OXIDATION AND AMMOXIDATION CATALYSTS AND THEIR USES

Abstract: Disclosed herein are catalysts useful for oxidation and ammoxidation of hydrocarbons. Such catalysts have the empirical formula BiMo a M b Sb c O x wherein a is 0.5-2, b is 0.05-1, c is 0.1-1.5 and x is selected to satisfy the valence requirements of the other elements present. In such catalysts, M is a metal element selected from Mn, Mg, Ag, Cr, Pb, Fe, Sn, Zn, Ce, Co, Ni, In, Ti, Zr, Tl and U. Catalysts according to the invention are prepared by forming a mixture of a metal antimonate component, a bismuth molybdate component, and optionally a support material and calcining to form the catalyst. Such catalysts are specifically useful for production of acrylonitrile from propylene, ammonia and an oxygen-­ containing gas.

Description: BACKGROUND OF THE INVENTION This invention relates to oxidation and/or ammoxidation catalysts containing the elements bismuth, molybdenum, antimony, an additional element, oxygen, and to a method of preparing such catalysts. In another aspect, this invention relates to a process employing such catalysts. It is well known that olefins can be oxidized to oxygenated hydrocarbons such as unsaturated aldehydes and acids, for example, acrolein and methacrolein, and acrylic and methacrylic acid. It is also well known that olefins can be ammoxidized to unsaturated nitriles such as acrylonitrile and methacrylonitrile. The value of such oxygenated hydrocarbons and unsaturated nitriles is generally well recognized with acrylonitrile being among the most valuable monomers available to the polymer industry for producing useful polymeric products. Various catalytic processes are known for the oxidation and/or ammoxidation of olefins. Such processes commonly react an olefin or an olefin-ammonia mixture with oxygen in the vapor phase in the presence of a catalyst. For the production of acrolein and acrylonitrile, propylene is the generally used olefin reactant and for the production of methacrolein and methacrylonitrile, isobutylene is the generally used olefin reactant. Many catalysts are disclosed as suitable in the foregoing reactions. One such catalyst is described in U.S. Patent 3,681,421. This catalyst employs oxides of antimony, vanadium, and at least one additional polyvalent metal in the proportion of 1 gram atom of antimony, 0.12-0.5 gram atoms of vanadium, and 0.25-0.5 gram atoms of the additional polyvalent metal. Under the conditions of the examples of this patent, a yield of 56% of acrylonitrile was obtained using propylene, ammonia, air and steam as reactants. More recently, U.S. Patent 4,093,558 discloses a catalyst composed of combined oxides of antimony, molybdenum, one of the group of iron and vanadium, and option ally one or more of a number of elements including bismuth. This catalyst is particularly useful for preparing maleic anhydride from butane by oxidative dehydrogenation. Preparation of ammoxidation catalysts by preforming bismuth molybdate and then mixing the preformed bismuth molybdate with other elements is disclosed in U.S. Patent 4,040,978. It is well known that the economics of acrylonitrile manufacture dictate increasingly higher yields and selectivity of conversion of the reactants to acrylonitrile in order to minimize the difficulties attending purification of the product and handling of large recycle streams. Moreover, it is known that prior art catalysts frequently produce relatively large quantities of undesired oxygen-containing by-products such as CO2, acrolein and/or acrylic acid which must be removed in purification of the acrylonitrile. SUMMARY OF THE INVENTION It is an object of this invention to provide a novel catalyst composition useful in the preparation of unsaturated aliphatic nitriles by ammoxidation of aliphatic olefins. Yet another object is to provide a catalyst which is useful for oxidation of aliphatic olefins to the corresponding unsaturated aldehyde. A more specific object of this invention is to provide a catalyst which gives surprisingly higher yields and selectivity of conversion of propylene, ammonia and air to acrylonitrile than do prior art catalysts. It is a further object to provide a catalyst which minimizes the production of oxygenated by-products of acrylonitrile, such as