SA91120245B1 - Catalysts containing a high percentage of silver for the production of ALKYLENE OXIDE - Google Patents

Abstract

Abstract: This invention discloses catalysts for the epoxidation of alkene, particularly ethylene, to the corresponding alkylene oxide, such as ethylene oxide. The invention also discloses methods of making such catalysts and methods of their use.

Description

Catalysts containing a ddle ratio of silver z GY silver alkylene oxide Full Description BACKGROUND: This invention relates to the field of supported catalysts containing silver to oxidize alkylene and in particular ethylene to the corresponding alkylene oxide; Such as ethylene oxide, and these catalysts contain a high percentage of silver carried on materials that have a wide surface area | 0 and a large pore size. Ethylene oxide is produced commercially by epoxidation of ethylene over silver-containing catalysts at elevated temperatures. Considerable research efforts have been devoted to providing catalysts that increase the efficiency or selectivity of the process for ethylene oxide. The manufacture of ethylene oxide by reacting oxygen or gases containing 0 oxygen with ethylene in the presence of a catalyst containing silver is Old and advanced industrial technology. For example, US Patent No. 704097487 granted on VY May 1977 describes the manufacture of ethylene oxide by reacting oxygen with ethylene in the presence of silver catalysts containing a layer of metal enhancer. (Lefort) reveals in a new issue of US Patent No. 07700 dated May 11, 1977 that it is possible to form olefin oxide by making olefin combine directly with molecular oxygen in the presence of silver as a catalyst. Since that time, prior art has focused its efforts on improving the efficiency of the catalyst in the production of ethylene oxide. It is common to use several terms to describe some of the parameters of the catalytic system. for example; Conversion has been defined as the percentage ratio of the amount of 0 reacted from the alkene or oxygen feed to the reactor. The efficiency or, as it is sometimes called, selectivity of the overall process is a sign of proportionality; ale is a percentage; For the metamorphic or resulting substance, which is alkene oxide. The economic success of a reaction system depends to a large extent on the efficiency of the system. Even a very small increase in efficiency will yield substantial economic benefits in terms of cost in a large-scale production process. The product of efficiency and conversion is equal to ov.

for the yield or percentage of the alkene fed into the reactor that has been converted to the corresponding oxide. The catalytic activity is a term used to indicate the amount of alkene oxide present in LAL leaving the reactor in relation to its amount in the incoming stream. It expresses effectiveness; m in general; by pounds of alkene oxide produced per cubic foot of catalyst per hour at specified reaction conditions and feed rates. The efficiency may also be expressed by the amount of alkylene oxide in the stream leaving the reactor or by the difference between the alkylene oxide content of the inlet and outlet streams. If the efficiency of a reaction system is low and all other factors are equal; the commercial value of 0 for that system will be low; The lower the efficiency of a reaction system, the lower the amount of product produced per unit time for a specific feed rate, a specific reactor temperature, a specific catalyst, and a certain surface area...etc. Decreased effectiveness may make any process; Even if it is highly efficient, it is not commercially practical. In some cases, the effectiveness is measured over a period of time by the amount of alkylene oxide produced at No, a specified uniform temperature. instead; Efficiency can be measured as a function of the temperature required to maintain the production of a fixed amount of alkylene oxide. The useful life of a reaction system is the length of time during which reactants can pass through the reaction system with acceptable activity observed. The term deactivation, when used in this statement, refers to a permanent loss of activity; Any loss of effectiveness is irreversible. According to the aforementioned, the effectiveness can be increased by raising the temperature. But the need to operate at a higher temperature to maintain a certain efficacy is representative of efficacy paralysis. add to that; The catalysts tend to lose their effectiveness more quickly when the reaction is carried out at higher temperatures. For the catalyst to be considered acceptable, it is not only a matter for the catalyst to have sufficient efficiency and for the catalytic system to provide acceptable efficiency; Rather, the catalyst should exhibit a minimum useful life or stability. When the catalyst is depleted; Normally, the reactor must be turned off and partially dismantled oY

¢ 5Y dismantled 3 spent catalyst resulting in loss of time and productivity. in addition; The catalyst should be replaced and the silver recovered or the catalyst renewed if possible. Even if the SUB catalyst for regeneration is in use; In general, production should be stopped for a period of time. catalyst replacement or renewal; require at best; additional loss of time to treat 0 exhausted catalyst and in the worst case; It requires catalyst replacement with concomitants since even small improvements in effectiveness, efficiency, or useful life may be significant in large-scale commercial production processes. These improvements have been the goal of a large amount of research into the direct epoxidation of alkenes. The Activity Center included 0 performance improvement attempts; catalyst efficiency, useful life, and system efficiency; areas such as adding (*) to or removing components from the feed stream; It also included methods for preparing the catalyst, precipitating or impregnating a special type or shape of silver, the support composition, composition, physical properties, general morphology, additives deposited or impregnated on the support, the shape of the support aggregates used in the reactor and the different types of reactors 1 and designs of catalyst layers such as stationary and fluidized beds (legac). In fact, the amount of silver in the catalyst to be disposed of was often considered an economic constraint, for example Jal Kelly x. in US Patent No. YY for ethylene oxide catalysts oxide 458 that its silver content is in the range from 71 to 775 by weight and it is stated: 0 “It does not exclude the use of larger quantities of silver, but in general it is economically unattractive” (column ;; two lines (Vise (*) Additives: Substances added to the feed stream in small amounts. vo similarly states Armstrong in US Patent No. 7475/97; in the column ;; Line 4 ff: ht

"Greater quantities of silver are disproportionately expensive, while smaller quantities are undesirable, as they reduce their useful life and efficacy.

Armstrong broadly suggests that ethylene oxide catalysts can contain anywhere from 75 to 750 silver by weight.

° Several previous researchers suggested using a high load of silver on ethylene oxide catalysts, for example; Maxwell in US Patent No. 5,077457 suggests using silver in an amount of 1 to 775 by weight, Hayden in US Patent No. EVIAYEY suggests using silver in an amount of 9 to Zon by weight, and Bhasin in Patent US Patent No. 4908747 Using silver in an amount of Y

0 to 740 wt.; Tamura suggests in US Patent No. 1,409,754; Use

silver in the amount of © to 7700 by weight; He suggests «©58016 in US Patent No

684?!?? the use of silver in the amount of 1 to 750 by weight; Calcagno proposes in a patent

US Invention No. 77705747 Application of silver in an amount from 7 to 770 by weight; And it gurgles

Demaio in US Patent No. 1,749,176 uses silver in an amount of * to

AY 1 wt. However, among all these patents, there is only one patent

US Patent No. 4,908,747 provides a practical example of a catalyst containing some amount of silver

greater than 775 by weight. And in fact; Many researchers have suggested that the largest proportion is silver

58 by weight or less for ap) ethylene oxide (give examples) containing catalysts

Only an amount of silver between 01 to 7710 by weight. It is believed at this time that the oxide catalysts

© _ ethylene oxide manufactured on commercial bases containing silver in an amount of about 711 to Ave by weight.

And it is possible to understand why previous researchers” generally tended to use silver contents

In the range from 01 to 7700 by weight from a comparison of the results of experiments using catalysts (47) and (57)

from US Patent No. EY 5176487. The two catalysts used in these experiments have

(£7) Same package as carrier and booster but differ in silver content in each. the catalyst vo

AYE contains by weight silver while the catalyst ZA (OF) contains silver by weight. That conversion rate

and 0

0 oxygen at an absolute pressure equal to 1 atmosphere psa for both catalysts was identical (748) and at an absolute pressure equal to VT atmosphere, the oxygen conversion ratio for the catalyst with a high silver content was 77 Lay, the oxygen conversion ratio for the catalyst with a lower content of silver to TY and under the conditions of both pressures; A catalyst with a lower silver content gives a better 0% transductivity than that shown by using a catalyst with a higher silver content. Jie says that these kind of results tend to confirm Armstrong Kilty's observations that there is little economic incentive to use catalysts with a high silver content. One of the inherent benefits of an increased silver content in the catalyst is increased efficiency. As for increasing efficiency, it is often possible to achieve increased efficiency easily using several techniques. 0 Unfortunately, many techniques for increasing lial efficacy, for example JB, increased silver content, types and amounts of catalyst bolsters, and operating conditions, including amounts of vapor phase medifiers such as cethylenedichloride, may led to efficiency losses. Accordingly; The desired catalysts can show not only enhanced efficiency but also retained efficiency or increased efficiency.

Vo, while SUB made an effort regarding ethylene oxide catalysts with a high silver content, the search was ongoing for Lad supports ale all 5 carriers for the catalysts. The mounts that have been used are typically made of inorganic materials; Usually metallic in nature. In most cases; The preferred carrier shall be made of calpha-alumina as described in the scientific publication of the patent; See for example; Related US Patents

3 Numbers: 7447, Akanga, Lot Mokht, and FONTAN, and the mounts that are used to make most of them; if not all; Commercially used ethylene oxide catalysts are produced by companies that do not produce these catalysts. As a rule, the methods of making such stands are very important trade secrets for the makers of these stands. Thus the catalyst maker cannot know how to make the carrier. The manufacture of a carrier for the ethylene oxide catalyst, Yo product, may require a number of factors, Jie the degree of purity and other physico-chemical properties of the raw materials used to make the carrier and the method by which it is manufactured.

ey.

pregnant. The carriers have been described by several researchers by means of the chemical and/or physical properties of the catalyst. DeMaio shows in US Patent No. 71,749,176 the importance of the physical properties for pregnant women when he says: “...the use of a support material of a porous nature and characterized by a limited range of 0 pore diameters; Now for halogenated inhibitors to moderate or “al” mode to adjust the activity of silver-containing catalysts used in the controlled partial oxidation of ethylene to ethylene oxide (column 7; lines 117 through (YE). Other DeMaio postulates:

0 "...it seems that a more homogeneous distribution of silver that is obtained results from the deposition of silver on a porous support material, where the diameters of a major part of its pores fall within the limits of a limited range, and where the average diameters of the pores fall within the limits of a narrow range, which is reduced to a minimum catalytic centers that exhibit undesirable activity" (column; lines 500 to 07) and the present invention anticipates that the "average pore diameter" will be of such size as that corresponding to the diffusion rate

5 is neither too low nor too high in practice (Sha 1 column 4 to “line 1” column).

And DeMaio's suggestions that it is optimal to have an average pore diameter of ; down to 10 microns without the need to use a halogenated inhibitor. The patentee states that at least 7,960 of the pores have diameters in the range from 1 to μm. The patentee did not provide information

0 Regarding the surface area of the carrier, the porosities of the carriers mentioned in the examples have reached up to Jet, and Tin and those with him mention in European Patent Application No. 7775876: “To increase the effectiveness of the catalysts, there must be a sufficient specific surface area of silver particles. Therefore, catalyst supports must have sufficient specific surface area. However, the surface area quality is greater than

The usual vo makes reaction heat transfer difficult, worsens the side reaction, and decreases the selectivity of the catalysts. In order to provide high selectivity of the catalysts, an ideal porous structure is required that matches the surface area of the catalyst oY.

A

In order to achieve conditions suitable for the transfer of heat and mass and to suppress the side reaction. Since the reaction takes place in nearly diffusion-controlled conditions, the search for catalysts that have the best contact between the porous substrate and the specific surface area has become an important topic in the development of Ve (lines 7 to oY) silver catalysts (page Cagle). selectivity °. For oxidation catalysts, Jin and Sala suggest epoxidation of silver with a specific surface area of 17 to 7 m'/g, preferably from 18 to 3.0 m'/g, and a pore size greater than 5. ,ml/g preferably from 9 to 71.0 mm/g and pore size with a pore radius smaller than “0 µm” includes TYE to 7980 of the total pore volume with a pore radius greater than 0 µm include from 78 to 70 of the total size.In the examples the predominant distribution of pores 0 in the mounts is in the range from 1.9 to ¾ microns.Jin and co. state that the silver content is between 711 and 7759 by weight; But examples use conventional silver loads.Hayden et al., in US Patent No. 4114875497, propose the use of a bimodal carrier dala for silver epoxidation catalysts.It is preferable that the pore size be at least ZV smaller than the total pore size It has an average pore diameter of 1.1 to . : No micron and for larger pores the average pore diameter is from YO to 50860 micron. Apparent porosity is not less than ZY for example from 790 to JA and the patent holders suggest that the amount of catalyst promoters present is proportional to the surface area of the support. Although silver contents ranging from 77 to +75 and more were proposed, and the preferred is from 77 to 770, the patent owners did not provide evidence or guidance on how to effectively use silver © except that it must be in the form of separate particles with equivalent diameters smaller than 00001 angstrom. As mentioned previously, the catalysts with higher silver content that Hayden and co have uncovered do not provide any demonstrable benefit over catalysts with a lower silver content. Cognion et al., US Patent No. EYEYYYO, further demonstrate the use of bi-mode carriers for silver oxidation catalysts; The patent holders stated: “Yo “…the presence of two bands together of porosity consisting of pores of different diameters was in favor of selectivity for ethylene oxide” (column; lines 01 to YY oY ..

The two ranges are from 1 to © micron and from 61 to Too micron. Preferably, each of these two ranges from ©” to 715 represents the total porosity. It is mentioned that the other distinguishing characteristics of the carrier are a surface area less than anf Tp 01 and usefully between 21 wm / g and porosity not exceeding 77000 and preferably between Yo 5 700 and the surface area of the carriers does not exceed in 0 practical examples about “, 10 m / g, and the maximum porosity is 4 8.7 cm / g.

Boehning and those with him disclose in the US patent No. FAY EY about ethylene oxide production catalysts in which carriers with certain physical properties are used to give a silver density in the reactor of not less than 100 kg / m. surface area from 4 to anf an, A and a pore size of not less than 1.40 mm/g.The patent holders confirm that the carrier is aga 0 for catalyst efficiency and state that if the carrier is a mono model, then the average diameter of; Its porosity is from 1 µm, but if the carrier is bimodal, then 7086 of the total pore size consists of pores with an average diameter of 01 to 56 microns, and the smaller ones have

diameter from 1,8 to ? micron. Saffer discloses in US Patent No. 7709797050 a composite support Ve for silver epoxidation catalysts. The outer edge is a porous material and the core is made of a dense, essentially non-porous material. The outer edge has a porosity of 719 to 6. The catalyst support in the example shown has a surface area of the outer edge smaller than 1 m anf and a porosity of 7748 and is composed of about “? micron. He stated that the composite carrier basically gives an enhanced efficiency when installed in a catalyst over the efficiency of a catalyst consisting of a homogeneous support.

0 is highly porous. Many workers revealed broad ranges of the physical characteristics of the pregnant woman. Among the examples of those statements is what Maxwell mentioned in US Patent No. 40,774957 that suitable carriers are characterized by having a surface area of less than 1 m / g, and preferably less than 1 m / g. It was mentioned that the carrier materials have an apparent porosity Jef porosityl vo of 770. See also, for example, what Lauritzen states in US Patent No. 7,117,494. Although there are wide ranges of range, carriers are

A. The actual examples in the examples shown are often completely limited in scope. Lauritzen gives an example of one carrier, and that the carrier contains only 7970 to 775 by weight alumina, with a surface area greater than 0 m. Oa. Ro 4H 1/1417, 817, and 871167 give examples of carriers for ethylene oxide production catalysts, which have a higher surface area, i.e. no 0 m '/g and higher. Although the previous documents indicate that work was devoted to developing an epoxidation catalyst carrier of silver, the workers on that gave little or no evidence regarding the effect of the physical properties of the carrier on the silver content in the catalysts. Tripods with a minimum surface area are often used; for example JB from OY to 10 m/g; Within the range of catalysts containing conventional amounts of silver. GENERAL DESCRIPTION OF THE INVENTION: The present invention provides portable silver-containing catalysts for the production of 1-alkylene oxide suitable for epoxidation of alkyne to alkylene oxide and having enhanced activity and/or gas stability. According to this invention; Silver epoxidation catalysts are provided, in which the benefits arising from the presence of a high silver content can be realized and the catalysts and processes of this invention can be used; in combination with a high silver content (i.e., about ZY by weight at least); It has high porosity and surface area. In some respects the invention is more preferable; The carrier has an average pore diameter between about 1 micron and 5 microns; And the favorite of about? to Yo microns; and between about 701 to 770 pore sizes (based on total pore size greater than 0.1 µm in diameter) having a pore diameter between about 55 and 1 µm; and a quantity of pores not less than 701 by size with a pore diameter between about 1 and 10 microns; On JAY are about 771 ve by size of the pores having pore diameters between about 01 and 1000 microns; Preferably between 01 and 10 microns. The estimated pore size of water is often greater than about 1.59 mm / (Bays can say; oY.

11 to? mm/_g. temporarily; The catalysts of this invention with a high content of about 1.5% of silver having the same other properties except for the pore distribution are able to show enhanced efficiency without Jie surface areas and pore distributions sacrificing efficiency compared to the efficiency of catalysts that do not have a high of like this.

° and the catalysts have a high DA concentration generally not less than about 08 or 270 wt; based on the total catalyst weight. more generally a concentration of silver in the range from about Ye or 770 to about 7760 by weight; And the more favorite in the range than about ©*? or TYE by weight to approximately 745 by weight silver. On the basis of volume (bulk density), the amount of silver present in the catalysts of the present invention is often greater

0. From about 14 g of silver cm" of the catalyst ready and generally in the range from about 1.4 to about 7.0 g/cm" and more preferred in the range from about 1.94 to about about 0.91 g/cm. The bulk density of the catalyst is typically much greater than that of the filler in a tubuler Je reactor, for example; Jie that is used commercially for the production of ethylene oxide (pil). The silver density per cubic centimeter of a catalyst packed tubular reactor according to this invention is almost

“g/cm 0.9 to 0.7 less than 7.10 g/cm”; For example from about 1

By containing this high level of silver, the catalysts of this invention are often able to increase the efficiency of the catalyst. As defined in standard conditions for the production process of ethylene oxide (defined in this statement) by an amount represented by reducing the temperature by at least 100 °C, preferably at least 10 °C; or SH in comparison to a catalyst that does not have the same carrier and/or a higher silver concentration.

