Highly calcined support for catalytic dehydrogenation
United States Patent Box, Jr. et al.  
 [ 1 Apr. 29, 1975 HIGHLY CALCINED SUPPORT FOR CATALYTIC DEHYDROGENATION Inventors: E. O. Box, Jr., Bartlesville. Okla; David A. Uhrick, Columbus. Ohio Assignee: Phillips Petroleum Company, Bartlesville, Okla.  
 Filed: June 7., 1973 Appl. No.: 367,803  
 Related U.S. Application Data Division of Scr. No. l5l.894. June 10. I971 abandoned. which is a division of Scr. No. 828.777. May 28, I969. Pat. No. 364L182.  
 U.S. Cl. 252/466 PT; 252/466 J Int. Cl BOlj 11/22 Field of Search 252/466 PT. 466 J [56] References Cited UNITED STATES PATENTS 3.668.15l 6/1972 Walker 252/466 PT Primary E.\&#39;uminerC. Dees Group ll aluminate spinel impregnated with a material selected from the group consisting of one or more Group VIII metals, a Group In metal. and a tin group metal and mixtures thereof.  
 10 Claims, No Drawings HIGHLY CALCINED SUPPORT FOR CATALYTIC DEIIYDROGENATION This is a division of application Ser. No. 151.894, filed June 10, 1971, now abandoned, which is a division of application Ser. No. 828,777, filed May-28, I969, now US. Pat. No. 3,641,182.  
  The invention relates to an improved process for the dehydrogenation of dehydrogenatable hydrocarbons wherein catalytic materials are supported on a highly calcined support. In another aspect the invention relates to a process of making the highly calcined support.  
  It is conventional in the dehydrogenation of paraffin hydrocarbons to utilize catalysts such as nickelkieselguhr, chromium oxide-alumina, zinc oxidealumina. platinum-alumina. and the like. In general. prior art processes are operated with a water-free feedstock and at a low pressure. Considerable advantages are inherent in any process that can operate with steam, for instance, heat of reaction can readily be supplied, coke deposition on the catalyst can be retarded, and expensive compression of products can be avoided since elevated pressures can be employed and steam can readily be condensed after dehydrogenation is effected. For reasons such as these, various attempts have been made to employ steam in processes for the dehydrogenation of paraffin hydrocarbons.  
 We have now found that highly active and exceptionally selective catalysts for the dehydrogenation of steam-diluted. alkanes, cycloalkanes, and arylalkanes can be prepared by highly calcining a support selected from the group consisting of alumina, zinc oxide, HF- treated alumina, silica, magnesia, zirconia, aluminum silicate, and Group II aluminate spinels and mixtures thereof. Of these, the Group II aluminate spinels are particularly effective and excellent results are obtained with zinc aluminate spinel. A catalyst composition is then formed by combining the highly calcined support with a metal selected from the group consisting of nickel, platinum, palladium, ruthenium, iridium, rhodium, osmium, and mixtures thereof. Other catalyst compositions are then formed by combining with this composition a material selected from the group consisting of a Group In metal and a tin group metal and mixtures thereof.  
 I The groups of metals referred to herein are as classified in the Periodic Table published in the Chemical Rubber Company&#39;s Handbook of Chemistry and Physics&#34;, 45th Edition (I964), page 3-2.  
  Aluminate spinels, as referred to herein, are compounds of the formula M(AIO- or MO.Al O wherein M is a Group Ila or III) metal with a valence of 2 such as Zn, Mg, Be, Ca, and the like.  
  The highly calcined novel supports of this invention can be prepared by calcining for a sufficient time and at a sufficient temperature an alumina, zinc oxide, HF- treated alumina, silica, magnesia, zirconia, aluminum silicate, or Group II aluminate spinels and mixtures thereof. The spinels of this&#39; invention can be prepared by any known method and in one embodiment are prepared by the coprecipitation method wherein appropriate amounts of suitable aluminum compounds and suitable Group II metal compounds are combined under spinel-forming conditions. It is preferred that the proportions of these ingredients by approximately stoichiometric or, alternatively, that the Group II metal compound be up to 10 percent or more in excess of stoichiometric.  
  According to this invention, the highly calcined support is prepared by calcination for about l-lOl) hours at about l50()2500F. In another embodiment, a highly calcined support is produced by calcining the support from about 2-50 hours at about 2000-2500F. and, in a preferred embodiment, the support is highly calcined by heating for about 12 hours at about 2282 F.  
