And Molecular Oxygen Or A Molecular Oxygen Containing Gas Patents (Class 558/319)
  • Patent number: 5556984
    Abstract: The saturated hydrocarbons, typically alkanes having from 3 to 12 carbon atoms, e.g., propane, are selectively ammoxidized into .alpha.,.beta.-unsaturated nitriles and olefins, e.g., acrylonitrile and propylene, by reacting such alkanes with ammonia and oxygen, in vapor phase and in the presence of a solid catalyst, such solid catalyst including a catalytically effective amount of an active catalytic phase which comprises molybdenum, oxygen and at least one element selected from among the alkaline earth metals, Mn, Fe, U, La, Co, Ni, Zn, Ag, Cd, W, Zr, Pb, Te, Ga, Al, B, Nb and Ta.
    Type: Grant
    Filed: March 23, 1994
    Date of Patent: September 17, 1996
    Assignee: Rhone-Poulenc Chimie
    Inventors: Gilbert Blanchard, Elisabeth Bordes, Gilbert Ferre
  • Patent number: 5534650
    Abstract: A method for producing a nitrile by a gas phase catalytic oxidation reaction of an alkane with ammonia in the presence of a catalyst, which comprises supplying the alkane and ammonia to an upper stream inlet of the catalyst layer, and separately supplying at least a part of the total amount of ammonia to a downstream position of the catalyst layer located downstream from the upper stream inlet of the catalyst layer.
    Type: Grant
    Filed: January 12, 1995
    Date of Patent: July 9, 1996
    Assignee: Mitsubishi Chemical Corporation
    Inventors: Takashi Ushikubo, Kazunori Oshima, Tatsuya Ihara, Hiroyuki Amatsu
  • Patent number: 5472925
    Abstract: 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.sub.a V.sub.b Te.sub.c X.sub.x O.sub.n (1)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; and2 the catalyst has X-ray diffraction peaks at the following angles of 2.theta. in its X-ray diffraction pattern:Diffractionangles of 2.theta. (.degree.)22.1.+-.0.328.2.+-.0.336.2.+-.0.345.2.+-.0.350.0.+-.0.3.
    Type: Grant
    Filed: February 7, 1994
    Date of Patent: December 5, 1995
    Assignee: Mitsubishi Chemical Corporation
    Inventors: Takashi Ushikubo, Kazunori Oshima, Atsushi Kayo, Tiaki Umezawa, Ken-ichi Kiyono, Itaru Sawaki, Hiroya Nakamura
  • Patent number: 5466837
    Abstract: An ethylene stream which contains ethane as an impurity or a propylene stream which contains propane as an impurity is subjected to adsorption at a temperature of 50.degree. to 200.degree. C. in a bed of adsorbent which selectively adsorbs ethylene or propylene, thereby adsorbing substantially all of the ethylene or propylene. The purified ethylene or propylene stream is then subjected to partial oxidation in the presence of oxygen and, optionally ammonia to produce various partial oxidation products. The process is operated on a low per pass conversion with recycle of unreacted ethylene or propylene. In the system of the invention the adsorption unit may be upstream or downstream of the partial oxidation reactor.
    Type: Grant
    Filed: April 22, 1994
    Date of Patent: November 14, 1995
    Assignee: The BOC Group, Inc.
    Inventors: Ramakrishnan Ramachandran, Loc H. Dao
  • Patent number: 5466857
    Abstract: A process for the reduction in the amount of waste material generated during the manufacture of acrylonitrile comprising introducing an additional amount of oxygen containing gas, preferably air, in the substantial absence of any oxygenate compounds, into the upper portion of the fluid bed reactor to react with at least some of the unreacted ammonia to reduce the amount of unreacted ammonia present in the reactor effluent.
    Type: Grant
    Filed: August 10, 1994
    Date of Patent: November 14, 1995
    Assignee: The Standard Oil Company
    Inventors: Vincent G. Reiling, Jeffrey E. Rinker, Timothy R. McDonel, Joseph C. Sarna
  • Patent number: 5457223
    Abstract: A process for the substantial or complete elimination of ammonium sulfate generated during the production of acrylonitrile by the direct ammoxidation of propylene/propane, ammonia and an oxygen containing gas (e.g. air) over a fluid bed catalyst wherein the improvement comprises introducing methanol into said reactor in the upper portion of the reactor at a location where the methanol reacts with at least a portion if not substantially all of the excess ammonia without affecting the acrylonitrile yield. Preferably, methanol is introduced into the reactor at below its coking temperature. In particular, when an oxygen lean fluid bed catalyst is utilized, an additional oxygen containing gas is introduced into the reaction at a distance between about 8 to 14 inches from the methanol feed location.
    Type: Grant
    Filed: August 11, 1993
    Date of Patent: October 10, 1995
    Assignee: The Standard Oil Company
    Inventors: Wilfrid G. Shaw, Kenneth L. Bigler, Louis R. Trott, Steve J. Miko, Vincent G. Reiling, Michael J. Seely, Dev D. Suresh, Maria S. Friedrich, Paul E. Bott, Edward J. Sockell, Albert R. Shuki, Jr., Kenneth P. Keckler, Frank J. Kocjancic, Steven J. Rowe
  • Patent number: 5422328
    Abstract: A process for preparing a catalyst useful for producing a nitrile by a gas phase catalytic oxidation reaction of an alkane with ammonia, which comprises drying a solution or slurry containing molybdenum, vanadium and tellurium by a spray drying method or a freeze-drying method and heat-treating the resulting dried product.
