JP2012030217A - Catalyst for producing methacrylic acid, manufacturing method therefor, and method for manufacturing methacrylic acid - Google Patents

Catalyst for producing methacrylic acid, manufacturing method therefor, and method for manufacturing methacrylic acid Download PDF

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JP2012030217A
JP2012030217A JP2011129951A JP2011129951A JP2012030217A JP 2012030217 A JP2012030217 A JP 2012030217A JP 2011129951 A JP2011129951 A JP 2011129951A JP 2011129951 A JP2011129951 A JP 2011129951A JP 2012030217 A JP2012030217 A JP 2012030217A
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methacrylic acid
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catalyst precursor
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JP5821301B2 (en
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Toshio Hasegawa
俊雄 長谷川
Kenichi Kitazono
健一 北園
Takuro Watanabe
拓朗 渡邉
Yuichi Tagawa
雄一 田川
Mieharu Sugiyama
美栄治 杉山
Masahide Kondo
正英 近藤
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Mitsubishi Rayon Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

PROBLEM TO BE SOLVED: To provide a method for stably preparing a catalyst for manufacturing methacrylic acid with a high conversion ratio of methacrolein and with a high yield of methacrylic acid.SOLUTION: The method for manufacturing methacrylic acid includes the steps of: preparing particles containing catalyst components by drying slurry prepared by mixing in water catalyst raw materials containing molybdenum trioxide, vanadium raw material and phosphorus raw material; preparing a kneaded object by kneading the particles, polysaccharide and water or alcohol; preparing a molded object by extrusion-molding of the kneaded object; preparing a catalyst precursor by drying the molded object; and heat-treating the catalyst precursor. The carbon atom content of the catalyst precursor is ≥2.0 mass%, and the mass reduction rate at 150-200°C is ≤1.8 mass% to the mass of the catalyst precursor used for measuring when the mass reduction rate of the catalyst precursor is measured under an air stream and at a temperature rise of 10°C/min.

Description

本発明は、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際に使用する触媒（以下、メタクリル酸製造用触媒という）の製造方法、この方法により製造される触媒及びこの触媒を用いたメタクリル酸の製造方法に関する。   The present invention relates to a method for producing a catalyst (hereinafter referred to as a catalyst for producing methacrylic acid) used for producing methacrylic acid by vapor phase catalytic oxidation of methacrolein with molecular oxygen, a catalyst produced by this method, and this The present invention relates to a method for producing methacrylic acid using a catalyst.

メタクリル酸製造用触媒としては、リンモリブデン酸に代表されるヘテロポリ酸化合物が知られている。この触媒の性能を向上させるために、触媒原料として特定の原料を用いる方法や、触媒成分を気相接触酸化反応に有効に作用させるために触媒内に細孔構造を形成する方法が提案されている。   As catalysts for producing methacrylic acid, heteropoly acid compounds represented by phosphomolybdic acid are known. In order to improve the performance of this catalyst, a method of using a specific raw material as a catalyst raw material and a method of forming a pore structure in the catalyst in order to make the catalyst component act effectively in the gas phase catalytic oxidation reaction have been proposed. Yes.

特許文献１では、少なくともモリブデン及びバナジウムを含む粒子に、天然起源の多糖類及び液体を加えて混練りしたものを押出成形する方法が提案されている。また、モリブデン原料として三酸化モリブデンを用いる方法が記載されている。   Patent Document 1 proposes a method of extruding a particle containing at least molybdenum and vanadium with a naturally occurring polysaccharide and liquid added and kneaded. In addition, a method using molybdenum trioxide as a molybdenum raw material is described.

特許文献２では、触媒成分の原料化合物を含む混合溶液又はスラリーに有機バインダーを添加した後乾燥し、得られた乾燥物と液体と有機バインダーとを混練りし、押出成形する方法が提案されている。   Patent Document 2 proposes a method of adding an organic binder to a mixed solution or slurry containing a raw material compound of a catalyst component and then drying, kneading the obtained dried product, liquid and organic binder, and extruding. Yes.

特開２００２−２８２６９６号公報JP 2002-282696 A 国際公開第２００９／０９９０４３号International Publication No. 2009/099043

特許文献１及び２に記載されているように、押出成形時に添加する成形助剤（多糖類）の添加量が多くなるほど成形性は向上する。しかしながら、その一方で成形後の熱処理において、成形助剤の添加量が多くなるほど成形助剤の分解に伴う発熱量が多くなり、触媒の失活が生じる場合があり、更なる改善が望まれる。   As described in Patent Documents 1 and 2, the moldability improves as the amount of the molding aid (polysaccharide) added during extrusion molding increases. However, on the other hand, in the heat treatment after molding, as the amount of the molding aid added increases, the amount of heat generated by the decomposition of the molding aid increases and the catalyst may be deactivated, and further improvement is desired.

本発明は、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おいて、メタクロレインの転化率が高く、かつメタクリル酸収率の高い触媒を安定して製造することができるメタクリル酸製造用触媒の製造方法を提供することを目的とする。   INDUSTRIAL APPLICABILITY The present invention can stably produce a catalyst having a high conversion rate of methacrolein and a high yield of methacrylic acid in a method for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen. It aims at providing the manufacturing method of the catalyst for methacrylic acid manufacture.

本発明に係るメタクリル酸製造用触媒の製造方法は、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際に用いられる、モリブデン、バナジウム及びリンを触媒成分として含むメタクリル酸製造用触媒の製造方法において、下記工程（Ｉ）から（Ｖ）；（Ｉ）モリブデン原料としての三酸化モリブデン、バナジウム原料及びリン原料を含む触媒原料を水中で混合しスラリーを調製後、該スラリーを乾燥し、触媒成分を含む粒子を製造する工程；（ＩＩ）前記粒子と、多糖類と、水又はアルコールとを混練りし、混練り体を製造する工程；（ＩＩＩ）前記混練り体を押出成形し、成形体を製造する工程；（ＩＶ）前記成形体を乾燥し、触媒前駆体を製造する工程；（Ｖ）前記触媒前駆体を熱処理する工程を含み、前記触媒前駆体の炭素原子含有量が２．０質量％以上であり、前記触媒前駆体を空気気流下、昇温速度１０℃／ｍｉｎの条件の下で質量減少率を測定した際、１５０℃〜２００℃の範囲における質量減少率が、測定に用いた触媒前駆体の質量に対して１．８質量％以下である。   The method for producing a catalyst for producing methacrylic acid according to the present invention is a method for producing methacrylic acid containing molybdenum, vanadium and phosphorus as catalyst components, which is used when producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen. In the method for producing a catalyst, the following steps (I) to (V); (I) a catalyst raw material containing molybdenum trioxide as a molybdenum raw material, a vanadium raw material and a phosphorus raw material are mixed in water to prepare a slurry; A step of drying and producing particles containing a catalyst component; (II) a step of kneading the particles, polysaccharide and water or alcohol to produce a kneaded body; (III) extruding the kneaded body Forming a molded body by molding; (IV) drying the molded body to produce a catalyst precursor; (V) heat-treating the catalyst precursor; When the carbon atom content of the catalyst precursor is 2.0% by mass or more and the mass reduction rate of the catalyst precursor is measured under a condition of a temperature rising rate of 10 ° C./min under an air stream, The mass reduction rate in the range of 200 ° C. is 1.8% by mass or less based on the mass of the catalyst precursor used for the measurement.

本発明に係る方法によれば、メタクロレインの転化率が高く、かつメタクリル酸収率の高い触媒を安定して製造することができる。   According to the method of the present invention, a catalyst having a high methacrolein conversion rate and a high yield of methacrylic acid can be stably produced.

［メタクリル酸製造用触媒の製造方法］
本発明に係るメタクリル酸製造用触媒の製造方法は、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際に用いられる、モリブデン、バナジウム及びリンを触媒成分として含むメタクリル酸製造用触媒の製造方法において、下記工程（Ｉ）から（Ｖ）；（Ｉ）モリブデン原料としての三酸化モリブデン、バナジウム原料及びリン原料を含む触媒原料を水中で混合しスラリーを調製後、該スラリーを乾燥し、触媒成分を含む粒子を製造する工程；（ＩＩ）前記粒子と、多糖類と、水又はアルコールとを混練りし、混練り体を製造する工程；（ＩＩＩ）前記混練り体を押出成形し、成形体を製造する工程；（ＩＶ）前記成形体を乾燥し、触媒前駆体を製造する工程；（Ｖ）前記触媒前駆体を熱処理する工程を含み、前記触媒前駆体の炭素原子含有量が２．０質量％以上であり、前記触媒前駆体を空気気流下、昇温速度１０℃／ｍｉｎの条件の下で質量減少率を測定した際、１５０℃〜２００℃の範囲における質量減少率が、測定に用いた触媒前駆体の質量に対して１．８質量％以下である。 [Method for producing catalyst for producing methacrylic acid]
The method for producing a catalyst for producing methacrylic acid according to the present invention is a method for producing methacrylic acid containing molybdenum, vanadium and phosphorus as catalyst components, which is used when producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen. In the method for producing a catalyst, the following steps (I) to (V); (I) a catalyst raw material containing molybdenum trioxide as a molybdenum raw material, a vanadium raw material and a phosphorus raw material are mixed in water to prepare a slurry; A step of drying and producing particles containing a catalyst component; (II) a step of kneading the particles, polysaccharide and water or alcohol to produce a kneaded body; (III) extruding the kneaded body Forming a molded body by molding; (IV) drying the molded body to produce a catalyst precursor; (V) heat-treating the catalyst precursor; When the carbon atom content of the catalyst precursor is 2.0% by mass or more and the mass reduction rate of the catalyst precursor is measured under a condition of a temperature rising rate of 10 ° C./min under an air stream, The mass reduction rate in the range of 200 ° C. is 1.8% by mass or less based on the mass of the catalyst precursor used for the measurement.

