Title of Invention

AN AMMOXIDATION PROCESS FOR INCREASING THE YIELD OF CO - PRODUCT HCN AND ACETONITRILE

Abstract

An ammoxidation process for increasing the yield of co-product HCN and acetonitrile produced during said acetonitrile manufacture comprising of (i) introducing a mixture of a hydrocarbon selected from the group consisting of polypropylene and propane, a mixture of at least two ketones and water, ammonia and an oxygen containing gas, into a reaction zone containing an ammoxidation catalyst selected from the group consisting of (a) catalyst of the formula AaBbCcDdMo120x Where A = Li, Na, K, Cs, Tl and combinations thereof, B = Ni, Co, Mn, Mg, Ca and combinations thereof, C = Fe, Cr, Ce, Cu, V, Sb, W, Sn, Ga, Ge, In, P and combinations thereof, D = Bi, Te and combinations thereof, a = 0.1-4.0, b = 0.1-10.0, and c,d = 0.1-10.0, and the value of x depends on the oxidation state of the elements used, and (b) catalyst of the formula AaBbSb12Ox Where A = Fe, Cr, Ce, V, U, Sn, Ti, Nb and combinations thereof, B = Mo, W, Co, Cu, Te, Bi, Zn, B, Ni, Ca, Ta and combinations thereof, a =0.1-16, b = 0.0-12, the value of x depends on the oxidation state of the elements used, (ii) reacting the hydrocarbon, said mixture of ketones, ammonia and oxygen over said catalyst at an elevated temperature of 410 C to 460 C and at a pressure of 101.3kPa to 506.6kPa (1 to 5 atm) to produce acrylonitrile, HCN and acetonitrile and (iii) recovering the HCN and acetonitrile from the said reaction zone.

