US3479385A - Process for the production of aromatic nitriles - Google Patents

Process for the production of aromatic nitriles Download PDF

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US3479385A
US3479385A US505651A US3479385DA US3479385A US 3479385 A US3479385 A US 3479385A US 505651 A US505651 A US 505651A US 3479385D A US3479385D A US 3479385DA US 3479385 A US3479385 A US 3479385A
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catalyst
ammonia
line
catalysts
aromatic
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Derk Th A Huibers
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Lummus Technology LLC
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Lummus Co
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • This invention has to do with a process for forming aromatic polynitriles, particularly for forming terephthalonitrile from p-xylene.
  • ammoxidation Another process has also been developed recently for producing nitriles. This is generally referred to as ammoxidation, wherein oxygen is used as a charge material with hydrocarbon and ammonia. Typical of ammoxidation catalysts are associations of bismuth oxide and molybdena. With oxygen, as in the form of air, oxygenated products are formed, making necessary a purification system to effect separation of desired nitrile and oxygenated contaminants.
  • aromatic polynitriles such as phthalonitrile and terephthalonitrile are of value, for example, in the dyestuff and fiber industries, respectively, it would be advantageous to have available an efficient and effective process for converting xylenes to aromatic polynitriles.
  • the present invention is directed to just such a process.
  • a process for preparing aromatic polynitriles comprising: contacting an aromatic hydrocarbon with ammonia, in gaseous phase, at a temperature from about 400 C. to about 500 C. in the presence of an oxide catalyst, with a contact time of from about 0.01 second to about 30 seconds and a catalyst-on-stream time of less than about 30 minutes.
  • the aromatic hydrocarbon is one which is: stable to thermal decomposition, in the vapor phase at said reaction conditions, and represent by the general formula L ArR wherein Ar is an arylene group, R is an alkyl group having from 1 to 3 carbon atoms, and n is a small whole number, at least 2.
  • Aromatic hydrocarbons useful herein include: xylenes; tri-, tetra-, pentaand hexa-rnethyl benzenes; diethyl and related polyethyl benzenes; polypropyl benzenes; diand further-methylated, -ethylated, and -propylated naphthalenes anthracenes, etc.
  • Preferred herein are xylenes and, particularly, p-xylene.
  • the arylene group can be a benzene, naphthalene, anthracene, etc. ring.
  • the catalysts used herein include those known as ammoniation catalysts, that is, catalysts used in the conversion of hydrocarbons and ammonia to nitriles without substantial addition of oxygen to the reaction charge.
  • Such catalysts include associations or mixed oxides of molybdenum and/ or tungsten, and of vanadium, iron and/or cobalt.
  • Molybdena/vanadia catalysts are effective catalysts in the process of this invention.
  • Ammoxidation catalysts can also be used in the present process although a free oxygen-containing gas is not used as a charge material.
  • Typical of such catalysts are the bismuth oxide/molybdena catalysts referred to above.
  • the catalyst can be used per se, or can be supported on or mixed with an inert support such as Carborundum, pumice, clay or the like, in which case texture, surface area and pore diameter can be suitably controlled.
  • the inert support can serve to provide mechanical strength and abrasion resistance to the catalyst.
  • the catalyst, with or without support can be in the form of fine particles such as suitable for use in a so-called fluidized reactor bed, pellets, granules, etc.
  • Contact time is the period of time during which a unit volume of the reactants is in contact with a unit volume of catalyst.
