PROMOTED BISMUTH CERIUM MOLYBDATE CATALYSTS AND USE THEREOF IN OXIDATION-TYPE REACTIONS

Abstract: A bismuth cerium molybdate catalysts oxide complex catalyst contains a promoting amount of an alkali metal Tl, Sm, Ag, Cu, Cr, Sb, rare earth metal other than Ce and Sm, Te, Ti, Zr, Th or mixture thereof. Such catalyst provides high yields of acrylonitrile in the ammoxidation of propylene and give improved results in other oxidation-type reactions.

Description: PROMOTED BISMUTH CERIUM MOLYBDATE CATALYSTS AND USE THEREOF IN OXIDATION-TYPE REACTIONS The present invention relates to new catalyst systems for ammoxidizing propylene to produce acrylonitrile and for carrying out other oxidation-type reactions such as the oxidation of unsaturated olefins to produce the corresponding aldehydes and acids and the oxydehydrogenation of various olefins to produce diolefins. The catalytic ammoxidation of propylene to produce acrylonitrile is a well known process. Many different catalysts have been proposed for this process. While such catalysts are capable of providing excellent yields of acrylonitr.ile, it is always desirable to provide new catalysts especially effective in this reaction. Accordingly, it is an object of the present invention to provide new catalysts which are especially useful in the ammoxidation of propylene to produce acrylonitrile. In addition, it is a further object of the present invention to provide new catalysts which are also useful in other oxidation-type reactions such as the oxidation of acrolein and methacrolein to produce the corresponding unsaturated aldehydes and acids and the oxydehydrogenation,of various olefins such as isoamylenes to produce the corresponding diolefins such as isoprene. We have found that the incoporation of certain elements into known bismuth cerium molybdate redox catalysts remarkably enhances the catalytic properties of such catalysts for use in various oxidation-type reactions such as the ammoxidation ot propylene to produce acrylonitrile. Thus, according to the present invention, known bismuth cerium molybdate redox catalysts are improved by the incorporation therein of a promoting amount of an alkali metal, TI, Sm, Ag, Cu, Cr, Sb, rare earth, other than Ce and Sm, Te, Ti, Zr, Th or mixture thereof. In addition, the present invention provides an improvement in the known process for ammoxidizing propylene to produce acrylonitrile by contacting propylene, ammonia and molecular oxygen with a bismuth cerium molybdate oxidation catalyst at an elevated temperature, the improvement wherein at least one of the above-noted promoter elements are incorporated into the catalyst. Catalysts Bismuth cerium molybdate redox catalysts are known. See, for example, U.S. Patents 3,173,957; 3,262,962 and 3,316,182. In accordance with the invention is has been found that the incorporation of certain additional elements into such catalysts will improve the catalytic properties of these materials. Usually this improvement will be reflected in an increase in product yields, which is a measure of the amount of product produced based on the amount of reactant fed. In some instances, however, this improvement will be reflected in an increase in product selectivity, which is a measure of the ability of the catalyst preferentially to form the desired product as opposed to unwanted byproducts. In any event, incorporation of one or more of these elements, either by adding such elements to a known bismuth cerium molybdate base system or substituting these elements for a part of the bismuth and/or cerium in the known base system, will provide a catalyst with better catalytic properties than the corresponding base system. Furthermore, catalysts of the invention produce byproduct effluents with very low chemical oxidation demand (COD) and are thus environmentally superior to many known redox catalysts such as the iron bismuth molybdates. The elements found to be effective promoters in accordance with the invention are (I) Sm or a monovalent element such as alkali metals, T1, Ag and Cu, preferably K, Rb and/or Cs, (2) elements whose most common valence state is 4+, e.g. Te, Ti, Zr and Th, and (3) Cr, Sb and rare earths other than Ce and Sm, such as La, Y, Pr, Nd and Di. These elements can be incorporated into the bismuth cerium molybdate base systems