JP2013053128A - Production method for methacrylic acid compound, and catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a methacrylic acid compound (II) in a high yield.SOLUTION: The production method for a methacrylic acid compound (II) is characterized by reacting a propionic acid compound (I) and at least one kind selected from the group consisting of formaldehyde, methylal, 1,3,5-trioxane and paraformaldehyde, in the presence of a catalyst containing a calcined product obtained by calcination of hydrotalcite. Preferably, the hydrotalcite is represented by formula (III): [M1M2(OH)][AnHO] or formula (IV): [M1M2M3(OH)][AnHO].

Description

  The present invention relates to a compound of formula (I)

(In the formula, R ¹ represents a hydrogen atom, an alkyl group, or an acyl group.)
[Hereinafter, it may be called propionic acid compound (I). ] And at least one selected from the group consisting of formaldehyde, methylal, 1,3,5-trioxane and paraformaldehyde [hereinafter sometimes referred to as a formaldehyde compound. And a compound of formula (II)

(Wherein R ¹ represents the same meaning as described above.)
[Hereinafter, it may be referred to as methacrylic acid compound (II). And a catalyst suitable for this production method.

  Conventionally, as a method for producing a methacrylic acid compound (II) by reacting a propionic acid compound (I) with a formaldehyde compound, for example, in Patent Document 1, in the presence of a silica catalyst containing zirconium and cesium, A method for producing methacrylic acid and methyl methacrylate by reacting methyl propionate, methanol, and formalin has been proposed.

Japanese translation of PCT publication No. 2002-511336

  However, the above conventional methods are not always satisfactory in terms of the yield of the methacrylic acid compound (II).

  Then, the objective of this invention is providing the method of manufacturing methacrylic acid compound (II) with a favorable yield.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have completed the present invention. That is, this invention consists of the following structures.

  (1) In the presence of a catalyst containing a calcined product obtained by calcining hydrotalcite, formula (I)

(In the formula, R ¹ represents a hydrogen atom, an alkyl group, or an acyl group.)
And a compound represented by the formula (II), wherein the compound is reacted with at least one selected from the group consisting of formaldehyde, methylal, 1,3,5-trioxane and paraformaldehyde

(Wherein R ¹ represents the same meaning as described above.)
The manufacturing method of the compound shown by these.
(2) The hydrotalcite has the formula (III)
[M1 _1-x M2 _x (OH) ₂ ] [A ^m- _{x / m} · nH ₂ O] (III)
(In the formula, M1 represents at least one divalent metal element selected from the group consisting of magnesium, zinc, copper, cobalt, manganese, iron, lead, nickel, calcium, barium and strontium, and M2 represents aluminum, iron , titanium, chromium, manganese, cobalt, is .m represents nickel, lanthanum, the at least one trivalent metal element selected from the group consisting of gallium and indium, a ^m-is representative of the m-valent anion 1-4 Represents an integer of 0 <x ≦ 0.5 and n> 0.)
The manufacturing method as described in said (1) which is shown by these.
(3) The hydrotalcite has the formula (IV)
[M1 _a M2 _b M3 _c (OH) ₂ ] [A ^m− _{(b + 2c) / m} · nH ₂ O]
(IV)
(In the formula, M1 represents at least one divalent metal element selected from the group consisting of magnesium, zinc, copper, cobalt, manganese, iron, lead, nickel, calcium, barium and strontium, and M2 represents aluminum, iron Represents at least one trivalent metal element selected from the group consisting of titanium, chromium, manganese, cobalt, nickel, lanthanum, gallium and indium, and M3 is at least one selected from the group consisting of tin, titanium and zirconium A ^m− represents an m-valent anion, m represents an integer of 1 to 4, 0.5 ≦ a <1, 0 <b <0.5, 0 <c <. 0.5, a + b + c = 1, 0 <b + c ≦ 0.5, and n> 0.)
The manufacturing method according to claim 1, wherein
(4) The above (2) or (3), wherein M1 is at least one selected from the group consisting of magnesium, zinc, lead and calcium, and M2 is at least one selected from the group consisting of aluminum and iron. The manufacturing method as described in.
(5) The manufacturing method according to any one of (1) to (4), wherein the baking is performed at 250 to 650 ° C.
(6) The production method according to any one of (1) to (5), wherein the reaction is further performed in the presence of water.
(7) Formula (I)

(In the formula, R ¹ represents a hydrogen atom, an alkyl group, or an acyl group.)
Is reacted with at least one selected from the group consisting of formaldehyde, methylal, 1,3,5-trioxane, and paraformaldehyde to give a compound of formula (II)

(Wherein R ¹ represents the same meaning as described above.)
The catalyst used when manufacturing the compound shown by these, Comprising: The catalyst characterized by including the baked material obtained by baking hydrotalcite.

  According to the present invention, methacrylic acid compound (II) can be produced in a good yield.

  In the present invention, in the presence of a catalyst containing a calcined product obtained by calcining hydrotalcite, formula (I)

(In the formula, R ¹ represents a hydrogen atom, an alkyl group, or an acyl group.)
[Propionic acid compound (I)] and at least one [formaldehyde compound] selected from the group consisting of formaldehyde, methylal, 1,3,5-trioxane and paraformaldehyde are reacted.

  In formula (I), the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t- A butyl group etc. are mentioned. Examples of the acyl group include formyl group, acetyl group, acryloyl group, propionyl group, butyryl group, isobutyryl group, methacryloyl group and the like. In particular, when propionic acid, methyl propionate or propionic anhydride is used as the propionic acid compound (I) as a raw material, the method of the present invention is advantageously employed.

Among these, formaldehyde is preferable as the formaldehyde compound. The formaldehyde compound may be used as it is, as an aqueous solution, as an organic solvent solution, or as a mixed solvent solution of water and an organic solvent. Examples of the organic solvent include methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, n-pentanol, n-hexanol, n-octanol, 2-ethylhexanol and the like having 1 to 1 carbon atoms. 8 alcohols; aliphatic hydrocarbons such as pentane, hexane, and octane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and the like. Two or more kinds can also be used. When formaldehyde is used as the formaldehyde compound, it is preferably used as an aqueous solution, an alcohol solution, or a mixed solvent solution of water and alcohol. The amount of the formaldehyde compound used is usually 0.05 to 20 mol in terms of formaldehyde with respect to 1 mol of the propionic acid compound (I). Here, 1 mol of methylal is converted to 1 mol of formaldehyde, 1 mol of 1,3,5-trioxane is converted to 3 mol of formaldehyde, and 1 mol of paraformaldehyde [HO (CH ₂ O) _n H] is formaldehyde. It shall be converted to nmoles. When using at least two selected from the group consisting of formaldehyde, methylal, 1,3,5-trioxane and paraformaldehyde, the total amount used may be in the above range in terms of formaldehyde.

