WO2005063388A1 - Procede pour elaborer un catalyseur acide solide, et procede pour produire un compose au lactame en utilisant un tel catalyseur - Google Patents

Procede pour elaborer un catalyseur acide solide, et procede pour produire un compose au lactame en utilisant un tel catalyseur Download PDF

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WO2005063388A1
WO2005063388A1 PCT/JP2004/019298 JP2004019298W WO2005063388A1 WO 2005063388 A1 WO2005063388 A1 WO 2005063388A1 JP 2004019298 W JP2004019298 W JP 2004019298W WO 2005063388 A1 WO2005063388 A1 WO 2005063388A1
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catalyst
compound
solid acid
acid catalyst
oxime
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PCT/JP2004/019298
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English (en)
Japanese (ja)
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Yasushi Yamamoto
Jun Haruta
Yukimasa Fukuta
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Ube Industries, Ltd.
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Priority to JP2005516624A priority Critical patent/JP4297115B2/ja
Publication of WO2005063388A1 publication Critical patent/WO2005063388A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D225/00—Heterocyclic compounds containing rings of more than seven members having one nitrogen atom as the only ring hetero atom
    • C07D225/02—Heterocyclic compounds containing rings of more than seven members having one nitrogen atom as the only ring hetero atom not condensed with other rings
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates

Definitions

  • the present invention relates to a method for preparing a solid acid catalyst and a method for producing a ratatum compound using the catalyst.
  • the present invention relates to a method for preparing an environment-friendly solid acid catalyst having a high activity in an acid-catalyzed reaction, and a method for producing a corresponding ratatum compound from a cycloalkanone oxime compound by Beckmann rearrangement using the same. Things.
  • the obtained ratatum compound is an important compound as a raw material for nylon.
  • acid catalysts such as sulfuric acid, aluminum chloride, hydrogen fluoride, and phosphoric acid have been used for acid catalyst reactions such as alkylation reaction, esterification reaction, and Beckmann rearrangement reaction.
  • acid catalyst reactions such as alkylation reaction, esterification reaction, and Beckmann rearrangement reaction.
  • these acid catalysts are difficult to separate and recover, and there are problems of equipment corrosion and waste acid treatment.
  • Acid catalysts that solve these problems include, for example, single metal oxides such as alumina and titania, composite oxides such as silica-alumina, silica-titania, and alumina-boria, ZSM_5, / 3-zeolite, and the like.
  • Many solid acid catalysts such as zeolite and clay minerals such as montmorillonite are known (for example, see Non-Patent Document 1). However, since these solid acid catalysts have a relatively weak acid strength, depending on the reaction system, they may not show sufficient activity as a solid acid catalyst.
  • a solid acid catalyst having a strong acidity a solution containing a Group IV metal hydroxide or oxide of 5 to 20 times by weight of a 0.01 to 5 molar concentration of a sulfate group-containing solution is used as a solid acid catalyst having strong acidity.
  • acid strength (H) is stronger than -10.
  • a solid acid catalyst has been proposed (for example, see Patent Document 1).
  • this treatment method in which the solution is brought into contact with the sulfate group-containing solution also causes problems such that the acid sites are poisoned by water in the solution, and that water remaining in the catalyst causes side reactions in the solid acid catalyst reaction.
  • this treatment method is applied to, for example, a mesoporous body having low acid resistance, the skeletal structure of the mesoporous body is destroyed (for example, see Non-Patent Document 2). Destruction of the skeletal structure causes a decrease in the pore diameter, pore volume, and surface area of the solid catalyst, and reduces the catalytic activity. It is not preferable because it has an adverse effect.
  • a method using a rhenium compound as a catalyst a method using a ⁇ -zeolite containing zinc as a catalyst, and a method using a group IV metal or a group III metal such as zirconium oxide, titanium oxide, or aluminum oxide.
  • a method using a catalyst that supports a Group VIII metal such as palladium, platinum, rhodium and ruthenium on an oxide carrier a method using a zeolite supporting iminium ion as a catalyst, and a method using a catalyst having a dielectric constant of 6-60 in the presence of a solid catalyst.
  • a method of performing a reaction in the presence of a compound in the range has been proposed.
  • beta containing zinc - zeolite in the method of the catalyst for example, see Patent Document 4
  • the conversion in the anti ⁇ of 130 ° C 47 mole 0/0 the power Puroratatamu selectivity 72 mole 0/0 (yield The rate is 34 mol%), and if the deviation is low, there is a problem.