本発明に係る方法においては、工程（ＩＶ）で調製される触媒前駆体を空気気流下、昇温速度１０℃／ｍｉｎの条件の下で質量減少率を測定した際、１５０℃〜２００℃の範囲における質量減少率が、測定に用いた触媒前駆体の質量に対して１．８質量％以下である。触媒前駆体中の１５０℃〜２００℃で質量減少を示す成分は、触媒前駆体中に含まれる炭素成分と硝酸イオンであると考えられる。この成分は熱処理を行った場合、発熱を伴い分解するため、この成分が触媒前駆体に多量に含まれる場合には、工程（Ｖ）において触媒前駆体を熱処理し触媒を製造する際に、過剰な発熱により触媒が失活する。本発明に係る方法では前記質量減少率を１．８質量％以下とすることで、工程（Ｖ）の熱処理における発熱を抑制し触媒の失活を防ぐことができるため、活性が高く、メタクリル酸収率の高い触媒を製造することができる。   In the method according to the present invention, when the mass reduction rate of the catalyst precursor prepared in the step (IV) is measured under a condition of a heating rate of 10 ° C./min in an air stream, the temperature is 150 ° C. to 200 ° C. The mass reduction rate in the range is 1.8% by mass or less with respect to the mass of the catalyst precursor used for the measurement. It is thought that the component which shows a mass reduction | decrease at 150 to 200 degreeC in a catalyst precursor is a carbon component and nitrate ion contained in a catalyst precursor. When this component is heat-treated, it decomposes with heat generation. Therefore, when this component is contained in a large amount in the catalyst precursor, an excessive amount is produced in the production of the catalyst by heat-treating the catalyst precursor in step (V). The catalyst is deactivated due to excessive heat generation. In the method according to the present invention, by setting the mass reduction rate to 1.8% by mass or less, heat generation in the heat treatment in the step (V) can be suppressed and deactivation of the catalyst can be prevented. A catalyst with a high yield can be produced.

なお、前記質量減少率の測定はＴＧ（Ｔｈｅｒｍｏｇｒａｖｉｍｅｔｒｙ、熱重量分析）により行うことができる。測定装置には、熱重量測定装置（商品名：ＴＧＡ−５０、（株）島津製作所製）を用いることができる。測定条件としては、成形体状の触媒前駆体を乳鉢を用いて粉砕し、粉状としたもの５０ｍｇをサンプルに用い、空気を３００ｍＬ／ｍｉｎで流通下、１０℃／ｍｉｎで昇温する。測定に用いたサンプル質量に対する１５０℃〜２００℃における質量減少率を算出することにより、前記質量減少率を求める。   The mass reduction rate can be measured by TG (Thermogravimetry). As the measuring device, a thermogravimetric measuring device (trade name: TGA-50, manufactured by Shimadzu Corporation) can be used. As measurement conditions, a compacted catalyst precursor is pulverized using a mortar and powdered, 50 mg is used as a sample, and air is heated at 10 ° C./min while flowing at 300 mL / min. The said mass reduction rate is calculated | required by calculating the mass reduction rate in 150 to 200 degreeC with respect to the sample mass used for the measurement.

本発明に係る方法においては、前記触媒前駆体の炭素原子含有量が２．０質量％以上である。前記炭素原子含有量が２．０質量％未満である場合、メタクリル酸収率の高い触媒が得られにくく、また成形性が低下するため好ましくない。前記炭素原子含有量は２．２質量％以上であることが好ましい。また、前記工程（Ｖ）の熱処理における発熱を抑制する観点から、前記炭素原子含有量は５．０質量％以下であることが好ましく、３．０質量％以下であることがより好ましい。なお、前記触媒前駆体中の炭素原子含有量は、元素分析装置（商品名：ｖａｒｉｏ ＥＬＩＩＩ、エレメンタール社製）を用いて有機元素分析によって測定した値とする。   In the method according to the present invention, the catalyst precursor has a carbon atom content of 2.0% by mass or more. When the carbon atom content is less than 2.0% by mass, it is difficult to obtain a catalyst having a high methacrylic acid yield and the moldability is lowered, which is not preferable. The carbon atom content is preferably 2.2% by mass or more. Further, from the viewpoint of suppressing heat generation in the heat treatment in the step (V), the carbon atom content is preferably 5.0% by mass or less, and more preferably 3.0% by mass or less. The carbon atom content in the catalyst precursor is a value measured by organic elemental analysis using an elemental analyzer (trade name: vario ELIII, manufactured by Elemental Co.).

また、前記触媒前駆体に含まれる硝酸イオンの量は、窒素原子として０．２質量％以下であることが、１５０℃〜２００℃における質量減少率を１．８質量％以下とすることができ、前述した工程（Ｖ）における発熱を抑制できる観点から好ましい。一方、硝酸イオンの量が前記範囲より多い場合には、工程（Ｖ）における触媒前駆体の熱処理時に、工程（ＩＩ）で添加する多糖類と、硝酸イオンがより低温で発熱分解するため、触媒の分解が起き易く触媒が失活しやすい。前記触媒前駆体に含まれる硝酸イオンの量は、窒素原子としてより好ましくは０．１質量％以下である。   The amount of nitrate ions contained in the catalyst precursor can be 0.2% by mass or less as nitrogen atoms, and the mass reduction rate at 150 ° C. to 200 ° C. can be 1.8% by mass or less. From the viewpoint of suppressing heat generation in the step (V) described above. On the other hand, when the amount of nitrate ions is larger than the above range, the catalyst added in step (II) and the nitrate ions are exothermically decomposed at a lower temperature during the heat treatment of the catalyst precursor in step (V). The catalyst is easily decomposed and the catalyst is easily deactivated. The amount of nitrate ions contained in the catalyst precursor is more preferably 0.1% by mass or less as nitrogen atoms.

なお、前記触媒前駆体に含まれる硝酸イオンの量は、以下の方法により測定することができる。まず、元素分析装置（商品名：ｖａｒｉｏ ＥＬＩＩＩ、エレメンタール社製）を用いて有機元素分析により触媒前駆体中の全窒素量を測定する。次に、ケールダール法により触媒前駆体中のアンモニウム体の窒素量を測定する。前者から後者を引くことにより窒素原子としての硝酸イオンの量を算出する。   The amount of nitrate ions contained in the catalyst precursor can be measured by the following method. First, the total nitrogen amount in the catalyst precursor is measured by organic elemental analysis using an elemental analyzer (trade name: vario ELIII, manufactured by Elemental Co.). Next, the nitrogen amount of the ammonium body in the catalyst precursor is measured by the Kjeldahl method. The amount of nitrate ions as nitrogen atoms is calculated by subtracting the latter from the former.

以下、本発明に係る方法における各工程の詳細を示す。   Hereafter, the detail of each process in the method concerning this invention is shown.

（工程（Ｉ））
工程（Ｉ）では、モリブデン原料としての三酸化モリブデン、バナジウム原料及びリン原料を含む触媒原料を水中で混合しスラリーを調製後、該スラリーを乾燥し、触媒成分を含む粒子を製造する。 (Process (I))
In step (I), a catalyst raw material containing molybdenum trioxide as a molybdenum raw material, a vanadium raw material, and a phosphorus raw material is mixed in water to prepare a slurry, and then the slurry is dried to produce particles containing a catalyst component.

工程（Ｉ）では、少なくともモリブデン、バナジウム及びリンを必須成分として含むスラリーを乾燥し触媒成分を含む粒子とする。スラリーの製造段階で用いる原料の種類及び量を適宜選択することにより、触媒前駆体中の硝酸イオン量を特定の範囲に調節することができる。これにより触媒前駆体の１５０℃〜２００℃における質量減少率を１．８質量％以下とすることができる。   In step (I), a slurry containing at least molybdenum, vanadium and phosphorus as essential components is dried to form particles containing a catalyst component. The amount of nitrate ions in the catalyst precursor can be adjusted to a specific range by appropriately selecting the type and amount of the raw material used in the slurry production stage. Thereby, the mass decreasing rate in 150 to 200 degreeC of a catalyst precursor can be 1.8 mass% or less.