  Hydrotalcite is a compound having a layered structure, and is a layered compound in which an anion exists between positively charged layers composed of a divalent metal element and a trivalent metal element. In general, the following formula (V)

^{_{[M II 1-x M III}} x (OH) 2] [A m- x / m · nH 2 O] (V)
^{(Wherein, M II} represents at least one divalent metal ^{element, M III} represents at least one trivalent metal ^{element, A m-is} .m representing the m-valent anion 1-4 Represents an integer of 0 <x ≦ 0.5 and n> 0.)
It is a compound shown by these. In addition, in the hydrotalcite, as long as the structure can be hold | maintained, a tetravalent or more metal element may also be included as a metal element which comprises a positively charged layer. In the present invention, among others, the formula (III)

[M1 _1-x M2 _x (OH) ₂ ] [A ^m- _{x / m} · nH ₂ O] (III)
(In the formula, M1 represents at least one divalent metal element selected from the group consisting of magnesium, zinc, copper, cobalt, manganese, iron, lead, nickel, calcium, barium and strontium, and M2 represents aluminum, iron , titanium, chromium, manganese, cobalt, is .m represents nickel, lanthanum, the at least one trivalent metal element selected from the group consisting of gallium and indium, a ^m-is representative of the m-valent anion 1-4 Represents an integer of 0 <x ≦ 0.5 and n> 0.)
The hydrotalcite represented by is preferably used. In the present invention, the formula (IV) further contains a tetravalent metal element as the metal element constituting the positively charged layer.

[M1 _a M2 _b M3 _c (OH) ₂ ] [A ^m− _{(b + 2c) / m} · nH ₂ O] (IV)
(In the formula, M1 represents at least one divalent metal element selected from the group consisting of magnesium, zinc, copper, cobalt, manganese, iron, lead, nickel, calcium, barium and strontium, and M2 represents aluminum, iron Represents at least one trivalent metal element selected from the group consisting of titanium, chromium, manganese, cobalt, nickel, lanthanum, gallium and indium, and M3 is at least one selected from the group consisting of tin, titanium and zirconium A ^m− represents an m-valent anion, m represents an integer of 1 to 4, 0.5 ≦ a <1, 0 <b <0.5, 0 <c <. 0.5, a + b + c = 1, 0 <b + c ≦ 0.5, and n> 0.)
The hydrotalcite represented by is preferably used.

  In Formula (III) and Formula (IV), M1 is preferably at least one selected from the group consisting of magnesium, zinc, lead and calcium, and M2 is preferably at least one selected from the group consisting of aluminum and iron. .

  In the formula (III) and formula (IV), examples of the m-valent anion include chloride ion, fluoride ion, bromide ion, iodide ion, nitrate ion, perchlorate ion, chlorate ion, acetate ion, Monovalent anions such as benzoate ion, methanesulfonate ion, p-toluenesulfonate ion, phenoxy ion, alkoxide ion; divalent anions such as carbonate ion, sulfate ion, terephthalate ion; phosphate ion, hexacyanoiron (III) trivalent anions such as acid ions; tetravalent anions such as hexacyanoferrate (II) acid ions, and the like. Among them, chloride ions, nitrate ions, carbonate ions, and sulfate ions are preferable.

  In the formula (III), x is preferably 1/6 ≦ x ≦ 0.5, more preferably 1 / 4.5 ≦ x ≦ 1/2.

  In the formula (IV), a, b and c are preferably 0.5 ≦ a ≦ 5/6, 1/6 <b <0.5, 1/6 <c <0.5, and more preferably 1.4 / 2.4 ≦ a ≦ 3.5 / 4.5, 1 / 4.5 <b <1 / 2.4, 1 / 4.5 <c <1 / 2.4, and b + c is Preferably, 1/6 ≦ b + c ≦ 0.5, and more preferably 1 / 4.5 ≦ b + c ≦ 1 / 2.4.

  The hydrotalcite represented by the formula (III) and the hydrotalcite represented by the formula (IV) can be prepared by a method such as a coprecipitation method or a hydrothermal synthesis method. The hydrotalcite represented by the formula (III) by the coprecipitation method is prepared, for example, by mixing a mixed solution A of a compound containing a divalent metal element, a compound containing a trivalent metal element, and water between layers. It mixes with the mixed solution B of the compound containing the anion to introduce | transduce, the compound containing a hydroxide ion, and water, and is performed by filtering and wash | cleaning the slurry containing the obtained crystal | crystallization as needed, and drying. The hydrotalcite represented by the formula (IV) by the coprecipitation method can be prepared, for example, by adding a compound containing a divalent metal element, a compound containing a trivalent metal element, and a tetravalent metal element. A slurry containing a crystal obtained by mixing a mixed solution C of a compound containing water and water with a mixed solution D of a compound containing an anion introduced between layers, a compound containing hydroxide ions, and water is necessary. After filtering and washing according to It can be carried out by 燥. Examples of the compound containing each metal element include halides, nitrates, sulfates, ammonium sulfates, carboxylates and oxoacid salts of each metal element. Examples of the compound containing an anion include sodium salt and potassium salt of the anion, and examples of the compound containing hydroxide ion include sodium hydroxide and potassium hydroxide. The presence or absence of the hydrotalcite structure can be confirmed by XRD (X-ray diffraction) analysis, and the composition of the hydrotalcite and the fired product obtained by firing the hydrotalcite (type and amount of constituent components). Can be analyzed by inductively coupled plasma (ICP) emission analysis or the like.

  In the present invention, the reaction is performed in the presence of a catalyst containing a calcined product obtained by calcining hydrotalcite. The calcination is usually performed by heating hydrotalcite in a gas atmosphere. The firing temperature is preferably 250 to 650 ° C, more preferably 400 to 550 ° C, and the firing time is preferably 0.5 to 48 hours, more preferably 2 to 24 hours. Examples of the gas include an oxidizing gas and a non-oxidizing gas. Examples of the oxidizing gas include air and oxygen. Examples of the non-oxidizing gas include inert gases such as nitrogen, argon, and helium. Examples of the reducing gas include carbon dioxide, hydrogen, and ammonia. Among these, nitrogen, air, or a mixed gas thereof is preferable.

  The content of the M1 contained in the fired product obtained by firing the hydrotalcite represented by the formula (III) is preferably 1.0 to 5.0 moles relative to 1 mole of the M2. 4-3.5 mol is more preferable. When said M1 and / or said M2 are 2 or more types of metal elements, the total ratio of each content should just become said range. Content of said M1 contained in the baked product obtained by baking the hydrotalcite shown by Formula (IV) is 1.0-5 with respect to the total of 1 mol of each content of said M2 and said M3. 0.0 mol is preferable, and 1.4 to 3.5 mol is more preferable. When said M1, said M2, and / or said M3 are 2 or more types of metal elements, the total ratio of each content should just become said range.