  • Catalyst-on-stream time is the time during which the catalyst is in use in converting an aromatic hydrocarbon and ammonia to the desired polynitrile, before it is reactivated or regenerated. It has been found that the contact time should be from about 0.01 second to about 30 seconds, preferably 0.1-l0 seconds, with a catalyst-on-stream of less than about 30 minutes, preferably less than 10 minutes.
  • the relatively short catalyston-stream times make possible maintenance of a high catalytic level, also avoiding any substantial coke deposit on the catalyst.
  • Reactivation of the catalyst with a free-oxygen containing gas such as air or oxygen can be accomplished readily, therefore, in a briefer period of time than in the prior processes alluded to above.
  • a suflicient quantity of oxygen to convert the used catalyst to an oxidized. state.
  • an excess of ammonia is generally used in relation to the stoichiometrical quantity of aromatic hydrocarbon.
  • volumes of ammonia can be used per volume of xylene, especially ratios of about 1:1 to 6:1.
  • larger ratios of ammonia to hydrocarbon are used as an Ar group is more substituted with R groups than is the benzene ring substituted with methyl groups to form xylenes. It is economical, however, not to use a large excess of ammonia or of an aromatic hydrocarbon, particularly in a continuous operation such as described below in order to simplify recycling of a reactant.
  • the aromatic hydrocarbon reactant can be used per se or can be present in admixture with other hydrocarbons inert in the reaction, such as parafiin or benzene.
  • the reaction system is diluted with an inert gas such as nitrogen, steam or water vapor.
  • an inert gas such as nitrogen, steam or water vapor.
  • steam or water vapor has the advantage of retaining the catalyst oxygen for a longer period of time than when the aromatic hydrocarbon is converted in the substantial absence of added steam or water vapor.
  • from about 3 .to about 10, and especially about 5 volumes of steam are used per volume of total reactants, namely, aromatic hydrocarbon and ammonia.
  • a diluent in the process of this invention is advantageous in several respects.
  • the process is operated with a net production of hydrogen and no net heat generation.
  • the diluent also serves to: carry off process heat thereby obviating the need for internal heat transfer surface, and diminish the partial pressures of the reducing compounds charged and formed.
  • Reacting temperature for forming a polynitrile is an important feature. Temperatures below about 400 C. are to be avoided since yields are insuflicient. Temperatures above about 500 C. are also to be avoided, since yields are reduced by virtue of decomposition of reactants and products. Preferably, temperatures of the order of 450- 460 C. are employed.
  • Reaction pressures generally range from about 1 to about atmospheres, absolute. Pressures of 1.5-2 atmospheres, absolute, are preferred.
  • the process can 'be conducted intermittently or continuously, with the latter preferred.
  • the latter is particularly advantageous and is illustrated generally in the accompanying drawing which constitutes a schematic flow diagram.
  • p xy1ene in line 10 and ammonia in line 11 are mixed in line 12 and are charged to reactor 13, wherein they are in reaction in the presence of a catalyst introduced into 13 from line 14.
  • Reactor 13 can comprise a lower preheating zone and an upper reaction zone.
  • Catalyst and reactants flow concurrently up through reactor 13, with catalyst being removed through line 15 to an upper portion of reactivator or regenerator 16.
  • Air or other suitable active oxygen-containing gas is introduced from line 17 to a lower portion of regenerator 16 and is in countercurrent contact with the catalyst for reactivation.
  • Gases formed during reactivation are removed through line 1-8.
  • Reactivated catalyst is recycled from 16 through line 14 to reactor 13.
  • make-up catalyst can be added to line 14 from line 19, and catalyst fines or catalyst rejected for any reason can be removed through line 20.
  • Reaction products comprising terephthalonitrile, tolunitrile, hydrogen and water, together with unreacted ammonia, are removed from reactor 13 through line 21 to separator 22, from which the nitriles are discharged through line 23.