本発明に係る方法においては、触媒原料に含まれる硝酸イオンの量が、該触媒原料に含まれるモリブデン原子の量を１２モルとしたとき、１．０モル未満であることが、触媒前駆体中の硝酸イオンの量を好ましい範囲とすることができるため好ましい。   In the method according to the present invention, the amount of nitrate ions contained in the catalyst raw material is less than 1.0 mol when the amount of molybdenum atoms contained in the catalyst raw material is 12 mol. This is preferable because the amount of nitrate ions can be within a preferable range.

触媒原料に含まれる各元素、イオンの組成は、下記式（Ａ）で示される組成であることが好ましい。   The composition of each element and ion contained in the catalyst raw material is preferably a composition represented by the following formula (A).

ＰaＭｏbＶcＸdＹeＺfＮ１gＮ２h （Ａ）
（式（Ａ）中、Ｐ、Ｍｏ、Ｖは、それぞれリン、モリブデン、バナジウムを示す。Ｘ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より選ばれる少なくとも１種類の元素を示す。Ｙは銅、鉄、亜鉛、クロム、マグネシウム、タンタル、コバルト、マンガン、バリウム、ガリウム、セリウム及びランタンからなる群より選ばれる少なくとも１種類の元素を示す。Ｚはカリウム、ルビジウム、セシウム及びタリウムからなる群より選ばれる少なくとも１種類の元素を示す。Ｎ１は硝酸イオンを示す。Ｎ２はアンモニア及びアンモニウムイオンの少なくとも１種類を示す。ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ及びｈは各元素又はイオンの原子比率を示し、ｂ＝１２のとき、ａ＝０．５〜３、ｃ＝０．０１〜３、ｄ＝０〜２、ｅ＝０〜３、ｆ＝０〜３、ｇ＜１．０、ｈ＝０．０１〜５である。ただし、ｇ及びｈは窒素原子に換算した値である。）
触媒原料に含まれる各元素、イオンの組成は、触媒調製時の各原料の仕込み量から算出する。 P a Mo b V c X d Y e Z f N1 g N2 h (A)
(In the formula (A), P, Mo, and V respectively represent phosphorus, molybdenum, and vanadium. X represents a group consisting of antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten, and boron. Y represents at least one element selected, and Y represents at least one element selected from the group consisting of copper, iron, zinc, chromium, magnesium, tantalum, cobalt, manganese, barium, gallium, cerium and lanthanum. Represents at least one element selected from the group consisting of potassium, rubidium, cesium and thallium, N1 represents nitrate ion, N2 represents at least one kind of ammonia and ammonium ion, a, b, c, d, e, f, g and h indicate the atomic ratio of each element or ion, and when b = 12. a = 0.5-3, c = 0.01-3, d = 0-2, e = 0-3, f = 0-3, g <1.0, h = 0.01-5. However, g and h are values converted to nitrogen atoms.)
The composition of each element and ion contained in the catalyst raw material is calculated from the charged amount of each raw material at the time of catalyst preparation.

本発明に係る方法においては、よりメタクリル酸収率の高い触媒を得る観点からモリブデン原料として三酸化モリブデンを用いる。バナジウム原料及びリン原料としては特に限定されない。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、五酸化バナジウム等を用いることができる。リン原料としては、正リン酸、メタリン酸、五酸化リン、ピロリン酸、リン酸アンモニウム等を用いることができる。前記式（Ａ）における任意成分のＸ、Ｙ、Ｚ元素の原料としては特に限定されず、各構成元素の硝酸塩、炭酸塩、酢酸塩、酸化物、ハロゲン化物等を用いることができる。これらは単独で、又は組み合わせて使用することができる。   In the method according to the present invention, molybdenum trioxide is used as a molybdenum raw material from the viewpoint of obtaining a catalyst having a higher methacrylic acid yield. It does not specifically limit as a vanadium raw material and a phosphorus raw material. As the vanadium raw material, for example, ammonium metavanadate, vanadium pentoxide, or the like can be used. As the phosphorus raw material, orthophosphoric acid, metaphosphoric acid, phosphorus pentoxide, pyrophosphoric acid, ammonium phosphate and the like can be used. There are no particular limitations on the raw materials for the optional X, Y, and Z elements in the formula (A), and nitrates, carbonates, acetates, oxides, halides, and the like of each constituent element can be used. These can be used alone or in combination.

スラリーの乾燥方法は特に制限されない。例えば、スプレー乾燥機を用いて乾燥する方法、スラリードライヤーを用いて乾燥する方法、ドラムドライヤーを用いて乾燥する方法、蒸発乾固する方法等が適用できる。スラリー調製後、有機バインダーを添加し、その後に乾燥を行う特許文献２に記載の方法を用いて粒子としてもよい。この中でも、適当な強度の乾燥粒子を得ることができ、それを押出成形して反応に理想的な細孔構造を有する触媒成形体を得ることができる観点から、有機バインダーを添加した後にスプレー乾燥を行う方法で乾燥することが好ましい。   The method for drying the slurry is not particularly limited. For example, a method of drying using a spray dryer, a method of drying using a slurry dryer, a method of drying using a drum dryer, a method of evaporating to dryness, and the like can be applied. It is good also as particle | grains using the method of the patent document 2 which adds an organic binder after slurry preparation and performs drying after that. Among these, from the viewpoint of obtaining dry particles having an appropriate strength and obtaining a catalyst molded body having an ideal pore structure for reaction by extrusion molding, spray drying is performed after adding an organic binder. It is preferable to dry by the method of performing.

（工程（ＩＩ））
工程（ＩＩ）では、前記粒子と、多糖類と、水又はアルコールとを混練りし、混練り体を製造する。前記粒子に多糖類と、水又はアルコールとを混練りすることにより、工程（ＩＩＩ）における押出成形において成形性が向上し、かつメタクリル酸製造において高い活性、収率を示す触媒を製造することができる。 (Process (II))
In step (II), the particles, polysaccharide, and water or alcohol are kneaded to produce a kneaded body. By kneading a polysaccharide and water or alcohol to the particles, it is possible to produce a catalyst having improved moldability in extrusion molding in step (III) and high activity and yield in methacrylic acid production. it can.

前記多糖類は特に限定されず、例えばβ−１，３グルカンやセルロース誘導体等を用いることができる。β−１，３グルカンとしては、例えば、カードラン、ラミナラン、パラミロン、カロース、パキマン、スクレログルカン等を挙げることができる。また、セルロース誘導体としては、例えば、メチルセルロース、エチルセルロース、カルボキシメチルセルロース、カルボキシルメチルセルロースナトリウム、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシエチルメチルセルロース、ヒドロキシブチルメチルセルロース、ヒドロキシプロピルセルロース等を挙げることができる。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。この中でも、多糖類としてヒドロキシプロピルメチルセルロースを用いることが好ましい。   The polysaccharide is not particularly limited, and for example, β-1,3 glucan or cellulose derivative can be used. Examples of β-1,3 glucan include curdlan, laminaran, paramylon, callose, Pakiman, scleroglucan and the like. Examples of the cellulose derivative include methyl cellulose, ethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxybutyl methyl cellulose, and hydroxypropyl cellulose. These may use only 1 type and may use 2 or more types together. Among these, it is preferable to use hydroxypropyl methylcellulose as the polysaccharide.

多糖類の使用量としては、前記触媒前駆体中の炭素原子含有量が２．０質量％以上であり、かつ前記１５０℃〜２００℃における質量減少率が１．８質量％以下となる量である。この範囲とするには、多糖類の使用量が工程（Ｉ）で得られた粒子１００質量部に対して０．１〜２０質量部であることが好ましく、０．５〜１０質量部であることがより好ましい。   The amount of polysaccharide used is such that the carbon atom content in the catalyst precursor is 2.0% by mass or more and the mass reduction rate at 150 ° C. to 200 ° C. is 1.8% by mass or less. is there. In order to make this range, it is preferable that the usage-amount of polysaccharide is 0.1-20 mass parts with respect to 100 mass parts of particle | grains obtained at process (I), and is 0.5-10 mass parts. It is more preferable.

前記アルコールとしては、例えばメチルアルコール、エタノール、プロピルアルコール、ブチルアルコール等の低級アルコールを用いることができる。水又は前記アルコールは一種のみを用いてもよく、二種以上を併用してもよい。   As said alcohol, lower alcohols, such as methyl alcohol, ethanol, propyl alcohol, butyl alcohol, can be used, for example. Only one kind of water or the alcohol may be used, or two or more kinds may be used in combination.

水又はアルコールの使用量としては、押出成形しやすい状態の混練り物を得る観点から、工程（Ｉ）で得られた粒子１００質量部に対して１０〜９０質量部であることが好ましく、２０〜８０質量部であることがより好ましい。   The amount of water or alcohol used is preferably 10 to 90 parts by mass with respect to 100 parts by mass of the particles obtained in the step (I) from the viewpoint of obtaining a kneaded product that is easily extruded. More preferably, it is 80 parts by mass.