  Among hydrotalcites, hydrotalcite having carbonate ions as interlayer anions is known to be dehydrated and decarboxylated into an oxide by firing at a temperature of 400 ° C. or higher. In the formula (III), when hydrotalcite whose m-valent anion is carbonate ion is baked at a temperature of 400 ° C. or higher, an oxide containing M1 and M2 is obtained. When the hydrotalcite whose m-valent anion is carbonate ion in the formula (IV) is calcined at a temperature of 400 ° C. or higher, an oxide containing the M1, the M2, and the M3 is obtained.

  In the reaction, an organic solvent may be used. Examples of the organic solvent include methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, n-pentanol, n-hexanol, n-octanol, 2-ethylhexanol, and the like. ~ 8 alcohols; aliphatic hydrocarbons such as pentane, hexane and octane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene, and the like. Two or more of these can also be used. Among these, alcohol having 1 to 4 carbon atoms is preferable.

  When using an organic solvent, the quantity is 10-1000 weight part normally with respect to 100 weight part of propionic acid compound (I), Preferably it is 50-500 weight part. In the case where the formaldehyde compound is used as an organic solvent solution or a mixed solvent solution of water and an organic solvent, the amount of the organic solvent used in the reaction is considered in consideration of the amount of the organic solvent contained in the formaldehyde compound solution. Should just become said range.

  In the present invention, the reaction is preferably carried out in the presence of water together with the catalyst. When water is present, the amount of water used is usually 0.1 mol or more, preferably 3 to 50 mol, more preferably 10 to 40 mol, relative to 1 mol of propionic acid compound (I). is there. When the formaldehyde compound is used as an aqueous solution or a mixed solvent solution of water and an organic solvent, the amount of water used in the reaction should be within the above range in consideration of the amount of water contained in the formaldehyde compound solution. That's fine.

  In the reaction, the reaction method may be a batch method or a continuous method. The reaction temperature is usually 50 to 400 ° C., preferably 100 to 200 ° C., and the reaction pressure is usually 0.1 to 10 MPa. In the continuous reaction, for example, the reaction can be carried out by employing a fixed bed type or a fluidized bed type under gas phase conditions. When performing the said reaction by a batch type, you may carry out in inert gas atmosphere and may carry out in oxidizing gas atmosphere. Moreover, when performing the said reaction by a continuous type, you may supply an inert gas and oxidizing gas with a raw material. Examples of the inert gas include nitrogen, argon, helium, carbon dioxide and the like. Examples of the oxidizing gas include air and oxygen. When performing the said reaction by a batch type, the usage-amount of the said catalyst is 1-50 g normally with respect to 1 mol of propionic acid compounds (I), Preferably it is 10-30 g.

  Thus, formula (II)

(Wherein R ¹ represents the same meaning as described above.)
To obtain a reaction mixture containing the compound [methacrylic acid compound (II)]. The post-treatment operation after the reaction is appropriately selected.For example, after separating the catalyst from the reaction mixture by filtration, decantation or the like, if necessary, by performing operations such as extraction, distillation, and crystallization, Methacrylic acid compound (II) can be separated.

When propionic acid [compound in which R ¹ is a hydrogen atom in formula (I)] is used as propionic acid compound (I), the reaction is carried out in the presence of the alcohol having 1 to 4 carbon atoms. By carrying out, as the methacrylic acid compound (II), methacrylic acid [a compound in which R ¹ is a hydrogen atom in the formula (II)] and an methacrylic acid alkyl ester which is an ester of the alcohol [in the formula (II), R ¹ can be obtained as compound] an alkyl group having 1 to 4 carbon atoms. Further, when propionic acid alkyl ester [compound in which R ¹ is an alkyl group in formula (I)] is used as propionic acid compound (I), water produced as a by-product by the reaction of propionic acid alkyl ester and formaldehyde compound Alternatively, the presence of water that is preferably used in the reaction may hydrolyze the propionic acid alkyl ester and / or the product of the reaction to produce methacrylic acid. Similarly, when propionic anhydride (a compound in which R ¹ is a propionyl group in formula (I)) is used as propionic acid compound (I), a by-product is formed by reaction of propionic anhydride and formaldehyde compound. Due to the presence of water and water preferably used for the reaction, propionic anhydride and / or the product of the reaction can be hydrolyzed to produce methacrylic acid. Therefore, when propionic acid anhydride is used as the propionic acid compound (I), the reaction is carried out in the presence of the alcohol having 1 to 4 carbon atoms, whereby the methacrylic acid compound (II) is converted into methacrylic acid compound (II). An acid alkyl ester [a compound in which R ¹ is an alkyl group having 1 to 4 carbon atoms in formula (II)] can be formed.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited to these.

  In addition, the composition (constituent element ratio) of the catalyst obtained in each of the following examples was obtained by analyzing the catalyst using an ICP emission spectroscopic analyzer (“715-ES” manufactured by Varian).

Example 1
<Preparation of catalyst>
Zinc nitrate hexahydrate _{[Zn (NO 3) 2 · 6H} 2 O ] 11.56 g (0.039 mol), and aluminum nitrate nonahydrate _{[Al (NO 3) 3 · 9H} 2 O ] 14.58g (0.039 mol) was dissolved in 41.32 g of water to obtain α1 solution. On the other hand, 5.49 g (0.052 mol) of sodium carbonate and 7.77 g (0.194 mol) of sodium hydroxide were dissolved in 51.82 g of water to obtain β1 solution. In a container equipped with a stirrer, the α1 liquid and the β1 liquid were each stirred at room temperature while being continuously supplied (co-feed) at a flow rate of 20 mL / h. The pH of the liquid phase of the mixture obtained after supplying all the α1 solution and β1 solution was 13. The resulting mixture was aged at 60 ° C. overnight, filtered, and the residue was washed with water until the pH of the washing filtrate was around 7, then dried at 60 ° C. for 18 hours, and hydrotalcite (A) [[Zn _0.60 Al _0.40 (OH) ₂ ] [CO ₃ ² _−0.20 · nH ₂ O]] was obtained. This hydrotalcite (A) was confirmed to have a hydrotalcite structure as a result of X-ray diffraction analysis using copper Kα rays. The obtained hydrotalcite (A) was calcined at 450 ° C. for 6 hours under a nitrogen flow of 100 mL / min to obtain a catalyst (A). As a result of the compositional analysis, the catalyst (A) contains 60 mol% Zn and 40 mol% [Zn / Al = 1.5 (molar ratio)] with respect to the total mol of Zn and Al. It was a thing.