  • the method using a zeolite supporting iminium ion as a catalyst has a problem that the method for preparing the catalyst is complicated and the conversion of cyclohexanone oxime is as low as 34%.
  • Non-patent document 1 Catalyst dictionary (Asakura Shoten) 236 pages
  • Non-Patent Document 2 Journal of Molecular Catalysis A: Chemical 192 (2003) 1 53-170
  • Patent Document 1 Japanese Patent Publication No. 59-006181
  • Patent Document 2 JP 08-151362 A
  • Patent Document 3 JP-A-09-301952
  • Patent Document 4 JP 2001-19670 A
  • Patent Document 5 JP-A-62-169769
  • Patent Document 6 Japanese Patent Application Laid-Open No. 09-040641
  • Patent Document 7 Japanese Patent Application Laid-Open No. 2001-072657
  • An object of the present invention is to provide a method for preparing a solid acid catalyst effective for an acid catalyzed reaction. Particularly, when producing a corresponding ratatum compound from a cycloalkanone oxime compound by a Beckmann rearrangement reaction, Ratatam compounds in high yields under mild reaction conditions It is an object of the present invention to provide a method for preparing a catalyst for producing a catalyst.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that at least one compound selected from the group consisting of oxides and hydroxides is brought into contact with a gas containing sulfur trioxide.
  • the inventors have found that the above object can be achieved by a method for preparing a solid acid catalyst, which is a feature of the present invention, and have completed the present invention.
  • a method for producing a corresponding ratatum compound by a Beckmann rearrangement reaction of a cycloalkanone oxime compound in the presence of the solid acid catalyst is provided.
  • the sulfur trioxide used in the present invention is not particularly limited as long as it is produced from a substance containing sulfur.
  • sulfur trioxide those that are gaseous at room temperature are used as sulfur trioxide by oxidation or thermal decomposition as it is or after dilution with an inert gas.
  • Those which are liquid or solid at room temperature can be used as sulfur trioxide by oxidizing, pyrolyzing, or pyrolyzing it and then oxidizing it.
  • sulfur trioxide (SO 2) obtained by oxidizing gaseous sulfur dioxide (SO 2) at room temperature is used.
  • SO for example, those diluted with an inert gas or the like can be used.
  • the oxidation of sulfur dioxide (SO 2) is usually carried out using oxygen in the presence or absence of an oxidation catalyst.
  • an oxidizing agent such as ozone or peroxide can be used.
  • the oxygen oxidation there is no particular limitation on the oxygen oxidation, and those diluted with pure oxygen, air, or an inert gas can be used.
  • the water content is small.
  • the amount of water in the gas to be introduced is preferably 100 ppm or less, more preferably 1 ppm or less.
  • the content is controlled to 00 ppm, more preferably 10 ppm or less, and most preferably the water content is controlled to 10 ppm or less.
  • the oxidation catalyst used in the oxidation reaction performed in the presence of the oxidation catalyst is not particularly limited as long as it has a capability of oxidizing sulfur dioxide, and examples thereof include vanadium, copper, iron, and cobalt.
  • a catalyst containing at least one of nickel and nickel can be preferably used. Preference is given to vanadium, copper and iron.
  • any compound selected from the oxides and hydroxides used in the present invention any compound can be used as long as it is surface-modified with sulfur trioxide.
  • porous oxides such as HMS and MCM41 and those in which metals are supported or introduced
  • zeolites such as ZSM-5 and ⁇ -zeolite and those in which metals are supported or introduced
  • silica alumina silica alumina
  • oxides such as silica, alumina, zirconia, and titania, and hydroxides serving as precursors of these, such as silica-zirconia and silica-titania.
  • At least one compound selected from oxides and hydroxides include Group 414 of the Periodic Table (using a serial number of 1-18 for the group number, according to the IUPAC inorganic chemical nomenclature revised in 1989). ), Oxides and hydroxides containing one or more elements (excluding carbon) selected from the group consisting of group numbers according to (1).
  • the specific surface area of these oxides and hydroxides is not particularly limited, but is preferably at least 300 m 2 / g, more preferably at least 700 m 2 Zg, and even more preferably ⁇ 700-1200 m 2 / g. is there.