混練りに使用する装置は特に限定されず、例えば、双腕型の攪拌羽根を使用するバッチ式の混練り機、軸回転往復式やセルフクリーニング型等の連続式の混練り機等が使用できる。しかしながら、混練り品の状態を確認しながら混練りを行うことができる観点からバッチ式が好ましい。混練りの条件についても特に限定されない。また、混練りの終点は、通常目視または手触りによって判断する。   The apparatus used for kneading is not particularly limited. For example, a batch-type kneading machine using a double-arm type stirring blade, a continuous kneading machine such as a shaft rotation reciprocating type or a self-cleaning type can be used. . However, the batch type is preferable from the viewpoint that kneading can be performed while checking the state of the kneaded product. The kneading conditions are not particularly limited. The end point of kneading is usually judged by visual observation or touch.

（工程（ＩＩＩ））
工程（ＩＩＩ）では、前記混練り体を押出成形し成形体を製造する。押出成形に用いる装置としては特に限定されないが、例えばオーガー式押出成形機、ピストン式押出成形機等を用いることができる。成形体の形状としては、特に限定はなく、リング状、円柱状、星型状等の任意の形状に成形することができる。 (Step (III))
In step (III), the kneaded body is extrusion molded to produce a molded body. Although it does not specifically limit as an apparatus used for extrusion molding, For example, an auger type extrusion molding machine, a piston type extrusion molding machine, etc. can be used. There is no limitation in particular as a shape of a molded object, It can shape | mold to arbitrary shapes, such as a ring shape, a column shape, and star shape.

（工程（ＩＶ））
工程（ＩＶ）では、前記成形体を乾燥し、触媒前駆体を製造する。前記成形体を乾燥することにより、工程（ＩＩ）で触媒成分を含む粒子に加えた水又はアルコールを取り除き、成形体状の触媒前駆体とする。乾燥後に触媒前駆体中に残存する水又はアルコールは少ない方が好ましい。具体的には、触媒前駆体中の含液率は１０質量％以下が好ましく、より好ましくは５質量％以下である。ここで、触媒前駆体中の含液率は一定量の触媒前駆体を１００℃の空気中で２４時間静置した際の質量減少率から算出される。乾燥方法としては、特に限定されず、熱風乾燥、減圧乾燥等の公知の方法で行うことができる。成形体が水又はアルコールの液を含有している状態で過剰に熱が加えられると、触媒の失活が起こる可能性があるため、乾燥温度は１２０℃以下であることが好ましい。乾燥時間については、触媒前駆体中の含液率が１０質量％以下となるように適宜調整することができるが、含液率を下げるためには１０時間以上乾燥処理を行うことが好ましい。本発明においては、前述したように工程（ＩＶ）で得られる触媒前駆体の炭素原子含有量は２．０質量％以上であり、該触媒前駆体の前記１５０℃〜２００℃の範囲における質量減少率は１．８質量％以下である。 (Process (IV))
In step (IV), the molded body is dried to produce a catalyst precursor. By drying the molded body, water or alcohol added to the particles containing the catalyst component in step (II) is removed to obtain a molded body catalyst precursor. Less water or alcohol remains in the catalyst precursor after drying. Specifically, the liquid content in the catalyst precursor is preferably 10% by mass or less, more preferably 5% by mass or less. Here, the liquid content in the catalyst precursor is calculated from the mass reduction rate when a certain amount of the catalyst precursor is allowed to stand in air at 100 ° C. for 24 hours. It does not specifically limit as a drying method, It can carry out by well-known methods, such as hot air drying and reduced pressure drying. If excessive heat is applied in a state where the molded product contains water or alcohol, the catalyst may be deactivated. Therefore, the drying temperature is preferably 120 ° C. or lower. About drying time, it can adjust suitably so that the liquid content in a catalyst precursor may be 10 mass% or less, but in order to reduce a liquid content, it is preferable to perform a drying process for 10 hours or more. In the present invention, as described above, the carbon atom content of the catalyst precursor obtained in the step (IV) is 2.0% by mass or more, and the mass reduction of the catalyst precursor in the range of 150 ° C. to 200 ° C. The rate is 1.8% by mass or less.

（工程（Ｖ））
工程（Ｖ）では、前記触媒前駆体を熱処理する。触媒前駆体を熱処理する温度としては、２００℃〜６００℃であることが触媒の主な構造であるヘテロポリ酸の分解による触媒の失活を抑える観点から好ましい。より好ましくは２５０℃〜５００℃である。触媒前駆体を熱処理する時間としては特に制限されず、例えば１〜２４時間行うことができる。熱処理に用いる焼成炉としては、電気式加熱炉やナイター式加熱炉を用いることができる。 (Process (V))
In step (V), the catalyst precursor is heat-treated. The temperature for heat-treating the catalyst precursor is preferably 200 ° C. to 600 ° C. from the viewpoint of suppressing the deactivation of the catalyst due to the decomposition of the heteropolyacid which is the main structure of the catalyst. More preferably, it is 250 degreeC-500 degreeC. The time for heat-treating the catalyst precursor is not particularly limited, and can be, for example, 1 to 24 hours. As a baking furnace used for the heat treatment, an electric heating furnace or a nighter heating furnace can be used.

［メタクリル酸の製造方法］
次に、本発明のメタクリル酸の製造方法について説明する。本発明のメタクリル酸の製造方法は、前記方法により得られたメタクリル酸製造用触媒の存在下で、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である。 [Method for producing methacrylic acid]
Next, the manufacturing method of methacrylic acid of this invention is demonstrated. The method for producing methacrylic acid of the present invention is a method for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen in the presence of the catalyst for producing methacrylic acid obtained by the above method.

気相接触酸化反応は、通常固定床で行う。触媒層は特に限定されず、触媒のみの無希釈層でも、不活性担体を含んだ希釈層でもよく、単一層でも複数の層からなる混合層であってもよい。   The gas phase catalytic oxidation reaction is usually performed in a fixed bed. The catalyst layer is not particularly limited, and may be an undiluted layer containing only a catalyst, a diluted layer containing an inert carrier, or a single layer or a mixed layer composed of a plurality of layers.

反応には、メタクロレインと分子状酸素とを含む原料ガスを用いることが好ましい。原料ガス中のメタクロレイン濃度は、広い範囲で変えることができるが、１容量％以上が好ましく、３容量％以上がより好ましい。また、２０容量％以下が好ましく、１０容量％以下がより好ましい。原料ガス中の分子状酸素濃度は、メタクロレイン１モルに対して０．４モル以上が好ましく、０．５モル以上がより好ましい。また、メタクロレイン１モルに対して４モル以下が好ましく、３モル以下がより好ましい。分子状酸素源としては空気を用いることが経済的であるが、必要ならば純酸素で富化した空気等も用いることができる。   In the reaction, it is preferable to use a source gas containing methacrolein and molecular oxygen. The concentration of methacrolein in the raw material gas can be varied within a wide range, but is preferably 1% by volume or more, and more preferably 3% by volume or more. Moreover, 20 volume% or less is preferable and 10 volume% or less is more preferable. The molecular oxygen concentration in the raw material gas is preferably 0.4 mol or more, more preferably 0.5 mol or more with respect to 1 mol of methacrolein. Moreover, 4 mol or less is preferable with respect to 1 mol of methacrolein, and 3 mol or less is more preferable. Although it is economical to use air as the molecular oxygen source, air or the like enriched with pure oxygen can also be used if necessary.

原料ガスは、メタクロレインと分子状酸素以外に、水（水蒸気）を含むことが好ましい。水の存在下で反応を行うことで、より高い収率でメタクリル酸が得られる。原料ガス中の水蒸気の濃度は、０．１容量％以上が好ましく、１容量％以上がより好ましい。また、５０容量％以下が好ましく、４０容量％以下がより好ましい。原料ガスは、低級アルデヒド等の不純物を少量含んでいてもよいが、その量はできるだけ少ないことが好ましい。また、窒素、炭酸ガス等の不活性ガスを含んでいてもよい。   The source gas preferably contains water (water vapor) in addition to methacrolein and molecular oxygen. By performing the reaction in the presence of water, methacrylic acid can be obtained in a higher yield. The concentration of water vapor in the raw material gas is preferably 0.1% by volume or more, and more preferably 1% by volume or more. Moreover, 50 volume% or less is preferable and 40 volume% or less is more preferable. The source gas may contain a small amount of impurities such as lower aldehyde, but the amount is preferably as small as possible. Moreover, inert gas, such as nitrogen and a carbon dioxide gas, may be included.