7 In the preferred aspects of this invention, the selectivity or efficiency of the catalysts for the production of alkylene oxide is maintained at the same level or it is preferred to be enhanced by increasing the silver content in the catalyst. The production efficiency of ethylene oxide for this catalyst is often greater than that of another type of Silas catalyst, but it has a silver content of about 11 to Ve by weight; Under standard conditions for the ethylene oxide production process, the oY difference is not less than about 1 degree.

ve and the favorite is about 1 or ? to 01 degrees; It can be said about? to 77 from efficiency.

oY.

1 Surprisingly, The useful carriers used in this invention are often less desirable than the carriers that have a smaller surface area when conventional (common) silver contents are used. 0 /

Ry—C ——C —R, l a 0 where both (l8) and (82) are low alkyl; For example, methyl or cethyle Ju) or preferably hydrogen (hydrogen) and more preferably ethylene sa cu LY oxide (ethylene sa cu LY) oxide, and alkylene oxides are made from the corresponding alkene, i.e. the alkene in the formula; R-HC=HC-R® For the purposes of facilitating understanding of this invention, discussion A000 will be conducted regarding the production of ethylene oxide from ethylene .01 | grams of silver per cubic centimeter of ready catalyst (packaged in a tubular reactor); And that silver is supported on a carrier that has a specific surface area greater than about 0.0 m/g and a pore size of not less than about 0.10 cm/g. 0.0 cm/g and generally in the range from about 5 to about 1 1.1 cm'/g; preferably greater than about 0.00 anf ae and most preferably from about 0.7 to about 0.4 cm'/g In conjunction with such a high concentration of silver; The catalysts of the present invention have a large surface area and a high pore volume. In general; Suitable mounts have a specific surface area measured by BET (All will be defined in this statement) greater than about 0.0 m/g; 0 and generally in the range from about 1.7 m"/g to about 01 anf. Preferably, the specific surface area of the carrier when measured according to the ABET method should be in the range from about VA to about anf 1,6 or more The BET method for determining the specific surface area is the oY method.

Lal described in detail by 5. Emmet P. 5 Brunauer, and Teller E. in the Journal of the American Chemical Society 10 pp. PIT-F +d (178) Am.

Chem. soc., 60, 309-316 (1938).1. Preferably these carriers also have a pore size measured with water measured according to conventional water absorption techniques greater than about 0 00 cm/g 0 and more preferably from about 1.76 to about 0 nf am A and the carrier can choose; or stent; The catalysts used in these catalysts are among a large number of refractory support materials that are relatively inert in the presence of alkene oxidation feeds, products and reaction conditions. pregnant women may form; For example, silicon carbide sl alpha-alumina, zirconia silicon dioxide, magnesia 01 and various types of Jala. The preferred carriers are alpha alumina particles bound to each other often with a bonding agent and have a very high degree of purity, i.e. the alpha alumina content is not less than 7948 by weight; and that any remaining ingredients are in other forms of silica alumina, alkali metal oxides (eg sodium oxide) and trace amounts of additives or other impurities, containing and/or not containing 10 metals There are many types of such carriers commercially available.The carriers are made of alumina by the United Catalyst, Inc., Louisville, ky. and Norton company, Akron, Ohio.The average range of pore diameters ranges from The above-described carriers are from about 1 to 50 μm with the most preferred range being from about 1 to TO μm and the most preferred in the range from about * to Yo μm. Polymodal (i.e., the particle distribution of the carriers, most of which fall within one, two, or more sizes). Useful carriers often have pore size distributions as shown in Table A. oY +

V¢(1) table sie and often acidic carrier surface as determined by irreversible adsorption of about J and preferably oY less than about 001" a at a temperature of ammonia micromoles per gm of pregnant women. 1 to 0.06 and often between about 8

° In one aspect of the invention the carrier consists of a particulate matrix in which there are at least 750 of the total number of carrier particles having a particle size greater than about 11 microns having at least one virtually flat principal surface which may be characterized by It has a lamellar-like shape. Some particles have two or sometimes more flat surfaces. The larger dimension of the principal part of the particles having a lamellar shape is smaller than about alpha-microns. When 1 0 microns, preferably smaller than about 1 0 microns, are used as a support material, the lamellar particles often have a shape resembling that of hexagonal alumina sheets. A full explanation of the plate-type mounts is contained in the patent application filed for publication on and incorporated in VY Aug 19485 U.S.A. with serial number 7165707 dated herein for reference.

In another aspect of the invention, the carrier, whether it has a lamellar shape or not, contains a fluorine-containing material. The containing substance is usually added 1 oY.

yo is somewhat volatile or the sale may volatilize to the stand during its preparation; It is preferable to be on dai in roasting conditions. And materials containing fluorine, which can be used as hydrofloric acid, ammonium fluoride, and aluminum tri fluoride, for example, but not limited to, in the request for fluorine, and a full explanation of the carriers containing edichloro difluoro methane and August 11 US Patent with serial number 7690718 and sent for publication on 0 whose statement is incorporated here for reference.‎ 158

As mentioned earlier, the making of the holder is considered a trade secret kept by the makers of the holders. However, insightful studies into the processes of making carriers and what affects the distribution of pore sizes in carriers are provided for example by Trim and co in a paper titled “The Control of Pore Size in Alumina Catalyst Supports” published in Apple.

Catal, vol. (1986) 21, 215, Young et al. in US Patent No. 575444, Belon et al. in US Patent No. 1774875, Lin et al. in US Patent No. 47851117; and Tam and his associates in US Patent No. 00877517, Peason and his associates in US Patent No. 4001144, Carithers 0 and his associates in US Patent No. 881/4, Kiovsky and his associates in US Patent No. 288048449 Robayashi and others with him in the patent

American No. 077567 ", whose data are all incorporated here to be references. Regardless of the nature of the carrier or support used, it is preferable that it be formed in the form of particles, short thick pieces, pieces, granules, rings, spherical bodies, cylinders, or in the form of truck wheels etc. Appropriately sized for use in fixed bed catalyst reactors Common commercial ethylene oxide fixed bed catalytic reactors are typically in the form of a series of parallel elongated tubes (in a suitable shell) with an outer diameter of 1,778 mm cm and 1,884 cm, and its inner diameter ranges between (an), YY and 1.78 cm, and its length is from 4.07 m to IVY m, and it is packed with catalyst Yo, and it is desirable in such reactors to use a support formed in the form of a round de oY.

yu

Spherical bodies, cylinders, particles, rings, discs, etc. cells of diameters of about

,cm to ?cm. : : : A: As with any supported catalyst, optimum performance will depend on the ideal carrier in terms of its chemical composition (including impurities), surface area, porosity, and pore size.

Effectiveness and stability It can be used in a standard range of practical conditions. The standard conditions for the ethylene oxide production process (“production conditions”) characteristic of the catalysts of this invention include the use of a standard back-mixer autoclave with recirculation of all gases including carbon dioxide. 0 Conditions may apply with some variation in the level of ethylene feed, oxygen and gas phase inhibitor shall. Two cases will be presented: aerobic process conditions which are similar to “in the back-mixer reactor”; Typical conditions used in commercial pneumatic type processes for ethylene oxide production where air is used to supply cmolecular oxygen —u ad and oxygen process conditions ve which are Bla in a backmixer reactor; Typical conditions used in commercial oxy-type processes to produce ethylene oxide where molecular oxygen is used by itself. Each Alla provides a different efficiency, but the general rule for all cases in practice is that the use of sell as a source of oxygen supply; And the use of smaller amounts of oxygen and ethylene will give an efficiency of producing ethylene oxide © that is less by about ? to 75 percentage points over the need for which molecular oxygen is used as an oxygen feed source of 0. Well known autoclaves with backmixed bottom-agitated (magnedrive) are used. ) 8 and described in Figure 7 in jm. berty on “Reactor for Vapor” Phase Catalytic Studies 00 in Chemical Engineering Progress, vol. 70, no. 5, pages oY.

No. 4, 78-84. Conditions use 77 moles of ethylene oxide in the gas leaving the reactor under the following standard entry conditions: Component Production Conditions in Process | Production conditions in the aerobic process Mole 7 Oxygen mole 7 Le he fl) ppmethyl chloride Half of this amount when using ethylene optimal for optimal efficiency (dichloride) and the pressure is kept constant at a value of 11 atmospheric pressure above the pressure Cubic feet per hour at standard temperature and pressure = SCFH(*) Cubic feet per hour at standard temperature and pressure = SCFH(*) 1. The concentration of ethylene oxide outside is maintained at 77 by adjusting the reaction temperature. Thus, the temperature (°C) and catalyst efficiency are obtained as responses that describe the performance of the catalyst. conditions The following steps: )= 0 names of the catalyst are placed in an autoclave with a back mixer. The volume of the catalyst is measured in a graduated cylindrical tester with an inner diameter of 1.94 cm after beating the tester several times to fulfill the catalytic agent. Alternatively, the volume of the catalyst is calculated from the density of the carrier fill, Vo, and the amount of silver and additives. Note the weight of the catalyst. oY +

A "-- The back-mixer autoclave is heated to about reaction temperature by means of a nitrogen stream with a flow rate of Yo 50711 and the fan runs at 10500 rpm. Then the nitrogen flow is stopped and the aforementioned feed stream enters the reactor. The flow is regulated The total outgoing gas is reduced to 77.7 501711 and the temperature is adjusted to 0 during the next few hours so that the concentration of ethylene oxide in the outgoing gas is about 77.0.”*_The oxide concentration in the outgoing gas is monitored during the subsequent four to six days to ensure that the catalyst has reached Ala is the peak of uniform performance.The temperature is adjusted periodically so that the percentage of oxide in the outgoing stream is 77.Thus, the selectivity of the catalyst for ethylene oxide 01 is obtained and the temperature.The standard deviation of the result of a single test to estimate the efficiency of the catalyst according to the above-described method is about 75 7, from the unit of efficiency. The standard deviation of the result of a single test to estimate the efficiency of the catalyst according to the method shown (Wl) estimated at temperatures is about 1.7 m. This deviation will vary. The results of the tests recorded in this statement are believed to be within the standard deviation range mentioned above. Running multiple tests will reduce the standard deviation by the square root of the number of tests. To determine the increase in efficiency the process and catalyst must be in steady state conditions and the increase can often be definitively verified when Alla steady state conditions are achieved. oy As with any catalyst for making ethylene oxide provides the best cold There is a correlation between several factors. Factors that are often considered include the following: (1) the nature of the support support aie (Y) silver in or on the support support ( ) -_ components (including promoters and their amounts that are present In support Yo on it ov.

Va support dale all associated with silver, cantaminants impurities, impurities, contaminants (¢) or other components. And Stal method of making (0). ethylene oxide for the production of ethylene oxide catalyst Conditions for using the catalyst (7)

° It is preferred that the catalysts of this invention include one or more enhancers or modifiers to enhance the performance of the catalyst, for example; To enhance the efficiency or reduce the burning of ethylene oxide or cause effectiveness. Generally, these enhancers or modifiers are available in the form of chemical compounds.

The term (compound) when used in this statement denotes the union of an independent element with 0 one or more different elements by a surface and/or chemical bond; such as ionic, covalent and/or coordination bonds; The term tonic or ion refers to an electrically charged chemi-calmoiety that is called a cationic or cation when positive and anionic or anion when negative. The term oxyanionic refers to a chemical radical with a negative charge and content of at least one oxygen atom 1 bonded to another element. Thus, the "oxy anion" is an anion containing oxygen. It is understood that ions do not exist in a vacuum; Rather, they are associated with companion ions of counter Tons of equivalent opposite charge. It is preferable that the catalyst includes at least one or more promoters of an amount sufficient to enhance the efficiency and/or effectiveness of the catalyst. (References to the periodic table herein refer to the periodic table of the Chemical Rubber Company of ca Dla, Ohio CRC 'Handbook of Chemistry and Physics' on the last inside cover page of the 46th edition. ) Preferred enhancers include halides such as florids and chlorides, and the oxy anions of elements other than oxygen with an atomic number from © to AY of groups (“b) to (ab) and (©a) to ( IV) of the periodic table. It is most preferred that 0 boosters be one or more of Nitrogen Oxyanions, manganese sulfur, tantalum, molybdenum and rhenium tungesten oY.

. Y. For ease of understanding, the promoters will be referred to as anion cation promoters, such as alkali metals, alkaline earth metals, and anionic cation promoters (MoO3). 5 Although it is anionic to ionic compounds; During the preparation of the catalyst or the use of cmolybdenum oxide, for example. Whether or not such a transformation occurs for these compounds, it is 0 alkali metal or molybdate. Jie cation and anion will be referred to by the terms anionic classes and often the catalyst includes an alkali metal and/or an alkaline earth metal as a cation promoter. Examples of alkali metal and/or alkaline earth metals are lithium, beryllium, cesium, rubidium, potassium, potassium -barium, strontium, calcium, and calcium. magnesium and magnesium 0 including QF series metals Other cationic enhancers include group metal ions Cesium Oa The enhancer includes in some examples a mixture of cations; lanthanide, an alkali metal and at least one other To obtain a cesium cooperative catalytic efficiency enhancement as described in British Patent No. 0474481 asynergistic officiency enhancement”; incorporated into this statement for reference

In many examples, it is preferable that the catalytic jelly be based on a salt or salts of an element other than oxygen, oxyanion, with an atomic number from © to AY, and be from groups (“B”) to (LAB) or groups (©A) to (IV ) from the periodic table. In some instances it was found useful to add an amount of anion more than required to combine with all the alkali metal and alkaline earth metal added to the catalyst. It is not known why this additional anion is useful in these cases, and the additional anion may be added in the form of acid, ammonium salt, camine salt, etc.; Or a portion of the alkali metal and/or the alkaline earth metal may be added in the form

acidic salt » such as cesium hydrogen sulfate The concentration of salts (including salts of any alkali metal and alkaline earth metal) in the prepared catalyst ve is not narrowly critical and may vary widely. and optimal focus clad

The cesium salt and other chelate concentrations for a specific order will be dependent on performance characteristics; Such as catalyst efficiency, catalyst aging rate, and reaction temperature. The salt concentration may vary (on the basis of the weight of the cation eg cesium) in the prepared catalyst from about 7,000,009 to 750:1 by weight of the catalyst and the preferred from about 0 Lovo to 70.1 by weight of the catalyst; The preferred amount of cation promoter to be deposited on or present on the surface of the carrier or catalyst generally lies between about 01 and 5000, preferably between about 0V and 0660", and most preferably between about 01 and 7900 (ppm)ppm by weight of the cation. Calculated on the basis of the total sald weight of the carrier.The most preferred amounts are often between about OR and 1000 (ppm)ppm and when cesium is used in a mixture with sal cations, the ratio of 0 is the ratio of cesium salt to any Salt or other alkali metal and earth metal salts, if used to achieve the desired performance, are narrowly non-critical and may vary over a wide range.The ratio of cesium salt to other salt or salts may vary from about 0.0090:0 0 to 05 preferably from about .1:00011 (Vien) preferably cesium constitutes at least about 701 and more preferably from about 771 to 7001 (by weight) of 1 total metal Alkali and alkali earth metal added inside the ready catalyst The anionic types of enhancers or modifiers suitable for use in the catalysts of this invention include, but are not limited to, oxyanions such as sulfates SO, 0,2-alkaline phosphates and titanates titanates, say 1102, tantalates such as #B0Y1, and molybdates, MoO,? Jie molybdates » vanadates such as 0 122042 and chromates such as 0:; And zirconates such as 70, polyphosphates, manganese, nitrates, chlorates 185, bromates, borates, silicates, and carbonates. Carbonates, tungstates, thiosulfates, cerates, and the like. Halide ions may exist in the form of anions, including fluoride, chloride, yo, bromide, and iodide, and other salts such as sulfides oY may be used. many complex chemical compositions and may exist in one form or different metavanadate and more orthovanadate; For example; Orthovanadates Rom 0 Yua 1. M07024° 110,7 Jie molybdate oxyanions Molybdate oxy anions, as well as oxy anions containing mixed metals, including poly oxyanions, and may include the composition of oxy molybdenum 2020880856 oxy anion. For example, manganese and molybdenum 0, whether supplied in anionic form or sal, can be a metal anion mixed with them. Likewise, metals may enter

cationic, organic, or covalent; in anionic structures. While oxy-anion or an oxy-anion-forming substance may be used in carrier impregnation solutions; It is possible for the special oxy anion or its constituent substance, which exists 0 at the beginning, to transform into another form during the catalyst preparation conditions and/or during its use. In fact, the element may turn into a cationic or covalent form, and it is preferred that the element unite with oxygen; any; It must be an oxy anion or a covalent oxide, or have an anion that contains oxygen. In many cases, analytical techniques may not be sufficient to accurately determine the type of chemical composition present. It is not intended that the invention be restricted to the type of exact chemical composition that may be found vo on the catalyst at the end during use, but it is intended to refer to the oxyanions in this

The statement is to give a guide to understanding and applying the invention. A prominently preferred anion enhancer includes sulfates, rhenium oxyanions, molybdenum, tungsten, and/or chromium. Examples of sulfur anions that may be appropriately used include sulfate, sulfite, bisulfite 0, bisulfate, sulfonate, persulfate, thiosulfate, and dithionate. dithionite, jie chalosulfate, fluoro sulfate, etc. The preferred compounds for use are ammonium sulfate and alkali metal sulfates. Examples of molybdenum, tungsten and chromium anions that can be used appropriately include molybdate vo, dimolybdate, paramolybdate and other heteropolymolybdate compounds cheteropoly molybdate etc.; and tungstat ov.

