JP7001982B2 - A method for producing a catalyst for producing an α, β-unsaturated carboxylic acid, and a method for producing an α, β-unsaturated carboxylic acid and an α, β-unsaturated carboxylic acid ester. - Google Patents
A method for producing a catalyst for producing an α, β-unsaturated carboxylic acid, and a method for producing an α, β-unsaturated carboxylic acid and an α, β-unsaturated carboxylic acid ester. Download PDFInfo
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- JP7001982B2 JP7001982B2 JP2020501082A JP2020501082A JP7001982B2 JP 7001982 B2 JP7001982 B2 JP 7001982B2 JP 2020501082 A JP2020501082 A JP 2020501082A JP 2020501082 A JP2020501082 A JP 2020501082A JP 7001982 B2 JP7001982 B2 JP 7001982B2
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- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/65—Halogen-containing esters of unsaturated acids
- C07C69/653—Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid esters
Description
本発明は、α，β－不飽和カルボン酸製造用触媒の製造方法に関する。また、α，β－不飽和カルボン酸の製造方法及びα，β－不飽和カルボン酸エステルの製造方法に関する。 The present invention relates to a method for producing a catalyst for producing an α, β-unsaturated carboxylic acid. The present invention also relates to a method for producing an α, β-unsaturated carboxylic acid and a method for producing an α, β-unsaturated carboxylic acid ester.
α，β－不飽和アルデヒドを分子状酸素により気相接触酸化してα，β－不飽和カルボン酸を製造する際に用いられる触媒としては、リンモリブデン酸、リンモリブデン酸塩等のヘテロポリ酸又はその塩を主成分とする触媒が知られている。この触媒は通常、まず触媒を構成する各元素を含む水溶液又は水性スラリーを調製し、その後これを乾燥、焼成することで製造される。 The catalyst used for producing α, β-unsaturated carboxylic acid by gas-phase catalytic oxidation of α, β-unsaturated aldehyde with molecular oxygen includes heteropolyacids such as phosphomolybdic acid and phosphomolybdate. A catalyst whose main component is the salt is known. This catalyst is usually produced by first preparing an aqueous solution or an aqueous slurry containing each element constituting the catalyst, and then drying and calcining the slurry.
触媒の製造方法の検討例として、例えば特許文献１には、調製した水性スラリーを毎分１．５℃以上の速度で冷却することで、メタクリル酸製造収率が高い触媒が得られることが記載されている。また、特許文献２には、アルカリ金属原料をＭｏ元素１２ｍｏｌあたり０．１～３．０ｍｏｌ／ｓの速度で添加することで、メタクリル酸製造収率が高い触媒が得られることが記載されている。また特許文献３には、単位体積当たりの撹拌所要動力０．０１～４．００ｋＷ／ｍ３で撹拌しながらアルカリ金属化合物を水性スラリーに添加することで、メタクリル酸製造収率が高い触媒が得られることが記載されている。また特許文献４には、水性スラリーへの原料の添加温度及び撹拌時間を規定することで、メタクリル酸製造収率が高い触媒が得られることが記載されている。As an example of studying a method for producing a catalyst, for example, Patent Document 1 describes that a catalyst having a high methacrylic acid production yield can be obtained by cooling the prepared aqueous slurry at a rate of 1.5 ° C. or higher per minute. Has been done. Further, Patent Document 2 describes that a catalyst having a high methacrylic acid production yield can be obtained by adding an alkali metal raw material at a rate of 0.1 to 3.0 mol / s per 12 mol of Mo element. .. Further, in Patent Document 3, a catalyst having a high methacrylic acid production yield can be obtained by adding an alkali metal compound to an aqueous slurry while stirring at a required stirring power of 0.01 to 4.00 kW / m 3 per unit volume. It is stated that it will be done. Further, Patent Document 4 describes that a catalyst having a high methacrylic acid production yield can be obtained by specifying the temperature at which the raw material is added to the aqueous slurry and the stirring time.
しかしながらα，β－不飽和カルボン酸製造用触媒には、更なる高収率化が望まれている。 However, a catalyst for producing an α, β-unsaturated carboxylic acid is desired to have a higher yield.
本発明は、高い収率でα，β－不飽和カルボン酸を製造できるα，β－不飽和カルボン酸製造用触媒を提供することを目的とする。 An object of the present invention is to provide a catalyst for producing an α, β-unsaturated carboxylic acid capable of producing an α, β-unsaturated carboxylic acid in a high yield.
本発明は、以下の［１］から［１０］である。
［１］α，β－不飽和アルデヒドを分子状酸素により気相接触酸化してα，β－不飽和カルボン酸を製造する際に用いられる、α，β－不飽和カルボン酸製造用触媒の製造方法であって、
（ｉ）少なくともモリブデン及びリンを含有するヘテロポリ酸塩を含む水性スラリー（Ｓ２）を得る工程と、
（ｉｉ）前記水性スラリー（Ｓ２）を５０℃未満で２．５～２４．５時間撹拌保持して水性スラリー（Ｓ３）を得る工程と、
（ｉｉｉ）前記水性スラリー（Ｓ３）を噴霧乾燥する工程と、
を含み、前記工程（ｉ）におけるヘテロポリ酸塩がケギン型構造を有し、前記触媒が焼成されたものである、α，β－不飽和カルボン酸製造用触媒の製造方法。
［２］前記工程（ｉ）におけるヘテロポリ酸塩が、金属カチオン塩及びアンモニウム塩からなる群より選択される少なくとも１つである、［１］に記載のα，β－不飽和カルボン酸製造用触媒の製造方法。
［３］前記工程（ｉ）において、少なくともモリブデン及びリンを含有する水性スラリー又は水溶液（Ｓ１）を７０～１３０℃に保持し、これを塩基含有化合物と混合することにより水性スラリー（Ｓ２）を得る、［１］又は［２］に記載のα，β－不飽和カルボン酸製造用触媒の製造方法。
［４］前記工程（ｉｉ）において、前記水性スラリー（Ｓ２）の前記撹拌保持を３．４時間以上１５時間未満行う、［１］から［３］のいずれかに記載のα，β－不飽和カルボン酸製造用触媒の製造方法。
［５］前記工程（ｉｉ）において、前記水性スラリー（Ｓ２）の前記撹拌保持を３０℃より高く５０℃未満で行う、［１］から［４］のいずれかに記載のα，β－不飽和カルボン酸製造用触媒の製造方法。
［６］前記触媒が下記式（１）で表される組成を有する、［１］から［５］のいずれかに記載のα，β－不飽和カルボン酸製造用触媒の製造方法。
ＰａＭｏｂＶｃＣｕｄＡｅＥｆＧｇ（ＮＨ４）ｈＯｉ （１）
（前記式（１）中、Ｐ、Ｍｏ、Ｖ、Ｃｕ、ＮＨ４及びＯは、それぞれ、リン、モリブデン、バナジウム、銅、アンモニウム根及び酸素を示す。Ａはアンチモン、ビスマス、砒素、ゲルマニウム、ジルコニウム、テルル、銀、セレン、ケイ素、タングステン及びホウ素からなる群から選択される少なくとも１種の元素を表す。Ｅは鉄、亜鉛、クロム、マグネシウム、カルシウム、ストロンチウム、タンタル、コバルト、ニッケル、マンガン、バリウム、チタン、スズ、タリウム、鉛、ニオブ、インジウム、硫黄、パラジウム、ガリウム、セリウム及びランタンからなる群より選択される少なくとも１種類の元素を示す。Ｇはリチウム、ナトリウム、カリウム、ルビジウム及びセシウムからなる群から選択される少なくとも１種の元素を表す。ａ～ｉは各成分のモル比率を表し、ｂ＝１２のとき、ａ＝０．５～３、ｃ＝０．０１～３、ｄ＝０．０１～２、ｅ＝０～３、ｆ＝０～３、ｇ＝０．０１～３、ｈ＝０～３０、ｉは前記各成分の価数を満足するのに必要な酸素のモル比率である。）
［７］［１］から［６］のいずれかに記載の方法により製造された触媒の存在下で、α，β－不飽和アルデヒドを分子状酸素により気相接触酸化するα，β－不飽和カルボン酸の製造方法。
［８］［１］から［６］のいずれかに記載の方法により触媒を製造し、該触媒を用いてα，β－不飽和アルデヒドを分子状酸素により気相接触酸化するα，β－不飽和カルボン酸の製造方法。
［９］［７］又は［８］に記載の方法により製造されたα，β－不飽和カルボン酸をエステル化するα，β－不飽和カルボン酸エステルの製造方法。
［１０］［７］又は［８］に記載の方法によりα，β－不飽和カルボン酸を製造し、該
α，β－不飽和カルボン酸をエステル化するα，β－不飽和カルボン酸エステルの製造方法。
The present invention is the following [1] to [ 10 ].
[1] Production of α, β-unsaturated carboxylic acid production catalyst used for gas-phase catalytic oxidation of α, β-unsaturated aldehyde with molecular oxygen to produce α, β-unsaturated carboxylic acid. It ’s a method,
(I) A step of obtaining an aqueous slurry (S2) containing a heteropolylate containing at least molybdenum and phosphorus, and
(Ii) A step of obtaining the aqueous slurry (S3) by stirring and holding the aqueous slurry (S2) at a temperature of less than 50 ° C. for 2.5 to 24.5 hours.
(Iii) The step of spray-drying the aqueous slurry (S3) and
A method for producing a catalyst for producing an α, β-unsaturated carboxylic acid , wherein the heteropolyrate in the step (i) has a Keggin-type structure and the catalyst is fired .
[2] The catalyst for producing an α, β-unsaturated carboxylic acid according to [1], wherein the heteropolymetalate in the step (i) is at least one selected from the group consisting of a metal cation salt and an ammonium salt. Manufacturing method.
[3] In the step (i), an aqueous slurry or aqueous solution (S1) containing at least molybdenum and phosphorus is held at 70 to 130 ° C. and mixed with a base-containing compound to obtain an aqueous slurry (S2). , [1] or [2], the method for producing a catalyst for producing an α, β-unsaturated carboxylic acid .
