JP4875480B2 - Method for producing metal-containing catalyst - Google Patents
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本発明は、プロピレン、イソブチレンまたは第三級ブチルアルコール（以下、ＴＢＡともいう）やメチル第三級ブチルエーテル（以下、ＭＴＢＥともいう）を分子状酸素を用いて気相接触酸化することにより、それぞれに対応する不飽和アルデヒド及び不飽和カルボン酸を合成する際に使用する金属含有触媒の製造方法に関する。 In the present invention, propylene, isobutylene, tertiary butyl alcohol (hereinafter also referred to as TBA) or methyl tertiary butyl ether (hereinafter also referred to as MTBE) is vapor-phase catalytically oxidized using molecular oxygen, respectively. The present invention relates to a method for producing a metal-containing catalyst used in the synthesis of a corresponding unsaturated aldehyde and unsaturated carboxylic acid.
従来から、プロピレンを気相接触酸化してアクロレイン及びアクリル酸を製造する際に用いる触媒や、イソブチレン又はＴＢＡや、ＭＴＢＥ等を気相接触酸化してメタクロレイン及びメタクリル酸を製造する際に用いる触媒としてモリブデン、ビスマス、鉄等の酸化物が使用されている。これらの金属の触媒成分は、その調製において調製条件の僅かな相違により化学的性質、物理的性質を大きく変えることから、二種類以上の水溶液に金属化合物を溶解又は分散させ、これらを滴下混合し、加熱攪拌下で濃縮乾固し、焼成して調製している。しかしながら、これらの調製過程において、混合する溶液温度、濃度、ｐＨ、混合順序、滴下速度、攪拌速度、沈殿槽の大きさ、形状等、種々の条件の微妙な相違により、脱水、核生成、吸着、沈殿、再溶解等複雑な液相又は固液相反応が生じ、生成される触媒の性能にバラツキが生じる。不飽和アルデヒド及び不飽和カルボン酸を安定して製造するため、安定した触媒性能を有する触媒の製造方法については数多くの提案がなされている。例えば、触媒成分を含む溶液を混合したときのｐＨが５以下となるよう硝酸を該溶液に加える方法（特許文献１）、モリブデンを必須成分として含み、ｐＨが６以上である金属元素含有スラリーと硝酸で溶解したビスマス化合物を混合する方法（特許文献２）等が報告されている。 Conventionally, catalysts used for producing acrolein and acrylic acid by vapor-phase catalytic oxidation of propylene, and catalysts used for producing methacrolein and methacrylic acid by vapor-phase catalytic oxidation of isobutylene, TBA, MTBE, etc. Oxides such as molybdenum, bismuth and iron are used. These metal catalyst components greatly change chemical and physical properties due to slight differences in preparation conditions in the preparation thereof, so that the metal compound is dissolved or dispersed in two or more aqueous solutions, and these are mixed dropwise. It is prepared by concentrating to dryness under heating and stirring and firing. However, in these preparation processes, dehydration, nucleation, and adsorption are caused by subtle differences in various conditions such as the temperature, concentration, pH, mixing order, dropping speed, stirring speed, size and shape of the precipitation tank. Complex liquid phase or solid-liquid phase reactions such as precipitation and re-dissolution occur, and the performance of the produced catalyst varies. In order to stably produce unsaturated aldehydes and unsaturated carboxylic acids, many proposals have been made on methods for producing catalysts having stable catalyst performance. For example, a method of adding nitric acid to the solution so that the pH when the solution containing the catalyst component is mixed is 5 or less (Patent Document 1), a metal element-containing slurry containing molybdenum as an essential component and having a pH of 6 or more A method of mixing a bismuth compound dissolved in nitric acid (Patent Document 2) has been reported.
しかしながら、現在知られている不飽和アルデヒド及び不飽和カルボン酸の合成用触媒は、収率の点でまだ十分とは言い難く、不飽和アルデヒド及び不飽和カルボン酸を安定して高収率で得ることができる触媒の製造方法の開発が望まれている。
本発明の課題は、不飽和アルデヒド及び不飽和カルボン酸を高収率で製造可能な触媒の製造方法を提供することである。 The subject of this invention is providing the manufacturing method of the catalyst which can manufacture unsaturated aldehyde and unsaturated carboxylic acid with a high yield.
