Highly active and selective catalysts for the production of unsaturated nitriles, methods of using the same

Abstract: An improved catalyst for the production of unsaturated nitriles from their corresponding olefins, the catalyst having the atomic ratios described by the empirical formula Bi a Mo b V c Sb d Nb e A f B g O x and methods of using the same.

Description: The present invention relates to a catalyst system according to claim 1 and to a process for the production of unsaturated nitriles according to claim 10. The present invention relates to new ammoxidation catalysts for the production of unsaturated nitriles from their corresponding olefins. More specifically, the present invention is directed to an improved ammoxidation catalyst containing niobium as an essential element for enhancing activity and selectivity of the catalyst system and methods of using the same. Several publications are referenced in this application. The references describe the state of the art to which this invention pertains. It is known in the art that the bismuth-molybdenum system plays a role in electron donor/acceptor mechanisms for selective oxidation and ammoxidation. Therefore different mechanisms have been proposed based on this property [Delmon et al. (New Development in Selective Oxidation by Heterogeneous Catalysis, Vol. 72, 1992, p. 399-413) and Encyclopedia of Chemical Technology (Kirk-Othmer, Vol. 1, 4th edition, page 358)]. In these mechanisms, molybdenum was shown to be responsible for oxygen and nitrogen uptake and insertion into the substrate, while bismuth plays the role of H-abstraction of the methyl group in the β position. Therefore, bismuth and molybdenum should be present on the catalyst surface and adjacent in order to form the suitable active phase for this reaction. It should be noted that the deficiency of bismuth on the catalyst surface leads to the total oxidation reaction of the substrate. It is also well known that antimony plays the role of a donor and thus could improve the selectivity of the catalyst. Antimony can also play an additional role of isolating the vanadium active centers which are highly active towards the oxidation reaction. This leads to minimizing the total oxidation reaction and directs the reaction towards the desired product. Many catalysts have been disclosed for the foregoing reactions. One such catalyst is described in U.S. -A-4,062,885, where BiMoSbV systems were used as active elements. The catalyst was used for the preparation of phthalonitrile by the ammoxidation of ortho-xylene. The use of such catalysts for oxidation or ammoxidation reactions involving unsaturated aliphatic hydrocarbons is not mentioned. U.S. -A- 4,040,978 relates to a catalyst for ammoxidation reactions containing bismuth molybdate mixed with other elements. U.S. -A- 4,405,498 relates to a catalyst for oxidation and ammoxidation reactions containing BiMoVSb with additional elements selected from groups IA, IIA, IVA, VA, VIA, IB, IVB and VIIB of the periodic Table of the Elements. Elements from group VB of the periodic table are not disclosed in this patent. U.S. -A- 4,600,541 relates to a catalyst comprising FeBiMo and promoters such as Pd, Pt, Os and Ir. More recently, European Patent Publication No. 0 475 351 A1 relates to a catalyst containing KFeSbMo which could be promoted by Nb and W. The best yield was achieved with a catalyst of the formula Fe 10 Sb 10 Mo 9 Bi 2 K 0.6 Ni 5.5 W 0.3 B 0.75 P 0.75 (SiO 2 ) 70 . European Patent Publication No. 0 573 713 B1 relates to a catalyst comprising MoBiFeCoNiCr promoted with at least three other promoters selected from alkali metals, alkaline earth metals, rare earth metals, Nb, Tl and As, with Fe, Co, Ni and Cr as essential catalyst components. U.S. -A- 5,688,739 relates to a multi-component catalyst. The base of this catalyst is bismuth molybdenum. Germanium was added as an essential element. The use of niobium was not disclosed in this patent. None of the prior art references discloses or suggests catalysts which provide high performance for the selective production of unsaturated nitriles from their corresponding US-A-5 472 925 describes a catalyst for the production of a nitrile from an alkane, which satisfies the following conditions 1 ○ and 2 ○: 1 ○ the catalyst is represented by the empirical formula: Mo a V b Te