  • Specific examples of the elements selected from Group 414 of the Periodic Table include titanium, zirconium, hafnium, group 5 vanadium, neodymium, tantalum, group 6 chromium, molybdenum, and tungsten. , Group 7 manganese, rhenium, group 8 iron, ruthenium, osmium, group 9 cono-noreth, rhodium, iridium, group 10 nickel, noradium, platinum, group 1 copper, silver, gold, group 12 Zinc, cadmium, mercury, group 13 boron, anoremium, gallium, indium, thallium, group 14 silicon, germanium, tin, and lead.
  • the treatment mode of at least one compound selected from oxides and hydroxides with sulfur trioxide is not particularly limited.
  • sulfur trioxide can be directly contacted in the gas phase, and can be contacted in the gas phase in the presence of sulfur dioxide (or a sulfur-containing compound), oxygen and an oxidation catalyst.
  • an oxide and a hydroxide are filled in a lower part of a glass tube, and an oxidation catalyst is filled in an upper part thereof, and sulfur dioxide (or a sulfur-containing compound) is charged.
  • an oxygen-containing gas in the gas phase at a temperature of 100-800 ° C, preferably 200-700 ° C, for a period of 10 minutes to 1000 hours. In this case, it is preferable to allow the gas to flow from the upper layer toward the lower layer.
  • the concentration of sulfur trioxide generated in the gas is not particularly limited, but the total supply amount of the sulfur-containing compound is preferably 0.1 mmol to 100 mol with respect to oxide and hydroxide lg.
  • the oxygen concentration is not particularly limited, either, but is preferably 0.1 to 1000 times the molar amount of the gaseous sulfur-containing compound.
  • Oxides and / or hydroxides before being subjected to contact treatment with sulfur trioxide in the gas phase may have water or organic substances attached thereto. It is preferable to perform calcination in an atmosphere (preferably while flowing air or an inert gas). In order to remove the sulfur-containing compound which is weakly physically adsorbed on the surface of the catalyst, it is also preferable to carry out the post-treatment by calcination in air or under an inert gas atmosphere (preferably while flowing air or an inert gas).
  • the firing temperature and the firing time for the pre-treatment and the post-treatment are not particularly limited, and the force that can be selected depending on the case is preferably 100 to 800 ° C, and one minute to one hundred hours.
  • the solid acid catalyst thus obtained can be effectively used as a catalyst in the production of a corresponding ratata compound by an acid catalysis reaction, particularly a Beckmann rearrangement reaction from a cycloalkanone oxime compound. Is done.
  • the cycloalkanone oxime compound used for producing the ratatum compound in the present invention is preferably a cycloaliphatic hydrocarbon oxime compound having 5 to 12 carbon atoms.
  • Cyclohexanone oxime and cyclododecanone oxime are examples of Cyclohexanone oxime and cyclododecanone oxime.
  • cycloalkanone oximes can also be used in the form of a salt.
  • the salt it is used as a hydrochloride or a sulfate.
  • cycloalkanone oxime compounds can be used alone or in combination of two or more without any problem.
  • corresponding ratatam compound obtained in the present invention include valerolatatum from cyclopentanone oxime, force prolatatam from cyclohexanone oxime, enantholactam and cyclododecanone oxime from cycloheptanone oxime. Is lau mouth ratatum.
  • the reaction conditions of the Beckmann rearrangement reaction of the present invention are not particularly limited, and the reaction is carried out by a gas phase reaction, a trickle reaction, and a liquid phase reaction, and preferably a liquid phase reaction.
  • a solvent In the liquid phase reaction, it is not always necessary to use a solvent.
  • nitrile compounds such as benzonitrile, acetonitrile, propionitrile, butyronitrile, forcepronitrile, adiponitrile, and tolunitrile; and benzene, toluene, xylene, mesitylene, and methoxybenzene.
  • Aromatic hydrocarbon compounds such as n-hexane, n-heptane, n-octane, n-dodecane, ester compounds such as dimethyl phthalate, dibutyl phthalate and dimethyl malonate, benzyl alcohol, cyclo Hexanol compounds, hexane compounds such as isopropyl alcohol, isopropyl alcohol compounds, aldehyde compounds such as acetoaldehyde, benzaldehyde, ketone compounds such as acetyl ketone, methyl ethyl ketone, cyclohexanone, and diethyl.
  • Examples thereof include ether compounds such as lenglycol dimethylethanol ether, and halogen-containing hydrocarbon compounds such as chlorobenzene. These can be used alone or in combination.
