Hydrogenation catalyst and hydrogenation process

Hydrogenation catalyst and hydrogenation process

hydrogenation catalyst and hydrogenation process

Full description

Background of the invention

The present invention relates to a multicomponent catalyst for the hydrogenation of highly unsaturated compounds including palladium (Pd), and a selection of modifiers on supports having properties particularly for the hydrogenation of unsaturated hydrocarbons and a more specifically selected hydrogenation process for very unsaturated hydrocarbons such as acetylenic acetylenes.

The invention relates more specifically to a selected hydrogenation process of acetylenic compounds in mixed olefin streams consisting of 2-4 carbon atoms.

Palladium- and nickel-supported catalysts have been used for various hydrogenation processes for some time. These processes include the hydrogenation process of selected acetylenic compounds and dienes in various mixed olefin streams and gasoline, and in the hydrogenation of benzene.

German Patent No. 2,412,191 discusses a process for purifying l,3-butadiene and isoprene streams by the selective hydrogenation process of acetylene compounds using a well-dispersed catalyst or a supported catalyst. The preferred catalyst metal is either a noble metal such as palladium or a non-noble metal such as cobalt (Co), iron (Fe) or molybdenum (Mo). The desired improvement is the use of cylcopentadiene, which improves the selectivity of 1,3-butadiene with either a noble or a non-noble catalyst.

The documentation is well supported that palladium-supported catalysts are unstable for the selected hydrogenation process of vinyl acetylene due to the formation of complex compounds of vinyl acetylene with palladium. Palladium complex compounds are dissolved in the hydrocarbon stream. It has been discovered that adding silver to a palladium catalyst (Pd catalyst) produces stability in the extinction of the catalyst, which causes the loss of palladium metal and an improvement in the selectivity of the desired olefin product. See MLDERRIEN et al. Studies in Surface Science and Catalytic Process, Volume 27, Page 3 1 6 (1 986) and ELSVIER AND K. JAMES SASAKI Petroleum Chemicals and Gas Processing Gas 113 PRQ Fall 1997.

US Patent No. 4,533,779 relates to a palladium-gold catalyst supported on supports such as alumina (1-100 m2/g) for a selected hydrogenation process of acetylene compounds. The alumina used in the examples has a surface area of 70 m2/g, a total pore volume of 0.6 cc/g and an average pore diameter of 200 ANG0. The deposition of palladium and Au was performed in two successive steps. Impregnation of the palladium compound Pd on alumina was carried out using an adsorption technique on an organic palladium compound (acetylacetonate) in a non-polar organic solvent on the alumina. The contents of palladium and gold in the catalysts are in the range of 0.03: 1% by weight and 0.003: 0.3% by weight, respectively.

US Patent No. 4,762,956 discusses an innovative new catalyst and process for the hydrogenation of dienes and acetylene impurities in the olefin supply. The catalyst is a palladium catalyst supported on mainly crystalline alpha alumina, which has an average pore radius of 2000:200 ANG. With at least 80% of the pores having a pore radius of over 3000:100 ANG. The metal surface of the active palladium was less than

Inoculation of ANG 50 m2/g with an average palladium molecule size of at least 25 was carried out on aqueous palldadium chloride alumina by spraying an aqueous palldium chloride solution.

Through an attached sprayer for drying at 80°C alumina US Patent No. 5,866,735 is announced for the hydrogenation process using a palladium catalyst supported on the reinforcement such as ammonia - but modified with strong forces such as iodide to reduce its formation of heavy products during the hydrogenation process selected potassium potassium hydrocarbon and/or acetylation compounds in Hydrocarbon streams diolefins to olefins

Renewable blend 0

U.S. Patent No. 5,877,363 discusses the selected hydrogenation process from l,2-butadiene to 2,1-butadiene isomerization of acetylation impurities and the carbon-rich sub-quaternary isomerization process in l,3-butadiene carbon streams using a palladium platinum catalyst. ..etc. olefin olefin European Patent 567198 discusses the catalyst ammonium / potassium - composition - dienes and dienes copper palladium alkynes for the hydrogenation process of alkenes 0.415 potassium Cu % 0 copper « - Pd preferred to be 2. 0 palladium catalyst catalyst 3 with D SUB3 aluminum gamma - alumina reinforcement preferred to be gamma - aluminum