    Type: Grant
    Filed: December 27, 1993
    Date of Patent: June 6, 1995
    Assignee: Mitsubishi Kasei Corporation
    Inventors: Takashi Ushikubo, Itaru Sawaki, Kazunori Oshima, Kei Inumaru, Satoshi Kobayakawa, Ken-ichi Kiyono
  • Patent number: 5336804
    Abstract: The alkanes, e.g., propane, are ammoxidized into admixtures containing .alpha.,.beta.-unsaturated nitriles, e.g., admixture of acrylonitrile and propylene, by reacting such alkane with ammonia and oxygen, in vapor phase, in the presence of a catalytically effective amount of a solid catalyst, at least one active catalytic phase of which having the empirical formula (I):VSb.sub.a Bi.sub.b O.sub.x (I)optionally also containing iron and/or gallium and/or indium, in which a is a whole or fractional number equal to or greater than 1, b is a whole or fractional number equal to or greater than 0.01, and x is a whole or fractional number provided by the oxidation number of the other elements of the at least one active catalytic phase.
    Type: Grant
    Filed: February 8, 1993
    Date of Patent: August 9, 1994
    Assignee: Rhone-Poulenc Chimie
    Inventors: Gilbert Blanchard, Gilbert Ferre
  • Patent number: 5334743
    Abstract: The alkanes, e.g., propane, are selectively converted (ammoxidized) into admixtures comprising .alpha.,.beta.-unsaturated nitriles, e.g., acrylonitrile, by reacting same with ammonia and oxygen, in vapor phase, and in the presence of a catalytically effective amount of a solid catalyst, the catalytically active phase of which comprising (1) molybdenum, vanadium and oxygen and (2) at least one of the elements, manganese, zinc, cobalt, copper, lithium, sodium, potassium and silver.
    Type: Grant
    Filed: December 16, 1992
    Date of Patent: August 2, 1994
    Assignee: Rhone-Poulenc Chimie
    Inventors: Gilbert Blanchard, Elisabeth Bordes, Gilbert Ferre
  • Patent number: 5332855
    Abstract: The alkanes, e.g., propane, are ammoxidized into admixtures containing .alpha.,.beta.-unsaturated nitriles, e.g., admixture of acrylonitrile and propylene, by reacting such alkane with ammonia and oxygen, in vapor phase, in the presence of a catalytically effective amount of a solid catalyst, at least one active catalytic phase of which having empirical formula (I):VSb.sub.a M.sub.b O.sub.x (I)in which a is a whole or fractional number equal to or greater than 1, M is iron and/or gallium and/or indium, b is a whole or fractional number equal to or greater than 0.5, and x is a whole or fractional number provided by the oxidation number of the other elements of the at least one active catalytic phase.
    Type: Grant
    Filed: February 12, 1993
    Date of Patent: July 26, 1994
    Assignee: Rhone-Poulenc Chimie
    Inventors: Gilbert Blanchard, Gilbert Ferre
  • Patent number: 5288473
    Abstract: A process for the substantial or complete elimination of ammonium sulfate generated during the production of acrylonitrile by the direct ammoxidation of propylene/propane, ammonia and an oxygen containing gas (e.g. air) over a fluid bed catalyst wherein the improvement comprises introducing an organic compound(s) into said reactor at a location where the compound(s) reacts with substantially all of the excess ammonia without affecting the acrylonitrile yield. Preferably, the organic compound is methanol which is introduced into the reactor at below its coking temperature.
    Type: Grant
    Filed: October 9, 1992
    Date of Patent: February 22, 1994
    Assignee: The Standard Oil Company
    Inventors: Wilfrid G. Shaw, Kenneth L. Bigler, Louis R. Trott, Steve J. Miko, Vincent G. Reiling, Michael J. Seely, Dev D. Suresh, Maria S. Friedrich, Paul E. Bott, Edward J. Sockell, Albert R. Shuki, Jr., Kenneth P. Keckler, Frank J. Kojancic
  • Patent number: 5281745
    Abstract: A process for producing a nitrile, which comprises subjecting an alkane and ammonia in the gaseous state to catalytic oxidation in the presence of a catalyst which satisfies the following conditions of (1) and (2):(1) the catalyst is represented by the empirical formula:Mo.sub.a V.sub.b Te.sub.c X.sub.x O.sub.n (1)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.theta. in its X-ray diffraction pattern: ______________________________________ Diffraction angles of 2.theta. (.degree.) ______________________________________ 22.1 .+-. 0.3 28.2 .+-. 0.3 36.2 .+-. 0.3 45.2 .+-. 0.3 50.0 .+-. 0.3.
    Type: Grant
    Filed: August 7, 1992
    Date of Patent: January 25, 1994
    Assignee: Mitsubishi Kasei Corporation
    Inventors: Takashi Ushikubo, Kazunori Oshima, Atsushi Kayo, Tiaki Umezawa, Ken-ichi Kiyono, Itaru Sawaki
  • Patent number: 5278319
    Abstract: An improved process is provided for the production of a partial oxidation product by the vapor phase reaction of a hydrocarbon with substantially pure oxygen in the presence of a suitable catalyst. In the improved process, the partial oxidation product is removed, carbon dioxide and excess carbon monoxide, present in the reactor effluent as by-products, are also removed and the remaining gaseous effluent, comprised mainly of carbon monoxide and unreacted hydrocarbon, is recycled to the reactor. The concentration of carbon monoxide throughout the system is maintained sufficiently high to prevent the formation of a flammable mixture in the reactor or associated equipment.
    Type: Grant
    Filed: April 14, 1992
    Date of Patent: January 11, 1994
    Assignee: The BOC Group, Inc.