Full Text

FORM 2 THE PATENTS ACT, 1970 [39 OF 1970] & THE PATENTS RULES, 2003 COMPLETE SPECIFICATION [See Section 10; rule 13] AN AMMOXIDATION PROCESS FOR INCREASING THE YIELD OF CO-PRODUCT HCN AND ACETONITRILE INEOS USA LLC, a limited liability company organized under the laws of the State of Delaware, United States of America, of 200 E Randolph Drive, Chicago, Illinois 60601, United States of America, The following specification particularly describes the nature of the invention and the manner in which it is to be performed:- GRANTED 21-12-2006 BACKGROUND OF THE INVENTION The present invention is directed to a novel process for the ammoxidation of a mixture of ketones to a mixture of nitriles. In particular, the present invention is directed to increasing the yield of co-product hydrogen cyanide and acetonitriie produced during the ammoxidation of propylene to acrylonitrile. There are patents which address the issue of the injection of acetone into a fluid bed reactor to produce acetonitriie. In addition, these references further disclose that the acetone may be introduced into a fluid bed reactor to increase the co-product acetonitriie while manufacturing acrylonitrile. In particular, Japanese Patent Application 2[1990J-38,333 is directed to improving acetonitriie yields by injecting acetone and/or ethyl alcohol into ammoxidation reactor containing ammoxidation catalyst. The process disclosed in the Japanese Patent Application includes simultaneously injecting the acetone and/or ethyl alcohol into the ammoxidation reactor while manufacturing acrylonitrile. The present invention is directed to a process which increases the yield of both main co-products (i.e. HCN and acetonitrile) during the manufacture of acrylonitrile while (1) saving on the raw material costs associated with the increase in co-product yields and (2) achieving the same or better conversion and selectivity to the desired co-product. The present invention relates to an ammoxidation process for increasing the yield of co-product HCN and acetonitrile produced during said acetonitrile manufacture comprising of (i) introducing a mixture of a hydrocarbon selected from the group consisting of polypropylene and propane, a mixture of at least two ketones and water, ammonia and an oxygen containing gas, into a reaction zone containing an ammoxidation catalyst selected from the group consisting of (a) catalyst of the formula AaBbCcDdMo120x Where A = Li, Na, K, Cs, Tl and combinations thereof, B = Ni, Co, Mn, Mg, Ca and combinations thereof, C = Fe, Cr, Ce, Cu, V, Sb, W, Sn, Ga, Ge, In, P and combinations thereof, D = Bi, Te and combinations thereof, a = 0.1-4.0, b = 0.1-10.0, and c,d = 0.1-10.0, and the value of x depends on the oxidation state of the elements used, and (b) catalyst of the formula AaBbSb12Ox Where A = Fe, Cr, Ce, V, U, Sn, Ti, Nb and combinations thereof, B = Mo, W, Co, Cu, Te, Bi, Zn, B, Ni, Ca, Ta and combinations thereof, a = 0.1-16, b = 0.0-12, the value of x depends on the oxidation state of the elements used, (ii) reacting the hydrocarbon, said mixture of ketones, ammonia and oxygen over said catalyst at an elevated temperature of 4100C to 4600C and at a pressure of 101.3kPa to 506.6kPa (1 to 5 arm) to produce acrylonitrile, HCN and acetonitrile and (iii) recovering the HCN and acetonitrile from the said reaction zone. SUMMARY OF THE INVENTION It is an object of the present invention to provide a process for the ammoxidation of a mixture of ketones and/or a crude ketone to hydrogen cyanide and acetonitrile. It is another object of the present invention to provide a process for substantially increasing the yields of co-product hydrogen cyanide and acetonitrile produced during the manufacture of acrylonitrile from propylene. It is a further object of the present invention to provide a process for the conversion of a mixture of ketones (e.g. acetone and methyl isobutyl ketone (MIBK)) into hydrogen cyanide and acetonitrile during the manufacture of acrylonitrile without substantially affecting the yield of the acrylonitrile. Additional objects and advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following, or may be learned by the practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims. To achieve the foregoing objects in accordance with the purpose of the present invention as broadly described herein, the method of the present invention comprises introducing a hydrocarbon selected from the group consisting of propylene and propane, a mixture of ketones In another aspect of the present invention, the process comprises introducing a mixture of ketones (eg. acetone and MBK) and/or a crude ketone, ammonia and oxygen-containing gas into reaction zone (e«g. fluid bed reactor) to react in the presence of a catalyst (e»g. fluid bed catalyst) to produce a reactor effluent comprising hydrogen cyanide and acetonitrile, passing the reactor effluent containing the hydrogen cyanide and acetonitrile into a quench column to cool the reactor effluent, and recovering the acetonitrile and hydrogen cyanide from the quench column. In the practice of this aspect of the present invention the ammoxidatton conditions used in the manufacture of acrylanitile as disclosed in U.S. 3,911,08% For purposes of the present invention, the mixture of ketones is intended to include mixtures of commercially available ketones such as acetone, ME3K, methyl ethyl ketone etc. In either their purified, substantially purified, or erode form. In addition, commercially available crude ketones may be used by Itself in the practice of the present invention. For purposes of this application the term "crude ketone" shall mean a mixture of at least two ketones and a diluent (e.g. crude acetone shall comprises primarily acetone containing other ketones as impurities and water as a diluent). In the practice of the present invention, it is envisioned that any ammoxidation catalyst can be utilized to achieve the desired results. Typical ammoxidation catalysts can be generalized by ute following two formulae: AaBbCcDdMo12OA where A = Li, Na, K, Cs„ Tl and combinations thereof, preferably Cs and K B = Ni, Co, Ma, Mg» Ca and combinations thereof, preferably Ni, Co and Mg C = Fe, Cr, Ce, Cu, V» So, W, Sn, Ga, Ge, In, P and combinations thereof, preferably Fe»Cr and Ce D = Bi and/or Te, preferably Bi a = 0.1-4.0, preferably 0,1 to 0,5, especially preferred being 0.1 to 0,2 b = 0.1 -10.0, preferably 5 to 9, especially preferred being 6 to 8, and c,d = 0.1 -10.0, preferably 0.5 to 4, especially preferred being .0.5 to 3; and AaBbSb12Oa where A = Fe, Cr Ce, V, U, Sn, Ti, Nb and combinations thereof, preferably Fe, V, Sn and Ti B - Mo, W, Co, Cu, Te, Bi, 2n, B, Ni Ca, Ta and combinations thereof, preferably Mo and Cu a — 0.1-16, preferably 2 to 12,especially preferred being 4 to 10 b = 0.0-12, preferably 1 to 10, especially preferred being 2 to 6, and the value of x depends on the oxidation state of the elements used. The catalyst can be used either unsupported, or be supported with silica, alumina, titania, zirconia and the like; however, silica is the preferred support. Typically, catalysts envisioned as suitable in die practice of the present mvention are disclosed in U.S. Patents 3,642,930; 4,485,079; 3,911,089,4,873,215; 5,134,105 and 5,093,299. Reference