  • it is a nitrile compound.
  • the amount of these solvents to be used is not particularly limited, but is 0.1 to 10,000 times by weight, preferably 1 to 1000 times by weight, more preferably 2 to 100 times by weight, based on the cycloalkanone oxime compound. It is by weight, more preferably 3 to 50 times by weight.
  • the amount of the solid acid catalyst produced by the above-mentioned method is not particularly limited.
  • the amount of the solid acid catalyst to be used is 0.00000001-10 times by weight based on the cycloalkanone oxime compound. preferable.
  • the Beckmann rearrangement reaction in a liquid phase which is a preferred embodiment of the present invention, is usually carried out by introducing a cycloanolecanone oxime compound and a solid acid catalyst into an appropriate solvent and then heating.
  • the reaction is usually carried out in the presence of air or a gas inert to the rearrangement reaction, preferably in the presence of a gas inert to the rearrangement reaction.
  • the gas inert to the rearrangement reaction include nitrogen, helium, and argon.
  • the reaction is usually carried out at a temperature of 30 to 350 ° C, preferably 50 to 250 ° C, more preferably 60 to 200 ° C.
  • the reaction pressure is not particularly limited, and the reaction is carried out under normal pressure or under pressure.
  • the reaction temperature is lower than the above range, the reaction may hardly proceed. On the other hand, if the reaction temperature is higher than the above range, a side reaction proceeds, and the yield of the desired product, ratatum, decreases, which is not preferable.
  • the reaction may be carried out in any of a batch reaction and a continuous flow reaction, and may be carried out in any of a suspended bed, a fixed bed and a fluidized bed.
  • the reaction time or residence time varies depending on the reaction conditions, but is carried out for 1 minute to 24 hours.
  • the obtained ratatum compound is separated and purified by a commonly used crystallization, distillation operation or the like.
  • the atomic ratio of the constituents of the oxide was determined by ICP analysis using an ICP-AES measuring device (ICAP-575II; manufactured by Nippon Jarrell's Ash Co.). BET specific surface area measurement (pretreatment under vacuum at 120 ° C for 30 minutes) by nitrogen adsorption using (NOVA-1200; manufactured by urea ionitas) and X-ray diffraction pattern (Cu-K ⁇ ray ) Were measured using a powder X-ray diffractometer (RAD-RX: manufactured by Rigaku Corporation).
  • the sulfur content of the solid acid catalyst was determined by a fully automatic X-ray fluorescence spectrometer (PW-2400: PHI
  • Firing was performed at 420 ° C. for 1 hour in a stream of air (100 ml / min) as a post-treatment for 1 hour.
  • the resulting catalyst had a sulfur content of 2.2% by weight.
  • the specific surface area was 828 m 2 / g.
  • the mixed gas (exhaust gas) after contact with the oxide was brought into contact with water for 1 hour, and ion chromatography analysis of sulfate ions and sulfite ions contained in the water was performed.
  • the ions were detected at 0.058 mmol and 0.019 mmol, respectively.
  • the dried product was heated in the air to a room temperature power of 400 ° C at a rate of 5 ° C / min and calcined at 400 ° C for 3 hours.
  • the specific surface area of the obtained catalyst was 579 m 2 / g.
  • a catalyst was prepared in the same manner as in Example 1 except that the 7 wt% vanadium pentoxide Z silica catalyst was changed to lOwf / o copper oxide / silica catalyst, and a Beckmann rearrangement reaction was performed using the prepared catalyst.
  • the conversion of cyclododecanone O oxime is 87.2 mol 0/0
  • the yield of Lau port Ratatamu was 79.8 Monore%.
  • a catalyst was prepared in the same manner as in Example 1 except that the 7 wt% vanadium pentoxide Z silica catalyst was changed to lOwf / o iron oxide / silica catalyst, and a Beckmann rearrangement reaction was performed using the prepared catalyst. It was. As a result, the conversion of cyclododecanone O oxime is 75.2 mol 0/0, the yield of Lau port Ratatamu was 72.0 Monore%.
  • a catalyst was prepared in the same manner as in Example 1 except that the 7 wt% vanadium pentoxide Z silica catalyst was changed to an lOwf / o cobalt oxide Z silica catalyst, and a Beckmann rearrangement reaction was performed using the prepared catalyst.
