoter and an alkali promoter can both be present in the catalyst system. Copromotors for use in combination with rhenium may include sulfur, molybdenum, tungsten and chromium.
    The silver is incorporated into the carrier by placing it in contact with a silver solution formed by dissolving a silver salt, or silver compound, or silver complex in a suitable solvent. The contact or impregnation is preferably done in a single impregnation step whereby the silver is deposited on the carrier so as to provide, for example, at least about 8% by weight of 25 silver to up to about 30% by weight , based on the total weight of the catalyst. In another preferred embodiment, a substantially larger amount of silver is deposited on the carrier, for example, at least 12% by weight of silver, based on the total weight of the catalyst, where the silver can be deposited in more than one impregnation step. , for example, in two, three or four impregnation steps.
    The one or more promoters can also be deposited on the carrier before, coincidentally with or subsequent to the deposit of the silver, but preferably, the one or more 5 promoters are deposited on the carrier coincidentally or simultaneously with the silver. When the catalyst comprises silver, rhenium and a rhenium copromotor, it may be advantageous to deposit the copromotor before or simultaneously with the silver deposit, and deposit rhenium 10 after at least a portion of the silver has been deposited. The advantage is that this sequence of deposit steps materializes in an improved stability of the catalyst, in particular in relation to its activity.
    Promoting amounts of alkali metal or mixtures of alkali metal can be deposited in a carrier using a suitable solution. Although alkali metals exist in a pure metallic state, they are not suitable for use in that form. They are generally used as compounds of the alkali metals dissolved 20 in a suitable solvent for impregnation purposes. The carrier can be impregnated with a solution of the alkali metal compound (s) before, during or after the impregnation of the silver in a suitable form has occurred. An alkali metal promoter can even be deposited on the carrier after the silver component has been reduced to metallic silver.
    The amount of alkali metal used will depend on several variables, such as, for example, the surface area and pore structure and chemical properties of the carrier used, the silver content of the catalyst and the particular ions and their quantities used in conjunction with the alkali metal cation.
    The amount of alkali metal promoter deposited on the carrier or present in the catalyst is generally in the range from 10 parts per million to about 3,000 parts per million, preferably between about 15 parts per million and about 2,000 parts per million and more preferably, between about 20 parts per million and 10 about 1,500 parts per million, by weight of the metal relative to the weight of the total catalyst.
    The carrier can also be impregnated with rhenium ions, salt (s), compound (s) and / or complex (s). This can be done at the same time that the alkali metal promoter is added, or before or after; or at the same time as the silver is added, or before or after. Rhenium, alkali metal, and silver can be in the same impregnation solution. Their presence in different solutions will provide suitable catalysts, and in some cases, up to 20 improved catalysts.
    The preferred amount of rhenium, calculated as the metal, deposited or present in the formatted agglomerate or catalyst is in the range of about 0.1 micromols (pmol) per gram to about 10 micromols per gram, plus 25 preferably about 0 , 2 micromols per gram to about 5 micromols per gram of the total catalyst, or, alternatively stated, from about 19 parts per million to about 1,860 parts per million, preferably from about 37 parts per million to about 30 930 parts per million by weight of the total catalyst. References to the amount of rhenium present in the catalyst are expressed as metal, regardless of the way in which rhenium is actually present.
    The rhenium compound used in the preparation of the instantaneous catalyst 5 includes rhenium compounds that can be solubilized in an appropriate solvent. Preferably, the solvent is a solvent that contains water. More preferably, the solvent is the same used to deposit the silver and the alkali metal promoter.
    Examples of suitable rhenium compounds in the production of the catalyst of the invention include rhenium salts such as rhenium halides, rhenium oxyhalides, rhenates, perrhenates, rhenium oxides and acids. A preferred compound for use in the impregnation solution is perrhenate, preferably ammonium perrhenate. However, alkali metal perrhenates, alkaline earth metal perrhenates, silver perrhenates, other perrhenates and rhenium heptoxide can also be used properly.