  The first catalyst composition of this invention can be prepared by combining, in any manner known to the art. certain Group VIII metals, or metal compounds capable of reduction to the metal, including nickel, platinum, ruthenium, palladium, iridium, rhodium, osmium, and mixtures thereof, with the highly calcined support of this invention. Platinum, which is very effective, is preferred. The Group VIII metal content of the catalyst can be in the range of about 0.01-5 weight percent of the support and. in one embodiment, is in the range of 0.1-1 weight percent of the support. Throughout this application the term weight percent of the support&#34; means parts by weight per 100 parts by weight of support.  
  Any platinum group metal compound that produces the desired results can be used. In the discussion of the compounds that can be used the platinum compounds will be used as nonlimiting examples. It is to be under stood that similar compounds of the other platinum group metals can be used. Examples of simple or noncoordination compounds that can be used are platinic chloride. chloroplatinic acid, ammonium chloroplatinate, and the like. Nonlimiting examples of coordination platinum compounds that can be used are: platinum amminoacetate, platinum dimethyl dioxime, tetraammineplatinum hydroxide, platinum diammine dinitrate, platinum tetraammine dihydroxide, platinum diammine dihydroxide, platinum hexammine dihydroxide, platinum hexammine tetrahydroxide, platinum diammine tetrahydroxide, platinum diammine dihydroxide dinitrate, platinum diammine tetranitrate, platinum diammine dinitrite, platinum tetraammine dicarbonate, platinum diammine oxalate, and the like. Additionally, many complex or coordination divalent and tetravalent platinum compounds are known and can be used.  
  When added to the support by impregnation from solution, some of the compounds can be added from aqueous solution, but others will require non-aqueous solvents such as alcohols, hydrocarbons. ethers, ketones, and the like.  
  The second catalyst composition of this invention is prepared by combining a Group Ia metal or metal compound with the components of the first composition with or without a tin group metal. This can be conveniently done by conventional impregnation. The amount of each alkali metal compound or combination of compounds can exist in the range of about 0.01-5 weight percent of the total catalyst; however, in one embodiment, a range of about 0.1-1 weight percent of said support is used. Although any Group Ia metal in compound form is suitable for use in this invention, in one embodiment lithium in lithium nitrate was used. Other convenient compounds are the carbonates. acetates, and hydroxides and the like of sodium, barium, potassium, calcium, and the like.  
  The third catalyst composition of this invention is prepared by combining a tin group metal including lead, tin and germanium with the components of the first catalyst composition with or without a Group In metal. The tin group metal can exist in the range of about 0.01- weight percent of said support and, in one embodiment, can exist in the range of about 0.ll weight percent of said support. Although any tin group metal in compound form is fully within the scope of this invention, some convenient tin group compounds are the halides, nitrates, oxalates, acetates, carbonates, propionates, tartrates, bromates, chlorates, oxides, hydroxides, and the like of tin, germanium and lead, Tin,  
 .itself, is the preferred tin group metal and impregnation of the supports with tin compounds such as the stannous halides is particularly effective and convenient.  
  Generally speaking, the Group la, VIII and tin group compounds, which are combined with the highly calcined supports to form the improved catalysts of the present invention, can be any compound in which all elements, other than those of Group Ia, VIII, the tin group or oxygen, are volatilized during calcination. These compounds can be sequentially combined with the support, in any order, or for convenience, can be applied simultaneously in a single impregnation operation. After impregnation, the composite solids are dried and calcined.  
  The catalyst systems of this invention are employed at temperatures between 750 and 1250 F., preferably between lOOO to 1 100 F., and at total pressures in the range of 0 to 500 psig, preferably 0 to 250 psig. Steam to hydrocarbon mol ratios of 0.5:1 to 30:1, preferably 2.511 to :1, are employed. Total space velocity (GHSV) of hydrocarbon and steam is between 100 and with steam-diluted air, such that the oxygen content of the mixture is about l-2 mol percent. The regeneration treatment can be carried out at temperatures and pressures within the dehydrogenation operating range for about 15 minutes to one hour.  