[4] The α, β-unsaturated according to any one of [1] to [3] , wherein in the step (ii), the stirring and holding of the aqueous slurry (S2) is performed for 3.4 hours or more and less than 15 hours. A method for producing a catalyst for producing a carboxylic acid.
[5] The α, β-unsaturation according to any one of [1] to [4] , wherein in the step (ii), the stirring and holding of the aqueous slurry (S2) is performed at a temperature higher than 30 ° C and lower than 50 ° C. A method for producing a catalyst for producing a carboxylic acid.
[6] The method for producing an α, β-unsaturated carboxylic acid according to any one of [1] to [5] , wherein the catalyst has a composition represented by the following formula (1).
P a Mo b V c Cu d A e E f G g (NH 4 ) h O i (1)
(In the above formula (1), P, Mo, V, Cu, NH 4 and O represent phosphorus, molybdenum, vanadium, copper, ammonium root and oxygen, respectively. A represents antimony, bismuth, arsenic, germanium and zirconium. Represents at least one element selected from the group consisting of, tellurium, silver, selenium, silicon, tungsten and boron. E represents iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium. , Titanium, tin, tarium, lead, nihonium, indium, sulfur, palladium, gallium, cerium and lanthanum; G represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium and cesium. It represents at least one element selected from the group. A to i represent the molar ratio of each component, and when b = 12, a = 0.5 to 3, c = 0.01 to 3, d = 0. 0.01 to 2, e = 0 to 3, f = 0 to 3, g = 0.01 to 3, h = 0 to 30, and i are the molar ratios of oxygen required to satisfy the valence of each of the above components. Is.)
[ 7 ] In the presence of the catalyst produced by the method according to any one of [1] to [ 6 ], α, β-unsaturated aldehyde is vapor-phase catalytically oxidized with molecular oxygen to α, β-unsaturated. Method for producing carboxylic acid.
[ 8 ] A catalyst is produced by the method according to any one of [1] to [ 6 ], and α, β-unsaturated aldehyde is vapor-phase catalytically oxidized with molecular oxygen using the catalyst. A method for producing a saturated carboxylic acid.
[ 9 ] A method for producing an α, β-unsaturated carboxylic acid ester that esterifies an α, β-unsaturated carboxylic acid produced by the method according to [ 7 ] or [ 8 ].
[ 10 ] A α, β-unsaturated carboxylic acid ester for producing an α, β-unsaturated carboxylic acid by the method described in [ 7 ] or [ 8 ] and esterifying the α, β-unsaturated carboxylic acid. Production method.
本発明によれば、高収率でα，β－不飽和カルボン酸を製造できるα，β－不飽和カルボン酸製造用触媒を提供することができる。また本発明によれば、高収率でα，β－不飽和カルボン酸及びα，β－不飽和カルボン酸エステルを得ることができる。 According to the present invention, it is possible to provide a catalyst for producing α, β-unsaturated carboxylic acid, which can produce α, β-unsaturated carboxylic acid in high yield. Further, according to the present invention, α, β-unsaturated carboxylic acid and α, β-unsaturated carboxylic acid ester can be obtained in high yield.
［α，β－不飽和カルボン酸製造用触媒の製造方法］
本発明に係るα，β－不飽和カルボン酸製造用触媒の製造方法で得られる触媒は、α，β－不飽和アルデヒドを分子状酸素により気相接触酸化してα，β－不飽和カルボン酸を製造する際に用いられる。本発明は、本触媒の製造方法であって、以下の工程（ｉ）～（ｉｉｉ）を含む。
（ｉ）少なくともモリブデン及びリンを含有するヘテロポリ酸塩を含む水性スラリー（Ｓ２）を得る工程。
（ｉｉ）前記水性スラリー（Ｓ２）を５０℃未満で２．５～２４．５時間撹拌保持して水性スラリー（Ｓ３）を得る工程。
（ｉｉｉ）前記水性スラリー（Ｓ３）を噴霧乾燥する工程。[Manufacturing method of catalyst for producing α, β-unsaturated carboxylic acid]
The catalyst obtained by the method for producing an α, β-unsaturated carboxylic acid according to the present invention is an α, β-unsaturated carboxylic acid obtained by vapor-phase catalytic oxidation of α, β-unsaturated aldehyde with molecular oxygen. Is used when manufacturing. The present invention is a method for producing the present catalyst, and includes the following steps (i) to (iii).
(I) A step of obtaining an aqueous slurry (S2) containing a heteropolylate containing at least molybdenum and phosphorus.
(Ii) A step of obtaining the aqueous slurry (S3) by stirring and holding the aqueous slurry (S2) at a temperature of less than 50 ° C. for 2.5 to 24.5 hours.
(Iii) A step of spray-drying the aqueous slurry (S3).
本発明に係る触媒の製造方法は前記工程（ｉ）～（ｉｉｉ）を含むことにより、水性スラリー中の溶解元素の析出反応が進行し、噴霧乾燥時に溶解元素が触媒表面の微細な孔を塞ぐことを抑制することで、得られる触媒の比表面積が向上すると考えられる。これにより触媒活性が向上し、α，β－不飽和アルデヒドを分子状酸素により気相接触酸化してα，β－不飽和カルボン酸を製造する際に、α，β－不飽和カルボン酸の収率を向上させることができる。 By including the steps (i) to (iii) in the method for producing a catalyst according to the present invention, the precipitation reaction of the dissolved element in the aqueous slurry proceeds, and the dissolved element closes the fine pores on the surface of the catalyst during spray drying. It is considered that the specific surface area of the obtained catalyst is improved by suppressing this. As a result, the catalytic activity is improved, and when α, β-unsaturated aldehyde is vapor-phase catalytically oxidized with molecular oxygen to produce α, β-unsaturated carboxylic acid, the yield of α, β-unsaturated carboxylic acid is obtained. The rate can be improved.
本発明に係る方法により製造されるα，β－不飽和カルボン酸製造用触媒は、少なくともモリブデン及びリンを含む。なかでも下記式（１）で表される組成を有することが、α，β－不飽和カルボン酸の製造において高収率でα，β－不飽和カルボン酸を製造できる観点から好ましい。なお、触媒における各元素のモル比は、触媒をアンモニア水に溶解した成分をＩＣＰ発光分析法で分析することによって求めた値とする。なお、アンモニウム根のモル比率は、触媒成分をケルダール法で分析することによって求めた値とする。 The catalyst for producing an α, β-unsaturated carboxylic acid produced by the method according to the present invention contains at least molybdenum and phosphorus. Above all, it is preferable to have a composition represented by the following formula (1) from the viewpoint that α, β-unsaturated carboxylic acid can be produced in high yield in the production of α, β-unsaturated carboxylic acid. The molar ratio of each element in the catalyst is a value obtained by analyzing a component obtained by dissolving the catalyst in aqueous ammonia by ICP emission spectrometry. The molar ratio of ammonium roots is a value obtained by analyzing the catalyst component by the Kjeldahl method.
ＰａＭｏｂＶｃＣｕｄＡｅＥｆＧｇ（ＮＨ４）ｈＯｉ （１）
式（１）中、Ｐ、Ｍｏ、Ｖ、Ｃｕ、ＮＨ４及びＯは、それぞれ、リン、モリブデン、バナジウム、銅、アンモニウム根及び酸素を示す。Ａはアンチモン、ビスマス、砒素、ゲルマニウム、ジルコニウム、テルル、銀、セレン、ケイ素、タングステン及びホウ素からなる群から選択される少なくとも１種の元素を表す。Ｅは鉄、亜鉛、クロム、マグネシウム、カルシウム、ストロンチウム、タンタル、コバルト、ニッケル、マンガン、バリウム、チタン、スズ、タリウム、鉛、ニオブ、インジウム、硫黄、パラジウム、ガリウム、セリウム及びランタンからなる群より選択される少なくとも１種類の元素を示す。Ｇはリチウム、ナトリウム、カリウム、ルビジウム及びセシウムからなる群から選択される少なくとも１種の元素を表す。ａ～ｉは各成分のモル比率を表し、ｂ＝１２のとき、ａ＝０．５～３、ｃ＝０．０１～３、ｄ＝０．０１～２、ｅ＝０～３、好ましくはｅ＝０．０１～３、ｆ＝０～３、ｇ＝０．０１～３、ｈ＝０～３０、ｉは前記各成分の価数を満足するのに必要な酸素のモル比率である。
なお、本発明において「アンモニウム根」とは、アンモニウムイオン（ＮＨ４
＋）になり得るアンモニア（ＮＨ３）、およびアンモニウム塩などのアンモニウム含有化合物に含まれるアンモニウムの総称である。P a Mo b V c Cu d A e E f G g (NH 4 ) h O i (1)
In formula (1), P, Mo, V, Cu, NH 4 and O represent phosphorus, molybdenum, vanadium, copper, ammonium root and oxygen, respectively. A represents at least one element selected from the group consisting of antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron. E is selected from the group consisting of iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin, thallium, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum. Shows at least one element to be made. G represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium and cesium. a to i represent the molar ratio of each component, and when b = 12, a = 0.5 to 3, c = 0.01 to 3, d = 0.01 to 2, e = 0 to 3, preferably. e = 0.01 to 3, f = 0 to 3, g = 0.01 to 3, h = 0 to 30, and i are molar ratios of oxygen required to satisfy the valence of each of the above components.
In the present invention, "ammonium root" is a general term for ammonia (NH 3 ) which can be an ammonium ion (NH 4+ ) and ammonium contained in an ammonium-containing compound such as an ammonium salt.
（工程（ｉ））
工程（ｉ）では、少なくともモリブデン及びリンを含有するヘテロポリ酸塩を含む水性スラリー（Ｓ２）を得る。該ヘテロポリ酸塩は、ヘテロポリ酸と塩基とからなる。塩基は特に限定されないが、例えばアルカリ金属などの金属カチオンや、アンモニウムイオンなどが挙げられる。触媒の活性や熱安定性の観点から、ヘテロポリ酸塩としては、金属カチオン塩及びアンモニウム塩からなる群より選択される少なくとも１つであることが好ましい。なお、複数の異なる金属カチオンの複合塩や、金属カチオンとアンモニウムの複合塩もこれに含まれる。また、前記式（１）で表される組成を有する触媒を製造する場合、前記式（１）で表される組成に含まれる元素を含有する水性スラリー（Ｓ２）を調製することが好ましい。(Step (i))
In step (i), an aqueous slurry (S2) containing a heteropolylate containing at least molybdenum and phosphorus is obtained. The heteropolyate consists of a heteropolyacid and a base. The base is not particularly limited, and examples thereof include metal cations such as alkali metals and ammonium ions. From the viewpoint of catalyst activity and thermal stability, the heteropolymate is preferably at least one selected from the group consisting of metal cation salts and ammonium salts. It should be noted that this also includes a composite salt of a plurality of different metal cations and a composite salt of a metal cation and ammonium. Further, when producing a catalyst having the composition represented by the formula (1), it is preferable to prepare an aqueous slurry (S2) containing an element contained in the composition represented by the formula (1).