100 : 0 h2 m2 / gm area of flat surface 0.4 : 0.7 m3 / gm area. US Patents Nos. 4,644,088 and 4,658,080 discuss the process of removing acetylene - a catalyst, a multi-component catalyst including the novelty of Table VIIB, VIB, IVB, IIB, IB, N and at least nickel other elements from the group - alkali metal and the periodic alkaline earth metal. Alkaline earth metal is prepared as a catalyst by mixing dry powders of zinc iron 452 - barium carbonate added to kneading the dry powder with a solution of NiC03, and nickel carbonate ZnFe2O4, BaCO3, With the formation of balls of aqueous size NaOH, aqueous sodium hydroxide includes a mixture of appropriate metal oxide catalyst that has been dried. Catalyst

Metal oxides, salts, and hydroxides as catalysts. The activated catalyst appears to be mainly composed of metals and metal oxides. Aluminum is not part of this catalyst. The continuous supply of the catalyst is deacetylated in a vapor phase over a temperature range of 0 - 25 - 900°C.

According to V.RIVES et al., the addition of zinc (Zn) to the aluminum (Al) and nickel (Ni) catalyst for the acetylene hydrogenation process in the formation of a renewable mixture of olefin current-impeding materials on the surface of the catalyst and the higher selectivity of ethylene, which is achieved with a zinc/nickel ratio of Zn-Ni. atomic B 4 - Applied clay sciences 13 year 1998 page (363: 379).

A.Sharkany has published an article on Pd-palladium and slightly alkyl silver-palladium catalysts supported on ammonia crystalline alpha for the hydrogenation process of 1,3-butadiene - the commonly used catalyst, No. 175 of 1998, pages 245 to 253. - Deposition of heavy, low-reactive hydrocarbons on the surface of the catalyst due to both inactivation of the catalyst and the end of the hydrogenation process of paraffinic products.

H.Uygur and others published an article (J.Chem.Eng. Japan - Volume - 31 - No. 178, 1998) concerned with the hydrogenation process of the selective liquid phase of methylacetylene and propadiene (MAPD). In a C3 renewable mixture resource, they found that they converted Methyl acetylene and propadiene (MAPD) 0300 palladium catalyst reduces the increase in temperature of the hydrogenation process S.Djackson et al. The catalyst used in general No. 134 of 1996 from p. 91: 99. It was found that the absorption of phenyl acetylene increases with decreasing temperature during their study of the hydrogenation process of the liquid phase of phenylacetylene and citrine on the palladium catalyst supported on carbon. M..RMSaseen and others have found a discussion of Ferrari

chem. Soc No. 89 of 1998, pages 331 to 320. The interesting types of ethylidyne on palladion Pd 3 increase the high temperature from 20 degrees to zero.

Celsius . We found that this is true for the C4:C3 acetylenic hydrogenation process of acetylation compounds in the crude butadiene resource mixed with the Pd-Ag supported silver palladium catalyst. This strange behavior appears to be a result of the combined effect of very low atomization energies greater than 0.5 kcal/mol - for the news hydrogenation process - dissolution of higher hydrogen in the renewable supply resource at lower temperatures and the expected temperatures on the adsorption of acetylation compounds on the palladium surface in the phase reaction system. Tripartite catalyst: gas, liquid and solid. In other words, the concentration of hydrogen in the liquid phase has a greater influence on the rate of the selective hydrogenation process of acetylation compounds than the effect of the apparent activation energy. General description of the invention:

The present invention includes a supported catalyst including:

1- Palladium, Pd, or Group 8 metal, including palladium, Pt. The other Group 8 metal, preferably, is the Group 8 metal chosen from palladium - edidium, RU, cobalt, Co, or nickel, Ni.

2- At least two metals chosen from silver Ag and zinc Zn or bismuth Bi. Preferably silver Ag and at least one from zinc Zn or bismuth Bi. Optionally, the catalyst may contain potassium. A level of potassium in the catalyst will usually be less than 0.5% by weight.