will now be made in detail to the present preferred embodiments of the invention. DETAILED DESCRIPTION OF THE INVENTION The present invention is primarily directed to the utilisation of a mixture of at least two ketones such as acetone and methyl isobutyl ketone as a source for the production of useful nitrite co-products (hydrogen cyanide and acetonitrile) produced during the manufacture of acrylonitrile. However, the process of the present invention is also applicable to the manufacture of on purpose acetonitrile and hydrogen cyanide by the direct ammoxidation of a mixture of C1 to C4 ketone and/or a crude ketone ammonia and oxygen in a reaction zone in the presence of an ammoxidation catalyst. In addition, crude ketone (as defined above), by itself may be utilized; in the practice of the present invention thereby further reducing the cost of the raw materials suitable for the production of viable co-products. The practice of the process of the present invention during the manufacture of acrylonitrile increases the yield of both HCN and acetonitrile during the manufacture of acrylonitrile. The practice of this aspect of the present invention comprises introducing a hydrocarbon selected from the group consisting of propylene and propane, a crude ketone, ammonia and air, into a reaction zone containing an ammoxidation catalyst, reacting the hydrocarbon, ketone, ammonia and oxygen over said catalyst at an elevated temperature to produce acrylonitrile, hydrogen cyanide and acetonitrile, and recovering the acrylonitrile, hydrogen cyanide and acetonitrile from the reactor. In another embodiment of this aspect of the present invention, the process comprises introducing a hydrocarbon selected from the group consisting of propylene and propane, a mixture of at least two C, to C4 ketones, ammonia and air, into a reaction zone containing an ammoxidation catalyst, reacting the hydrocarbon, ketones, ammonia and oxygen over said catalyst at an elevated temperature to produce acrylonitrils, hydrogen cyanide and acetonitrile, and recovering the acryionitrile, hydrogen cyanide and acetonitrile from the reactor. In the preferred embodiment of this aspect of the present invention, it is necessary that the reactor conditions be adjusted to obtain the increased yield in acetonitrile and hydrogen cyanide obtained by utilizing the mixture of ketones and/or crude ketone. In the practice of the present invention, the ammoxidation reaction conditions should be within the following parameters: Crude ketone is between 1 and 50% of propylene or propane rate on a total carbon basis. The temperature of the reaction is between 410o to 460°C, preferably 405° to 440°C. Typically, the pressure is maintained at between 1 to 5 atmospheres with 1 to 3-atrnospheres being preferred. In a further preferred embodiment of this aspect of the present invention the crude ketone mixture comprises a mixture containing acetone, MBBK and water. In a still further preferred embodiment of this aspect of the present invention the process is performed in a fluid bed reactor, In another preferred embodiment of this aspect of the present invention the mixture of ketones comprises crude ketone in combination with at least one substantially pure C, to C4 ketone. In still another preferred embodiment of this aspect of the present invention, the ketone is separately introduced into the reactor zone. In a still Anther preferred embodiment of this aspect of the present invention, the mixture of ketones and/or crude ketone is separately introduced into the fluid bed reactor, preferably at a location above the point where the hydrocarbon is fed into the reactor, especially preferred being a location in the upper portion of the reactor. The following examples are set forth below for illustrative purposes and are not considered as limiting to the practice of the present invention. The catalyst utilized in all of the examples was a promoted BiFeMoOz known for its suitability in the ammoxidation of pmpylene to acrylonitrile. Five, 10 and 15% of the propylene feed (in terms of total carbon) was replaced with a ketone to give the results set forth below in Table I, In each of the following examples the reactor temperature was 430°C, the pressure was 9.5 psig and the feed ratio of propylene + alcohol/ammonia/air was 1/1.2/93. The wwh was 0.06 (grams of hydrocarbon/ grams of catalyst-hour) Table I As a farther example of the value of using crude ketones, 10% by weight water was blended with the acetone above and tills was co-fed to the same propylene ammoxidation reactor. The results are shown below in Table II and indicate that water dilution has no deleterious effect on performance. Table II In general, all ketones can be ammoxidized to a mixture of nitriles. The preferred ketones include C, to C4 ketones. The following example illustrates the use of a C4 ketone in the form of methyl ethyl ketone (MEK). Table III The following examples are illustrative of the practice of the present invention for direct ammoxidation of ketones to acetonitrile and HCN. The feed ratio for the ketone/ammorria/air nsed in Example 12 and 13 were 1/1.7/13.1 and 1/2/15.1 respectively. The temperature of the reaction was 413°C for Example 12 and 411°C for Example 13. The reactor pressure was 10 psig for both examples and the wwh was 0.133 and 0.149 for Examples 12 and 13, respectively. Table IV below sets forth the results for Examples 12 and 13. Table IV While the examples are illustrative of the piactice of the present invention, they are not intended to limit applicants' invention to that illustrated and obviously many modifications and variations may be utilized in light of the above teaching. It is intended that the scope of applicants invention be defined by the claims appended hereto. We Claim: 1. An ammoxidation process for increasing the yield of co-product HCN and acetonitrile produced during said acetonitrile manufacture comprising of (i) introducing a mixture of a hydrocarbon selected from the group consisting of polypropylene and propane, a mixture of at least two ketones and water, ammonia and an oxygen containing gas, into a reaction zone containing an ammoxidation catalyst selected from the group consisting of (a) catalyst of the formula AaBbCcDdMo120x Where A = Li, Na, K, Cs, Tl and combinations thereof, B = Ni, Co, Mn, Mg, Ca and combinations thereof, C = Fe, Cr, Ce, Cu, V, Sb, W, Sn, Ga, Ge, In, P and combinations thereof, D = Bi, Te and combinations thereof, a = 0.1-4.0, b = 0.1-10.0, and c,d = 0.1-10.0, and the value of x depends on the oxidation state of the elements used, and (b) catalyst of the formula AaBbSb12Ox Where A = Fe, Cr, Ce, V, U, Sn, Ti, Nb and combinations thereof, B = Mo, W, Co, Cu, Te, Bi, Zn, B, Ni, Ca, Ta and combinations thereof, a =0.1-16, b = 0.0-12, the value of x depends on the oxidation state of the elements used, (ii) reacting the hydrocarbon, said mixture of ketones, ammonia and oxygen over said catalyst at an elevated temperature of 410 C to 460 C and at a pressure of 101.3kPa to 506.6kPa (1 to 5 atm) to produce acrylonitrile, HCN and acetonitrile and (iii) recovering the HCN and acetonitrile from the said reaction zone. Dated this 21st day of March, 2005. [RANJNA MEHTA-DUTT] OF REMFRY AND SAGAR ATTORNEY FOR THE APPLICANTS