本発明者らは上記課題を解決すべく、鋭意研究を重ねた。その結果、触媒成分のうち、II価の金属を分散又は溶解し、特定のｐＨを有するように調整した液と、モリブデンを分散又は溶解した液を混合して金属含有液を調製し、これを用いて金属含有触媒を調製することにより、安定して高収率で不飽和アルデヒド及び不飽和カルボン酸を得ることができることを見い出し本発明を完成するに至った。 The inventors of the present invention have made extensive studies to solve the above problems. As a result, among the catalyst components, a metal-containing liquid was prepared by mixing a liquid prepared by dispersing or dissolving a divalent metal and adjusting the pH so as to have a specific pH and a liquid obtained by dispersing or dissolving molybdenum. It was found that an unsaturated aldehyde and an unsaturated carboxylic acid can be stably obtained in a high yield by preparing a metal-containing catalyst by using the catalyst, and the present invention has been completed.
本発明は、プロピレン、イソブチレン、第三級ブチルアルコール又はメチル第三級ブチルエーテルを分子状酸素を用いて気相接触酸化することにより、それぞれに対応する不飽和アルデヒド及び不飽和カルボン酸を合成する際に使用される、少なくとも、モリブデン、ビスマス、並びに、Ｆｅ、Ｃｏ、Ｎｉ及びＰｂから選ばれるＩＩ価の金属を含む金属含有触媒の製造方法であって、金属含有触媒を構成する前記ＩＩ価の金属を分散又は溶解し、アルカリを加えてｐＨを０．５〜３．５に調整してＩＩ価金属含有液（Ａ液）を調製する工程と、少なくともモリブデンを分散又は溶解したモリブデン含有液（Ｂ液）を調製する工程と、前記ＩＩ価金属含有液（Ａ液）と前記モリブデン含有液（Ｂ液）とを混合して、金属含有液を調製する工程とを有することを特徴とする金属含有触媒の製造方法に関する。 In the present invention, propylene, isobutylene, tertiary butyl alcohol or methyl tertiary butyl ether is subjected to gas phase catalytic oxidation using molecular oxygen to synthesize the corresponding unsaturated aldehyde and unsaturated carboxylic acid. A method for producing a metal-containing catalyst containing at least molybdenum, bismuth , and a divalent metal selected from Fe, Co, Ni, and Pb , which is used in the above-mentioned method, and which constitutes the metal-containing catalyst And a step of preparing a divalent metal-containing liquid (liquid A) by adjusting the pH to 0.5 to 3.5 by adding an alkali, and a molybdenum-containing liquid (B) in which at least molybdenum is dispersed or dissolved. Liquid), the step of preparing the metal-containing liquid by mixing the II-valent metal-containing liquid (liquid A) and the molybdenum-containing liquid (liquid B), Method for producing a metal-containing catalyst, characterized in that it comprises about.
本発明の金属含有触媒の製造方法は、不飽和アルデヒド及び不飽和カルボン酸を安定して高収率で得ることができる触媒を容易に製造することができる。本発明の金属含有触媒を用いることにより、不飽和アルデヒド及び不飽和カルボン酸を安定して高収率で得ることができる。 The method for producing a metal-containing catalyst of the present invention can easily produce a catalyst capable of stably obtaining an unsaturated aldehyde and an unsaturated carboxylic acid in a high yield. By using the metal-containing catalyst of the present invention, an unsaturated aldehyde and an unsaturated carboxylic acid can be stably obtained in a high yield.