In practice, the hydrogenation of unsaturated compounds occurs by contact with streams of renewable hydrocarbons containing small quantities of acetylation compounds with the catalyst of the invention in various arrangements and compositions, part of the present invention.

The preferred reinforcement is very perforated with an average pore diameter larger than about 180 ANG, with no pores narrower than 35 ANG. Total pore volume greater than about 220.65/g and preferably smaller than about 100 m2/g surface area bet 0

Detailed description

The present invention includes the hydrogenation catalyst and the process of hydrogenation of hydrocarbons using a catalyst, in particular the hydrogenation process by the processes of hydrogenation of polyunsaturated compounds such as acetylation compounds and di-adanes to monovalent or divalent saturated or unsaturated products depending on the purpose of the process and the process of hydrogenation of aromatic compounds such as benzene to a compound My throat. The hydrogenation process may be carried out in a vapor phase, a liquid phase, and in the presence of a mixed vapor and liquid phase. The hydrogenation process may be performed in any fixed-bed reactor, a liquid distillation reactor, a preparatory distillation reactor, or any combination thereof, in the presence or absence of a solvent. The preferred solvent example is tetrahydrofuran.

- Benzene - toluene - etc.

This invention is particularly useful in removing acetylation and adenyl compounds in C1:C2 organic compounds by the process of selective hydrogenation of saturated or unsaturated mono- or di-organic compounds. Examples of renewable supply streams are pure steam of C5-C4-C3-C2 mixture or C6:C2 fuel of boiling gasoline type.

The catalyst disclosed in this invention is composed of a multi-component catalyst supported by highly saturated supports such as alumina - silica - silica.

- Ammonia - Carbon...etc. with a total pore volume of 0.65 cm3/g with an average pore diameter greater than 180 ANG. Aluminum oxide is the preferred reinforcement whose surface area bet in the range of 10: 100 m2/g in detail from 0 2: 0 7 m2/g The natural forms of corundum may be - spherical bodies - pellets - granules or formed

The formed aluminum oxide reinforcement will have an apparent bulk density of less than 0.7 g/cm3 but not higher than about 0.8 g/cm3. Corundum is aluminum oxide

Transitional mixed crystalline forms of alpha-eta-rho-kappa-ha-tar-gamma and dependences on the calcination temperature and crystalline structure of the raw material, maerial alumina monohydrate. Corundum consists mostly of a crystalline form of gamma Y or chi, which does not favor reinforcement. To prepare aluminum oxide, the preferred aluminum oxide raw materials are heated, such as aluminum oxide gel or aluminum monoxide, from about 650 to 1250 degrees Celsius. Final calcination temperature

Determine the natural properties of aluminum oxide reinforcement to obtain the best performance for the urban hope of the particular process.

The preferred aluminum oxide declared in this invention can be prepared using a number of well-known techniques, starting with those skilled in the method of preparing aluminum oxide - alumina - one of the preferred aluminum oxides declared in this invention can be prepared using what is called the falling oil analysis technique. Examples of the previous method are announced in US Patent No. 2920314, 4273735 and 4179408 The spherical aluminum oxide is prepared from a colloidal liquid of aluminum hydroxychloride.

Aluminum oxide is prepared by digesting aluminum metal in aqueous hydrochloric acid solution. The colloidal solution materials are spherical aluminum oxide produced in the form of droplets that are collected in a basic liquid oil phase, achieving superiority in washing, drying, and calcination to aluminum oxides with a transitional state at various temperatures depending on the desired property of aluminum oxide. Alternatively, aluminum oxide in the preferred spherical shape can also be prepared by the drop glaze technique using colloidal solutions of aluminum oxide, boehmite or pseudoboehmite alumina. Aluminum oxide solutions are prepared by distributing pseudoboehmite or suitable pseudoboehmite or mixtures of