    Inventors: Ramakrishnan Ramachandran, Loc Dao, Donald L. MacLean
  • Patent number: 5268497
    Abstract: A process for the production of an ethylenically unsaturated nitrile from a hydrocarbon feed stream comprised of a mixture of an alkene and an alkane by reaction with an oxygen-containing gas and ammonia. The alkene is converted to unsaturated nitrile by reaction with the oxygen and ammonia in the presence of a suitable catalyst in an ammoxidation reactor; the nitrile product is recovered from the product stream; some of the byproduct carbon oxides and some of the inert gas introduced into the system with the reactants are removed from product stream and the remainder of this stream, now rich in unreacted alkene and alkane, and containing the rest of the byproduct gases and inert gases is introduced into a reactor which contains a catalyst that causes alkane contained in the gas stream to convert to the corresponding alkene. The effluent from the dehydrogenation reactor is recycled to the ammoxidation reactor.
    Type: Grant
    Filed: February 24, 1992
    Date of Patent: December 7, 1993
    Assignee: The BOC Group, Inc.
    Inventor: Ramakrishnan Ramachandran
  • Patent number: 5264608
    Abstract: A process for the production of an ethylenically unsaturated nitrile from a hydrocarbon feed stream comprised of a mixture of an alkene and an alkane by reaction with an oxygen-containing gas and ammonia. The alkene is converted to unsaturated nitrile by reaction with the oxygen and ammonia in the presence of a suitable catalyst in a first ammoxidation reactor; the nitrile product is recovered from the product stream; some of the byproduct carbon oxides and some of the inert gas introduced into the system with the reactants are removed from product stream and the remainder of this stream, now rich in unreacted alkene and alkane, and containing the rest of the byproduct gases and inert gases is introduced with additional oxygen-containing gas and ammonia into a second ammoxidation reactor which contains a catalyst that catalyzes reaction between the alkane, oxygen and ammonia to produce additional unsaturated nitrile.
    Type: Grant
    Filed: February 24, 1992
    Date of Patent: November 23, 1993
    Assignee: The BOC Group, Inc.
    Inventor: Ramakrishnan Ramachandran
  • Patent number: 5231214
    Abstract: A process for producing a nitrile, which comprises subjecting an alkane and ammonia in the gaseous state to catalytic oxidation in the presence of an oxide of the formula:Mo.sub.a V.sub.b Te.sub.c Nb.sub.d X.sub.x O.sub.n ( 1)wherein X is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, Al, Ga, Tl, In, Ti, Zr, Hf, Ta, Cr, Mn, W, Fe, Ru, Co, Rh, Ni, Pd, Pt, Zn, Sn, Pb, As, Sb, Bi, La and Ce,when a=1,b=0.01 to 1.0,c=0.01 to 1.0,d=0 to 1.0, andx=0.0005 to 1.0,and n is a number such that the total valency of the metal elements is satisfied.
    Type: Grant
    Filed: May 8, 1992
    Date of Patent: July 27, 1993
    Assignee: Mitsubishi Kasei Corporation
    Inventors: Takashi Ushikubo, Kazunori Oshima, Tiaki Umezawa, Ken-ichi Kiyono
  • Patent number: 5220090
    Abstract: A method for preparing an unsaturated compound mainly comprising monoolefins, or a mixture of .alpha., .beta.-unsaturated nitriles and monoolefins comprises coming a mixed gas which comprises paraffins and oxygen, or paraffins, oxygen and ammonia in contact with a catalyst which comprises (1) an oxide of phosphorus and (2) at least one oxide selected from the group consisting of indium oxide and tin oxide or comprises, in addition to the foregoing catalytic components, (3) at least one oxide selected from the group consisting of vanadium oxide, tungsten oxide and molybdenum oxide. The method makes it possible to prepare monoolefins, or a mixture of .alpha., .beta.-unsaturated nitriles and monoolefins in high yield and high selectivity from cheap starting materials, parafins.
    Type: Grant
    Filed: November 9, 1990
    Date of Patent: June 15, 1993
    Assignee: Mitsui Toatsu Chemicals, Inc.
    Inventors: Tadatoshi Honda, Kazuhiro Terada
  • Patent number: 5220049
    Abstract: A method for preparing an unsaturated compound mainly comprising monoolefins, or a mixture of .alpha., .beta.-unsaturated nitriles and monoolefins comprises coming a mixed gas which comprises paraffins and oxygen, or paraffins, oxygen and ammonia in contact with a catalyst which comprises (1) an oxide of phosphorus and (2) at least one oxide selected from the group consisting of indium oxide and tin oxide or comprises, in addition to the foregoing catalytic components, (3) at least one oxide selected from the group consisting of vanadium oxide, tungsten oxide and molybdenum oxide. The method makes it possible to prepare monoolefins, or a mixture of .alpha., .beta.-unsaturated nitriles and monoolefins in high yield and high selectivity from cheap starting materials, parafins.
    Type: Grant
    Filed: November 17, 1992
    Date of Patent: June 15, 1993
    Assignee: Mitsui Toatsu Chemicals, Inc.
    Inventors: Tadatoshi Honda, Kazuhiro Terada
  • Patent number: 5171876
    Abstract: Disclosed is a process for making an .alpha., .beta.-unsaturated mononitrile by the catalytic reaction of a paraffin containing 3-5 carbon atoms with molecular oxygen and ammonia by catalytic contact of the foregoing reactants in a reaction zone with a metal oxide catalyst containing the elements indicated by the empirical formula,Cr.sub.a Mo.sub.b Te.sub.c M.sub.d O.sub.x (formula 1)whereM=one or more of Mg, Ni, Sb, Ti, La, P, Ce, Fe, Nb, W, V, and Cu, each of a, b & c is 0.1 to 10d is zero to 10a+b+c>1.5d, andx is determined by the valence requirements of the other elements present, andwherein the reactants fed to the reaction zone contain a mole ratio of said paraffin:NH.sub.3 in the range from 2.5 to 16 and a mole ratio of said paraffin:O.sub.2 in the range from 1 to 10.