    The one or more co-motors can be deposited on the carrier in any suitable manner known to those skilled in the art. The co-promoter is deposited in the carrier before, coincidentally with or subsequent to the deposit of the silver, but, preferably, the one or more co-motors are deposited in the coincident carrier or simultaneously with the silver. A copromotor amount of copromotor is deposited on the carrier and can generally be in the range of about 0.01 to about 25, or more, pmols per gram of the total catalyst.
    The catalysts according to the present invention have a particularly high activity and selectivity for producing ethylene oxide in direct oxidation of ethylene with molecular oxygen to ethylene oxide. For example, the catalyst of the invention may have an initial selectivity of at least about 86.5 mol%, preferably at least 87 mol%, and more preferably at least 88.5 mol%. It is a benefit of this invention that packaging the catalyst of the invention in a catalyst bed provides a catalyst bed that has a relatively high silver charge, without causing an increased pressure drop on the catalyst bed when in use in the process to produce ethylene oxide, and / or has an improved packing density balance in relation to such a pressure drop. When the hole diameter is reduced, the balance of the pressure drop / packing density behaves favorably in a typical reactor tube in ethylene oxide production, compared to predictions based on theoretical models, for example, the Correlation from Ergun, see WJ Beek and KMK
    Muttzall, "Transport Phenomena", J. Wiley and Sons Ltd, 1975, p. 114. In practicing the present invention, it may be achievable that the silver loading of the catalyst can be at least 150 kg of silver / m3 in the catalyst bed, preferably at least 170 kg of silver / m3 in the catalyst bed, more preferably at least 200 kg of silver / m3 in the catalyst bed, and in particular at least 250 kg of silver / m3 in the catalyst bed. Often silver loading is at most 800 kg of silver / m3 in the catalyst bed, more often at maximum 30 kg of silver / m3 in the catalyst bed, even more often at most 550 kg of silver / m3 in the catalyst bed . The high silver loading allows the application of relatively light conditions in the ethylene oxide manufacturing process, in particular temperature, 5 to achieve a given work rate, along with the achievement of an improved selectivity and catalyst life, in particular in activity stability and selectivity stability.
    As used in this document with reference to the selectivity of a catalyst, the term "selectivity", Sw, means the mol% (%) of the desired ethylene oxide formed in relation to the total ethylene converted. Selectivity can be specified at a given work rate, w, for a catalyst with a work rate 15 which is defined as the amount of ethylene oxide produced per unit volume of catalyst (eg kg per m3) per hour . As used in this document with reference to the activity of a catalyst, the term "activity", Tw, means the temperature required to achieve a given rate of work.
    The conditions for carrying out the epoxidation reaction in the presence of the catalysts according to the present invention comprehensively comprise those already described in the prior art. This applies, for example, to suitable temperatures, pressures, residence time, diluent materials such as carbon dioxide, steam, argon, methane or other saturated hydrocarbons, in the presence of moderating agents to control catalytic action, 30 for example , 1,2-dichloroethane, vinyl chloride, ethyl chloride or chlorinated polyphenyl compounds, to the desirability of employing recycling operations or applying successive conversions in different reactors to increase ethylene oxide yields, and any other 5 special conditions that can be selected in processes for preparing ethylene oxide. Pressures in the range from atmospheric to about 3,450 kPag (500 psig) are generally employed. Higher pressures, however, are not excluded. The molecular oxygen employed as a reagent can be obtained from any suitable source, including conventional sources. A suitable oxygen load can include relatively pure oxygen, or a concentrated oxygen stream that comprises more oxygen with less or one or more diluents, such as hydrogen and argan, or any other stream that contains oxygen, such as air. The use of those present in ethylene oxide reactions is by no means limited to the use of specific conditions among those known to be effective.
    For illustration purposes only, the following table shows the range of conditions that are frequently used in current commercial ethylene oxide reactor units: Table I

    * Cubic meters of gas at standard temperature and pressure that pass through 0.3 cubic meters (one cubic foot) of packaged catalyst per hour.