Aluminum oxides obtained by hydrolyzing alkaline aluminum alkoxides and by crystallizing them or reacting a solution of sodium aluminate with an aluminum salt solution such as aluminum sulfate or aluminum nitrate and then crystallizing them. Various aluminum oxides or colloidal solutions of aluminum oxides available in Market - Condea is one of the suppliers of the preferred spherical aluminum, which expresses the natural properties of this invention. Spread HP 2/14 Deperal No. 11 VO Deperal No. 23 N 2004 Spread Hp 14 deperal No. 0 4 -200- 100- etc. Or mixtures of these and other materials may be used to prepare the preferred corundum reinforcements disclosed in this invention due to their very high surface area. Very narrow pore diameter and very small pore size. Productivity of these materials is similar to the aluminum oxides announced in US Patent No. 4493906 - 440956. Aluminum oxides preferred in various extrusion molding or tablet shapes. It can be prepared by extrusion forming aluminum oxides or the previously announced preferred ones and calcining at high temperatures from 650: 1250 °C Optionally, various composite coating materials made of metal materials or ceramic materials for the distillation column used as a support.

The potassium content in the catalyst will usually be less than 0.5% by weight. The metal content in the catalyst will be palladium (Pd).

It ranges from 0.005% to 1% by weight, and most preferably it ranges from

- By weight, in nickel, it is preferable to range from 0.0: 15% by weight, and most preferably, it is to range from 0: 10% by weight. In silver, Ag, it is preferable to range from 0.002: 20% by weight - most preferably, from 0.005: 5% by weight - and zinc. Zn is preferably ranged from 0 to 5% by weight, which is most preferable

From 0.002: 1% by weight - Zimuth Bi preferably ranges from 0 to 5% by weight

Most preferred 0.01: 3% by weight 0

The elements required to be deposited on the support include multiple techniques, such as the rotary evaporator used for the impregnation solution - the impregnation of the first pores - the airbrush - used for the impregnation of the covering spray, the vapor deposition technique, the combined condensation techniques, etc. The preferred techniques in this invention are the covering spray impregnation and the primary pore impregnation, in particular the covering spray impregnation is the most preferred technique in this invention.

Depending on the specific type of hydrogenation reaction that determines what elements and how much is needed

In the catalyst, single and double impregnation takes place if it requires the elements palladium, silver, and zinc - a mixed solution of palladium, silver, and zinc, compounded in water or an organic solvent, has been prepared. The solution is sprayed on the flow support, such as aluminum oxide, in a circular inoculator attached to drying with a hot gas such as air or nitrogen at a temperature ranging from 60 to 300 C. The dry inoculation product is usually calcined at a temperature of about 250 to 600 C in the air. If double impregnation requires significant working air, the first impregnation to reinforce the appropriate layer is carried out by impregnating the first pore with an aqueous solution of the zinc compound and a mixed solution of silver and zinc compounds or palladium Pd, silver and zinc compounds, depending on the specific performance goal of the catalyst. The inoculation product was dried at a temperature of 300-60 Celsius, suspended in a calcination process at a temperature of 600-250 Celsius, and the second inoculation was carried out by spray-coating with a solution of the second mixture of palladium and silver compounds or palladium Pd, silver Ag, and zinc compounds Zn on the first inoculation product with drying. Added to the dilution and calcination at a suitable temperature described previously. For most of the selected hydrogenation reactions, such as the removal of acetylation compounds in various renewable mixed streams of olefins or dienes, palladium permeates from the outer geometric surface of the suspended materials towards the interior and the supported materials, which plays an important role in determining the selectivity and properties of the catalyst.

10 A ml of 0.08 mm preferably less than about 0.06 M for palladium permeation is very much required. The goal can be achieved by spreading the baby liquid from the leech inoculation solution into the gas phase using a compressed gas spray. Also, the volume of the liquid impregnation solution for a given amount of support material is important - the required volume of solution is less than about 855 volumes and preferably less than 65% by volume of the total pore volume of the support material -