    Type: Grant
    Filed: September 16, 1991
    Date of Patent: December 15, 1992
    Assignee: The Standard Oil Company
    Inventors: Dev D. Suresh, Michael J. Seeley, Jeanette R. Nappier, Maria S. Friedrich
  • Patent number: 5049692
    Abstract: Disclosed herein is a process for producing a nitrile which comprises subjecting an alkane to a gas-phase catalytic oxidation reaction with ammonia in the presence of a complex oxide solid catalyst composed of molybdenum, vanadium, tellurium and niobium.According to the process of the present invention, it is possible to produce the objective nitrile at a high selectivity without using a halide, water, etc., moreover, at a relatively low temperature of about 350.degree. to 480.degree. C., particularly about 400.degree. to 450.degree. C.
    Type: Grant
    Filed: April 26, 1990
    Date of Patent: September 17, 1991
    Assignee: Mitsubishi Kasei Corporation
    Inventors: Masakatsu Hatano, Atsushi Kayo
  • Patent number: 5015756
    Abstract: An improved process is provided for the production of nitriles from hydrocarbons by reaction with an oxygen-containing gas comprising oxygen, air or a gas enriched in oxygen relative to air and ammonia in the presence of a suitable catalyst. In the process, a selective separator provides recycle of a substantial portion of the unreacted hydrocarbon as well as for a controlled amount of a gaseous flame suppressor in the system. The gaseous flame suppressor comprises a substantially unreactive hydrocarbon containing 1 to 5 carbon atoms, carbon dioxide and nitrogen when present in the feed to the ammoxidation reactor. The use of air or oxygen-enriched air in the feed to the ammoxidation reactor is particularly advantageous from an economic view in combination with a pressure swing adsorption unit as the selective separator. The process is characterized by high selectivity to the formation of the product.
    Type: Grant
    Filed: May 1, 1989
    Date of Patent: May 14, 1991
    Assignee: The BOC Group, Inc.
    Inventors: Ramakrishnan Ramachandran, Yagya Shukla, Donald L. MacLean
  • Patent number: 5008427
    Abstract: Disclosed is a process for making an .alpha., .beta.-unsaturated mononitrile, acrylonitrile or methacrylonitrile, by the catalytic reaction in the vapor phase of a paraffin selected from propane and isobutane with molecular oxygen and ammonia and optionally a gaseous diluent, by catalytic contact of the foregoing reactants in a reaction zone with a catalyst, the feed to said reaction zone containing a mole ratio of said paraffin to NH.sub.3 in the rnage from 2.5 to 16 and a mole ratio of said paraffin to O.sub.2 in the range from 1 to 10, said catalyst having the elements and the proportions indicated by the empirical formula:VSb.sub.m A.sub.a D.sub.d O.sub.xwhereA is one or more Ti, Sn, Fe, Cr, GaD is one or more Li, Mg, Ca, Sr, Ba, Co, Ni, Zn, Ge, Nb, Zr, Mo, W, Cu, Te, Ta, Se, Bi, Ce, In, As, B, Mn andm is 0.8-4a is 0.01-2d is 0-2x is determined by the oxidation state of the cations present,which catalyst has been heated at a calcination temperature of at least 780.degree. C.
    Type: Grant
    Filed: December 23, 1988
    Date of Patent: April 16, 1991
    Assignee: The Standard Oil Company
    Inventors: James F. Brazdil, Jr., Mark A. Toft, Linda C. Glaeser
  • Patent number: 4978764
    Abstract: Disclosed is a process f9or making an .alpha., .beta.-unsaturated mononitrile by the catalytic reaction of a paraffin containing 3-5 carbon atoms with molecular oxygen and ammonia by catalytic contact of the foregoing reactants in a reaction zone with a metal oxide catalyst composition that has 10-90 weight percent of a diluent/support and 90-10 weight percent of a catalyst containing the elements indicated by the empirical formula,A.sub.a D.sub.d Bi.sub.c Fe.sub.f Mo.sub.12 O.sub.xin the proportions indicated by the said formula, said diluent/support containing 10 to 100 weight percent Al.sub.2 O.sub.3 and zero to 90 weight percent SiO.sub.2 whereinA is one or more of Li, Na, K, Rb, Cs, Tl B, W, Sn and La;D is one or more of Cr, Sb, Pb, P, Cu, Ni, Co, Mn and Mg;a is zero to 10;c is 0.1 to 10;d is zero to 10; andf is 0.2 to 10; andwherein the reactants fed to the reaction zone contain a mole ratio of said paraffin:NH.sub.3 in the range from 2 to 16 and a mole ratio of said paraffin to O.sub.
    Type: Grant
    Filed: September 25, 1989
    Date of Patent: December 18, 1990
    Assignee: The Standard Oil Company
    Inventors: Michael J. Seely, Maria S. Friedrich, Dev D. Suresh
  • Patent number: 4960921
    Abstract: Certain novel multiply promoted Mn-Sb oxides are superior catalysts for the ammoxidation of olefins to the corresponding unsaturated nitriles, the selective oxidation of olefins to unsaturated aldehydes and acids, and the oxydehydrogenation of olefins to diolefins.