CO2, acrolein, acrylic acid and the like. Still another object is to provide a catalyst which exhibits substantially its full activity immedi- ately upon startup of an ammoxidation process, i.e., which requires no break-in period under ammoxidation conditions in order to exhibit its full efficiency in terms of activity and selectivity. A further object of this invention is to provide a process for manufacture of such a catalyst. In another aspect, it is an object of this invention to provide an ammoxidation process which employs such a catalyst. To achieve these and other objects which will become apparent, a catalyst is provided having the empirical formula of BiMoaMbSbc0x wherein a is from 0.5 to 2.0, b is from 0.05 to 1.0, c is from 0.1 to 1.5, and x is chosen to satisfy the valence requirements of the other elements present, and wherein M is selected from Mn, Mg, Ag, Cr, Pb, Fe, Sn, Zn, Ce, Co, Ni, In, Ti, Zr, T1 and U. According to the present invention, such a catalyst is prepared by forming a bismuth molybdate, forming a metal antimonate, mixing these two component compounds and calcining the resultant mixture. As used herein, the term "bismuth molybdate" means a chemical compound of bismuth, molybdenum and oxygen. Such compounds may be formed by the interaction of bismuth compounds in which bismuth acts as a cation with salts of molybdic acids such as ammonium molybdate, for example. The "bismuth molybdate" component of catalysts according to this invention may contain oxides of bismuth and/or molybdenum, in addition to bismuth molybdate compounds. Likewise, as used herein, the term "metal antimonate" is employed to designate complex mixtures of the selected metal, antimony and oxygen. Compounds which may be formed by the interaction of antimony compounds and the selected metal compounds are intended to be included within the term "metal antimonate'1 as used herein. The "metal antimonate" component of these catalysts may contain free oxides of antimony and/or the selected metal. The metal antimonate component may be a compound which is formed under conditions of calcination in air at elevated temperatures; however, as used herein, the term metal antimonate also includes precursors of true metal antimonate compounds. Such precursors are preferably formed by preparing an aqueous slurry of a metal compound and an antimony compound. The slurry is boiled until the contained solids have had an opportunity to react to form a metal antimonate precursor. The metal antimonate precursor may, if necessary, be calcined to form a true metal antimonate compound as will be more fully explained hereinafter. The bismuth molybdate component of catalysts according to this invention is preferably prepared by forming an aqueous solution of a bismuth salt, forming an aqueous solution of a molybdenum-containing salt, oxide or hydroxide, combining these two solutions, and recovering the precipitated bismuth molybdate by filtration or decantation. Suitable bismuth compounds include, but are not limited to bismuth metal when used as a solution with nitric acid, bismuth oxide, bismuth trinitrate, pentahydrate and bismuth halides when hydrolyzed. Similarly, suitable molybdenum compounds include molybdenum trioxide, molybdic acid, ammonium molybdates, such as ammonium dimolybdate and ammonium heptamolybdate and molybdenum halides. The bismuth molybdate component of catalysts according to this invention is preferably prepared in the absence of the metal antimonate component. However, the bismuth molybdate component may, if desired, be prepared in the presence of preformed metal antimonate. It is known that bismuth molybdate may exist in alpha, beta and gamma forms or phases. An interesting and informative source of information on these forms of bismuth molybdate is found in Journal of SoLid- State Chemist Vol. 13, pp. 228-297 (1975), authored by Tu Chen and G. S. Smith. The alpha bismuth molybdate has the molecular formula Bi2(MoO4)3, while the beta form is Bi2Mo2O9 and the gamma form has the formula Bi2MoO6. Particularly preferred catalysts according to this invention employ predominantly the beta bismuth molybdate phase with lesser amounts of the alpha phase present. The metal antimonate component of these catalysts is preferably formed by