YY

And other compounds of metatungstate, paratubgstate, tungstate, dichromate, etc., chetero-polytungstate iso, heterochromate polytungstate, etc. Preferred are chalochromate, chromite, dichromate dichromate, chromate tungstates, tungstates, molybdates, molybdates sulfates, and sulfates © Laie. The catalyst includes rhenfum. It is possible to supply the rhenium component in forms Various, for example, in the form of a metal or in the form of a covalent compound or in the form of a cation or anion. The type of rhenium that enhances the efficiency and/or effectiveness is not certain (agreed) as it may be the component added or it may also be a component produced during the preparation of the catalyst or during its use. Examples of 0 - rhenium compounds include rhenium salts such as rhenium halide, rhenium oxy halides, rhenates, super renats per 05, and rhenium oxides and acids. On the other hand, it can also be used appropriately over alkaline metal rhenes, over alkaline earth metal rhynates, over silver per rhenates, over omitted rhynates, and rhenium heptoxide 0 is appropriate. As a result, rhenium per rhenic acid is dissolved in water to form Re;07 heptaoxide, and therefore, for the purposes of this statement, hydrogen per rhenate is sold as hydrogen per rhenate, that is; at 0 m. It is possible, “ly above rhenium heptoxide, rhenium heptoxide and molybdenium can be considered to show similar chemical compositions to other metals such as molybdenum, tungsten 0, and a range of other enhancers include manganese compounds, and manganese compounds can manganese in many examples enhance the effectiveness, efficiency and/or stability of the catalysts. The class of manganese that would enhance the effectiveness, efficiency and/or stability of the catalyst is uncertain; It may be the component added or it may also be a component produced during the preparation of the catalyst vo use as a catalyst. Manganese compounds include but are not limited to manganese acetate and manganese ammonium sulfate oY.

Y¢ manganese dithionate manganese citrate ammonium sulfate manganese nitrate manganese oxalates manganese dithionate manganous anion manganous sulfates manganous nitrate manganate anion permanganate anion permanganate “Jie canion” and so on. oo 70.0006 to 70.000 and the amount of anionic booster may vary widely from about 70 to 77 by weight, preferably from about 70.009 to 70.2 by weight based on the total weight, as it is often found in an amount of no Less than about the rhenium fraction of the catalyst. And when using a rhenium compound to 10 one per million, it can be said that it is not less than about © parts per million; Any of about rhenium 000 (by weight calculated as the weight of rhenium metal 0001 and 01 and often between 0 1 h as the basis of the total catalyst weight. The least of a member of an oxidation-reduction pair that is intended to be used in oxidation processes in which there is at least one gaseous efficiency-enhancing member of an epoxidation-reduction pair (as described below).The term means (oxidation-reduction reaction) vo those found in the equations presented in Je used in this statement are half-reactions Tables for standard redox potentials, also known as unipolar or standard potentials, of the type found, for example, in " Chemistry handbook

"handbook of chemistry

CRC Handbook of or "Handbook (YAY) 17148 to 1711 Pages Book Company 30 pages D (Boca Raton, Fla., CRC 10th Edition" Press ("Chemistry and Physics" to 137) 1984). The middlemen in this statement are to include members of the class Jie nomenclature vo substances that provide the desired performance enhancement rather than the mechanism of chemistry involved.

P: compounds when conjugated to the catalyst in the form of salts of the members of a half-reaction pair; salts in which the anions are oxy-anions; The preferred oxy-anion is a multiple atom “SSE”, that is, the anion atom with which the oxygen unites is able to exist in different equivalence states when it is united with a hetero-dissimilaration atom. Potassium is the preferred cation, but it may use sodium and rubidium

© and cesium as well, and the preferred anions are nitrate, nitrite, and other anions that, through displacement or another chemical reaction, can form nitrate anions under epoxidation conditions. KNO;3

The member salt of the redox reaction pair, ail, is added in an amount sufficient to enhance the efficiency of the oxidation reaction 0©800l0*1m©. The exact amount will vary depending on such variables as the gaseous member used to enhance the efficiency of the redox reduction reaction and its concentration; the concentration of the other components in the gas phase, the amount of silver present in the catalyst, the surface area of the support, and the process conditions; (Jia) space yelocity, temperature, and shape of the support. In general, the appropriate range for the concentration of added salt that enhances efficiency is calculated on the basis of 1 _ the weight of the cation, which is from about 70.01 to about 78, and the preferred range is from about 70207 to about 77 by weight, based on weight. The total of the catalyst.and the most preferred of all to be added

Salt in an amount ranging from about 70.07 to about 77 by weight. In any case, cationic or anionic enhancers are present in an enhanced quantity. As used in this statement, the term “promoting amount of a particular catalyst component” refers to the amount of ys of that component that affords an improvement efficiency in one or more of the catalytic properties of the catalyst when compared to a catalyst that does not contain said component. Examples of such catalytic properties are Sal's include, among others, operability (resistance to run-away), selectivity, potency, conversion rate, stability, and yield. An industrial technologist understands that one or more individual catalytic properties can be "quantity enhanced" in While other catalytic properties of Yo may or may not be enhanced or may also be decreased it is understood that other catalytic properties may be enhanced under different operating conditions.For example a catalyst having oY may be used.

Enhanced selectivity at a range of operating conditions. Improvements appear in efficiency rather than selectivity. The operator of the ethylene oxide production plant will change operating conditions on a global scale to take advantage of certain catalytic properties, albeit at the expense of other catalytic properties, in order to maximize profits, as well as take advantage of Consider feedstock cost©, energy cost, by-product removal cost, etc. The effect of reinforcement provided by reinforcers may be affected by a number of variables. Jie reaction conditions, catalyst preparation techniques, support surface area, pore structure, and surface chemical properties; The silver content of the catalyst, the co-promoter, the presence of other cations and anions on the catalyst, and the presence of activators, stabilizers, catalysts, and other promoters or other catalytic improvers affect the enhancement effects. Various methods can be used to prepare the catalysts according to the present invention. It is desirable that the silver and at least one or more promoters be evenly distributed over the catalyst. The Favorite 45 includes the following steps: 1. Imregrating a porous catalyst carrier with a solution comprising the cule or solubiling agent Vo, silver complex and the aforementioned anionic and/or catalytic enhancers on the carrier. LY then treated the impregnated carrier to convert the silver salt into silver metal and induce precipitation of silver and anionic and/or cationic enhancers on the outer and inner surfaces of the support. and for the purpose of the possibility of return; In the Use and Reuse of Impregnation Solutions © > _ It is preferable that the carrier does not contain unnecessary quantities of ions dissolved in the impregnation solution and/or interchangeable with the promoter provided (liad) either in the preparation of the catalyst or when using it; This is to change the amount of the booster that provides the required boost for the catalyst. And if the carrier contains such ions; In general the ions must be removed by standard chemical techniques such as leaching* eg; Otherwise, Yo must be taken into account during catalyst preparation. The deposition of the silver and the promoter is generally completed by heating the carrier to high temperatures to vaporize the liquid from within the support oY.

And the events of deposition of silver and enhancers on the outer and inner surfaces of the carrier. Carrier impregnation is the preferred technique for silver deposition because it utilizes silver more efficiently than Cua coating methods. These latter methods, in general, cannot cause large amounts of silver to be deposited on the interior surface of the carrier. In addition, coated catalysts are more susceptible to silver loss through mechanical obrasion. Leaching | * = Leaching: It is the extraction of the soluble ALG from a mixture by washing or dissolving in a liquid in preparation for its separation.

The silver slurry used to impregnate the carrier consists of a silver compound, solvent or dissolving agent 0, and Jie complexing sulubilizing agent, the silver solutions shown in the manufacturing methods known as art theart in this field. The special silver compound used as oJ can be chosen from among silver complexes, nitrates, silver oxides, silver carboxylates, Jia, silver acetate, oxalates, citrates, phthalates, lactate, propionate, butyrate and salts of higher fatty acids. desirable; It is considered a complex silver oxide

vo with amines is the preferred form in ead application of the invention. A wide variety of solvents or dissolving and complexing agents may be used to dissolve the silver to the desired concentration in the impregnation medium. Among the solvents that seem suitable for this purpose are lactic acid (USP. 797/7577 granted to Aries and US.P. 03501417 0 granted to De Maio) and ammonia (patent US Patent No. 7,177,748 granted to West, et al.

Al and alcohols are ethylene glycol (US Patent No. 78701761 - Granted — Endler. Co. and US Patent No. 0779145 Granted Wattiming, Amines and Aqueous Mixtures of Amines (US Patent No. 74997847 Granted to Schwartz Schvarts | 0, US Patent No. YOUVE granted to wattimina, US Patent No. 77,169,756 granted to Benisi, US Patent No.

ov.

Ya

US Patents Nos. 50,997,914 and Nielsen granted to 74 (Cavitt granted to 70711 and 5) Generally speaking, the amount of silver compound that dissolves in a silver impregnation solution is at the end Dad can be dissolved More than that quantity that is supplied in the catalyst ready for each impregnation, ethylene and ethylene diamine oxalic acid m silver oxide 0e in a vacuum oxalic acid solution by weight approximately. (in vacuum) on an alpha-alumina support with a porosity approximately equal to impregnation to produce a catalyst containing 775 by weight of silver on the basis of the total weight of the catalyst mg / “m0; and identically; in order to obtain catalysts with a load of silver Higher than about 770 or more It is required to subject the carrier to two or more consecutive impregnations of silver with or 0 270 without enhancers until the desired amount of silver is deposited on the carrier Usually two or more impregnations are used to make the catalysts of this invention. In some cases, the concentration of silver salt is higher in the last impregnation solutions than in the first, for example, if the silver concentration is to be 701, a low amount of silver of about [Te] will precipitate in the catalyst; Let's say about 770 in silver to precipitate the Al by weight on the carrier as a result of the first impregnation, then follow with 1 impregnation by the remaining weight. In other cases, approximately equal amounts of silver are deposited in each impregnation step. In order to achieve equal precipitation in each impregnation step, it is often necessary that the concentration of silver in the subsequent impregnation solutions be greater than it is in the primary impregnation field. In other cases, amounts of silver are deposited on the carrier in the initial impregnation, greater than the amounts of silver deposited in the subsequent toasting or impregnation. Each impregnation may be followed by a roasting process or any other process to make the silver insoluble. The follow-up of the impregnation or deposition of silver and enhancers on the carrier surfaces is optional. Thus the impregnation and sedimentation of the silver and the salts may be carried out simultaneously or sequentially; That is, the enhancers can be deposited before, during, or after the addition of silver to the carrier. Yo can deposit the reinforcers together or sequentially. Od may precipitate one or more salts at the beginning and this will be followed by the automatic or sequential precipitation of silver and additional or other salts. oY.

Yq The catalyst may be impregnated with one or more silver-containing solutions and promoters according to known methods of automatic or sequential precipitation. For instantaneous precipitation that follows impregnation, the impregnated carrier is heated or chemically treated to reduce the silver compound to silver metal and precipitate salts on the catalyst surfaces. For consecutive precipitation; The carrier is preliminarily impregnated with silver or tonic (depending on the sequence applied) and then heated or chemically treated as described above. This is followed by an impregnation step to produce the finished catalyst containing a second Allee silver and heating or chemical treatment and enhancers. In a preferred embodiment of the present invention; One or more boosters are added at the same time as Silver. However, it is more preferred that the single promoter or promoters be added to the catalyst in step 0 of the last silver impregnation. It was found that these embodiments help to increase the efficiency and effectiveness of the resulting catalysts, especially when catalysts enhanced with nitrate are used. On the support with silver and subjected to heating so that the silver compound turns into silver metal, the salts remain as they are, in a basic way, without change. Of course, it is known that the salts of alkali metals and alkaline earth metals that have an unstable anion oxidation state will change to a stable state or oxidation states;

Oil to sulfate 9, 9015816. And when sulfites precipitate, for example; The alkali or alkaline earth metal sulfites are converted into hydroxide or carbonate; it may transform in the presence of amines; Which may be used to impregnate the catalyst to a different salt form (ie to nitrate) according to the heating (or roasting) step, depending on the roasting conditions. If the precipitated material is volatile enough, some of it may be lost during roasting as a result of its volatilization. After each impregnation of the catalyst with silver and booster, the impregnated carrier particles are separated from any remaining unabsorbed solution. This is conveniently achieved by draining off the excess impregnating medium or alternatively by centrifugation. Separation techniques such as filtration or centrifugation. Ye The impregnated carrier is generally heated (e.g. roasted) in order to decompose the silver metal complex (oY complexes). .

in most cases) and reduces to metallic silver and precipitates salts of alkali metals and salts of alkaline earth alkali. Such roasting may be carried out at a temperature of about 1007°C to -0”°C and preferably from 0100°C to 70000°C for a period of time sufficient to convert essentially all the silver salt into silver metal. Generally speaking, the higher the temperature the higher the shorter the oo period of reduction required. For example, at a temperature of about Jaton 08 "C the reduction takes place within about 1 to ÷ minutes. Wide range heating times have been proposed in manufacturing methods (known as art) for curing thermal impregnated support; ole) eg; US Patent #70,779,134 suggests heating of less than ©0,000 sec to dry the catalyst but not calcining it to reduce the catalyst and US Patent #3,707754 0 indicates heating times from 2 hours to A hours at a temperature of 100 °C to 75 °C “for the reduction of the silver salt in the catalyst” and US Patent No. 977177 suggests a heating period of half an hour to A hours for the same range of temperatures); however, it is only important that the reduction time is related to temperature such that The reduction of the silver salt essentially achieves complete reduction to silver.It is desirable to use for this purpose a continuous or step heating programme. 1 Continuous roasting of the catalyst for a short period of time is preferred; Sle does not exceed an hour; This can be effectively made in the manufacture of the catalysts of this invention. When more than one roasting step is used, the roasting conditions need not be identical in each roasting step. It is preferable to heat treatment in air but a nitrogen or carbon dioxide atmosphere may also be used. The device used for heat treatment may use a static or flowing atmosphere of these gases to bring about reduction, and it is better to use a flowing atmosphere of the aforementioned gases. In another embodiment of the present invention; After impregnating the carrier with silver solution and before any roasting step; The carrier impregnated with a solubilizing agent, a silver compound, is washed off. This washing step helps remove excess silver that is present on the surface of the support, thus helping vo to avoid the acclusion and/or agglomeration that the removed excess silver may cause. This helps maintain the porosity of the carrier and prevents its pores from becoming clogged with oY particles

A

Lumpy silver. The conditions of this washing step must be mild enough to essentially remove only the excess silver that is on the surface. Generally, the solvent comes into contact with the impregnated carrier

No contact mixing, no more than about 1 minute, then dispensed. It is taken into account in the manufacture of the catalyst of the invention to avoid the use of strong acidic or basic solutions that may attack the support and deposit impurities on it that may adversely affect the performance of the catalyst. The preferred impregnation method in UK Patent No. 7,047,441 coupled with the high roasting temperature and short roasting residence time described in the patent is particularly useful in minimizing contamination of this catalyst. However, the use of promoter salts combined with high purity support materials allows for the use of lower temperatures while being preferred

0 short roasting times.

Some of the previous manufacturing methods in this field coordinate the particle size of the silver metal deposited on the carrier to be effective in relation to the used catalyst preparation method. This may appear to be true because of the limited ability of present-day analytical techniques to meaningfully visualize the carrier surface. Thus, the space between the silver particles seen on the stand was not distinguished by a degree

1 is sufficient to determine whether these particles alone represent silver on the stand. However, the particular choice of solvent and/or complexing agent, silver compound, heat-treatment conditions, and catalyst carrier may influence to varying degrees the range of resulting silver particle sizes seen on the carrier. In general important carriers for the production of ethylene oxide, it is common for the silver particle size distribution to be in the range from 1006 to 17 microns.

The silver catalysts of the subject of the invention are particularly suitable for use in the production of ethylene oxide by gas-phase oxidation of ethylene with molecular oxygen “WDLD” 1H. The reaction conditions for carrying out the oxidation reaction are well known and have been described extensively in the manufacturing methods. This applies to reaction conditions such as temperature, pressure, residence time, concentration of reactants, and gas phase diluents (Sle).

Yo eg nitrogen, methane, carbon dioxide) and gas phase inhibitors

oY.

ry ethylene SL 55 ethylene chloride (eg dichloride etc.) Feed gases to the reactor may contain modifiers, inhibitors or additives such as these

Sos YYVAET in the two US patents No. 1809, et AL, which included (Lou) and those with him, nitrogen oxides and nitrogen oxide-generating compounds. Jie 77745497. The European patent No. 347 uses catalysts that include an efficiency-enhancing salt At least one oxidation-reduction-half-reaction pair in union with at least one gaseous proficiency-enhancing member from an oxidation-reduction-semi-reaction pair. From a pair of oxidation-reduction half-reactions” or similar terms referred to in this statement 0 have a similar meaning to the term “salt of a member of an oxidation-reduction pair” or similar to that defined above. That is, these terms refer to members of the reactions Half-terms in the single or standard electrode potential tables in the texts of standard references AL Se or approved books that these members are in the gaseous state; standard reference text Substances that are oxidized and reduced in the reaction equations shown in these scientific references. Vo, the preferred gas that enhances efficiency, is compounds that contain an element capable of existing in more than two valence states, preferably nitrogen, and another element, preferably oxygen. Examples of favored efficiency-enhancing gaseous members include redox pairs

NO, and nitrogen dioxide NO is half at least one member of nitric oxide and nitrogen dioxide 11:04 and dinitrogen tetroxin and dinitrogen tetroxin 0 gaseous capable of forming one sale and 11:0 or any dinitrotri oxide under conditions NO, and nitrogen dioxide NO, especially nitric oxide Wi of the aforementioned gases, monoxide PH, and mixtures thereof with one or more compounds of phosphine, epoxidation, oxidation, carbon 00, sulfur trioxide, 50, sulfur dioxide, 80, phosphorous trioxide, phosphorus pentoxide, 070. And nitric oxide is often the 200 Yo performance-enhancing compound of choice. ov.

yy

In some cases it is preferable to use members of the same half-reaction pair in the reaction system; any; The two members are both the efficiency-enhancing salt member coupled to the catalyst and the gaseous member in the feed stream; As is the case, for example, with the preferred combination of potassium nitrate and nitric oxide, but this is not necessary in all cases to achieve satisfactory results. Other assemblies may be used in the same system such as KNOy/N,O3, A010/0 and KNO3/SO; 5 KNO3/N,Os 3 nor/boring and KNOy/NO, [KNO;, SO mixture; and NO, and in some cases; The salt member and the gaseous member may exist in different half-reactions representing the first and last reactions in the series of half-reaction equations of the reaction

total.

