Title of Invention

PROCESS FOR OLEFIN EPOXIDATION AND CO - PRODUCTION OF NYLON PRECURSOR

Abstract

An integrated process combines olefin epoxidation with production of cyclohexanone and cyclohexanol for nylon. Cyclohexanone and cyclohexanol normally produced by the oxidation of cyclohexane, in which cyclohexyl hydroperoxide is generated and is removed or decomposed down stream. However, this invention utilizes the intermediate of cyclohexyl hydroperoxide as an oxidant for the olefin epoxidation and meanwhile generates a valuable product.

Full Text

FORM 2 THE PATENT ACT 1970 (39 Of 1970) The Patents Rules, 2003 COMPLETE SPECIFICATION (See Section 10, and rule 13) TITLE OF INVENTION PROCESS FOR OLEFIN EPOXIDATION AND CO-PRODUCTION OF NYLON PRECURSOR APPLICANT(S) a) Name b) Nationality c) Address ABB LUMMUS GLOBAL INC. AMERICAN Company 1515 BROAD STREET, BLOOMFIELD, NJ 07003, U.S.A. PREAMBLE TO THE DESCRIPTION The following specification particularly describes the invention and the manner in which it is to be performed : - PROCESS FOR OLEFIN EPOXIDATION AND CO-PRODUTION 5 OF NYLON PRECURSOR BACKGROUND 1. Field of the Invention The present invention relates to a catalytic 10 conversion process, and particularly to a process for olefin epoxidation with the co-production of a nylon precursor. 2. Background of the Art 15 Epoxidation of olefin is a well-established reaction, which usually requires heterogeneous catalysts containing transition metals. An early version of commercial Catalyst is titanium supported on amorphous silica (cf. R.A. Sheldon, I.WL.C.E. Arends, H.E.B. Lempers, Catal Today 20 1998, 41, 387-407). If used in an aqueous system the catalytically active component, titanium, leaches out; and the catalyst loses catalytic activity proportionate to the loss of titanium content. Thus, organic oxidants such as tert-butyl hydroperoxide have been used. However, use of 25 tert-butyl hydroperoxide in an organic system leads to the production of alcohol, i.e., tert-butanol, as a reaction 2- byproduct. Reprocessing of this alcohol to its hydroperoxide significantly adds to the production cost of the epoxide. In 1983 Taramasso et al showed a crystalline 5 microporous titanosilicate (TS-1), isostructural to ZSM-5, exhibited high catalytic activity for olefin epoxidation in either organic or inorganic reaction systems (M. Taramasso, G. Perego, B. Notari, U.S. Patent No. 4,410,501). While virtually all titanium catalysts leach when exposed to an 10 aqueous environment, the titanium active species in TS-1 is one of the most stable in this regard. TS-1 opened a new area to use hydrogen peroxide as an oxidant, which gives water as a byproduct. Here, this epoxidation process is more environmentally friendly. However, crystalline 15 microporous TS-1 and other transitional metal-containing •zeolites have small pores (normally less than 1.2 nm in diameter), which prevent access of some important, bulky reactants to the active sites. For certain large . reactants, a catalyst with large pores is required to have 20 good catalytic performance. Transition metal-containing mesoporous materials (i.e. having pore diameters between 1.5 and 30 nm) have been disclosed, such as Ti-MCM-41 and Ti-MCM-48 (Pinnavaia et 3 al. J. Am. Chem. Soc, 1996, 118, pgs. 9164-1971). These materials have unique pore structures: Ti-MCM-4l possesses one-dimensional pores that are regularly arranged in parallel, whereas Ti-MCM-48 has three-dimensional, ordered 5 pores. Now, a new mesoporous material (denoted as TUD-1, U.S. Patent No. 6,358,486 B1) has been disclosed, having a three-dimensionally interconnected pores system. This pore system has advantages over that of MCM-41 because it 10 facilitates mass transfer of reactants and products and reduces the possibility of pore blockage. This mesoporous material can be functionalized by adding transition metals and can then be used as a catalyst for epoxidation. The TUD-1 mesoporous material mentioned above has an 15 amorphous character. Other, amorphous Ti materials generally have the above-cited leaching problem.' Use of an organic medium rather than water can minimize metal leaching, but causes another problem, i.e., formation of undesirable byproduct alcohols. What is needed is a 20 process to effectively utilize the corresponding byproduct alcohol as a valuable product and to permit the use of bulky reactants and organic oxidants for epoxidation without net generation of a co-product alcohol. 