alone or in admixture. The catalysts of the invention correspond to the following general formula RrQqAaBibCecWdVeMofOx (I) wherein A is alkali metal, T1, Sm, Ag, Cu or mixtures thereof, preferably K, Rb, Cs or mixtures thereof, Q is Ti, Zr, Th, Te or mixtures thereof, R is Cr, Sb or a rare earth element other than Sm and Ce, preferably La, Y, Pr, Nd, Di or mixtures thereof, and wherein a is O to 6, b is 0.01 to 24, c is 0.01 to 24, O d+e Cf, d+e+f is 8 to 16, q is O to 24, r is O to 24, a + q + r > O x is a number sufficient to satisfy the valence requirements of the other elements present, said catalyst being free of the combination of A and Te. Preferred catalysts are those in which a+q+r#b+c+2. Also preferred are catalysts which satisfy the relationship 2d+2e+2f=a+3b+3c+4q+3r+z wherein z -l0, preferably z'54. ot these those in which a > 0 are especially preferred. In this regard, catalysts of special interest are those containing Sm or a monovalent promotor, i.e. an A element and optionally Cr and/or Sb. These catalysts can be defined by the formula R A BibCecWdVeMOf0x (2) wherein A is alkali metal, T1, Sm, Ag, Cu-or mixtures thereof, preferably K, Rb, Cs or mixture thereof; and r = Cr and /or Sb wherein a is greater than zero to 6; b is 0.01 to 24; c is 0.01 to 24; r is O to 12 0 # d+e # f; d+e+f=8 to 16; and x is a number sufficient so that the valence requirements of the other elements present are r satisfied. Preferred catalysts of this type are those in which b+c' fed+e, more preferably those which satisfy the relation 1 # b+c # 5 2 f+d+e 6 Of these catalyst even more preferred are those in which d+e+t=12 to 12.5; a is 0.01 to 2; b is 1 to 11; and c is 1 to 11. r is 0 to 5. Still more preferred are those of the above catalysts in which a is 0.02 to less than 0.3, preferably 0.02 to 0.2. Another interesting group of catalysts containing the monovalent A promoter is those of the above formula (2) which satisfy the relation 2d+2e+2f=a+3b+3c+3r+z, wherein z' 6, 6 preferably 12. The above formulae in general describe the catalysts produced by the invention. However, as will be appreciated by those skilled in the art, such formulae descriptions do not connote that every material following therein will exhibit superior effectiveness as a catalyst. Rather such descriptions connote only that catalysts of the invention will have compositions corresponding to the above formulas. Those skilled in the art readily understand that a catalyst in order to exhibit good catalytic properties must have an appropriate balance of ingredients and that too much of any one element can drastically reduce its effectiveness or even inactivate the catalyst. The same considerations apply to this invention. The base catalyst systems must be compounded so as to have an appropriate balance of ingredients for catalyzing the specific reaction of interest. In addition, the exact amount of A, R or Q promoter element to be incorporated therein, either by adding the promoter to the existing system or substituting some of the Bi and/or Ce content of the base system with promoter, must also be appropriately selected. In accordance with the invention, the incorporation of the above-described A, R and Q elements into known bismuth cerium molybdate catalysts will exhibit a promoting effect on the catalysts in various oxidation-type reactions. Those skilled in the art can easily determine how much of a particular A, Q or R elements should be incorporated into a particular bismuth cerium molybdate base system to promote a particular oxidation-type reaction by simple routine experimentation, especially in view of the following working examples. Also, it has been found that some combinations of A, Q and R elements do not result in catalyst improvements but may indeed drastically reduce catalyst effectiveness. > For example, the inclusion of even very small amounts of potassium in a tellurium-containing catalyst will essentially inactivate the catalyst. Obviously, such combinations should also be avoided. The catalysts of the invention, at least in its preferred embodiment, are essentially single-phase systems being isostructural with lanthanum molybdate (La2Mo3012). See W. Jeitschko, Acta, Cryst. B29, 2074 (1973). They are therefore different from the known iron. bismuth molybdates which are multi-phase