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    • 专利摘要:
    HIGH CONCENTRATION SILVER SOLUTIONS FOR THE PREPARATION OF ETHYLENE OXIDE CATALYST. A silver impregnation solution comprising: (i) silver ions, (ii) a silver concentration enhancer selected from at least one ammonium salt having an anionic component that is thermally capable of decomposing; or at least one amino acid, or a combination thereof, (iii) at least one organic amine; and (iv) water; wherein said components (i) - (iii) are dissolved in said impregnation solution, and oxalic acid may or may not be included. The silver impregnation solution can achieve significantly higher concentrations of silver including at least or above 33, 34, or 35% by weight. Methods for producing a silver catalyst by impregnating silver from a refractory support followed by calcination are also described. The resulting silver catalysts have high silver fillers, typically at least 17, 18, or 19% by weight.
    公开号:BR112016014540B1
    申请号:R112016014540-2
    申请日:2014-12-18
    公开日:2020-12-01
    发明作者:Lixin Cao；Andrzej Rokicki
    申请人:Scientific Design Company, Inc.；
    IPC主号:
    专利说明:

    [0001] [001] The present invention claims benefit from US Provisional Application Serial No. 61 / 918,342, filed on December 19, 2013, the entire contents of which are incorporated herein by reference. FIELD OF INVENTION
    [0002] [002] The present invention relates to silver-based ethylene oxide catalysts for the oxidative conversion of ethylene to ethylene oxide, and in particular, to their preparation. More particularly, the present disclosure relates to silver impregnation solutions with a high concentration of silver, and their use in the production of silver-based ethylene oxide catalysts that have high activity and selectivity. BACKGROUND
    [0003] [003] A high silver charge on an ethylene oxide catalyst is generally known to result in increased selectivity, activity and stability. For these reasons, a high silver charge is generally desirable. A method known in the art to increase the silver charge in the catalyst is the use of a high water absorption carrier. However, the use of a water-absorbing carrier generally leads to a loss of mechanical strength in the catalyst. Another method known in the art to increase the silver load on a catalyst is the use of a double impregnation process. However, double impregnation generally decreases the productivity of the catalyst and increases the complexity of the process when incorporating promoter species.
    [0004] [004] Conventional silver impregnation solutions in the art typically contain silver oxalate, or a combination of silver oxide and oxalic acid, together, in ethylenediamine (EDA). In the conventional oxalic acid formulation, oxalate in oxalic acid provides oxalate anion (C2O42-) to neutralize the cationic charge balance of silver (Ag +) in the water / EDA solution to form a soluble [Ag2C2O4] -EDA complex. For this reason, oxalic acid is often called an "anion contributor". The maximum permissible silver concentration in these solutions is generally 31% by weight under ambient conditions. Attempts to increase the silver concentration beyond this value generally result in the precipitation of silver salts and thus the silver concentration in conventional silver solutions is generally adjusted to no more than 31% by weight.
    [0005] [005] As indicated, there would be a significant advantage and benefit in an impregnation solution that can retain a silver salt in concentrations significantly higher than those permitted in the technique, being stable during storage and use, that is, with complete dissolution of silver in the absence of precipitation. Such an impregnation solution can be useful in the production of ethylene oxide catalysts having a high silver charge by more direct means, without the complexity and other disadvantages of conventional methods of the technique, such as the use of a water absorption carrier or a double impregnation process. SUMMARY
    [0006] [006] In one aspect, the present invention is directed to an impregnation solution (i.e., "solution containing liquid silver"), having a higher silver concentration than conventional. The impregnation solution of the present description includes: (i) silver ions, (ii) a silver concentration enhancer selected from at least one ammonium salt having an anionic component that is thermally capable of decomposing, or at least an amino acid, or a combination thereof; (iii) at least one organic amine; and (iv) water; wherein components (i) - (iii) are dissolved in the impregnation solution. The silver in the impregnation solution is typically present in a concentration of at least 33% by weight. In some embodiments, oxalic acid is included in the impregnation solution, while in other embodiments, oxalic acid is excluded. In particular embodiments, the organic amine is an alkylenediamine, such as ethylenediamine.
    [0007] [007] In another aspect, the present invention is directed to a process for producing a charged catalyst with a high silver content useful in converting ethylene to ethylene oxide. In the process, a refractory support is impregnated with silver using the high silver impregnation solution described above, and the impregnated carrier is then calcined to convert the ions from silver to metallic silver, by methods known in the art of preparation of silver catalyst. The resulting high-silver loaded catalyst generally has better activity, selectivity and / or stability, compared to silver catalysts that have lower silver concentrations. DETAILED DESCRIPTION
    [0008] [008] In one aspect, the present disclosure relates to a silver impregnation solution having a higher silver concentration than the conventional one dissolved in it. In order to be dissolved, the silver in the impregnation solution is necessarily present in the form of silver ions which, by necessity, are associated with anions in the form of a salt or silver compound. Silver ions may or may not be complexed with a neutral binder, such as an amine, diamine or triamine. Silver salts useful for impregnation include, for example, silver oxalate, silver nitrate, silver oxide, silver carbonate, silver carboxylates, silver citrate, silver phthalate, silver lactate, silver propionate, butyrate silver, as well as salts of higher fatty acids and combinations thereof. A wide variety of complexing or solubilizing agents can be used to solubilize silver to the desired concentration in the impregnation medium. Useful complexing or solubilizing agents include amines, ammonia, lactic acid and combinations thereof.
    [0009] [009] In addition to silver ions, the impregnation solution described here contains at least one organic amine compound. The organic amine can be any of the amine compounds known in the art, which function as complexing and / or solubilizing agents for the silver ion. In general, the organic amine has at least one primary or secondary amine group. The organic amine must be completely soluble in an aqueous-based solvent, which can be water or water mixed with a water-soluble solvent. The organic amine can be, for example, an alkylamine, alkylenediamine, dialkylenetriamine or alkane laminin. Some examples of alkylamines include ethylamine, diethylamine, n-propylamine, di (n-propylamine), isopropylamine, diisopropylamine, n-butylamine, isobutylamine, sec-butylamine, and i-butylamine. Some examples of alkylenediamines include ethylenediamine (EDA), 1,2-propylene diamine, 1,3-propylene diamine and 1,4-butylenediamine. Some examples of dialkylenetriamines include diethylenetriamine and dipropylenetriamine. Some examples of alkanolamines include ethanolamine, diethanolamine, propanolamine (i.e., 1-amino-2-propanol or 1-amino-3-propanol) and di-propanolamine. The organic amine is typically present in the impregnation solution in an amount of about 0.1 to about 5.0 moles per mole of silver, or about 0.2 to about 4.0 moles per mole of silver, or about 0.3 to about 3.0 moles per mole of silver. As used herein, the term "about" generally indicates no more than ± 10%, ± 5%, ± 2%, or ± 1% of a number. For example, the term "about 1 mol" indicates generally a value in the range of 0.9 to 1.1 mol in its widest sense.
    [0010] [010] The impregnation solution described here further includes a silver concentration enhancer, in particular at least an ammonium salt having an anionic component that is thermally capable of decomposing, or at least an amino acid, or an combination thereof. The silver concentration enhancer, which can be a single compound or a combination of compounds (for example, one or more ammonium salts, or one or more amino acids, or one or more ammonium salts in combination with one or more amino acids) , is generally present in the silver impregnation solution in an amount of at least 1% by weight with respect to the total weight of the impregnation solution. In different embodiments, the silver concentration enhancer can be included in the impregnation solution in an amount of precisely about at least above, up to, or less than, for example, 1, 2, 5, 10, 15, 20 , 25, 30, 35, 40, 45, 50, 55, or 60% by weight, or in an amount within a range limited by any two of the above exemplary values.