When zymuth is one of the required components of the catalyst, the preparation of the catalyst may be carried out in one or two steps - for the individual impregnation step - impregnating the mixed solution of palladium, zinc, silver and zymuth compounds on the supporter, which is carried out using either the coating spray technique or the flow booster inside a circular inoculator. Or purification by impregnation of primary pores attached to drying for calcination as previously described - if the second impregnation step is required in the solution of the first step of the zimuth compound or the mixed solution of the zimuth compounds Bi and Zn used either To prevent inoculation, the primary pore or spray coating technique is accompanied by drying and calcination at an appropriate temperature described previously. Another alternative technology combines compounds of zimuth Bi and zinc Zn on uncalcined alumina, followed by drying and calcination of the impregnation product at temperatures ranging from 650 to 1300 degrees Celsius. The second impregnation of the mixed solution of palladium compounds Pd and zinc Zn or compounds of palladium Pd, silver Ag, zinc Zn and zmuth. On the product of the initial inoculation step performed by coating spray inoculation or first pore inoculation followed by a second drying and calcination as previously described.

To prepare zinc or both zinc and zinc containing multi-component catalyst, zinc or both zinc and zinc bi have been combined with falling oil gelatinization technique to prepare corundum reinforcement. A colloidal solution of the fallen aluminum oxide, dissolved in the zinc compound or both zinc and zmuth compounds, can be prepared to

Essential oil ox to form the gel attached to aging - washing - drying and calcination at a temperature ranging from 650 to 1250 degrees Celsius. The aluminum oxide support may optionally be prepared with an impregnation solution of a zinc compound, Zn or zimuth Bi, or a mixed solution of zinc compounds and zimuth Bi on aluminum oxide powders that have the normal properties of the preferred supports described previously. Preparing the appropriate raw materials, such as corundum powders, to be powders as described previously. The raw materials were calcined at temperatures ranging from 350 to 750 Celsius. Before the inoculation process, the inoculation products were calcined at a temperature ranging from 250 to 600 Celsius, and formed to the desired size of the formed materials in vetch. Or pellets. Finally, the formed materials were calcinated in air and at a high temperature ranging from 650 to 1300 degrees Celsius. The mixed solution containing palladium and silver compounds or palladium silver and zinc compounds was impregnated on a very catalytic aluminum oxide reinforcement using one of the previously described impregnation techniques attached to drying and the calcination process. .

The hydrogenation process was performed for unsaturated organic compounds by loading one or more catalysts. For the optional hydrogenation process, one, two or more catalysts may be used to improve the productivity of the required products. For example, the complete or nearly complete conversion of vinyl acetylene - ethyl acetylene and methyl acetylene into absolute butadiene vapor streams - two or more catalysts that have different compositions and charges of the metals may be used to obtain a high quality product with the best result. Commercial required. Catalysts may be charged in a single reactor or in two reactors - the highest active catalyst in front of the lowest active catalyst. In a single reactor process - a ceramic or stabilized distillation reactor process so that the regenerative supply stream passes first through the region of the highest active catalyst in front of the lowest catalyst.

Activity in a Single Reactor Process - Catalytic distillation or stabilized reactor process The regenerative supply stream first passes through the region of the highest active catalyst.

The renewable hydrogen supply stream may be fed to the renewable hydrocarbons supply stream at a single point before entering the catalytic reaction zone or supplied to two or more different locations along the reactor for a more demanding result - due to two different catalysts or supplied to two or more different locations along the length of the reactor to obtain a more desirable result due to two catalysts with different activity usually having different optimum ratios of hydrogen compounds to acetylene in the supply for the given case of the concentration of the particular acetylation compound. The temperature, pressure, and flow rate of hydrocarbons, if used, effectively charges the catalyst to the highest activity in the first reactor. The process of hydrogenation by catalytic distillation is the preferred method for the process of selective hydrogenation of acetylation compounds in various renewable mixture streams to obtain the best selection and long life of the catalyst in the absence or presence of the solvent.