<Catalyst activity test>
To a 2.5 mL glass microreactor, 0.30 g (4.0 mmol) of propionic acid [compound in which R ¹ is a hydrogen atom in formula (I)], 0.61 g of a 24.6 wt% formaldehyde aqueous solution (formaldehyde 5.0 mmol, 25.7 mmol of water), 0.26 g (8.0 mmol) of methanol, and 0.075 g of the catalyst (A) obtained above were introduced, and nitrogen was introduced into the gas phase in the microreactor. The pressure inside the microreactor was increased to 1.5 MPa (gauge pressure). Next, the microreactor was heated to 120 ° C. while stirring and reacted for 4 hours. The reaction solution was analyzed by gas chromatography. Based on the following formula, propionic acid conversion rate (%), methyl methacrylate [compound in which R ¹ is a methyl group in formula (II)] selectivity (%), methacrylic acid The selectivity (%) for the acid [compound in which R ¹ is a hydrogen atom in formula (II)] and the total yield (%) of methacrylic acid and methyl methacrylate are shown in Table 1.

Propionic acid conversion (%) = [number of moles of reacted propionic acid ÷ number of moles of propionic acid supplied] × 100
Methyl methacrylate selectivity (%) = [number of moles of methyl methacrylate produced / number of moles of all products produced] × 100
Methacrylic acid selectivity (%) = [number of moles of methacrylic acid produced ÷ number of moles of all products produced] × 100
Total yield of methacrylic acid and methyl methacrylate (%) = [propionic acid conversion (%) × (methyl methacrylate selectivity (%) + methacrylic acid selectivity (%))] ÷ 100

Example 2
<Preparation of catalyst>
Zinc nitrate hexahydrate _{[Zn (NO 3) 2 · 6H} 2 O ] 13.65 g (0.046 mol), and aluminum nitrate nonahydrate _{[Al (NO 3) 3 · 9H} 2 O ] 11.47g (0.031 mol) was dissolved in 41.05 g of water, and this was designated α2 solution. On the other hand, 5.40 g (0.051 mol) of sodium carbonate and 7.34 g (0.184 mol) of sodium hydroxide were dissolved in 51.82 g of water, and this was used as β2 solution. In a container equipped with a stirrer, the α2 liquid and the β2 liquid were each stirred at room temperature while being continuously supplied (co-feed) at a flow rate of 20 mL / h. The pH of the liquid phase of the mixture obtained after supplying all the α2 solution and β2 solution was 13. The resulting mixture was aged at 60 ° C. overnight, then filtered, and the residue was washed with water until the pH of the washing filtrate was around 7, then dried at 60 ° C. for 18 hours, and hydrotalcite (B) [[Zn _0.67 Al _0.33 (OH) ₂ ] [CO ₃ ^{2 −} _{0.33 / 2} · nH ₂ O]] was obtained. This hydrotalcite (B) was confirmed to have a hydrotalcite structure as a result of X-ray diffraction analysis using copper Kα rays. The obtained hydrotalcite (B) was calcined at 450 ° C. for 6 hours under a nitrogen flow of 100 mL / min to obtain a catalyst (B). As a result of composition analysis, the catalyst (B) contains 67 mol% Zn and 33 mol% Al [Zn / Al = 2.0 (molar ratio)] with respect to the total moles of Zn and Al. It was a thing.

<Catalyst activity test>
In <Catalyst activity test>, an activity test was conducted in the same manner as in Example 1 except that the catalyst (B) obtained above was used instead of the catalyst (A). The results are shown in Table 1.

Example 3
<Preparation of catalyst>
Zinc nitrate hexahydrate _{[Zn (NO 3) 2 · 6H} 2 O ] 14.52 g (0.049 mol), and aluminum nitrate nonahydrate _{[Al (NO 3) 3 · 9H} 2 O ] 10.17g (0.027 mol) was dissolved in 40.94 g of water to obtain α3 solution. On the other hand, 5.36 g (0.051 mol) of sodium carbonate and 7.16 g (0.179 mol) of sodium hydroxide were dissolved in 50.62 g of water to obtain β3 solution. In a container equipped with a stirrer, the α3 solution and the β3 solution were each stirred at room temperature while being continuously fed (co-feed) at a flow rate of 20 mL / h. The pH of the liquid phase of the mixture obtained after supplying all the α3 solution and β3 solution was 13. The resulting mixture was aged at 60 ° C. overnight, filtered, and then the residue was washed with water until the pH of the washing filtrate was around 7, then dried at 60 ° C. for 18 hours, and hydrotalcite (C) [[Zn _0.69 Al _0.31 (OH) ₂ ] [CO ₃ ^{2 −} _{0.31 / 2} · nH ₂ O]] was obtained. This hydrotalcite (C) was confirmed to have a hydrotalcite structure as a result of X-ray diffraction analysis using copper Kα rays. The obtained hydrotalcite (C) was calcined at 450 ° C. for 6 hours under a nitrogen flow of 100 mL / min to obtain a catalyst (C). As a result of compositional analysis, the catalyst (C) contains 69 mol% Zn and 31 mol% [Zn / Al = 2.2 (molar ratio)] with respect to the total mol of Zn and Al. It was a thing.

<Catalyst activity test>
In <Catalyst activity test>, the activity test was conducted in the same manner as in Example 1 except that the catalyst (C) obtained above was used instead of the catalyst (A). The results are shown in Table 1.

Example 4
<Preparation of catalyst>
Zinc nitrate hexahydrate _{[Zn (NO 3) 2 · 6H} 2 O ] 15.00 g (0.050 mol), and aluminum nitrate nonahydrate _{[Al (NO 3) 3 · 9H} 2 O ] 9.46g (0.025 mol) was dissolved in 40.88 g of water to obtain α4 solution. On the other hand, 5.34 g (0.050 mol) of sodium carbonate and 7.06 g (0.177 mol) of sodium hydroxide were dissolved in 50.42 g of water to obtain β4 solution. In a container equipped with a stirrer, the α4 liquid and the β4 liquid were each stirred at room temperature while being continuously fed (co-feed) at a flow rate of 20 mL / h. The pH of the liquid phase of the mixture obtained after supplying all the α4 solution and β4 solution was 13. The resulting mixture was aged at 60 ° C. overnight, then filtered, and the residue was washed with water until the pH of the washing filtrate was close to 7, then dried at 60 ° C. for 18 hours, and hydrotalcite (D) [[Zn _0.71 Al _0.29 (OH) ₂ ] [CO ₃ ² _{−0.29 / 2} · nH ₂ O]] was obtained. This hydrotalcite (D) was confirmed to have a hydrotalcite structure as a result of X-ray diffraction analysis using copper Kα rays. The obtained hydrotalcite (D) was calcined at 450 ° C. for 6 hours under a nitrogen flow of 100 mL / min to obtain a catalyst (D). As a result of the compositional analysis, the catalyst (D) contains 71 mol% Zn and 29 mol% Al [Zn / Al = 2.5 (molar ratio)] with respect to the total mol of Zn and Al. It was a thing.