    [0011] [011] In a first set of modalities, the silver concentration intensifier is at least an ammonium salt having an anionic component that is thermally capable of decomposing. As used in this document, the term "thermally capable of decomposing" indicates that the anion decomposes, usually for the gaseous species, which temporarily leaves the ammonium ion isolated. Without adhering to the theory, it is believed that the ion of isolated ammonium, in the presence of the alkaline organic amine, reacts with the organic amine to form ammonia, which is still complex with silver ions to form a polyamine-silver complex (ie, Ag (NH3) n +), where n is generally 2 or 3. In some embodiments, the anion contains at least one carbon atom (that is, containing carbon), and in more particular embodiments, the anion is organic in nature because it contains at least one carbon-hydrogen bond. and / or carbon-carbon bond Some examples of suitable ammonium salts include ammonium carboxylates, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium phosphate, diamonium hydrogen phosphates, and ammonium dihydrogen phosphate Some examples of carboxylates of ammonium include ammonium formate, ammonium acetate, ammonium propionate, ammonium butyrate, ammonium valerate, ammonium oxalate, ammonium hydrogen oxalate, ammonium malonate, ammonium hydrogen malate, ammonium succinate, ammonium hydrogen succinate, ammonium maleate, ammonium hydrogen maleate, ammonium fumarate, ammonium hydrogen fumarate, ammonium malate, ammonium hydrogen malate, ammonium citrate, ammonium tartrate, ammonium lactate, ammonium aspartate and ammonium glutamate.
    [0012] [012] Some ammonium salts can be included in impregnation solutions of the technique in order to incorporate promoter species in the support and subsequent catalyst. However, the ammonium salts used in the art in general, do not have anions capable of decomposing. Some examples of ammonium salts containing an anionic promoter species include ammonium fluoride, ammonium chloride, ammonium sulfate, ammonium renate (NH4ReO4), and ammonium vanadate, none of which have an anion capable of decomposing. In contrast to ammonium salts in the art, the ammonium salt used here includes an anion that is thermally capable of decomposing in the manner described above.
    [0013] [013] The impregnation solution can contain any suitable solvent in which all components of the impregnation solution are completely miscible. The solvent is typically water-based, that is, aqueous. In one embodiment, the solvent is just water. In other embodiments, the solvent includes water mixed with a water-soluble co-solvent, such as an alcohol (for example, methanol or ethanol), glycol (for example, ethylene glycol or propylene glycol), or a ketone (for example, acetone) .
    [0014] [014] The silver concentration in the impregnation solution is generally at least 33% by weight. In different embodiments, the silver concentration in the impregnation solution is about at least or greater than 34, 35, 36, 37, 38, 39, or 40% by weight of the impregnation solution, or the concentration silver is within a range limited by any two of the above values.
    [0015] [015] In one embodiment, oxalic acid is included in the impregnation solution when the ammonium salt of the present description is present. In another embodiment, oxalic acid is excluded from the impregnation solution when the ammonium salt of the present description is present. When oxalic acid is included, the ammonium salt of the present disclosure can be in any suitable molar ratio with oxalic acid. In different embodiments, the molar ratio of the ammonium salt (of the present description) to oxalic acid is about at least above, up to, or less than, for example, 100: 1, 90: 1, 80: 1, 50: 1, 40: 1, 30: 1, 20: 1, 10: 1, 5: 1, 2: 1, 1: 1, 1: 2, 1: 5, 1:10, 1:20, 1: 30, 1:40, 1:50, 1:80, 1:90, or 1: 100, or a molar ratio within a range limited by any two of the above values. When a simple ammonium salt (of the present disclosure) is included, then the previous molar ratios refer to the single ammonium salt, regardless of whether ammonium salts that are not of the present disclosure can also be included. When a combination of ammonium salts of the present disclosure (for example, two, three, four or more) is included, then the molar ratios mentioned above can be taken as the total molar ratio of the ammonium salts of the present disclosure, or the Previous molar ratios can independently be taken as molar ratios of the individual ammonium salts of the present disclosure, regardless of whether non-ammonium salts can also be included in the present disclosure. Alternatively, the amount of ammonium salt (of the present disclosure) in relation to oxalic acid can be expressed in terms of molar percentage (mol%), such as 98, 95, 90, 85, 80, 75, 70, 65, 60 , 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, or 1 mol% of ammonium salt in relation to the total ammonium salt and oxalic acid.
    [0016] [016] In a second set of modalities, the silver concentration intensifier is at least one amino acid. The amino acid can be any of the known natural or unnatural amino acids and, in particular, any of the known essential amino acids, which generally refer to the amino acids found in abundance in living organisms. The amino acid must have a non-derivatized amino end (that is, -NH2 or -NH3 +) and a non-derivatized carboxylic acid end (for example, - COOH or -COO-). In the case of a charge at either or both of the amino and carboxyl ends, the amino acid is known to have a suitable counterion. The one or more amino acids can be selected from, for example, glycine, alanine, valine, leucine, isoleucine, cysteine, methionine, phenylalanine, tyrosine, tryptophan, proline, serine, threonine, asparagine, glutamine, aspartic acid, glutamic acid , histidine, lysine and arginine. Generally speaking, the amino acid considered here is an alpha-amino acid, as typically found in living organisms. However, beta-amino acids (e.g., beta-alanine) and gamma-amino acids (e.g., gamma-aminobutyric acid, also known as GABA) are also considered here as amino acids.
    [0017] [017] The amino acid is typically characterized by the nature of its side chain, which, in the case of alpha-amino acids, is located on the alpha carbon atom. In a first embodiment, the amino acid lacks a side chain (that is, different from a hydrogen atom), as found in glycine, beta-alanine, and gamma-aminobutyric acid. In a second embodiment, the amino acid has an aliphatic side chain, as found in alanine, valine, leucine and isoleucine. An example of a less common aliphatic amino acid, but considered here, is alpha-aminobutyric acid, also known as homoalanine, which has an ethyl group as its side chain, instead of the methyl group of the alanine side chain. In a third embodiment, the amino acid has an aromatic side chain, as found in phenylalanine, tyrosine, tryptophan and histidine. In a fourth embodiment, the amino acid has one or more nitrogen atoms in its side chain, such as those found in lysine, arginine, histidine, tryptophan, asparagine and glutamine. In a fifth embodiment, the amino acid has a group containing sulfur in its side chain, such as those found in cysteine, homocysteine and methionine. In some embodiments, the amino acid does not contain a heteroatom (that is, an atom other than carbon and hydrogen) in its side chain, while in other embodiments, the amino acid may have a heteroatom in its side chain.
    [0018] [018] In specific embodiments, the amino acid is selected from one or more of glycine, alanine, valine, leucine and isoleucine or, more particularly, glycine, alanine and valine, or, more particularly, glycine and alanine, or more particularly , glycine. In some embodiments, any of the amino acid groups provided in this disclosure indicates a defined minimum from which one or more amino acids are selected, without excluding amino acids not belonging to the indicated set. In other embodiments, any of the above-described groups of amino acids indicates a closed set from which one or more amino acids are selected, with the complete or partial exclusion of amino acids not belonging to the indicated set. In addition, any two or more examples of sets of amino acids provided above can be combined as a larger set from which one or more amino acids are selected. In still other embodiments, any one or more specific groups or types of amino acids provided above may be excluded.
    [0019] [019] The term "amino acid" may also include here dipeptides or tripeptides, provided that the dipeptide or tripeptide has non-derivatized amine and carboxylic acid ends. The dipeptide or tripeptide necessarily has one or two amide bonds, respectively, and can contain any two or three amino acids, such as those described above, linked by one or two amide bonds, respectively. The dipeptide can be, for example, glycylglycine, i.e., H2NCH2C (O) NHCH2C (O) OH, or glycylalanine, i.e., H2NCH2C (O) NHCH (CH3) C (O) OH. The tripeptide can be, for example, glycine-glycine-glycine, glycine-alanine-glycine, glycine-glycine-alanine, glycine-glycine-valine and glycine-alanine-valine.
    [0020] [020] In one embodiment, oxalic acid is included in the impregnation solution when the amino acid is present. In another embodiment, oxalic acid is excluded from the impregnation solution when the amino acid is present. When oxalic acid is included, the amino acid of the present disclosure can be in any suitable molar ratio with oxalic acid. In different embodiments, the molar ratio of amino acid to oxalic acid is about at least above, up to, or less than, for example, 100: 1, 90: 1, 80: 1, 50: 1, 40: 1 , 30: 1, 20: 1, 10: 1, 5: 1, 2: 1, 1: 1, 1: 2, 1: 5, 1:10, 1:20, 1:30, 1:40, 1 : 50, 1:80, 1:90, or 1: 100, or a molar ratio within a range limited by any two of the above values. When a single amino acid is included, then the previous molar ratios refer to the single amino acid. When a combination of amino acids (for example, two, three, four or more) is included, then the molar ratios mentioned above can be taken as the total molar ratio of amino acids, or the molar ratios mentioned above can independently be taken. in molar ratios of the individual amino acids. Alternatively, the amount of amino acids in relation to oxalic acid can be expressed in terms of molar percentage (mol%), such as 98, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45 , 40, 35, 30, 25, 20, 15, 10, 5, 2, or 1 mol% of amino acids in relation to the total amino acid and oxalic acid.