c X x O n wherein X is at least one element selected from the group consisting of Nb, Ta, W, Ti, Al, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Sb, Bi, B and Ce, when a=1 b=0.01 to 1.0 c=0.01 to 1.0 x=0.01 to 1.0, and n is a number such that the total valency of the metal elements is satisfied; and 2 ○ the catalyst has X-ray diffraction peaks at the following angles of 2 in its X-ray diffraction pattern: Diffraction angles of 2 (°) 22.1±0.3 28.2±0.3 36.2±0.3 45.2±0.3 50.0±0.3. EP-A-0 603 836 discloses a process for preparing a catalyst useful for producing a nitrile or slurry containing molybdenum, vanadium and tellurium by a spray drying method or a freeze-drying method and heat-treating the resulting dried product. None of the prior art references discloses or suggests catalysts which provide high performance for the selective production of unsaturated nitriles from their corresponding olefins. Accordingly, it would be desirable to produce an improved catalyst for use in the selective production of unsaturated nitriles from their corresponding olefins. It is an object of the invention to overcome the above-identified deficiencies. It is another object of the invention to provide a useful, improved catalyst for the production of nitriles from their corresponding olefins, particularly for the production of acrylonitrile from propylene. It is a further object of the invention to provide a process for the production of acrylonitrile at high yields by vapor phase catalytic ammoxidation of propylene in a fluidized or fixed bed reactor. The foregoing and other objects and advantages of the invention will be set forth in or apparent from the following description. The catalyst system is defined in claim 1 and the process for the production of unsaturated nitriles is defined in claim 10. The present invention relates to an improved catalyst for the production of unsaturated nitriles from their corresponding olefins, the catalyst having the atomic ratios described by the empirical formula set forth below: Bi a Mo b V c Sb d Nb e A f B g O x , wherein A = one or more elements selected from groups VB (e.g. V, Nb, Ta), VIB (e.g. Cr, Mo, W), VIIB (e.g. Mn, Tc, Re) or VIII (e.g. Fe, Co, Ni) of the periodic table; B = at least one alkali promoter selected from groups IA (e.g., Li, Na, K) or IIA (e.g., Mg, Ca) of the periodic table; a = 0.01 to 12; b = 0.01 to 12; c = 0.01 to 2; d = 0.01 to 10; e = 0.01 to 1; f = 0 to 2, preferably from 0.01 to 1; g = 0 to 1, preferably from 0.001 to 0.5; and x = the number of oxygen atoms required to satisfy the valency requirements of the elements present. The numerical values of a, b, c, d, e, f, g, and x represent the relative gram-atom ratios of the elements, respectively, in the catalyst, where x is a number required to satisfy the valence requirements of the other elements. The elements are present in combination with oxygen, preferably in the form of various oxides. The invention also relates to an improved selective low temperature catalytic process for the production of nitriles from their corresponding olefins, particularly for the production of acrylonitrile from propylene. Other objects as well as aspects, features and advantages of the present invention will become apparent from a study of the present specification, including the claims and specific examples. In order that the application may be fully understood, reference is made to the accompanying drawing: Fig. 1 is a graphical representation of X-ray diffraction (XRD) patterns of a catalyst according to one embodiment of the invention and a comparative catalyst. One aspect of the invention relates to an improved ammoxidation catalytic system for the production of unsaturated nitriles from their corresponding olefins, in particular, for the production of acrylonitrile from propylene. More specifically, the present invention is directed to an improved ammoxidation catalyst containing niobium as an essential element for enhancing activity and selectivity of the catalyst system. The aim of the present invention is to incorporate a new element into the Bi/Mo system which can improve the catalyst performance. This is achieved by incorporating niobium into a bismuth/molybdenum/vanadium/antimony catalyst system. The improved ammoxidation catalytic system of the invention comprises the atomic