<Catalyst activity test>
In <Catalyst activity test>, the activity test was performed in the same manner as in Example 1 except that the catalyst (D) obtained above was used instead of the catalyst (A). The results are shown in Table 1.

Example 5
<Preparation of catalyst>
Zinc nitrate hexahydrate _{[Zn (NO 3) 2 · 6H} 2 O ] 15.95 g (0.054 mol), and aluminum nitrate nonahydrate _{[Al (NO 3) 3 · 9H} 2 O ] 8.04g (0.021 mol) was dissolved in 40.76 g of water to obtain α5 solution. On the other hand, 5.30 g (0.050 mol) of sodium carbonate and 6.86 g (0.172 mol) of sodium hydroxide were dissolved in 50.03 g of water to obtain β5 solution. In a container equipped with a stirrer, the α5 liquid and the β5 liquid were each stirred at room temperature while being continuously fed (co-feed) at a flow rate of 20 mL / h. The pH of the liquid phase of the mixture obtained after supplying all the α5 solution and β5 solution was 13. The resulting mixture was aged at 60 ° C. overnight, filtered, and then the residue was washed with water until the pH of the washing filtrate was close to 7, then dried at 60 ° C. for 18 hours, and hydrotalcite (E) [[Zn _0.75 Al _0.25 (OH) ₂ ] [CO ₃ ²⁻ _{0.25 / 2} · nH ₂ O]] was obtained. This hydrotalcite (E) was confirmed to have a hydrotalcite structure as a result of X-ray diffraction analysis using copper Kα rays. The obtained hydrotalcite (E) was calcined at 450 ° C. for 6 hours under a nitrogen flow of 100 mL / min to obtain a catalyst (E). As a result of the compositional analysis, the catalyst (E) contains 75 mol% of Zn and 25 mol% of Al [Zn / Al = 3.1 (molar ratio)] with respect to the total mol of Zn and Al. It was a thing.

<Catalyst activity test>
In <Catalyst activity test>, the activity test was performed in the same manner as in Example 1 except that the catalyst (E) obtained above was used instead of the catalyst (A). The results are shown in Table 1.

Example 6
<Preparation of catalyst>
Zinc nitrate hexahydrate _{[Zn (NO 3) 2 · 6H} 2 O ] 16.65 g (0.056 mol), and aluminum nitrate nonahydrate _{[Al (NO 3) 3 · 9H} 2 O ] 7.00g (0.019 mol) was dissolved in 40.67 g of water to obtain α6 solution. On the other hand, 5.27 g (0.050 mol) of sodium carbonate and 6.72 g (0.168 mol) of sodium hydroxide were dissolved in 49.75 g of water to obtain β6 solution. In a container equipped with a stirrer, the α6 liquid and the β6 liquid were each stirred at room temperature while being continuously fed (co-feed) at a flow rate of 20 mL / h. The pH of the liquid phase of the mixture obtained after supplying all the α6 solution and β6 solution was 13. The resulting mixture was aged at 60 ° C. overnight and filtered, and then the residue was washed with water until the pH of the washing filtrate was around 7, then dried at 60 ° C. for 18 hours, and hydrotalcite (F) [[Zn _0.77 Al _0.23 (OH) ₂ ] [CO ₃ ^{2 −} _{0.23 / 2} · nH ₂ O]] was obtained. This hydrotalcite (F) was confirmed to have a hydrotalcite structure as a result of X-ray diffraction analysis using copper Kα rays. The obtained hydrotalcite (F) was calcined at 450 ° C. for 6 hours under a nitrogen flow of 100 mL / min to obtain a catalyst (F). As a result of the compositional analysis, the catalyst (F) contains 77 mol% Zn and 23 mol% Al (Zn / Al = 3.3 (molar ratio)) with respect to the total mol of Zn and Al. It was a thing.

<Catalyst activity test>
In <Catalyst activity test>, an activity test was conducted in the same manner as in Example 1 except that the catalyst (F) obtained above was used instead of the catalyst (A). The results are shown in Table 1.

Example 7
<Preparation of catalyst>
Magnesium nitrate hexahydrate [Mg (NO ₃ ) ₂ .6H ₂ O] 7.76 g (0.030 mol), calcium nitrate tetrahydrate [Ca (NO ₃ ) ₂ .4H ₂ O] 7.15 g ( 0.030 mol), and aluminum nitrate nonahydrate _{[Al (NO 3) 3 · 9H} 2 O ] 11.36g of (0.030 mol) was dissolved in water of 50.19G, which was used as a α7 solution . On the other hand, 6.42 g (0.061 mol) of sodium carbonate and 8.48 g (0.212 mol) of sodium hydroxide were dissolved in 60.56 g of water to obtain β7 solution. In a container equipped with a stirrer, the α7 liquid and the β7 liquid were each stirred at room temperature while being continuously supplied (co-feed) at a flow rate of 20 mL / h. The pH of the liquid phase of the mixture obtained after supplying all the α7 solution and β7 solution was 13. The resulting mixture was aged at 60 ° C. overnight and filtered, and then the residue was washed with water until the pH of the washing filtrate was close to 7, then dried at 60 ° C. for 18 hours, and hydrotalcite (G). [[Mg _0.40 Ca _0.19 Al _0.41 (OH) ₂ ] [CO ₃ ^{2 −} _{0.41 / 2} · nH ₂ O]] was obtained. This hydrotalcite (G) was confirmed to have a hydrotalcite structure as a result of X-ray diffraction analysis using copper Kα rays. The obtained hydrotalcite (G) was calcined at 450 ° C. for 6 hours under a nitrogen flow of 100 mL / min to obtain a catalyst (G). As a result of the composition analysis, the catalyst (G) is 40 mol% Mg, 19 mol% Ca and 41 mol% Al [(Mg + Ca) /Al=1.5 with respect to the total mol of Mg, Ca and Al. (Molar ratio)].

<Catalyst activity test>
In <Catalyst activity test>, the activity test was performed in the same manner as in Example 1 except that the catalyst (G) obtained above was used instead of the catalyst (A). The results are shown in Table 1.