4 SUMMARY A process for olefin epoxidation is provided herein. The process comprises contacting at least one olefin with 5 an organic hydroperoxide under olefin epoxidation reaction conditions in the presence of a catalyst to provide ah epoxidation reaction product containing olefin epoxide(s), wherein the catalyst comprises a transition metal and an amorphous porous inorganic oxide having randomly 10 interconnected mesopores wherein said mesopores comprise at least about 97 volume percent of the pore volume based upon mesopores and micropores, and wherein the porous inorganic oxide is characterized by an X-ray diffraction pattern having a peak between 0.5° and 3.0° in 20. Preferably, the 15 organic hydroperoxide is cyclohexyl hydroperoxide, which can be obtained from the oxidation of cyclohexane. The process utilizes the by-product alcohol to form valuable products such as nylon precursors (e.g., adipic acid and caprolactam) . 20 BRIEF DESCRIPTION OF THE DRAWINGS Various embodiments are described below with reference to the drawings wherein: 5 FIG. 1 is a schematic diagram of the process of the present invention; FIG. 2 is an X-ray diffraction pattern of the material obtained in example 1; 5 FIG. 3 is a TEM image of the material obtained in example 1; FIG. 4 depicts the nitrogen adsorption isotherm pore size distribution for the material obtained in example 1; and 10 FIG. 5 shows the x-rays diffraction patterns of the material obtained in Example 2, 3, 4 and 5. DETAILED DESCRIPTION OF PREFFERED EMBODIMENT(S) This invention discloses a new integrated process for 15 the epoxidation of olefin and conversion of an organic hydroperoxide to the corresponding alcohol, particular cyclohexyl hydroperoxide to cyclohexanol. This integrated process can use a transition metal-containing mesoporous material, the transition metals,the transition metals being selected from the 20 group consisting titanium(Ti), chromium (Cr),vanadium (v), iron (Fe), tungsten (W)and molybdenum(Mo) or their combination. It also can use a zeolite-containing mesoporous material, such as that disclosed in US patent application Publication No. 2002/0074263, in which some silicon of the zeolite is isomorphously substituted by Ti, Cr, V, Fe, W, Mo, etc., thereby providing epbxidation activity. This process also can use the combination of two 5 catalytic materials mentioned above, having transition metal(s) in both mesoporous framework and zeolite framework. All three types of catalytic materials have three-dimensionally randomly interconnected mesopores, improving bulky organic accessibility to active sites and 10 reducing mass-transfer limitations. An advantageous feature of a preferred Embodiment of the invention is the production of adipic acid or caprolactam, which are precursors for the subsequent production of nylon. Conventionally, the oxidization of 15 cyclohexane using a gas containing O3 provides a mixture of cyclohexanol, cyclohexanone and cyclohexyl hydroperoxide ("CHHP"). The CHHP then decomposes to cyclohexanol and cyclohexanone. Finally, a mixture of cyclohexanol and cyclohexanone is further oxidized to produce adipic acid. 20 Alternatively, the cyclohexanol can undergo dehydrogenation to form cyclohexanone, the cyclohexanone can react with hydroxylamine to form cyclohexanone oxime, followed by Beckmann rearrangement to obtain caprolactam. The present 7 invention can effectively utilize the intermediate CHHP as an oxidant to oxidize olefin, and meanwhile produce an important, useful alcohol, viz. cyclohexanol. Thus, the CHHP intermediate can be fully used and its decomposition 5 process can be eliminated. Moreover, the