US3530169A - Production of methacrylic esters - Google Patents

Production of methacrylic esters Download PDF

Info

Publication number
US3530169A
US3530169A US561011A US3530169DA US3530169A US 3530169 A US3530169 A US 3530169A US 561011 A US561011 A US 561011A US 3530169D A US3530169D A US 3530169DA US 3530169 A US3530169 A US 3530169A
Authority
US
United States
Prior art keywords
esters
oxygen
reaction
production
isobutyric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US561011A
Other languages
English (en)
Inventor
Rolf Platz
Heinz Nohe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DEB82648A external-priority patent/DE1286022B/de
Application filed by BASF SE filed Critical BASF SE
Application granted granted Critical
Publication of US3530169A publication Critical patent/US3530169A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/14—Silica and magnesia
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters

Definitions

  • This invention relates to a process for the production of esters of methacrylic acid by dehydrogenation of esters of isobutyric acid with oxygen in the presence of iodine.
  • olefinically unsaturated organic compounds may be prepared by dehydrogenation of the corresponding saturated compounds with oxygen in the presence of free or combined halogen.
  • the dehydrogenation of esters of isobutyric acid into esters of methacrylic acid cannot however be carried out with satisfactory yields and conversions.
  • dehydrogenatable organic compounds may be advantageously reacted with oxygen in the presence of free or combined halogen using a solid catalyst which contains an oxide, hydroxide or salt of a metal of Group I-A, IIA, II-B, IIIA, III-B, IVA, IVB, V-A, V-B, VIA, VIIA, VIII or the lanthanide group of the Periodic System of Elements.
  • a solid catalyst which contains an oxide, hydroxide or salt of a metal of Group I-A, IIA, II-B, IIIA, III-B, IVA, IVB, V-A, V-B, VIA, VIIA, VIII or the lanthanide group of the Periodic System of Elements.
  • the yield for the dehydrogenation of isobutyric esters are not given however.
  • Esters of isobutyric acid are used as starting materials, particularly isobutyric esters which have a boiling point of less than 300 C. at atmospheric pressure.
  • Esters of lower alcohols such as methyl isobutyrate, ethyl isobutyrate isopropyl isobutyrate and butyl isobutyrate, are pre ferred, methyl isobutyrate being particularly suitable.
  • Pure oxygen is usually employed in an amount equivalent to about that theoretically calculated or in excess, particularly 0.35 to 1 mole of oxygen per mole of ester.
  • the oxygen is advantageously metered in at such a rate that the off-gas is as free as possible from oxygen.
  • Oxygencontaining gas such as air, may also be used instead of pure oxygen but there is no further advantage in this.
  • Iodine is usually used in a small amount, generally from 1 to 10, particularly 1 to 5, mole percent on the organic compound.
  • Dehydrogenation is carried out in the presence of an inert heat carrier having a specific internal surface area and a specific mean pore radius. All solid materials whose surface structure does not change appreciably at the reaction temperature and under the reaction conditions are suitable. Examples of suitable heat carriers are petroleum coke, silicon carbide, porcelain, quartz powder or pumice. Heat carriers which contain at least one of the oxides, hydroxides or salts of metals of Group I-A, IIA, II-B, IIIA, III-B, IV-A, IVB, V-A, V-B, VI-A, VIIA, VIII or the lanthanide group of the Periodic System of Elements as described in British patent specifications Nos. 1,007,489, 977,146, 988,619 and in U.S.
  • patent specifications Nos. 3,207,806 and 3,207,805 or which consist of at least one of the said hydroxides, oxides or salts may be used with particular advantage.
  • the groups of the Periodic System of Elements are as set out in Chemiker-208, Springer-Verlag, Berlin 1956, page 2. it is particularly advantageous to use substances which contain basic and acid components, the basic components, such as oxides or hydroxides of metals of groups I-A, II-A and IIB of the Periodic System of Elements not being present in stroichiometric excess with respect to the acid components, such as oxides of metals of Groups IVA, IVB, VA, V-B and VIA of the Periodic System of Elements.
  • heat carriers examples include stoichiometric and non-stoichiometric silicates, aluminosilicates and phosphates of the metals: potassium, sodium, magnesium, calcium, barium, aluminum and boron; oxides of iron, titanium, manganese, cobalt, copper, nickel, zinc, boron, tungsten, molybdenum, chromium, cerium and zirconium, and mixtures of the said compounds. Natural and synthetic products may be used, such as are obtained by coprecipitation.