Example 8
<Preparation of catalyst>
Magnesium nitrate hexahydrate [Mg (NO ₃ ) ₂ .6H ₂ O] 14.93 g (0.058 mol), iron nitrate (III) 9 hydrate [Fe (NO ₃ ) ₃ .9H ₂ O] 1 .81G (0.0045 mol) and aluminum nitrate nonahydrate _{[Al (NO 3) 3 · 9H} 2 O ] 11.76g of (0.031 mol) was dissolved in water of 50.59G, this α8 Liquid. On the other hand, 6.65 g (0.063 mol) of sodium carbonate and 8.78 g (0.220 mol) of sodium hydroxide were dissolved in 62.69 g of water to obtain β8 solution. The α8 liquid and β8 liquid were each stirred at room temperature while being continuously supplied (co-feed) at a flow rate of 20 mL / h into a container equipped with a stirrer. The pH of the liquid phase of the mixture obtained after supplying all the α8 solution and β8 solution was 13. The resulting mixture was aged at 60 ° C. overnight, filtered, and then the residue was washed with water until the pH of the washing filtrate was close to 7, then dried at 60 ° C. for 18 hours, and hydrotalcite (H) [[Mg _0.65 Fe _0.05 Al _0.30 (OH) ₂ ] [CO ₃ ^{2 −} _{0.35 / 2} · nH ₂ O]] was obtained. This hydrotalcite (H) was confirmed to have a hydrotalcite structure as a result of X-ray diffraction analysis using copper Kα rays. The obtained hydrotalcite (H) was calcined at 450 ° C. for 6 hours under a nitrogen flow of 100 mL / min to obtain a catalyst (H). As a result of the compositional analysis, the catalyst (H) is 65 mol% Mg, 5 mol% Fe, and 30 mol% Al with respect to the total mol of Mg, Fe and Al [Mg / (Fe + Al) = 1.9. (Molar ratio)].

<Catalyst activity test>
In <Catalyst activity test>, the activity test was performed in the same manner as in Example 1 except that the catalyst (H) obtained above was used instead of the catalyst (A). The results are shown in Table 1.

Example 9
<Preparation of catalyst>
Zinc nitrate hexahydrate [Zn (NO ₃ ) ₂ .6H ₂ O] 13.98 g (0.047 mol), iron nitrate (III) 9 hydrate [Fe (NO ₃ ) ₃ .9H ₂ O] 1 .46G (0.0036 mol) and aluminum nitrate nonahydrate _{[Al (NO 3) 3 · 9H} 2 O ] 9.49g of (0.025 mol) was dissolved in water of 40.83G, this α9 Liquid. On the other hand, 5.36 g (0.051 mol) of sodium carbonate and 7.08 g (0.177 mol) of sodium hydroxide were dissolved in 50.59 g of water, and this was designated as β9 solution. In a container equipped with a stirrer, the α9 liquid and the β9 liquid were each stirred at room temperature while being continuously fed (co-feed) at a flow rate of 20 mL / h. The pH of the liquid phase of the mixture obtained after supplying all the α9 solution and β9 solution was 13. The resulting mixture was aged at 60 ° C. overnight, then filtered, and the residue was washed with water until the pH of the washing filtrate was close to 7, then dried at 60 ° C. for 18 hours, and hydrotalcite (I) [[Zn _0.66 Fe _0.05 Al _0.29 (OH) ₂ ] [CO ₃ ^{2 −} _0.17 · nH ₂ O]] was obtained. This hydrotalcite (I) was confirmed to have a hydrotalcite structure as a result of X-ray diffraction analysis using copper Kα rays. The obtained hydrotalcite (I) was calcined at 450 ° C. for 6 hours under a nitrogen flow of 100 mL / min to obtain catalyst (I). As a result of the compositional analysis, the catalyst (I) was found to contain 66 mol% Zn, 5 mol% Fe, 29 mol% Al with respect to the total mol of Zn, Fe and Al [Zn / (Fe + Al) = 1.9. (Molar ratio)].

<Catalyst activity test>
In <Catalyst activity test>, an activity test was conducted in the same manner as in Example 1 except that the catalyst (I) obtained above was used instead of the catalyst (A). The results are shown in Table 1.

Example 10
<Preparation of catalyst>
Zinc nitrate hexahydrate [Zn (NO ₃ ) ₂ .6H ₂ O] 17.82 g (0.060 mol), lead nitrate [Pb (NO ₃ ) ₂ ] 1.54 g (0.0047 mol) and aluminum nitrate nonahydrate _{[Al (NO 3) 3 · 9H} 2 O ] 12.10g of (0.032 mol) was dissolved in water of 49.66G, which was α10 solution. On the other hand, 1.71 g (0.016 mol) of sodium carbonate and 7.74 g (0.194 mol) of sodium hydroxide were dissolved in 31.39 g of water, and this was designated as β10 solution. In a container equipped with a stirrer, the α10 liquid and the β10 liquid were each stirred at room temperature while being continuously fed (co-feed) at a flow rate of 20 mL / h. The pH of the liquid phase of the mixture obtained after supplying all the α10 solution and β10 solution was 13. The resulting mixture was aged at 60 ° C. overnight and filtered, and then the residue was washed with water until the pH of the washing filtrate was close to 7, then dried at 60 ° C. for 18 hours, and hydrotalcite (J) [[Zn _0.64 Pb _0.05 Al _0.31 (OH) ₂ ] [CO ₃ ^{2 −} _{0.31 / 2} · nH ₂ O]] was obtained. This hydrotalcite (J) was confirmed to have a hydrotalcite structure as a result of X-ray diffraction analysis using copper Kα rays. The obtained hydrotalcite (J) was calcined at 450 ° C. for 6 hours under a nitrogen flow of 100 mL / min to obtain a catalyst (J). As a result of the compositional analysis, the catalyst (J) has a Zn content of 64 mol%, a Pb content of 5 mol%, and an Al content of 31 mol% [(Zn + Pb) /Al=2.2 based on the total mol of Zn, Pb and Al. (Molar ratio)].

<Catalyst activity test>
In <Catalyst activity test>, an activity test was conducted in the same manner as in Example 1 except that the catalyst (J) obtained above was used instead of the catalyst (A). The results are shown in Table 1.

Example 11
<Preparation of catalyst>
Zinc nitrate hexahydrate [Zn (NO ₃ ) ₂ · 6H ₂ O] 13.50 g (0.045 mol), tin chloride pentahydrate [SnCl ₄ · 5H ₂ O] 1.22 g (0.0035 mol) ) and aluminum nitrate nonahydrate _{[Al (NO 3) 3 · 9H} 2 O ] 9.17g of (0.024 mol) was dissolved in water of 39.70G, which was α11 solution. On the other hand, 5.18 g (0.049 mol) of sodium carbonate and 7.12 g (0.178 mol) of sodium hydroxide were dissolved in 48.88 g of water, and this was designated as β11 solution. In a container equipped with a stirrer, the α11 solution and the β11 solution were each stirred at room temperature while being continuously fed (co-feed) at a flow rate of 20 mL / h. The pH of the liquid phase of the mixture obtained after supplying all the α11 solution and β11 solution was 13. The resulting mixture was aged at 60 ° C. overnight and filtered, and then the residue was washed with water until the pH of the washing filtrate was around 7, then dried at 60 ° C. for 18 hours, and hydrotalcite (K). [[Zn _0.64 Al _0.26 Sn _0.10 (OH) ₂ ] [CO ₃ ^{2 −} _0.23 · nH ₂ O]] was obtained. This hydrotalcite (K) was confirmed to have a hydrotalcite structure as a result of X-ray diffraction analysis using copper Kα rays. The obtained hydrotalcite (K) was calcined at 450 ° C. for 6 hours under a nitrogen flow of 100 mL / min to obtain a catalyst (K). As a result of the compositional analysis, the catalyst (K) has a Zn content of 64 mol%, an Al content of 26 mol%, and an Sn content of 10 mol% [Zn / (Al + Sn) = 1.8, based on the total mol of Zn, Al and Sn. (Molar ratio)].