気相接触酸化反応の反応圧力は、常圧（大気圧）から５気圧の範囲が好ましい。反応温度は、２３０℃以上が好ましく、２５０℃以上がより好ましい。また、４５０℃以下が好ましく、４００℃以下がより好ましい。原料ガスの流量は特に限定されず、適切な接触時間になるように適宜設定することができる。接触時間は、１．５秒以上が好ましく、２秒以上がより好ましい。また、１５秒以下が好ましく、１０秒以下がより好ましい。   The reaction pressure of the gas phase catalytic oxidation reaction is preferably in the range of normal pressure (atmospheric pressure) to 5 atm. The reaction temperature is preferably 230 ° C. or higher, more preferably 250 ° C. or higher. Moreover, 450 degrees C or less is preferable and 400 degrees C or less is more preferable. The flow rate of the raw material gas is not particularly limited, and can be appropriately set so as to have an appropriate contact time. The contact time is preferably 1.5 seconds or longer, and more preferably 2 seconds or longer. Moreover, 15 seconds or less are preferable and 10 seconds or less are more preferable.

以下、本発明を実施例及び比較例を用いて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。下記の実施例及び比較例中の「部」は質量部である。   EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example and a comparative example, this invention is not limited to these Examples. The “parts” in the following examples and comparative examples are parts by mass.

触媒組成および触媒原料に含まれる硝酸イオンのモル比は、触媒調製時の各原料の仕込み量をもとに決定した。   The molar ratio of the nitrate ion contained in the catalyst composition and the catalyst raw material was determined based on the charged amount of each raw material at the time of catalyst preparation.

原料ガスおよび生成物の分析は、ガスクロマトグラフィーを用いて行った。ガスクロマトグラフィーの結果から、メタクロレインの反応率、メタクリル酸の選択率、およびメタクリル酸の収率を下記式にて求めた。
メタクロレインの反応率（％）＝（Ｂ／Ａ）×１００
メタクリル酸の選択率（％）＝（Ｃ／Ｂ）×１００
メタクリル酸の収率（％）＝（Ｃ／Ａ）×１００
式中、Ａは供給したメタクロレインのモル数、Ｂは反応したメタクロレインのモル数、Ｃは生成したメタクリル酸のモル数である。 The analysis of the raw material gas and the product was performed using gas chromatography. From the results of gas chromatography, the reaction rate of methacrolein, the selectivity of methacrylic acid, and the yield of methacrylic acid were determined by the following formula.
Reaction rate of methacrolein (%) = (B / A) × 100
Methacrylic acid selectivity (%) = (C / B) × 100
Methacrylic acid yield (%) = (C / A) × 100
In the formula, A is the number of moles of methacrolein supplied, B is the number of moles of reacted methacrolein, and C is the number of moles of methacrylic acid produced.

［実施例１］
（工程（Ｉ））
三酸化モリブデン１００００部及びメタバナジン酸アンモニウム４１０部を純水２００００部に加えた。次にここに、硝酸銅１４０部を純水１０００部に溶解した溶液を加え、３時間加熱還流しながら攪拌した。その後、スラリーを５０℃に降温し、重炭酸セシウム１３４８部を純水２０００部に溶解した溶液を添加し、１５分攪拌した。次に炭酸アンモニウム６９５部を純水２０００部に溶解した溶液を添加し、１５分攪拌した。さらに、８５質量％リン酸８３４部を純水６００部に溶解した溶液を添加し、１５分攪拌した。このようにして得られたスラリーを、スプレー乾燥機を用いてスプレー噴霧乾燥を行い、スプレー粒子を得た。 [Example 1]
(Process (I))
10000 parts of molybdenum trioxide and 410 parts of ammonium metavanadate were added to 20000 parts of pure water. Next, the solution which melt | dissolved 140 parts of copper nitrate in 1000 parts of pure waters was added here, and it stirred, heating and refluxing for 3 hours. Thereafter, the temperature of the slurry was lowered to 50 ° C., a solution obtained by dissolving 1348 parts of cesium bicarbonate in 2000 parts of pure water was added, and the mixture was stirred for 15 minutes. Next, a solution obtained by dissolving 695 parts of ammonium carbonate in 2000 parts of pure water was added and stirred for 15 minutes. Further, a solution obtained by dissolving 834 parts of 85% by mass phosphoric acid in 600 parts of pure water was added and stirred for 15 minutes. The slurry thus obtained was spray spray dried using a spray dryer to obtain spray particles.

触媒原料に含まれる各元素、イオンの組成（酸素、水素、炭素は省略、以下同様）は、次の通りであった。   The composition of each element and ions contained in the catalyst raw material (oxygen, hydrogen, carbon omitted, the same applies hereinafter) was as follows.

Ｐ1.25Ｍｏ12Ｖ0.6Ｃｕ0.1Ｃｓ1.2Ｎ１0.2Ｎ２3.1
（工程（ＩＩ））
前記スプレー粒子１００部に対し、成形補助剤としてヒドロキシプロピルメチルセルロースを４．０部、カードランを１．５部加え、さらに、メチルアルコールを８０部加えて、混練りを行い、混練り体を得た。 P 1.25 Mo 12 V 0.6 Cu 0.1 Cs 1.2 N1 0.2 N2 3.1
(Process (II))
To 100 parts of the spray particles, 4.0 parts of hydroxypropylmethylcellulose and 1.5 parts of curdlan are added as molding aids, and further 80 parts of methyl alcohol are added and kneaded to obtain a kneaded body. It was.

（工程（ＩＩＩ））
前記混練り体を押出器で押出成形し、外径４ｍｍ、長さ４ｍｍの円柱状の成形体を得た。 (Step (III))
The kneaded body was extruded using an extruder to obtain a cylindrical molded body having an outer diameter of 4 mm and a length of 4 mm.

（工程（ＩＶ））
前記成形体を常圧、窒素気流下、９０℃で２０時間乾燥を行い、メチルアルコールを除去し、触媒前駆体とした。 (Process (IV))
The molded body was dried at 90 ° C. for 20 hours under normal pressure and nitrogen stream to remove methyl alcohol to obtain a catalyst precursor.

（触媒前駆体中の炭素原子含有量、硝酸イオン含有量、含液率及び質量減少率の測定）
前記触媒前駆体中の炭素原子含有量を元素分析装置（商品名：ｖａｒｉｏ ＥＬＩＩＩ、エレメンタール社製）を用いて有機元素分析によって測定した。前記触媒前駆体中の炭素原子含有量は２．６質量％であった。 (Measurement of carbon atom content, nitrate ion content, liquid content and mass reduction rate in catalyst precursor)
The carbon atom content in the catalyst precursor was measured by organic elemental analysis using an elemental analyzer (trade name: vario ELIII, manufactured by Elemental Co.). The carbon atom content in the catalyst precursor was 2.6% by mass.

また、前記触媒前駆体中の硝酸イオンの量を測定した。測定は、まず、元素分析装置（商品名：ｖａｒｉｏ ＥＬＩＩＩ、エレメンタール社製）を用いて有機元素分析により触媒前駆体中の全窒素量を測定した。次に、ケールダール法により触媒前駆体中のアンモニウム体の窒素量を測定した。前者から後者を引くことで窒素原子としての硝酸イオンの量を算出した。前記触媒前駆体中の硝酸イオンの量は、窒素原子として０．０３質量％未満であった。   Further, the amount of nitrate ions in the catalyst precursor was measured. In the measurement, first, the total nitrogen amount in the catalyst precursor was measured by organic element analysis using an elemental analyzer (trade name: vario ELIII, manufactured by Elemental Co.). Next, the nitrogen amount of the ammonium body in the catalyst precursor was measured by the Kjeldahl method. The amount of nitrate ion as a nitrogen atom was calculated by subtracting the latter from the former. The amount of nitrate ions in the catalyst precursor was less than 0.03% by mass as nitrogen atoms.

また、前記触媒前駆体の含液率を、該触媒前駆体１０ｇを１００℃の恒温乾燥器中で２４時間静置した前後での質量減少率から算出した。前記触媒前駆体の含液率は１．５質量％であった。   Further, the liquid content of the catalyst precursor was calculated from the mass reduction rate before and after 10 g of the catalyst precursor was left in a constant temperature dryer at 100 ° C. for 24 hours. The liquid content of the catalyst precursor was 1.5% by mass.

また、１５０℃〜２００℃の範囲における触媒前駆体の質量減少率をＴＧにより測定した。測定装置には、熱重量測定装置（商品名：ＴＧＡ−５０、（株）島津製作所製）を用いた。測定条件としては、成形体状の触媒前駆体を乳鉢を用いて粉砕し、粉状としたもの５０ｍｇをサンプルに用い、空気を３００ｍＬ／ｍｉｎで流通下、１０℃／ｍｉｎで昇温することにより測定した。１５０℃〜２００℃における質量減少率は、測定に用いたサンプル質量に対して１．８質量％であった。   Moreover, the mass decreasing rate of the catalyst precursor in the range of 150 degreeC-200 degreeC was measured by TG. As the measuring device, a thermogravimetric measuring device (trade name: TGA-50, manufactured by Shimadzu Corporation) was used. As measurement conditions, a compacted catalyst precursor was pulverized using a mortar and powdered, 50 mg was used as a sample, air was circulated at 300 mL / min, and heated at 10 ° C./min. It was measured. The mass reduction rate at 150 ° C. to 200 ° C. was 1.8% by mass with respect to the sample mass used for the measurement.