materials. z The catalysts of the invention can be used either in unsupported form or-supported on suitable carriers such as SiO2, A12D3, BPO4, SbPO4, ZrO2, TiO2, Alundum and the like. The catalysts can also be coated on these supports by special techniques known in the art. These catalysts can be prepared by conventional techniques such as disclosed in U.S. Patent No. 3,642,930. These catalysts are most easily prepared by slurry techniques wherein an aqueous slurry containing all of the elements in the obj-ective catalyst is produced, the water removed from the aqueous slurry to-form a precatalyst precipitate or powder and the precatalyst then heated in the presence of an oxygen-containing gas such as air at elevated temperature to calcine the precatalyst thereby forming the catalyst. Liquids other than water, such as C1 to C8 alcohols can also be used to form the precatalyst slurry. Ammoxidation The catalysts of the invention find significant use in the ammoxidation of propylene to produce acrylonitrile. This reaction is well known and described, for example, in the above-noted U.S. Patent 3,642,930. In general, the ammoxidation reaction is accomplished by contacting the reactant, oxygen and ammonia with a particular catalyst in the vapour phase. The reaction according to the invention is carried out in the same manner and under the conditions generally set fourth in that patent. In a preferred aspect, the process of the invention comprises contacting a mixture comprising propylene, ammonia and oxygen with the catalyst according to the invention at an elevated temperature and at atmospheric or near atmospheric pressure. Any source of oxygen may be employed in this process. For economic reasons, however, it is preferred that air be employed as the source of oxygen. From a purely technical view point, relatively pure molecular oxygen will give similar results. The molar ratio of oxygen to the olefin in the feed to the reaction vessel should be in the range of 0.5:1 to 4:1 and a ratio of about 1:1 to 3:1 is preferred. Low molecular weight saturated hydrocarbons do not appear to influence the reaction to an appreciable degree, and these materials can be present; consequently, the addition of saturated hydrocarbons to the reaction feed is within the scope of this invention. Likewise, diluents such as nitrogen and the oxides of carbon may be present in the reaction mixture without deleterious effect. The molar ratio of ammonia to olefin in the feed to the reactor may vary between about 0.05:1 to 5:1. There is no real upper limit for the ammonia/olefin ratio, but there is generally no reason to exceed the 5:1 ratio. At ammonia/olefin ratios appreciably less than the stoichiometric ratio of 1:1, various amounts of oxygenated derivatives of the olefin will be formed. Significant amounts of unsaturated aldehydes, as well as nitriles, will be obtained at ammonia-olefin ratios substantially below 1:1, i,. in the range of 0.15:1 to 0.75:1. Above the upper limit of this range, the amount of aldehydes produced rapidly decreases. Within the ammonia-olefin range stated, maximum utilization of ammonia is obtained and this is highly desirable. It is generally:. possible to recycle any unreacted olefin and unconverted ammonia. Water can also be included in the feed although it is not essential. In some instances, e.g. fixed-bed systems, water may improve the selectivity of the reaction ard the yield of nitrile. However, reactions not including water inthe feed are within the scope of the present invention and are preferred in the fluid-bed operation. In general, the molar ratio of added water to olef in, when water is added, is in the neighbourhood of 0.1:1 or higher. Ratios on the order of 1:1 to 6:1 are particularly desirable, but higher ratios may be employed, i.e. up to about 10:1. The reaction is carried out at an elevated temperature such as 200 to 6000C, preferably 4000C to 5500C, more preferably 4200C to 5000C. The reaction should be carried out at about atmospheric or slightly above atmospheric (2 to 3 atmospheres (2.02 to 3.03 bars)) f pressure. In general, high pressure, i.e. above 15 atmospheres.