    Type: Grant
    Filed: February 12, 1990
    Date of Patent: October 2, 1990
    Assignee: The Standard Oil Company
    Inventors: Dev. D. Suresh, Robert K. Grasselli, Frances I. Ratka, James F. Brazdil
  • Patent number: 4943650
    Abstract: An improved process is provided for the production of nitriles and oxides from hydrocarbons by reaction with oxygen, air or a gas enriched in oxygen relative to air, preferably the latter, and ammonia where a nitrile is desired, in the presence of a suitable catalyst. An alkane, e.g. propane, is converted to an alkene in a catalytic dehydrogenator. The product stream is introduced into an ammoxidation reactor. The product formed therein is recovered in a conventional quench tower. The pressure of the gaseous effluent from the quench tower is raised and it is introduced into an absorber/stripper unit to form a recycle stream containing unreacted alkane and alkene as well as a minor amount of oxygen, typically 1-2 percent by volume, and a waste stream comprising the remainder of the quench tower gaseous phase. The recycle stream is introduced into a selective oxidation unit to remove the oxygen therefrom and then recycled to the dehydrogenator.
    Type: Grant
    Filed: January 30, 1989
    Date of Patent: July 24, 1990
    Assignee: The BOC Group, Inc.
    Inventors: Ramakrishnan Ramachandran, Mark J. Andrecovich, Donald L. MacLean, Donald P. Satchell, Jr.
  • Patent number: 4918214
    Abstract: Disclosed is the reaction of propane and isobutane with O.sub.2 and NH.sub.3 to make .alpha.,.beta.-unsaturated nitriles and olefins, using certain complex metal oxide catalyst compositions and an excess of the paraffin over both the O.sub.2 and the NH.sub.3. Also disclosed are suitable catalyst compositions for such reactions.
    Type: Grant
    Filed: July 3, 1989
    Date of Patent: April 17, 1990
    Assignee: The Standard Oil Company
    Inventors: James F. Brazdil, Jr., Linda C. Glaeser, Mark A. Toft
  • Patent number: 4897504
    Abstract: Disclosed is ammoxidation of C.sub.3 to C.sub.5 acyclic alkanes with NH.sub.3 and O.sub.2 using (1) a mole ratio of alkane:NH.sub.3 in the range from 2 to 16 and a mole ratio of alkane:O.sub.2 in the range 1 to 10 and (2) a mixture of particulate catalyst compositions, the first being especially effective to promote formation of an unsaturated nitrile and an olefin from the paraffin, and the second catalyst composition being especially effective to promote the conversion of the olefin to the unsaturated mononitrile. Catalyst compositions useful in the process are also disclosed.
    Type: Grant
    Filed: November 14, 1988
    Date of Patent: January 30, 1990
    Assignee: The Standard Oil Company
    Inventors: Linda C. Glaeser, James F. Brazdil, Jr., Mark A. Toft
  • Patent number: 4888438
    Abstract: Disclosed is ammoxidation of C.sub.3 to C.sub.5 acyclic alkanes with NH.sub.3 and O.sub.2 using (1) a mole ratio of alkane:NH.sub.3 in the range from 2 to 16 and a mole ratio of alkane:O.sub.2 in the range 1 to 10 and (2) a mixture of particulate catalyst compositions, the first being especially effective to promote formation of an unsaturated nitrile and an olefin from the paraffin, and the second catalyst composition being especially effective to promote the conversion of the olefin to the unsaturated nitrile. Catalyst compositions useful in the process are also disclosed.
    Type: Grant
    Filed: October 31, 1988
    Date of Patent: December 19, 1989
    Assignee: The Standard Oil Company
    Inventors: Linda C. Glaeser, James F. Brazdil, Jr., Mark A. Toft
  • Patent number: 4883896
    Abstract: Disclosed is ammoxidation of C.sub.3 to C.sub.5 acyclic alkanes with NH.sub.3 and O.sub.2 using (1) a mole ratio of alkane:NH.sub.3 in the range from 2 to 16 and a mole ratio of alkane:O.sub.2 in the range 1 to 10 and (2) a mixture of particulate catalyst compositions, the first being especially effective to promote formation of an unsaturated nitrile and an olefin from the paraffin, and the second catalyst composition being especially effective to promote the conversion of the olefin to the unsaturated mononitrile. Catalyst compositions useful in the process are also disclosed.
    Type: Grant
    Filed: November 14, 1988
    Date of Patent: November 28, 1989
    Assignee: The Standard Oil Company
    Inventors: Linda C. Glaeser, James F. Brazdil, Jr., Mark A. Toft
  • Patent number: 4883895
    Abstract: Disclosed is the reaction of propane and isobutane with O.sub.2 and NH.sub.3 to make .alpha.,.beta.-unsaturated nitriles and olefins, using certain complex metal oxide catalyst compositions and an excess of the paraffin over both the O.sub.2 and the NH.sub.3. Also disclosed are suitable catalyst compositions for such reactions.
    Type: Grant
    Filed: May 8, 1989
    Date of Patent: November 28, 1989
    Assignee: The Standard Oil Company
    Inventors: James F. Brazdil, Jr., Linda C. Glaeser, Mark A. Toft
  • Patent number: 4877764
    Abstract: Disclosed is ammoxidation of C.sub.3 to C.sub.5 acyclic alkanes with NH.sub.3 and O.sub.2 using (1) a mole ratio of alkane:NH.sub.3 in the range from 2 to 16 and a mole ratio of alkane:O.sub.2 in the range 1 to 10 and (2) a mixture of particulate catalyst compositions, the first being especially effective to promote formation of an unsaturated nitrile and an olefin from the paraffin, and the second catalyst composition being especially effective to promote the conversion of the olefin to the unsaturated nitrile. Catalyst compositions useful in the process are also disclosed.