    [0021] [021] In some embodiments, the silver concentration enhancer is a combination of at least one ammonium salt according to the present disclosure, together with at least one amino acid. For example, in some embodiments, one or more of the amino acids disclosed above may be combined with one or more ammonium carboxylates, or one or more of any of the ammonium salts described above may be combined with one or more amino acids selected from among glycine, alanine, valine, leucine and isoleucine, or one or more of any of the ammonium carboxylates disclosed above can be combined with one or more amino acids selected from glycine, alanine, valine, leucine and isoleucine. The present patent application considers any combination of ammonium salt with amino acids, although in some embodiments, one or more combinations may be prohibited if they are reactive with each other or have an adverse effect on the solubility of silver or on another characteristic of silver impregnation solution.
    [0022] [022] In some embodiments, the impregnation solution contains one or more promoter species. The one or more promoter species can be any of the species, known in the art, that work to improve the activity or selectivity of the silver catalyst. The promoter species can be, for example, an alkaline earth, alkaline, transition element or an element of the main group, normally included in the form of a salt, for example, lithium nitrate, cesium hydroxide, ammonium sulfate, and / or ammonium renate. In other embodiments, the impregnation solution does not include a promoter species.
    [0023] [023] In another aspect, the present disclosure is directed to a method for the production of a catalyst effective in the oxidative conversion of ethylene to ethylene oxide. In the method, a refractory support is impregnated with the silver impregnation solution described above, and the silver impregnated carrier subjected to a calcination process to convert ionic silver to metallic silver by methods well known in the art, and as further described below . In some embodiments, the carrier can be impregnated, and the carrier impregnated with silver can be stored for a while, and possibly transported to a different location, before being calcined. In other modalities, the carrier is impregnated and directly subjected to a calcination process in the same installation.
    [0024] [024] The carrier, which is typically porous, can be selected from any of the solid refractory carriers known in the art for use in silver-based catalysts. Some examples of carrier materials include alumina (eg, alpha-alumina), coal, pumice, magnesia, zirconia, titanium, diatomaceous earth, floor tile, silicon carbide, silica, silicon carbide, clays , artificial zeolites, natural zeolites, silicon dioxide and / or titanium dioxide, ceramics and combinations thereof.
    [0025] [025] In some embodiments, the carrier includes, or is entirely composed of alumina, which may be a single type of alumina (eg, alpha-alumina) or a mixture of alumina compositions (eg, gamma and alpha-alumina) ). Alpha-alumina can be of high purity, that is, at least, or greater than 95% by weight or 98% by weight of alpha-alumina. The alpha-alumina carrier may or may not also include inorganic oxides other than alpha-alumina, such as silica, alkali metal oxides (eg sodium oxide) and trace amounts of other additives or impurities containing metal or not metals.
    [0026] [026] Carrier precursor particles can be of any suitable size, and are typically microparticles. In different embodiments, carrier microparticles can have a particle size (i.e., the diameter, if substantially spherical) of precisely, about, at least, greater than, up to, or less than, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, or 20 microns (µm), or the carrier microparticles may be of a size within a range limited by any two of the above exemplary values. Carrier precursor particles can also be composed of two or more portions of microparticles of different sizes or size ranges, usually selected from the exemplary sizes above. In addition, each portion of the carrier precursor particles may be at an appropriate weight percentage by total weight of the carrier precursor or finished carrier (prior to impregnation with silver). In different embodiments, one or more portions of carrier micro-particles in different size ranges can be present in an amount of, precisely, at least about greater than, up to, or less than, for example, 1% by weight, 2% by weight, 5% by weight, 20% by weight, 25% by weight, 30% by weight, 40% by weight, 50% by weight, 60% by weight, 70% by weight, 80% by weight, 90% by weight, 95% by weight, 98% by weight, or 99% by weight, or within a weight percentage (% by weight) range limited by any of the foregoing values.
    [0027] [027] The carrier can be produced by conventional techniques well known to those skilled in the art, such as by combining alumina microparticles, a solvent (eg water), a temporary or neutralizing binder material, a binder permanent, and / or a porosity control agent, and subjecting to the conformation, molding, or extrusion of the resulting paste, before firing (ie, calcination) of the preform by methods well known in the art. Temporary binders, or neutralizing materials, include cellulose, substituted celluloses, for example, methylcellulose, ethylcellulose and carboxy-tilcellulose, stearates (such as, organic stearate esters, for example, methyl or ethyl stearate), waxes, granulated polyolefins (for example, polyethylene and polypropylene), nutshell flour, and the like, which are capable of decomposing at the temperatures employed. Binders are responsible for providing porosity to the carrier material. The neutralization material is mainly used to ensure the preservation of a porous structure during the green (ie, the unburned phase) in which the mixture can be molded into particles by molding or extrusion processes. The neutralization materials are essentially completely removed during firing to produce the finished carrier. Alternatively, the carrier can be purchased from a catalyst carrier supplier. Some specific carrier formulations and methods for their preparation are described in US Patent Application Publication No. 2007/0037991, the content of which is incorporated herein by reference in its entirety.
    [0028] [028] The formed paste is extruded or molded into the desired shape and burned at a temperature typically from about 1200 ° C to about 1600 ° C to form the carrier. In embodiments where particles are formed by extrusion, it may be desirable to include conventional extrusion auxiliaries. In general, the carrier's performance is improved if it is treated by immersing the support in an alkaline hydroxide solution, such as sodium hydroxide, potassium hydroxide, or an acid such as HNO3 as described in the Patent Application Publication US No. 2006/0252643 A1. After the treatment, the carrier is preferably washed, for example, with water, to remove the dissolved unreacted material and the treatment solution, and then, optionally, dried.
    [0029] [029] The carrier is typically porous, usually with a B.E.T. The surface area of up to 20 m2 / g. The B.E.T. it is more typically in the range of about 0.1 to 10 m2 / g, and more typically from 1 to 5 m2 / g. In other modalities, the carrier is characterized by a B.E.T. of about 0.3 m2 / g to about 3 m2 / g, or a surface area of about 0.6 m2 / g to about 2.5 m2 / g, or a surface area of about 0.7 m2 / about 2.0 m2 / g. The B.E.T. described herein can be measured by any suitable method, but is most preferably obtained by the method described in Brunauer, S., et al., J. Am. Chem. Soc., 60, 309-16 (1938) .. The final carrier typically has a water absorption value (volume of water pores) ranging from about 0.10 cc / g to about 0.80 cc / g, more typically, from about 0.2 cc / g to about 0.8 cc / g, and more typically, from about 0.25 cc / g to about 0.6 cc / g.
    [0030] [030] The carrier, if porous, can have any other suitable distribution of pore diameters. As used herein, the term "pore diameter" is intended to indicate a pore size. The pore volume (and pore size distribution) described herein can be measured by any suitable method, such as the porosimeter method of conventional mercury described in, for example, Drake and Ritter, Ind. Eng. Chem. Anal. Ed., 17, 787 (1945). Typically, pore diameters are at least about 0.01 micron (0.01 pm) and, more typically, at least about 0.1 µm. Typically, the pore diameters are not greater than or less than about 10, 15, 20, 25, 30, 35, 40, 45, or 50 pm In different embodiments, the pore diameters are about at least above, up to, or less than, for example, 0.2 µm, 0.5 µm, 1.0 µm, 1.2 µm, 1.5 µm, 1.8 µm, 2.0 µm, 2.5 µm, 3 µm, 3.5 µm, 4 µm, 4.5 µm, 5 µm, 5.5 µm, 6 µm, 6.5 µm, 7 µm, 7.5 µm, 8 µm, 8.5 µm, 9 µm, 9.5 µm, 10 µm, or 10.5 µm, or the pore diameters are within a range limited by any two of the valves previous exemplifiers. Any range of pore sizes, as particularly derived from any of the above exemplary values, can also contribute with any suitable percentage of the total pore volume, such as at least greater than, up to, or less than, for example, 1, 2, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 95, or 98% of the total pore volume. In some embodiments, a range of pore sizes can provide the total pore volume (ie, 100%).