(15.19 bars) are not suitable since higher pressures tend to favour the formation of undesirable byproducts. The apparent contact time is not critical, and contact times in the range from 0.1-40 seconds may be employed. The optimal contact time will, of course, vary depending upon the reactant being used, but in general, contact time of from 1-15 seconds is preferred. The inventive ammoxidation reaction is carried out in the vapour phase. Normally, the process is conducted on a continuous basis using either a fixed-bed or a fluidbed catalyst. However, a batch operation can be employed. The reaction product passing out of the reactor is normally in the form of a vapour. Conventionally, this gaseous reaction product is treated to remove NH3 and then partially condensed either by indirect contact with a cooling medium or direct contact with water to form a liquid phase containing acrylonitrile, acrolein, acrylic acid, HCN and acetonitrile and a vapour phase containing CO2, CO, N2 and 02. The acrylonitrile is then separated from the liquid phase by a number of different techniques such as, for example, distillation or water extraction/ distillation. Additional steps can be employed to separately recover HCN and/or acetonitrile from the gross reaction product. In addition to propylene, other hydrocarbons and oxygenated hydrocarbons can be ammoxidized with the catalyst. of the invention. For example, alcohols such as isopropanol, n-propanol, t-butyl alcohol, and aldehydes such as acrolein and methacrolein can be readily converted to nitriles in accordance with the present invention. In addition to propylene, other preferred starting materials are aldehydes and alcohols containing three or four carbon atoms. The general ammoxidation process for converting olefins, alcohols and aldehydes to nitrile is well known and described for example in U.S. 3,456,138. Oxidation The catalysts of this invention can also be employed in the catalyst oxidation of olefins to various different reaction products. The reactants used in the oxidation to oxygenated compounds are oxygen and anolefinsuch as propylene, isobutylene and other olefins having up to three contiguous carbon atoms (i.e. three carbon atoms arranged in a straight chain). Instead of olefins, alcohols such as isopropanol, :1 n-propanol or tert-butanol can be used as reactants. The olefins or alcohols may be in admixture with paraffinic hydrocarbons, such as ethane, propane, butane and pentane. For example, a propylene-propane mixture may constitute the feed. This makes it possible to use ordinary refinery streams without special preparation. The temperature at which this oxidation is conducted may vary considerably depending upon the catalyst, the particular olefin being oxidised and the correlated conditions of the rate of throughput or contact time and the ratio of olefin to oxygen. In general, when operating at pressures near atmospheric, i.e. 0.1 to 10 atmospheres (0.102 to 10.13 bars), temperatures in the range of 150 to 6000C may be advantageously employed. However, the process may be conducted-at other pressures, and in the case where superatmospheric pressures, e.g. above 5 atmospheres (5.06 bars) are employed, somewhat lower temperatures are possible. In the case where this process is employed to convert propylene to acrolein, a temperature range of 200 to 5000C has been found to be optimum at atmospheric pressure. While pressures other than atmospheric may be employed, it is generally preferred to operate at or near atmospheric pressure, sirlce the reaction proceeds well at such pressures and the use of expensive high pressure equipment is avoided, and formation of undesired byproductN and waste is diminished. he apparent contact time employed in the process is not critical and it may be selected; from a broad operable range which may vary from 0.1 to 50 seconds. The apparent contact time may be defined as the length of time in seconds which a unit volume of gas measured under the conditions of reaction is in contact with the apparent unit volume of the catalyst. It may be calculated, for example, front the apparent volume of the catalyst bed,. the average temperature and pressure of the reactor, and the flow rates of the several components of the reaction mixture. The optimum contact time will, of course, vary depending upon the olefin being treated, but in the case of propylene and isobutylene, the preferred contact time is 0.15 to 15- seconds. A molar ratio of oxygen