Title of Invention

AMMOXIDATION OF A MIXTURE OF KETONES TO ACETONITRILE AND HYDROGEN CYANIDE

Abstract A process increasing the yield of both HCN and acetonitrile produced during the manufacture of acrylonitrile comprising introducing a hydrocarbon selected from the group consisting of propylene and propane, a crude ketone and/or a mixture of at least two ketones, ammonia and air, into a reaction zone containing an ammoxidation catalyst, reacting the hydrocarbon, the 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.
Full Text FORM 2
THE PATENTS ACT 1970
[39 OF 1970]
COMPLETE SPECIFICATION
[See Section 10]
"AMMOXIDATION OF A MIXTURE OF KETONES TO ACETONITRILE AND HYDROGEN CYANIDE"
THE STANDARD OIL COMPANY, a corporation organized and existing under the laws of the State of Ohio, United States of America, of 200 East Randolph Drive, Chicago, Illinois 60601, United States of America,
The following specification particularly describes the nature of the invention and the manner in which itis to be performed :-


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 acetonitrile 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 acetonitrile. In addition, these references further disclose that the acetone may be introduced into a fluid bed reactor to increase the co-product acetonitrile
while manufacturing acrylonitrile. In particular, Japanese Patent Application 2[1990]-38,333 >
is directed to improving acetonitrile yields by injecting acetone and/or ethyl alcohol into ammoxidation reactor containing ammoxidation catalyst. The process disclosed in the
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Japanese Patent Application includes simultaneously injecting the acetone and/or ethyl alcohol into the arnmoxidation 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-products.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a process for the arnmoxidation 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
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means of the instrumentalities and combinations particularly pointed out in the appended
r
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, (e.g. acetone and MIBK), 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 acrylonitrile, hydrogen cyanide and
acetonitrile, passing the reactor effluent containing acrylonitrile, hydrogen cyanide and acetonitrile into a quench column to cool the reactor effluent, and recovering the acrylonitrile, acetonitrile and hydrogen cyanide from the quench column.
In another aspect of the present invention, the process comprises introducing a mixture of ketones (e.g. acetone and MIBK) 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 ammoxidation conditions used in the manufacture of acrylonitrile as disclosedjin U.S. ,3;911,089 herein incorporated by reference may be utilized..
For purposes of the present invention, the mixture of ketones is intended to include mixtures of commercially available ketones such as acetone, MIBK, methyl ethyl ketone etc.
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in either their purified, substantially purified, or crude form. In addition, commercially available crude ketones may be used by itself in-the practice of the present invention. For
s
purposes of this application the term "crude ketone" shall mean a mixture of at JeasjMtwp^ ketones and a diluent (e.g. crude acetone shall comprises primarily acetone containing other ketones as impurities and water, as^ajdiluent).
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 the following two formulae:
AaBbCcDdMoI20)1 where
A = Li, Na, K, Cs, Tl and combinations thereof, preferably Cs and K
B = Ni, Co, Mn, Mg, Ca and combinations thereof, preferably Ni, Co and
Mg C = Fe, Cr, Ce, Cu, V, Sb, W, Sn, Ga, Ge/ln, 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 AaBbSb,jOx where
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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, Zn, 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 catalyjs|,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 the practice of the present invention are disclosed in U.S. Patents 3,642,93%^.
4,485^079; 3,911,089,4,873,215; 5,134,105 and 5,093,2?9j herein incorporated byTeference
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 utilization of a mixture of at least two ketones such as acetone and methyl isobutyl ketone as a source for the production of useful nitrile 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
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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 acrylonitnle 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 C 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
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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 410° to 460°C, preferably 405° to 440°C. Typically, the pressure is maintained at between 1 to 5 atmospheres with 1 to 3 atmospheres being preferred.
In a further preferred embodiment of this aspect of the present invention the crude ketone mixture comprises a mixture containing acetone, MIBK 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 C« 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 further 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, especml]yj)referred being ajtocation injhe upperportion 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
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the examples was a promoted EiiFeMoO, known for its suitability in the ammoxidation of propylene 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 430CC, the pressure was 9.5 psig and the feed ratio of propylene + alcohol/ammonia/air was 1/1.2/9.3. The wwh was 0.06 (grams of hydrocarbon/ grams of catalyst-hour)
Table I

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As a further example of the value of using crude ketones, 10% by weight water was blended with the acetone above and this 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 C1 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 acetonirrile and HCN. The feed ratio for the ketone/ammonia/air used 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.
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Table IV