composition described by the empirical formula set forth below: Bi a Mo b V c Sb d Nb e A f B g O x , wherein A = one or more elements selected from groups VB (e.g. V, Nb, Ta), VIB (e.g. Cr, Mo, W), VIIB (e.g. Mn, Tc, Re) or VIII (e.g. Fe, Co, Ni) of the periodic table; B = at least one alkali promoter selected from groups IA (e.g., Li, Na, K) or IIA (e.g., Mg, Ca) of the periodic table; a = 0.01 to 12; b = 0.01 to 12; c = 0.01 to 2; d = 0.01 to 10; e = 0.01 to 1; f = 0 to 2, preferably from 0.01 to 1; g = 0 to 1, preferably from 0.001 to 0.5; and x = the number of oxygen atoms required to satisfy the valency requirements of the elements present. The catalysts of the invention can be used with or without a support. Suitable supports for the catalysts include alumina, silica, titania, zirconia, zeolites, silicon carbide, molecular sieves and other micro/nonporous materials, and mixtures thereof. When used on a support, the supported catalyst usually comprises from 10 to 50% by weight of the catalyst composition, with the remainder being the support material. Another aspect of the invention relates to methods of using the catalyst system of the invention. More specifically, the invention relates to an improved method of producing unsaturated nitriles from their corresponding olefins. One preferred embodiment of the invention relates to an improved process for the catalytic preparation of acrylonitrile or metha acrylonitrile by the reaction of propylene or isobutylene with molecular oxygen and ammonia at a temperature of between 200 to 550°C using the ammoxidation catalytic system of the invention. Preferably, the process achieves a propylene conversion of at least 65%, more preferably at least 70% and most preferred at least 75% using the catalytic system of the invention. Preferably, the selectivity in mol % to acrylonitrile is greater than 80%, more preferably greater than 85%. The yield of acrylonitrile in mol% is preferably greater than 50%, more preferably greater than 55%, even more preferably greater than 60% and most preferred greater than 65%. The following examples are illustrative of some of the catalysts and methods of making and using the same falling within the scope of the present invention. They are, of course, not to be considered in any way limitative of the invention. Numerous changes and modifications can be made with respect to the invention. The basic catalyst of the present invention is a mixed metal oxide catalyst, which could be prepared according to any procedure well known by those skilled in the art. Methods used to prepare a catalyst with niobium as an essential element according to one embodiment of the invention and a comparative catalyst are given below. The catalysts were prepared by the methods described in U.S. -A- 4,405,498. 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 catalyst in grams divided by the flow rate of the reactant stream in ml/sec measured at S.T.P. 2. "Propylene (C 3 H 6 ) conversion" is defined as: Mols C 3 H 6 in feed - mols C 3 H 6 in effluent Mols C 3 H 6 in feed x 100 3. "Acrylonitrile (ACN) selectivity" is defined as: Mols ACN in effluent Mols C 3 H 6 converted x 100% 4. "Acrylonitrile (ACN) yield" is defined as: Mols ACN formed Mols C 3 H 6 in feed x 100% Comparative Example 1 : Bi Mo V 0.175 Sb 0.35 O x /50% Silica Part A 10.2g of Sb 2 O 3 was slurried in 20ml water along with 3.18g V 2 O 5 . The mixture was boiled until a paste was formed. The paste was then dried at 120°C and calcined under airflow at 760°C for 2 hrs. Part B 97g Bi(NO 3 ) 3 5H 2 O was dissolved in 184ml water and 30ml HNO 3 (concentrated). Separately, 28.78g MoO 3 was dissolved in 72 ml water and 30ml concentrated NH 4 OH. The two solutions were mixed together and the pH was adjusted to 4 using NH 4 OH. The mixture was then boiled ca. 2 hours, filtered and washed with ca. 1000ml water. Part C The pH of 297g of a silica solution 30 wt% was adjusted with HNO 3 to pH=2 to form Part C. Parts A and B were then added to Part C. The mixture was stirred for several hours, then dried at 120°C and calcined under airflow at 550°C. The resultant catalyst was characterized by means of an XPS technique. The results are shown in Figure 1. EXAMPLE 2 : Bi Mo Nb 0.1 V 0.175 Sb 0.35 O x /50% Silica This catalyst was prepared according to the above described method set forth in Example 1. Niobium was introduced to the system using the required amount of niobium pentaoxide added to the molybdenum solution in part B. However, any source of niobium could be used for the same purpose. The catalyst was characterized by means of an XPS technique. The results are shown in Figure 1. CATALYST TEST The calcined catalysts of Examples 1 and 2 were crushed to 35-60 mesh fraction. 