addition of a metal-containing compound to an aqueous slurry of an antimony-containing compound and drying the resultant slurry. In a preferred preparation, the metal and antimony compounds are the oxides. The slurry is boiled until the contained solids exhibit a color change indicating the interaction or partial reaction of the two metal compounds to form a precursor of the metal antimonate. In a particularly preferred embodiment of this invention, the metal antimonate precursor is dried and calcined for one-half to 24 hours at a temperature of 500 to 8000C, preferably 550 to 750 0C to form a stable metal antimonate compound. Although it is preferred to use the oxides of the metal and antimony as described above in preparing the antimonate component of the catalyst, other antimony and metal-containing compounds may be employed. Exemplary of such antimony compounds are antimony trioxide, antimony tetroxide, antimony pentoxide and antimonic acid. Compounds which form an oxide of antimony after chemical reaction or calcination are also suitable, for example, metallic antimony, antimony hydroxides and antimony halides, such as antimony trichloride, tribromide and antimony pentachloride. Suitable metal compounds include the oxides, nitrates, acetates, oxalates and halides. Following preparation of the bismuth molybdate and metal antimonate components to the catalyst, these components are preferably combined in the desired proportions in an aqueous slurry and well mixed. At this point a suitable catalyst support may be added, if desired, as described below. The slurry, after intimate mixing, is then heated to remove the bulk of the aqueous phase. The concentrated slurry contains a certain amount of water and it is desirable to remove this water by some form of drying process to form a dry catalyst precursor. This can take the form of a simple oven-drying process in which the water containing solid phase is subjected to a temperature that is sufficiently high to vaporize the water and completely dry the solid phas-e. An alternate drying process which may be employed is the so-called spray-drying process in which water-containing solid phase particles are sprayed into contact with hot gas (usually air) so as to vaporize the water. The drying is controlled by the temperature of the gas and the distance the particles travel in contact with the gas. It is generally undesirable to adjust these parameters to achieve too rapid drying as this results in a tendency to form dried skins on the partially dried particles of the solid phase which are subsequently ruptured as water occluded within the particles vaporized and attempts to escape. By the same token, it is desirable to provide the catalyst in a form having as little occluded water as possible. Therefore, where a fluidized bed reactor is to be used and microspheroidal particles are desired, it is advisable to choose the conditions of spray-drying with a view of achieving substantially complete drying without particle rupture. Following the drying operation, the catalyst precursor is calcined to form the catalyst. The calcination process is usually conducted in air at essentially atmospheric pressure and at a temperature of about 5000 to about 8000C, such as from about 5250C to about 650Or The time to complete the calcination can be anything up to 10 hours, but for most purposes, the calcination need take only from about 1 to 2 hours. In some applications, it may be advantageous to include in the catalyst a support material which functions by providing a large surface area for the catalyst and by creating a harder and more durable catalyst for use in the highly abrasive environment of a fluidized bed reactor. This support material can be any of those commonly proposed for such use, such as, for example, silica, zirconia, alumina, titania, antimony pentoxide sol or other oxide substrates. From the point of view of availability, cost and performance, silica is usually a satisfactory support material and is preferably in the form of silica sol for easy dispersion. In a less preferred embodiment of this invention, the metal antimonate component and bismuth molybdate component of the catalyst may be mixed in dry form, optionally, with a support material and then calcined in air. The