 EXAMPLE I A catalyst support was prepared wherein 7.87 kilograms of hydrated zinc nitrate and 20.455 kilograms of hydrated aluminum nitrate were dissolved in 10 gallons of deionized water. This solution and concentrated ammonia water (28 weight percent NHg) were separately added to gallons of deionized water with stirring over a l-hour period, the addition rate being adjusted such that the pH was constant at about 7.5. The mixture was stirred 2 additional hours and allowed to stand for 3 days. A precipitate was washed three times by reslurrying in 50 gallons of fresh water, spray dried at about 925 F., dried in an oven about 17 hours at 625 F., formed into 4-inch pellets, and ground three times. The granules were divided into a number of portions, subjected to various calcination treatments which will be subsequently explained, steamed about 5 hours at about 1025 F. and used in the form of l835 mesh granules.  
  A first portion of these granules was then calcined at 2000 F. for 4 hours and formed into a catalyst composition by contact with sufficient aqueous tetraammine platinum hydroxide solution to impregnate the granules with 0.25 weight percent platinum based on the weight of the granules. Resulting catalyst was dried under a heat lamp, heated to reaction temperature in air, and tested for dehydrogenation ability with an n-butane feed as indicated in Runs 1 and 2 of Table I.  
 TABLE I Support Caleincd at 2000F. for 4 Hours 0.25 weight percent platinum Run 2 50,000, preferably between 500 and 20,000 volumes of gas/volume of catalyst/hour (32 F., 15 psi absolute pressure).  
  The catalysts of the invention are particularly well adapted to the dehydrogenation of alkanes, cycloalkanes, and arylalkanes containing from 2 to 12 carbon atoms. These hydrocarbons include ethane, propane, butane, isobutane, isopentane, heptane, hexanes. octanes, dodecanes, cyclohexane, cyclododecane, cyclopentane, ethylbenzene, n-butylbenzene, and the like, and mixtures thereof. In one embodiment of the invention, n-butane is dehydrogenated to a butene and butadiene-containing product.  
  During the dehydrogenation operation, the catalyst, which can be in any suitable form such as granules, pills, pellets, spheres, and the like, will slowly lose some activity and will periodically require regeneration by conventional means. This can be conveniently accomplished by cutting off the feed and treating the catalyst These data clearly indicate the operability of the invention and the exceptionally high selectivity characteristics of the catalyst, when the support is calcined for 2000 F. for 4 hours.  
 EXAMPLE ll Runs were conducted in order to demonstrate the increased selectivity obtained when the highly calcined catalyst of the invention is used in place of a conventional catalyst calcined below the calcination temperatures of this invention. In order to demonstrate the increased selectivity obtained when the catalyst is calcined according to the practice of this invention, a conventional support made in the same manner as in Example I, except calcined at the indicated temperature for the indicated time, was impregnated with platinum and lithium and tested for dehydrogenation with an nbutane stream, the results of which are indicated in Run 1 of Table 11. The practice of the invention was TABLE 11 Run 1 Run 2 Run 3 Run 4 Run 5 Run 6 Calcining Temperature, F. l 100 1600 2012 2012 2012 2282 Calcining Time. hours 4 5 5 5 12 platinum based on wt. of 0.25 0.1 0.25 0.25 0.25 0.25  
  support 7r lithium based on wt. of 0.25 0.25 0.25 0.25 0.25 0.25  
  support I? rhodium based on wt. of 0.066  
  support Pressure (psig) 95 95 95 95 95 95 Temperature (F.) 1046 1046 1042 1046 1045 1035 Hours on stream v 2.75 2.0 0.5 6.5 3. 3.25 GHSV (total) 1180 1255 1310 1300 1300 1320 mols of steam/mo] o1 nC H, 4.55 4.32 4.3 4.2 4.2 4.3 Conversion (/1 nC.,H,,,) 39.6 30.5 37.1 33.1 30. 24.9 Distribution of products in mol percent 1 olefin and diolefin 87.0 93.0 93.5 93.7 94.0 96.3  
 cracked products and carbon 13.0 7.0 6.5 6.3 6.0 3.7  
 oxides then demonstrated by selecting five separate portions 30 over a long period of time and after repated operationof the granular catalyst support of Example 1. calcining the support for the indicated time at the indicated temperature. and impregnating with platinum from chloroplatinic acid and lithium from lithium nitrate. The results are indicated in Runs 2. 3. 4. 5. and 6 in Table 11.  