（工程（Ｖ））
１８０℃に加熱した焼成管内に前記触媒前駆体を１０ｇ充填し、空気流通下、１００℃／ｈで３８０℃まで昇温し、３８０℃で５時間熱処理を行い触媒とした。 (Process (V))
10 g of the catalyst precursor was filled in a calcining tube heated to 180 ° C., heated to 380 ° C. at 100 ° C./h under air flow, and heat-treated at 380 ° C. for 5 hours to obtain a catalyst.

（触媒の反応評価）
前記触媒を固定床反応器に充填し、温度を２９０℃とした。該固定床反応器に、メタクロレイン５体積％、酸素１０体積％、水蒸気３０体積％、窒素５５体積％の混合ガスを接触時間３．６秒で通じてメタクリル酸合成反応を行った。この反応の生成物を捕集してガスクロマトグラフィーで分析したところメタクロレインの転化率は７６．０％、メタクリル酸の選択率は８５．１％、及びメタクリル酸の収率は６４．７％であった。これらの測定結果と反応結果をまとめて表１に示す。 (Evaluation of catalyst reaction)
The catalyst was charged into a fixed bed reactor and the temperature was 290 ° C. A methacrylic acid synthesis reaction was conducted by passing a mixed gas of 5% by volume of methacrolein, 10% by volume of oxygen, 30% by volume of water vapor, and 55% by volume of nitrogen through the fixed bed reactor at a contact time of 3.6 seconds. The product of this reaction was collected and analyzed by gas chromatography. The conversion of methacrolein was 76.0%, the selectivity of methacrylic acid was 85.1%, and the yield of methacrylic acid was 64.7%. Met. These measurement results and reaction results are summarized in Table 1.

［実施例２］
工程（Ｉ）において、重炭酸セシウム水溶液、炭酸アンモニウム水溶液及び８５質量％リン酸水溶液の添加温度を７０℃とした以外は実施例１と同様の操作により触媒を調製し、反応評価を行った。結果を表１に示す。 [Example 2]
In step (I), a catalyst was prepared by the same operation as in Example 1 except that the addition temperature of the aqueous cesium bicarbonate solution, the aqueous ammonium carbonate solution, and the 85 mass% phosphoric acid aqueous solution was 70 ° C., and the reaction was evaluated. The results are shown in Table 1.

［実施例３］
工程（Ｉ）において、炭酸アンモニウム６９５部を純水２０００部に溶解した溶液を添加し１５分攪拌する代わりに、炭酸アンモニウム５５６部を純水１６００部に溶解した溶液を添加し１５分攪拌した後に、硝酸アンモニウム２３２部を純水４００部に溶解した溶液を添加し１５分攪拌した。それ以外は、実施例１と同様の操作により触媒を調製し、反応評価を行った。結果を表１に示す。 [Example 3]
In step (I), instead of adding a solution prepared by dissolving 695 parts of ammonium carbonate in 2000 parts of pure water and stirring for 15 minutes, a solution prepared by dissolving 556 parts of ammonium carbonate in 1600 parts of pure water was added and stirred for 15 minutes. A solution prepared by dissolving 232 parts of ammonium nitrate in 400 parts of pure water was added and stirred for 15 minutes. Other than that, a catalyst was prepared by the same operation as in Example 1, and the reaction was evaluated. The results are shown in Table 1.

［実施例４］
実施例１の工程（Ｉ）について、以下のように変更した。三酸化モリブデン３００部及びメタバナジン酸アンモニウム１２部を純水１２００部に加えた。次に８５質量％リン酸２４部を純水１８部と混合した溶液と、硝酸銅４部を純水９部に溶解した溶液とを加え、３時間加熱還流しながら攪拌した。その後スラリーを２５℃に降温し、重炭酸セシウム４０部を純水６０部に溶解した溶液を添加し、１５分攪拌した。次に炭酸アンモニウム２１部を純水９４部に溶解した溶液を添加し、１５分攪拌した。このようにして得られたスラリーを、スプレー乾燥機を用いてスプレー噴霧乾燥を行い、スプレー粒子を得た。以降の工程（ＩＩ）〜（Ｖ）については、実施例１と同様の操作により触媒を調製し、反応評価を行った。結果を表１に示す。 [Example 4]
About the process (I) of Example 1, it changed as follows. 300 parts of molybdenum trioxide and 12 parts of ammonium metavanadate were added to 1200 parts of pure water. Next, a solution prepared by mixing 24 parts of 85 mass% phosphoric acid with 18 parts of pure water and a solution prepared by dissolving 4 parts of copper nitrate in 9 parts of pure water were added and stirred while heating under reflux for 3 hours. Thereafter, the slurry was cooled to 25 ° C., a solution obtained by dissolving 40 parts of cesium bicarbonate in 60 parts of pure water was added, and the mixture was stirred for 15 minutes. Next, a solution obtained by dissolving 21 parts of ammonium carbonate in 94 parts of pure water was added and stirred for 15 minutes. The slurry thus obtained was spray spray dried using a spray dryer to obtain spray particles. For the subsequent steps (II) to (V), a catalyst was prepared by the same operation as in Example 1, and the reaction was evaluated. The results are shown in Table 1.

［実施例５］
工程（Ｉ）において、加熱還流後のスラリーを降温させる際の温度を７５℃とした以外は実施例４と同様の操作により触媒を調製し、反応評価を行った。結果を表１に示す。 [Example 5]
In step (I), a catalyst was prepared by the same operation as in Example 4 except that the temperature at which the slurry after heating under reflux was lowered to 75 ° C., and the reaction was evaluated. The results are shown in Table 1.

［実施例６］
工程（Ｉ）において、炭酸アンモニウム２１部を純水９４部に溶解した溶液を添加して１５分攪拌する代わりに、炭酸アンモニウム１７部を純水７５部に溶解した溶液を添加して１５分攪拌し、さらに硝酸アンモニウム６部を純水１２部に溶解した溶液を添加して１５分攪拌した。それ以外は実施例４と同様の操作により触媒を調製し、反応評価を行った。結果を表１に示す。 [Example 6]
In step (I), instead of adding a solution of 21 parts of ammonium carbonate dissolved in 94 parts of pure water and stirring for 15 minutes, a solution of 17 parts of ammonium carbonate dissolved in 75 parts of pure water was added and stirred for 15 minutes. Further, a solution prepared by dissolving 6 parts of ammonium nitrate in 12 parts of pure water was added and stirred for 15 minutes. Otherwise, a catalyst was prepared in the same manner as in Example 4, and the reaction was evaluated. The results are shown in Table 1.

［比較例１］
工程（Ｉ）において、炭酸アンモニウム６９５部を純水２０００部に溶解した溶液を添加し１５分攪拌する代わりに、炭酸アンモニウム５０１部を純水１４４０部に溶解した溶液を添加し１５分攪拌した後に、硝酸アンモニウム６９５部を純水１２００部に溶解した溶液を添加し１５分攪拌した。それ以外は、実施例１と同様の操作により触媒を調製し、反応評価を行った。結果を表１に示す。 [Comparative Example 1]
In Step (I), instead of adding a solution prepared by dissolving 695 parts of ammonium carbonate in 2000 parts of pure water and stirring for 15 minutes, a solution prepared by dissolving 501 parts of ammonium carbonate in 1440 parts of pure water was added and stirred for 15 minutes. Then, a solution prepared by dissolving 695 parts of ammonium nitrate in 1200 parts of pure water was added and stirred for 15 minutes. Other than that, a catalyst was prepared by the same operation as in Example 1, and the reaction was evaluated. The results are shown in Table 1.

［比較例２］
工程（Ｉ）において、炭酸アンモニウム６９５部を純水２０００部に溶解した溶液を添加し１５分攪拌する代わりに、炭酸アンモニウム３６２部を純水１０４０部に溶解した溶液を添加し１５分攪拌した後に、硝酸アンモニウム９２７部を純水１６００部に溶解した溶液を添加し１５分攪拌した。それ以外は、実施例１と同様の操作により触媒を調製し、反応評価を行った。結果を表１に示す。 [Comparative Example 2]
In step (I), instead of adding a solution prepared by dissolving 695 parts of ammonium carbonate in 2000 parts of pure water and stirring for 15 minutes, a solution prepared by dissolving 362 parts of ammonium carbonate in 1040 parts of pure water was added and stirred for 15 minutes. A solution prepared by dissolving 927 parts of ammonium nitrate in 1600 parts of pure water was added and stirred for 15 minutes. Other than that, a catalyst was prepared by the same operation as in Example 1, and the reaction was evaluated. The results are shown in Table 1.