5 g of each catalyst were charged into a tubular fixed bed stainless steel reactor. The reaction was carried out under 475°C at atmospheric pressure with the following feed composition: propylene/O 2 /NH 3 /He=7.9/16.8/10/65.3 and a space velocity "W/F" of 3. COMPARISON The catalysts of Example 1 and Example 2 were tested under the similar conditions listed above. After reaching the steady state, the reactor effluents were analyzed using a modern gas chromatograph (HP 6890), equipped with both FID and TCD detectors. HCN was collected for a given period of time and then titrated. Activity results were calculated according to the equations given above. Results are summarized in the following table. Propylene Conversion ACROLEIN CO x Example 1 62.9 48.7 77.5 3.1 4.9 0 0 10.0 16.0 0.6 0.9 Example 2 77.4 67.9 87.7 2.6 3.4 0.9 1.1 5.3 6.9 0.3 0.3 As shown in the above Table I, the activity of catalyst of Example 2 (containing niobium) is higher than the comparative catalyst of Example 1. The selectivity was significantly enhanced at the cost of total oxidation and HCN formation. The activity and selectivity improvement is believed to be attributed to the catalyst surface enrichment with bismuth as a result of niobium introduction to the system. This is demonstrated in the XPS results shown in Figure 1.

Claims: A catalyst system for the production of unsaturated nitriles from the corresponding olefins comprising a catalyst having the empirical formula: Bi a Mo b V c Sb d Nb e A f B g O x , wherein A = one or more elements from groups VB, VIB, VIIB or VIII of the periodic table; B = at least one alkali promoter selected from groups IA or IIA of the periodic table; a = 0.01 to 12; b = 0.01 to 12; c = 0.01 to 2; d = 0.01 to 10; e = 0.01 to 1; f = 0 to 1; g = 0 to 0.5; and x = the number of oxygen atoms required to satisfy the valency requirements of the elements present. The catalyst of claim 1, wherein e is from 0.05 to 0.5. The catalyst of claim 1, wherein said oxide catalyst is supported on a catalyst support material selected from silica, alumina, zirconia, titania, alundum, silicon carbide, alumina-silica, inorganic phosphates, silicates, aluminates, borates and carbonates, pumice, montmorillonite, or mixtures thereof. The catalyst system of claim 3, wherein said catalyst support material is silica. The catalyst system of claim 3, wherein the support material comprises 40-70% by weight of the oxide catalyst. The catalyst system of claim 4, wherein the support material comprises from 40-70% by weight of the oxide catalyst. The catalyst system of claim 1, wherein said catalyst contains niobium derived from nobium pentoxide soluble in water. The catalyst system of claim 1, wherein f ranges from 0.01 to 1 and g ranges from 0.001 to 0.5. The catalyst system of claim 1, wherein said catalyst contains niobium derived from a niobium source soluble in water. A process for the production of unsaturated nitriles from the corresponding olefins which comprises reacting the olefins with a gas containing molecular oxygen and ammonia in the vapour phase at a temperature from 200°C to 550°C in the presence of the catalyst of claims 1 to 9. The process of claim 10, wherein said olefins are selected from propylene, isobutylene or mixtures thereof and said nitriles are selected from acrylonitrile, methacrylonitrile or mixtures thereof. The process of claim 11, wherein said process achieves an olefin conversion of at least 65%. The process of claim 11, wherein said process achieves a selectivity in mol % to nitriles greater than 80%. The process of claim 11, wherein said process achieves a nitriles yield in mol % greater.than 50%.

Inventors: ABDULWAHED MAZHAR, EL YAHYAOUI KHALID, ABDULWAHED, MAZHAR, EL YAHYAOUI, KHALID
Applicants: SAUDI BASIC IND CORP SABIC, SAUDI BASIC INDUSTRIES CORPORATION (SABIC)
Application year: 2000
Main classification: C07C253
IPC codes: B01J23, C07C255, C07C253, C07B61