    [0031] [031] The carrier may have a pore size distribution (for example, within a range as defined above), characterized by the presence of one or more pores sizes of peak concentration, that is, one or more maximums ( where the slope is approximately zero) on a pore size versus pore volume distribution graph. A maximum concentration pore size is also referred to here as a peak pore size, peak pore volume, or peak pore concentration. In addition, each pore size distribution can be characterized by a single average pore size value (average pore diameter). As a consequence, an average pore size value determined for a pore size distribution does not necessarily correspond to a range of pore sizes that results in the indicated average pore size value. Any of the exemplary pore sizes provided above can alternatively be understood to indicate an average (i.e., the average or weighted average) or the average pore size of a pore size distribution. Any of the pore sizes provided above can also be interpreted as the lower and upper limits of a peak in a graph of the pore volume distribution.
    [0032] [032] In some embodiments, the carrier has a multimodal pore size distribution within any of the pore size ranges described above. The multimodal pore size distribution can be, for example, bimodal, trimodal, or a higher modality. The multimodal pore size distribution is characterized by the presence of different peak concentration pore sizes (i.e., different peak pore sizes) in a pore size chart versus the pore volume distribution. The different peak pore sizes are preferably within the range of pore sizes provided above. Each peak pore size can be considered within its own pore size distribution (mode), that is, when the concentration of the pore size on each side of the distribution drops to approximately zero (actually or theoretically). In one embodiment, different pore size distributions, each with a peak pore size, are not overlapping because they are separated by a pore volume concentration of about zero (that is, at the baseline). In another embodiment, the different pore size distributions, each having a peak pore size, are superimposed because they are not separated by a pore volume concentration of approximately zero. Each pore mode can contribute any suitable percentage of the total pore volume such as any of the percentages or ranges thereof, provided above.
    [0033] [033] The macroscale shape and the carrier morphology, that is, after the mixing and calcination of the carrier particles, can be any of the numerous shapes and morphologies known in the art. For example, the carrier may be in the form of particles, pieces, pellets, rings, spheres, three-hole, type wagon wheels, partitioned hollow transversal cylinders and the like, of a size, preferably suitable for use in reactors fixed bed epoxidation. In particular embodiments, macroscopic carrier units may have an equivalent diameter of about, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 mm, or an equivalent diameter within a range limited by any two of the previous example values. As is known in the art, the term "equivalent diameter" is used to express the size of an object irregularly by expressing the size of the object in terms of the diameter of a sphere having the same volume as the irregularly shaped object. The equivalent diameter is preferably compatible with the inner diameter of the tubular reactors in which the catalyst is placed. Alternatively, the equivalent diameter is the diameter of a sphere having the same ratio of external surface area (that is, neglecting the surface area within the particle's pores) to volume as the carrier units being used.
    [0034] [034] In order to produce a catalyst for the oxidation of ethylene to ethylene oxide, a carrier having any of the above characteristics is first supplied with a catalytically effective amount of silver by impregnating the carrier with the above silver impregnation solution. described. The carrier can be impregnated with silver and any desired promoters by any of the conventional methods known in the art, for example, by excess impregnation solution (immersion), incipient moisture impregnation, spray coating and the like. Typically, the carrier material is placed in contact with the solution containing silver until a sufficient amount of the solution is absorbed by the carrier. In some embodiments, the amount of the silver-containing solution used to impregnate the carrier is no more than necessary to fill the carrier's pore volume. The infusion of the solution containing silver to the carrier can be aided by the application of a vacuum. A single impregnation or a series of impregnations, with or without intermediate drying, can be used, depending in part on the concentration of the silver component in the solution. Impregnation procedures are described, for example, in US Patents 4,761,394, 4,766,105, 4,908,343, 5,057,481, 5,187,140, 5,102,848, 5,011,807, 5,099,041 and 5,407,888, all which are incorporated herein by reference. The known procedures for pre-deposition, co-deposition, and post-deposition of the various promoters can also be used.
    [0035] [035] After impregnation with silver and any promoters (for example, one or more of Cs, Re, Li, W, F, P, Ga and / or S), the impregnated carrier is removed from the solution and calcined for enough time to reduce the silver component to metallic silver and to remove volatile decomposition products from the silver containing carrier. Calcination is typically carried out by heating the impregnated carrier, preferably at a gradual rate, to a temperature in the range of about 200 ° C to about 600 ° C, more typically, from about 200 ° C to about 500 ° C, more typically, from about 250 ° C to about 500 ° C, and more typically, from about 200 ° C or 300 ° C to about 450 ° C, at a reaction pressure in a range of about 0.5 to about 35 bar. In general, the higher the temperature, the shorter the required calcination period. A wide range of heating periods has been described in the art for the heat treatment of impregnated substrates. Reference is made, for example, to US Patent No. 3,563,914, which indicates heating for less than 300 seconds, and US Patent No. 3,702,259, which describes heating from 2 to 8 hours at a temperature of 100 °. C to 375 ° C to reduce the silver salt in the catalyst. A continuous or step by step heating program can be used for this purpose. During calcination, the impregnated support is typically exposed to a gas atmosphere comprising an inert gas, such as nitrogen. The inert gas can also include a reducing agent. After calcination, the amount of silver in the catalyst is typically at least 16, 17, 18, 19, or 20% by weight.
    [0036] [036] After calcination of the high selectivity catalyst, the calcined catalyst is normally loaded into the reactor tubes of an epoxidation reactor, typically a fixed bed tubular reactor, using conventional loading methods well known to those skilled in the art. After loading, the catalyst bed can be swept by passing an inert gas such as nitrogen through the catalyst bed.
    [0037] [037] The produced catalyst preferably has a selectivity of at least 85% for the conversion of ethylene to ethylene oxide. In different modalities, the produced catalyst has a selectivity of about or at least, for example, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, or 93%, or a selectivity within a range limited by any two of the above values.
    [0038] [038] The produced catalyst can also contain one or more promoter species. As used herein, a "promoting amount" of a given component of a catalyst refers to an amount of that component that works effectively to provide an improvement in one or more of the catalytic properties of the catalyst when compared to a catalyst not containing said component. Examples of catalytic properties include, inter alia, operability (leak resistance), selectivity, activity, conversion, stability and yield. It is understood by one skilled in the art that one or more of the individual catalytic properties can be enhanced by the "promoting amount", while other catalytic properties may or may not be enhanced or may even be decreased. It is further understood that different catalytic properties can be enhanced under different operating conditions. For example, a catalyst with enhanced selectivity over a set of operating conditions can be operated under a different set of conditions where the improvement is displayed in the activity rather than in the selectivity. All promoters, in addition to alkali metals, can be in any suitable form, including, for example, as zero valence metal ions or higher valence metal ions.
    [0039] [039] In some embodiments, the catalyst produced may include a promoting amount of an alkali metal or a mixture of two or more alkali metals. Suitable alkali metal promoters include, for example, lithium, sodium, potassium, rubidium, cesium or combinations thereof. Cesium is often preferred, with combinations of cesium and other alkali metals also being preferred. The amount of alkali metal will typically be in the range of about 10 ppm to about 3000 ppm, more typically, from about 15 ppm to about 2000 ppm, more typically, from about 20 ppm to about 1500 ppm, and still more typically from about 50 ppm to about 1000 ppm by weight of the total catalyst, expressed in terms of the alkali metal.
    [0040] [040] The catalyst produced may also include a promoter amount of Group IIA alkaline earth metal or a mixture of two or more Group IIA alkaline earth metals. Suitable alkaline earth metal promoters include, for example, beryllium, magnesium, calcium, strontium and barium or combinations thereof. The amounts of alkaline earth metal promoters can be used in amounts similar to those used for alkali or transition metal promoters.
    [0041] [041] The catalyst produced may also include a promoting amount of one element of the main group or a mixture of two or more elements of the main group. Suitable core group elements include any of the elements from Groups IIIA (boron group) to VIIA (halogen group) in the Periodic Table of Elements. For example, the carrier or catalyst may include a promoting amount of sulfur, phosphorus, boron, halogen (for example, fluorine), gallium, or a combination thereof. The main element group can be present in the form of a compound. In addition to the halogen atoms, the element of the main group may be present in its elemental form.