［比較例３］
工程（Ｉ）において、炭酸アンモニウム６９５部を純水２０００部に溶解した溶液を添加し１５分攪拌する代わりに、炭酸アンモニウム２２３部を純水１０００部に溶解した溶液を添加し１５分攪拌した後に、硝酸アンモニウム１１５９部を純水２０００部に溶解した溶液を添加し１５分攪拌した。それ以外は、実施例１と同様の操作により触媒を調製し、反応評価を行った。結果を表１に示す。 [Comparative Example 3]
In step (I), instead of adding a solution prepared by dissolving 695 parts of ammonium carbonate in 2000 parts of pure water and stirring for 15 minutes, a solution prepared by dissolving 223 parts of ammonium carbonate in 1000 parts of pure water was added and stirred for 15 minutes. A solution prepared by dissolving 1159 parts of ammonium nitrate in 2000 parts of pure water was added and stirred for 15 minutes. Other than that, a catalyst was prepared by the same operation as in Example 1, and the reaction was evaluated. The results are shown in Table 1.

［比較例４］
工程（Ｉ）において、重炭酸セシウム１３４８部を純水２０００部に溶解した溶液を添加する代わりに、硝酸セシウム１３５４部を純水２５００部に溶解した溶液を添加した。また、炭酸アンモニウム６９５部を純水２０００部に溶解した溶液を添加し１５分攪拌する代わりに、炭酸アンモニウム５０１部を純水２２５０部に溶解した溶液を添加し１５分攪拌した後に、硝酸アンモニウム６９５部を純水１２００部に溶解した溶液を添加し１５分攪拌した。これら以外は、実施例１と同様の操作により触媒を調製し、反応評価を行った。結果を表１に示す。 [Comparative Example 4]
In step (I), instead of adding a solution of 1348 parts of cesium bicarbonate dissolved in 2000 parts of pure water, a solution of 1354 parts of cesium nitrate dissolved in 2500 parts of pure water was added. Further, instead of adding a solution obtained by dissolving 695 parts of ammonium carbonate in 2000 parts of pure water and stirring for 15 minutes, after adding a solution prepared by dissolving 501 parts of ammonium carbonate in 2250 parts of pure water and stirring for 15 minutes, 695 parts of ammonium nitrate Was added to a solution of 1200 parts of pure water and stirred for 15 minutes. Except for these, a catalyst was prepared by the same operation as in Example 1, and the reaction was evaluated. The results are shown in Table 1.

［比較例５］
実施例１の工程（Ｉ）について、以下のように変更した。三酸化モリブデン５０００部及びメタバナジン酸アンモニウム２０５部を純水２００００部に加えた。次に８５質量％リン酸４１８部を純水３００部と混合した溶液と、硝酸銅７０部を純水１５０部に溶解した溶液とを加え、３時間加熱還流しながら攪拌した。その後スラリーを２５℃に降温し、重炭酸セシウム６７３部を純水１０００部に溶解した溶液を添加し、１５分攪拌した。次に炭酸アンモニウム１１１部を純水５００部に溶解した溶液を添加し、１５分攪拌した後、硝酸アンモニウム５７９部を純水１０００部に溶解した溶解を添加し、１５分攪拌した。このようにして得られたスラリーを、スプレー乾燥機を用いてスプレー噴霧乾燥を行い、スプレー粒子を得た。以降の工程（ＩＩ）〜（Ｖ）については、実施例１と同様の操作により触媒を調製し、反応評価を行った。結果を表１に示す。 [Comparative Example 5]
About the process (I) of Example 1, it changed as follows. 5000 parts of molybdenum trioxide and 205 parts of ammonium metavanadate were added to 20000 parts of pure water. Next, a solution obtained by mixing 418 parts of 85 mass% phosphoric acid with 300 parts of pure water and a solution obtained by dissolving 70 parts of copper nitrate in 150 parts of pure water were added and stirred for 3 hours while heating under reflux. Thereafter, the slurry was cooled to 25 ° C., a solution obtained by dissolving 673 parts of cesium bicarbonate in 1000 parts of pure water was added, and the mixture was stirred for 15 minutes. Next, a solution of 111 parts of ammonium carbonate dissolved in 500 parts of pure water was added and stirred for 15 minutes, and then a solution of 579 parts of ammonium nitrate dissolved in 1000 parts of pure water was added and stirred for 15 minutes. The slurry thus obtained was spray spray dried using a spray dryer to obtain spray particles. For the subsequent steps (II) to (V), a catalyst was prepared by the same operation as in Example 1, and the reaction was evaluated. The results are shown in Table 1.

［比較例６］
実施例１の工程（Ｉ）について、以下のように変更した。三酸化モリブデン３００部及びメタバナジン酸アンモニウム１２部を純水１２００部に加えた。次に８５質量％リン酸２４部を純水１８部と混合した溶液と、硝酸銅４部を純水９部に溶解した溶液とを加え、３時間加熱還流しながら攪拌した。その後スラリーを２５℃に降温し、重炭酸セシウム４０部を純水６０部に溶解した溶液を添加し、１５分攪拌した。次に硝酸アンモニウム４９部を純水８４部に溶解した溶液を添加し、１５分攪拌した。このようにして得られたスラリーを、スプレー乾燥機を用いてスプレー噴霧乾燥を行い、スプレー粒子を得た。以降の工程（ＩＩ）〜（Ｖ）については、実施例１と同様の操作により触媒を調製し、反応評価を行った。結果を表１に示す。 [Comparative Example 6]
About the process (I) of Example 1, it changed as follows. 300 parts of molybdenum trioxide and 12 parts of ammonium metavanadate were added to 1200 parts of pure water. Next, a solution prepared by mixing 24 parts of 85 mass% phosphoric acid with 18 parts of pure water and a solution prepared by dissolving 4 parts of copper nitrate in 9 parts of pure water were added and stirred while heating under reflux for 3 hours. Thereafter, the slurry was cooled to 25 ° C., a solution obtained by dissolving 40 parts of cesium bicarbonate in 60 parts of pure water was added, and the mixture was stirred for 15 minutes. Next, a solution obtained by dissolving 49 parts of ammonium nitrate in 84 parts of pure water was added and stirred for 15 minutes. The slurry thus obtained was spray spray dried using a spray dryer to obtain spray particles. For the subsequent steps (II) to (V), a catalyst was prepared by the same operation as in Example 1, and the reaction was evaluated. The results are shown in Table 1.

［比較例７］
工程（Ｉ）において、硝酸アンモニウム４９部を純水８４部に溶解した溶液を添加して１５分攪拌する代わりに、炭酸アンモニウム１５部を純水６８部に溶解した溶液を添加して１５分攪拌し、さらに、硝酸アンモニウム２１部を純水３６部に溶解した溶液を添加して１５分攪拌した。それ以外は、比較例６と同様の操作により触媒を調製し、反応評価を行った。結果を表１に示す。 [Comparative Example 7]
In step (I), instead of adding a solution of 49 parts of ammonium nitrate in 84 parts of pure water and stirring for 15 minutes, a solution of 15 parts of ammonium carbonate in 68 parts of pure water was added and stirred for 15 minutes. Further, a solution prepared by dissolving 21 parts of ammonium nitrate in 36 parts of pure water was added and stirred for 15 minutes. Otherwise, a catalyst was prepared by the same operation as in Comparative Example 6, and the reaction was evaluated. The results are shown in Table 1.

［比較例８］
工程（Ｉ）において、硝酸アンモニウム４９部を純水８４部に溶解した溶液を添加して１５分攪拌する代わりに、炭酸アンモニウム１１部を純水４９部に溶解した溶液を添加して１５分攪拌し、さらに、硝酸アンモニウム２８部を純水４８部に溶解した溶液を添加して１５分攪拌した。それ以外は、比較例６と同様の操作により触媒を調製し、反応評価を行った。結果を表１に示す。 [Comparative Example 8]
In step (I), instead of adding a solution prepared by dissolving 49 parts of ammonium nitrate in 84 parts of pure water and stirring for 15 minutes, a solution prepared by dissolving 11 parts of ammonium carbonate in 49 parts of pure water was added and stirred for 15 minutes. Further, a solution obtained by dissolving 28 parts of ammonium nitrate in 48 parts of pure water was added and stirred for 15 minutes. Otherwise, a catalyst was prepared by the same operation as in Comparative Example 6, and the reaction was evaluated. The results are shown in Table 1.