  Analysis of the above data clearly indicates that the selectivity for olefin and diolefin is significantly higher when the platinum and lithium are supported on the highly calcined support of the invention (Runs 2 through 6 as opposed to the conventional support of 30 Run 1).  
 EXAMPLE 111 Additional runs were conducted to demonstrate the outstanding catalytic qualities of the catalyst made from a support which was prepared the same as in Example except that it was calcined at 2282 F. for 12 hours after which it was impregnated with sufficient chloroplatinic acid. lithium nitrate. and stannous chloride to produce a catalyst composition containing 0.25 weight percent platinum, 0.25 weight percent lithium. and 0.15 weight percent tin based on the weight of the support. This catalyst composition was then tested for dehydrogenation of an n-butane stream at 85 psig. at 10351045 F.. at a GHSV of 7000 (total), and at 4.3/1 to 4.8/1 molar ratio of steam to n-butane. The improved conversion and selectivity as well as the long life of the catalyst is illustrated by the data in the table below which shows the effectiveness of the catalyst TABLE 111 Support Calcined at 1 100 F. Support Calcined at 2282 F.  
 0.5 wt. 71 Li 0.25 wt. &#39;71 Li 0.15 wt. Sn  
  Total 7? 71&#34; Total 71 &#39;71 Cycle Hours Conv. Sel. Cycle Hours Conv. Sel.  
 &#39;to hutenes and butatlicne regeneration cycles with operating periods as long as 24 hours between regenerations. For purposes of comparison. similar data are also shown in the table with a catalyst system which is similar but which does not contain tin and whose zinc aluminate spinel support was not highly calcined.  
  The data in the table above show the high conversions and high selectivity in the invention dehydrogenation process. They further show that the catalyst is extremely long lived, being capable of repeated use and repeated regeneration while still retaining its high effectivcness. Still further. the decrease in activity within a cycle is much more gradual. In general. it is seen that the invention catalyst system and process is a very significant improvement over the prior art processes such as that shown above which does not employ a highly calcined support.  
 EXAMPLE 1V Several other hydrogenatable hydrocarbons were dehydrogenated using a catalyst and process of the present invention. The catalyst comprised a zinc aluminate spinel support which had been calcined at 1850-2280 F. The highly calcined support was then impregnated with platinum, tin, and lithium to the extent indicated in the table below. The table also contains theessential operating conditions of the tests as well as the results of the tests.  
  These data show that the catalyst system of the present invention is also very effective in dehydrogenating other feeds including branched alkanes.  
  Various modifications of the invention can be made by one reasonably skilled in the art from the disclosure and appended claims.  
 We claim:  
  1. A catalyst composition suitable for use in the dehydrogenation of a dehydrogenatable hydrocarbon having from 2 to 12 carbon atoms in the absence of free oxygen consisting essentially of a calcined support consisting essentially of at least one aluminate spinel composition having the formula M(AlO- or MO-Al O wherein M is selected from the group consisting of Group IIa or Group lIb metals, said support having been calcined at a temperature in the range of about l500 to about 2500 F. for from about I to about 100 hours; and  
  at least one Group VIII metal selected from the group consisting olnickel, platinum, palladium, ruthenium, iridium, rhodium, and osmium.  
 2. A catalyst composition according to claim 1 range of about 0.01 to about 5 weight percent, based on weight of said calcined support.  
  3. A catalyst composition according to claim 2 further including at least one Group Ia metal and at least one tin group metal selected from the group consisting of tin, germanium or lead.  
  4. A catalyst composition according to claim 2 wherein said aluminate spinel is zinc aluminate spinel.  
  5. A catalyst composition according to claim 3 wherein said tin group metal is present in an amount in the range of about 0.01 to about 5 weight percent, based on weight of support.  
  6. A catalyst composition according to claim 5 wherein said tin group metal is tin.  
  7. A catalyst composition according to claim 6 wherein said Group VIII metal is platinum.  
  8. A catalyst composition according to claim 7 wherein said aluminate spinel is zinc aluminate spinel.  
  9. A catalyst composition according to claim 8 wherein said zinc aluminate spine] is calcined at a temperature of 2282 F. for about 12 hours.  
  10. A catalyst composition according to claim 9 wherein the amount of said platinum is 0.25 weight percent, the amount of said tin is 0.15 weight percent. and the Group Ia metal is lithium. said lithium being present in an amount of 0.25 weight percent.