使用する触媒原料としては特に限定されず、各元素の硝酸塩、炭酸塩、酢酸塩、アンモニウム塩、酸化物、ハロゲン化物、オキソ酸、オキソ酸塩等を単独で、又は二種類以上を組み合わせて使用することができる。モリブデン原料としては、例えばパラモリブデン酸アンモニウム、三酸化モリブデン、モリブデン酸、塩化モリブデン等が挙げられる。リン原料としては、例えば正リン酸、五酸化リン又はリン酸セシウム等のリン酸塩等が挙げられる。銅原料としては、例えば硫酸銅、硝酸銅、酸化銅、炭酸銅、酢酸銅、塩化銅等が挙げられる。バナジウム原料としては、例えばメタバナジン酸アンモニウム、五酸化バナジウム、塩化バナジウム等が挙げられる。これらは一種のみを用いてもよく、二種以上を併用してもよい。 The catalyst raw material to be used is not particularly limited, and nitrates, carbonates, acetates, ammonium salts, oxides, halides, oxoacids, oxoacids, etc. of each element may be used alone or in combination of two or more. can do. Examples of the molybdenum raw material include ammonium paramolybdate, molybdenum trioxide, molybdic acid, molybdenum chloride and the like. Examples of the phosphorus raw material include phosphates such as orthophosphoric acid, phosphorus pentoxide, and cesium phosphate. Examples of the copper raw material include copper sulfate, copper nitrate, copper oxide, copper carbonate, copper acetate, copper chloride and the like. Examples of the vanadium raw material include ammonium metavanadate, vanadium pentoxide, vanadium chloride and the like. These may be used alone or in combination of two or more.
また、モリブデン、リン、バナジウムの原料としては、モリブデン、リン、バナジウムのうちの少なくとも一つの元素を含むヘテロポリ酸を原料として用いてもよい。ヘテロポリ酸としては、例えばリンモリブデン酸、リンバナドモリブデン酸、ケイモリブデン酸等が挙げられる。これらは一種のみを用いてもよく、二種以上を併用してもよい。 Further, as the raw material of molybdenum, phosphorus and vanadium, a heteropolyacid containing at least one element of molybdenum, phosphorus and vanadium may be used as a raw material. Examples of the heteropolyacid include phosphomolybdic acid, limbanadomolybdic acid, silicate molybdic acid and the like. These may be used alone or in combination of two or more.
前記水性スラリー（Ｓ２）は、少なくともモリブデン及びリンを含有する水性スラリー又は水溶液（Ｓ１）を７０～１３０℃に保持し、これを塩基含有化合物と混合することにより調製することが好ましい。
前記水性スラリー又は水溶液（Ｓ１）の調製方法には特に制限はないが、水に触媒を構成する各元素の原料の一部、又は全てを加え、加熱撹拌する方法により行うことが簡便であり好ましい。水に触媒を構成する各元素の原料の水溶液、水性スラリー又は水性ゾルを添加することもできる。水１００ｇに添加するモリブデンのモル数は、０．０１～１モルが好ましく、下限は０．０５モル以上、上限は０．５モル以下がより好ましい。
水性スラリー又は水溶液（Ｓ１）は、成分や温度等の条件により、水性スラリーと水溶液のいずれになる場合もあり、どちらでもよい。The aqueous slurry (S2) is preferably prepared by holding an aqueous slurry or aqueous solution (S1) containing at least molybdenum and phosphorus at 70 to 130 ° C. and mixing it with a base-containing compound.
The method for preparing the aqueous slurry or aqueous solution (S1) is not particularly limited, but it is convenient and preferable to add a part or all of the raw materials of each element constituting the catalyst to water and heat and stir. .. It is also possible to add an aqueous solution, an aqueous slurry or an aqueous sol as a raw material of each element constituting the catalyst to water. The number of moles of molybdenum added to 100 g of water is preferably 0.01 to 1 mol, more preferably 0.05 mol or more at the lower limit and 0.5 mol or less at the upper limit.
The aqueous slurry or aqueous solution (S1) may be either an aqueous slurry or an aqueous solution depending on conditions such as components and temperature, and may be either.
調製時の水性スラリー又は水溶液（Ｓ１）の温度は、８０～１３０℃が好ましく、９０～１３０℃がより好ましい。水性スラリー又は水溶液（Ｓ１）の温度を８０℃以上とすることで、ヘテロポリ酸の生成速度を十分に速めることができる。また、水性スラリー又は水溶液（Ｓ１）の温度を１３０℃以下とすることで、ヘテロポリ酸以外の副生成物の生成や水性スラリー又は水溶液（Ｓ１）中の水の蒸発を抑制することができる。水性スラリー又は水溶液（Ｓ１）のｐＨは４以下が好ましく、２以下がより好ましい。水性スラリー又は水溶液のｐＨを十分低くすることにより、ケギン型構造を有するヘテロポリ酸を安定に形成することができる。なお、水性スラリー又は水溶液のｐＨは、ＨＯＲＩＢＡ製ポータブル型ｐＨメーターＤ－２１（商品名）等により測定することができる。 The temperature of the aqueous slurry or aqueous solution (S1) at the time of preparation is preferably 80 to 130 ° C, more preferably 90 to 130 ° C. By setting the temperature of the aqueous slurry or the aqueous solution (S1) to 80 ° C. or higher, the rate of formation of the heteropolyacid can be sufficiently increased. Further, by setting the temperature of the aqueous slurry or aqueous solution (S1) to 130 ° C. or lower, it is possible to suppress the formation of by-products other than the heteropolyacid and the evaporation of water in the aqueous slurry or aqueous solution (S1). The pH of the aqueous slurry or aqueous solution (S1) is preferably 4 or less, more preferably 2 or less. By sufficiently lowering the pH of the aqueous slurry or aqueous solution, a heteropolyacid having a Keggin-type structure can be stably formed. The pH of the aqueous slurry or aqueous solution can be measured with a portable pH meter D-21 (trade name) manufactured by HORIBA.
次いで、前記水性スラリー又は水溶液（Ｓ１）を７０～１３０℃に保った状態で、塩基含有化合物と混合する。これによりヘテロポリ酸塩が生成する。好ましくは、水性スラリー又は水溶液（Ｓ１）に塩基含有化合物を添加する。
塩基含有化合物は、ヘテロポリ酸と塩を形成する塩基を含む化合物であれば良く、特に限定されないが、好ましくは、塩基として金属カチオンやアンモニウムイオンを含有する。前記水性スラリー又は水溶液（Ｓ１）と、金属カチオン含有化合物及びアンモニウム含有化合物からなる群より選択される少なくとも１つを混合することにより、ヘテロポリ酸の金属塩又はアンモニウム塩を含む水性スラリー（Ｓ２）を得ることができる。
塩基含有化合物と混合する際の前記水性スラリー又は水溶液（Ｓ１）の温度は、７０～１３０℃の範囲に調整することが好ましい。これにより、得られる触媒をα，β－不飽和カルボン酸の製造に用いる際に、触媒層のホットスポット生成を抑制しやすい。前記水性スラリー又は水溶液（Ｓ１）の温度の下限は８０℃以上、上限は１００℃以下がより好ましい。
金属カチオン含有化合物としては、アルカリ金属を含む化合物を含む化合物を用いることが好ましく、リチウム、ナトリウム、カリウム、ルビジウム及びセシウムからなる群から選択される少なくとも１種の元素（前記式（１）のＧに相当）を含む化合物を用いることがより好ましい。金属カチオン含有化合物を添加することにより、触媒の熱安定性が向上し、熱劣化が抑制できる。アンモニウム含有化合物としては、炭酸水素アンモニウム、炭酸アンモニウム、硝酸アンモニウム、アンモニア水等が挙げられる。これらの塩基含有化合物は、１種で用いてもよく複数種を併用してもよい。アンモニウム含有化合物を添加することにより、α，β－不飽和アルデヒドの分子状酸素による気相接触酸化に好適な結晶構造が形成される。なお、複数種の金属カチオン含有化合物や複数種のアンモニウム含有化合物を併用したり、金属カチオン含有化合物とアンモニウム含有化合物とを併用することにより、それぞれの好ましい特性が現れるため優れた性能を示す。
塩基含有化合物は、溶媒に溶解又は懸濁させて混合することが好ましい。溶媒としては、水、エチルアルコール、アセトン等が挙げられるが、水を溶媒として用いることが好ましい。塩基含有化合物混合後は、７０～１３０℃で５～６０分撹拌保持することが好ましい。なお、撹拌保持とは、撹拌した状態に置いておくことを言う。撹拌保持時間の下限は１０分以上、上限は３０分以下がより好ましい。撹拌保持時間を５分以上とすることで、ヘテロポリ酸の塩を十分に形成させることができる。一方、撹拌保持時間を６０分以下とすることで、目的とするヘテロポリ酸塩の形成以外の副反応を抑制することができる。Next, the aqueous slurry or aqueous solution (S1) is mixed with the base-containing compound while being kept at 70 to 130 ° C. This produces a heteropolylate. Preferably, the base-containing compound is added to the aqueous slurry or aqueous solution (S1).
The base-containing compound may be a compound containing a base forming a salt with the heteropolyacid, and is not particularly limited, but preferably contains a metal cation or an ammonium ion as the base. By mixing the aqueous slurry or aqueous solution (S1) with at least one selected from the group consisting of a metal cation-containing compound and an ammonium-containing compound, an aqueous slurry (S2) containing a metal salt or an ammonium salt of a heteropolyacid is obtained. Obtainable.