Documents:

215-mumnp-2005-assignment(23-11-2006).pdf

215-mumnp-2005-cancelled pages(21-12-2006).pdf

215-mumnp-2005-claims(21-3-2005).pdf

215-mumnp-2005-claims(amanded)-(21-12-2006).pdf

215-mumnp-2005-claims(granted)-(21-12-2006).doc

215-mumnp-2005-claims(granted)-(21-12-2006).pdf

215-mumnp-2005-correspondence(26-12-2007).pdf

215-mumnp-2005-correspondence(ipo)-(17-5-2006).pdf

215-mumnp-2005-correspondence(ipo)-(24-12-2007).pdf

215-mumnp-2005-description(complete)-(21-3-2005).pdf

215-mumnp-2005-form 1(17-10-2006).pdf

215-mumnp-2005-form 13(23-11-2006).pdf

215-mumnp-2005-form 18(13-9-2005).pdf

215-mumnp-2005-form 2(21-3-2005).pdf

215-mumnp-2005-form 2(granted)-(21-12-2006).doc

215-mumnp-2005-form 2(granted)-(21-12-2006).pdf

215-mumnp-2005-form 2(title page)-(21-3-2005).pdf

215-mumnp-2005-form 3(20-4-2006).pdf

215-mumnp-2005-form 3(21-3-2005).pdf

215-mumnp-2005-form 4(17-4-2006).pdf

215-mumnp-2005-form 5(18-3-2005).pdf

215-mumnp-2005-form 6(23-11-2006).pdf

215-mumnp-2005-form-pct-ipea-409(21-3-2005).pdf

215-mumnp-2005-form-pct-isa-210(21-3-2005).pdf

215-mumnp-2005-petition under rule 138(17-10-2006).pdf

215-mumnp-2005-power of authority(18-10-2006).pdf

215-mumnp-2005-specification(amanded)-(21-3-2005).pdf

215-mumnp-2005-wo international publication report(17-4-2006).pdf