  • suitable compounds are potassium aluminosilicate, sodium aluminosilicate, calcium aluminosilicate, pumice, barium silicate, aluminum sili cate, calcium phosphate, boron phosphate, aluminum phosphate, aluminum oxide and silicon dioxide. It is preferred to use silicates of the alkaline earth metals, particularly of magnesium, or products which have a high content of magnesium silicates, as for example the natural minerals: soapstone, enstatite or olivine.
  • the suitable pore size and internal surface area of the magnesium silicates may be set up in the conventional way by roasting the raw material. Thus soapstone for example is converted by roasting at 900 to 1300 C. into steatite or protoenstatite which has a suitable porosity for the process.
  • a heat carrier which has a mean pore radius of from 200 to 20,000 A., particularly from 500 to 10,000 A., and an internal surface area of from 0.05 to 10.0, particularly from 0.5 to 5, sq. m./ g.
  • the reaction is carried out in the gas phase at temperatures of from 400 to 700 C., particularly from 450 to 580 C. Atmospheric pressure is generally used but the 3 reaction may be carried out at subatmospheric or superatmospheric pressure.
  • the heat carrier is usually stationary, but a fluidized bed may be used.
  • the residence time of the reaction mixture in the reaction chamber is about 0.1 to seconds, preferably 1 to 20 seconds. It is preferred not to use any diluent.
  • the reaction is carried out in the conventional way.
  • iodine may be dissolved in the isobutyric ester, the solution evaporated and the gas mixture introduced with oxygen into the reaction chamber filled with heat carrier.
  • the gaseous reaction mixture is cooled, the condensate separates into an aqueous phase and an organic phase, and the methacrylic ester formed is separated from the organic phase.
  • EXAMPLE 1 1 mole of methyl isobutyrate, 0.025 mole of iodine and 0.67 mole of oxygen per hour are supplied at 500 C. to the bottom of a quartz reactor having a diameter of 20 mm. which is provided at the bottom with a quartz frit and which contains 300 ml. of rings of magnesium silicate (steatite magnesia) having a mean pore radius of 595 A. and an internal surface area of 1.57 sq. m./g. and whose porosity is about 12%.
  • the residence time under the reaction conditions in contact with the rings is ten seconds.
  • the gas leaving the reactor is cooled in an efiicient cooler and the liquid fraction is condensed out.
  • the total throughput of methyl isobutyrate is 408 g.
  • the organic reaction product is 397 g. and has a methyl methacrylate content of 49.7% by weight and a methyl isobutyrate content of 41.5% by weight.
  • the yield, calculated from this, is 82.8% of the theory at a conversion of 59.7%.
  • Example 2-21 The procedure of Example 1 is followed but using other heat carriers. Heat carriers whose surface properties are within the ranges according to the invention are used in Examples 2 to 17, while in Examples 18 to 21 heat carriers are used whose surface properties are outside the ranges according to the invention. The following table gives the internal surface area in sq. m./g.
  • esters of methacrylic acid and lower alcohols by dehydrogenation of esters of isobutyric acid and lower alcohols with oxygen in the presence of iodine and, as an inert heat carrier, magnesium silicate at a temperature of from 400 to 600 C., a residence time of the reaction mixture in the reaction chamber of about 0.1 to 30 seconds, a mole ratio of oxygen to isobutyric ester of from about 0.35 to 1, the iodine being used in an amount of from 1 to 10 mole percent based on the isobutyric ester, the improvement which comprises: using a heat carrier which has a mean pore radius of from 200 to 20,000 A. and an internal surface area of from 0.05 to 10 sq. m./ g.
  • a process as in claim 1 wherein said inert heat carrier has a mean pore radius of from 500 to 10,000 A. and an internal surface area of from 0.5 to 5 sq. m./ g.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US561011A 1965-07-02 1966-06-28 Production of methacrylic esters Expired - Lifetime US3530169A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEB82648A DE1286022B (de) 1965-07-02 1965-07-02 Verfahren zur Herstellung von Metharcrylsaeureestern durch Dehydrierung von Isobuttersaeureestern
DE1286022 1965-07-02