eboxidation's alcohol byproduct is a desired chemical precursor for apidic acid or caprolactam production. As such, this invention provides an integrated process, which combines olefin epoxidation and subsequent production of the nylon 10 precursor. Referring now to FIG. 1, an integrated system 100 using CHHP for the epoxidation of olefin and co-production of nylon precursor is shown. CHHP can be obtained by cyclohexane oxidation. First, cyclohexane feed l01 is 15 introduced into an oxidation reaction zone 110 where it is oxidized with O2 or O2-containing gas 102 to provide an effluent 103 containing a mixture of CHHP, cyclohexanol, cyclohexanone, and unreacted cyclohexane. Various methods of cyclohexane oxidation are known in 20 the art. For example, at a temperature between 130°C and • 200°C and pressure between 4 and 50 bars CHHP can be obtained using an oxygen-containing gas in the absence of a catalyst. US Patent No. 5,043,481 has similar features of 8 adding oxidation products of cycloalkanes. EP-A-1,209,143 discloses a process using a catalyst comprising a cyclic N-hydroxyimide and a transition metal compound. US 4,675,450 discloses a process using cobalt-containing catalyst in the 5 presence of a phosphate ester. US 3,987,100 discloses a process which uses a cyclohexane-soluble binary catalyst comprising cobalt and chromium salts. Cyclohexane oxidation normally gives about 2 to 12 wt % CHHP in a mixture of unconverted cyclohexane, 10 cyclohexanol, and cyclohexanone. Optionally, the CHHP can be first concentrated in the effluent mixture 103 before reacting with olefin by conventional methods. One example of a conventional method includes distillation. For example, U.S. Patent No. 15 4,080,387 discloses a method which uses tert-butyl alcohol to form an azeotrope with cyclohexane. Hence, the bottom zone of the distillation column has a concentration of CHHP of about 10 wt.% to 3 0 wt. %. The effluent mixture 103 is then introduced into an 20 epoxidation reaction zone 120 where it is contacted with a stream 104 containing the desired olefin (s) in the presence, of an epoxidation catalyst. In this step the olefin is 9 partially oxidized to an epoxide, and the CHHP is converted into cyclohexanol. In principle, an extra solvent for the epoxidation is not necessary because the CHHP-containing effluent 103 has 5 relatively large quantities of cyclohexane and some cyclohexanol and cyclohexanone. Optionally, however, some conventional solvents for epoxidation, such as methanol, can be added to effluent 103 if desired. Suitable olefins for the integrated process are 10 selected from the group of linear chain, branched chain, or cyclic olefins with carbon number of from 3 to about 25, preferably from 3 to about 16. Suitable olefins include, but are not limited to, propylene, butenes (e.g., 1-butene, 2-butene, isobutene), pentenes, hexenes, heptenes, octenes, 15 nonenes, decenes, cyclohexene, etc. The olefin stream can be a pure olefin, a mixture of two or more olefins, or a mixture of one or more olefins with inert substances. The preferred epoxidation catalyst is comprises TUD-l, an amorphous mesoporous inorganic oxide having a unique 20 pore structure with three-dimensionally randomly interconnected mesopores. The mesopores comprise at least about 97 volume percent of the pore volume based upon mesopores and micropores. Moreover, its mesopore size can 10 be tuned from 1.5 nm to 30 nm to meet the requirements of various catalytic processes. TUD-1 has been Shown to have an unusually high surface area (e.g., 400 to 1100 m3/g) and pore volume (0.4 to 2.0 cm3/g) . with the trade-off being 5 pore size. Its X-ray diffraction pattern shows an intensive reflection peak between 0.5 and 3.0 degree in 26, corresponding to a lattice d-spacing between 25 nm and 350 nm. TUD-1 material has been disclosed in U.S. Patent No. 6,358,486, which is herein incorporated by reference. The 10 catalyst contains at least one type of transitional metal or could have a combination of several transition metals. Said transition metals include Ti, Cr, V, Fe, Mo, W, Sn, Ga, etc. The amount of the transition metals can be varied from 0.01 wt.