    [0042] [042] The catalyst produced may also include a promoting amount of a transition metal or a mixture of two or more transition metals. Suitable transition metals may include, for example, elements from Groups IIIB (scandium group), IVB (titanium group), VB (vanadium group), VIB (chromium group), VIIB (manganese group), VIIIB (groups of iron, cobalt, nickel), IB (group of copper), and Hg (group of zinc) of the Periodic Table of the Elements, as well as combinations thereof. More typically, the transition metal is an early transition metal, that is, from Groups IIIB, IVB, VB or VIB, such as, for example, hafnium, yttrium, molybdenum, tungsten, rhenium, chromium, titanium, zirconium , vanadium, tantalum, niobium, or a combination thereof. In one embodiment, the transition metal promoter is present in an amount of about 10 ppm to about 1000 ppm of total carrier or catalyst expressed as the metal. In another embodiment, the transition metal promoter is present in an amount of about 20 ppm to about 500 ppm of the total carrier or catalyst expressed as the metal. In another embodiment, the transition metal promoter is present in an amount of about 30 ppm to about 350 ppm of the total carrier or catalyst expressed as the metal. Alternatively, the transition metal can be present in an amount of about 0.1 micromol per gram to about 10 micromoles per gram, more typically, from about 0.2 micromoles per gram to about 5 micromoles per gram, and even more typically from about 0.5 micromoles per gram to about 4 micromoles per gram of the silver-containing carrier or catalyst, expressed in terms of the metal.
    [0043] [043] Of the listed transition metal promoters, Rênio (Re) is a particularly effective promoter for the high selectivity catalyst for ethylene epoxidation. The rhenium component in the carrier or catalyst can be in any suitable form, but it is more typically one or more compounds or complexes containing rhenium (for example, a rhenium oxide). Rhenium can be present in an amount of, for example, about 0.001% by weight to about 1% by weight. More typically, rhenium is present in amounts of, for example, about 0.005% by weight to about 0.5% by weight, and even more typically, from about 0.01% by weight to about 0.05 % by weight based on the weight of the total carrier, that is, the weight of the catalyst, including the carrier, expressed as metallic rhenium.
    [0044] [044] The catalyst produced may also include a promoting amount of a rare earth metal or a mixture of two or more rare earth metals. Rare earth metals include any of the elements with an atomic number from 57 to 103. Some examples of these elements include lanthanum (La), cerium (Ce), and samarium (Sm). The amount of rare earth metal promoters can be used in amounts similar to those used for transition metal activators.
    [0045] [045] In a first set of modalities, the carrier, before impregnation, contains one or more of any of the promoters described above. In a second set of modalities, the carrier is provided with one or more promoters during impregnation with silver, including the promoters in the solution containing silver. In the latter mode, the carrier, before impregnation with silver, may or may not contain any or all of the promoters described above. In a third set of modalities, the carrier, after impregnation with silver and calcination, is supplied with one or more promoters in a post-processing stage. In the latter mode, the carrier, before impregnation or calcination, may or may not contain any or all of the promoters described above.
    [0046] [046] In another aspect, the present disclosure is directed to a method for the vapor phase production of ethylene oxide by converting ethylene to ethylene oxide, in the presence of oxygen with the use of the catalyst described above. Generally, the ethylene oxide production process is conducted by continuously contacting an oxygen-containing gas with ethylene in the presence of the catalyst at a temperature in the range of about 180 ° C to about 330 ° C, more typically, about 200 ° C to about 325 ° C, and more typically, from about 225 ° C to about 270 ° C, at a pressure that can vary from about atmospheric pressure to about 30 atmospheres, depending on the speed of the mass and desired productivity. Pressures in the range of about atmospheric to about 500 psi are generally used. Higher pressures can, however, be used within the scope of this disclosure. Residence times in large-scale reactors are generally in the range of about 0.1 to about 5 seconds. A typical process for the oxidation of ethylene to ethylene oxide comprises vapor-phase oxidation of ethylene with molecular oxygen in the presence of the catalyst of the invention in a fixed bed tubular reactor. Conventional commercial fixed bed ethylene oxide reactors are typically in the form of a plurality of elongated parallel tubes (in a suitable enclosure). In one embodiment, the tubes have approximately 0.7 to 2.7 inches of O.D. and 0.5 to 2.5 inches I.D. and 15 to 45 feet of full length with catalyst.
    [0047] [047] The catalysts of the invention are particularly active and selective in converting ethylene to ethylene oxide. The conditions for carrying out such an oxidation reaction in the presence of the catalyst described herein in general terms include those described in the prior art. This applies, for example, to suitable temperatures, pressures, residence times, diluent materials (eg, nitrogen, carbon dioxide, steam, argon, methane or other saturated hydrocarbons), the presence or absence of moderation to control the catalytic action (for example, 1,2-dichloroethane, vinyl chloride or ethyl chloride), the convenience of employing recycling operations or successive conversion applications in different reactors to increase ethylene oxide yields, and other particular conditions that may be beneficial for converting ethylene to ethylene oxide. The molecular oxygen used as a reagent can be obtained from conventional sources, and can be relatively pure oxygen, or a concentrated oxygen stream comprising oxygen in a major amount with smaller amounts of one or more diluents, such as nitrogen or argon, or air.
    [0048] [048] In ethylene oxide production, reactive feed mixtures typically contain from about 0.5 to about 45% ethylene and from about 3 to about 15% oxygen, with the balance comprising materials comparatively inerts including substances such as nitrogen, carbon dioxide, methane, ethane, argon and the like. Only a portion of the ethylene is typically reacted by passing over the catalyst. After separation of the desired ethylene oxide product and removal of an appropriate purge stream and carbon dioxide to prevent uncontrolled accumulation of inert products and / or by-products, unreacted materials are typically returned to the oxidation reactor. For illustration purposes only, the following are the conditions that can be used in a conventional industrial ethylene oxide reactor unit: an hourly space gas velocity (GHSV) of 1500 to 10,000 h-1, an inlet pressure of 150 to 400 psig reactor, a coolant temperature of 180 to 315 ° C, an oxygen conversion level of 10 to 60%, and an EO (work rate) production of 100 to 300 kg of EO per meter cubic cubic meters per hour. Typically, the feed composition at the reactor inlet comprises 1-40% ethylene, 3-12% oxygen, 0.3-40% CO2, 0-3% ethane, 0.3-20 ppmv of total concentration of organic chloride moderator, with the balance of food being argon, methane, nitrogen, or mixtures thereof.
    [0049] [049] Some examples of organic chloride moderators that can be used in the present invention include, for example, organic halides, such as C1 to C8 halohydrocarbons, which, for example, may be methyl chloride, ethyl chloride , ethylene dichloride, vinyl chloride, or a mixture thereof. Also suitable are hydrogen-free chlorine sources, such as perhalogenated hydrocarbons and diatomic chlorine, both of which are particularly effective as gaseous epoxidation moderators. Perhalogenated hydrocarbons refer to organic molecules, where all hydrogen atoms in a hydrocarbon have been replaced with halogen atoms. Some examples of perhalogenated hydrocarbons include trichlorofluoromethane and perchlorethylene. The moderator's concentration should be controlled to balance a number of competing performance characteristics. For example, the moderator's concentration levels that result in better activity can simultaneously decrease selectivity. The control of the moderator concentration level is particularly important with rhenium-containing catalysts of the present invention, because, as rhenium-containing catalysts age, the moderator's concentration must be carefully monitored in order to continuously increase, within small increments, once that optimal selectivity values are only obtained within a narrow range of moderator concentrations.
    [0050] [050] In other modalities, the ethylene oxide production process includes the addition of oxidizing gases to the feed to increase the efficiency of the process. For example, US Patent No. 5,112,795 discloses the addition of 5 ppm of nitric oxide to a gas supply having the following general composition: 8% by volume of oxygen, 30% by volume of ethylene, about 5 ppm by weight of ethyl chloride, with nitrogen balance.