<Catalyst activity test>
<Catalyst activity test> In the same manner as in Example 1, except that the catalyst (K) obtained above was used instead of the catalyst (A) and the microreactor was heated to 140 ° C. went. The results are shown in Table 1.

Example 12
<Preparation of catalyst>
Catalyst (D) was obtained in the same manner as in Example 4.

<Catalyst activity test>
<Catalyst activity test> In the same manner as in Example 1 except that 0.040 g of the catalyst (D) obtained above was used instead of 0.075 g of the catalyst (A), and the microreactor was heated to 160 ° C. The activity test was conducted by the method described above. The results are shown in Table 1.

Example 13
<Preparation of catalyst>
A catalyst (K) was obtained in the same manner as in Example 11.

<Catalyst activity test>
In <Catalyst activity test>, except that the catalyst (K) obtained above was used in place of the catalyst (A), and the microreactor was heated to 160 ° C. and reacted for 0.5 hours, Example The activity test was conducted in the same manner as in 1. The results are shown in Table 1.

Example 14
<Preparation of catalyst>
A catalyst (K) was obtained in the same manner as in Example 11.

<Catalyst activity test>
In <Catalyst activity test>, 0.11 g of the catalyst (K) obtained above was used instead of 0.075 g of the catalyst (A), and the microreactor was heated to 160 ° C. and reacted for 0.5 hours. The activity test was performed in the same manner as in Example 1 except that. The results are shown in Table 1.

Comparative Example 1
<Preparation of catalyst>
Cesium carbonate [Cs ₂ CO ₃ ] 0.516 g (0.0016 mol) was dissolved in water to make a 200 mL aqueous solution. To the obtained aqueous solution, 10.00 g of silica gel [SiO ₂ ] was added and stirred at room temperature for 4 hours. After stirring, water was distilled off using a rotary evaporator, and the resulting solid was dried overnight at 120 ° C. in an air atmosphere. The obtained dried product was calcined at 450 ° C. for 3 hours in an air atmosphere to obtain a cesium-containing silica catalyst (R1) having a cesium content of 4% by weight.

<Catalyst activity test>
In <Catalyst activity test>, the activity test was performed in the same manner as in Example 1 except that the catalyst (R1) obtained above was used instead of the catalyst (A). The results are shown in Table 1.

Comparative Example 2
<Preparation of catalyst>
Zirconium oxychloride octahydrate [Zr (Cl ₂ O) · 8H ₂ O] (0.644 g, 0.0020 mol) was dissolved in water to obtain a 200 mL aqueous solution. To the obtained aqueous solution, 10.00 g of silica gel [SiO ₂ ] was added and stirred at room temperature for 4 hours. After stirring, water was distilled off using a rotary evaporator, and the resulting solid was dried overnight at 120 ° C. in an air atmosphere. 9.80 g of the obtained dried product was added to an aqueous solution in which 0.516 g (0.0016 mol) of cesium carbonate [Cs ₂ CO ₃ ] was dissolved in water to make 200 mL, and stirred at room temperature for 4 hours. After stirring, water was distilled off using a rotary evaporator, and the resulting solid was dried overnight at 120 ° C. in an air atmosphere. The obtained dried product was calcined at 450 ° C. for 3 hours in an air atmosphere, and the cesium-zirconium-containing silica catalyst (R2) having a cesium content of 3.9 wt% and a zirconium content of 1.2 wt% )

<Catalyst activity test>
In <Catalyst activity test>, an activity test was conducted in the same manner as in Example 1 except that the catalyst (R2) obtained above was used instead of the catalyst (A). The results are shown in Table 1.

Comparative Example 3
<Preparation of catalyst>
A catalyst (R1) was obtained in the same manner as in Comparative Example 1.

<Catalyst activity test>
<Catalyst activity test> In the same manner as in Example 1, except that the catalyst (R1) obtained above was used instead of the catalyst (A) and the microreactor was heated to 160 ° C. went. The results are shown in Table 1.

Comparative Example 4
<Preparation of catalyst>
A catalyst (R2) was obtained in the same manner as in Comparative Example 2.

<Catalyst activity test>
<Catalyst activity test> In the same manner as in Example 1, except that the catalyst (R2) obtained above was used instead of the catalyst (A) and the microreactor was heated to 160 ° C. went. The results are shown in Table 1.

  In Table 1, the activity test results PA, MMA, and MAA are as follows.

PA: propionic acid MMA: methyl methacrylate MAA: methacrylic acid

Example 15
<Preparation of catalyst>
Catalyst (D) was obtained in the same manner as in Example 4.

<Catalyst activity test>
To a 2.5 mL glass microreactor, 0.35 g (4.0 mmol) of methyl propionate [compound in which R ¹ is a methyl group in formula (I)], 0.61 g of a 24.6 wt% aqueous formaldehyde solution ( Formaldehyde 5.0 mmol, water 25.7 mmol), methanol 0.26 g (8.0 mmol), and catalyst (D) 0.075 g obtained above were charged, and nitrogen was introduced into the gas phase part in the microreactor. The pressure inside the microreactor was set to 1.5 MPa (gauge pressure). Next, the microreactor was heated to 120 ° C. while stirring and reacted for 4 hours. The reaction solution was analyzed by gas chromatography, and based on the following formula, methyl propionate conversion (%), methyl methacrylate selectivity (%), methacrylic acid selectivity (%), and the total of methacrylic acid and methyl methacrylate The yield (%) was determined and shown in Table 2.

Conversion rate of methyl propionate (%) = [number of moles of reacted methyl propionate / number of moles of supplied methyl propionate] × 100
Methyl methacrylate selectivity (%) = [number of moles of methyl methacrylate produced / number of moles of all products produced] × 100
Methacrylic acid selectivity (%) = [number of moles of methacrylic acid produced ÷ number of moles of all products produced] × 100
Total yield of methacrylic acid and methyl methacrylate (%) = [methyl propionate conversion (%) × (methyl methacrylate selectivity (%) + methacrylic acid selectivity (%))] ÷ 100

Example 16
<Preparation of catalyst>
Catalyst (D) was obtained in the same manner as in Example 4.