% to 90 wt%. The catalyst mainly contains 15 silicon, oxygen and transition metals. However, it might contain some other elements such as aluminum, which can be intentionally added. From a structural point of view, the TUD-1 may further comprise microporous zeolites (e.g., TS-1 and/or TS-2), as disclosed in US patent application 20 Publication No. 2002/0074263, which is herein incorporated by reference. The zeolite may contain transition metals mentioned above in the framework. 11 Various oxidants can be used for the epoxidation of alkenes, such as molecular oxygen, hydrogen peroxide, organic hydroperoxide (e.g. tert-butyl hydroperoxide) and organic peracids (e.g. peroxyformic acid). While many 5 different alky! hydroperoxides can be employed in this general reaction system, cyclohexyl hydroperoxide (CHHP) is preferable according to this specific invention. It is preferably used in organic reaction systems, With minimal water in the reaction system. 10 In the epoxidation reaction zone 120 the olefin stream is contacted with a CHHP-containing stream in the presence of an epoxidation catalyst at a temperature of from about 0°C to about 200PC and a pressure up to about 10O bars, preferably a temperature of from about 20°C to about 80°C 15 and a pressure of from about atmospheric to about 30 bars. The epoxidation effluent 105 contains epoxide, cyclohexanol, cyclohexanone, unreacted olefin, and unreacted cycloalkane. Separation can then be carried out by, for example, distillation, at separation stage 130 to 20 obtain the desired products of epoxide 106, cyclohexanol 107 and cyclohexanone 108, or a mixture of cyclohexanol and cyclohexanone (also known as "KA oil"). The unconverted olefin is returned to the epoxidation reaction zone 120 via 12- olefin recycle stream 109, and unreacted cyclohexane ie returned to the oxidation reaction" zone 110 via cyclohexane recycle stream 1ll. The cyclohexanol 107 is preferably sent to a dehydrogenation reaction zone 150 where it undergoes dehydrogenation under conventional reaction conditions to produce cyclohexanone, which is then added to cyclohexanone stream 108. The cyclohexanone 108 is then sent to ah ammoxidation reaction zone 160 where it is reacted with hydroxylamine and converted into cyclohexanone oxime. The cyclohexanone oxime is then sent to reaction zone 170 where it is converted by Beckmann rearrangement to caprolactam, a nylon precursor, which is drawn off as a valuable product P. Dehydrogenation, ammoxidation and Beckmann rearrangement are conventional processes known in the art. In an alterative embodiment, the KA oil mixture of cyclohexanol and .cyclohexanone can be oxidized to provide adipic acid, HOOCfCHa^COOH, another nylon precursor. Processes for the oxidation of KA oil with, for example, nitric acid are known in the art. The following Examples are provided to illustrate the invention. X-ray power diffraction (XRD) patterns of the resulting materials were recorded using on a Philips PW 13 1840 diffractometer (with CuKα radiation) equipped with a graphite monochromator. The samples were scanned in the range of 0.5-40° 2 with steps of 0.02°. Transmission electron microscope (TEM) measurements were performed using 5 a Philips CM30T electron microscope with a LaB6 filament as the electron source operated at 300 kV. Nitrogen sorption isotherms were measured at 77°K on a Quantachrbme Autosorb-6B. Mesoporosity was calculated using the BJH (Barrett-Joyner-Halenda) model. Gas Chromatography (GC) analysis was 10 conducted using WAX 52 CB. EXAMPLE 1 First, 1.1 parts by weight of titanium (IV) n-butoxide (purity 99%, ACROS) was mixed with 35.0 parts by weight of tetra ethyl orthosilicate ("TEOS") (98+%, ACROS). Then, 15 25.3 parts of triethanolamine ("TEA") (97%, ACROS) was added drop-wise into the above mixture while stirring. After 1 hr of stirring, 17.3 parts of tetraethylammonium hydroxide ("TEAOH") (25%, Aldrich) was added drop-wise