to olefin between about 0.5:1 to 5:1 generally gives the most satisfactory results. For the conversion of propylene to acrolein, a preferred ratio of oxygen to olefin is from about 1:1 to about 2.5:1. The oxygen used in the process may be derived from any source; however, air is the least expensive source of oxygen and is preferred for that reason. The addition of water to the reaction mixture in oxidation reactions can have a beneficial influence on the conversion and yields of the desired product especially in fixed-bed reactions. The manner in which water affects the reaction is not fully understood. In any event, it . is preferred in fixed-bed operation to include water in the reaction mixture, and in general a ratio of olefin to water in the reaction mixture of from 1:0.25 to 1:10 will give very satisfactory results while a ratio of 1:0.5 to 1:6 has been found the optimum when converting propyleneto acrolein. Inert diluents such as oxygen and carbon dioxide may be present in the reaction mixture. Oxydehydrogenation In accordance with the present invention, the catalyst system of the present invention can also be employed in the catalytic oxidative dehydrogenation of olefins to diolefins and aromatic compounds. In this process, the feed stream in vapour form containing the olefin to be dehydrogenated and oxygen is conducted over the catalyst at a comparatively low temperature to obtain the corresponding diolefin. By the term "olefin11 as used herein is meant open chain as well as cyclic olefins. The olefins deydrogenated in accordance with this invention have at least four and up to about nine nonquaternary carbon atoms, of which at least four are arranged in series in a straight chain or ring. The olefins preferably are either normal straight chain or tertiary olefins. Both cis and trans isomers, where they exist, can be dehydrogenated. Among the many olefinic compounds which can be dehydrogenated in this way are butene-l; butene-2; pentene i;; pentene-2; pentenes, hexenes, etc. such as 2-methylbutene-l, 2-methylbutene-2, 3-methylbutene-1, 2-methylpentene-1, 3-methylpentene-2, 4-methylpentene-2; heptene-l; 3,4-dimethyl-pentene-1; octene-l; cyclopentene; cyclohexene, 3-methyl cyclohexene and cycloheptene. Open chain olefins yield diolefins, and, in general six-membered ring olefins yield aromatic ring compounds. The higher molecular weight open chain olefins may cyclize to aromatic ring compounds. The feed stock in addition to the olefin and oxygen can contain one or more paraffins or naphthenic hydrocarbons having up to about ten carbon atoms, which may be present as impurities in some petroleum hydrocarbon stocks and which may also be dehydrogenated in some cases. The amount of oxygen can be within the range of from about 0.3 to about 4 mols per mole of double-bond created. Stoichiometrically, 0.5 mole of oxygen is required for the dehydrogenation of one mole of monolefin to a r diolefin. It is preferred to employ an excess of oxygen, e.g. an oxygen/olefin ratio of from 0.6 to about 3, in order to ensure a higher yield of diolefin per pass. The oxygen can be supplied as pure or substantially pure oxygen or as air. When pure oxygen is used, it may be desirable to incorporate a diluent in the mixture such as steam, carbon dioxide or nitrogen. The feed stock can be catalytically dehydrogenated in the presence of steam, but this is not essential. When steam is used, from about 0.1 to about 6 moles of steam per mole Of olefin reactant is employed, but amounts larger than this can be used. The dehydrogenation proceeds at temperatures within the range of from about 200 to 8000C. Optimum yields are obtainable at temperatures within the range from about 300 to 6000C. The preferred reaction pressure is approximately atmospheric, within the range of from about 0.1 to about 5 atmospheres (0.102-5.06 bars). Only a brief contact time with the catalyst is required for effective oxydehydrogenation. The apparent contact time with the catalyst can vary from about 0.1 up tc about 50 seconds but higher contact times can be used if desired. At the short contact times, comparatively small reactors and small amounts of catalyst can be used effectively. Process Conditions In carrying out the foregoing processes, any apparatus of the type suitable for carrying out the oxidation