本発明の金属含有触媒の製造方法により製造される触媒は、プロピレン、イソブチレン、ＴＢＡ、ＴＢＡ又はＭＴＢＥを分子状酸素を用いて気相接触酸化し、それぞれに対応する不飽和アルデヒド及び不飽和カルボン酸の合成用であり、少なくともモリブデン、ビスマス及びII価の金属を含むものである。かかる金属含有触媒としては、更に、鉄、コバルト、ニッケルや、アルカリ金属、タリウム等を含有することが好ましい。具体的には、原子の組成式（１）
ＭｏaＢｉbＦｅcＭdＸeＹfＺgＳｉhＯi （１）
で表される組成物であることが、高収率で不飽和アルデヒド及び不飽和カルボン酸を得られるため好ましい。組成式（１）中、Ｍはコバルト又はニッケルの何れか１種又は２種を示す。Ｘは、クロム、鉛、マンガン、カルシウム、マグネシウム、ニオブ、銀、バリウム、スズ、タンタル、又は亜鉛の何れか１種又は２種以上を示す。Ｙは、リン、ホウ素、硫黄、セレン、テルル、セリウム、タングステン、アンチモン、又はよびチタンの何れか１種又は２種以上を示す。Ｚは、リチウム、ナトリウム、カリウム、ルビジウム、セシウム、又はよびタリウムの何れか１種又は２種以上を示す。更に、ａ〜ｉは原子組成比を示し、ａが１２のとき、ｂは０．０１〜３、ｃは０．０１〜５、ｄは１〜１２、ｅは０〜８、ｆは０〜５、ｇは０．００１〜２、ｈは０〜２０であり、ｉは金属原子全体の原子価を満足するのに必要な酸素原子比を示す。
The catalyst produced by the method for producing a metal-containing catalyst of the present invention is obtained by subjecting propylene, isobutylene, TBA, TBA or MTBE to gas phase catalytic oxidation using molecular oxygen, and corresponding unsaturated aldehyde and unsaturated carboxylic acid. And containing at least molybdenum, bismuth and a divalent metal. The metal-containing catalyst preferably further contains iron, cobalt, nickel, alkali metal, thallium and the like. Specifically, atomic composition formula (1)
Mo a Bi b Fe c M d X e Y f Z g Si h O i (1)
It is preferable that an unsaturated aldehyde and an unsaturated carboxylic acid can be obtained in a high yield. In the composition formula (1), M represents one or two of cobalt and nickel. X represents one or more of chromium, lead, manganese, calcium, magnesium, niobium, silver, barium, tin, tantalum, or zinc. Y represents one or more of phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony, and titanium. Z represents one or more of lithium, sodium, potassium, rubidium, cesium, and thallium. Further, a to i represent an atomic composition ratio. When a is 12, b is 0.01 to 3, c is 0.01 to 5, d is 1 to 12, e is 0 to 8, and f is 0 to 0. 5, g is 0.001-2, h is 0-20, i represents the oxygen atom ratio required to satisfy the valence of the entire metal atom.
本発明の金属含有触媒の製造方法は、金属含有触媒を構成するII価の金属を分散又は溶解し、アルカリを加えてｐＨを０．５〜３．５に調整してII価金属含有液（Ａ液）を調製する工程と、少なくともモリブデンを分散又は溶解したモリブデン含有液（Ｂ液）を調製する工程と、前記II価金属含有液（Ａ液）と前記モリブデン含有液（Ｂ液）とを混合して金属含有液を調製する工程とを有する。 In the method for producing a metal-containing catalyst of the present invention, a II-valent metal constituting the metal-containing catalyst is dispersed or dissolved, an alkali is added to adjust the pH to 0.5 to 3.5, and a II-valent metal-containing liquid ( A step of preparing a liquid A), a step of preparing a molybdenum-containing liquid (liquid B) in which at least molybdenum is dispersed or dissolved, the II-valent metal-containing liquid (liquid A), and the molybdenum-containing liquid (liquid B). And preparing a metal-containing liquid by mixing.
上記ＩＩ価金属含有液（Ａ液）の調製において用いるＩＩ価の金属は、Ｆｅ、Ｃｏ、Ｎｉ及びＰｂから選ばれるＩＩ価の金属である。これらのＩＩ価の金属は金属塩、例えば、硫酸塩、硝酸塩、炭酸塩及び水酸化物等として使用することができるが、媒体に溶解するものが好ましく、また、金属塩の分解後、金属原子以外の成分が残らない点から、硝酸塩が好ましい。媒体としては、いずれであってもよいが、水、低級アルコール等を単独または混合したものが、上記ＩＩ価金属の金属塩に対する溶解度が高く、取り扱いが容易であることから好ましい。これらの媒体を用いたＩＩ価金属を含有するＡ液は、ＩＩ価金属を溶解した溶液であっても、分散した分散液、スラリーであってもよいが、溶液であることが、安定した触媒性能を有するものとなるため、好ましい。Ａ液中のＩＩ価金属原子の含有量は、モリブデン原子１ｍｏｌに対し、０．６７〜３．０８ｍｏｌであることが好ましい。ＩＩ価金属含有液（Ａ液）中には、ＩＩ価金属以外の金属を含んでいてもよいが、ＩＩ価金属以外の金属の含有量は少ない方が好ましい。 The II-valent metal used in the preparation of the II-valent metal-containing liquid (A liquid) is a II-valent metal selected from Fe, Co, Ni and Pb. These divalent metals can be used as metal salts such as sulfates, nitrates, carbonates and hydroxides, but those which are soluble in the medium are preferred, and after decomposition of the metal salt, a metal atom Nitrate is preferable because no other components remain. Any medium may be used as the medium, but water, lower alcohol, or the like, alone or in combination, is preferable because of its high solubility in the metal salt of the divalent metal and easy handling. The liquid A containing the divalent metal using these media may be a solution in which the divalent metal is dissolved, or may be a dispersed dispersion or a slurry. Since it has performance, it is preferable. The content of the II-valent metal atom in the liquid A is preferably 0.67 to 3.08 mol with respect to 1 mol of the molybdenum atom. The II-valent metal-containing liquid (A liquid) may contain a metal other than the II-valent metal, but it is preferable that the content of the metal other than the II-valent metal is small.