    In a preferred application, ethylene oxide is produced when a gas containing oxygen with ethylene in the presence of the catalysts of the invention under suitable epoxidation reaction conditions such as at a temperature in the range of about 180 ° C to about 330 ° C ° C, and preferably 200 ° C to 325 ° C, and a pressure in the atmospheric range of about 3,450 kPag (500 psig) and, preferably, from 1,034 kPa to 2,758 kPag (150 psig at 400 psig) . In the normal practice of the ethylene oxide manufacturing process, the feed stream that comes in contact with the catalyst, and which comprises ethylene and oxygen, additionally comprises a low concentration of carbon dioxide, because carbon dioxide is a by-product process and appears, in part, in the feed stream as a result of recycling. It is advantageous to reduce the carbon dioxide concentration in the feed stream to a low level, as this will improve the performance of the catalyst in terms of activity, selectivity and life of the catalyst. It is preferred that the amount of carbon dioxide in the feed is at most 4 mol%, more preferably at most 2 mol%, in particular at most 1 mol%, in relation to the total feed. Often, the amount of carbon dioxide will be at least 0.1 mol%, more often at least 0.5 mol%, relative to the total feed. The ethylene oxide produced can be recovered from the reaction mixture using methods known in the art, for example, by absorbing ethylene oxide from the outlet stream in the reactor in water and optionally recovering ethylene oxide from of the aqueous solution by distillation. The ethylene oxide produced in the epoxidation process can be converted to ethylene glycol, an ethylene glycol ether or an alkanolamine.
    Conversion to ethylene glycol or ethylene glycol ether may comprise, for example, reacting ethylene oxide with water, suitably using an acid or basic catalyst. For example, to produce predominantly ethylene glycol and less ethylene glycol ether, 25 ethylene oxide can be reacted with a decimal molar excess of water, in a liquid phase reaction in the presence of an acid catalyst, for example, 0.5 to 1,0% by weight of sulfuric acid, based on the total reaction mixture, at 50 to 70 ° C at 100 kPa absolute, or in a gas phase reaction at 30 130 to 240 ° C and 2,000 to 4,000 kPa absolute, preferably in the absence of a catalyst. If the proportion of water is decreased, the proportion of ethylene glycol ethers in the reaction mixture is increased. The ethylene glycol ethers thus produced can be a diether, 5 triether, tetraether or a subsequent ether. Alternative ethylene glycol ethers can be prepared by converting ethylene oxide with an alcohol, in particular, a primary alcohol, such as methanol or ethanol, by replacing at least a portion of the water with alcohol.
    The conversion to alkanolamine may comprise reacting ethylene oxide with an amine, such as ammonia, an alkyl amine or a dialkylamine. Aqueous ammonia or anhydrous ammonia can be used. Anhydrous ammonia is typically used to promote the production of monoalkanolamine. For methods applicable to the conversion of ethylene oxide to alkanolamine, reference may be made to, for example, US Patent No. 4,845,296, which is incorporated by reference into this document. Ethylene glycol and ethylene glycol ethers can be used in a wide variety of industrial applications, for example, in the fields of food, beverages, tobacco, cosmetics, thermoplastic polymers, curable resin systems, detergents, heat transfer systems, etc. Alcanolamines can be used, for example, in the treatment ("sweetening") of natural gas.
    The above description is considered to be that of particular modalities only. Modifications of the invention will occur to those skilled in the art and to those who produce or use the invention. Therefore, it should be understood that the 30 modalities shown in the drawings and described above are for illustrative purposes only and are not intended to limit the scope of the invention, which is defined by the following claims in accordance with the interpretation of the principles of patent laws , including Doctrine 5 of the Equivalents.
    权利要求:
    Claims (30)
    [0001]
    1. Porous ceramic body characterized by the fact that it comprises: a first end; a second end; and a wall disposed between said ends, said wall comprising at least three projections formed in the length of the wall, wherein said first end and said wall intersect in a first circumferential line that has a non-uniform transition radius .
    [0002]
    2. Porous ceramic body, according to claim 1, characterized by the fact that it also comprises at least one passage arranged inside said wall between said ends.
    [0003]
    Porous ceramic body, according to claim 1, characterized by the fact that it also comprises at least three passages arranged inside said wall between said ends.
    [0004]
    4. Porous ceramic body, according to claim 3, characterized by the fact that said wall comprises no more than eight shoulders.