    [0051] [051] The resulting ethylene oxide is separated and recovered from the reaction products by methods known in the art. The ethylene oxide process can include a gas recycling process, in which a portion or substantially all of the reactor effluent is readmitted to the reactor inlet after substantially removing the ethylene oxide product and its derivatives. In recycling mode, the concentrations of carbon dioxide in the gas inlet to the reactor can be, for example, from about 0.3 to about 6 percent by volume, and more typically, from about 0.3 to about 2.0 percent by volume.
    [0052] [052] Examples have been presented below for the purpose of further illustrating the invention. The scope of the present invention should in no way be limited by the examples presented here. EXAMPLES Silver impregnation solutions containing one or more ammonium salts as a silver concentration enhancer
    [0053] [053] In the following examples, oxalic acid has been replaced, in whole or in part, with one or more anion contributors containing ammonium having an anion capable of decomposing, such as ammonium carbonate, ammonium bicarbonate, ammonium formate and / or ammonium oxalate. It was found that the use of ammonium-based anion contributors increases the silver solubility in impregnation solutions, even in the absence of oxalic acid. Silver solubility can also be improved by mixing ammonium based salts with oxalic acid in different molar fractions.
    [0054] [054] To illustrate the composition of the mixture, the molar fraction of each anion contributor is defined as follows:
    [0055] [055] In Formula (1) above, ni is the number of moles of anion i contributor, and ei is the charge number of anion i. The charge numbers for oxalate (C2O42-), carbonate (CO32-), bicarbonate (HCO3-), and format (HCOO-) are 2, 2, 1 and 1, respectively. The denominator in Equation 1 is total negative charge mole. The numerator is the negative charge of the anion contributor i. For example, to make 1.0 kg of Ag solution with 35% Ag solubility, the following starting materials were used: Silver oxide: 375.94 g Water: 203.72 g Ethylenediamine: 195.00 g Oxalic acid: 81.81 g Ammonium oxalate: 69.16 g Ammonium bicarbonate: 51.30 g Ammonium format: 20.50 g
    [0056] [056] The molar fraction for each anion contributor is calculated as follows:
    [0057] [057] In this Example, the Total moles of negative charge, 3.2446 mol, are oxalic acid, ammonium oxalate, ammonium bicarbonate and ammonium formate. A positive charge of making Ag + is the same number, 3.2446 mol, calculated from the amount of silver oxide. The sum of the molar fraction is equal to 1. In various modalities, as individual molar fractions (χι) for ammonium salts of the present disclosure can be selected independently from, for example, 0.05, 0.1, 0.2 , 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 0.95, or a molar fraction within a range limited by any two of the previous values ( or a molar fraction of 1 if oxalic acid is not present). Alternatively, any of the previous exemplary molar fraction values may represent a total mole fraction of ammonium salts of the present disclosure.
    [0058] [058] By the method described, silver loading in the carrier increases by 10-20% compared to the conventional oxalic acid method, and the high silver loading results in an intensified activity with comparable selectivity. This method is also useful for producing an ethylene oxide catalyst on a low water absorption support. Example 1
    [0059] [059] A carrier having a surface area of 0.67 m2 / g and a water absorption of 43.8 cc / 100 g was washed with 0.025 N NaOH solution followed by thorough washing with Dl Water. The carrier was dried at 150 ° C for use.
    [0060] [060] 1500 g of silver solution was prepared using the following components, with a target silver content of 35% in solution. Ammonium oxalate was the only source of anions (ie, 1 molar fraction). Silver oxide: 563.9 g Water: 297.8 g Ethylenediamine: 292.5 g Ammonium oxalate: 345.8 g Preparation of the solution:
    [0061] [061] The water was gradually mixed with ethylenediamine in a container placed in an ice bath to control the temperature of the solution between 20 and 30 ° C with vigorous stirring. Ammonium oxalate was subsequently added to the solution, while the temperature was maintained at 20-30 ° C. After the ammonium oxalate was completely dissolved, silver oxide was added to the solution at a temperature between 20 to 30 ° C. Once all the silver oxide was added, the solution was stirred for an additional 30 to 40 minutes to ensure proper mixing. The solution was filtered using the vacuum pump as a silver stock solution for the preparation of the catalyst. The solution was covered to prevent the release of ammonia. Catalyst preparation: The. Addition of Promoter:
    [0062] [062] The formulation for high selectivity catalysts has been optimized with the addition of Cs and Re. The promoters were mixed with the silver stock solution before impregnation. B. Impregnation:
    [0063] [063] A 120 g carrier sample was placed in a pressure vessel and then vacuumed until the pressure was reduced to less than 10 mm Hg. 360 g of the adjusted silver / promoters solution was introduced into the flask while the sample was still under vacuum. The reactor pressure was allowed to rise to atmospheric pressure. The catalyst was separated from the solution and was now ready for calcination. ç. Calcination:
    [0064] [064] The calcination was carried out by heating the impregnated carrier to the decomposition temperature of the silver salts. This was achieved by heating in an oven that has several heating zones in a controlled atmosphere. The impregnated carrier was loaded onto a moving belt that entered the oven at room temperature. The temperature was gradually increased as the impregnated carrier moved from one zone to the next. Then, the temperature was increased, up to 400 ° C, as the impregnated charger passed through the four heating zones. After the heating zones, the belt passed through a cooling zone that gradually cooled the catalyst to a temperature below 100 ° C. The furnace atmosphere was controlled by using a nitrogen flow in the different heating zones. The final analytical result indicated that the catalyst contained 18.90% Ag. Catalyst tests:
    [0065] [065] The catalyst was tested in a stainless steel tube. A gas mixture containing 15% ethylene, 7% oxygen and 78% inert, mainly nitrogen and carbon dioxide, was passed through the catalyst at 300 psig. The reaction temperature was adjusted in order to obtain the ethylene oxide productivity of 432 kg per hour per ton of the catalyst. Example 2
    [0066] [066] Example 1 was repeated with the exception of the use of ammonium bicarbonate and the weight of the starting material. Ammonium bicarbonate was the only source of anions (ie, 1 molar fraction). 1500 g of the silver solution was prepared using the following components with a target Ag content of 36% in solution: Silver oxide: 580.0 g Water: 223.3 g Ethylenediamine: 300.9 g Ammonium bicarbonate: 395.8 g Example 3
    [0067] [067] Example 1 was repeated with the exception of the use of the mixture of ammonium bicarbonate, ammonium formate and oxalic acid. Thus, oxalic acid, ammonium bicarbonate, and ammonium formate were the sources of anions. The molar fractions of oxalic acid, ammonium bicarbonate, and ammonium formate used were 0.8, 0.1, and 0.1, respectively. 1500 g of the silver solution was prepared using the following components, with a target Ag content of 36% in solution: Silver oxide: 580.0 g Water: 295.5 g Ethylenediamine: 300.9 g Ammonium bicarbonate: 39.6 g Ammonium format: 31.6 Oxalic acid: 252.4 Example 4
    [0068] [068] Example 1 was repeated with the exception of the use of the mixture of ammonium oxalate and oxalic acid. Thus, oxalic acid and ammonium oxalate were the sources of anions. The molar fractions for oxalic acid and ammonium oxalate were 0.5 and 0.5, respectively. 1500 g of silver solution was prepared using the following components with a 35% target Ag content in solution: Silver oxide: 563.9 g Water: 317.3 g Ethylenediamine: 292.5 g Ammonium oxalate: 172.9 g Oxalic acid: 153.4 g Comparative Example 5
    [0069] [069] Example 1 was repeated with the exception of the use of oxalic acid. Oxalic acid was the only source of anions (ie, molar fraction of 1). 1500 g of the silver solution was prepared using the following components, with the target Ag content of 30% in solution: Silver oxide: 490.0 g Water: 416.0 g Ethylene diamine: 333.0 g Oxalic acid: 261.0 g
    [0070] [070] The results of the catalyst and test composition are summarized in Table 1 below: Table 1. Catalyst composition and performance
    [0071] [071] In the following examples, oxalic acid has been replaced, in whole or in part, by amino acid glycine. It was found here that the use of an amino acid increases the solubility of silver in impregnation solutions, even in the absence of oxalic acid. The solubility of silver can also be improved by mixing the amino acid with oxalic acid in different molar fractions. In particular, the solubility of silver in ethylenediamine can be increased from 31% to, for example, 36%, by replacing all or part of the oxalic acid with glycine. The application of high concentration solutions on a support can increase the silver charge on the catalyst support, for example, 10% to 20% in a single impregnation compared to an impregnation solution containing oxalic acid and without amino acid. Example 6
    [0072] [072] 500 g of silver impregnation solution was prepared using the following components, with a 35% target Ag content in solution. Glycine was the only source of anions. Silver oxide: 187.97 g Water: 92.74 g Ethylene diamine: 97.50 g Glycine: 121.79 g Preparation of the solution
    [0073] [073] The water was gradually mixed with ethylenediamine in a container placed in an ice bath to control the temperature of the solution to values between 20 and 30 ° C with vigorous stirring. Glycine was subsequently added to the solution, while the temperature was maintained at 20 to 30 ° C. After the glycine was completely dissolved, silver oxide was added to the solution at a temperature between 20 and 30 ° C. Once all of the silver oxide was added, the solution was stirred for an additional 30-40 minutes to ensure proper mixing. The solution was filtered using a vacuum pump to provide a silver stock solution for use in preparing the catalyst. The content of Ag in the filtered solution found was 34.62%. Preparation of the catalyst The. Addition of Promoter:
    [0074] [074] The formulation for high selectivity catalysts has been optimized with the addition of Cs and Re promoters. The promoters were mixed with the silver stock solution before impregnation. B. Catalyst impregnation:
    [0075] [075] A 120 g carrier sample was placed in a pressure vessel and then exposed to vacuum until the pressure was reduced to less than 10 mm Hg. Then, 360 g of the adjusted silver / promoters solution was introduced into the flask while the sample was still under vacuum, and the reactor pressure was allowed to rise to atmospheric pressure. The impregnated carrier was then separated from the solution before proceeding with the calcination process. ç. Calcination of the catalyst.