In the hydrogenation process by catalytic distillation, the starting polymer and hole polymers are continuously washed with the liquid phase and removed as part of the logic of the catalyst surfaces retaining the renewable substrates from the fixed base process. Usually, the selection of desired products is better than that of the saturated base process - higher concentrations of acetylation compounds in the reaction zone. urbanization that can be saved by operating the distillation column reactor appropriately from that evaporator in the case of a fixed base process. If a solvent is used, the catalytic distillation column may be operated in two ways. It may operate the distillation column. In a total solvent inflow setup, the solvent may be fed to the upper section of the column above the catalytic reaction zone as part of a regenerative bottom stream based on the boiling point of the solvent. The recovered solvent from the regenerative bottom stream is recycled again to the location above the catalyst zone of the catalytic distillation column. Examples Control Example No. (1):

A slightly polished commercial grade Pd-Ag silver palladium catalyst No. G 681 obtained from UCI was used to remove trace compounds in renewable raw steam fired butadiene streams. 36 g of commercial catalyst (2.0% palladium pd- 0.01%g alumina) was mixed with 100 ml of 3 mm diameter glass balls and charged in a vertically upward flowing solid reactor, horn diameter - 20 horn length - ABD. of catalyst 0.97 g / 22 average volume of catalyst

The catalyst is 2.5 millimeters in diameter by 6 millimeters in length, extruded and then activated at 230°F by passing 1 ml/minute isobutane measured at ambient temperature - H1/min hydrogen (10% volume 2H in helium He) - under 200 atm. For two hours. The reactor was cooled to a previously specified temperature and then the reactor pressure was set to a previously specified pressure for the hydrogenation process. After blocking both hydrogen and isobutane at the reactor, the hydrocarbon and hydrogen feed was introduced slowly while the reactor temperature was monitored due to the external heat of the hydrogenation reaction. A sudden increase in temperature may occur if there is no temperature limit at the starting point of the catalyst. There are vectors from the end to the starting point of the catalyst.

Acetylation impurities were removed in the C4 steam mixture containing 570 ppm propyne, 6550 ppm phenylacetylene, 1497 ppm ethyl acetylene, 55.4% - 1,3-butadiene and 0.22%, 1,2-butadiene. And 15.41% 1-butene, etc., by weight, by performing the selective hydrogenation process using the activated catalyst G No. 0681.

The improvements made in this invention through the previous method are higher than the average amount of energy being processed. Higher quality of renewable product streams. Higher productivity of the desired product and saving hydrogen. Example No. (1):

Spherical gamma corundum - diameter of a spherical y-alumina (2 millimeters) - was used to prepare a suitable support suspended in this invention, and spherical gamma corundum - gamma.-alumina is not suitable for reinforcement while it is due to the surface area.

The very high acidity is the low nature of this aluminum oxide. It is listed in Table No. 1. The aluminum oxide was calcinated at 1150 degrees Celsius for 3 hours in air.

Table, US Patent No. 0001, and Joule No. 1 ABC, single point, bet 53. 0 g/2 2 and multiple point BET e.7 h1 m2/g, pore area and Si 170.2 m2/g - zero surface area 170.2 m2/g, accumulated absorption surface area 0 m2/g, accumulated condensation surface distance 172 m2/g, and total hole size 4.0 3 2 m2/g for an area of less than 493 ANG of diameter over the volume of accumulated absorption pores 0.912 / A / PO v 0.901 for an area of 0.852 (20:30) ANG radius - volume of accumulated absorption pores for pores 0.93 (17.5-300 AND radius) Average pore diameter 214.4 ANG.

The mixture solution was prepared by dissolving 3.79 g of zinc (N03)2 6H2) -

0.52g of AGN03 and 13g-10 palladium nitrate in hydrogen nitrate solution

Aqueous 10% in 100 g of deionized water. This mixed solution was sprayed on 300 g of calcined alumina using a compressed air sprayer and a circular impeller and dried with hot air at about 200 C for an hour? The dried product was calcinated at 350 C for two hours. The estimated composition of this catalyst, based on the quantities of chemicals used, is 20% palladium Pd, 0.11 silver Ag, and 0.28% Zn by weight.