1 The efficiency-enhancing gaseous member of the redox reaction pair Lia is present in sufficient quantity to enhance the efficiency of the catalyst and in particular; The efficiency of the epoxidation reaction and the exact amount needed is determined in part by the particular efficiencies-enhancing salt of the oxidation-reduction pair member used; his focus; the particular alkene that is oxidized and other factors mentioned above that affect the amount of the efficiency-enhancing salt of the redox reaction pair member

ve and filtering shorthand. It is common for the appropriate concentration of the gaseous member of the redox pair to oxidize most alkenes, including proplyene, to be from about 1.1 to about 50,000 10 vol of the gaseous feed when nitrogen, Ny, is used as a process. For balancing, ballast, and when a gaseous element is used from the oxidation-reduction reaction pair, such as NO, in the propylene epoxidation, the preferred concentration is

vo is about 0001 paallppm when nitrogen, Np, is the equilibrating volume. However, focus

The appropriate oxidation rate for ethylene is from about 1.1 to about 001 (0017 by volume of constituents of

Gas feed stream. Preferably, the efficiency-enhancing gaseous member is present from the oxidation reaction pair

and half-reduction of about 1 to about 8+0 dieppm, the presence of IY by the size of a second

carbon dioxide (COp) in the reaction mixture. When using nitric oxide as a gaseous compound

ve enhanced efficiency in the ethylene oxidation system and in the presence of CO2:00 in the oY mixture.

Yi by volume, nitric oxide should be present by the amount of JY reaction; In amounts up, for example, to about ppm. fr to about 1 0010, and it is preferred from about 01 to about 1.1, if the desire is to recycle the unreacted feedstock or to use a single-pass system Increasing the rate of ethylene conversion using successive or single-pass reactors in series can be easily grasped by those skilled in the technique. The economics of the process will dictate the particular mode of operation chosen. In general; Commercial operations are conducted by feeding a feedstock containing ethylene and oxygen continuously into a reactor containing a catalyst at a temperature and pressure that may vary between about © atmospheric pressure to about 0” Too about 1007 m to residence times Atmospheric pressure depending on mass velocity and desired throughput. and the lifetime of Yoo 0 to © seconds. 1.1 can be supplied in production reactors on a large scale, usually ranging from about an air stream or a commercial oxygen stream. oxide, preferably ethylene oxide, using the usual traditional methods

1 In commercial operations, typical operating conditions may change and the amounts of ingredients used can be adjusted to achieve optimum efficiency. In particular, the quantities of ethane, carbon dioxide, and organic chloride can be changed to obtain the ideal efficiency for making ethylene oxide after giving. And ethane is one of the impurities that are found in varying quantities in the raw ethylene. Ethane can also be added to a commercial reactor to better control the chloride inhibitor reaction.

© In an ideal process, the amount of ethane used in commercial processes can vary from about 001 to about 78 moles to achieve the ideal situation under both air and oxygen process conditions. It is believed that the higher the ethane concentration in celia, the lower the effective surface chloride concentration will be to enhance the inhibition of reactions that increase the efficiency of making alkylene oxide. The amount of chloride can be changed; and for example; ethyl chloride

m ethyl chloride or ethylene dichloride to provide the required enhanced reaction Ly dl equivalent to the corresponding ethane levels found in a special process as well as

oy.

Yo The type of reinforcing material or modifier used in the catalyst. The amount of chloride can change

Spm +) of about organic sad) used in commercial processes typically in air and Led 0010 conditions to achieve ideal process conditions that use about 01 of the process in which oxygen is used. Carbon dioxide is carbon dioxide. generally discouraged; The inhibitory effect of carbon dioxide on the efficiency of the process may change with the change of its concentration. With the various types of enhancing or modifying agents used in the preparation of the catalysts of this invention, it may be more desirable to have different concentrations of carbon dioxide in certain commercial processes. Typically, the amount of carbon dioxide used in commercial processes can range from about 0 mol of CO2 being optimized under both process conditions in which 711 is used to about 77 0 air and process conditions in which it is used. oxygen. The amount of CO2 depends on the size and type of CO2 stripping system 90055108 used. Determining the used amounts of ethane, carbon dioxide and organic chloride provides catalysts that are particularly suitable for obtaining the desired efficiency in a commercial process for the manufacture of ethylene oxide 01. And as a basis for making an appropriate comparison with previous industrial methods in this field. The conditions for the production of ethylene oxide were standardized in this statement and in many examples of the conditions that were conducted in these conditions. However, it is also to prove that the catalysts of the present invention are effective, and also to show that epoxidation is able to work in various conditions of the oxidation process, how to achieve the optimal state for these conditions; Many of the following examples have also been made, as is v. ethylene in that statement specifically under conditions different from the standard She 6 e production conditions for ethylene oxide. And we have to realize, of course, as those who are skilled in this industrial technique realize that the efficiency of using a specific catalyst in a certain set of processing conditions is not epoxidation. The oxidation process using the same catalyst under epoxidation can be compared indiscriminately with the efficiency of the oxidation process Yo under different process conditions. oY.

7 1 lad The following detailed methods are given as an illustration of the useful methods and carriers for the preparation of catalysts according to the invention. This example is for illustrative purposes only and is not intended to specify the purpose of this invention. In the examples, all parts and percentages of solids and liquids are on the basis of weight and gases on the basis of volume, unless otherwise stated or clarified in the context of 0 speech.

The carrier drinks as stated Led served under vacuum (WA) as described below with a complex solution of silver and salts of alkali metal and/or alkaline earth metal. There is no need to add components containing alkali metals and/or alkaline earth metals in the form of salts. For example, ys; Cesium hydroxide can be used in combination with an ammonium salt (ammonium sulfate, for example) or an acid (sulfuric acid (Ph) or an organic compound (ethyl sulphonate, for example) and under the conditions of preparing or using the catalyst, a Conversion to the desired compounds.Impregnation solutions are prepared with such concentrations that the final catalyst contains the desired quantities of silver and the promoter or (sald) modified.The required concentration of silver and promoter is drawn into a solution of a specific carrier from AES packing. (Tana) dencity The size of the pores occupied by the water in the carrier which is either known or can be easily estimated. The relationship can change based on the nature of the carrier, for example, pore size may affect the amount of silver precipitated from a given solution. It is obtained The desired concentration of promoter in solution is determined by dividing the concentration of the silver solution by the ratio of silver to promoter 0 desired in the final catalyst.As mentioned above due to the high amount of silver needed in

The catalysts are the subject of the present invention; In general, two or more impregnations are required. in the preparation of catalysts; In general, the desired amount of ethylene diamine (high purity) is mixed; with the mentioned quantities of distilled water; Then oxalic acid dihydrate (reagent purity (brade Yo) is slowly added to the solution at ambient temperature YY "m) with continuous stirring. During this addition of oxalic acid, the oxalic acid rises temperature to about 40 “C since oY”

B. The reaction is exothermic, then silver oxide powder is added to a diamine-oxalic acid salt-water solution, maintaining the temperature of the solution at less than about 50 "*m. Finally, the solution or solutions are doubled. monoethanolamine, an alkali metal salt Ale, and distilled water to complete the solution.

° The stand can be impregnated in a vessel equipped with a stopcock 80000016 suitable for draining the stand after impregnation; However, flasks of other suitable sizes and types may be used. A suitable sized separating funnel to contain the impregnation solution is installed above the impregnation vessel, and the aforementioned vessel is equipped with a vacuum line. The impregnation vessel containing the carrier is inflated to a pressure of 0 to 4 cmHg (absolute pressure) approximately for about 10 minutes, after which a solution is added.

0 Slowly impregnate the holder by opening the cock between the separating funnel and the infusion vessel until the holder is completely immersed in the solution and the pressure in the vessel is maintained at a pressure (©cm hg (lai im) absolute) of approx. After adding the solution, the vessel is opened so that the pressure inside the vessel becomes equal to atmospheric pressure. The carrier remains immersed in the impregnation solution at ambient conditions for about one hour; The excess solution is then drained off for about 11 to 0© minutes. Then the impregnated stand is heat treated

1s as follows (unless otherwise specified) to reduce the silver salt and deposit the enhancer on the surface. Spread out 0 The impregnated carrier is spread in a single layer on a continuous stainless steel belt

1 cm (spiral weave) and transported through a square heating zone

The figure has dimensions cA X 5.006 cm with a duration of 0.¥ min; It maintains the temperature of the heating area

At a temperature of 00 "C, by passing hot air to Jel through the belt and around particles

_ The catalyst at a rate of 7175 80211 at YE,YY m" per hour. Hot air is generated by passing it inside a stainless steel tube of length 1©7.4 cm and inner diameter A, cm, which is heated from the outside

An electric oven (Lindberg (Ake) commercial) tubular oven with an inner diameter of 1.79 cm and a heating zone length of 91,454 cm can supply ©5010 watts. The heated air in the tube is discharged from

Square port A X 0.0 A © 0.0 cm located directly under the conveyor belt that carries the stand

ve the catalyst. After being roasted in the heating zone, the final catalyst is weighed; And on the basis of the weight gained for the pregnant woman; known ratios of silver to promoter in the impregnation solution; Calculated quantity

oy.

Ya

of the promoter(s) contained in (ppm) silver 7 by weight and ppm of the catalyst. The following discussion applies to all examples. Next: a milligram weight sample is crushed. Dissolve the silver 1.1 g of the crushed sample rounded to the nearest 10 mill and weigh 0 "m). The leaching (A) by volume hot 0 70 present in the catalyst sample in a nitric acid solution non-alumina particles Soluble and washed with distilled water to remove all adhering salts in a flask of 760 mm of silver nitrate, cesium ... etc. The solution is completed to adhering

Gohl in mm of this solution according to volumetric yo using distilled water. Titrate a known ammonium volume fraction of ammonium thiocyanate 1,1 standard titration using solution 0 as reagent «10016810. The amount of silver estimated by this fernic nitrate and ferric nitrate thiocyanate mm was then used to calculate the percentage by weight of silver in the YOu quantitative solution to the volume of the catalyst sample. The concentrations of silver and promoter for all the catalysts described in this statement are values calculated as Described above unless otherwise specified. Vo ant, VAEX 0 YAEL TVA The toroidal mounts are considered bypass and their dimensions are from or about 0.7178 178771787 , the following; A detailed statement explaining the contents and preparation method of each catalyst from (1) and in the table, the amount of support material (YA) was also included in (1) the catalysts tested in the examples used in each impregnation step for each catalyst The table also includes a reference to the specific carrier number used in the preparation of the catalyst, and the details of the properties of these carriers in detail have been included in the following. Measurement "adsorption surface area and porosity" described in reference "Adsorption surface area, porosity, and method" 3271-711 pp. (V4) S.G. Greig and K.S.W. Singh Academic Press Yo Pore size measurement is the method described in the ASTM oY method.

Yq The calculated value of the density of the filling is based on the usual measurement (ASTM C20-26) C20-46 test number of the weight of the carrier in a container of known volume. The method for measuring the average pore diameter is described in “Using Mercury Permeability in Material Analysis” by S. Ur Al-Amsgar (Powder Technique); folder?;

Lk crushing strength Gaull estimated mean and resistance range (VAY) 177-1117 pages Norton Corporation; Akron Catalyst carriers Jalsa catalysts for test No. (1) referred to in 0

NAVE OV = Ohio Bulletin; C with nitric acid carrier pills. The acid-leachable impurities are estimated by contact with the carrier seed for one hour at a temperature of about 0 "C. The extracted cations are estimated by 0. atomic absorption spectroscopy. Standard techniques of atomic absorption spectroscopy inducticely Lia Coupled plasma spectroscopy techniques can also be used 0 for these determinations. coupled plasma spectroscopy The quality and quantity of the water leachable contents of the carriers can be determined with any suitable condonsate analytical technique. Generally the carriers are heated in distilled water, eg as a product condensing ado to 00 at a temperature of about recycling reflux from a reflux apparatus for re-cycling 1 hour, say 1 hour and reducing liquid Y to about 56 to 30 Wey 1 jon later for chromatographic adsorption techniques Ion chromatography and spectroscopy of inductively coupled plasma. Surface acidity is estimated by the chemical adsorption method of ammonia. For this purpose, a conventional adsorption vacuum bottle is used, the basic pressure of which is chemisorption, approximately mm Hg. Grease-free valves are used. to avoid contamination. And pre-treat a sample, that is, to pass through a sieve of 14/70 mesh or of an ALIS size of approximately gm (granules 15 to 10 in size; cm/min) at a temperature of 0100°C for an hour with helium flowing at a speed of (© 1/14) with eyes of a capacity of "m" for a procedure of 100 minutes at this temperature. The samples are cooled in a vacuum to the degree of Vo and then vacuumed for a period of acidity measurements. By the volumetric method at static mode and measured Static ammonia chemisorption Yo Samples were exposed to known amounts of ammonia (10 mm Hg) in a volume of 27 001 oY at temperature.

0 calibrated) for ©; minutes (or longer until the ammonia adsorption is completed). Ammonia consumption is measured by monitoring its pressure in the system. The ideal gas law is used to calculate the amount of ammonia adsorbed in micromoles. The sample is then degassed for 11 minutes at ep” 001 and the chemisorption measurement is repeated. The amount of ammonia consumed in the second measurement is subtracted from the amount of adsorption of ammonia 0 adsorbed in the first measurement to obtain the amount of ammonia adsorbed steadily (or strongly). This measurement is included as the number of micromoles of strongly adsorbed ammonia per gram of sample as an indication of the acidity of the sample. The catalysts mentioned in Table (1) were prepared using the general methods mentioned in 0 Preparation of the impregnation solutions: The impregnation solution is prepared on the basis of the pore size of the non-impregnated support (shown in Table (7)) or on the basis of the size of the pores of the pre-impregnated and roasted support. 1. Mix ethylene diamine (high purity) with distilled water. 7 Add oxalic acid dihydrate (purity grade B, reactive) slowly to the aqueous solution of ethylene diamine. In ambient conditions, an exothermic reaction occurs and the temperature of the solution rises to about 0, then “silver oxide is slowly added to the step (7) solution; monoethanolamine (free of iron and chlorine) is added to the solution vy. Step (?). Distilled water is then used to adjust the volume of the solution. Yo Each catalyst is prepared by impregnating it once or more with the solution prepared as described above with or without the addition of booster salts as indicated in Table (1). For any of the oY process.

1 first or subsequent impregnation; The solution may or may not contain promoter salts [see In addition, some catalysts are made by adding promoter salts from solutions. ](1) Table aqueous, i.e., not in the silver impregnation solution, after the last addition and roasting of the support containing silver (sequential precipitation of the booster). Carrier impregnation: 0 The carrier is placed in a vacuum vessel at a temperature the chamber and the appropriate impregnating solution is added to the stand under vacuum. Drain the solution. Drain off the excess solution. 7 00 : Washing the Freshly Impregnated Support The freshly impregnated support can be washed at this point to reduce the amount of large silver particles (accumulation) on the outer surfaces of the catalyst which may occur during roasting. The washing solution used after impregnation with a solution that does not contain boosters is the same solution, i.e. it is a solution of ethylene diamine, water and oxalic acid. cond silver and monoethanol 1 and the washing solution used after the last impregnation that contains boosters is Essentially the same impregnation solution still containing the boosters and ethanolamine but devoid of silver oxide.The wash solution is then allowed to drain from the material through the outlet cock of the impregnation tube for approximately minutes. : catalytic calcination 0 Roast the impregnated carrier (washed or unwashed) in hot air using a 1-minute conveyor belt. The air flow rate is about 0.000 Y.m for a duration of about 000 Mga roaster at SCFH. The catalysts were tested under the specific conditions listed in each of the following table ( ): (Vv) ve oY.