into the above mixture. The final homogenous mixture was aged 20 at room temperature for 24 hr, dried at 100° for 24 hr and then calcined at 700°C for 10 hr with a heating ramp rate of 1°C min"1 in air. 14 The XRD pattern of the resulting material, depicted in FIG. 2, shows only one intensive peak at about 1.0° in 20, indicating it is a meso-structured material. The TBM image in PIG. 3 show that curved and tortuous pores are randomly 5 connected to form a three-dimensional pore network. Nitrogen adsorption revealed its BET surface area of 917 m2/g, an average mesopore diameter 4.5 nm and total pore volume isotherm of 0.89 cm3/g, as shown in PIG. 4. EXAMPLE 2 10 1.7 Parts of titanium (IV) n-butoxide (99%) were mixed with 106 parts of TBOS (98%) . Then a mixture of '77 parts TEA (97%) and 58 .parts of deionized water was added drop-wise into the above mixture while stirring. After about 1 hr stirring, 63 parts of TEAOH (25%) were added drop-wise 15 to the mixture. The synthesis mixture's Si/Ti molar ratio was 100. The final, homogeneous mixture was aged at room temperature for 24 hours, dried at 98°C for 24 hours and then calcined at 650°C for 10 hours at a heating ramp rate of l°C/min in air. The XRD pattern of the material is shown 20 in PIG. 5. 15 EXAMPLE 3 The same procedure as in Example 2 was followed except that 3.4 parts by weight of titanium (IV) n-butoxide were used, and the mixture's Si/Ti ratio was 50. The XRD 5 pattern of the resulting material is shown in PIG. 5. EXAMPLE 4 The same procedure as in Example 2 was followed except that 8.6 parts of titanium (IV) n-butoxide were used, and the reactant mixture Si/Ti ratio was 20. The XRD pattern 10 of the resulting material is shown in FIG. 5. EXAMPLE 5 The same procedure as in Example 2 was followed; however, 17.2 parts of titanium (IV) n-butoxide were used, and the reactant mixture Si/Ti ratio was 10. The XRD 15 pattern of the resulting material is shown in PIG. 5. As can be seen, adding the appropriate amounts of titanium compound in the initial synthesis mixture can 'easily control the titanium loading of the catalyst material of the present invention (Examples 2-5). The XRD 20 patterns of the resulting materials of Examples 2-5 indicate that these materials are mesoporous. 16 EXAMPLE 6 This example demonstrates the auto-oxidation of cyclohexane to cyclohexyl hydroperoxide. In a Teflon* lined autoclave, 15 parts of cyclohexane by weight, 1 part of chlorobenzene as internal standard and 0,01 parts of dicumyl peroxide as initiator were charged. Into the mixture in the autoclave , a gas mixture of oxygen and nitrogen having an oxygen concentration Of 8% by volume was fed for one hour at a rate of 50 ml/min, and then pressurized to about 10 bars. The mixture was heated up to 120°C, acid the pressure was adjusted to 15 bats using the above-mentioned oxygen-containing nitrogen gas. In the course of the reaction, oxygen was gradually consumed, and the pressure dropped. After every hour, the pressure was adjusted to 15 bars by refilling oxygen-containing nitrogen. After 22 hours, the reaction was stopped by cooling and depressurizing. Upon cooling to room temperature, the reaction mixture was recovered for analysis and subsequent epoxidation. GC analysis was used to measure cyclohexanone, cyclohexanol, and CHHP content. The CHHP content was also confirmed via titration with Na2S203 solution. The final reaction mixture had cyclohexanone (0.50 wt%), cyclohexanol 17 (0.76 wt%) and cyclohexyl hydroperoxide (6.3 wt%) . The conversion of cyclohexane was 6.2 wt%, and a selectivity to cyclohexyl hydroperoxide was 76.4 wt%. The final reaction mixture was dried using anhydrous MgS04 before the 5 epoxidation reaction. EXAMPLE 7 The procedure is the same as Example 6, but the reaction was held at 1S0°C, and the reaction time was shortened to 4.5 hr. Finally the reaction mixture 10 contained cyclohexanone (0.47 wt.%), cyclohexanol (0.74 wt.%) and cyclohexyl hydroperoxide (6.8 wt.%). The conversion of cyclohexane was 7.6 wt.