US3497545A - Preparation of polynitriles by ammoxidation of polyalkyl substituted aromatic hydrocarbons utilizing recycle of unreacted hydrocarbons and intermediate nitriles - Google Patents

Preparation of polynitriles by ammoxidation of polyalkyl substituted aromatic hydrocarbons utilizing recycle of unreacted hydrocarbons and intermediate nitriles Download PDF

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Publication number
US3497545A
US3497545A US533237A US3497545DA US3497545A US 3497545 A US3497545 A US 3497545A US 533237 A US533237 A US 533237A US 3497545D A US3497545D A US 3497545DA US 3497545 A US3497545 A US 3497545A
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ammoxidation
reaction
polynitriles
preparation
hydrocarbons
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US533237A
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Richard L Golden
Hyung-Duk D Yoo
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Scientific Design Co Inc
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Halcon International Inc
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Assigned to SCIENTIFIC DESIGN COMPANY, INC. reassignment SCIENTIFIC DESIGN COMPANY, INC. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: HALCON SD GROUP, INC.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C07C253/28—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing six-membered aromatic rings, e.g. styrene

Definitions

  • the present invention pertains to the production of nitriles from polyalkyl substituted aromatic hydrocarbons. Particularly, the invention is concerned with the improved ammoxidation of a dialkyl aromatic hydrocarbon such as para xylene to the dinitrile product.
  • Aromatic dinitriles such as terephthalonitrile and isophthalonitrile are chemicals of very considerable importance primarily because these materials can be conveniently converted to aromatic diacids such as terephthalic acid. Such acids, of course, are used in very large amounts in the synthetic fiber field.
  • ammoxidation selectivity can be very markedly improved by the employment of fluidized solid contact techniques, by the regulation of the reaction to provide only a partial conversion per pass and through the provision of the separation and recycle of intermediate mononitrile ammoxidation products.
  • a polyalkyl aromatic hydrocarbon is ammoxidized during contact with a fluidized solid catalyst at ammoxidation conditions such that about 20 to 80% and preferably 30 60% of the polyalkyl aromatic is reacted per pass.
  • the reaction mixture is separated into its various components, polynitrile aro- 3,497,545 Patented Feb.
  • the invention is especially applicable to the ammoxidation of dialkyl aromatic hydrocarbons to dinitriles although included is the conversion of trialkyl aromatics to dinitriles or trinitriles.
  • the aromatic compounds have one' aromatic ring and 2 or 3 alkyl substituents, each of which has no more than about 3 carbon atoms.
  • the invention is applicable to the ammoxidation of xylenes and most notably to the ammoxidation of para xylene with the production of terephthalonitrile.
  • Examples of specific practices of the invention include the ammoxidation of meta xylene to isophthalonitrile, the ammoxidation of mesitylene to the corresponding trinitrile, the ammoxidation of paradiethylbenzene to terephthalonitrile, and the like.
  • the fluidized solid ammoxidation reaction is carried out in continuous fashion.
  • the hydrocarbon together with appropriate amounts of ammonia or an ammonia yielding compound and an oxygen containing gas are fed to the reaction continuously in amount necessary to make up for that proportion reacted per pass.
  • Also fed to the reactor is recycle hydrocarbon as well as mononitrile formed in a previous pass through the reaction zone.
  • These gases are passed through an appropriate ammoxidation catalyst in such a way that the catalyst is kept in fluidized motion resembling a boiling liquid.
  • the overall composition by volume of the gases entering the reaction zone is 1.0 to 3.0% polyalkyl aromatic, 6 to 18% ammonia or ammonia-yielding compound expressed as the equivalent of ammonia, 7.0 to 9.0% molecular oxygen, 1.0 to 2.0% aromatic mononitrile and the remainder inert gases including steam and nitrogen. Since the preferred source of the molecular oxygen is air, the reaction mixture will normally contain nitrogen. It is not necessary but generally preferred to add steam such that the steam comprises up to 15%, and preferably about 0.5 to 2.5% of the total feed to the reaction. Below 0.5% steam conversion drops oif somewhat while above 2.5% steam there is little or no further advantage.
  • Suitable ammoxidation temperatures are generally in the range of 300 to 800 C. and preferably 425 to 500 C. Substantially atmospheric pressure conditions are satis factory although higher pressures can be employed if desired.
  • the gaseous mixture is continuously introduced into the fluidized solid reaction zone at a rate suflicient to maintain the catalyst influid motion.
  • the rate of gas flow is generally 1.3 gr. mole/cm. hr. to 1.6 g. mole/cm. hr. and preferably 1.4 to 1.5 gr. mole/cm. hr. with catalyst particle size of 60/ mesh.