(1) Table of catalyst preparations according to Le foe oe Ty first impregnation

CC [CC D. #» [a ws Dara Laa 11 7/1 77 1 7 6 1 M Ahla Yo vy Grams 0 support Latak | Raqt | ov, YA for you Yo vy VY EA VV, EA AA 17717 | Bam Grams ethlenedia 1 mine As a solution | Ellkha | ev, vA Ye, Yan Mullah Mullah 1Y£0,) | Grams 0 oxalic acid 710 8 67 1,711 7571 18 YE, vo Grams silver 1 006 70 0.6 TAY AY Grams monoethan olamine

YY EA,” 14.1 oY, YA 14.40 14.40 YY, YY 1/7 Yo, os throw m Grams distilled 1 water

kno; And 1110 Grams + EYTE 0156 promoter

Grams promoter

Grams promoter cake talk ppm promoter nick-up ppm promoter nick-up ppm promoter pick-up

Yeo 1 YY,Y 11 Ed 1 LY Yo VY, A AY Silver pick-up second Impregnation 108 Fla 10 VY, EA Grams ethlenedia mine

EERE 1 ' 0 b oxalic acid 10 ml 10,A% 76.71 va Grams silver oxide oO y 0 ty monoethan olamine re distilled 1 water

kno; | kno; | kno; | mo KNO; | kno; KNOs; 1 Grams 8 01 Ya Ara Ma YAY RA promoter ee promoter

CL]ee promoter

CTE pick-up Es

Silver

Pick-up

I I I A

Lal promoter pick-up

Ppm promoter pick-up

Ppm promoter pick-up

YoY Grams ethlenedia mine

CC TE oxalic acid 571 Grams silver oxide

Ye Grams monoethan olamine 14.40 Grams distilled water

CT A promoter FE promoter Ce promoter rr pick-up Total Silver Pick-up oY.

a

Total ppm promoter (1) Table of catalyst preparations ssa ol (first impregnation) oc [ele [Fle qa] [oo | © | 6 [mm £4.7 rk] | AYY ire 57,711 oY, YY | ov,.v bahh | YATAYT | 4 Grams support

TY, YY A | YA ATEY,. 0 Cufflinks no vive | #Not easy for | 1 gram Grams ethlene diamine 7 Y. Vo YoY, V1 6 75 YA. Yav, 1 Grams. oxalic acid ov, VY Trag | Ar 1 oYrRY,. |ovvia. Tego | 3 Teo | Harfa | 24 Grams of silver oxide

YY, YE v1 Traction | EVE, VY, 0A VY, AA 17.51 Ed 14.1 14.41 Grams monoethanolamine

Yoon | Veen | 17 | 6 YLEY | Fahk | Aw? vases | Vaden Grams distilled water

RbNO, Grams 7171 promoter

Grams promoter

Grams promoter

You're a promoter of pick-up

Ppm promoter pick-up

Ppm promoter pick-up

Yo,A EY Yar YY, Yo 1 L 1 711 Silver nick-up (second Impregnation)

YY, ry m YLYY | I revolted overve 1 as | Read Grams ethlenedia mine rele | silver oxide 0 y 0

M YY Grams and YY,AA 01 YY,AQ Ferla A monoethan olamine TY, 8 FY, $v 00 TH, EY YY, Y LE TY,Y YY Grams distilled water RbNO; kno; kno; kno; kno; kno; KNO;3 KNO, KNO; Grams 1 0 AVY SAVVY 4 3 promoter Brain YAR SITY “AYA” Grams promoter Grams promoter YN VE, ¢ 7 Silver 1 6 pick-up Total Nrq v1, v4,Y rk Yov YY, YY, ¥4,8 Silver Pick-up 99AK | 4YAK |e vn K | ¢AVK Ppm | to make | Rb of K [Ve¥TK | avYK Yous promoter pick-up Ppm promoter pick-up Ppm promoter pick-up Third Impregnation Grams uncle ethlenedia mine Grams mi oxalic acid ov, YY Grams silver oxide Grams “arla monoethan olamine iv, 00 Grams distilled water KNO;, Grams 011 promoter Grams promoter Grams promoter Silver 7 pick-up TYLY Total Silver Pick-up o 7 0

0101 K Total ppm promoter (1) table, first impregnation to | knock [aw] [ws emphasizing 4 oY AY YOu, 011 A 0 B Ma 10 Bm Grams 0 0 0 ... support Uncle YPV,YT 1 Ara 1 AAY,Yo | .H17 | AAY Yo | YYYIY | #to see them AAY,Ye 1 Grams v ethlenedia 1 mine

YAY YYA vo YV,YA AAY YY AAT AY Lahra Lala AAY ANY AAY VY VYVY, o Grams . . oxalic acid

SAVY 7 Bit Ma Ma 1 Marked Aa 01 Rahaq Lamkham 0111 Grams silver

A. A 0 A A . . oxide for AY, VY 4,04 Kharf | EVE Ee [YA FA DL YVAN) | Lamarv TARA | Barak Grams monoethan olamine

Yq, by 0 Mother's Brother Qul | 1 Arrah | AYYA | 01 Ba 1 for Khawalakh | AYY,AA | 111 Grams distilled. . 7 E water 50 and Cs,S0, KNO, Grams

Voy at q, YAfo promoter

Grams promoter

Grams promoter for oft ony Ppm promoter pick-up

Ppm promoter pick-up

Ppm promoter nick-up 14,4 14, 14,4 X10 77 Yo,0 YX Yo,¥ Yo,v ERY Silver nick-up (second Impregnation)

YYV, YY AMY, Yo | YoY. | AAY, Vo AAY, YO 1 AAY, VO | 78 Grams v ethlenedia 1 mine

YYA, os AAT OY | Done AAT OY Taracham | AATAY | 11 5 Grams 0 ° oxalic acid 0 y 0

As oxide meen] Te monoethan olamine as 0 talam | ATT, | Mother AA AVY, AA | YOELAA | Don't miss Grams

I T =) water

Cs2504 KNO; KNO, KNO; RbNO3 | RbNO3 | RbNO3 Grams

CAT YLT 4,6) Karha Y1,A4 7 each | promoter me] promoter

Lb promoter

CT aaa pick-up no a

Silver

Pick-up A A A L A A L Yous promoter nick-up

Ppm SS pick-up Ppm promotor nick-up CL] ee ethlenedia

HE 3 A L oxalic acid

Grams of silver oxide

CL M monoethan olamine Grams Cs water I I TT A promoter

Ch]ee promoter

I EE TR A A promoter

CL ee] pick-up rr Tom o y 0

B Silver Pick-up Total ppm promoter Table (1) Sad Raq ol Alm Iw [mle [www ne] first impregnation) 1 « wigs | Waa Daa Malak ox [xR 1 ert | 4 Grams Aram oY, A 1 | Lalah TAY LNA | vee 124 solve 0 support YAXY YAY XV, EA Grams A 7 77 Ago, A TVA YY, A.

YY, A ethlenedia mine Grams oh no YV, A YY,A 706 YAY YAYY oY, VY YA,XY oxalic acid Grams 71 7 Dippers of Lime thyroid VEAL ,Q £AVY £AVY SAVY TV, silver 1 oxide (ERE Grams) olamine Te,ee Ve, Yo, Yo,.. Yo,0. Yo, .Yo, Grams ,1,0 1 rum Distilled water Cs,S0;, Cs,S0, Cs, S0, Cs,S0, Cs,S0, Cs,S0, Grams GY ety 7 NARS LUN INE INE YY YET promoter K380, Grams promotor 4 promoter oYA Cs | 194 Cs V+4 Cs TAY ppm promotor pick-up 011 Cs ppm promotor pick-up Ppm promotor pick-up for : 1 0 0 " - " ْ ْ' ْ A 0 "]1 pick-up (second Impregnation) AE AO YV,A YV, 0) YA, YY YAY YTV, EA Grams ethienedia mine ee 7 1 ’ 0 5 ca a to channel per [va oxalic acid o vv 0

£9 ll TE silver A oxide jd FH a A == monoethan olamine

See the distilled water

Cs,S0, 1 Rkyo 1 Magio Yugyo Mugeo KNOs Grams 13 for 7 in “promoter”

K,80, Grams

CT Te

TE nick-up "| 7 a TT Tes

Silver

Pick-up that a from nan an sa ee <1 promoter nick-up a fe promoter pick-up

ppm

CLL] a pick-up HENNE ethlenedia CL 5 a 1 Grams silver oxide

Grams

CE olamine

Grams of distilled water

I

A for | 1 s promoter I pick-up rr rr the (oY.

oO

Silver

Pick-up

Total ppm promoter (V) Table I — (first Impregnation) ov ov lor le le lols bos | 1 |p | sess

Yq, £4, 00.01 07 5 96 870.6 Awra 000101 | Grams 0 support

TV, 1. 8 7710 1 86 ara AE 7 Merck NY, + | Grams ethlenedia mine

VY, 1. A 6 YY YAYY 80 Lamca YoY, Y, M 176 Grams oxalic acid roan YY, oN, YY £4,0) 1,0. ugh | Yo, M LE. ved1, e | Grams 0 silver oxide

TA £,8 Vy, Yo 9,4. 0 q (YY, eo AN A 7 00 Grams monoethan olamine Yerca 887 17.1, £Y, 6 Tee 1 YYE A048 vo. Xe | Avo | Grams distilled water

Cs, Mo Cs, Mo 1 Jul 850, | Grams 0, 04 yor 1,001 | promoter in ER

Cs;Mo K,S0, | Grams 04 111No 1 promoter vy SO

Rb, SO, Grams

Led promoter

Cs(Mo) 00 Cs later Cs | ppm

Ye promoter pick-up

Cs(SO, YAK | Ppm 175 ( promoter o y 0

01 SSA 0.1. Rb Ppm promoter pick-up for Vat YY,v Pal Yo 7 Vo, LY YAY 011 Silver pick-up (second Impregnation)

YY, Yo. Vo,4¢ AA R Yo Vo, Grams ethlenedia mine 6 AA YY, Ve M “Grams oxalic acid

Ta 1y,0. YA 10,84 17 Grams silver oxide

TY 7, 8,6 Yo §,0. 777 grams of monoethanolamine

YY, £V,Y is 1.11 m 7 Grams distilled water

Cs;Mo | Cs;Mo0O, | Cs;Mo Cs;Mo | Cs;Mo Cs;Mo | Cs;Mo Grams (ON YoY Oy 0 0 Oy Oy promoter

LOA yov, RY Vea Tim

Cs,80, | Barqo Cs,Mo Cs,Mo Grams eve GeV 0. Oy promoter

Rb,SO4 Rb,SO, Rb,SO, Rb,SO4 Grams Brain supplement ETE Cary promoter 14.1 YY, Yat for YY 7 Silver pick-up F ro Yo Yo, Y1,4 Both VAY Total

Silver

Pick-up

Cs(Mo) 1 Cs(Mo) | Cs(Mo) | Cs(Mo) 1 Cs(Mo) | 001 Cs o\Y Cs | oY. Cs ppm

TY. v1 YY. Yi. Malla promoter pick-up

Cs(SO4 | Cs(SO4) | Cs(SO4) Cs(SO, Ppm 144) Ya. Ya.) 175 ( promoter pick-up

YY. Rb | YYRb | YY. Rb 001 Rb Ppm promoter pick-up (Third Impregnation)

Grams ethlenedia mine

Grams of oxalic acid

Grams silver oy.

oy rrr TT TTT Toxide MS A monoethan olamine

Ce Es distilled water

Tee promoter

CE promoter

FE promoter

Cl Te 01 ck-up NSS

Silver

Pick-up

CCT promoter (V) Catalyst preparation schedule, Labmar

IR wv ta | 9 | © support

EEE ethlenedia mine ANA oxalic acid silver oxide monoethan 1 olamine

Th, Yo, Yo Yo, EA, EV, £1,010 Yeon Say 01.0. | Grams

TE only water Cs3804 Cs,5804 Grams % YY promoter

I 1 n a l promoter

CE promoter Ata promoter pick-up oY.

ov

CE promoter pick-up

CL Ee promoter pick-up if ej pick-up (second Impregnation)

CL A ethlenedia mine Ce ee ee Ee oxalic acid £Y,YA 511 m Ye YY, lite bm | Grams

EE oxide

LT S monoethan olamine ee distilled water Cs,S0, Cs,S0, Cs,S0, Cs.Mo 0550 550 Cs,S0, Cs;Mo Grams 0 1 7 M A | v0.06 | 6 pm 0 promoter lal ll

Cs;Mo | Cs, SO, Cs, Mo 08250 | Grams

Oy AYE 0 .,YYo. | promoter

Yay Mel is an ee promoter

TT Il I pick-up M A A

Silver

Pick-up

Cs(SO, | Cs(Mo) | vo. j | Cs(SO, Cs Cs(Mo) | Ppm

ETT TE pick-up

Cs(Mo) | Cs(SO4 Cs(Mo) Cs(SO, | Ppm 1 P) Nor 70 ) promoter pick-up

CLL] fe promoter pick-up

Cr] [E ethlenedia mine

TT Alice oxalic acid

Oo y 0 of

Grams of silver oxide

Grams monoethanolamine

Grams distilled water

I nan anan promoter

CE promoter

CTEE promoter

FE pick-up

Total

Silver

Pick-up

CEE promoter o y 0

00 (V) Table of catalyst preparations es] bb m Jw fo [oe (first impregnation} pr br pk pk 0 | 0 | weds] pe ee Te support

Ll Te ethlenedia mine

Lp AA fe oxalic acid ees silver oxide

LT ae monoethanolamine a. distilled water 05250 | 250 | 250 | 250 250 and | Grams 84 m 4 4 for a bear Y,0A 4 | promoter SS mee

Grams bE ee ata" "77 a promoter pick-up

HEE promoter pick-up CL Ee promoter pick-up

Ce ee ee nick-up

XV, EA Grams

HEE A Mine Ce] ae oxalic acid SAN SAN N N N N N silver oxide SAN MNS SAS Ee monoethan olamine oY.

on

Yo, Grams distilled water 0250 Grams 0,¢ 4 promoter

CE promoter

CL ae pick-up

FY, Y Total

Silver

Pick-up promoter pick-up

Ppm promoter pick-up

Ppm promoter pick-up

Grams ethlenedia mine S | Oxalic acid

Grams of silver oxide

Grams monoethanolamine

Grams distilled water

Cb eee promoter

I I TE A I promoter

CL ee promoter A Lala Al pick-up

Total

Silver

Pick-up for ee promoter oy.

ov ppm in the form of molybdate Cs parts = Cs(Mo) : note in per million in the form of Cs sulfate parts Cs(SOy) 1 support data table

Tee re Te TE Ta

outside.cm

Surface area Mar 1 0, Mar 7 A 2.17 Lita Cr

Pore size YY,o 1, ¢ ALA vy AY,” YA, ¢ i Aa CT Es

The average diameter is 5 by 1 p

71 No 1 No YE Ee YY Ye Fluoride

(Fluoride)

#7 Remaining LL] ees

(Sa) kg

convertible compounds 1 ss

03 sus a a a a a a a a a a a a a a “shtsim a a a a deaf a a a bbb] potassium | a s a s by bbb magnesium | a a a ee SS es

ov.

oA table? Support data: support the support property

Pp Jo and 1 a la l a 17 © la la la +, YAY YAY 6 +, YAY YAY “Ivo for diameter == external cm surface area m” 1 Vad 0 a 6 | Laih | ©

Tex Almasa 0 TA YE | Rakah | IA | VAY Veo | von gt es 7 estimated by water. Ed Medium - 7,1 YY V1 7,1 VA Medium Diameter BA 7 Pores Fluoride 1715 "1 DA | Because 4 does not dissolve because (Fluoride) 7 Residual power of grinding A! 1 . 2S (Gad) Compounds that are leaching ppmeldl LASN NAM NKN NAN NAN NAN N A MLSAM || Aa A Aa Aa Dn Ce Aaana ee Anaan Nick Na An An Nan Sin Sm Ah || A The Sunnah of Nim for Magnesium is 1 SS | Ta Rastnen that Sinn Nin that Sinn Anas o y 0 |

Schedule ? Support data for Tr eT Tel Ce er ee [en [aa eT mes] Reply label Ce oe TT ea Cea [ere | TT es TTT mses TT eee TT Te TT ee em | M Tw Als eT Cee | TE TT ease CTT eee Name Cove ve LT TT Te Tee Leaching: leaching: extracting a soluble substance from a mixture by washing or dissolving in a liquid in preparation 0 Examples from (1) relate to (YA) ) By performing the aforementioned catalysts: Examples (1) = (6): In the form (1) to oT, the catalysts with numbers from 1 to +7 were tested under the conditions mentioned in the table ( ©) to show the effect of different silver loads on efficiency and effectiveness. The table (©) shows that the catalysts made with Ale silver loads, that is, the catalysts with numbers; And 0 and 1 are more effective both at the beginning and throughout the life of the catalyst than catalysts with numbers (1), (7) and (Y), which are the catalysts that have lower silver loads. oY.

Table (¥) No. | Rum | (Tashreeb | No. 7 7 Addition

Maala Ta Taif Ish Aa Aa

[oe Ln Iv [Tv oo] Ht ag May First conditions: Autoclave ZY + autoclave ZY ethylene oxygen © cethylchloride cethylchloride ppm © cqm nitric oxide «nitricoxide ppm 61157 = Avan Nka Oa

The second conditions: autoclave 771 ethylene cethylene 78 oxygen 77 oxygen carbon dioxide LY ethane 01 cethane c ethyl chloride Yo cethylchloride ppm c nitric oxide (GHSV) ¢ nitricoxide ppm nebel rak Oa “ppm” Gas hourly space velocity “GHSV”. = Gas hourly space velocity.

01: (11) - (7) Examples

In examples from (7) to (11), the mentioned catalysts were tested to demonstrate the effect of sequential impregnation in comparison with simultaneous coinadental impregnation of potassium on catalysts with an Alle load of silver. As shown in Table (4); High efficiency appears initially when using these 1 catalysts manufactured by synchronous impregnation with 0:00M potassium. However, after a period of time, the efficiency of the catalysts made by these two methods becomes almost equal. what

D schedule (4)

Kaw | He a | 70 Example 1 Catalyst Stent | 7 7 ethylene efficiency | Cthlene asd | efficiency | Today in silver (potassium). p0<10 7 oxide / re Te oT ve | Ask Tre TT | See | A vn Toe is the first condition: autoclave 770 cautoclave ethylene 7/8 oxygen © JF

= GHSV «nitricoxide ppm © cethylchloride ppm Jf) m chloride 0 a Yeo Avan

0 Second conditions: autoclave 7701 autoclave ZA cethylene oxygen 77 carbon dioxide, 7 ethane Yo cethane cfm ethyl chloride VO cethylchloride ppm c stand m nitric oxide 0a YY «Ave = (GHSV) «nitricoxide ppm" in mm .611917" Gas hourly space velocity = gas hourly space velocity.