    Type: Grant
    Filed: July 22, 1988
    Date of Patent: October 31, 1989
    Assignee: The Standard Oil Company
    Inventors: Linda C. Glaeser, James F. Brazdil, Jr., Mark A. Toft
  • Patent number: 4874738
    Abstract: Disclosed is the reaction of propane and isobutane with O.sub.2 and NH.sub.3 to make .alpha.,.beta.-unsaturated nitriles and olefins, using certain complex metal oxide catalyst compositions and an excess of the paraffin over both the O.sub.2 and the NH.sub.3. Also disclosed are suitable catalyst compositions for such reactions.
    Type: Grant
    Filed: September 9, 1988
    Date of Patent: October 17, 1989
    Assignee: The Standard Oil Company
    Inventors: James F. Brazdil, Jr., Linda C. Glaeser, Mark A. Toft
  • Patent number: 4871706
    Abstract: Disclosed is the reaction of C.sub.3 to C.sub.4 paraffins with O.sub.2 and NH.sub.3 to make .alpha.,.beta.-unsaturated nitriles and olefins, using certain complex metal oxide catalysts containing V, Sb, W and certain optional elements.
    Type: Grant
    Filed: December 16, 1987
    Date of Patent: October 3, 1989
    Assignee: The Standard Oil Company
    Inventors: James F. Brazdil, Jr., Linda C. Glaeser, Mark A. Toft
  • Patent number: 4870201
    Abstract: An improved process is provided for the production of nitriles from hydrocarbons by reaction with oxygen, air or a gas enriched in oxygen relative to air, preferably the latter, and ammonia in the presence of an ammoxidation catalyst. An alkane, e.g., propane, is converted to an alkene in a catalytic dehydrogenator. The product stream is introduced into an ammoxidation reactor. The product formed therein is recovered in a conventional quench tower. The gaseous effluent from the quench tower is treated in a PSA unit comprising at least two pairs of adsorptive beds. The first bed forms a gas stream containing the unreacted alkane and alkene as well as a minor amount, typically 1-2 percent by volume, of oxygen and a vent stream containing oxygen, nitrogen if present, and hydrogen. The vent stream is introduced into the second adsorptive bed to thereby form an oxygen-containing stream which also contains, nitrogen, if present, and a hydrogen-enriched stream.
    Type: Grant
    Filed: December 8, 1988
    Date of Patent: September 26, 1989
    Assignee: The BOC Group, Inc.
    Inventors: Ramakrishnan Ramachandran, Virginia A. Malik, Donald L. MacLean, Donald P. Satchell, Jr.
  • Patent number: 4868330
    Abstract: An improved process is provided for the production of nitriles from hydrocarbons by reaction with an oxygen-containing gas comprising oxygen, air or a gas enriched in oxygen relative to air and ammonia in the presence of a suitable catalyst. In the process, a selective separator provides recycle of a substantial portion of the unreacted hydrocarbon as well as for a controlled amount of a gaseous flame suppressor in the system. The gaseous flame suppressor comprises a substantially unreactive hydrocarbon containing 1 to 5 carbon atoms, carbon dioxide and nitrogen when present in the feed to the ammoxidation reactor. The use of air or oxygen-enriched air in the feed to the ammoxidation reactor is particularly advantageous from an economic view in combination with a pressure swing adsorption unit as the selective separator. The process is characterized by high selectivity to the formation of the product.
    Type: Grant
    Filed: July 7, 1988
    Date of Patent: September 19, 1989
    Assignee: The BOC Group, Inc.
    Inventors: Ramakrishnan Ramachandran, Yagya Shukla, Donald L. MacLean
  • Patent number: 4866195
    Abstract: Ammoxidation of C.sub.3 to C.sub.5 acyclic alkanes with NH.sub.3 and O.sub.2 using (1) a mole ratio of alkane:NH.sub.3 in the range from 2 to 16 and a mole ratio of alkane:O.sub.2 in the range 1 to 10 and (2) a mixture of particulate catalyst compositions, the first being especially effective to promote formation of an unsaturated nitrile and an olefin from the paraffin, and the second catalyst composition being especially effective to promote the conversion of the olefin to the unsaturated nitrile. Catalytic compositions useful in the process are disclosed.
    Type: Grant
    Filed: August 22, 1988
    Date of Patent: September 12, 1989
    Assignee: The Standard Oil Company
    Inventors: James F. Brazdil, Jr., Linda C. Glaeser, Mark A. Toft
  • Patent number: 4866194
    Abstract: Disclosed is ammoxidation of C.sub.3 to C.sub.5 acyclic alkanes with NH.sub.3 and O.sub.2 using (1) a mole ratio of alkane:NH.sub.3 in the range from 2 to 16 and a mole ratio of alkane:O.sub.2 in the range 1 to 10 and (2) a mixture of particulate catalyst compositions, the first being especially effective to promote formation of an unsaturated nitrile and an olefin from the paraffin, and the second catalyst composition being especially effective to promote the conversion of the olefin to the unsaturated mononitrile. Catalyst compositions useful in the process are also disclosed.
    Type: Grant
    Filed: November 14, 1988
    Date of Patent: September 12, 1989
    Assignee: The Standard Oil Company
    Inventors: Linda C. Glaeser, James F. Brazdil, Jr., Mark A. Toft
  • Patent number: 4866024
    Abstract: Disclosed is the reaction of propane and isobutane with O.sub.2 and NH.sub.3 to make .alpha.,.beta.-unsaturated nitriles and olefins, using certain complex metal oxide catalyst compositions and an excess of the paraffin over both the O.sub.2 and the NH.sub.3. Also disclosed are suitable catalyst compositions for such reactions.