The temperature of the aqueous slurry or aqueous solution (S1) when mixed with the base-containing compound is preferably adjusted to the range of 70 to 130 ° C. As a result, when the obtained catalyst is used for producing an α, β-unsaturated carboxylic acid, it is easy to suppress the formation of hot spots in the catalyst layer. The lower limit of the temperature of the aqueous slurry or the aqueous solution (S1) is more preferably 80 ° C. or higher, and the upper limit is more preferably 100 ° C. or lower.
As the metal cation-containing compound, it is preferable to use a compound containing a compound containing an alkali metal, and at least one element selected from the group consisting of lithium, sodium, potassium, rubidium and cesium (G of the above formula (1)). It is more preferable to use a compound containing (corresponding to). By adding the metal cation-containing compound, the thermal stability of the catalyst can be improved and thermal deterioration can be suppressed. Examples of the ammonium-containing compound include ammonium hydrogen carbonate, ammonium carbonate, ammonium nitrate, aqueous ammonia and the like. These base-containing compounds may be used alone or in combination of two or more. By adding the ammonium-containing compound, a crystal structure suitable for gas-phase catalytic oxidation of α, β-unsaturated aldehyde with molecular oxygen is formed. In addition, by using a plurality of types of metal cation-containing compounds and a plurality of types of ammonium-containing compounds in combination, or by using a metal cation-containing compound and an ammonium-containing compound in combination, each preferable property appears, and thus excellent performance is exhibited.
The base-containing compound is preferably dissolved or suspended in a solvent and mixed. Examples of the solvent include water, ethyl alcohol, acetone and the like, but it is preferable to use water as the solvent. After mixing the base-containing compound, it is preferable to keep stirring at 70 to 130 ° C. for 5 to 60 minutes. In addition, stirring and holding means keeping in a stirred state. The lower limit of the stirring holding time is more preferably 10 minutes or more, and the upper limit is more preferably 30 minutes or less. By setting the stirring holding time to 5 minutes or more, a salt of a heteropolyacid can be sufficiently formed. On the other hand, by setting the stirring retention time to 60 minutes or less, side reactions other than the formation of the desired heteropolylate can be suppressed.
得られるヘテロポリ酸塩は、α，β－不飽和カルボン酸の収率の観点からケギン型構造を有することが好ましい。ケギン型構造を有するヘテロポリ酸塩を析出させる方法としては、例えば原料化合物やアンモニウムの添加量等を適宜選択し、硝酸、シュウ酸等を適宜添加する等の方法により、水性スラリー（Ｓ２）のｐＨを４以下、好ましくは３以下に調整する方法が挙げられる。なお、得られるヘテロポリ酸塩の構造は、ＮＩＣＯＬＥＴ６７００ＦＴ－ＩＲ（製品名、Ｔｈｅｒｍｏ ｅｌｅｃｔｒｏｎ社製）を用いた赤外吸収分析より判断することができる。該ヘテロポリ酸塩がケギン型構造を有する場合、得られる赤外吸収スペクトルは、１０６０、９６０、８７０、７８０ｃｍ－１付近に特徴的なピークを有する。The obtained heteropolyrate preferably has a Keggin-type structure from the viewpoint of the yield of α, β-unsaturated carboxylic acid. As a method for precipitating a heteropolylate having a Keggin-type structure, for example, the pH of the aqueous slurry (S2) is appropriately selected by appropriately selecting the amount of the raw material compound or ammonium added, and adding nitric acid, oxalic acid or the like as appropriate. Is 4 or less, preferably 3 or less. The structure of the obtained heteropolylate can be determined by infrared absorption analysis using NICOLET6700FT-IR (product name, manufactured by Thermo eletronic). When the heteropolylate has a Keggin-type structure, the obtained infrared absorption spectrum has a characteristic peak near 1060, 960, 870, 780 cm -1 .
（工程（ｉｉ））
工程（ｉｉ）では、前記工程（ｉ）で得られた水性スラリー（Ｓ２）を冷却して、５０℃未満で２．５～２４．５時間撹拌保持することで、水性スラリー（Ｓ３）を得る。冷却は、水性スラリー（Ｓ２）を冷媒に接触させて冷却し降温させても良く、水性スラリー（Ｓ２）を室温に置くことで降温させても良い。冷却は水性スラリー（Ｓ２）を撹拌しながら行うことが好ましい。析出したヘテロポリ酸塩等が撹拌により均一に分散し、後述する工程（ｉｉｉ）の噴霧乾燥時に、性状の安定した均質な乾燥物が得られやすい。ヘテロポリ酸塩の析出を促進する観点から、降温速度は毎分０．１℃以上が好ましく、毎分０．３℃以上がより好ましい。ただし、降温速度は通常、毎分１０℃以下である。
水性スラリー（Ｓ２）の保持温度を５０℃未満、かつ撹拌保持時間を２．５時間以上とすることで、水性スラリー（Ｓ２）に含まれる元素を十分析出させることができるため、乾燥後に得られる触媒の比表面積が向上し、α，β－不飽和カルボン酸製造において収率が向上する。また水性スラリーの保持温度を５０℃未満とすることで、水性スラリー（Ｓ２）に含まれる揮発性化合物の過剰な揮発を抑制でき、α，β－不飽和カルボン酸収率の観点から有利である。また、水性スラリー（Ｓ２）の保持時間を２４．５時間以下とすることで、工程（ｉｉｉ）で得られる触媒の嵩密度の低下を抑制し、反応器に充填できる触媒量を多く維持することができるため、触媒を長時間連続使用する観点から有利である。水性スラリー（Ｓ２）を撹拌保持する温度は、水性スラリー（Ｓ２）を撹拌翼や撹拌羽根等を用いて撹拌可能な温度（例えば、水性スラリー（Ｓ２）の凝固点）以上であり、α，β－不飽和カルボン酸収率の観点から１０℃以上が好ましく、３０℃より高い温度がより好ましい。また、撹拌保持を行う時間の下限は３．４時間以上が好ましく、上限は１５時間未満が好ましい。
なお本発明において、撹拌保持を行う時間とは、水性スラリー（Ｓ２）の温度が５０℃未満であり、かつ撹拌翼や撹拌羽根等を用いて水性スラリー（Ｓ２）を撹拌して流動性を与えている時間を言う。水性スラリー（Ｓ２）の撹拌は連続して２．５～２４．５時間行っても良く、あるいは撹拌を断続的に行い、その合計時間を２．５～２４．５時間としても良い。撹拌により、析出したヘテロポリ酸塩等が均一に分散し、後述する工程（ｉｉｉ）の噴霧乾燥時に、性状の安定した均質な乾燥物が得られやすい。工程（ｉｉ）では、このようにして、液中の元素が充分に析出した水性スラリー（Ｓ３）を得る。(Step (ii))
In the step (ii), the aqueous slurry (S2) obtained in the step (i) is cooled and kept stirred at a temperature of less than 50 ° C. for 2.5 to 24.5 hours to obtain the aqueous slurry (S3). .. For cooling, the aqueous slurry (S2) may be brought into contact with the refrigerant to cool and lower the temperature, or the aqueous slurry (S2) may be kept at room temperature to lower the temperature. Cooling is preferably performed while stirring the aqueous slurry (S2). The precipitated heteropolylate or the like is uniformly dispersed by stirring, and it is easy to obtain a uniform dried product having stable properties during spray drying in the step (iii) described later. From the viewpoint of promoting the precipitation of the heteropolylate, the temperature lowering rate is preferably 0.1 ° C. or higher per minute, more preferably 0.3 ° C. or higher per minute. However, the temperature lowering rate is usually 10 ° C. or less per minute.
By setting the holding temperature of the aqueous slurry (S2) to less than 50 ° C. and the stirring holding time to 2.5 hours or more, the elements contained in the aqueous slurry (S2) can be sufficiently precipitated, and thus obtained after drying. The specific surface area of the catalyst is improved, and the yield is improved in the production of α, β-unsaturated carboxylic acid. Further, by setting the holding temperature of the aqueous slurry to less than 50 ° C., excessive volatilization of the volatile compound contained in the aqueous slurry (S2) can be suppressed, which is advantageous from the viewpoint of the yield of α, β-unsaturated carboxylic acid. .. Further, by setting the holding time of the aqueous slurry (S2) to 24.5 hours or less, it is possible to suppress a decrease in the bulk density of the catalyst obtained in the step (iii) and maintain a large amount of catalyst that can be filled in the reactor. This is advantageous from the viewpoint of continuous use of the catalyst for a long period of time. The temperature at which the aqueous slurry (S2) is agitated and held is equal to or higher than the temperature at which the aqueous slurry (S2) can be agitated using a stirring blade, a stirring blade, or the like (for example, the freezing point of the aqueous slurry (S2)), and α, β- From the viewpoint of unsaturated carboxylic acid yield, 10 ° C. or higher is preferable, and a temperature higher than 30 ° C. is more preferable. Further, the lower limit of the stirring and holding time is preferably 3.4 hours or more, and the upper limit is preferably less than 15 hours.
In the present invention, the time for stirring and holding means that the temperature of the aqueous slurry (S2) is less than 50 ° C., and the aqueous slurry (S2) is stirred with a stirring blade, a stirring blade, or the like to give fluidity. Say the time you are. The aqueous slurry (S2) may be continuously stirred for 2.5 to 24.5 hours, or the aqueous slurry (S2) may be stirred intermittently for a total time of 2.5 to 24.5 hours. By stirring, the precipitated heteropolyrate and the like are uniformly dispersed, and it is easy to obtain a uniform dried product having stable properties during spray drying in the step (iii) described later. In the step (ii), the aqueous slurry (S3) in which the elements in the liquid are sufficiently precipitated is obtained in this way.