  • Catalysts which are employed in the present invention are of the type which are known ammoxidation catalysts.
  • a particularly preferred catalyst is a vanadium and antimony supported on a suitable support.
  • other catalysts comprising a compound of vanadium oxide preferably in combination with a tin, chromium, bismuth, platinum or molybdenum oxide can be employed.
  • the catalysts are suitably supported on alumina, silicon carbide, pumice, zirconia and the like.
  • the catalyst most desirably has a particle size between 16 and 325 mesh, preferably between about 40 and mesh.
  • the ammoxidation reaction is carefully controlled so as to provide for only a partial conversion of the polyalkyl aromatic charged to the reaction zone. This can conveniently be accomplished by skilled persons by adjusting the residence time, temperature and ratio of reactants in order to achieve the desired conversion per pass. Polyalkyl aromatic conversion per pass of about 20 to 80% and preferably 30 to 60% are maintained during practice of the invention.
  • the reaction mixture is separated by conventional techniques.
  • An extremely important advantage of this invention is the fact that the aromatic polynitrile product is recovered in extremely high purity due to the high overall selectivity of this reaction. This is particularly important since the primary use of the product nitrile is in the production of diacids for fiber use; an essential of fiber grade diacids is extreme purity.
  • the unreacted hydrocarbon as well as mononitrile produced as an intermediate is continuously recycled to the ammoxidation wherein the recycle material is admixed with suflicient net fresh ammonia, oxygen, dialkyl hydrocarbon, and steam or other inert gas to maintain substantially constant feed to the reactor.
  • EXAMPLE 1 Paraxylene is ammoxidized to terephthalonitrile in accordance with the invention.
  • the catalyst which is employed is a low surface area alumina powder of 60-140 mesh having impregnated thereon 1.3% by weight V and 8.1% by Weight Sb O
  • the reactor has a two inch inner diameter and a 40 inch length including the disengaging section.
  • the feed to the reactor is vaporized before being introduced into the reactor through a distributor having 97 holes each of 0.03 inch diameter.
  • the feed rate is 29.5 moles/hr.
  • the reaction temperature is about 454 C.
  • reaction pressure is about 5 p.s.i.g.
  • feed space velocity is about 1100 hrr
  • the catalyst bed expansion is about 24%
  • Including recycle of the mononitrile (p-tolunitrile), unreacted p-xylene, and nitrogen the composition of the total vapor feed to the reactor on a mol percent basis is about 2.5% p-xylene plus moronitrile, 1.3% H 0, 14.0% NH and 82.2% oxygen plus nitrogen (of which 8.3% by volume is oxygen).
  • Ammonia, xyene, and air are added to recycle materials at the rate needed to form the above total feed.
  • reaction about 50% of the xylene is reacted per pass.
  • the reaction mixture is withdrawn from the reactor, and cooled to about 65 C.
  • the condensed product comprises on a mol basis about 29.0% terephthalonitrile, about 38.0% p-tolunitrile, about 3.2% other materials, and about 29.8% unreacted pxylene.
  • the condensate is distilled in a first distillation and p-xylene and p-tolunitrile are taken over head and re cycled with a portion of the nitrogen to the ammoxidation.
  • the crude terephthalonitrile is distilled at atmospheric;
  • the overall yield of terephthalonitrile is 90% based on the net paraxylene fed to the system.
  • the product terephthalonitrile is readily converted to high purity terephthalic acid as by refluxing in aqueous sodium hydroxide with ammonia removal and subsequent acidification as with aqueous dilute sulfuric acid.
  • a process for preparing terephthalonitrile which comprises the continuous oxygen ammoxidation in the vapor phase at a temperature between 300800 C. of paraxylene, said ammoxidation being conducted with a fluidized solid catalyst selected from the group consisting of vanadium oxide, antimony oxide and combinations of vanadium oxide with tin, chromium, bismuth, platinum or mloybdenum oxide on a support selected from the group consisting of alumina silicon carbide, pumice and zirconia; maintaining the conversion per pass of paraxylene in the range of 30 to and continuously recycling unreacted paraxylene as well as intermediate nitrile formed during a previous reaction pass to the ammoxidation reaction, the ammoxidation being carried out such that the overall yield of terephthalonitrile is at least based on paraxylene.
  • a fluidized solid catalyst selected from the group consisting of vanadium oxide, antimony oxide and combinations of vanadium oxide with tin, chromium, bismuth,

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Detergent Compositions (AREA)
US533237A 1966-03-10 1966-03-10 Preparation of polynitriles by ammoxidation of polyalkyl substituted aromatic hydrocarbons utilizing recycle of unreacted hydrocarbons and intermediate nitriles Expired - Lifetime US3497545A (en)

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US53323766A 1966-03-10 1966-03-10