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While the examples are illustrative of the practice 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. A process for increasing the yield of co-product HCN and acetonitrille produced during the manufacture of acrylonitrile comprising introducing a hydrocarbon selected from the group consisting of propylene and propane, a crude ketone of the kind such as herein described ammonia and oxygen containing gas into a reaction zone containing an ammoxidation catalyst of the kind such as herein described reacting the hydrocarbon, crude ketone, ammonia and oxygen over said catalyst at an elevated temperature to produce acrylonitrile, hydrogen cyanide and acetonitrile from the reactor, wherein the temperature ranges from 410°C to 460°C and pressure ranges from 1 to 5 atmosphere.
2. The process as claimed in claim 1, wherein the crude ketone comprises a mixture of at least two Ci to C4 ketones and water.
{
3.
The process as claimed in claim 1, wherein the feed ratio of hydrocarbon : ketone ranges from 1 : 0.01 to 1 : 0.5, on a total carbon basis.
4. The process as claimed in claim 1, wherein the temperature ranges from 405° to 440°C.
5. The process as claimed in claim 1 wherein the crude ketone comprises crude acetone.
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6. The process as claimed in claim 1 wherein the ammoxidation catalyst
is of the formula:
AaBbCcDdMo12Ox, 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 and/or Te, preferably Bi
a * 0.1-4.0, preferably 0.1 to 0.5
b * 0.1-10.0, preferably 5 to 9, and
c, d = 0.1-10.0, preferably 0.5 to 4,
value of *x" depends on the oxidation state of the element used.
7. The process as claimed in claim 1, wherein the said ammoxidation
catalyst is 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, preferably 2 to 12
b= 0.0-12, preferably 1 to 10, and
the value of x depends on the oxidation state of the elements used.
8. The process as claimed in any of the preceding claims, wherein the mixture of ketone comprises at least two C1 to C4 ketones.
9. The process as claimed in claim 8, wherein the mixture of ketones comprises acetone and methyl isobutyl ketone.

Documents:

in-pct-2001-01474-mum-cancelled pages(16-3-2005).pdf

in-pct-2001-01474-mum-cancelled pages(27-4-2005).pdf

in-pct-2001-01474-mum-claims(amanded)-(16-3-2005).pdf

in-pct-2001-01474-mum-claims(complete)-(23-11-2001).pdf

in-pct-2001-01474-mum-claims(granted)-(17-10-2007).pdf

in-pct-2001-01474-mum-claims(granted)-(27-4-2005).pdf

in-pct-2001-01474-mum-correspondence(11-5-2006).pdf

in-pct-2001-01474-mum-correspondence(20-10-2003).pdf

in-pct-2001-01474-mum-correspondence(ipo)-(25-4-2005).pdf

in-pct-2001-01474-mum-correspondence(ipo)-(31-12-2007).pdf

in-pct-2001-01474-mum-description(complete)-(23-11-2001).pdf

in-pct-2001-01474-mum-descriptiongranted)-(17-10-2007).pdf

in-pct-2001-01474-mum-form 1(23-11-2001).pdf

in-pct-2001-01474-mum-form 1(31-12-2001).pdf

in-pct-2001-01474-mum-form 13(27-4-2005).pdf

in-pct-2001-01474-mum-form 19(29-3-2004).pdf

in-pct-2001-01474-mum-form 1a(16-3-2005).pdf

in-pct-2001-01474-mum-form 1a(27-4-2005).pdf

in-pct-2001-01474-mum-form 2(complete)-(23-11-2001).pdf

in-pct-2001-01474-mum-form 2(granted)-(17-10-2007).pdf

in-pct-2001-01474-mum-form 2(granted)-(27-4-2005).pdf

in-pct-2001-01474-mum-form 2(title page)-(complete)-(23-11-2001).pdf

in-pct-2001-01474-mum-form 2(title page)-(granted)-(17-10-2007).pdf

in-pct-2001-01474-mum-form 3(16-3-2005).pdf

in-pct-2001-01474-mum-form 3(20-10-2003).pdf

in-pct-2001-01474-mum-form 3(23-11-2001).pdf

in-pct-2001-01474-mum-form 5(23-11-2001).pdf

in-pct-2001-01474-mum-form 5(26-11-2001).pdf

in-pct-2001-01474-mum-form 5(29-4-2005).pdf

in-pct-2001-01474-mum-form-pct-ipea-409(27-4-2005).pdf

in-pct-2001-01474-mum-form-pct-isa-210(27-4-2005).pdf

in-pct-2001-01474-mum-petition under rule 137(16-3-2005).pdf

in-pct-2001-01474-mum-petition under rule 138(16-3-2005).pdf

in-pct-2001-01474-mum-power of authority(16-3-2005).pdf

in-pct-2001-01474-mum-power of authority(30-10-2001).pdf

in-pct-2001-01474-mum-wo international publication report(20-10-2003).pdf

in-pct2001-01474-mum-claims(granted)-(27-4-2005).doc

in-pct2001-01474-mum-form 2(granted)-(27-4-2005).doc


Patent Number 211102
Indian Patent Application Number IN/PCT/2001/01474/MUM
PG Journal Number 45/2007
Publication Date 09-Nov-2007
Grant Date 17-Oct-2007
Date of Filing 23-Nov-2001
Name of Patentee INEOS USA LLC
Applicant Address 200 EAST RANDOLPH DRIVE, CHICAGO, ILLINOIS 60601, UNITED STATES OF AMERICA
Inventors:
# Inventor's Name Inventor's Address
1 1)MICHAEL J. SEELY 2)SANJAY P. GODBOLE 3)DEV D. SURESH 1581 RAYMOND ROAD, #202, NAPERVILLE, ILLINOIS 60563, USA
2 SANJAY P .GODBOLE 7260 WINCHESTER DRIVE, SOLON, OHIO 44139, USA
3 DEV D. SURESH 2547 CEDARWOOD COURT, HUDSON, OHIO 44036, USA
PCT International Classification Number C07C 253/24, C07C 253/26
PCT International Application Number PCT/US00/13374
PCT International Filing date 2000-05-16
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 09/320,937 1999-05-27 U.S.A.