    [0076] [076] The calcination was carried out by heating the impregnated support to the decomposition temperature of silver salts to cause the deposition of elemental silver. This was achieved by heating in an oven having several heating zones in a controlled atmosphere. The catalyst was loaded onto a moving belt that entered the oven at room temperature. The temperature was gradually increased as the loaded carrier moved from one zone to the next. The temperature was increased to 400 ° C, as the loaded carrier passed through the four heating zones. After the heating zones, the belt passed through a cooling zone that gradually cooled the catalyst to a temperature below 100 ° C. The furnace atmosphere was controlled by the use of a nitrogen flow in the different heating zones. The final analytical result indicated that the catalyst contained about 18.50% Ag. Example 7
    [0077] [077] Example 6 was repeated with the exception of the use of glycine and oxalic acid as the anion contributors. The molar ratio of glycine to oxalic acid was 1: 2.
    [0078] [078] 500 g of silver solution was prepared using the following components, with a target Ag content of 34% in solution. Oxalic acid was added, before the addition of glycine and after the addition of EDA and with water for mixing. The Ag content of the filtered solution was 33.78%. Ag loading of the catalyst was 17.75%. Silver oxide: 182.60 g Water: 119.55 g Ethylenediamine: 94.72 g Oxalic acid: 79.47 Glycine: 23.66 g Comparative Example 8
    [0079] [079] Example 6 was repeated with the exception of the use of oxalic acid. 100 g of the silver solution was prepared using the following components, with a target Ag content of 30% in solution. Oxalic acid was the only source of anions. The Ag content of the filtered solution was 30.20%, and the Ag load of the catalyst was 16.5%. Silver oxide: 32.67 g Water: 27.73 g Ethylene diamine: 22.20 g Oxalic acid: 17.40 g
    [0080] [080] While what has been presently believed to be the preferred modalities of this disclosure, those skilled in the art will understand that other additional modalities and modalities can be made without departing from the spirit and scope of this disclosure, and this disclosure includes all such modifications are part of the intended scope of the claims presented here.
    权利要求:
    Claims (16)
    [0001]
    Silver impregnation solution, CHARACTERIZED by the fact that it comprises: (i) silver ions, (ii) a silver concentration enhancer selected from at least one ammonium salt having an anionic component that is thermally capable of decomposing, or at least one amino acid, or a combination thereof; (iii) at least one organic amine; and (iv) water; wherein said components (i) - (iii) are dissolved in said impregnation solution; and said impregnation solution contains silver in a concentration of at least 33% by weight and up to 40% by weight.
    [0002]
    Silver impregnation solution, according to claim 1, CHARACTERIZED by the fact that it also comprises oxalic acid, or in which oxalic acid is excluded.
    [0003]
    Silver impregnation solution, according to claim 1, CHARACTERIZED by the fact that said silver concentration enhancer is at least one amino acid and, optionally, said said at least one amino acid is selected from glycine, alanine , and valine.
    [0004]
    Silver impregnation solution, according to claim 1, CHARACTERIZED by the fact that said organic amine is selected from alkylamines, alkylenediamines, and alkanolamines.
    [0005]
    Silver impregnation solution according to claim 1, CHARACTERIZED by the fact that said organic amine comprises an alkylenediamine and, optionally, said alkylenediamine comprises ethylenediamine.
    [0006]
    Silver impregnation solution, according to claim 1, CHARACTERIZED by the fact that it also comprises a promoter species selected from alkaline, alkaline earth and transition metals.
    [0007]
    Method for the production of a catalyst effective in the oxidative conversion of ethylene to ethylene oxide, CHARACTERIZED by the fact that it comprises subjecting a refractory carrier impregnated with a solution containing liquid silver to a calcination process, wherein said solution containing liquid silver comprises : (i) silver ions, (ii) a silver concentration enhancer selected from at least one ammonium salt having an anionic component that is thermally capable of decomposing, or at least one amino acid, or a combination thereof; (iii) at least one organic amine; and (iv) water; wherein said components (i) - (iii) are dissolved in said solution containing liquid silver, and said impregnation solution contains silver in a concentration of at least 33% by weight and up to 40% by weight.
    [0008]
    Method, according to claim 7, CHARACTERIZED by the fact that the refractory support is composed of an alumina.
    [0009]
    Method according to claim 7, CHARACTERIZED by the fact that said solution containing liquid silver further comprises oxalic acid, or wherein said solution containing liquid silver excludes oxalic acid.
    [0010]
    Silver impregnation solution, according to claim 1, or method, according to claim 7, CHARACTERIZED by the fact that said silver concentration enhancer is at least an ammonium salt having an anionic component that is thermally capable decompose and, optionally, in which said ammonium salt has an anion containing carbon.
    [0011]
    Silver impregnation solution, according to claim 10, or method, according to claim 10, CHARACTERIZED by the fact that said ammonium salt is selected from ammonium carboxylates, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium phosphate, diamonium hydrogen phosphate and ammonium dihydrogen phosphate.
    [0012]
    Silver impregnation solution, according to claim 10, or method, according to claim 10, CHARACTERIZED by the fact that said ammonium salt comprises at least one ammonium carboxylate and, optionally, said ammonium carboxylate is selected from ammonium format, ammonium acetate, ammonium propionate, ammonium butyrate, ammonium valerate, ammonium oxalate, ammonium hydrogen oxalate, ammonium malonate, ammonium hydro-genomalonate, ammonium succinate, ammonium hydrogen sulfate, ma -ammonium leate, ammonium hydrogen maleate, ammonium fumarate, ammonium hydrogen smoke mouse, ammonium malate, ammonium hydrogen malate, ammonium citrate, ammonium tartrate, ammonium lactate, ammonium aspartate and ammonium glutamate.
    [0013]
    Method according to claim 7, CHARACTERIZED by the fact that said silver concentration enhancer is at least one amino acid and, optionally, in said said at least one amino acid is selected from glycine, alanine and valine.
    [0014]
    Method according to claim 7, CHARACTERIZED by the fact that said organic amine is selected from alkylamines, alkylenediamines and alkanolamines.
    [0015]
    Method according to claim 7, CHARACTERIZED by the fact that said organic amine comprises an alkylenediamine and, optionally, said alkylenediamine comprises ethylenediamine.
    [0016]
    Method, according to claim 7, CHARACTERIZED by the fact that said solution containing liquid silver further comprises a promoter species selected from alkaline, alkaline earth and transition metals.