  • the conversion of cyclododecanone O oxime is 39.4 mol 0/0
  • the yield of Lau port rata Tam was 36.7 mol 0/0.
  • a catalyst was prepared in the same manner as in Example 1 except that the 7 wt% vanadium pentoxide / silica catalyst was changed to a 10 wt% nickel oxide / silica catalyst, and a Beckmann rearrangement reaction was performed using the prepared catalyst.
  • the conversion of cyclododecanone O oxime is 25.4 mol 0/0, Lau port rata Tam yield 23-4 mole 0 /. Met.
  • a catalyst was prepared in the same manner as in Example 1 except that the catalyst was not charged with 7 wt% of vanadium pentoxide / silica, and a Beckmann rearrangement reaction was performed using the prepared catalyst.
  • the conversion of cyclododecanone O oxime is 18, 5 mole 0/0
  • the yield of Lau port Ratatamu was 14.8 mol 0/0.
  • the catalyst was prepared in the same manner as in Example 1 except that the flow rate of G2 grade pure air (JFP product standard) was changed to 250 mlZ, and the contact time was changed to 9 hours. A rearrangement reaction was performed. As a result, the conversion of cyclododecanone O oxime 9 4.0 Monore 0/0, the yield of Lau port Ratatamu was 86.6 mol 0/0.
  • a catalyst was prepared in the same manner as in Example 6 except that the amount of the 7 wt% vanadium pentoxide Z silica catalyst was changed to 8 g, and a Beckmann rearrangement reaction was performed using the prepared catalyst.
  • the cyclod Conversion of Dekanonokishimu is 61.7 mol 0/0
  • the yield of Lau port Ratatamu is 56.9 mole 0/0 der ivy.
  • a catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to Zr-MS-87, and a Beckmann rearrangement reaction was performed using the prepared catalyst.
  • the conversion of cyclododecanone O oxime is 76.1 mole 0/0
  • the yield of Lau port Ratatamu is 71.4 mol 0 /. Met.
  • the catalyst had a sulfur content of 2.1% by weight.
  • a catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to Ga-MS-50, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime is 97.8 Monore 0/0, the yield of Lau port Ratatamu is 93.3 mol 0 /. Met.
  • the catalyst had a sulfur content of 2.1% by weight.
  • a catalyst was prepared in the same manner as in Comparative Example 1 except that the oxide was changed to Ga-MS-50, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime is 55.3 Monore 0/0, the yield of Lau port Ratatamu was 48.2 Monore 0/0.
  • a Beckmann rearrangement reaction was performed in the same manner as in Example 1 except that the catalyst was changed to untreated Ga-MS-50. As a result, the conversion of cyclododecanone O oxime is 18.7 mol 0/0, Lau port rata Tam yield was 12.3 mol 0/0.
  • a catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to A1-MS-50, and a Beckmann rearrangement reaction was performed using the prepared catalyst.
  • the conversion of cyclododecanone O oxime is 90.9 Monore 0/0
  • the yield of Lau port Ratatamu is 86.4 mol 0 /. Met.
  • the catalyst sulfur The content was 2.0% by weight.
  • a catalyst was prepared in the same manner as in Comparative Example 1 except that the oxide was changed to A1-MS-50, and a Beckmann rearrangement reaction was performed using the prepared catalyst.
  • the conversion of cyclododecanone O oxime is 33.4 Monore 0/0
  • the yield of Lau port Ratatamu was 32.0 Monore 0/0.
  • a catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to ⁇ -zeolite (manufactured by UOP) which had been calcined in air at 600 ° C for 2 hours, and a Beckmann rearrangement reaction was performed using the prepared catalyst.
  • cyclododecanone O conversion of oxime is 92.4 Monore 0/0, the yield of Lau port Ratatamu was 89.1 mol%.
  • the catalyst had a sulfur content of 3.0% by weight.
  • a catalyst was prepared in the same manner as in Comparative Example 1, except that the oxide was changed to ⁇ -zeolite (manufactured by UOP) which had been calcined in air at 600 ° C for 2 hours, and a Beckmann rearrangement reaction was performed using the prepared catalyst.
  • the conversion of cyclododecanone O oxime is 23.1 mole 0/0
  • the yield of Lau port Ratatamu was 5 mol% 19..
  • a Beckmann rearrangement reaction was carried out in the same manner as in Example 1, except that the catalyst was changed to untreated / 3-zeolite (manufactured by UOP) which had been calcined in air at 600 ° C for 2 hours in advance.