  • Terephthalonitrile and tolunitrile can be separated from one another and tolunitrile can be recycled (not shown) with the hydrocarbon in line 10.
  • Hydrogen, water and ammonia are removed from 22 through line 24 to hydrogen separator 25.
  • Hydrogen is removed from 25 via line 26.
  • Ammonia and water are taken from separator 25 through line 27 and can be passed through line 28 to line 12 for use in reactor 13 or can be passed through line 29 to ammonia recovery unit 30.
  • Ammonia is removed from unit 30 through line 31 and is combined with ammonia charge in line 11. Water is removed from unit 30 through line 32. Diluent can also be charged through line 33.
  • the temperature should be controlled lest the catalyst be damaged.
  • the maximum temperature to be used will vary with catalysts employed. Air is preferred as an oxidation medium; however, oxygen and other free oxygen-containing gas can be used satisfactorily.
  • catalyst was reactivated with air after each B run of a series of A and B runs, or after a C run in a series of ABC runs.
  • TPN Terephthalonitrile
  • TN tolunitrile
  • x/a represents the mole fraction of pxylene converted to p-tolunitrile and y/a represents the mole fraction of p-xylene converted to terephthalonitrile.
  • Run 76A the mole conversion is 39 percent; whereas, in Run 76B, it is only 7 percent.
  • the same pattern is revealed for A and B of Runs 77 through 83, inclusive.
  • the data indicate that the catalyst is reduced in activity with respect to formation of terephthalonitrile, but has greater activity for the production of tolunitrile. This is due to oxygen loss of the catalyst.
  • catalyst activity can be maintained for relatively longer on-stream times but conversion is meager and uneconomical. If contact time is very short, catalyst-on-stream time can be extended even beyond about 30 minutes, but the results are similarly uneconomical. With longer contact times, as 5-30 seconds, catalyst-on-stream time is of shorter duration but conversion of aromatic hydrocarbon to desired polynitrile is higher. For example, it is to be understood that catalysts employed herein differ in activity. Thus, contact times of 5-30 seconds are preferred when using Fe O Mo O rather than briefer contact times.
  • EXAMPLE 2 A mixture of p-xylene and ammonia was passed downwardly through a static bed of the molybdena/vanadia catalyst described in Example 1, at 460 C. at a contact time of about 3 seconds. During the first 10 minute period, the product was predominantly terephthalonitrile. Then, a mixture of terephthalonitrile and tolunitrile was formed. Finally, after about one hour, substantially only tolunitrile was formed. When about 30 moles of ammonia are charged per mole of p-xylene, about 8 parts by weight of terephthalonitrile are produced per 1000 parts by weight of catalyst. When, however, part of the ammonia is replaced by nitrogen diluent such that the mole ratio p-xylene/ammonia/N is 1/ 3/ 30 and the same contact time and the same on-stream time are employed,
  • Terephthalonitrile for example, is formed from p-xylene and can be used for the formation of terephthalic acid, which is of importance in the manufacture of synthetic fibers.
  • Phthalonitrile can be formed from o-Xylene, and can be used in the formation of phthalocyanine dyes. Other uses will be evident to those familar with the art.
  • an aromatic nitrile by contacting ammonia with an aromatic hydrocarbon in the gaseous phase, in the presence of an oxidized form of an oxide catalyst selected from the group consisting of ammoniation catalysts and ammoxidation catalysts, the aromatic hydrocarbon being selected from the group consisting of alkyl substituted benzene, alkyl substituted naphthalene and alkyl substituted anthracene wherein the alkyl group has 1-3 carbon atoms and there are at least two alkyl substituent groups, the improvement for producing aromatic polynitriles comprising: effecting said contacting of ammonia, aromatic hydrocarbon and catalyst in the absence of molecular oxygen at a temperature from about 400 C.
  • catalystone-stream time is from about 0.01 second to about 10 minutes.