proportions in which the components of the supported catalyst are present can vary widely, but it is usually preferred that the support provides from 10 to 90% and more preferably about 35 to 60% by weight of the total combined weight of the catalyst and the support. To incorporate a support into the catalyst, the support material is preferably added to the slurry containing the active components discussed above. As has been stated, catalysts according to this invention are those having the empirical formula BiMoaMbSbcOx, where a is from 0.5-2, b is from 0.05-1, c is from 0.1-1.5 and x is taken to satisfy the valence requirements of the other elements present. In more preferred embodiments of such catalysts, a is from 0.7-1.5, b is from 0.08-1 and c is from 0.1-1.2. The catalyst preparation of the invention yields a catalyst that is particularly useful in the production of acrylonitrile from propylene and in which follows specific reference is made to that process although it should be understood that the described catalyst is also useful for ammoxidation of other olefins and for oxidation of aliphatic olefins to aldehydes and acids. In the most frequently used ammoxidation processes, a mixture of olefin, ammonia and oxygen (or air) is fed into a reactor and through a bed of catalyst particles. The reaction temperature is usually in the range of 4000C to 5500C and preferably 45OOC to 525OC, and the pressure is 1 to 6 atmospheres (101 to 608 kPa). The ammonia and olefin are required stoichimetrically in equimolar amounts, but it is usually necessary to operate with a molar ratio of ammonia to olefin in excess of 1 to reduce the incidence of side reactions. Likewise, the stoichiometric oxygen requirement is 1.5 times the molar amount of olefin. The feed mixture is commonly introduced into the catalyst bed at a-W/F (defined as the weight of the catalyst in grams divided by the flow of reactant stream in ml/sec. at standard temperature and pressure) in the range of about 2 to about 15, preferably from about 4 to about 10. The ammoxidation reaction is exothermic and for convenience in heat distribution and removal, the catalyst bed is desirably fluidized, however, fixed catalyst beds may be employed with alternative heat removal means such as cooling coils within the bed. The catalyst prepared by the process of the present invention is particularly well adapted for use in such a process and in which follows its effectiveness and advantages over prior art catalysts are demonstrated in the context of that process. SPECIFIC EMBODIMENTS As has been stated above, the catalyst of the invention has the empirical formula BiMOaMoSbcOx, wherein a is from 0.5 to 2.0, b is from 0.05 to 1.0 and c is from 0.1 to 1.5 and x is a number taken to satisfy the valence requirements of the other elements present in the catalyst and wherein M is selected from Mn, Mg, Ag, Cr, Pb, Fe, Sn, Zn, Ce, Co, Ni, In, Ti, Zr, U and Tl, optionally dispersed on a finely divided support which represents from 10 to 90% of the supported catalyst weight. In the examples that are presented below, specific compositions within this range were prepared and employed as catalysts in the ammoxidation of propylene to produce acrylonitrile. As used in the following examples, the following terms are defined in the following manner: 1. "W/F" is defined as the weight of the cata lyst in grams divided by the flow rate of reactant stream in ml/sec. measured at S.T.P. 2. "Propylene (C3H) conversion" is defined as: Mols C3H6 in feed - mols C3H6 in effluent X 6 3 6 X 100% Mols C H in feed 3. "Acrylonitrile (AS selectivity" is defined as: Mols AN in effluent X 100% Mols C H converted 4. "Acrylonitrile (AN) yield" is defined as: Mols AN formed X 100% Mols C3H6 feed In the following examples, unless otherwise noted, the catalysts of the examples were evaluated to determine acrylonitrile selectivity and yield and propylene conversion in a fluidized bed reaction vessel having an inside diameter of about 13 millimeters. Approximately 25 grams of catalyst was used in each case. A reactant mixture of 17-17.8 volume % 02' 7.6-8.3 volume % propylene (C3H6), 8-9 volume % NH3, and the balance helium was passed upward through the catalyst bed at a rate sufficient to give the value of W/F shown