（工程（ｉｉｉ））
工程（ｉｉｉ）では前記工程（ｉｉ）により得られた水性スラリー（Ｓ３）を噴霧乾燥する。水性スラリー（Ｓ３）の乾燥は、工程（ｉｉ）に連続して行う。好ましくは、水性スラリー（Ｓ２）の５０℃未満での撹拌保持開始から水性スラリー（Ｓ３）の乾燥終了までを、２．５～２４．５時間で行う。また、噴霧乾燥を一度に行わず、撹拌保持しながら、２．５時間以上経過後に水性スラリーの一部を徐々に噴霧乾燥機に供給して乾燥させても良い。乾燥温度は１２０～５００℃が好ましく、下限は１４０℃以上、上限は３５０℃以下がより好ましい。乾燥は、得られる乾燥物の水分含有率が０．１～４．５質量％となるように行うことが好ましい。なおこれらの条件は、所望する触媒の形状や大きさにより適宣選択することができる。
工程（ｉｉｉ）で得られた乾燥物は触媒性能を示し、これをα，β－不飽和カルボン酸製造用触媒として用いることができるが、更に、後述する成形や焼成を行うことで触媒としての性能が向上するため好ましい。本発明では、これら成形後、焼成後のものを含めて触媒と総称する。(Step (iii))
In the step (iii), the aqueous slurry (S3) obtained in the step (ii) is spray-dried. Drying of the aqueous slurry (S3) is carried out continuously in the step (ii). Preferably, from the start of stirring and holding the aqueous slurry (S2) at less than 50 ° C. to the end of drying of the aqueous slurry (S3) is carried out in 2.5 to 24.5 hours. Further, instead of spray-drying all at once, a part of the aqueous slurry may be gradually supplied to the spray-drying machine and dried after 2.5 hours or more have passed while stirring and holding. The drying temperature is preferably 120 to 500 ° C., the lower limit is 140 ° C. or higher, and the upper limit is 350 ° C. or lower. The drying is preferably performed so that the water content of the obtained dried product is 0.1 to 4.5% by mass. These conditions can be appropriately selected depending on the shape and size of the desired catalyst.
The dried product obtained in the step (iii) exhibits catalytic performance and can be used as a catalyst for producing α, β-unsaturated carboxylic acid, but can be further used as a catalyst by performing molding or firing described later. It is preferable because it improves the performance. In the present invention, the catalysts including those after molding and after firing are collectively referred to as catalysts.
（成形工程）
成形工程では、前記工程（ｉｉｉ）で得られた乾燥物を必要に応じて粉砕し、成形する。なお、成形は後述する焼成工程の後に行っても良い。成形方法は特に制限されず、公知の乾式又は湿式の成形方法が適用できる。例えば、打錠成形、押出成形、加圧成形、転動造粒等が挙げられる。成形品の形状としては特に制限はなく、球形粒状、リング状、円柱形ペレット状、星型状、成形後に粉砕分級した顆粒状等の任意の形状が挙げられる。成形後の触媒の形状が球形粒状である場合、直径が０．１ｍｍ以上１０ｍｍ以下であることが好ましい。直径が０．１ｍｍ以上であることにより、反応管内の圧力損失を小さくすることができる。また、直径が１０ｍｍ以下であることにより、触媒活性がより向上する。成形する際には担体に担持してもよく、その他の添加剤を混合してもよい。(Molding process)
In the molding step, the dried product obtained in the step (iii) is crushed and molded as needed. The molding may be performed after the firing step described later. The molding method is not particularly limited, and a known dry or wet molding method can be applied. For example, tableting molding, extrusion molding, pressure molding, rolling granulation and the like can be mentioned. The shape of the molded product is not particularly limited, and examples thereof include spherical granules, ring-shaped, cylindrical pellet-shaped, star-shaped, and granules crushed and classified after molding. When the shape of the catalyst after molding is spherical and granular, the diameter is preferably 0.1 mm or more and 10 mm or less. When the diameter is 0.1 mm or more, the pressure loss in the reaction tube can be reduced. Further, when the diameter is 10 mm or less, the catalytic activity is further improved. When molding, it may be supported on a carrier or may be mixed with other additives.
（焼成工程）
前記工程（ｉｉｉ）又は前記成形工程で得られた触媒を焼成することが、α，β－不飽和カルボン酸収率の観点から好ましい。焼成条件としては、特に限定はないが、例えば空気等の酸素含有ガス及び不活性ガスの少なくとも一方の流通下で行うことができる。前記焼成は、空気等の酸素含有ガス流通下で行われることが好ましい。また、「不活性ガス」とは触媒活性を低下させない気体のことを示し、例えば窒素、炭酸ガス、ヘリウム、アルゴン等が挙げられる。これらは一種を用いてもよく、二種以上を混合して使用してもよい。α，β－不飽和カルボン酸の収率の観点から、焼成温度は２００～５００℃が好ましく、下限は３００℃以上、上限は４５０℃以下がより好ましい。また、焼成時間の下限は０．５～４０時間が好ましく、１～４０時間がより好ましい。(Baking process)
It is preferable to calcin the catalyst obtained in the step (iii) or the molding step from the viewpoint of the yield of α, β-unsaturated carboxylic acid. The firing conditions are not particularly limited, but can be carried out under the flow of at least one of an oxygen-containing gas such as air and an inert gas. The firing is preferably performed under the flow of an oxygen-containing gas such as air. The "inert gas" refers to a gas that does not reduce the catalytic activity, and examples thereof include nitrogen, carbon dioxide, helium, and argon. These may be used alone or in admixture of two or more. From the viewpoint of the yield of α, β-unsaturated carboxylic acid, the firing temperature is preferably 200 to 500 ° C., the lower limit is 300 ° C. or higher, and the upper limit is 450 ° C. or lower. The lower limit of the firing time is preferably 0.5 to 40 hours, more preferably 1 to 40 hours.
［α，β－不飽和カルボン酸の製造方法］
本発明に係るα，β－不飽和カルボン酸の製造方法は、本発明に係る方法により製造された触媒存在下で、α，β－不飽和アルデヒドを分子状酸素により気相接触酸化してα，β－不飽和カルボン酸を製造する。また、本発明に係るα，β－不飽和カルボン酸の製造方法は、本発明に係る方法により触媒を製造し、該触媒を用いてα，β－不飽和アルデヒドを分子状酸素により気相接触酸化してα，β－不飽和カルボン酸を製造する。これらの方法によれば、高い収率でα，β－不飽和カルボン酸を製造することができる。[Method for producing α, β-unsaturated carboxylic acid]
In the method for producing an α, β-unsaturated carboxylic acid according to the present invention, α, β-unsaturated aldehyde is vapor-phase contact-oxidized with molecular oxygen in the presence of a catalyst produced by the method according to the present invention. , Β-Unsaturated carboxylic acid is produced. Further, in the method for producing an α, β-unsaturated carboxylic acid according to the present invention, a catalyst is produced by the method according to the present invention, and the α, β-unsaturated aldehyde is vapor-phase contacted with molecular oxygen using the catalyst. It is oxidized to produce α, β-unsaturated carboxylic acid. According to these methods, α, β-unsaturated carboxylic acid can be produced in high yield.
本発明に係る方法において、前記α，β－不飽和アルデヒドとしては、（メタ）アクロレイン、クロトンアルデヒド（β－メチルアクロレイン）、シンナムアルデヒド（β－フェニルアクロレイン）等が挙げられる。中でも、目的生成物の収率の観点から（メタ）アクロレインであることが好ましく、メタクロレインであることがより好ましい。製造されるα，β－不飽和カルボン酸は、前記α，β－不飽和アルデヒドのアルデヒド基がカルボキシル基に変化したα，β－不飽和カルボン酸である。具体的には、α，β－不飽和アルデヒドが（メタ）アクロレインの場合、（メタ）アクリル酸が得られる。なお、「（メタ）アクロレイン」はアクロレイン及びメタクロレインを示し、「（メタ）アクリル酸」はアクリル酸及びメタクリル酸を示す。 In the method according to the present invention, examples of the α, β-unsaturated aldehyde include (meth) acrolein, crotonaldehyde (β-methylacrolein), and cinnamaldehyde (β-phenylacrolein). Among them, (meth) acrolein is preferable, and methacrolein is more preferable, from the viewpoint of the yield of the target product. The α, β-unsaturated carboxylic acid produced is an α, β-unsaturated carboxylic acid in which the aldehyde group of the α, β-unsaturated aldehyde is changed to a carboxyl group. Specifically, when the α, β-unsaturated aldehyde is (meth) acrolein, (meth) acrylic acid is obtained. In addition, "(meth) acrolein" indicates acrolein and methacrolein, and "(meth) acrylic acid" indicates acrylic acid and methacrylic acid.
以下、代表例として、本発明に係る方法により製造された触媒の存在下、メタクロレインを分子状酸素により気相接触酸化してメタクリル酸を製造する方法について説明する。 Hereinafter, as a representative example, a method for producing methacrylic acid by gas-phase catalytic oxidation of methacrolein with molecular oxygen in the presence of a catalyst produced by the method according to the present invention will be described.
前記方法では、メタクロレイン及び分子状酸素を含む原料ガスと、本発明に係る触媒とを接触させることでメタクリル酸を製造する。この反応では固定床型反応器を使用することができる。反応管内に触媒を充填し、該反応器へ原料ガスを供給することにより反応を行うことができる。触媒は１層として充填してもよく、活性の異なる複数の触媒をそれぞれ複数の層に分けて充填してもよい。また、活性を制御するために触媒を不活性担体により希釈し充填してもよい。 In the above method, methacrylic acid is produced by contacting a raw material gas containing methacrolein and molecular oxygen with the catalyst according to the present invention. A fixed-bed reactor can be used for this reaction. The reaction can be carried out by filling the reaction tube with a catalyst and supplying the raw material gas to the reactor. The catalyst may be packed as one layer, or a plurality of catalysts having different activities may be packed in a plurality of layers. Further, the catalyst may be diluted with an inert carrier and filled in order to control the activity.
原料ガス中のメタクロレインの濃度は特に限定されないが、１～２０容量％が好ましく、下限は３容量％以上、上限は１０容量％以下がより好ましい。原料であるメタクロレインは、低級飽和アルデヒド等の本反応に実質的な影響を与えない不純物を少量含んでいてもよい。 The concentration of methacrolein in the raw material gas is not particularly limited, but is preferably 1 to 20% by volume, more preferably 3% by volume or more at the lower limit and 10% by volume or less at the upper limit. The raw material, methacrolein, may contain a small amount of impurities such as lower saturated aldehydes that do not substantially affect this reaction.