<Catalyst activity test>
In <Catalyst activity test>, the procedure was carried out except that 1.00 g of 15 wt% formaldehyde aqueous solution (5.0 mmol of formaldehyde, 47.1 mmol of water) was used instead of 0.61 g of 24.6 wt% formaldehyde aqueous solution. The activity test was conducted in the same manner as in Example 15. The results are shown in Table 2.

Comparative Example 5
<Preparation of catalyst>
A catalyst (R2) was obtained in the same manner as in Comparative Example 2.

<Catalyst activity test>
In <Catalyst activity test>, an activity test was conducted in the same manner as in Example 15 except that the catalyst (R2) obtained above was used instead of the catalyst (D). The results are shown in Table 2.

  In Table 2, the activity test results MP, MMA, and MAA indicate the following.

MP: methyl propionate MMA: methyl methacrylate MAA: methacrylic acid

Example 17
<Preparation of catalyst>
Catalyst (D) was obtained in the same manner as in Example 4.

<Catalyst activity test>
To a 2.5 mL glass microreactor, propionic anhydride [a compound in which R ¹ is a propionyl group in formula (I)] 0.52 g (4.0 mmol), 24.6 wt% aqueous formaldehyde solution 0.61 g (Formaldehyde 5.0 mmol, water 25.7 mmol), methanol 0.26 g (8.0 mmol), and 0.075 g of the catalyst (D) obtained above were charged, and nitrogen was added to the gas phase in the microreactor. Was introduced to adjust the pressure in the microreactor to 1.5 MPa (gauge pressure). Next, the microreactor was heated to 120 ° C. while stirring and reacted for 4 hours. The reaction solution was analyzed by gas chromatography, and based on the following formula, propionic anhydride conversion (%), methyl methacrylate selectivity (%), methacrylic acid selectivity (%) and methacrylic acid and methyl methacrylate The total yield (%) was determined and shown in Table 3.

Conversion rate of propionic anhydride (%) = [number of moles of reacted propionic anhydride ÷ number of moles of supplied propionic anhydride] × 100
Methyl methacrylate selectivity (%) = [number of moles of methyl methacrylate produced / number of moles of all products produced] × 100
Methacrylic acid selectivity (%) = [number of moles of methacrylic acid produced ÷ number of moles of all products produced] × 100
Total yield of methacrylic acid and methyl methacrylate (%) = [propionic anhydride conversion (%) × (methyl methacrylate selectivity (%) + methacrylic acid selectivity (%))] ÷ 100

Example 18
<Preparation of catalyst>
Catalyst (D) was obtained in the same manner as in Example 4.

<Catalyst activity test>
In <Catalyst activity test>, an activity test was conducted in the same manner as in Example 17, except that the microreactor was heated to 160 ° C. and reacted for 1 hour. The results are shown in Table 3.

Example 19
<Preparation of catalyst>
Catalyst (D) was obtained in the same manner as in Example 4.

<Catalyst activity test>
In <Catalyst activity test>, the activity test was performed in the same manner as in Example 17, except that the amount of catalyst (D) used was 0.040 g, and the reaction was carried out for 1 hour by heating the microreactor to 160 ° C. went. The results are shown in Table 3.

Example 20
<Preparation of catalyst>
A catalyst (K) was obtained in the same manner as in Example 11.

<Catalyst activity test>
In <Catalyst activity test>, 0.11 g of the catalyst (K) obtained above was used instead of 0.075 g of the catalyst (D), and the microreactor was heated to 160 ° C. and reacted for 0.5 hours. The activity test was performed in the same manner as in Example 17 except that. The results are shown in Table 3.

  In Table 3, the activity test results PAnh, MMA, and MAA indicate the following.

PAnh: propionic anhydride MMA: methyl methacrylate MAA: methacrylic acid

Claims (7)

In the presence of a catalyst containing a calcined product obtained by calcining hydrotalcite, formula (I)

(In the formula, R ¹ represents a hydrogen atom, an alkyl group, or an acyl group.)
And a compound represented by the formula (II), wherein the compound is reacted with at least one selected from the group consisting of formaldehyde, methylal, 1,3,5-trioxane and paraformaldehyde

(Wherein R ¹ represents the same meaning as described above.)
The manufacturing method of the compound shown by these. The hydrotalcite has the formula (III)
[M1 _1-x M2 _x (OH) ₂ ] [A ^m- _{x / m} · nH ₂ O] (III)
(In the formula, M1 represents at least one divalent metal element selected from the group consisting of magnesium, zinc, copper, cobalt, manganese, iron, lead, nickel, calcium, barium and strontium, and M2 represents aluminum, iron , titanium, chromium, manganese, cobalt, is .m represents nickel, lanthanum, the at least one trivalent metal element selected from the group consisting of gallium and indium, a ^m-is representative of the m-valent anion 1-4 Represents an integer of 0 <x ≦ 0.5 and n> 0.)
The manufacturing method according to claim 1, wherein The hydrotalcite has the formula (IV)
[M1 _a M2 _b M3 _c (OH) ₂ ] [A ^m− _{(b + 2c) / m} · nH ₂ O]
(IV)
(In the formula, M1 represents at least one divalent metal element selected from the group consisting of magnesium, zinc, copper, cobalt, manganese, iron, lead, nickel, calcium, barium and strontium, and M2 represents aluminum, iron Represents at least one trivalent metal element selected from the group consisting of titanium, chromium, manganese, cobalt, nickel, lanthanum, gallium and indium, and M3 is at least one selected from the group consisting of tin, titanium and zirconium A ^m− represents an m-valent anion, m represents an integer of 1 to 4, 0.5 ≦ a <1, 0 <b <0.5, 0 <c <. 0.5, a + b + c = 1, 0 <b + c ≦ 0.5, and n> 0.)
The manufacturing method according to claim 1, wherein   The manufacturing method according to claim 2 or 3, wherein the M1 is at least one selected from the group consisting of magnesium, zinc, lead and calcium, and the M2 is at least one selected from the group consisting of aluminum and iron.   The manufacturing method in any one of Claims 1-4 which perform the said baking at 250-650 degreeC.   Furthermore, the manufacturing method in any one of Claims 1-5 which perform the said reaction in presence of water. Formula (I)

(In the formula, R ¹ represents a hydrogen atom, an alkyl group, or an acyl group.)
Is reacted with at least one selected from the group consisting of formaldehyde, methylal, 1,3,5-trioxane, and paraformaldehyde to give a compound of formula (II)

(Wherein R ¹ represents the same meaning as described above.)
The catalyst used when manufacturing the compound shown by these, Comprising: The catalyst characterized by including the baked material obtained by baking hydrotalcite.