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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)
US505651A 1965-10-29 1965-10-29 Process for the production of aromatic nitriles Expired - Lifetime US3479385A (en)

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US505649A Expired - Lifetime US3478082A (en) 1965-10-29 1965-10-29 Process for the production of acrylonitrile or methacrylonitrile

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3879435A (en) * 1972-10-05 1975-04-22 Bp Chem Int Ltd Process for the production of acrylonitrile
US3883573A (en) * 1973-06-15 1975-05-13 Standard Oil Co Commercial fixed-bed acrylonitrile or methacrylonitrile
US3895047A (en) * 1970-05-29 1975-07-15 Sumitomo Chemical Co Catalytic process for the production of acrylonitrile
US3898267A (en) * 1972-04-28 1975-08-05 Montedison Spa Process for preparing methacrylonitrile from isobutene, ammonia and oxygen, in the presence of catalysts
US4058547A (en) * 1970-05-29 1977-11-15 Sumitomo Chemical Company, Limited Catalytic process for the production of acrylonitrile
US4139552A (en) * 1974-01-04 1979-02-13 The Standard Oil Company Production of unsaturated nitriles
US20030114701A1 (en) * 2001-12-13 2003-06-19 Kenichi Nakamura Process for producing a polynitrile compound

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3699147A (en) * 1969-04-04 1972-10-17 Lummus Co Process for preparing nitriles
US4000178A (en) * 1975-09-19 1976-12-28 Monsanto Company Paraffin ammoxidation process
US4377534A (en) * 1978-02-27 1983-03-22 The Standard Oil Co. Production of unsaturated nitriles
US4284583A (en) * 1979-10-29 1981-08-18 Uop Inc. Ammoxidation process with external catalyst regeneration zone
US4246192A (en) * 1979-10-29 1981-01-20 Uop Inc. Ammoxidation process with isolated catalyst regeneration zone
CN113509965B (zh) * 2021-06-24 2021-12-07 潍坊中汇化工有限公司 一种醋酸氨化法制取乙腈工艺用催化剂的再生方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2478464A (en) * 1947-08-15 1949-08-09 Socony Vacuum Oil Co Inc Production of aromatic nitriles
US2496660A (en) * 1947-08-15 1950-02-07 Socony Vacuum Oil Co Inc Production of aromatic nitriles
US2518295A (en) * 1948-09-22 1950-08-08 Socony Vacuum Oil Co Inc Production of nitriles
US2833807A (en) * 1956-06-26 1958-05-06 Allied Chem & Dye Corp Production of phthalonitriles

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US2418562A (en) * 1942-05-22 1947-04-08 Sinclair Refining Co Production of nitriles from propylene and ammonia
US2520181A (en) * 1946-08-31 1950-08-29 Sinclair Refining Co Process of preparing amines and nitriles from ammonia and olefins
US2450678A (en) * 1947-03-26 1948-10-05 Socony Vacuum Oil Co Inc Production of nitriles
US2455995A (en) * 1947-07-05 1948-12-14 Du Pont Production of nitriles from certain olefins and hcn
US2535082A (en) * 1947-12-15 1950-12-26 Phillips Petroleum Co Acetonitrile production
US2463466A (en) * 1948-09-29 1949-03-01 Socony Vacuum Oil Co Inc Production of nitriles
US2540787A (en) * 1948-12-01 1951-02-06 Socony Vacuum Oil Co Inc Production of benzonitrile
BE603032A (enrdf_load_html_response) * 1960-04-26
IT701822A (enrdf_load_html_response) * 1961-11-30
US3200141A (en) * 1963-05-27 1965-08-10 Standard Oil Co Process for the manufacture of acrylonitrile
US3152697A (en) * 1963-12-09 1964-10-13 Berman Jacob Modular dispensing display rack
USB375303I5 (enrdf_load_html_response) * 1964-06-15
US3308151A (en) * 1965-01-11 1967-03-07 Standard Oil Co Process for the oxidation of olefinammonia mixtures to unsaturated nitriles

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2478464A (en) * 1947-08-15 1949-08-09 Socony Vacuum Oil Co Inc Production of aromatic nitriles
US2496660A (en) * 1947-08-15 1950-02-07 Socony Vacuum Oil Co Inc Production of aromatic nitriles
US2518295A (en) * 1948-09-22 1950-08-08 Socony Vacuum Oil Co Inc Production of nitriles
US2833807A (en) * 1956-06-26 1958-05-06 Allied Chem & Dye Corp Production of phthalonitriles

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3895047A (en) * 1970-05-29 1975-07-15 Sumitomo Chemical Co Catalytic process for the production of acrylonitrile
US4058547A (en) * 1970-05-29 1977-11-15 Sumitomo Chemical Company, Limited Catalytic process for the production of acrylonitrile
US3898267A (en) * 1972-04-28 1975-08-05 Montedison Spa Process for preparing methacrylonitrile from isobutene, ammonia and oxygen, in the presence of catalysts
US3879435A (en) * 1972-10-05 1975-04-22 Bp Chem Int Ltd Process for the production of acrylonitrile
US3883573A (en) * 1973-06-15 1975-05-13 Standard Oil Co Commercial fixed-bed acrylonitrile or methacrylonitrile
US4139552A (en) * 1974-01-04 1979-02-13 The Standard Oil Company Production of unsaturated nitriles
US20030114701A1 (en) * 2001-12-13 2003-06-19 Kenichi Nakamura 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

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CA794856A (en) 1968-09-17
DE1568969C3 (de) 1978-04-27
NL6615284A (enrdf_load_html_response) 1967-05-02
DE1568969B2 (de) 1977-08-25
IT822930A (enrdf_load_html_response) 1900-01-01
DE1568968A1 (de) 1970-04-02
NL141176B (nl) 1974-02-15
NL6615283A (enrdf_load_html_response) 1967-05-02
US3478082A (en) 1969-11-11
ES332832A1 (es) 1968-03-16
DE1568969A1 (de) 1970-04-02
FR1515045A (fr) 1968-03-01
GB1138696A (en) 1969-01-01

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