in the experimental results for each example. The temperatures shown in the examples are expressed in degrees Celsius and in each instance the pressure at which the reaction was carried out was 205 kPa. In each of the following examples the bismuth molybdate and the final catalyst were prepared according to the following generalized procedures. The metal antimonate component of each catalyst was prepared by a standardized procedure differing from example to example only in the specific metal compound employed as the metal source and in the calcination conditions for the antimonate component. Preparation of Bismuth Molybdate Component 100 grams of molybdenum oxide (MoO3) were dissolved in a mixture of 1000 ml of water and 150 ml of concentrated (58%) ammonium hydroxide, added to a solution of 340 grams of bismuth nitrate pentahydrate in # 200 ml of water and 200 ml of concentrated nitric acid with stirring and the pHof the resulting mixture was adjusted to about -- 3.65 using 29% ammonium hydroxide and diluted to a total volume of 3500 ml with water. The slurry was then heated and stirred for approximately 3 hours. The resulting precipitate was filtered and washed thoroughly with distilled water. Preparation of Antimonate Component A slurry was formed of Sb203 and distilled water in the approximate ratio of 1 gram Sb203 to 1 ml water. To this slurry was added the metal compound shown in the following Table (Column 2) which had previously been finely ground in a mortar and pestle. The resultant slurry was heated at 50-800C with stirring until almost dry and then heated to about 130 0C for several hours to dry it thoroughly. Finally, the dried metal antimonate precursor was calcined in air for two hours at the temperature shown in the following Table (Column 3). The only exception to the two-hour calcination was in Example 2 n which the manganese antimonate precursor was calcined. for 6 hours. Preparation of Catalyst A slurry of 90 grams of a silica sol containing 40% silica was adjusted to a pH of 3.5 with 10% nitric acid and added with vigorous stirring to the appropriate amount of bismuth molybdate component prepared as above. The antimonate component was then added to the prescribed amount. The catalyst mixture was stirred and heated to obtain a homogeneous dispersion of ingredients. The mixture was thoroughly tray dried and then calcined at 550 0C for one hour in air to obtain the final catalyst having catalytic elements in the atomic proportions reported in the examples. TABLE ANTIMONATE COMPONENT FINISHED CATALYST CATALYST PERFORMANCE STARTING CALCINATION EMPIRICAL SILICA TEMP %AN %AN %PROPYLENE EXAMPLE METAL COMPOUND TEMP. ( C) FORMULA (%) W/F ( C) YIELD SELECTIVITY CONVERSION 1 MnO2 700 BiMo1Mn0.5Sb1Ox 50 5.4 465 69 74 93 2 Mn(C2H3O2)#4H2O 6 hrs BiMa1Mn0.375Sb0.75Ox 42 4.8 472 72 75 95 &commat; 700 3 CeO2 650 BiMo1Ce.25Sb1Ox 50 4.0 455 67 71 95 4 CeO2 650 BiMo1Ce.4Sb1Ox 50 5.0 470 69 72 96 5 Ce(NO3)4#(NH4NO3)2 6 hrs BiMo1Ce.48Sb1Ox 45 5.2 460 65 71 92 &commat; 750 6 PbO2 700 BiMo1Pb.5Sb1Ox 50 7.0 455 54 67 81 7 PbO2 700 BiMo1Sn.25Sb1Ox 50 6.5 455 64 73 88 8 SnO 800 BiMo1Sn.33Sb1Ox 45 3.2 470 70 75 94 9 Fe(NO3)3#9H2O 750 BiMo1Fe.33Sb1Ox 45 4.2 470 71 76 93 10 ZnCO3 750 BiMo1Zn.25Sb1Ox 45 3.2 475 71 74 95 11 Ag2CO3 800 BiMo1Ag.05Sb.5Ox 45 3.9 475 73 77 95 TABLE ANTIMONATE COMPONENT FINISHED CATALYST CATALYST PERFORMANCE STARTING CALCINATION EMPIRICAL SILICA TEMP. %AN %AN %PROPYLENE EXAMPLE METAL COMPOUND TEMP.( C) FORMULA ( C) W/F ( C) YIELD SELECTIVITY CONVERSION 12 Ag2CO3 800 BiMo1Ag0.1Sb1Ox 45 5.0 465 73 76 95 13 Ag2CO3 600 BiMo1Ag0.25Sb1Ox 50 5.4 465 66 73 91 14 CrO3 700 BiMo1Cr0.25Sb.5Ox 45 5.1 457 73 77 95 15 CrO3 700 BiMo1Cr.5Sb1Ox 45 6.5 450 70 75 94 16 CrO3 600 BiMo1Cr.25Sb1Ox 50 4.0 465 71 75 95 17 MgCO3 650 BiMo1Mg.25Sb.5Ox 45 2.9 480 72 76 95 18 MgCO3 650 BiMo1Mg.5Sb1Ox 45 3.8 465 69 74 94 19 MgCO3 650 BiMo1Mg.25Sb1Ox 50 5.4 453 67 72 93 20 Co2O3 750 BiMo1Co.5Sb1Ox 50 5.0 455 66 73 91 21 Co2O3 700 BiMo1Co.25Sb1Ox 50 4.0 455 63 72 88 22 In2O3 650 BiMo1In.4Sb1Ox 50 4.4 455 66 71 94 23 NiCO3 700 BiMo1Ni.25Sb1Ox 50 5.1 465 70 74 95 24 NiCO3 650 BiMo1Ni.5Sb1Ox 50 5.1 465 68 73 94