reactions in the vapour phase may be employed. The processes may be conducted either continuously or intermittently. The catalyst may be a fixed-bed employing a particulate or pelleted catalyst or, in the alternative, a fluid-bed catalyst may be employed which is normally micro-spheroidal. WORKING EXAMPLES In order to more thoroughly describe the present invention, the following working examples are presented. In these examples, the following definitions apply: moles product formed "Yield" means #################### x 100 "Selectivity" means ################### x 100 moles reactant reacted In each of the examples and comparative example, a catalyst having the composition set forth in the following tables was prepared in accordance with a standard laboratory preparation. For example, the catalyst of Examples 1 to 3 was prepared as follows: 42.55 gms. of ammonium heptamolybdate was dissolved in about 100 ml. of distilled water. To this was added 41.59 gs. of a 40% silica sol. In a separate beaker, 38.81 gums. of Bi(NO3)35H20, 43.86 gms. of (NH4)4Ce(NO3)6 and0.20 gms KNO3 were dissolved in 10% aqueous nitric acid. The metal nitrate solution was then slowly added to the ammonium heptamolybdate/silica sol mixture along with approximately 50 ml. of distilled water and the pH of the mixture was adjusted to 3.0 by the addition of concentrated NH40H. The mixture was then refluxed for 3 hours. After approximately 30 minutes of reflexing, the mixture began to thicken and accordingly an additional 150 ml. of distilled water was added. After reflexing, the mixture was evaporated to dryness on a hotplate, dried at 1200C for 16 hours and then calcined at 2900C for 3 hours and then at 4250C for 3 hours. The partially calcined catalyst was then ground, screened to 25 to 35 mesh and then calcined at 5500C for 16 hours to produce the desired catalyst. Examples 1 to 10 and Comparative Examples A to C Eight catalysts according to the invention and three comparative catalysts-were-tested in the known V ammoxidation reaction for producing acrylonitrile from propylene. In -each example and comparative example, 5 cc. of the catalyst was charged into a 6 cc. reactor and contacted with a feed comprising 1 propylene/l.l NH3/ 10.6 air/4 H2O at elevated temperature for a contact time of 3 seconds. The gross reaction product recovered from each experiment was then analyzed. The composition of the catalysts, the reaction temperatures and the results obtained are set forth in the following Table 1. Table 1 Ammoxidation of Propylene Feed: 1 propylene/l.l NH3/10.6 air/4 H2O Contact Time: 3 seconds 3 Catalyst Support: 20% SiO2 AN HCNk Ex Temp Propy Selec Yield Yield No Catalyst Composition (C) Conv to An (%) (%) 1 K0.1Bi4Ce4Mo12.05 X 430 83.6 78.4 65.5 3.1 2 " 445 92.8 81.5 75.6 3.3 3 " 460 99.3 80.4 79.8 3.1 4 K0.05CS0.02Bi4Ce4 460 95.2 82.5 78.5 2.5 0.03 0.02 g g Mo12.03Ox 5 Tl0.03Bi4Ce4Mo12Ox 460 98.8 80.3 79.3 3.4 6 Cs0.02Bi4Ce4Mo12Ox 445 98.4 75.6 74.4 3.6 7 K0.1Bi9Ce1Mo12Ox 460 95.5 83.0 79.3 2.5 8 K 0.05Bi4Ce4W2Mo10 460 98.5 81.8 80.5 3.1 0 x A Bi4Ce4Mo12O 430 100.0 65.8 65.8 3.0 x B " 460 100.0 71.5 71.5 2.9 C Bi4Ce4W2Mo10Ox 430 98.6 70.5 69.5 3.5 D Bi9Ce1Mo12Ox 460 75.7 71.9 3.1 9 Cs0.04Bi4Ce4W4Mo8Ox* 460 99.5 82.2 81.8 3.1 10 Cs0.05Bi4Ce4W2Mo12* 460 96.5 81.6 78.8 2.8 11 Cs0.04Bi4Ce4Sb1W2Mo10Ox* 460 97.9 81.7 80.0 2.0 * Catalyst contained 508 SiO2 and was calcined at 650 C. From the foregoing, it can be seen that the catalysts of the invention provide significant yields of acrylonitrile when used in the conventional ammoxidation reaction. Thus, these catalysts are of significant commercial interest in this field. Moreover, these catalysts are also advantageous because they are redox stable and they provide an environmentally acceptable effluent (i.e. a byproduct effluent with a very low COD). Comparative Examples E Example 3 was repeated except that the bismuth content of the catalyst was replaced with tellurium. The results obtained, as well as the results of Example 3 and Comparative Example B, are set forth in the following Table 2. Table 2 Ex AN Selec Temp Yield to AN No Catalyst (+20 SiO2) Temp Lel B Bi4Ce4Mo12O 460 71.5 71.5 x 3 K 01Bi4Ce4Mo12O 460 79.8 80.4 x E K0.1Te4Ce4Mo12Ox 460 10.4 24.2 The above table shows that the addition of alkali metal to the known bismuth cerium