    Type: Grant
    Filed: September 29, 1988
    Date of Patent: September 12, 1989
    Assignee: The Standard Oil Company
    Inventors: James F. Brazdil, Jr., Linda C. Glaeser, Mark A. Toft
  • Patent number: 4849537
    Abstract: An improved process is provided for the production of nitriles from hydrocarbons by reaction with oxygen, air or gas-enriched in relative to an air, and ammonia, in the presence of an ammoxidation catalyst. An alkane, e.g. propane, is converted to an alkene in a multistage dehydrogenator. The product stream is withdrawn from a reactor in the dehydrogenator other than the first and the last reactor and introduced into an ammoxidation reactor. The product is recovered in a conventional quench tower. The gaseous effluent from the quench tower is treated in a pressure swing adsorption unit to form a gas stream containing the unreacted alkane and alkene as well as a minor amount of oxygen. The gas stream, which may or may not contain hydrogen depending on the absorbent in the pressure swing adsorption unit, is introduced into the reactor in the dehydrogenator following that from which the product stream was withdrawn.
    Type: Grant
    Filed: July 6, 1988
    Date of Patent: July 18, 1989
    Assignee: The BOC Group, Inc.
    Inventors: Ramakrishnan Ramachandran, Donald L. MacLean, Donald P. Satchell, Jr.
  • Patent number: 4849538
    Abstract: An improved process is provided for the production of nitriles from hydrocarbons by reaction with oxygen, air or a gas enriched in oxygen relative to air, preferably the latter, and ammonia in the presence of an ammoxidation catalyst. An alkane, e.g. propane, is converted to an alkene in a dehydrogenator. The product stream is introduced into an ammoxidation reactor. The product formed therein is recovered in a conventional quench tower. The gaseous effluent from the quench tower is treated in a PSA unit to form a gas stream containing the unreacted alkane and alkene as well as a minor amount, i.e. less than about 1 percent by volume, of oxygen and nitrogen, if present in the feed to the ammoxidation reactor. The gas stream, which may or may not contain hydrogen depending on the absorbent in the PSA unit, is introduced into a selective oxidation unit to remove the remaining oxygen and then recycled to the dehydrogenator.
    Type: Grant
    Filed: July 6, 1988
    Date of Patent: July 18, 1989
    Assignee: The BOC Group, Inc.
    Inventors: Ramakrishnan Ramachandran, Donald L. MacLean, Donald P. Satchell, Jr.
  • Patent number: 4843055
    Abstract: Disclosed is ammoxidation of C.sub.3 to C.sub.5 acyclic alkanes with NH.sub.3 and O.sub.2 using (1) a mole ratio of alkane:NH.sub.3 in the range from 2 to 16 and a mole ratio of alkane:O.sub.2 in the range 1 to 10 and (2) a mixture of particulate catalyst compositions, the first being especially effective to promote formation of an unsaturated nitrile and an olefin from the paraffin, and the second catalyst composition being especially effective to promote the conversion of the olefin to the unsaturated mononitrile. Catalyst compositions useful in the process are also disclosed.
    Type: Grant
    Filed: May 16, 1988
    Date of Patent: June 27, 1989
    Assignee: The Standard Oil Company
    Inventors: Linda C. Glaeser, James F. Brazdil, Jr.
  • Patent number: 4837233
    Abstract: Ammoxidation of C.sub.3 to C.sub.5 acyclic alkanes with NH.sub.3 and O.sub.2 using (1) a mole ratio of alkane:NH.sub.3 in the range from 2 to 16 and a mole ratio of alkano:O.sub.2 in the range 1 to 10 and (2) a mixture of particulate catalyst composition, the first being especially effective to promote formation of an unsaturated nitrile and an olefin from the paraffin, and the second catalyst composition being especially effective to promote the conversion of the olefin to the unsaturated nitrile. Catalytic compositions useful in the process are disclosed.
    Type: Grant
    Filed: May 15, 1987
    Date of Patent: June 6, 1989
    Assignee: The Standard Oil Company
    Inventors: Linda C. Glaeser, James F. Brazdil, Jr., Mark A. Toft
  • Patent number: 4837191
    Abstract: Disclosed is ammoxidation of C.sub.3 to C.sub.5 acyclic alkanes with NH.sub.3 and O.sub.2 using (1) a mole ratio of alkane:NH.sub.3 in the range from 2 to 16 and a mole ratio of alkane:O.sub.2 in the range 1 to 10 and (2) a mixture of particulate catalyst compositions, the first being especially effective to promote formation of an unsaturated nitrile and an olefin from the paraffin, and the second catalyst composition being especially effective to promote the conversion of the olefin to the unsaturated mononotrile. Catalyst compositions useful in the process are also disclosed.
    Type: Grant
    Filed: June 9, 1988
    Date of Patent: June 6, 1989
    Assignee: The Standard Oil Company
    Inventors: Linda C. Glaeser, James F. Brazdil, Jr., Mark A. Toft
  • Patent number: 4835125
    Abstract: Disclosed is ammoxidation of C.sub.3 to C.sub.5 acyclic alkanes with NH.sub.3 and O.sub.2 using (1) a mole ratio of alkane:NH.sub.3 in the range from 2 to 16 and a mole ratio of alkane:O.sub.2 in the range 1 to 10 and (2) a mixture of particular catalyst compositions, the first being especially effective to promote formation of an unsaturated nitrile and an olefin from the paraffin, and the second catalyst composition being especially effective to promote the conversion of the olefin to the unsaturated mononitrile. Catalyst compositions useful in the process are also disclosed.