Claims: I CLAIM: 1. A catalyst for oxidation and ammoxidation of hydrocarbons characterized by catalytic elements having the empirical formula BiMOaMbSb c0x wherein a is from 0.5 to 2, b is from 0.05 to 1, c is from 0.1 to 1.5 and x is taken to satisfy the valence requirements of the other elements present and wherein M is a metal selected from Mn, Mg, Cr, Pb, Fe, Sn, Zn, Ag, Ti, Ce, Co, Ni, In, Zr, Tl, U and mixtures thereof, said catalyst being prepared by forming a mixture containing a selected metal antimonate component, a bismuth molybdate component and, optionally, a support material and calcining at a temperature of from 500 to 85OOC. 2. A catalyst according to Claim 1 characterized in that M is selected from Mn, Sn, Fe, Zn, Ag, Cr and Mg. 3. A catalyst according to Claim 1 characterized in that a is from 0.7 to 1.5, b is from 0.08 to 1 and c is from 0.1 to 1.2. 4. A catalyst according to Claim 2 characterized in that said antimonate component is calcined prior to forming said mixture. 5. A catalyst according to Claim 4 characterized in that said bismuth molybdate component is separately formed prior to forming said mixture. 6. A catalyst according to Claim 4 characterized in that said metal antimonate component is preformed and said bismuth molybdate component is formed in the presence of said preformed antimonate component. 7. A catalyst according to Claim 5 characterized in that said mixture is in the form of an aqueous slurry. 8. A catalyst according to Claim 7 characterized in that a support material comprising from about 10 to about 90% of the total weight of said catalyst is added to said slurry. 9. A catalyst according to Claim 4 characterized in that said mixture contains an excess of an antimony compound over that stoicheometrically required to combine with the selected metal in said metal antimonate component. 10. A process for the production of acrylonitrile which comprises reacting at an elevated temperature in the vapor phase propylene, ammonia and molecular oxygen over a catalyst characterized by catalytic elements having the empirical formula BiMOaMb SbcOx wherein a is from 0.5 to 2, b is from 0.05 to 1, c is from 0.1 to 1.5 and x is taken to satisfy the valence requirements of the other elements present and wherein M is a metal selected from Mn, Mg, Cr, Pb, Fe, Sn, Zn, Ag, Ti, Ce, Co, Ni, In, Zr, T1, U and mixtures thereof, said catalyst being prepared by forming a mixture containing a selected metal antimonate component, a bismuth molybdate component, and, optionally, a support material and calcining at a temperature of from 500 to 8500C. 11. A process according to Claim 10 characterized in that M is selected from Mn, Sn, Fe, Zn, Ag, Cr and Mg. 12. A process according to Claim 10 characterized in that a is from 0.7 to 1.5, b is from 0.08 to 1 and c is from 0.1 to 1.2. 13. A process according to Claim 12 characterized in that said mixture is an aqueous slurry. 14. A process according to Claim 13 characterized in that said antimonate component is calcined prior to forming said slurry. 15. A process according to Claim 14 characterized in that said metal antimonate component and said bismuth molybdate component are separately formed prior to forming said slurry. 16. A catalyst according to Claim 14 characterized in that said metal antimonate component is preformed and said bismuth molybdate component is formed in the presence of said preformed antimonate component. 17. A catalyst according to Claim 15 characterized in that a support material comprising from about 0 to about 80% of the total weight of said catalyst is added to said slurry. 18. A catalyst according to Claim 14 characterized in that said slurry contains an excess of an antimony compound over that stoicheometrically required to combine with the selected metal in said metal antimonate component. 19. A process according to Claim 17 characterized in that said process is conducted at a pressure of about 100 to about 600 kPa and a temperature of about 400 to about 5500C. 20. A process according to Claim 19 characterized in that said temperature is about 450 to about 5250C. 21. A process according to Claim 19 characterized in that the flow rate W/F is in the range of about 2 to about 15 gm sec/ml.

Inventors: EBNER, JERRY RUDOLPH
Applicants: MONSANTO COMPANY
Application year: 1980
Main classification: B01J23
IPC codes: B01J23, B01J35, C07B61, C07C255, C07C253, C07C67