原料ガス中の分子状酸素の濃度は、メタクロレイン１モルに対して０．４～４モルが好ましく、下限は０．５モル以上、上限は３モル以下がより好ましい。なお、分子状酸素源としては、経済性の観点から空気が好ましい。必要であれば、空気に純酸素を加えて分子状酸素を富化した気体を用いてもよい。 The concentration of molecular oxygen in the raw material gas is preferably 0.4 to 4 mol per 1 mol of methacrolein, more preferably 0.5 mol or more at the lower limit and 3 mol or less at the upper limit. As the molecular oxygen source, air is preferable from the viewpoint of economy. If necessary, a gas enriched with molecular oxygen by adding pure oxygen to air may be used.
原料ガスは、メタクロレイン及び分子状酸素を、窒素、炭酸ガス等の不活性ガスで希釈したものであってもよい。さらに、原料ガスに水蒸気を加えてもよい。水蒸気の存在下で反応を行うことにより、メタクリル酸をより高い収率で得ることができる。原料ガス中の水蒸気の濃度は、０．１～５０容量％が好ましく、下限は１容量％以上、上限は４０容量％以下がより好ましい。 The raw material gas may be a gas obtained by diluting methacrolein and molecular oxygen with an inert gas such as nitrogen or carbon dioxide. Further, water vapor may be added to the raw material gas. By carrying out the reaction in the presence of water vapor, methacrylic acid can be obtained in a higher yield. The concentration of water vapor in the raw material gas is preferably 0.1 to 50% by volume, more preferably 1% by volume or more at the lower limit and 40% by volume or less at the upper limit.
原料ガスと触媒との接触時間は、１．５～１５秒が好ましい。反応圧力は、０．１ＭＰａ（Ｇ）～１ＭＰａ（Ｇ）が好ましい。ただし、（Ｇ）はゲージ圧であることを意味する。反応温度は２００～４５０℃が好ましく、下限は２５０℃以上、上限は４００℃以下がより好ましい。 The contact time between the raw material gas and the catalyst is preferably 1.5 to 15 seconds. The reaction pressure is preferably 0.1 MPa (G) to 1 MPa (G). However, (G) means that it is a gauge pressure. The reaction temperature is preferably 200 to 450 ° C., the lower limit is 250 ° C. or higher, and the upper limit is 400 ° C. or lower.
［α，β－不飽和カルボン酸エステルの製造方法］
本発明に係るα，β－不飽和カルボン酸エステルの製造方法は、本発明に係る方法により製造されたα，β－不飽和カルボン酸をエステル化するものが挙げられる。また、本発明に係るα，β－不飽和カルボン酸エステルの製造方法は、本発明に係る方法によりα，β－不飽和カルボン酸を製造し、該α，β－不飽和カルボン酸をエステル化するものが挙げられる。これらの方法によれば、α，β－不飽和アルデヒドの気相接触酸化により得られるα，β－不飽和カルボン酸を用いて、α，β－不飽和カルボン酸エステルを得ることができる。α，β－不飽和カルボン酸と反応させるアルコールとしては特に限定されず、メタノール、エタノール、イソプロパノール、ｎ－ブタノール、イソブタノール等が挙げられる。得られるα，β－不飽和カルボン酸エステルとしては、例えば（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル等が挙げられる。反応は、スルホン酸型カチオン交換樹脂等の酸性触媒の存在下で行うことができる。反応温度は５０～２００℃が好ましい。[Method for producing α, β-unsaturated carboxylic acid ester]
Examples of the method for producing an α, β-unsaturated carboxylic acid ester according to the present invention include esterification of the α, β-unsaturated carboxylic acid produced by the method according to the present invention. Further, in the method for producing an α, β-unsaturated carboxylic acid ester according to the present invention, α, β-unsaturated carboxylic acid is produced by the method according to the present invention, and the α, β-unsaturated carboxylic acid is esterified. There is something to do. According to these methods, α, β-unsaturated carboxylic acid ester can be obtained by using α, β-unsaturated carboxylic acid obtained by vapor phase catalytic oxidation of α, β-unsaturated aldehyde. The alcohol that reacts with the α, β-unsaturated carboxylic acid is not particularly limited, and examples thereof include methanol, ethanol, isopropanol, n-butanol, and isobutanol. Examples of the obtained α, β-unsaturated carboxylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. The reaction can be carried out in the presence of an acidic catalyst such as a sulfonic acid type cation exchange resin. The reaction temperature is preferably 50 to 200 ° C.
以下、実施例及び比較例により本発明を詳細に説明するが、本発明はこれらの実施例に限定されるものではない。実施例及び比較例中の「部」は質量部を意味する。なお、実施例１３は、比較例１０と読み替えるものとする。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. "Parts" in Examples and Comparative Examples means parts by mass. In addition, Example 13 shall be read as Comparative Example 10.
触媒における各元素のモル比は、触媒をアンモニア水に溶解した成分をＩＣＰ発光分析法で分析することによって算出した。 The molar ratio of each element in the catalyst was calculated by analyzing the components of the catalyst dissolved in aqueous ammonia by ICP emission spectrometry.
原料ガス及び生成物の分析は、ガスクロマトグラフィー（装置：島津製作所製ＧＣ－２０１４、カラム：Ｊ＆Ｗ社製ＤＢ－ＦＦＡＰ、３０ｍ×０．３２ｍｍ、膜厚１．０μｍ）を用いて行った。ガスクロマトグラフィーの結果から、メタクリル酸収率を下記式にて求めた。
メタクリル酸収率（％）＝（生成したメタクリル酸のモル数／反応器へ供給したメタクロレインのモル数）×１００Analysis of the raw material gas and the product was performed using gas chromatography (apparatus: GC-2014 manufactured by Shimadzu Corporation, column: DB-FFAP manufactured by J & W, 30 m × 0.32 mm, film thickness 1.0 μm). From the result of gas chromatography, the yield of methacrylic acid was determined by the following formula.
Methacrylic acid yield (%) = (number of moles of methacrylic acid produced / number of moles of methacrolein supplied to the reactor) x 100
（実施例１）
純水４００部に三酸化モリブデン１００部、メタバナジン酸アンモニウム３．４部、純水６．０部で希釈した８５質量％リン酸水溶液９．４部及び純水４．５部に溶解した硝酸銅（ＩＩ）三水和物２．１部を添加した。この水性スラリーを撹拌しながら２５℃から９５℃に昇温し、液温を９５℃に保ちつつ２時間撹拌し、水性スラリー（Ｓ１）を得た。さらに液温を９５℃に保って撹拌しながら、純水２４部に溶解した重炭酸セシウム１３．５部と純水２６部に溶解した炭酸アンモニウム９．２部を滴下して撹拌し、ヘテロポリ酸のセシウム塩及びアンモニウム塩を析出させた。析出したヘテロポリ酸塩はケギン型構造を有していた。得られた水性スラリー（Ｓ２）を９５℃から４０℃まで撹拌しながら冷却した。このとき、水性スラリー（Ｓ２）が５０℃未満となってから４０℃になるまでの時間は０．４時間であった。続いて水性スラリー（Ｓ２）を４０℃で３．０時間撹拌しながら保持した。その後、撹拌保持後の水性スラリー（Ｓ３）を噴霧乾燥した。得られた乾燥物を加圧成形した後粉砕し、空気流通下３８０℃で５時間焼成した。得られた触媒のアンモニウム根及び酸素を除く組成は、Ｐ１．４Ｍｏ１２Ｖ０．５Ｃｕ０．１５Ｃｓ１．２であった。(Example 1)
Copper nitrate dissolved in 400 parts of pure water, 100 parts of molybdenum trioxide, 3.4 parts of ammonium metavanadate, 9.4 parts of 85 mass% phosphoric acid aqueous solution diluted with 6.0 parts of pure water, and 4.5 parts of pure water. (II) 2.1 parts of trihydrate was added. The temperature of this aqueous slurry was raised from 25 ° C. to 95 ° C. while stirring, and the mixture was stirred for 2 hours while maintaining the liquid temperature at 95 ° C. to obtain an aqueous slurry (S1). Further, while maintaining the liquid temperature at 95 ° C. and stirring, 13.5 parts of cesium bicarbonate dissolved in 24 parts of pure water and 9.2 parts of ammonium carbonate dissolved in 26 parts of pure water were dropped and stirred to obtain a heteropolyacid. Cesium salt and ammonium salt were precipitated. The precipitated heteropolyrate had a Keggin-type structure. The obtained aqueous slurry (S2) was cooled with stirring from 95 ° C. to 40 ° C. At this time, the time from when the aqueous slurry (S2) became less than 50 ° C to 40 ° C was 0.4 hours. Subsequently, the aqueous slurry (S2) was held at 40 ° C. for 3.0 hours with stirring. Then, the aqueous slurry (S3) after stirring and holding was spray-dried. The obtained dried product was pressure-molded, pulverized, and calcined at 380 ° C. for 5 hours under air flow. The composition of the obtained catalyst excluding the ammonium root and oxygen was P 1.4 Mo 12 V 0.5 Cu 0.15 Cs 1.2 .
この触媒を反応管に充填し、メタクロレイン５容量％、酸素１０容量％、水蒸気３０容量％、窒素５５容量％の原料ガスを反応温度２８５℃、原料ガスと触媒との接触時間２．４秒で通じた。反応器から得られる生成物を捕集し、ガスクロマトグラフィーで分析してメタクリル酸収率を算出した。触媒の製造条件及び評価結果、反応結果を表１に示す。なお表中、水性スラリー（Ｓ２）撹拌保持時間Ｔは、水性スラリー（Ｓ２）が５０℃未満となってから撹拌保持温度Ｒになるまでの時間、及び、撹拌保持温度Ｒでの保持時間の合計である。 This catalyst is filled in a reaction tube, and a raw material gas having 5% by volume of methacrolein, 10% by volume of oxygen, 30% by volume of water vapor, and 55% by volume of nitrogen is charged at a reaction temperature of 285 ° C. and a contact time between the raw material gas and the catalyst is 2.4 seconds. I got through. The product obtained from the reactor was collected and analyzed by gas chromatography to calculate the methacrylic acid yield. Table 1 shows the catalyst production conditions, evaluation results, and reaction results. In the table, the stirring holding time T of the aqueous slurry (S2) is the total of the time from when the aqueous slurry (S2) becomes less than 50 ° C. to the stirring holding temperature R and the holding time at the stirring holding temperature R. Is.