    类似技术:
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB1170663A|1967-03-22|1969-11-12|Shell Int Research|Process for preparing Silver Catalysts|
    US3702259A|1970-12-02|1972-11-07|Shell Oil Co|Chemical production of metallic silver deposits|
    US4097414A|1976-08-30|1978-06-27|Texaco Development Corp.|Modified ethylene oxide catalyst and a process for its preparation|
    US4229321A|1979-02-26|1980-10-21|Texaco Development Corp.|Process for making a silver catalyst|
    US4224194A|1979-02-26|1980-09-23|Texaco Development Corp.|Process for preparing an ethylene oxide catalyst|
    US4766105A|1986-10-31|1988-08-23|Shell Oil Company|Ethylene oxide catalyst and process for preparing the catalyst|
    US4761394A|1986-10-31|1988-08-02|Shell Oil Company|Ethylene oxide catalyst and process for preparing the catalyst|
    US5057481A|1987-02-20|1991-10-15|Union Carbide Chemicals And Plastics Technology Corporation|Catalyst composition for oxidation of ethylene to ethylene oxide|
    US4908343A|1987-02-20|1990-03-13|Union Carbide Chemicals And Plastics Company Inc.|Catalyst composition for oxidation of ethylene to ethylene oxide|
    EP0357292A1|1988-08-30|1990-03-07|Imperial Chemical Industries Plc|Production of ethylene oxide and catalysts therefor|
    DE3905578A1|1989-02-23|1990-08-30|Basf Ag|METHOD FOR PRODUCING A SILVER CATALYST|
    US5187140A|1989-10-18|1993-02-16|Union Carbide Chemicals & Plastics Technology Corporation|Alkylene oxide catalysts containing high silver content|
    US5102848A|1990-09-28|1992-04-07|Union Carbide Chemicals & Plastics Technology Corporation|Catalyst composition for oxidation of ethylene to ethylene oxide|
    US5407888A|1992-05-12|1995-04-18|Basf Aktiengesellschaft|Silver catalyst|
    US5380697A|1993-09-08|1995-01-10|Shell Oil Company|Ethylene oxide catalyst and process|
    US5504052A|1994-12-02|1996-04-02|Scientific Design Company, Inc.|Silver catalyst preparation|
    US5739075A|1995-10-06|1998-04-14|Shell Oil Company|Process for preparing ethylene oxide catalysts|
    CA2343783C|1998-09-14|2008-02-12|Shell Internationale Research Maatschappij B.V.|Process for removing ionizable species from catalyst surface to improve catalytic properties|
    RU2234370C2|1998-09-14|2004-08-20|Шелл Интернэшнл Рисерч Маатсхаппий Б.В.|Method of production of catalysts with improved catalytic properties|
    US7232918B2|2001-11-06|2007-06-19|Shell Oil Company|Catalyst composition|
    US8383342B2|2002-04-24|2013-02-26|The University Of North Carolina At Greensboro|Compositions, products, methods and systems to monitor water and other ecosystems|
    WO2005023418A1|2003-08-22|2005-03-17|Union Carbide Chemicals & Plastics Technology Corporation|Improved alumina carriers and silver-based catalysts for the production of alkylene oxides|
    TW200600190A|2004-04-01|2006-01-01|Shell Int Research|Process for preparing a silver catalyst, the catalyst, and use thereof in olefin oxidation|
    KR20070106032A|2005-02-25|2007-10-31|스미또모 가가꾸 가부시끼가이샤|Process for production of olefin oxide|
    US7507844B2|2005-05-09|2009-03-24|Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg|Nanometer scale restructuring of alumina carrier surface and catalysts for the production of alkene oxides|
    EP1901842B8|2005-06-07|2019-10-30|Saint-Gobain Ceramics & Plastics, Inc.|A catalyst carrier|
    US8791280B2|2005-08-10|2014-07-29|Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg|Process for preparation of catalyst carrier and its use in catalyst preparation|
    EP2012916B1|2006-04-18|2020-10-07|Dow Global Technologies LLC|A process for producing an alkylene oxide catalyst|
    US20100140098A1|2008-05-15|2010-06-10|Solopower, Inc.|Selenium containing electrodeposition solution and methods|
    US20120214293A1|2011-02-22|2012-08-23|Serdar Aksu|Electrodepositing doped cigs thin films for photovoltaic devices|
    US7553980B2|2007-09-26|2009-06-30|Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg|Process for initiating a highly selective ethylene oxide catalyst|
    DE102008014910A1|2008-03-19|2009-09-24|Basf Se|Use of a supported noble metal-containing catalyst for oxidative dehydrogenation|
    US8742147B2|2010-12-08|2014-06-03|Shell Oil Company|Process for improving the selectivity of an EO catalyst|
    CN102527384B|2010-12-29|2014-04-30|中国石油化工股份有限公司|Preparation method of silver catalyst for producing ethylene oxide, silver catalyst prepared thereby and application thereof|
    KR101531891B1|2011-04-20|2015-06-29|주식회사 잉크테크|Silver ink composition|
    EP2830759A1|2012-03-27|2015-02-04|Dow Technology Investments LLC|Method of making a manganese containing supported silver catalyst intermediate|CN108607614B|2016-12-09|2020-07-21|中国石油化工股份有限公司|Silver catalyst and preparation method and application thereof|
    CN106732569A|2016-12-15|2017-05-31|哈尔滨师范大学|A kind of composite and preparation method thereof|
    WO2019020793A1|2017-07-28|2019-01-31|Basf Se|Process for producing a shaped catalyst body comprising silver applied to an alumina support|
    US20190176130A1|2017-12-13|2019-06-13|Scientific Design Company, Inc.|Silver impregnation solution containing high-boiling oxygenated additive and its use in ethylene oxide catalyst preparation|
    CN108043401A|2017-12-29|2018-05-18|中海油天津化工研究设计院有限公司|Using amino acid as high-efficiency silver catalyst for oxidizing ethylene into epoxy ethane of directed agents and preparation method thereof|
    CN108144604A|2017-12-29|2018-06-12|中海油天津化工研究设计院有限公司|Using amino acid as 1,3- butadiene oxidation 3,4- butadiene monoxide efficient silver catalysts of directed agents and preparation method thereof|
    CN108160075A|2017-12-29|2018-06-15|中海油天津化工研究设计院有限公司|Using polypeptide as the preparation method of the high-efficiency silver catalyst for oxidizing ethylene into epoxy ethane of three-dimensional directed agents|
    CN108212154A|2017-12-29|2018-06-29|中海油天津化工研究设计院有限公司|Using polypeptide as the preparation method of the 1,3- butadiene oxidation 3,4- butadiene monoxide efficient silver catalysts of directed agents|
    EP3749449B1|2018-02-07|2022-02-02|Basf Se|Method for preparing a silver impregnation solution|
    US10722874B2|2018-04-16|2020-07-28|Chevron Phillips Chemical Company Lp|Methods of preparing a catalyst utilizing hydrated reagents|
    CN110605116A|2018-06-15|2019-12-24|中国石油化工股份有限公司|Silver impregnation liquid and silver catalyst for producing ethylene oxide by ethylene epoxidation and preparation method thereof|
    EP3639923A1|2018-10-15|2020-04-22|Basf Se|Process for producing ethylene oxide by gas-phase oxidation of ethylene|
    EP3639924A1|2018-10-15|2020-04-22|Basf Se|Catalyst for producing ethylene oxide by gas-phase oxidation|
    EP3659703A1|2018-11-28|2020-06-03|Basf Se|Catalyst for producing ethylene oxide by gas-phase oxidation|
    EP3885038A1|2020-03-27|2021-09-29|Basf Se|Process for producing an epoxidation catalyst|
    WO2021260185A1|2020-06-26|2021-12-30|Basf Se|Tableted alpha-alumina catalyst support|
    WO2021260138A1|2020-06-26|2021-12-30|Basf Se|Shaped catalyst body for the production of ethylene oxide|
    WO2021260140A1|2020-06-26|2021-12-30|Basf Se|Production of porous alpha-alumina supports from boehmitic derived aluminas|
    法律状态:
    2018-02-20| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|
    2018-05-29| B08G| Application fees: restoration [chapter 8.7 patent gazette]|
    2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-01| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/12/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201361918342P| true| 2013-12-19|2013-12-19|
    US61/918,342|2013-12-19|
    PCT/US2014/071131|WO2015095508A1|2013-12-19|2014-12-18|High-concentration silver solutions for ethylene oxide catalyst preparation|
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