%, and the selectivity to cyclohexyl hydroperoxide was 84 .9 wt. %. EXAMPLE 8 15 The procedure was the same as in Example 6, but the reaction' temperature was held at 160°C, and the reaction time was shortened to 0.5 hr. The reaction mixture contained cyclohexanone (0.12 wt. %), cyclohexanol (0.34 wt.%) and cyclohexyl hydroperoxide (4.8 wt.%). The 20 conversion of cyclohexane was 4.4 wt.%, and the selectivity to cyclohexyl hydroperoxide was 85.3 wt.%. 18 EXAMPLE 9 This example demonstrates epoxidation of 1-octene. The catalyst prepared in Example 1 was dried in an oven at 180°C overnight in air. 1 part (by weight) of dried 5. catalyst, was transferred into a flask in an oil bath with a temperature controller. The flask, connected to a vacuum system, was heated up to 140°C under vacuum for 2 hr to remove any moisture. The catalyst was then cooled to 80°C under flowing nitrogen. After the temperature was stable, 10 4 parts of 1-octene and 28 parts of the reaction product from Example 6 were injected into the flask under a nitrogen blanket. After a reaction for 20 hr, the reaction mixture was analyzed by GC. Almost all of the CHHP was converted (1- 15 octene conversion was about 42 wt.%) with a 1-octene oxide selectivity of about 90% based on CHHP conversion. Finally, the reaction mixture contained about 6.4 wt.% cyclohexanone and cyclohexanol, 4.6 wt.% 1-octene oxide, 81 wt.% of cyclohexane and 7.0 wt.% of 1-octene. 19 EXAMPLE 10 Epoxidation of 1-octene was conducted in the same procedures as Example 9. However, here the reaction mixture containing cyclohexyl hydroperoxide was from 5 Example 8. After the reaction for 48 hr, the reaction mixture was analyzed by GC. Almost all of the CHHP was converted with selectivity to 1-octene oxide of 89%. The conversion of 1-octene reached about 32 wt.% with a selectivity to l-octene 10 oxide of about 98.5 wt.%. EXAMPLE 11 Propylene is used as a reactant to demonstrate the production of propylene oxide using CHHP. A reaction mixture of concentrated CHHP is used as an oxidant arid 15 solvent, which has 20 wt.% cyclohexyl hydroperoxide, 2 wt.% cyclohexanorie, 2 wt.% cyclohexanol and 76 wt.% cyclohexane. The catalyst prepared in Example 3 is dried at 180°C overnight. Five (5) parts of the catalyst are transferred into a Teflon-lined batch reactor under flowing nitrogen. 20 The batch reactor is heated up to 180°C under nitrogen flow for 0.5 hr and subsequently cooled at 80°C. One hundred (100) parts of the reaction mixture containing 20 wt.% of CHHP is charged into the reactor under stirring. Then the 20 reactor is pressurized using dried propylene to 20 bare. As the gaseous reactant become a liquid, the pressure dropped due to propylene consumption. After every hour of reaction propylene is refilled to resume the total pressure of 20 5 bars. After 12 hr the reaction mixture is analyzed by GC. The reaction mixture contains 7.6 wt.% propylene oxide, 19.9 wt.% cyclohexanone and cyclohexanol, and about 0.9 wt.% CHHP. The conversion of CHHP is about 95%, and the 10 selectivity to propylene oxide is about 85%. While the above description contains many Specifics, these specifics should not be construed as limitations of the invention, but merely as exemplifications of preferred embodiments thereof. Those skilled in the art will 15 envision many other embodiments within the scope and epirit of the invention as defined by the claims appended hereto. 21 We Claims: 1., A process for olefin epoxidation comprisingr contacting at least one olefin with an organic ■ i .■'■'■ ' '*■'■'/■ hydroperoxide under olefin epoxidation reaction conditions in the presence of a catalyst to provide an epoxidation reaction effluent containing olefin epoxide, wherein aid catalyst comprises a transition metal and an amorphous porous inorganic oxide having randomly interconnected mesopores wherein said mesopores comprise at least about 97 volume percent of the pore volume based upon mesopores and micropores, and wherein said pojrdiis inorganic oxide is characterized by ah X-ray diffjpacljpion patteitt having a peak between 0.5° and 3.0° in 2©. 