（実施例２～１０）
水性スラリー（Ｓ２）を９５℃から４０℃まで冷却した後の保持時間を変更した以外は、実施例１と同様に触媒を製造し、メタクリル酸収率を算出した。それぞれの撹拌保持時間Ｔと評価結果、反応結果を表１に示す。(Examples 2 to 10)
A catalyst was produced in the same manner as in Example 1 except that the holding time after cooling the aqueous slurry (S2) from 95 ° C. to 40 ° C. was changed, and the methacrylic acid yield was calculated. Table 1 shows the respective stirring holding time T, the evaluation result, and the reaction result.
（実施例１１）
実施例１と同様にして得られた水性スラリー（Ｓ２）を、９５℃から２０℃まで撹拌しながら冷却した。このとき、水性スラリー（Ｓ２）が５０℃未満となってから２０℃になるまでの時間は０．５時間であった。続いて水性スラリー（Ｓ２）を２０℃で３．０時間撹拌しながら保持した以外は、実施例１と同様に触媒を製造し、メタクリル酸収率を算出した。触媒の製造条件及び反応結果を表２に示す。
（実施例１２）
水性スラリー（Ｓ２）を９５℃から２０℃まで冷却した後の保持時間を１６．０時間に変更した以外は、実施例１１と同様に触媒を製造し、メタクリル酸収率を算出した。撹拌保持時間Ｔ及び反応結果を表２に示す。
（実施例１３）
純水４００部に三酸化モリブデン１００部、メタバナジン酸アンモニウム３．４部、純水６．０部で希釈した８５質量％リン酸水溶液９．４部及び純水４．５部に溶解した硝酸銅（ＩＩ）三水和物２．１部を添加した。この水性スラリーを撹拌しながら２５℃から９５℃に昇温し、液温を９５℃に保ちつつ２時間撹拌し、水性スラリー（Ｓ１）を得た。さらに液温を９５℃に保って撹拌しながら、純水２８．３部に溶解した硝酸セシウム１３．５部と３０質量％のアンモニア水４０．０部を滴下して撹拌し、ヘテロポリ酸のセシウム塩及びアンモニウム塩を析出させた。析出したヘテロポリ酸塩はドーソン型構造を有していた。得られた水性スラリー（Ｓ２）を９５℃から４０℃まで撹拌しながら冷却した。このとき、水性スラリー（Ｓ２）が５０℃未満となってから４０℃になるまでの時間は０．４時間であった。続いて水性スラリー（Ｓ２）を４０℃で３．０時間撹拌しながら保持した。その後、撹拌保持後の水性スラリー（Ｓ３）を噴霧乾燥した。得られた乾燥物を加圧成形した後粉砕し、空気流通下３８０℃で５時間焼成した。得られた触媒の酸素を除く組成は、Ｐ１．４Ｍｏ１２Ｖ０．５Ｃｕ０．１５Ｃｓ１．２であった。
該触媒について、実施例１と同様にメタクリル酸収率を算出した。触媒の製造条件及び反応結果を表２に示す。(Example 11)
The aqueous slurry (S2) obtained in the same manner as in Example 1 was cooled with stirring from 95 ° C. to 20 ° C. At this time, the time from when the aqueous slurry (S2) became less than 50 ° C to 20 ° C was 0.5 hours. Subsequently, a catalyst was produced in the same manner as in Example 1 except that the aqueous slurry (S2) was held at 20 ° C. for 3.0 hours with stirring, and the methacrylic acid yield was calculated. Table 2 shows the catalyst production conditions and reaction results.
(Example 12)
A catalyst was produced in the same manner as in Example 11 except that the holding time after cooling the aqueous slurry (S2) from 95 ° C. to 20 ° C. was changed to 16.0 hours, and the methacrylic acid yield was calculated. Table 2 shows the stirring holding time T and the reaction results.
(Example 13)
Copper nitrate dissolved in 400 parts of pure water, 100 parts of molybdenum trioxide, 3.4 parts of ammonium metavanadate, 9.4 parts of 85 mass% phosphoric acid aqueous solution diluted with 6.0 parts of pure water, and 4.5 parts of pure water. (II) 2.1 parts of trihydrate was added. The temperature of this aqueous slurry was raised from 25 ° C. to 95 ° C. while stirring, and the mixture was stirred for 2 hours while maintaining the liquid temperature at 95 ° C. to obtain an aqueous slurry (S1). Further, while maintaining the liquid temperature at 95 ° C. and stirring, 13.5 parts of cesium nitrate dissolved in 28.3 parts of pure water and 40.0 parts of 30% by mass of aqueous ammonia were added dropwise and stirred, and the heteropolyacid cesium was stirred. Salts and ammonium salts were precipitated. The precipitated heteropolylate had a Dawson-type structure. The obtained aqueous slurry (S2) was cooled with stirring from 95 ° C. to 40 ° C. At this time, the time from when the aqueous slurry (S2) became less than 50 ° C to 40 ° C was 0.4 hours. Subsequently, the aqueous slurry (S2) was held at 40 ° C. for 3.0 hours with stirring. Then, the aqueous slurry (S3) after stirring and holding was spray-dried. The obtained dried product was pressure-molded, pulverized, and calcined at 380 ° C. for 5 hours under air flow. The composition of the obtained catalyst excluding oxygen was P 1.4 Mo 12 V 0.5 Cu 0.15 Cs 1.2 .
For the catalyst, the methacrylic acid yield was calculated in the same manner as in Example 1. Table 2 shows the catalyst production conditions and reaction results.
（比較例１及び２）
水性スラリー（Ｓ２）を９５℃から４０℃まで冷却した後の保持時間を、それぞれ１．０時間及び２．０時間に変更した以外は、実施例１と同様に触媒を製造し、メタクリル酸収率を算出した。反応結果を表２に示す。(Comparative Examples 1 and 2)
A catalyst was produced in the same manner as in Example 1 except that the holding time after cooling the aqueous slurry (S2) from 95 ° C. to 40 ° C. was changed to 1.0 hour and 2.0 hours, respectively, and the methacrylic acid yield was obtained. The rate was calculated. The reaction results are shown in Table 2.
（比較例３）
水性スラリー（Ｓ２）を９５℃から７０℃まで冷却し、７０℃で０．３時間撹拌しながら保持した以外は、実施例１と同様に触媒を製造し、メタクリル酸収率を算出した。反応結果を表２に示す。
（比較例４）
水性スラリー（Ｓ２）を９５℃から５５℃まで冷却し、５５℃で３．０時間撹拌しながら保持した以外は、実施例１と同様に触媒を製造し、メタクリル酸収率を算出した。反応結果を表２に示す。
（比較例５）
水性スラリー（Ｓ２）を９５℃から４０℃まで冷却した後の保持時間を、２．０時間に変更した以外は、実施例１３と同様に触媒を製造し、メタクリル酸収率を算出した。評価結果を表２に示す。
（比較例６）
撹拌保持後のスラリー（Ｓ３）を蒸発乾固法により乾燥した以外は、実施例１と同様に触媒を製造し、メタクリル酸収率を算出した。反応結果を表２に示す。
（比較例７）
水性スラリー（Ｓ２）を９５℃から４０℃まで冷却した後の保持時間を、２．０時間に変更した以外は、比較例６と同様に触媒を製造し、メタクリル酸収率を算出した。反応結果を表２に示す。
（比較例８）
撹拌保持後のスラリー（Ｓ３）を減圧濃縮法により乾燥した以外は、実施例１と同様に触媒を製造し、メタクリル酸収率を算出した。反応結果を表２に示す。
（比較例９）
水性スラリー（Ｓ２）を９５℃から４０℃まで冷却した後の保持時間を、２．０時間に変更した以外は、比較例８と同様に触媒を製造し、メタクリル酸収率を算出した。反応結果を表２に示す。(Comparative Example 3)
A catalyst was produced in the same manner as in Example 1 except that the aqueous slurry (S2) was cooled from 95 ° C. to 70 ° C. and held at 70 ° C. with stirring for 0.3 hours, and the methacrylic acid yield was calculated. The reaction results are shown in Table 2.
(Comparative Example 4)
A catalyst was produced in the same manner as in Example 1 and the methacrylic acid yield was calculated, except that the aqueous slurry (S2) was cooled from 95 ° C. to 55 ° C. and held at 55 ° C. with stirring for 3.0 hours. The reaction results are shown in Table 2.
(Comparative Example 5)
A catalyst was produced in the same manner as in Example 13 except that the holding time after cooling the aqueous slurry (S2) from 95 ° C. to 40 ° C. was changed to 2.0 hours, and the methacrylic acid yield was calculated. The evaluation results are shown in Table 2.
(Comparative Example 6)
A catalyst was produced in the same manner as in Example 1 except that the slurry (S3) after stirring and holding was dried by the evaporation to dryness method, and the methacrylic acid yield was calculated. The reaction results are shown in Table 2.
(Comparative Example 7)
A catalyst was produced in the same manner as in Comparative Example 6 except that the holding time after cooling the aqueous slurry (S2) from 95 ° C. to 40 ° C. was changed to 2.0 hours, and the methacrylic acid yield was calculated. The reaction results are shown in Table 2.
(Comparative Example 8)
A catalyst was produced in the same manner as in Example 1 except that the slurry (S3) after stirring and holding was dried by a vacuum concentration method, and the methacrylic acid yield was calculated. The reaction results are shown in Table 2.
(Comparative Example 9)
A catalyst was produced in the same manner as in Comparative Example 8 except that the holding time after cooling the aqueous slurry (S2) from 95 ° C. to 40 ° C. was changed to 2.0 hours, and the methacrylic acid yield was calculated. The reaction results are shown in Table 2.