    [0005]
    5. Porous ceramic body, according to claim 4, characterized by the fact that it comprises an identical number of shoulders and passages.
    [0006]
    6. Porous ceramic body, according to claim 5, characterized by the fact that it comprises at least four shoulders and no more than six shoulders.
    [0007]
    7. Porous ceramic body, according to claim 4, characterized by the fact that it comprises a different number of shoulders and passages.
    [0008]
    8. Porous ceramic body according to claim 7, characterized by the fact that it comprises an even number of shoulders and an odd number of passages.
    [0009]
    9. Porous ceramic body, according to claim 7, characterized by the fact that it comprises an odd number of shoulders and an even number of passages.
    [0010]
    10. Porous ceramic body, according to claim 1, characterized by the fact that said transition radius of the circumferential line comprises a first radius located at the apex of a shoulder and a second radius located in the nadir between two adjacent shoulders in which the said first radius is greater than said second radio.
    [0011]
    11. Porous ceramic body according to claim 10, characterized by the fact that said first radius is at least three times greater than said second radius.
    [0012]
    Porous ceramic body, according to claim 1, characterized by the fact that said second end and said wall intersect in a second circumferential line that has a non-uniform transition radius.
    [0013]
    13. Porous ceramic body according to claim 3, characterized by the fact that it also comprises a theoretical central geometric axis that extends through said ceramic body from said first end to said second end and said passages are asymmetrically distributed around said central geometric axis.
    [0014]
    14. Porous ceramic body, according to claim 2, characterized by the fact that said at least one passage has a non-circular cross-sectional shape.
    [0015]
    15. Porous ceramic body, according to claim 14, characterized by the fact that said non-circular cross-sectional shape is selected from the group consisting of an oval, rectangular and polygonal shape.
    [0016]
    16. Porous ceramic body, according to claim 1, characterized by the fact that each shoulder has a radius R, 5 the general diameter of said ceramic body is D, the ratio of D to R is between 3 and 8, the height of said ceramic body is H, and the ratio of H to D is between 0.5 and 3.
    [0017]
    17. Porous ceramic body, according to claim 16, characterized by the fact that the diameter D of the porous ceramic body 10 is between 4 and 18 millimeters, the radius R of a shoulder is between 1 and 20 millimeters, the ratio of D for R it is between 1 and 8 and the height H of the ceramic body is between 4 and 18 millimeters.
    [0018]
    18. Porous ceramic body according to claim 1, 15 characterized by the fact that it has a surface area between 0.03 m2 / g to 10 m2 / g.
    [0019]
    19. Porous ceramic body according to claim 1, characterized by the fact that it has an average pore diameter of more than 0.5 pm, a 20 pore size distribution in which at least 80% of the total pore volume is contained in pores with diameters in the range from 0.1 to 10 pm and at least 80% of the pore volume contained in pores with diameters in the range from 0.1 to 10 pm is contained in pores with diameters in the range of from 0.3 25 to 10 pm.
    [0020]
    Porous ceramic body according to claim 1, characterized by the fact that it comprises a pore size distribution that has at least two peaks of different pore volume log distribution in a range 30 of 0.01 pore diameter at 100 pm and at least one peak from the peaks above is present in a pore diameter range of 0.01 to 1.0 pm in the pore size distribution measured by mercury intrusion, where each peak is a maximum value of log distribution of pore volume differentiated from 0.2 cm3 / g or greater.
    [0021]
    21. Porous ceramic body according to claim 1, characterized by the fact that it has a bimodal pore size distribution, with a first pore mode that has an average diameter in the range from about 0.01 pma to about 5 pm, and a second pore mode that has an average diameter in the range from about 5 pm to about 30 pm.
    [0022]
    22. Porous ceramic body according to claim 1, characterized by the fact that it has a pore volume of less than 1 micron in diameter of less than 0.20 ml / g, a pore volume of more than than 5 microns in diameter of less than 0.20 ml / g, and a pore volume between 1 micron in diameter and 5 microns in diameter at least 40% of a total pore volume.
    [0023]
    23. Catalyst characterized by the fatode comprising porous ceramic body, as defined in claim 1, silver and one or more promoters useful for the epoxidation of olefins.