2. The process of claim 1 wherein the organic hydroperoxide i& cyclohexyl hydroperoxide. 3. The process of claim I wherein said olefin has a carbon number of from 3 to 25. 4. The process of claim 1 wherein said olefin has a carbon number of from 3 to 16. 5. The process of claim 1 wherein said olefin is selected form the group consisting of propylene, 1-butene, 2-butene, isobutene, pentenes, hexenes, heptenes, octenes, nonenes, decenes, cyclohexene and combinations thereof. 22 6. The prdcess of claim 1 wherein the olefin epoxidktion xfeacfcion conditions include a temperature of from about 0°C to about 200°C and a pressure up to about 100 5 bars. 7. The process of claim l wherein the transition metal is selected from the group consisting of Ti, Cr, V, Fe, Mo, W, Sn and Ga. 8. The process of claim 6 wherein the transition metal 10 is Ti. 9. The process of claim 1 wherein the catalyst further comprises a microporous crystalline zeolite. 10. The process of claim 9 wherein the zeolite is selected from the group consisting of TS-1 and TS-2. 15 11. The process of claim 2 wherein the cyelohexyl hydroperoxide is provided by the oxidation of cyclohexane. 12. The process of claim 11 wherein the cyclohexyl hydroperoxide is provided in a stream further containing cyclohexanol and cyclohexanone. 20 13. The process of claim 1 wherein the epoxidation reaction effluent further contains cyclohexanol and cyclohexanone. 23 14. The process of claim 13 wherein the cyclohexanol and cyclohexanone in the effluent are oxidized to provide adipic acid. 15. The process of claim 13 wherein the cyclohexanone 5 in the effluent is converted by ammoxidation to cyclohexanone oxime, which is then converted to caprolactam by Beckmann rearrangement. 16. The process of claim 15 wherein the cyclohexanol in the effluent is dehydrogenated to form additional 10 cyclohexanohfe, which is then combined with the cyclohexanone in the effluent prior to ammoxidation. 17. An integrated process for the production of nylon precursor comprising the steps of: a) oxidation of cyclohexane in a first oxidation 15 reaction zone with an oxygen-containing gas to provide a first intermediate stream containing cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone/ b) contacting at least one olefin with the cyclohexyl hydroperoxide under olefin epoxidation reaction conditions 20 in the presence of a catalyst to provide an epoxidation reaction effluent containing olefin epoxide, cyclohexanol and cyclohexanone, 24 c) separating the olefin epoxide from the epoxidation reaction effluent; and, d) converting the cyclohexanol and/or cyclohexanone in the epoxidation reaction effluent to a nylon precursor. 5 18. The process of claim 17 wherein said catalyst comprises a transition metal and an amorphous porous inorganic oxide having randomly interconnected mesopores, Wherein said mesopores range in diameter from about 1.5 to 10 about 30 nm and comprise at least about 97 volume percent of the pore volume based upon mesopores and micropores, and wherein said porous inorganic oxide is characterized by an X-ray diffraction pattern having a peak between 0.5° and 3.0° in 2, and wherein said porous inorganic oxide has a 15 surf ace area of from about 400 to 1,100 m2/g; 19. The process of claim 17 wherein the cyclohexanol and cyclohexanone in the epoxidation reaction effluent are oxidized and the nylon precursor is adipic acid. 20. The process of claim 17 wherein the nylon 20 precursor is caprolactam, which is provided by the ammoxidation of epoxidation reaction effluent cyclohexanone to produce cyclohexanone oxime, and the Beckmann 25 rearrangement of the cyclohexanone oxime to produce the caprolactam nylon precursor. 21. the process of claim 17 wherein the transition metal is titanium. 5 22. the process of claim 17 wherein the said catalyst further comprises at least one zeolite with amorphous substituted titanium. Dated this 13th day of july,2006. HIRAL CHANDRAKANT JOSHI AGENT FOR ABB LUMMUS GLOBAL INC.

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