molybdate catalyst significantly improves the ability of the catalyst to produce acrylonitrile. In addition, this table further shows that the addition of alkali metal to a corresponding tellurium cerium molybdate catalyst effectively inactivates the catalyst. Specifically, Example 3 and Comparative Example E show that bismuth and tellurium are not equivalent in this system. Examples 12 to 29 and Comparative Examples F to H Examples 1 to 10 were repeated using various different R and Q promoters of the invention. In these examples a portion of the cerium and/or-bismuth was replaced with the R or Q element so that a stoichiometric balance with respect of molybdenum could be maintained. The results are set forth in the following Table 3. Table 3 Ammoxidation of Propylene Feed: 1 propylene/l.l NH3/10.6 air/4 H2O Contact Time: 3 seconds 2 Catalyst Support: 20 % SiO2 AN HCN Ex Temp Propy Selec Yield Yield No Catalyst Composition ( C) Conv to AN (%) (%) 12 Cr2Ce2Bi4Mo12Ox 430 94.4 77.2 72.9 3.4 13 " " 445 98.6 74.9 73.8 3.6 14 K0.05Cr2Ce2Bi4 460 89.5 77.6 69.4 2.6 Mo12.03Ox 15 Te2Ce2Bi4Mo12Ox 430 98.9 72.2 71.4 3.4 F K0 0.05Te2Ce2Bi4 460 68.2 50.0 34.1 0.2 Mo12.03Ox 16 La2Ce2Bi4Mo12Ox 430 98.7 67.3 66.4 3.1 G La4Bi4Mo12Ox 430 94.6 56.0 53.0 3.7 17 K0.05La2Ce2Bi4 430 93.4 77.5 72.4 3.0 Mo12.030x 18 " 445 98.1 77.1 75.6 3.0 19 K0 0.1 La2Ce2Bi4Mo12.05 430 75.4 83.8 63.2 3.0 0 x 20 " 460 90.5 81.3 73.6 2.6 21 K0.1La4Ce2Bi2Mo12.05 445 95.7 75.3 72.1 3.0 Ox x r 22 II 460 98.8 75.1 74.2 3.0 23 K0.1La6Ce1Bi1Mo12.05 460 92.1 70.7 65.1 2.6 x x 24 Y2Ce2Bi4Mo12Ox 420 92.4 67.3 62.2 3.9 25 K0.05Y2Ce2Bi4Mo12.03 460 98.7 76.3 75.3 2.8 Ox x 26 K0.1Pr2Ce2Bi4Mo12.05 460 94.7 76.2 72.1 6.9 0 x 27 K0.1Nd2Ce2Bi4Mo12.05 460 97.6 75.8 74.0 2.9 Ox 28 K0.1Di2Ce2Bi4Mo12.05 430 93.7 76.8 72.0 2.5 Ox x 29 Cr2Ce3Bi4Mo120x 430 98.7 68.4 67.5 2.7 H Cr2Ce3Te4Mo12Ox 430 46.0 . 75.5 34.7 0.5 From the above Table 3 it can be seen that the various R and Q elements set forth above also exert a promoting effect on bismuth cerium molybdate catalysts. In addition, it can be seen that alkali metal, specifically potassium, tends to decrease the activity (conversion) of catalysts but that this activity decline can be largely ameliorated by increasing the temperature without significant loss of acrylonitrile selectivity. However, even at very low concentrations, potassium essentially inactivates a tellurium containing catalyst in that not only is the activity of the catalyst significantly reduced but also its selectivity. Examples 30, 31 and Comparative Example I A number of catalysts were used to ammoxidize propylene to produce acrylonitrile and a waste effluent, which was tested to determine chemical oxidation demand. In each example, the gross reactor effluent was scrubbed with aqueous sodium phosphate and the scrubber solution then vacuum distilled to remove acrylonitrile, HCN and acetonitrile. After diluting with water back to original volume, the scrubber solutions were analysed for COD by a technique essentially the same as ASTM D1252. The compositions of the catalysts and the relative COD's obtained are set forth in the following Table 4. In this table, the COD of the prior art iron bismuth molybdate catalyst is taken as 1.00 and the COD's of the other catalysts compared thereto. Table 4 Relative Chemical Oxygen Demand Ex No Catalyst Composition Relative COD I 50 % K0.1Ni2.5Co4.5Fe3BiP0.5Mo12Ox + 50 % SiO2 1.00 30 50% Cs0.04Bi4Ce4Mo8W4Ox 2 50 % SiO2 0.46 31 80% Ko lBi4Ce4Mol2Ox + 20 % SiO2 0.42 Table 4 shows that the catalyst of the invention are vastly superior to known complex bismuth molybdate in terms of producing environmentally acceptable effluents. Thus, it will be appreciated that the catalysts of the invention are particularly attractive from a commercial standpoint in that they provide both excellent produce yields (Example 3 and 9 above) and much cleaner waste effluents than known bismuth molybdates. Although only a few embodiments of the present invention have been described above, it should be appreciated that many modifications can be made without departing from the spirit and scope of the invention. All such modifications are intended to be included within the scope of the present invention, which is to be limited only by the follpwing claims:

Claims: CLAIMS 1. A bismuth cerium molybdate oxide complex catalyst characterised in that it contains a promoting amount of an alkali metal, T1, Sm, Ag, Cu., Cr, Sb, rare earth metal other than Ce and Sm, Te, Ti, Zr, Th or mixture thereof. 2. A catalyst as claimed in claim 1 containing alkali metal. 3. A catalyst as claimed in claim 1 or claim 2, characterised in that it is a single-phase material isostructural with lathanum molybdate. 4. In a bismuth cerium molybdate oxide complex catalyst for use in an oxidation-type reaction to produce a desired end-product, said catalyst having the formula Bi ibCecMOfOx wherein b is 0.01 to 24; c is 0.01 to 24; f is 8 to 16; and x is a number sufficient to satisfy the valence requirements of the other elements present, the improvement wherein saidscatalyst further contains a promoter selected from the group consisting of alkali metal, T1, Sm, Ag, Cu, Cr, Sb, rare earth other than Ce and Sm, Te, Ti, Zr, Th or mixture thereof, the amount of said promoter in said catalyst being sufficient to increase the ability of the catalyst to produce said end-product in said oxidation-type reaction, said catalyst being free of iron. 5. A catalyst as claimed claim 4 characterised in that the promoter is alkali metal, TI, Sm, Ag, Cu or mixture thereof. 6. A catalyst as claimed in claim 4 or 5 characterised in that it has the formula: RrQqAaBibCecWdVeMofOx wherein A is alklai metal, Tl, Sm, Ag, Cu or mixtures thereof; Q is Te, Ti, Zr, Th or mixtures thereof; R is Cr, Sb-or a rare earth element other than Ce and Sm or mixtures thereof; and wherein a is 0 to 6, b is 0.01 to 24, c is 0.01 to 24, O # d+e # f, d+e+f is 8 to 16, q is 0 to 24, r is 0 to 24, a + q + r > 0 x is a number sufficient to satisfy the valence requirements of the other elements present, said catalyst being free of the combination of A and Te. 7. A catalyst as claimed in claim 6 characterised in that 2d+2e+2f=a+3b+3c+4qi3r+z wherein ZAlO. 8. A catalyst as claimed in claim 6 characterised in that said catalyst has the formula RrAaBibCecWdVeMofOx wherein A is alkali metal, T1, Sm, Ag, Cu or mixture thereof, R is Cr and/or Sb, and wherein a is greater than zero to 6; b is 0.01 to 24; c is 0.01 to 24; R is 0 to 12, O # d+e # f. 9. A catalyst as claimed in claim 8 characterised in that A is K, Rb, Cs or mixture thereof. 10. A catalyst as claimed in claim 9 characterised in that b+c # f+d+e. 11. A catalyst as claimed in claim -9 characterised in that 1 # b+c 5 2 f+d+e 6 12. A catalyst as claimed in claim 11 characterised in that d+e+f=12 to 12.5; a is 0.01 to 2; b is 1 to 11; and c is 1 to 11, r is 0 to 5. 13. A catalyst as claimed in claim 12 characterised in that a is 0.02 to less than 0.3. 14. A catalyst as claimed in claim 13 characterised in that 2d + 2e + 2f = a + 3b + 3c +z, wherein z # 6. 15. A catalyst as claimed in claim 8 characterised in that 2d+2e+2f=a+3b+3c+z, wherein z4-6. 16. A catalyst as claimed in claim 15 characterised in that the catalyst is a single-phase material isostructural with lanthanum molybdate. 17. - A process for ammoxidizing propylene to produce acrylonitrile wherein propylene, ammonia and an oxygencontaining gas are contacted with an oxidation catalyst at elevated temperature to produce said acrylonitrile, characterised in that there is used as catalyst an oxide complex as claimed in any of claims 1 to 16. 18. An oxidation process for oxidizing an olefin to unsaturated aldehyde-and/or acid having no more than 13 contiguous carbon atoms wherein the olefin and oxygen are contacted at elevated temperature in the vapour phase with a catalyst to form the corresponding unsaturated aldehyde and/or acid, characterised in that there is used as catalyst an oxide complex as claimed in any of claims 1 to 16. 19. An oxydehydrogenation process wherein an olefin having four or more contiguous carbon atoms and oxygen are contacted at elevated temperature in the vapour phase with a catalyst to produce the corresponding diolefin, characterised in that the catalyst used is an oxide complex as claimed in any of claims 1 to 16.

Inventors: BRAZDIL, JAMES FRANK, GRASSELLI, ROBERT KARL, SURESH, DEV DHANARAJ
Applicants: THE STANDARD OIL COMPANY
Application year: 1982
Main classification: B01J23
IPC codes: C07C51, C07C1, C07C45, B01J23, C07C57, B01J27, C07C255, C07C5, C07C67, C07C253, C07C47, C07C11, C07B61