(Ye) - (VY) Examples 0 To demonstrate the effect of (08) SOF) and (VY) the catalysts tested the numbers (Yo) to (VY) in the impregnation examples (1) (Especially after ethylene diamine washing the newly impregnated catalysts with ethylene diamine)*(the first and second impregnation both. And as shown in the first table (Y) of this type and after, before roasting, some surplus accumulated silver is removed from it. Washing old impregnated catalysts prevents clogging of the support pores and thus increases efficiency. The catalyst prepared with one wash is more Yo than the catalyst that was not washed. Washing after each impregnation leads to a decrease in efficiency. 701 percent effective

Given ANY lot of silver. ov

+ table (°) efficiency / example 1 catalyst oxide ppm silver 7 heat or test conditions: autoclave 771 cautoclave ethylene LA cethylene oxygen put and < e » 0.1 / SB carbon dioxide 1 cfm ethylene chloride 01 cethylchloride ppm cfm nitric oxide ppm .m Catalyst support 11, 17 and 14 is the support CD No. Examples (0) - (1?): In examples from (11) to (YY), catalysts with high and low percentages of silver were tested in autoclaves under air and oxygen treatment conditions. As shown in Table (6); as expected The catalysts produced using air 0 are less effective than those produced using oxygen.The decrease in efficiency results in operating at a higher temperature to compensate for this lack of efficiency, which in turn increases the rate of deactivation of catalyst activity. Alle of silver is more effective than catalysts containing low percentages of silver. Damo oxygen © C Qom ZA “ethylene 770 autoclave Oxygen: Autoclave Av vv = 01157 Aol” Maasti ppm nitric oxide a <2 c © cethylchloride ppm Ethyl chloride

La Yin II 7% oxygen 77 cethylene ZA cautoclave Air conditions: autoclave Qom = A cethylchloride ppm gfm ethyl chloride VY cethane ethane 7 0.7 oxide Carbon” to opac = (GHSV) cnitricoxide ppm nitric oxide “blood” ppm. Gas hourly space velocity “011577” ov.

G4 Examples (YY) = (YY): In the examples from (YY) to (YY), the catalysts with numbers (VA) to (TY) were tested, and they show the effect of carrying silver and the concentration of rubidium and carbon dioxide content on these catalysts as shown in the following table (7). ov

Table (V) No. | No. 1 number of times | No. 1 Silver | rubidium | Operating Conditions Degree of Ethylene Efficiency 1 Jed Catalytic Impregnation | stent | 7 7 temperature C 5 oxide 7 7 Ag

YY,” Yet yyy 70

Arye 1,00 except Le) oxygen OY m G 7 4 YY (CO, OY ¥4,4 G Y Y. Y¢ oxygen (77 YY p mm (CO, AY, 2,6 YY. 7 0) L oxygen £0, H 7 71 Yo (CO, YE, YAY YY. 77) oxygen Ye | fae H Y 71 1 (CO, Ave 6 YY. 7x ) oxygen oY r4,4 H 7 YY Lal (CO, operating conditions: autoclave 771 autoclave ZA ethylene oxygen © cf m ethyl chloride cethylchloride ppm © cf GHSV nitric oxide ppm = : Aves oY.

Examples (YY) - (YA): In the examples from (YA) (17), catalysts No. (YY) and (YE) were tested, where catalysts containing a high percentage of silver were compared. with those containing a low percentage of silver in a pilot industrial unit. The results are included in the following table (A). ° Table (A) Metal 1 Catalyst | impregnation | stent | 7 7 Heat | Feet/hour days in silver on a eee » Asan ee ee oe te asan oe Tee Lele Te Lajla Balqa Val Sasa Tee Conditions: 0.1 (1) cethylene oxide oxide 77.5 oxygen A + CoH, ZY ethylene 77.0 carbon dioxide LY 1.5 mL ethane cethylene chloride 1 cethylenechloride ppm c mouth nitric oxide YVo cnitricoxide ppm pounds per square ol GHSV (PSIA H Ba 0) Conditions: (¥) “Yo ZA, cethylene oxide CoHy ZY 4 oxygen 7000 cethylene second Carbon dioxide “70.7 CoH ethane Gz YY cethane m athene chloride 01 cethylenechloride ppm cfm nitric oxide YY + cnitricoxide ppm ppm / inch GHSV Y = 49700 Conditions: (7) Y,YY ethylene oxide 78.8 oxygen “CoHy 771 oxygen vo 1 W/carbon dioxide” “CoH, 7 0.7 6 gfm chloride” ethylenechloride ppm (pil YA cfa m nitric oxide ppm ppm 010160"10; Yoo lbs/inch 7 IBY) Ye = GHSV PTE) = (YY) in examples FY through FE Catalysts with numbers (V8), (YO) and (V3) were tested to show a comparison of the operation of the experimental industrial unit under the conditions of using both air and oxygen (0) as shown in Table (3) ov ..

Ty (1) Table Efficiency Aging rate 1 Temp Maximum Load 1 Force K Ag | No. | No. | No. ethylene 7) Operation mft / h 7 Io] Catalyst | Prop 1 Example 0 days) 8

I aaa l oo «| Jah | fee [ofp CoH 717 carbon dioxide;

OTs + = GHSV lb/sht 7701 CoH 727 (CoH 770 oxygen 748.5 : TO) oxygen conditions cfam nitric oxide 560 cethylenechloride ppm cnam chloride Ethylene 50 “CoH 7 101 = GHSV ppm 010 nitricoxide (38 dioxide) 75.5 “CoHy 770 oxygen conditions and 0” : 78.5 oxygen

Sy ii cethylenechloride ppm (pL) cfm chloride 5 “CoH A 13 = GHSV 001 cpitricoxide bpm 0 (£Y) = (Yo) Examples To indicate (YE) (YY) to (47); The catalysts with FO numbers were tested in the examples from the comparison of catalysts containing a high percentage of silver and containing a low percentage of silver using an autoclave under air conditions; And those catalysts have residual support materials, the appearance of which is lamellar, and they contain a substance or materials containing residual fluorine 1. Retaining high efficiency. TFs oY.

TA

(V+) Efficiency table temperature "m at Cs ppm 7 number of times silver number 1 number | ethylene oxide number 0.4 | ethylene 64 K ppm metal | catalyst impregnation of the oxide support with silver L ow Lowe foe Jee [EL fe]

L ow Love deme LL [ee 70.9 CO2] 77.5 (CoHy 78 coxygen) Air conditions: 776 oxygen bard/inch 01157 = p YVo cethylchloride ppm Ye «CoH (£ 1) — (£7) Examples 0 In examples from (€Y) to (£7) I tested catalysts bearing the numbers (FO) C All (YA) have carriers of type Non-lamellar with the surface area of Alle, and the examples show the effect of high and low silver content, as shown in Table (11).

A z

Table (11) Bishm | Rum | Rum | wml wo: To Le eee “a. Method 1: A single standard joint impregnation process for silver and enhancer. Method?: Two impregnations (first) a standard impregnation By 700 of the booster (II) pore size method (Jb) primary (incipient wetness) using 750 of the booster. 0 method?: Two standard impregnations and 790 of the booster is added each time.: Test conditions: Conditions Standard air process (77 CoHy ZA coxygen 71 Dioxide cs SH 7.5 cfm ethylchloride ppm). These catalysts were prepared using batch of 082507 which seems to have led to a decrease in efficiency - by 71,9-1 due to the presence of TH impurities

Examples (/497) - (27):

In examples from (7;) to (OF), catalysts No. (9”) and No. (£4) were tested under different conditions with high and low silver contents in an experimental industrial unit. The results were included in Table (VY), where they showed that Catalysts with higher silver content have better oY activity »

Vv. (VY) AVL Table Silver 7 | operating conditions | efficiency | temperature | Age 1 No. | No. | number of times | Fee number oh oh oh bit

Te Te Tr Toa Tele oe ow Te Te Ga Teo ee Tee Te Toa To TTT Operating conditions: 75.0 billion; 701 oxygen 78.8 ethylene oxide: 77.7 Ethylene oxide 00 cethylchollride ppm cfm Allyl chloride 1 “CoH Le) carbon dioxide” 0.001 = GHSV 0-7 lb/in

Lv Pelia ZY Oxygen Sauce 78.6 ethylene oxide 77.8: dull 001 cethylcholride ppm J) cfm chloride 1.10 CoH 70.1 carbon dioxide. GHSV = 30 lbs/inch CoH, 0.1 Oxygen WOH 71.8 cethylene oxide Superfine: 1.126 cethylcholride ppm cfm El chloride 4.0 CoH 7 1,1a/ carbon dioxide” a.

OY ev = 61157 oY iil aig ? > (67) - (7) ay (£4) to (01) Catalysts with numbers from ((£) to (OF) in examples from or co-impregration To compare catalysts enhanced with molybdate and prepared by simultaneous impregnation, it is from A (VF) “clean” H. As shown in the table, the successive molybdite with cesium molybdate 1 is most appropriate to add molybdite with silver by simultaneous impregnation to obtain On the desired enhancement of efficiency, and the successive addition of molybdate after silver precipitation does not increase the efficiency either.

Ya

(VY) Efficiency table 7 ethyl chloride ethylene degree Cs ppm catalyst number silver method ethyl 1 heat then | 0108 Mall | (MoO) 7 example (Number of impregnation | chloride support) p 7 m" chem TY. oY. VY successive ov

I

rice y,0 AY +, E80 YY. oy YA consecutive of ty 0 arkum 77 YY. Yo synchronous 5 £,0 Ag, ey vy. Ye £4 synchronous 01 1,1 YA,o Yot¢ 1 7,0 oxygen ZA (CoHy 701 autoclave)

Aves = GHSV zero carbon dioxide / no psi 1 l «C,H; (11) - (ov) Examples to (07) in terms of comparison of (OF) with examples from (VV) to (OV) Examples of molybdate catalysts prepared with different silver impregnation techniques relate to In these examples, catalysts with numbers from (£0) (£9) were prepared by adding molybdate promoter during impregnation. It is better to add molybdate promoter (V2) second silver. As much silver as possible, meaning that the second impregnation solution that contains molybdate enhancer is more appropriate to contain a higher concentration of silver than its concentration in the first impregnation 0 solution.

Table (0) No. No. Total silver Rb* Cs Temperature Impregnation efficiency 1 Impregnation Oxide mol Example 1 Catalyst | ppm ppm ose M i hungry p a high i ee PS a blah sat sas “AM AM | AA | OW |e | Je fe ETE IEE ER ES Loo foe Joe Jw fe | fe foe fan] Oxygen conditions: autoclave LA (CoH, 71 autoclave oxygen 71.0 “CoH 76.5 carbon dioxide? cfm alkyl chloride YVe cethylchloride ppm BUT/ach Aven = GHSV 0 *: 740 anions were added to The form of molybdate and the rest in the form of sulfate The support number RA is the support of all catalysts Examples (17) = (14): In examples from (17) to (14), the catalysts with numbers from (0*) to (OF) were tested Respectively, at a high content of silver on a carrier having a surface area of anf a 1 and 0 results were included in Table (10) Table (Vo) gua | (SO) m oxide mol 7 Fo fee fe oe Le fe or poe Looe feed Le fe ee oY.

Oxygen conditions: autoclave “C,Hy 71 78 Expigen coxtgen 7,0 (CoH 7,5 CO2” ¥ gfm ethyl chloride YVo cethylchloride ppm ppm Ace = GHSV The support in each catalyst is the support number 1. Examples (Te) - (17): In examples from (10) to (TV), the effect of the level of the activator on a catalyst that contains a high percentage of silver was estimated, and the results were included in the table. (V1) Table (V1) No. No. Gross Surface Area Cs ppm Cs ppm Grade Ethylene Efficiency / Example Catalyst Silver 7 Prop (S04) (MoO) Heat M Oxide By weight, M /GM Mall 7, except that the jaf or the (OW AAEE for the OE Ara A, that the Conditions of the Axin: Autoclav La « CoHy 71 autoclave 00 oxygen 7 0 116 0 ;7,5 carbon dioxide” ? cethylchloride cethylchloride ppm Jaf) 6/7 lb/inch Aves = GHSV The support in every catalyst is the support D oy number.

Vie : (YY) - (TA) Examples Meal | for temperature (m) yet? days | aff

Aaa Aa Aa Aa EE Aa | ow oe l aa a | Ha « ah ah ah | ER AH AH AH AH AH AH AN EN ER WAS NOT | ox ee [ae] the secret of a dam for « | Um um uh | brs

These examples clearly show that catalysts with higher silver content give increased efficiency and effectiveness depending on the properties of the support. As it is noted, the greater the surface area of the support, the greater the effectiveness of the catalyst with a high content of silver, as can be achieved by decreasing the

The operating temperature required to obtain a constant oxide production rate of 71.4 m.

(YA) example

In this example a comparison was made to show the effect of a higher silver content on a support having a lower surface area; gf surface area is less than that required in the present invention.

A catalyst containing a low percentage of silver (silver percentage 716

0 wt silver from the final catalyst) reinforced with potassium and cesium sulfate and having a low surface area, low porosity carrier (Support No. A). This catalyst was tested under oxygen conditions with two different levels of gas flow rate. Operating conditions included SCH, 771 Clg 10.05 CO, £1,050, 74 10 ppm ethyl chloride) and a gas hourly spice velocity (GHSV) of 01 c') 0 in the process ov. vo the second process. (HT) Tosh ve is equivalent to the first (GHSV) and a spatial gas velocity per hour ethylene oxide (i.e. ethylene oxide Cols) and the effect of doubling the spatial velocity at the production rate This (the resultant turn over frequency) is equivalent to the effect of doubling the catalyst rate.

° The results of this study show that adding a high content of silver to a support with a low surface area, as expected, will be of little benefit to the efficiency of the catalyst. The special results have been included in the following table (117).

Table (VY) Ethylene oxide 60608 Aves m s =———— A AY At vay YY, 3 Y, .0 Carrier description: The mentioned properties were measured for each carrier used in the following examples following the methods described above. Carrier AAT Carrier AA is an alpha-alumina carrier with the following properties:- 0 surface area lar af" ana rated water pore 6 cm anf resistivity 1" crush strength kg total pore volume (35) Ye total pore volume, Hg cm/g packing density Tos pn VO EA packing density ov.

l Particle size distribution as a percentage of total pore size Pore size in microns Total pore size 7)

YY, (Vem) 0) m £Y, (Veim1e,0) m

VY. (Yer > Ta) leachable impurities (*) by acid 10 sodium, 17 10 (potassium. 8 water leachable impurities: © 4 phosphate; 010(Potassium “1 0 Magnesium”); 01 The acidity of the carrier AA is 1.45 μmol ammonium and 1411 per g of the carrier The carrier “AB”: The carrier “AB” is an alpha alumina carrier with the following properties: Surface area p m/g ana water pore volume 0.864 cm/g 0 crush strength V,AQY crush strength kg aaa total pore volume; (3): 0.807 total pore volume, Hg cm/g particle size distribution as a percentage of total pore volume pore volume in microns total pore volume 7 oy.

vy ie ). Acid leaching impurities 010 0 sodium and 4 569 010 potassium. 5 : μmol surface pH and 1111 per g carrier. (00°F) AC) +0; colin number is Alpha-alumina carrier (Norton result; ACY) A carrier with the following properties: m / g A surface area cm g 77-0176 water pore volume 01 kg 9,091 crush strength 0 cm/g +,Y&=+,Yo total pore volume, Hg (3:5) Total pore volume; pore volume distribution as a percentage of total pore volume : 7 pore size in microns total pore size zero (+) < 1 0 (1k) v0 (L.-Ya)

YA,” (Yoo =o ) Ya of, (Ve 6 ) ta 1, (YermYe,) oa

Y,” (Yoo > m) Chemical analysis: oy.

VA

744.1 (AL,03) alumina SiO,

Le N > Fe 0 3 A TiO,

TosMnO

CaO

Lo MgO 87 > Na,O

LXK,O

VEE <: surface acidity

PAD" μmol and 1111 per g of carrier. The carrier VY =: is an alpha alumina carrier with the following properties AD carrier 'aviv) surface area © anf' m cm water pore volume Estimated pore volume of water kg 1 7 crush strength Crush strength cm/g GEA total pore volume, Hg (3:5) « ASN pore volume Distribution of pore volume as a percentage of pore volume Total: pore volume in microns m of total pore volume 8 0 >), x (ne =) Ye

Yo,¥ (Vo -1.9 ( Ya

YA, ¢ (Vo - 10( m b ) 0 0 (yr oa zero 0001 > (+

DAE Pregnant 0 oY.

va -: is an alpha alumina carrier with the following properties AE carrier "g oY, av surface area anf cm +, 0A total pore volume, Hg 35) « ASU pore size distribution Pore size as a percentage of total pore size 7 Pore size in microns Total pore size zero (29 >) 7” )..5 - +) m m (Farah) for 4) 0 - 011 ( M 1 ) 001-011 ( M 0 ) 001 < + 1 Trace Analysis Chemical purity 0 ppmGa 011 sppmTi 1 ppmFe 00 ppmSi ¢ +

AF carrier =: It is an alpha alumina carrier with the following properties AF carrier anf m surface area cm/g "1 total pore volume, Hg 33) total pore volume; 0 μm 6.51 median pore diameter Mean pore diameter Chemical purity (element trace analysis) .ppmGa 0001 “ppmTi 14 ppmSi 0+—¥. ppmFe YA. : “AG” carrier = ‎ Alumina with the following properties WE is the carrier AG the carrier _ + anf cm ,¥ surface area cm / g “YY total pore volume, Hg total pore volume; hg μm , 0 median pore diameter Mean Pore Diameter Distribution of Pore Size as a Percentage of Total Pore Volume Forest | sei v0

Av

Ge | (>) 1, (v.00) ) Ya (Vor mee) Ye 0 B( (Vem 0 M (Yor Yee) 0 001> (1+) zero Element Effects Analysis YY. “ppmSi 01-101” ppmGa 01 ppmTi 4 Carrier “AH”: © Carrier AH is an alpha alumina carrier with the following properties: +- SOA surface area M af water pore volume 11" cm af crush strength 0 kg total pore volume, 353 GAVE total pore volume, Hg cm a 0 -packing density v0 packing density g ona median pore diameter 57 µm pore size distribution as a percentage of total pore volume pore volume in microns total pore volume 7 m ( < .2) m" VY , (vo =) Ya Yy,e (Yo —0) m Yo, ()- =, ) fa Yq, )001 sol oa YE, 6 Yo > a : acid leaching impurities p55 ppm OT 001 sodium; 00 cesta dlppm 01776 “limit calcium;

AN

The carrier “1h” = is the alpha m alumina carrier with the following properties AT carrier anf prepared m surface area surface area l cm / g water pore volume estimated water pore ans kg 4 crush strength © cm / g IE total pore volume, Hg (3:5) ¢ ASI pore volume of an +, 0 packing density 4 median pore diameter Mean pore diameter Pore size distribution as a percentage of total pore volume 7 Pore size in microns Total pore volume zero ( =>).