36 g of this catalyst - (palladium Pd / silver Ag / zinc - Zn corundum A1O3) - was mixed with 100 ml of charged 3 mm diameter sulfur balls in the same reactor used in control example No. 1 - the catalyst was activated by the method

Next - The reactor was purged with a flow of 22.20/min of nitrogen under 15 atm, it was slowly heated to 235 F. A flow of 100/min hydrogen gas was cut into the nitrogen flow and held for an hour after the gas nitrogen supply was activated and the flow was increased. Hydrogen gas gas hydrogen to 300 cc/min and then raise the temperature to 550 degrees Fahrenheit for two hours - the reactor cooled the hydrogen gas flow to the required hydrogenation reaction temperature. It was cleaned with (150 CC/min) nitrogen and placed at a previously determined pressure for the hydrogenation reaction. The supply of hydrocarbon and the hydrogen supply to a renewable nitrogen resource were slowly cut off while the reactor temperature was monitored and the flow of nitrogen gas was slowly cut off. The hydrocarbon supply was in the same materials used in Control example No. 1. The results of Control Example No. 1 and Example No. 1 Prediction are in Table No. 2.

It is clear from the results listed in Table 2 that the three-component catalyst - palladium, Pd, silver, Ag, and zinc, Zn - supported by corundum has superior performance to the conventional catalyst. The quality of the product in Example No. 1 is superior to the product in Control Example No. 1.0 The phenylcytylene impurities in the supply of Example No. 1 are completely removed so that the recovery of 1,3-butadiene is better by more than 4% by weight. It is generally very rare for a catalyst with current activity to have a higher yield of the product required in the conversion or than for those with lower catalyst activity. Example (2):

The spherical corundum has been spherical calcined. gamma.-alumina used to prepare the corundum supplement for Example 1 at 1100°C for 3 hours in air.

A solution of bismuth nitrate was prepared by dissolving 4.31 g of bismuth nitrate - 6 water in 285 ml of deionized water acidified with 6 drops of concentrated nitric acid solution. An initial high impregnation was carried out with this solution on 300 g of previously calcinated aluminum oxide. . The cold inoculum product was flowed for 10 minutes in a circular inoculator and then dried with hot air at 200°C for an hour. The dry product was calcinated at 450°C in air for two hours. The mixed solution was prepared by dissolving 3.79 g of aqueous zinc nitrate Zn(No.sub.3) - 0.52 g of silver heritage, 13.3 g of 10% by weight, palladium nitrate solution in a 10% nitric acid solution in 100 ml of water. The effect of ions. This mixed solution was sprayed on the aforementioned calcified product using a compressed air sprayer and a circular inoculator, then dried with hot air at about 200 degrees Celsius for an hour, and the required product was calcinated at 350 degrees for two hours. The composition of this estimated catalyst based on the quantities of chemicals used is 0.20% palladium Pd, 0.11% silver Ag, 0.27% zinc Zn, and 1.42 bismuth Bi by weight.

36 grams of this catalyst - palladium - silver - zinc - bismuth - corundum - were mixed with 100 ml of glass balls with a diameter of 3 mm and charged in the same reactor used in Control Example No. 1. The catalyst was activated in the same way as in Example No. 1. The feed of the same hydrocarbons used has been cut

In example, control No. 1, or the renewable hydrogen resource in a banana, slowly regenerates nitrogen while watching the reactor temperature and slowly separating the flow of nitrogen gas gradually.

Table No. 2.

USA Table No. 0002 for Table No. 2 for Control Example No. 1 For Example 1 Temperature Fahrenheit 120-110-120- Atmospheric Pressure 108 125 108 and WHSV of HC Supply 4-3-4-6.1 Hydrogen Rate and IB/SCFT- From HC

1.34-56. 1 - 34. 1 - 31. 1 to install the product ppm VA -85- 36- zero -fahr and EZ 278- 159- 91- zero and MA 38- 18- 6- 1 propamine 08 1-80-81-110-2. 1- and 322 1-0 72 1-2 1 2 1-1230 and recover the square sign of and 9109 - 89.6- 94.3- 92.5- 3.1 BD of temperature on the end of the catalyst basis by weight and sign.

The result of the clearly superior performance of the four-component catalyst - silver - palladium - zinc - bismuth - supported on oxide shows that all the C4 acetylation impurities in the supply were completely removed even through the 50% higher supply rate. Until recovery 3. 1- Butadiene 1,3-butadiene is similar to the previous method.