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US (1) US3497545A (en)van)
BE (1) BE694694A (en)van)
CH (1) CH471086A (en)van)
DE (1) DE1618497A1 (en)van)
ES (1) ES337833A1 (en)van)
GB (1) GB1181391A (en)van)
IL (1) IL27564A (en)van)
LU (1) LU53090A1 (en)van)
NL (1) NL6701607A (en)van)
NO (1) NO121660B (en)van)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3927007A (en) * 1970-08-08 1975-12-16 God Und Silber Scheideanstalt Catalysts for the production of aromatic and heteroaromatic nitriles
US4065487A (en) * 1976-07-20 1977-12-27 Ramiz Gasan Kuli Ogly Rizaev Process for producing benzonitrile
FR2465714A1 (fr) * 1979-03-06 1981-03-27 Inst Neftekhimicheskikh Prot Procede de preparation de phtalonitriles
US4336205A (en) * 1980-04-01 1982-06-22 Takeda Chemical Industries, Ltd. Method for producing aromatic nitriles
US20030126073A1 (en) * 2001-03-20 2003-07-03 David Lawrence Charitable transaction risk management clearinghouse
EP1319653A3 (en) * 2001-12-13 2004-01-07 Mitsubishi Gas Chemical Company, Inc. Process for producing a polynitrile compound

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH686133A5 (de) * 1993-02-23 1996-01-15 Basf Ag Verfahren zur Herstellung von Dicyanobenzolen mittels Ammonoxidation.

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2496661A (en) * 1947-11-28 1950-02-07 Socony Vacuum Oil Co Inc Production of nitriles
GB645754A (en) * 1943-11-10 1950-11-08 Socony Vacuum Oil Co Inc Production of nitriles
CA512864A (en) * 1955-05-17 K. Dixon James Preparation of nitriles
US2833807A (en) * 1956-06-26 1958-05-06 Allied Chem & Dye Corp Production of phthalonitriles
US2838558A (en) * 1955-09-27 1958-06-10 Distillers Co Yeast Ltd Catalytic production of aromatic nitriles and imides
CA619842A (en) * 1961-05-09 F. Hardy George Production of phthalonitriles
DE1141274B (de) * 1960-08-20 1962-12-20 Bayer Ag Verfahren zur Herstellung von aromatischen Nitrilen
GB956892A (en) * 1962-02-02 1964-04-29 Socony Mobil Oil Co Inc Synthesis of aromatic nitriles

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA512864A (en) * 1955-05-17 K. Dixon James Preparation of nitriles
CA619842A (en) * 1961-05-09 F. Hardy George Production of phthalonitriles
GB645754A (en) * 1943-11-10 1950-11-08 Socony Vacuum Oil Co Inc Production of nitriles
US2496661A (en) * 1947-11-28 1950-02-07 Socony Vacuum Oil Co Inc Production of nitriles
US2838558A (en) * 1955-09-27 1958-06-10 Distillers Co Yeast Ltd Catalytic production of aromatic nitriles and imides
US2833807A (en) * 1956-06-26 1958-05-06 Allied Chem & Dye Corp Production of phthalonitriles
DE1141274B (de) * 1960-08-20 1962-12-20 Bayer Ag Verfahren zur Herstellung von aromatischen Nitrilen
GB956892A (en) * 1962-02-02 1964-04-29 Socony Mobil Oil Co Inc Synthesis of aromatic nitriles

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3927007A (en) * 1970-08-08 1975-12-16 God Und Silber Scheideanstalt Catalysts for the production of aromatic and heteroaromatic nitriles
US4065487A (en) * 1976-07-20 1977-12-27 Ramiz Gasan Kuli Ogly Rizaev Process for producing benzonitrile
FR2465714A1 (fr) * 1979-03-06 1981-03-27 Inst Neftekhimicheskikh Prot Procede de preparation de phtalonitriles
US4336205A (en) * 1980-04-01 1982-06-22 Takeda Chemical Industries, Ltd. Method for producing aromatic nitriles
US20030126073A1 (en) * 2001-03-20 2003-07-03 David Lawrence Charitable transaction risk management clearinghouse
EP1319653A3 (en) * 2001-12-13 2004-01-07 Mitsubishi Gas Chemical Company, Inc. Process for producing a polynitrile compound
US7161021B2 (en) 2001-12-13 2007-01-09 Mitsubishi Gas Chemical Company, Inc. Process for producing a polynitrile compound

Also Published As

Publication number Publication date
LU53090A1 (en)van) 1968-12-09
NL6701607A (en)van) 1967-09-11
ES337833A1 (es) 1968-03-01
GB1181391A (en) 1970-02-18
DE1618497A1 (de) 1971-01-14
BE694694A (en)van) 1967-08-28
NO121660B (en)van) 1971-03-29
CH471086A (fr) 1969-04-15
IL27564A (en) 1970-09-17

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