Publications (1)

Publication Number Publication Date
US3530169A true US3530169A (en) 1970-09-22

Family

ID=25751617

Family Applications (1)

Application Number Title Priority Date Filing Date
US561011A Expired - Lifetime US3530169A (en) 1965-07-02 1966-06-28 Production of methacrylic esters

Country Status (2)

Country Link
US (1) US3530169A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
NL (1) NL6609252A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3846472A (en) * 1971-09-03 1974-11-05 Basf Ag Dehydrogenation of organic compounds
US4364856A (en) * 1981-01-16 1982-12-21 The Standard Oil Company Mixed metal phosphorus oxide coated catalysts for the oxidative dehydrogenation of carboxylic acids
US4473707A (en) * 1981-01-16 1984-09-25 The Standard Oil Company Oxidative dehydrogenation of carboxylic acids with mixed metal phosphorus oxide coated catalysts
US4742035A (en) * 1980-12-31 1988-05-03 The Standard Oil Co. Mixed metal phosphorus oxide catalysts for the oxidative dehydrogenation of carboxylic acids
US4864057A (en) * 1980-12-31 1989-09-05 Pedersen S Erik Dehydrogenation of carboxylic acids with mixed metal phosphorus oxide catalysts

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2719171A (en) * 1951-03-28 1955-09-27 Du Pont Oxidative dehydrogenation process
FR1342464A (fr) * 1961-12-04 1963-11-08 Petro Tex Chem Corp Procédé de déshydrogénation de composés organiques
DE1169921B (de) * 1955-09-13 1964-05-14 Chempatents Inc Verfahren zur Herstellung eines Katalysators fuer die Oxydation von Benzol zu Maleinsaeure-anhydrid
GB973564A (en) * 1960-10-14 1964-10-28 Shell Int Research A process for the dehydrogenation of hydrocarbons
GB977406A (en) * 1960-02-02 1964-12-09 Halcon International Inc Catalytic compositions and their use in making maleic anhydride
GB988619A (en) * 1961-06-23 1965-04-07 Petro Tex Chem Corp Dehydrogenation process
US3207805A (en) * 1960-06-17 1965-09-21 Petro Tex Chem Corp Dehydrogenation in the presence of oxygen and an ammonium halide
US3207806A (en) * 1960-11-23 1965-09-21 Petro Tex Chem Corp Dehydrogenation process
US3207808A (en) * 1962-12-04 1965-09-21 Petro Tex Chem Corp Dehydrogenation
GB1007489A (en) * 1960-08-30 1965-10-13 Petro Tex Chem Corp Dehydrogenation process
US3308194A (en) * 1965-10-22 1967-03-07 Petro Tex Chem Corp Oxidative dehydrogenation process