VY,” (+0 - ) Ya

Yo,. (Vem 0) Ya

YY, (Vo = .) m YA, (Vermy eye) m te (001 > m): acid leaching impurities 0 potassium; 0100 OEY 000 sodium” 04 Aluminium. (10 VAAN “1 Calcium”; YY: ) 1+ (corresponding to the carrier “AT” The carrier which was washed according to the following method: Washing for 0 minutes with AA water is the carrier AT Jalal Celsius and wash each time 1000 cm of boiled YO and wash “> times (rinse) at a temperature of 0 C. 01 of water. : "liv sippm 7 fluoride" 0170 1 calcium;

AY

10 mMsilicon.‎ 0 4 ca 533 sappm ©) micromoles of ammonia per gm of carrier. 0.17 is AT and acidity of the carrier SAK The carrier -: is an alpha alumina carrier with the following properties AK Bearing m'/g +A surface area © cm/g 5 water pore volume Rated pore volume of water kg 7 crush strength cm/g 01 total pore volume, Hg thick pas g/cm 1 packing density pore size distribution as a percentage of total pore volume 0 7 #pore size in microns total pore size be (>) "8 (no =) Ye vy, (Vo = +0) Ya 8 () ta £o,0 y y on

A, (001 > M76): Water Leachable Impurities 010 Phosphate 1 ppm Fluoride; Yo M Aluminium; 4 170 [Ca]; Af 10 p. Silicon.‎ 1 50 10 M Sodium. of high purity) with ethylene diamine 118 g ethylene diamine mixes approximately 1 01160 ophthalmic. distilled water slo g Yoo 0 oy.

AY

7 About 171 g oxalic acid (two-part oxalic acid water; reactive purity) is slowly added to the aqueous ethylene diamine solution at ambient conditions. An exothermic reaction takes place and the temperature of the solution is raised to about 50 "C. YF. After that, about 7011 g of silver oxide powder is slowly added to the solution of Step 0 (Y) with continuous stirring. 4 To the solution of step (7) above, about ? To the first part is added 7.51 g of a standard cesium hydroxide solution containing 001091 g of cesium per g of solution (prepared by dissolving 05017 in distilled water); then AY g of potassium carbonate solution is added Standard (containing 00070711 g of potassium per g of solution). An additional 5.17 g of distilled water is added to the solution. The total weight of the solution is 71.056 g with a volume of You mm 1 and added to the second part 7.17 gm of the previous standard cesium hydroxide solution and 0.04 gm of the previous potassium carbonate solution. An additional 1.47 gm of distilled water is added. The total weight of the solution is 71.90 gm with a volume of You mm. Carrier impregnation: 1 Two separate batches JS (of which 006 g) of the AC Carrier were subjected to vacuum at a pressure of 0 10350 atm; at room temperature. These two batches are impregnated with the first solution section (for the catalyst (TT) and the second solution section (for the catalyst (TY) mentioned in step (0) above, respectively, under vacuum for one hour. 7" The excess solution is drained for a period of Yo min. Catalytic roasting: 0?1 Each batch of impregnated carrier is roasted in hot air using a belt roasting device:© at a temperature of ©0000"C for 7.5 minutes. Air flow rate 11, 0 ft/hr at a standard temperature of 50113 square inches. The Ladle VA table shows the two examples (79) oY.

At as col sgl) and evaluate the catalyst using an autoclave under standard conditions using (Ar) described above. (YA) Table Temperature then | 7 | ethylenecoxise | and 0Aik 1 | CSOH | impregnation | Blusen A | Ad was named as (Ar) in the following examples. The same methods used in examples (79) and essential were used, unless expressly stated otherwise. 0: (all of which are comparative examples) (Af) to (AY) Examples from (V4) and (©) According to the general method described in examples (Y) and (1), catalysts are prepared for use in preparing stock solutions. Three impregnation solutions ( Basic solutions (Ar) and shows the detailed data for each basic solution. Table (V9) summarizes these catalysts. Table prepares these catalysts. (Yo) 0 under conditions of use (AT) to (AY) the performance of the catalysts. Examples were taken from (01) and the table summarizes the conditions for using oxygen. ~~ rr oY.

M " º sol TT Z A LY AA Cs,S0, Cs,S0,

TT ee] (a) Use the excess that is drained from the initial impregnation. oy.

Table (YY) Example | catalyst | Jalal) | number of times | Silver/Cs as # ethylene oxide Efficiency 7 Degree of impregnation by weight ethylene oxide Cs,S0,4 Temperature [oe | a la a la a la a (*) that the numbers in parentheses are then extrapolated from experimental information to compare them with other catalysts. Examples (5+) and (AT) (ideal comparison): : Making the two catalysts (;) and (0) in a way A preparation similar in its functional features by the method of preparing the two catalysts in the two examples ((v q) and ((A 0). A summary of the catalyst data and test data was included in Table YY. Table (YY) Example catalyst carrier number of times silver / Cs as K as 7 ethylene oxide Efficiency Temperature Impregnation conditions Wt* ethylene oxide | K,COs Cs,S0, 1 7 C Process eee A “Arim 1 AB AY L 774 Yio Yee AY Oxygen A * Analyzed values. 0 7 0

AY

(Exemplary comparison) (AA) and (AY) Examples: A basic solution (;) is prepared with the following ingredients 07 ethylene diamine (al ethylene diamine) 1 g oxalic acid dihydrate Oxalic acid dihydrate g. YovYo, silver oxide g. 06 monoethanolamine monoethanolamine g. YYEAA distilled water hia water using 777.44 g of AB to prepare the catalyst 1) By impregnating 87,948 g of the carrier, 01 minutes, and the impregnation time is 11, with the basic solution No. (;). The carrier is exposed to emptying for a period

Y,0 for 00 00 minutes. The catalyst is roasted at a temperature of 10 Bad © min by drain on a roasting belt at an air flow rate of 76 cubic feet per hour at a temperature wt. This drinks 719.47 scpi 50711 per square inch. The rate of silver recovery is the catalyst roasted again with the drained solution 707.01 g from the first impregnation, to which a g of cesium is added for every + YAY g of an aqueous cesium sulfate solution containing Y, A004 to which g of the solution is added . The impregnation and roasting method is the same as the initial impregnation step. It is 771.58 0 by weight. The total recovery is 791,017 Silver recovery rate in the second impregnation rp ppm YVO by weight silver and for catalyst data (1) and its performance. The following Ladle contains (YF) and table (YY) Table Process percentage Z|ethylene oxide by weight ppm by weight 1 qual oY.

AA

: and (34) (ideal comparison) (AY) of the two examples. By re-impregnating two small batches of catalyst (£) from example (A), the two catalysts (7) and

Ce cada again according to the method (Ao)

AYE catalyst (7): Offer 80.059 g of catalyst (4) for 10 minutes to vacuum at a pressure of 1 minute using a solution prepared as follows: Ve at atmospheric pressure and then an impregnation process for a period of (1,)? ethylene diamine (pel ethylene diamine) 08 g oxalic acid dihydrate hydrate (AU) oxalic acid 6 g silver oxide 17 g monoethanolamine (smal monoethanol) EY, 0 distilled water. The impregnated catalyst is filtered for 1 minute on a calcining belt (air flow 16 scf/h at temperature Y,0.: standard 50711 per square inch). The total silver recovered for silver and cesium recovered is as follows by weight silver and 577 Mc. 77,548: Prepare an impregnation solution as follows: (A) catalyst 0 gm 0 ethylene diamine (el ethylene diamine) 7 kg g oxalic acid dihydrate oxalic acid dihydrate 1 g silver silver oxide 16 g monoethanolamine (ie! monoethanol OV, 0 distilled water standardized booster solution 6 g per g of solution). C5380, Fig. Cs gm +, 0 YO) ov.

Unpacking 87,500 grams of catalyst (£) was impregnated again in the manner described for catalyst (7) above. The total amount recovered from silver and cesium was: 7776.148 by weight silver and 0.0 cesium. Table (7) shows A summary of the catalysts and performance data ° Table (74) sas asn lla ms example 1 catalyst | impregnating carrier | by weight * | 80 and | 0a | ethylene oxide | 7 process percentage eee | example (91) (Comparative example): The catalyst (4) was prepared using the following impregnation solution: TY ethylene diamine (al) g oxalic acid dihydrate 1.17 g silver oxide 1.17 g monoethanol monoethanolamine (el 77 g distilled water 98 g standard booster solution "7 g) 010+ g cesium as 50:65 per g solution). Exposure: 15.71 g carrier AD To vacuum at + AYE pressure, atmospheric for 10 minutes, then impregnate with the above solution, sad for one hour. Roasting belt with airflow of +16 cfm at standard temperature per square inch. The recovered silver was 713.77 by weight and the recovered enhancer was 8547© M cesium. Table (Yo) shows a summary of the catalyst data and its performance. oy

Table 0 (Yo) ppm by weight oxide percentage of process (() Both efficiency and temperature changed during approximately one week of testing. The efficiency decreased and the temperature increased. Examples (3Y) and (3%)

° 9.14 g of a solution of cesium sulfate containing 10195 g of cesium per g of solution is added to a portion equivalent to 1Y0 mm of a solution containing 778.88 by weight silver, 715.07 by weight ethylene diamine and 796.57 by weight oxalic acid dihydrate and 78.77 by weight monoethanolamine (el) and 778.57 by weight distilled water. A sample weighing 19,748 g of carrier AD was subjected to vacuum for Ye min at AVE pressure

0 atmospheric, then Bam was drunk using 1706 ml of the previous solution for one hour. The wet catalyst is drained for 900 minutes and roasted at ©5000"C for 7.5 minutes on a roasting belt where air flows at 17.5 cubic feet per hour at standard temperature per square inch. The recoverer was silver pick up is equivalent to 719.51 by weight and recovered from the booster is YAA “m” cesium After keeping a sample weighing 6.17 g of this catalyst for analysis, he drank

_ The remainder again by using 176 mm of the previous solution after adding 1.77 g of the same cesium sulfate solution to it. The impregnation and roasting method was basically identical to that used in the initial impregnation step. The total recoverable amount of silver was 775.85 by weight and the total recovered from the booster was of 0mCesium. Table (16) summarizes the catalyst and its performance. oY

(Y1) Table Efficiency | degree | adverbs wl) 7 | On ppm © image: | 7 Example | Silver by weight PE / Temp | Reaction 6.90, 1 wt m ethylene oxide (39) Examples from (4€) to Two basic solutions are used to prepare the catalysts for these examples. The first is the basic solution and the other basic solution is solution No. (AA) And (AY) No. (€) described in the two examples ©: Prepared as follows (9) g 4 ethylene diamine g 111,000 oxalic acid dihydrate 8 g silver oxide ARE monoethanolamine 6 g distilled water AE methods using stand (V6), (OF) and ) (17), (11) and (01) the catalysts prepared (YY) data summary and included in the table (Ar) identical to those used in examples (79) and (YA) preparation and included Performance data in the oY table.

(77) Table oe ms) eee ee sae aT 1 vl zero aT booster added (g)* qmu rr rr ees

I I I

I

Je XYVE Booster Additive 0250 C ees oe eee or SS Low | LL snes] rrr rr bm 0 ay Use the excess solution from the first impregnation discharge. (1) g of cesium per g of 1074889 as an aqueous solution containing canal * (YA) solution. The table is a sliding drawer | Ttrot | 2s | wens | and then as 6 p 7 7 oxide | Cs;804 wt | by weight k

A LMS IEEE (a) Microreactors - Amount of catalyst used a) Sieve passes 0/04 = Total

m pressure (GHSV) pm 151 gas spatial hourly velocity = 1100/hr. The microreactor used in these examples is a quarter-inch tube. (b) It also contains ppm YA potassium in the form of ,50 O2a. (C) Comparative example.* The numbers in brackets are calculated from extrapolation of experimental data to compare with other catalysts. ov

Examples (Yoo) and (1) an impregnation solution is prepared with the following composition: ethylene diamine (yal) 8 gm oxalic acid dihydrate 110 oxalic acid body 08 dihydrate gm silver oxide V4, A silver oxide 010 g monoethanolamine (al g distilled water) To half of this solution (¥ 0 g) add 7 g of a standard cesium sulfate solution containing 1076 g cesium per g of solution. This solution is used with the booster at first to prepare a catalyst on the AA carrier, and part of the drained solution is used to prepare the (10) and (VY) catalysts: The catalyst (V0) is prepared by impregnating 70.57 g of Yl from the carrier AF by mm (54, ag) of the previously drained solution and then calcined as described in Examples (1) (v) and (A1). Then another impregnation process is carried out identical to the roasted catalyst. The total silver recovered was 4 779.7 0 by weight and total recovered from the promoter 1711 “M” cesium The catalyst (1) is prepared similarly to the catalyst (Yo) by impregnating Yo, first g of carrier AG using a g of The drained solution is then calcined, then the roasted catalyst is drunk again in a similar manner. The total recovered silver was 717.99 by weight, and the total recovered from the booster was 599 «m» cesium. \o The catalysts and their performance are summarized in Table (719). A microreactor using o Y 0 granules was used

m" Table (Y4) By weight Weight oxide ppm—7 7 Percentage of process * Comparative example. Examples from (01) to (011) An impregnation solution basically similar to that described in the two examples ( 17) and (3%) 0, except that it contains 4.01 77 by weight silver. Catalysts (VY), (VA) and (V4) are prepared using carrier 811. For each catalyst 176 cm" of the carrier is drunk using 70 g of the previous solution according to the method described in Examples (79) and (80). Appropriate amounts of promoter, 05:50, are added to each solution to ensure the desired promoter concentration (Cs) on the superheated catalyst as Shown in table (Fe) The excess solution 0 from the drain was used with appropriate amounts of promoter as shown in table (Fe) sale Each catalyst was impregnated a second time and then calcined again. The promoter which is deposited in the two phases is about 78 0 in each impregnation. The catalysts (01), (11) and (YY) are prepared in a similar manner to the catalysts (VY), (VA) and ( ) 0 (but using CAT carrier 0 > The catalysts' data and performance are summarized in Table (Yr) and the performance has been evaluated under oxygen conditions. oY.

3a Table (9?)

Carrier catalyst number number of times silver 7 ethylene Cs,804 —S Cs | Efficiency 1 Temp Example Impregnation ods wt — x / oxide ( ) ppm 2 (a) Add about 0 75 at each impregnation.

ALY from (018) to (VY) (all are comparative examples)

Malol attends AS

ethylene diamine (yl) 06 gr

Oxalic acid dihydrate 06 gm

silver oxide 84 g

Monoethanolamine 4 g

Distilled water hia 90.7 g

. To half of the previous solution, add (61 g) of a standard cesium sulfate solution

It contains 1075 g of cesium per g of solution and 78.0 g of water to adjust the volume to 1 mm. This solution is used to prepare the catalyst (YY). Another solution is made to prepare catalysts (18) and (10) and the solution is prepared using:

ethylene diamine 08 g

Oxalic acid dihydrate 08 gm

silver oxide 84 g

04 monoethanolamine (el g cle distilled eh distilled water

oy.

qv Divide the previous solution into two equal halves. To the first half, 7.85 g of cesium sulfate is added to the second half. To the second half, (VE) is added to the previous cesium sulfate solution and used to prepare the catalyst. (Yo) g of cesium sulfate solution is used to prepare the catalyst (7). (©01) The data for the preparation of the catalyst are summarized in the table. Performance is evaluated using the pulverized catalyst in a microreactor using the methods that (TY) table 0 (4) described in the example (31) Table ew g cesium For each g of solution. +0 V0 was added as an aqueous solution containing *oY.