    [0024]
    24. Catalyst according to claim 23, characterized by the fact that silver is present in an amount in the range between 10 and 30% by weight of the total weight of the catalyst.
    [0025]
    25. Catalyst according to claim 23, characterized by the fact that one or more promoting components are selected from the group consisting of rare earth metals, magnesium, rhenium and alkali metals.
    [0026]
    26. Catalyst according to claim 25, characterized by the fact that the amount of said rhenium promoter is at least 1.25 mmol / kg, in relation to the total weight of the catalyst.
    [0027]
    27. Catalyst according to claim 26, characterized by the fact that it further comprises a rhenium co-promoter selected from the group consisting of sulfur, molybdenum, tungsten and chromium and in which at least one of said alkali metals is selected a from the group consisting of lithium, potassium, rubidium and cesium.
    [0028]
    28. Process characterized by the fact that it is for preparing an olefin oxide by reacting a feed that comprises an olefin and oxygen in the presence of a catalyst, as defined in claim 23.
    [0029]
    29. Process according to claim 28, characterized by the fact that the olefin comprises ethylene.
    [0030]
    30. Process for the preparation of a 1,2-diol, a 1,2-diol ether, a 1,2-carbonate, or an alkanolamine characterized by the fact that it comprises converting an olefin oxide to 1,2-diol, 1,2-diol ether, 1,2-carbonate or alkanolamine, wherein the olefin oxide was prepared by the process to prepare an olefin oxide, as defined in claim 28.
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    同族专利:
    公开号 | 公开日
    EP2658829A4|2014-08-13|
    WO2012091898A3|2012-08-23|
    JP5957005B2|2016-07-27|
    US10618041B2|2020-04-14|
    WO2012091898A2|2012-07-05|
    US8871677B2|2014-10-28|
    TWI615196B|2018-02-21|
    US20150045565A1|2015-02-12|
    CN103270001A|2013-08-28|
    JP2014508028A|2014-04-03|
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    US20170297010A1|2017-10-19|
    US20120171407A1|2012-07-05|
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    KR101577613B1|2015-12-15|
    US8999887B2|2015-04-07|
    TW201226056A|2012-07-01|
    RU2621730C2|2017-06-07|
    BR112013016091A2|2016-09-20|
    CA2823026A1|2012-07-05|
    US20190126261A1|2019-05-02|
    RU2013134405A|2015-02-10|
    US20150209774A1|2015-07-30|
    CA2823026C|2016-05-24|
    US9694355B2|2017-07-04|
    CN103270001B|2015-11-25|
    KR20130097236A|2013-09-02|
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    法律状态:
    2016-09-27| B15I| Others concerning applications: loss of priority|Free format text: PERDA DA PRIORIDADE US 61/428,009 DE 29/12/2010 REIVINDICADA NO PCT/US2011/064345, CONFORME AS DISPOSICOES PREVISTAS NA LEI 9.279 DE 14/05/1996 (LPI) ART. 167O, ITEM 28 DO ATO NORMATIVO 128/97 E NO ART. 29 DA RESOLUCAO INPI-PR 77/2013. ESTA PERDA SE DEU PELO FATO DE O DEPOSITANTE CONSTANTE DA PETICAO DE REQUERIMENTO DO PEDIDO PCT SER DISTINTO DAQUELE QUE DEPOSITOU A PRIORIDADE REIVINDICADA E NAO APRESENTOU DOCUMENTO COMPROBATORIO DE CESSAO, CONFORME AS DISPOSICOES PREVISTAS NA LEI 9.279 DE 14/05/1996 (LPI) ART. 166O, ITEM 27 DO ATO NORMATIVO 128/97 E NO ART. 28 DA RESOLUCAO INPI-PR 77/2013. |
    2017-01-10| B12F| Appeal: other appeals|
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-06-11| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2020-07-28| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-11-10| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/12/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201061428009P| true| 2010-12-29|2010-12-29|
    US61/428,009|2010-12-29|
    PCT/US2011/064345|WO2012091898A2|2010-12-29|2011-12-12|A multi-lobed porous ceramic body and process for making the same|
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