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2719171A (en) * 1951-03-28 1955-09-27 Du Pont Oxidative dehydrogenation process
DE1169921B (de) * 1955-09-13 1964-05-14 Chempatents Inc Verfahren zur Herstellung eines Katalysators fuer die Oxydation von Benzol zu Maleinsaeure-anhydrid
GB977406A (en) * 1960-02-02 1964-12-09 Halcon International Inc Catalytic compositions and their use in making maleic anhydride
US3207805A (en) * 1960-06-17 1965-09-21 Petro Tex Chem Corp Dehydrogenation in the presence of oxygen and an ammonium halide
GB1007489A (en) * 1960-08-30 1965-10-13 Petro Tex Chem Corp Dehydrogenation process
GB973564A (en) * 1960-10-14 1964-10-28 Shell Int Research A process for the dehydrogenation of hydrocarbons
US3207806A (en) * 1960-11-23 1965-09-21 Petro Tex Chem Corp Dehydrogenation process
GB988619A (en) * 1961-06-23 1965-04-07 Petro Tex Chem Corp Dehydrogenation process
FR1342464A (fr) * 1961-12-04 1963-11-08 Petro Tex Chem Corp Procédé de déshydrogénation de composés organiques
US3207808A (en) * 1962-12-04 1965-09-21 Petro Tex Chem Corp Dehydrogenation
US3308194A (en) * 1965-10-22 1967-03-07 Petro Tex Chem Corp Oxidative dehydrogenation process

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3846472A (en) * 1971-09-03 1974-11-05 Basf Ag Dehydrogenation of organic compounds
US4742035A (en) * 1980-12-31 1988-05-03 The Standard Oil Co. Mixed metal phosphorus oxide catalysts for the oxidative dehydrogenation of carboxylic acids
US4864057A (en) * 1980-12-31 1989-09-05 Pedersen S Erik Dehydrogenation of carboxylic acids with mixed metal phosphorus oxide catalysts
US4364856A (en) * 1981-01-16 1982-12-21 The Standard Oil Company Mixed metal phosphorus oxide coated catalysts for the oxidative dehydrogenation of carboxylic acids
US4473707A (en) * 1981-01-16 1984-09-25 The Standard Oil Company Oxidative dehydrogenation of carboxylic acids with mixed metal phosphorus oxide coated catalysts

Also Published As

Publication number Publication date
NL6609252A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1967-01-03

Similar Documents

Publication Publication Date Title
US4220560A (en) Spinel dehydrogenation catalyst
US3686334A (en) Direct hydration of ethylene to ethanol
US4254293A (en) Dehydrocoupling of toluene
US4336403A (en) Preparation of methyl methacrylate by reaction of methyl propionate and methanol
US3530169A (en) Production of methacrylic esters
US3631213A (en) Process for the preparation of meta-and para-tertiarybutylstyrenes
US3957897A (en) Method of oxydehydrogenation of alkyl aromatic compounds
US2502678A (en) Method for preparing acrylonitrile by vapor phase catalytic reaction of acetylene and hydrogen cyanide
US3745194A (en) Oxidative dehydrogenation of paraffinic hydrocarbons
US3308197A (en) Oxidative dehydrogenation in the presence of chlorine
US3440276A (en) Process for preparing acrylic esters
US4232174A (en) Catalyst and dehydrogenation process
EP0030837B1 (en) Dehydrocoupling of toluene
US3790500A (en) Oxidative dehydrogenation catalyst
US4950830A (en) Dehydration of aliphatic and alicyclic hydrocarbons and aliphatic and alicyclic substituted aromatic hydrocarbons
US3313856A (en) Preparation of acrolein or methacrolein
US2595266A (en) Production of alpha-naphthol by catalytic reduction of alphatetralol and alpha-tetralone
US4268704A (en) Dehydrocoupling of toluene
US4278825A (en) Dehydrocoupling of toluene
US2628985A (en) Production of phenols
US3641130A (en) Process for the production of aromatic polycarboxylates
US4278824A (en) Dehydrocoupling of toluene
US2438164A (en) Process for the production of methacrylic acid
US4410727A (en) Oxydehydrogenation of isobutyric acid and its lower alkyl esters
US4459234A (en) Process for producing anthraquinone