表１に示すように、実施例１～１２の触媒の製造方法は水性スラリー（Ｓ２）を撹拌保持する際の温度及び時間が本発明の範囲内にあり、メタクリル酸収率が高い触媒が得られることが確認された。一方、水性スラリー（Ｓ２）を撹拌保持する時間が本発明の範囲外である比較例１及び２は、実施例１～１２と比較してメタクリル酸収率が低い触媒が得られた。また水性スラリーを撹拌保持する温度及び時間の両方が本発明の範囲外である比較例３、及び水性スラリーを撹拌保持する温度が本発明の範囲外である比較例４は、更にメタクリル酸収率が低い触媒が得られた。また、水性スラリー（Ｓ２）を撹拌保持する温度が３０℃より高い実施例１及び９は、同程度の時間撹拌保持している実施例１１及び１２と比較して、それぞれメタクリル酸収率が高い結果となった。更に水性スラリー（Ｓ２）を撹拌保持する時間が１５時間未満である実施例１～８は、触媒の嵩密度の低下が抑制されており、実施例９及び１０と比較して、触媒を長時間連続使用できる観点から優れていた。 As shown in Table 1, in the method for producing the catalyst of Examples 1 to 12, the temperature and time for stirring and holding the aqueous slurry (S2) are within the range of the present invention, and a catalyst having a high methacrylic acid yield can be obtained. It was confirmed that it was possible. On the other hand, in Comparative Examples 1 and 2 in which the time for stirring and holding the aqueous slurry (S2) was outside the range of the present invention, a catalyst having a lower methacrylic acid yield than in Examples 1 to 12 was obtained. Further, Comparative Example 3 in which both the temperature and time for stirring and holding the aqueous slurry are outside the range of the present invention and Comparative Example 4 in which the temperature for stirring and holding the aqueous slurry is outside the range of the present invention further have a methacrylic acid yield. A low catalyst was obtained. Further, Examples 1 and 9 in which the temperature for stirring and holding the aqueous slurry (S2) is higher than 30 ° C. have higher methacrylic acid yields, respectively, as compared with Examples 11 and 12 in which the aqueous slurry (S2) is stirred and held for the same period of time. The result was. Further, in Examples 1 to 8 in which the time for stirring and holding the aqueous slurry (S2) for less than 15 hours is suppressed, the decrease in the bulk density of the catalyst is suppressed, and the catalyst is used for a longer time as compared with Examples 9 and 10. It was excellent from the viewpoint of continuous use.
工程（ｉ）におけるヘテロポリ酸塩がドーソン型構造を有する場合、水性スラリー（Ｓ２）を撹拌保持する際の温度及び時間が本発明の範囲内である実施例１３は、メタクリル酸収率が高い触媒が得られていることが確認された。一方、水性スラリー（Ｓ２）を撹拌保持する時間が本発明の範囲外である比較例５は、実施例１３と比較してメタクリル酸収率が低い触媒が得られた。
一方、撹拌保持後の水性スラリー（Ｓ３）を蒸発乾固法により乾燥している比較例６及び７、並びに減圧濃縮法により乾燥している比較例８及び９は、水性スラリー（Ｓ２）を撹拌保持する際の温度及び時間が本発明の範囲内であっても、メタクリル酸収率はほとんど向上しなかった。
なお、本実施例で得られたメタクリル酸をエステル化することで、メタクリル酸エステルを得ることができる。When the heteropolylate in step (i) has a Dawson-type structure, the temperature and time for stirring and holding the aqueous slurry (S2) are within the range of the present invention. In Example 13, a catalyst having a high methacrylic acid yield is used. Was confirmed to be obtained. On the other hand, in Comparative Example 5 in which the time for stirring and holding the aqueous slurry (S2) was outside the range of the present invention, a catalyst having a lower methacrylic acid yield than in Example 13 was obtained.
On the other hand, in Comparative Examples 6 and 7 in which the aqueous slurry (S3) after stirring and holding is dried by the evaporation-drying method, and Comparative Examples 8 and 9 in which the aqueous slurry (S3) is dried by the vacuum concentration method, the aqueous slurry (S2) is stirred. Even when the temperature and time for holding were within the range of the present invention, the yield of methacrylic acid was hardly improved.
A methacrylic acid ester can be obtained by esterifying the methacrylic acid obtained in this example.
この出願は、２０１８年２月２６日に出願された日本出願特願２０１８－０３１５６４を基礎とする優先権を主張し、その開示の全てをここに取り込む。
以上、実施形態及び実施例を参照して本願発明を説明したが、本願発明は上記実施形態及び実施例に限定されるものではない。本願発明の構成や詳細には、本願発明のスコープ内で当業者が理解し得る様々な変更をすることができる。This application claims priority on the basis of Japanese application Japanese Patent Application No. 2018-031564 filed on February 26, 2018 and incorporates all of its disclosures herein.
Although the present invention has been described above with reference to the embodiments and examples, the present invention is not limited to the above embodiments and examples. Various changes that can be understood by those skilled in the art can be made within the scope of the present invention in terms of the configuration and details of the present invention.
本発明によれば、α，β－不飽和アルデヒドから高い収率でα，β－不飽和カルボン酸を製造することができるα，β－不飽和カルボン酸製造用触媒を提供することができ、工業的に有用である。 According to the present invention, it is possible to provide a catalyst for producing α, β-unsaturated carboxylic acid, which can produce α, β-unsaturated carboxylic acid from α, β-unsaturated aldehyde in a high yield. Industrially useful.
Claims (10)
（ｉ）少なくともモリブデン及びリンを含有するヘテロポリ酸塩を含む水性スラリー（Ｓ２）を得る工程と、
（ｉｉ）前記水性スラリー（Ｓ２）を５０℃未満で２．５～２４．５時間撹拌保持して水性スラリー（Ｓ３）を得る工程と、
（ｉｉｉ）前記水性スラリー（Ｓ３）を噴霧乾燥する工程と、
を含み、前記工程（ｉ）におけるヘテロポリ酸塩がケギン型構造を有し、前記触媒が焼成されたものである、α，β－不飽和カルボン酸製造用触媒の製造方法。 A method for producing a catalyst for producing α, β-unsaturated carboxylic acid, which is used when α, β-unsaturated aldehyde is vapor-phase catalytically oxidized with molecular oxygen to produce α, β-unsaturated carboxylic acid. hand,
(I) A step of obtaining an aqueous slurry (S2) containing a heteropolylate containing at least molybdenum and phosphorus, and
(Ii) A step of obtaining the aqueous slurry (S3) by stirring and holding the aqueous slurry (S2) at a temperature of less than 50 ° C. for 2.5 to 24.5 hours.
(Iii) The step of spray-drying the aqueous slurry (S3) and
A method for producing a catalyst for producing an α, β-unsaturated carboxylic acid , wherein the heteropolyrate in the step (i) has a Keggin-type structure and the catalyst is fired .
ＰａＭｏｂＶｃＣｕｄＡｅＥｆＧｇ（ＮＨ４）ｈＯi （１）
（前記式（１）中、Ｐ、Ｍｏ、Ｖ、Ｃｕ、ＮＨ４及びＯは、それぞれ、リン、モリブデン、バナジウム、銅、アンモニウム根及び酸素を示す。Ａはアンチモン、ビスマス、砒素、ゲルマニウム、ジルコニウム、テルル、銀、セレン、ケイ素、タングステン及びホウ素からなる群から選択される少なくとも１種の元素を表す。Ｅは鉄、亜鉛、クロム、マグネシウム、カルシウム、ストロンチウム、タンタル、コバルト、ニッケル、マンガン、バリウム、チタン、スズ、タリウム、鉛、ニオブ、インジウム、硫黄、パラジウム、ガリウム、セリウム及びランタンからなる群より選択される少なくとも１種類の元素を示す。Ｇはリチウム、ナトリウム、カリウム、ルビジウム及びセシウムからなる群から選択される少なくとも１種の元素を表す。ａ～ｉは各成分のモル比率を表し、ｂ＝１２のとき、ａ＝０．５～３、ｃ＝０．０１～３、ｄ＝０．０１～２、ｅ＝０～３、ｆ＝０～３、ｇ＝０．０１～３、ｈ＝０～３０、ｉは前記各成分の価数を満足するのに必要な酸素のモル比率である。） The method for producing an α, β-unsaturated carboxylic acid production catalyst according to any one of claims 1 to 5 , wherein the catalyst has a composition represented by the following formula (1).
P a Mo b V c Cu d A e E f G g (NH 4 ) h O i (1)
(In the above formula (1), P, Mo, V, Cu, NH 4 and O represent phosphorus, molybdenum, vanadium, copper, ammonium root and oxygen, respectively. A represents antimony, bismuth, arsenic, germanium and zirconium. Represents at least one element selected from the group consisting of, tellurium, silver, selenium, silicon, tungsten and boron. E represents iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium. , Titanium, tin, tarium, lead, nihonium, indium, sulfur, palladium, gallium, cerium and lanthanum; G represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium and cesium. It represents at least one element selected from the group. A to i represent the molar ratio of each component, and when b = 12, a = 0.5 to 3, c = 0.01 to 3, d = 0. 0.01 to 2, e = 0 to 3, f = 0 to 3, g = 0.01 to 3, h = 0 to 30, and i are the molar ratios of oxygen required to satisfy the valence of each of the above components. Is.)
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| KR20150020541A (en) | 2012-05-18 | 2015-02-26 | 닛뽄 가야쿠 가부시키가이샤 | Catalyst for use in production of methacrylic acid, method for producing said catalyst, and method for producing methacrylic acid using said catalyst |
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2019
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140141964A1 (en) | 2012-11-21 | 2014-05-22 | Shanghai Huayi Acrylic Acid Co., Ltd. | Heteropoly acid salt catalyst and its preparation method |
| JP2014226614A (en) | 2013-05-23 | 2014-12-08 | 住友化学株式会社 | Method for producing catalyst for producing methacrylic acid, and method for producing methacrylic acid |
| WO2015037611A1 (en) | 2013-09-11 | 2015-03-19 | 三菱レイヨン株式会社 | Method of preparing catalyst for production of methacrylic acid |
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| CN111770795B (en) | 2024-01-30 |
| CN111770795A (en) | 2020-10-13 |
| KR102476427B1 (en) | 2022-12-09 |
| JPWO2019163984A1 (en) | 2021-01-14 |
| KR20200123807A (en) | 2020-10-30 |
| SG11202007557WA (en) | 2020-09-29 |
| WO2019163984A1 (en) | 2019-08-29 |
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