［比較例９］
実施例１と同様に工程（Ｉ）を行った。実施例１の工程（ＩＩ）において、前記スプレー粒子１００部に対し、成形補助剤としてヒドロキシプロピルメチルセルロースを４．０部添加する代わりに２．０部添加し、カードランを１．５部添加する代わりに０．７部添加し、さらに、メチルアルコールを８０部加えて、混練りを行い、混練り体を得た。工程（ＩＩＩ）において、実施例１と同様に前記混練り体を押出器で押出成形を行ったが、成形性が低いために成形体を得ることができず、その後の熱処理および反応評価を行うことができなかった。結果を表１に示す。なお、工程（ＩＩＩ）において成形はできなかったが、混練り体を実施例１の工程（ＩＶ）と同様に乾燥し、乾燥物について同様に炭素原子含有量、硝酸イオン含有量及び質量減少率を測定した。 [Comparative Example 9]
Step (I) was carried out in the same manner as in Example 1. In step (II) of Example 1, instead of adding 4.0 parts of hydroxypropylmethylcellulose as a molding aid to 100 parts of the spray particles, 2.0 parts are added and 1.5 parts of curdlan are added. Instead, 0.7 part was added, and further 80 parts of methyl alcohol was added and kneaded to obtain a kneaded body. In step (III), the kneaded product was extruded using an extruder in the same manner as in Example 1. However, the molded product could not be obtained because of low moldability, and the subsequent heat treatment and reaction evaluation were performed. I couldn't. The results are shown in Table 1. In addition, although it could not be molded in the step (III), the kneaded body was dried in the same manner as in the step (IV) in Example 1, and the carbon atom content, nitrate ion content, and mass reduction rate were similarly obtained for the dried product. Was measured.

［比較例１０］
工程（ＩＩ）において、前記スプレー粒子１００部に対し、成形補助剤としてヒドロキシプロピルメチルセルロースを４．０部添加する代わりに１２．０部添加し、カードランを１．５部添加する代わりに４．５部添加し、さらに、メチルアルコールを８０部加えて、混練りを行い、混練り体を得た。その他の工程については、実施例１と同様に行い触媒を調製し、反応評価を行った。結果を表１に示す。 [Comparative Example 10]
In step (II), instead of adding 4.0 parts of hydroxypropylmethylcellulose as a molding aid to 100 parts of the spray particles, 12.0 parts are added, and instead of adding 1.5 parts of curdlan, 4. 5 parts were added, and further 80 parts of methyl alcohol was added and kneaded to obtain a kneaded body. About the other process, it carried out similarly to Example 1, the catalyst was prepared, and reaction evaluation was performed. The results are shown in Table 1.

Figure 2012030217
Figure 2012030217

表１から分かるように、触媒前駆体の１５０℃〜２００℃での質量減少率が１．８質量％よりも大きな触媒前駆体を熱処理した触媒は、メタクロレイン転化率が著しく低く、メタクリル酸収率も低い。一方、触媒前駆体の１５０℃〜２００℃での質量減少率が１．８質量％以下の触媒前駆体を熱処理した触媒は、メタクロレイン転化率が高く、高いメタクリル酸収率を示す。また、そのような触媒前駆体中の硝酸イオン量は窒素原子として０．２質量％以下であり、そのような触媒前駆体を得るためには、触媒調製時の触媒原料に含まれる硝酸イオンの量がモリブデン原子の量を１２モルとしたとき１．０モル未満となるようにすれば良いことがわかる。   As can be seen from Table 1, a catalyst obtained by heat-treating a catalyst precursor having a mass reduction rate from 150 ° C. to 200 ° C. larger than 1.8% by mass of the catalyst precursor has a significantly low methacrolein conversion rate and a methacrylic acid yield. The rate is also low. On the other hand, the catalyst which heat-processed the catalyst precursor whose mass reduction rate in 150 to 200 degreeC of a catalyst precursor is 1.8 mass% or less has a high methacrolein conversion rate, and shows a high methacrylic acid yield. Further, the amount of nitrate ions in such a catalyst precursor is 0.2% by mass or less as nitrogen atoms, and in order to obtain such a catalyst precursor, the nitrate ions contained in the catalyst raw material at the time of catalyst preparation It can be seen that the amount may be less than 1.0 mol when the amount of molybdenum atoms is 12 mol.

なお、触媒前駆体に含まれる硝酸イオンの量は、触媒調製時の触媒原料に含まれる硝酸イオンの量に限らず、触媒調製の条件によっても変化する。具体的には、アルカリ金属、アンモニウム塩添加時のスラリーの温度、アンモニウム原料の種類と混合比率、リン酸添加の時期等の条件により、スラリーｐＨが変化する。これにより、乾燥前のスラリー中に含まれるヘテロポリ酸の種類や量が変化し、乾燥操作において飛散する成分の量が変化するため、最終的に触媒前駆体に含まれる硝酸イオンの量はこれらの条件の影響を受けると推測される。   Note that the amount of nitrate ions contained in the catalyst precursor is not limited to the amount of nitrate ions contained in the catalyst raw material at the time of catalyst preparation, but also varies depending on the conditions for catalyst preparation. Specifically, the slurry pH varies depending on conditions such as the temperature of the slurry at the time of alkali metal and ammonium salt addition, the type and mixing ratio of the ammonium raw material, the timing of phosphoric acid addition, and the like. As a result, the type and amount of the heteropolyacid contained in the slurry before drying changes, and the amount of components scattered in the drying operation changes, so the amount of nitrate ions finally contained in the catalyst precursor is Presumed to be affected by conditions.

Claims (6)

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際に用いられる、モリブデン、バナジウム及びリンを触媒成分として含むメタクリル酸製造用触媒の製造方法において、
下記工程（Ｉ）から（Ｖ）
（Ｉ）モリブデン原料としての三酸化モリブデン、バナジウム原料及びリン原料を含む触媒原料を水中で混合しスラリーを調製後、該スラリーを乾燥し、触媒成分を含む粒子を製造する工程
（ＩＩ）前記粒子と、多糖類と、水又はアルコールとを混練りし、混練り体を製造する工程
（ＩＩＩ）前記混練り体を押出成形し、成形体を製造する工程
（ＩＶ）前記成形体を乾燥し、触媒前駆体を製造する工程
（Ｖ）前記触媒前駆体を熱処理する工程
を含み、
前記触媒前駆体の炭素原子含有量が２．０質量％以上であり、
前記触媒前駆体を空気気流下、昇温速度１０℃／ｍｉｎの条件の下で質量減少率を測定した際、１５０℃〜２００℃の範囲における質量減少率が、測定に用いた触媒前駆体の質量に対して１．８質量％以下であるメタクリル酸製造用触媒の製造方法。 In a method for producing a methacrylic acid production catalyst containing molybdenum, vanadium, and phosphorus as catalyst components, which is used in producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen,
The following steps (I) to (V)
(I) Step of producing particles containing catalyst components after mixing a catalyst raw material containing molybdenum trioxide as a molybdenum raw material, a vanadium raw material and a phosphorus raw material in water to prepare a slurry, and drying the slurry (II) The particles And kneading the polysaccharide and water or alcohol, producing the kneaded body (III) extruding the kneaded body, producing the molded body (IV) drying the molded body, A step of producing a catalyst precursor (V) comprising a step of heat-treating the catalyst precursor;
The carbon content of the catalyst precursor is 2.0% by mass or more,
When the mass reduction rate of the catalyst precursor was measured under a condition of a heating rate of 10 ° C./min under an air stream, the mass reduction rate in the range of 150 ° C. to 200 ° C. was the same as that of the catalyst precursor used for the measurement. The manufacturing method of the catalyst for methacrylic acid manufacture which is 1.8 mass% or less with respect to mass. 前記触媒前駆体に含まれる硝酸イオンの量が、窒素原子として０．２質量％以下である請求項１に記載のメタクリル酸製造用触媒の製造方法。   The method for producing a catalyst for methacrylic acid production according to claim 1, wherein the amount of nitrate ions contained in the catalyst precursor is 0.2 mass% or less as nitrogen atoms. 前記触媒原料に含まれる硝酸イオンの量が、該触媒原料に含まれるモリブデン原子の量を１２モルとしたとき、１．０モル未満である請求項１又は２に記載のメタクリル酸製造用触媒の製造方法。   3. The catalyst for producing methacrylic acid according to claim 1, wherein the amount of nitrate ions contained in the catalyst raw material is less than 1.0 mol when the amount of molybdenum atoms contained in the catalyst raw material is 12 mol. Production method. 前記工程（Ｖ）において、触媒前駆体を２００℃〜６００℃の範囲で熱処理する請求項１から３のいずれか１項に記載のメタクリル酸製造用触媒の製造方法。   The method for producing a methacrylic acid production catalyst according to any one of claims 1 to 3, wherein in the step (V), the catalyst precursor is heat-treated in a range of 200 ° C to 600 ° C. 請求項１から４のいずれか１項に記載の方法により製造されるメタクリル酸製造用触媒。   The catalyst for methacrylic acid manufacture manufactured by the method of any one of Claim 1 to 4. 請求項５に記載の触媒の存在下、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メタクリル酸の製造方法。   A method for producing methacrylic acid, wherein methacrolein is subjected to gas phase catalytic oxidation with molecular oxygen in the presence of the catalyst according to claim 5 to produce methacrylic acid.
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