AA

(YY) Table 25 yall 7 7 oxide impregnation by weight as usual. ppm 01 instead of ethylene oxide ppm 8# using (1) (111): (to) (111) examples from 00.008 g of water to prepare the catalyst (77) From the following solution 00.10 g ethylene diamine, 19.08 g hydrate, 97.54 g silver oxide, JW distilled, and 05.60 g dioxalic acid © g monoethanolamine. Divide this solution into two parts equal to add to the first half g cesium/g of 1075 g of standard cesium sulphate solution containing 4 ml. Drink 176 of the solution” and add an additional 7.00 g of distilled water to adjust the volume to (V4) mm of this solution and roasted as in the two examples 1 YO using AY g of carrier 4 “m” cesium. The recovered silver was equivalent to 778.77 by weight and the recovered enhancer L (A) and 0 g of cesium sulphate solution YoYo and to the second half of the previous solution gm of distilled water is added This solution is used to impregnate the roasted catalyst in the previous standard step TT and the first in a basically identical way The total recovered silver was equivalent to 777 ,7 by weight ppm TYA The total recovered cesium capture was as follows: (YA) catalysts (77) and \o an impregnation solution containing 00.70 g ethylene diamine were prepared And 00.00 gm of distilled water, 59.60 gm of oxalic acid dihydrate, 997.54 gm of silver oxide, and 19.54 gm of amine. This solution is divided into two equal parts. (J sill) mono. To the first half of the previous solution, 7,900 g of sulfate solution is added, in addition to 7,086 g of distilled water. The standard cesium (YT) that was used to make the catalyst oy was impregnated (YT) with this solution and roasted as in the AT catalyst, 7 g of carrier 59.00 ppm. A fraction of the VAT used is 770.05 wt. of recovered cesium.

mm (19.6 g) of the drained solution to impregnate the catalyst again using the wet method

The first aaa) incipiper wetness method pore) and the roasting step is identical to the roasting process

The first. The total silver recovered was 777.45 by weight and the total booster recovered was 151.

M cesium. This catalyst is the catalyst (YY) > The catalyst (YA) is prepared from the second half of the previous solution, to which TAL g is added

of the standard cesium sulphate solution used in it, in addition to 7,060 g of distilled water.

It uses 65.17g of AT carrier for impregnation and roasting. The silver recovered was 715.70

By weight and the recovered booster OAS «Mc. Use 197.14g of the solution from

Drainage to impregnate the catalyst a second time as for the catalyst (TV) using the initial 0 wetting method (pore size). The total silver recovered was 777.05 by weight and the total booster

The recovered is 596 000 cesium.

Catalyst data and their performance are summarized in Table (YY) ov.

Va 3 EE BE EE 3 = a 4 aa aE EEE 0 > q =5 2 a i 4 =D =~ — y 2 1 x 3 << << << : i 3 4 4 7 3 Su Sir 1 d > > > > J 7 — : _ 0M . ’ 3 3 .. J i} 1 0| Ahem 1 r r Sahu r S < a 9 3 =~ - = = “-”. - 0 43 da aa aaa aga 3 5 4 =, > 3 3 0 0 lah secret ba eh 4 3- | 3 b b. . 'Ty, . << Soo | tell what to all = 0 by, 3 | 3 | 3 3 3 free 5 33 = 3 aaa aa nD d 4 8 1 3- | Q3 3 3 0 © 9, = . 3) E bq A

Fi & 77 < < yib -— - - 7 ِ 3 3 4 > > lih beid 0 a 8 _

Ral =, ~ | mo | Aw on « | a at 3b. +a a 4 2 3

L

<9> - ~~~*. 0 - - . 1 a |Z AEE Aral A = 5 ~ 3 a”. 4 - © > . | a | . Als < > > < = > 1 1 < > > < > > < > > A: Um. a : a wah — fah liya secret 0 — a 0 all su | Secret | bitter | if | su a d | ho | 3D | 2-d here. 1 J 5 3 el Ol Ol An Ohm ol N N Ba: 9 o “9 9 9 ~ 3 1 cadfa dss] 5 * l Q - > > . Qo > " 1 o y 0

011 autoclave AC autoclave reactor using a powder catalyst” microreactor MD

At and microreactor conditions have been included in the example (VY). Example Using parts of the impregnation solution used in AK with carrier (Y9) the catalyst is made

HOY) (OV) Examples from 0 for discharge at a pressure equivalent to 0.59 atm AR mm (from carrier) YYO) in grams AE AE min. 00 g of the previous solution was shaken for TIAN 0 minutes, then drunk using 11 for 11 minutes on a V0°C belt for 000 minutes and roasted at a catalytic temperature of 11 for roasting (with air flow). 136.7 cubic feet per hour at a standard temperature of 50711 per square inch. The silver recovered was 718.18 by weight.-0 This roasted catalyst is impregnated again with the solution obtained from the first impregnation filtration to which 50.7777 was added. g of standard cesium sulfate solution containing 0.0747 g of cesium per g of solution.The impregnation and roasting processes are essentially identical to those used in the first impregnation.The total silver recovered was 775.77 by weight “m” cesium. 811 and total recovered booster 1 (VE) Catalyst performance data are summarized in Table Table (4?) for |] (VY) to (118) Examples from: and (7) As follows (YY) and (Fr) the catalysts are prepared, which is drunk twice. AA is made using 7787 g of carrier (Fh) the catalyst is prepared 7 g ethylene di-111", 6: First impregnation using 7075 g of a solution having the following composition: 1 gm oxalic acid dihydrate, 1990.00 gm silver oxide, 111 "6 amine, gm water, 7,500,000 gm monoethanolamine and 5,918 gm cesium sulfate 10 powder minutes in order. Roasted carrier Ve and 61 distilled. The impregnation and filtering time are 20 t

01 minutes on a roasting belt with airflow of 176.5 cubic feet per y.0 at 0860©"m for 51496 hours per square inch. The silver recovered was 719,448 by weight and strengthened Mc. g of AAV A solution is prepared that is basically identical to the previous solution, with the exception of the use of cesium sulfate powder, and this solution is used to impregnate the carrier again in a similar manner, 0 771.86, basically, to the method used in the first impregnation. The total silver recovered was 00" cesium. VY by weight and the total recovered booster is

SOA) and (VY) from the same impregnation solution used in the catalysts (TY) prepare the catalyst

AA g of carrier YEVA drank (VV) to (VY) in Examples (71), (01) and (V9) using 17497 g of the previous solution without adding cesium sulfate By using a similar method 0 above. The recovered silver was 718:19 by weight. (Fr) for the first impregnation method of the catalyst, and the solution resulting from the drainage is used to impregnate the carrier again after adding 1 gm of sulfate powder to it cesium and more of the impregnation solution to make the total weight 411 gm before impregnation The method used for impregnation and roasting is the same method that 174 by weight and a total of 770.90 was used in the first impregnation The total silver recovered was 1 casa mpm YAY The recovered promoter is by using a solution containing 00.60 g ethylene diamine and (YY) catalyst prepared g distilled water, 805.10 g oxalic acid dihydrate and 97.54 g silver oxide g of A solution of 7.71 g monoethanolamine To half of this solution add 19.04 W standard cesium sulfate containing 0.076 g of cesium / g of solution in addition to 0 AA g distilled water is emptied and used The solution is then to impregnate 0.0 g of the carrier for 8 minutes and roasted at a temperature of Ye min, then drained for 10 minutes and drunk in the carrier for 10 “m for two and a half minutes on a roasting belt with a flow rate of 17.8 cubic feet in 000 heat 739.87 kph at standard temperature per square inch. The recovery of the silver was by weight and the recovery of the booster 5494 «©m» cesium. The other half of the solution to which ve was added is used 3.97 g of standard cesium sulfate solution in addition to 7,080 g of distilled water oY.

Vey is 777,997 by weight and recovers the JS booster in the first impregnation. Silver recovery was blood cesium. Total V1 is the methods of preparation and performance of the catalysts. (YO) Table (YY) summarizes the efficiency | heat | ethylene | The number of method destroyers 1 pregnant lay | A m for conditions 1 70106 i al-tashreeb Jad

NEE. on fo eee |p Fb FF] on Joffe | pf FL LT] of the booster each time. 78 0 Two standard impregnations using about : 1 Method (1) All of the booster is added during the second impregnation only. : Y Method Analyzed values. * (VYY) to (1"1) Examples (Fo) (FY) The following general method is used to prepare the catalysts: With continuous stirring of the following materials, ale 001 is added to a 80 gm pyrex cup. ethylene diamine mm water 00 g oxalic acid (V,0) g silver oxide 7 g monoethanolamine YY and 1 The cup is covered with a glass bottle for an hour between additions.The temperature of the solution varies after and 0, then Yo. Each addition is between mm Yo. This mixture is then diluted with distilled water to oY.

Vet containing cesium per rhenate A standard solution of cesium per renate is prepared from an equimolar gm of cesium per gm of solution by adding an equivalent molecular amount of 0071 to distilled water. Ammonium per rhenate and cesium hydroxide and ammonium per renate are prepared with a standard cesium sulfate solution containing 0.019 g of cesium for each g of the solution by adding cesium sulfate to distilled water. 0 Standard solutions are added to a solution containing silver oxide to give the impregnation solution m to make sure that the salt has dissolved; the desired VO. The cesium perrinate solution is heated to a temperature of 500 C to ensure the dissolution of the cesium perrinate. The impregnation solution is heated to about g of the support in a pyrex impregnation vessel. The vessel pressure is reduced to 10 mm Hg is added. The impregnation solution is slowly added to the vessel and the vessel pressure is left to +©, +-7.1 for about 0 minutes. Calcined resulting from filtering in a covered cup. Then calcined then for a period of minutes. The impregnation and calcination processes are repeated using the resulting solution © 000 temperature data of the catalysts. (Y1) From filtration to impregnation. Table summarizes 77 Vo lose [ew

I EVEE

EE | Aja l aa a sad ET sa oY.

Veo

Catalysts (YF), (YE) and (YO) are used in a microreactor for performance evaluation. In the microreactor test, the catalyst granules were crushed in a mortar and pestle and permeated to the desired size (= 00 mesh). It holds two grams of powdered catalyst in a long stainless steel tube of Yee 0 cm in diameter and 1.97 cm in length. The tube is placed inside the test furnace and connected to the gas feed system. The temperature of the furnace is set with the temperature control knob, and the pressure is set at 071 atmospheres with a groves back pressure regulator. The gas flow rate is set to the spatial gas velocity per hour desired (1 liters per hour) at the temperature and standard pressure) and the reaction temperature is measured using two thermocouples inside the reactor. One is sunk into the catalyst bed about two inches below the reactor top; The other is located at the outlet of the reactor. The average of the two thermocouple readings is taken as the reaction temperature. The gas feed composition includes 701 by volume ethylene, 78 by volume oxygen and 776.5 by volume carbon dioxide »ethane and chlorides

As listed in table (YY), nitrogen makes up the remainder of the volume of the gas.

oY.

01 (YY) Table Ethane Yo catalyst veo catalyst ?* catalyst ethyl ? >< Change | Wim A Re Efficiency 1 F degrees) | Altair 1. change f | yen ppm | ethane | Temp. 1 ethylene | Temp. 1 ethylene | temperature 7 ethylene / oxide 5 7 oxide mm 7 oxide not that ye Ao, t B AR AV, Y and 1 4 a dream 1

AY, ee To en | oe ee ا - Ahla oa Te Loa for the pulp oe or ea oer [on on smooth for its chain |e oe Te s ro are | oe ee Weak. ABS (A) is equivalent to oY.

Claims (1)

UV protection elements 1 1 A method for preparing a catalyst for the manufacture of alkylene oxide by means of Y epoxidation of alkene in a vapor phase phase: 806 that includes: A providing a refractory solid support having a surface area ¢ of at least 1.7 m'/g; a pore size of about 00+ cm/g at least 8; the average pore diameter ranges from about 1 to YO μm; and where 1 is between 701 and 7708 in size from the support pores having a pore diameter between about 1.8 and 1 micron; At least about 701 are of size A support with a pore size between about 0 9 and 1010 microns; first impregnating support B impregnating support 01 “dissolved silver contains a dissolved silver compound impregnating solution 11 impregnating support impregnating support AJ _ VY containing the mentioned Wil support dale all «first impregnating solution VY impregnating and exposing the impregnated support ¢ silver compound 6 1176 and metal compound to conditions leading to the formation of silver metal support Vo «silver compound silver 11 second with a solution impregnating support dele all impregnating — 2 VY silver compound containing an additional impregnating solution dissolved in it; csecond impregnating solution Y) The aforementioned support Lil contains an additional silver compound; Exposing the impregnating support YY to conditions leading to the formation of silver metal Y¢ from the additional silver compound; And (Yo and sale) the two steps (3) and (e) until the amount of silver treasure reaches silver metal oY. - 11.8 to 770 by weight at least based on the support present in the support 13 the total weight of the catalyst. At least one enhances the effectiveness of the promoter having solution Y .catalyst 1 promoter only in the promoter solution where the promoter oY is located) method according to claim 7 1 . The last silver impregnating solution Y on molybdate promoter method according to claim (); where the promoter comprises 1 ¢ molybdate Y with a solution containing support method according to the claim (\ ); where the support contacts 1 efficiency at least one promoter contains the Y . of the catalyst oy silver A — The method according to the protection element ( \ ) » where the concentration of the 1 second silver compound in the second chrysanthemum solution 41 first is higher than it is in the impregnating solution 1 . impregnating solution ¢ impregnating The method according to the protection element (1); where and after impregnating the support 17 1 but before exposing the first impregnating solution J saa support Y silver to conditions leading to the formation of silver metal impregnating support impregnating dale al 7 suitable Cuda support The support is rinsed with the silver compound of the accumulated metal ¢. silver compound to remove the silver compound © o v 0 101.8 - - A _ method according to claim (1); where the amount of impregnated silver metal is in the range from about AR to about 0 by weight based on the total weight of the catalyst “catalyst 1 4 - the method according to the claim (o)) where the amount of impregnated silver metal Y is in the range from about 778 to about 7 fee by weight on the basis of weight JS For catalyst “catalyst 01 1 method according to claim (1) where the support has a Y-lamellar shape morphology 11 1 method according to claim (10); where the support le support 5 About Alfa- .alpha-alumina iw Y VY 1 Method Gig of protection (VY) where the support is at least 744 pure alpha-alumina Y. VY) method according to claim “(1) where support dele dl contains a fluorine-containing substance Y VE) method according to claim (VY) where support containing a substance containing 7 florine having a lamellar shape morphology 11 1 _method according to claim (7); Cua promoter is a compound containing at least one element selected from groups “b to ab and groups IV ITY 1 of the periodic table of elements. oY. 101 - 11 1 method (according to claim oY) wherein the promoter comprises a cation Y selected from the group of alkali metal and alkali earth metal cations. -1171 Method according to claim (V0) in which the promoter enhances at least one Y of dled activity of the efficiency stability as v is determined under Standard Ethylene Oxide Manufacturing Conditions - (Process Conditions ¢ dD lll IA) According to protection element (10) Cua chooses the promoter from Y5 halides and oxyanions Non-oxygen elements have an atomic number ranging ¥ from 7 to AY and are of groups QF to /ab; implying and ?a to baa dV from 2 of the periodic table of the elements. 11 1 _ Method according to claim (VA ) where the promoter is an oxygen anion oXyanion including sulfate 701 1 method according to the claim (VA) where the promoter is an oxygen anion Y oxyanion including molybdate -molybdate 71 1 catalyst for making alkylene oxide by oxidation in a vapor phase Y of an alkene vapor phase epoxidation of alkene containing dad impregnated with silver impregnating 3 in at least two impregnation steps with a weight ratio of about 791 ¢ on a retractory solid support having a surface area of about 0 p °" g over J at least; a pore size of about 0 + anf ans at least 31 and an average diameter of 1 pore between about 1 and YO μm; and wherein between 701 vol and 776 lv are of the support pores having a pore diameter between about 9 and 1 A micron”; It is about 701 by the size of at least the support pores of diameter oY. - 11101 - A has pores between about 1 and 01 microns and is about 7710 at least the size of the yo support pores with a pore size between about yo and yo µm ¢ 1 and a booster amount of at least one promoter to enhance the effectiveness of the catalyst Cua VY the amount of silver on the support is sufficient to increase the efficiency of the catalyst; As for "determined according to the standard ethylene oxide manufacturing process conditions of about #*m" at least; tn" when compared to the same catalyst but containing less silver YY 1 catalyst according to the element of protection (17); Cus activity increases by an amount of Y about 10 m" at least. 1 “7 catalyst according to claim (71) contains silver in a ratio ranging from about Y 7700 to about 7760 by weight. (YE) The catalyst according to the claim (VV) contains silver with a percentage ranging from Y to about 778 to about Lge by weight. Yo 1 catalyst catalyst according to claim (YY) where the support has a lamellar Y shape -hamellate morphology 71 1 catalyst according to claim (YO) where the support has a alpha-alumina .alpha-alumina YY 1 catalyst according to claim ( 1 Cua support) is pure alpha-alumina with a ratio of not less than JAA 1 101L catalyst according to the protection element ) \ oY where the support contains a material containing fluorine oY. 1107 - - 7*1 catalyst pursuant to claim 0 (YA) where the support has a lamellar morphology “1 1” catalyst pursuant to claim Cua » (Y 1 promoter is a Y-cationic promoter “1 1 catalyst according to oF protection) where the cationic promoter selects Y from the set of potassium, rubidium, cesium, and mixtures thereof. FY 1 catalyst of claim (17); Cus the promoter is a Y-anionic promoter (osu! 1 “7 catalyst according to the element of protection) 0 ¢ choosing the anionic promoter from the set of Halides and oxyanions of 7 elements other than oxygen have an atomic number ranging from to AY inclusive and consist of 3 elements of groups “B to cc inclusive and from ?A to IY inclusive of the periodic table of elements 0 _¥E 1 catalyst of claim (77); Cua selects the anionic promoter Y from the group consisting of sulfate sulfate fluorsulfate nitrate nitrate manganate vanadate chromate 3 molybdate cmolybdate tungstate ctangstate renate crhenate cerate cerate and mixtures thereof. _Yo 1 catalyst according to claim (YE) also includes a cationic promoter oy. 1117 - - cationic promoter Y includes at least one of the alkali metals and the alkaline earth y metals. “1 1 The catalyst according to the claim (YO) chooses the cationic promoter Y from the group consisting of ccesium rubidium 7 potassium and mixtures thereof. 0 7 m