    Type: Grant
    Filed: May 31, 1988
    Date of Patent: May 30, 1989
    Assignee: The Standard Oil Company
    Inventors: Linda C. Glaeser, James F. Brazdil, Jr., Mark A. Toft
  • Patent number: 4814478
    Abstract: Disclosed is ammoxidation of C.sub.3 to C.sub.5 acyclic alkanes with NH.sub.3 and O.sub.2 using (1) a mole ratio of alkane:NH.sub.3 in the range from 2 to 16 and a mole ratio of alkane:O.sub.2 in the range 1 to 10 and (2) a mixture of particulate catalyst compositions, the first being especially effective to promote formation of an unsaturated nitrile and an olefin from the paraffin, and the second catalyst comosition being especially effective to promote the conversion of the olefin to the unsaturated nitrile. Catalyst compositions useful in the process are also disclosed.
    Type: Grant
    Filed: March 28, 1988
    Date of Patent: March 21, 1989
    Assignee: The Standard Oil Company
    Inventors: Linda C. Glaeser, James F. Brazdil, Jr., Mark A. Toft
  • Patent number: 4801727
    Abstract: Ammoxidation of C.sub.3 to C.sub.5 acyclic alkanes with NH.sub.3 and O.sub.2 using (1) a mole ratio of alkane:NH.sub.3 in the range from 2 to 16 and a mole ratio of alkane:O.sub.2 in the range 1 to 10 and (2) a mixture of particulate catalyst compositions, the first being especially effective to promote formation of an unsaturated nitrile and an olefin from the paraffin, and the second catalyst composition being especially effective to promote the conversion of the olefin to the unsaturated nitrile. Catalytic compositions useful in the process are disclosed.
    Type: Grant
    Filed: March 28, 1988
    Date of Patent: January 31, 1989
    Assignee: The Standard Oil Company
    Inventors: Linda C. Glaeser, James F. Brazdil, Jr., Mark A. Toft
  • Patent number: 4788317
    Abstract: Disclosed is a process for ammoxidation of paraffins containing 3-5 C atoms using a complex metal oxide catalyst which is essentially free of bismuth, and has the elements and the proportions which are represented by the following empirical formula:VSb.sub.m P.sub.n A.sub.a D.sub.b C.sub.c O.sub.xwhereA is one of more of W, Sn, B, Mo and As;D is one or more of Fe, Co, Ni, Cr, Mn, Cu, Pb, Zn, Se, Te and As;C is one or more of an alkali metal, Ca, Sr, Ba, T1 and where m is greater than 1 and up to 20; n is 0-10; a is 0.2-10; b is 0-5; c is 0-1; a is equal to or less than m; b is equal to or less than m; wherein x is determined by oxidation state of the other elements present, and wherein the antimony has an average valency higher than +3 and the vanadium has an average valency lower than +5, wherein A includes at least 0.2 atoms of W, crystalline Sb.sub.2 O.sub.4 is present in said catalyst, and wherein the foregoing catalyst is on a specified inorganic oxide support material.
    Type: Grant
    Filed: May 8, 1987
    Date of Patent: November 29, 1988
    Assignee: Standard Oil Company
    Inventors: Andrew T. Guttmann, Robert K. Grasselli, James F. Brazdil, Jr.
  • Patent number: 4783545
    Abstract: Ammoxidation of C.sub.3 to C.sub.5 acyclic alkanes with NH.sub.3 and O.sub.2 using (1) a mole ratio of alkane:NH.sub.3 in the range from 2 to 16 and a mole ratio of alkane:O.sub.2 in the range 1 to 10 and (2) a mixture of particulate catalyst compositions, the first being especially effective to promote formation of an unsaturated nitrile and an olefin from the paraffin, and the second catalyst composition being especially effective to promote the conversion of the olefin to the unsaturated nitrile. Catalytic compositions useful in the process are disclosed.
    Type: Grant
    Filed: December 23, 1987
    Date of Patent: November 8, 1988
    Assignee: The Standard Oil Company
    Inventors: Linda C. Glaeser, James F. Brazdil, Jr., Mark A. Toft
  • Patent number: 4774352
    Abstract: The activity of a tellurium-free metal oxide catalyst used for ammoxidation of organic compounds at a temperature of from 300.degree. C. to 600.degree. C. is improved in the presence of (a) elemental tellurium or a tellurium compound which is in contact with said catalyst or in the presence of (a) elemental tellurium or a tellurium compound and (b) a molybdenum compound which are in contact with said catalyst. This activity improvement process can be applied to both the fresh catalysts and the spent catalyst having a deteriorated activity. The above described component (a) is preferably composed of a tellurium containing solid to be used in a state of a dry physical mixture with said catalyst. The above described components (a) and (b) are preferably composed of a tellurium containing solid and a molybdenum containing solid respectively or a tellurium-molybdenum containing solid to be used in a state of a dry physical mixture with said catalyst.
    Type: Grant
    Filed: December 17, 1985
    Date of Patent: September 27, 1988
    Assignee: Nitto Chemical Industry Co., Ltd.
    Inventors: Yutaka Sasaki, Yutaka Kiyomiya, Toshio Nakamura
  • Patent number: 4769355
    Abstract: Ammoxidation of C.sub.3 to C.sub.5 acyclic alkanes with NH.sub.3 and O.sub.2 using (1) a mole ratio of alkane:NH.sub.3 in the range from 2 to 16 and a mole ratio of alkane:O.sub.2 in the range 1 to 10 and (2) a mixture of particulate catalyst compositions, the first being especially effective to promote formation of an unsaturated nitrile and an olefin from the paraffin, and the second catalyst composition being especially effective to promote the conversion of the olefin to the unsaturated nitrile. Catalytic compositions useful in the process are disclosed.
    Type: Grant
    Filed: April 20, 1987
    Date of Patent: September 6, 1988
    Assignee: The Standard Oil Company
    Inventors: Linda C. Glaeser, James F. Brazdil, Jr., Mark A. Toft