  • the conversion of Shikurodode Kanonokishimu is 26.5 Monore 0/0
  • the yield of Lau port Ratatamu was filed with 23.8 mole 0/0.
  • a catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to MS, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime 49. 4 mol 0/0, the yield of Lau port Ratatamu is 45.8 mol 0 /. Met. The sulfur content of the catalyst was 1.3% by weight.
  • a catalyst was prepared in the same manner as in Comparative Example 1 except that the oxide was changed to MS, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime 17. 9 moles 0/0, the yield of Lau port Ratatamu was 7.3 mol%. Sulfur was not detected in the catalyst.
  • a catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to MCM41, 0.7 g, and a Beckmann rearrangement reaction was performed using the prepared catalyst.
  • the conversion of cyclododecanone O oxime is 83.4 Monore 0/0
  • the yield of Lau port Ratatamu is 76.3 mol 0 /. Met.
  • the catalyst had a sulfur content of 1.8% by weight.
  • a catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to AEROSIL 200 (manufactured by Nippon AEROSIL) and 0.7 g, and a Beckmann rearrangement reaction was performed using the prepared catalyst.
  • AEROSIL 200 manufactured by Nippon AEROSIL
  • the conversion of cyclododecanone O oxime is 21.7 mol 0/0
  • the yield of Lau port Ratatamu was 18.7 mol%.
  • the catalyst had a sulfur content of 0.5% by weight.
  • a catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to CARIACT Q_30 (manufactured by Fuji Silicon Chemicals) and 1.2 g, and a Beckmann rearrangement reaction was performed using the prepared catalyst. As a result, the conversion of cyclododecanone O oxime is 12.8 Monore 0/0, the yield of Lau port Ratatamu was 9. 9 mole percent.
  • the catalyst had a sulfur content of 0.4% by weight.
  • the catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to 1.6 g of aluminum hydroxide, which is a hydroxide, and the pretreatment was not performed, and the Beckmann rearrangement reaction was performed using the prepared catalyst. Responded. As a result, the conversion of cyclododecanone O oxime is 12.5 mole 0/0, Lau port rata Tam yield was 0 mol% 8.. The catalyst had a sulfur content of 9.8% by weight.
  • the catalyst was prepared in the same manner as in Example 1 except that the oxide was changed to zirconium hydroxide, which is a hydroxide, and 3.Og, and the pretreatment was not performed, and the Beckmann rearrangement reaction was performed using the prepared catalyst. went. As a result, the conversion of cyclododecanone O oxime is 37.2 mol 0/0, Lau port rata Tam yield was 32.3 mol%. The sulfur content of the catalyst was 0.8% by weight.
  • At least one compound selected from the group consisting of oxides and hydroxides By using, it is possible to produce a solid acid catalyst having a high activity for an acid catalyst reaction. In addition, by using this catalyst, even in the absence of a strong acid, the Beckmann rearrangement reaction of a cycloalkanone oxime compound proceeds efficiently, and the corresponding ratatam compound with a small amount of by-product oligomers can be advantageously produced in high yield. Can be.

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Abstract

La présente invention concerne un procédé permettant l'élaboration d'un catalyseur acide solide caractérisé en ce que l'un au moins des composés choisis parmi les oxydes et hydroxydes est mis en contact avec un gaz contenant du trioxyde de soufre. L'invention concerne également un procédé de production d'un composé à base de lactame, caractérisé en ce qu'un composé lactame correspondant est produit par réorganisation Beckmann d'un composé cycloalcanone-oxime en présence d'un catalyseur acide solide obtenu par le procédé déjà énoncé.
PCT/JP2004/019298 2003-12-25 2004-12-24 Procede pour elaborer un catalyseur acide solide, et procede pour produire un compose au lactame en utilisant un tel catalyseur WO2005063388A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100463718C (zh) * 2005-10-21 2009-02-25 哈尔滨工业大学 促进乳酸铵酯化反应的二元催化体系中磁性固体酸催化剂的制备方法
CN109516941A (zh) * 2017-09-20 2019-03-26 万华化学集团股份有限公司 一种十二内酰胺的生产方法

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JPH05228369A (ja) * 1991-10-25 1993-09-07 Inst Fr Petrole パラフィン類のアルキル化触媒
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