上記II価金属含有液（Ａ液）はｐＨを０．５以上３．５以下、好ましくは１．０以上で３．０以下に調整する。II価金属含有液のｐＨがこの範囲であれば、触媒活性が安定して優れたものを得ることができる。II価金属含有液のｐＨの調整には、例えば、アンモニア、ヒドラジン、ヒドロキシルアミン、アルカリ金属化合物、アルカリ土類金属化合物などのアルカリを用いる。 The above-mentioned II-valent metal-containing liquid (A liquid) is adjusted to a pH of 0.5 to 3.5, preferably 1.0 to 3.0. When the pH of the II-valent metal-containing liquid is within this range, a catalyst having a stable and excellent catalytic activity can be obtained. The adjustment of the pH of II valent metal-containing solution, if example embodiment, ammonia, hydrazine, hydroxylamine, an alkali metal compound, Ru with an alkali such as an alkaline earth metal compound.
このようなII価金属含有液（Ａ液）は、これらの金属塩の所定量を媒体に加え、加熱攪拌して調製することができる。加熱温度は、４０〜１００℃が好ましく、５０〜８０℃がさらに好ましい。上記アルカリを加え攪拌することで、ｐＨを調整することができる。II価の金属として硝酸塩を用い、アルカリでｐＨ調整してII価金属含有液（Ａ液）を調製するのが好ましい。 Such a II-valent metal-containing liquid (A liquid) can be prepared by adding a predetermined amount of these metal salts to a medium and heating and stirring. The heating temperature is preferably 40-100 ° C, more preferably 50-80 ° C. By stirring was added over SL alkali, it is possible to adjust the pH. It is preferable to prepare a divalent metal-containing liquid (liquid A) by using nitrate as the divalent metal and adjusting the pH with an alkali.
本発明の金属含有触媒の製造方法において、モリブデン含有（Ｂ液）を調製する。モリブデン含有液（Ｂ液）の調製に当たり、モリブデン原料としては、アンモニウム塩や酸化物が好適に使用でき、例えば、前者はモリブデン酸アンモニウム、後者は三酸化モリブデンを用いることができる。媒体としてはII価金属含有液に用いる媒体に限定されずいずれであってもよいが、水、低級アルコール等を単独又は混合したものが、モリブデン塩に対する溶解度が高く、取り扱いが容易であることから好ましい。これらの媒体を用いたモリブデンを含有するＢ液は、モリブデンを溶解した溶液であっても、分散した分散液、スラリーであってもよい。Ｂ液中のモリブデンの含有量は、２０〜８０質量％であることが好ましい。モリブデン含有液（Ｂ液）中には、モリブデン以外の金属を含有していてもよいが、媒体に不要又は難溶の金属塩等はＡ液よりＢ液に含有することが好ましい。 In the method for producing a metal-containing catalyst of the present invention, molybdenum-containing (liquid B) is prepared. In preparing the molybdenum-containing liquid (liquid B), ammonium salts and oxides can be suitably used as the molybdenum raw material. For example, the former can be ammonium molybdate, and the latter can be molybdenum trioxide. The medium is not limited to the medium used for the divalent metal-containing liquid, and any medium may be used, but water, a lower alcohol, etc., alone or mixed, has high solubility in molybdenum salt and is easy to handle. preferable. Liquid B containing molybdenum using these media may be a solution in which molybdenum is dissolved, or a dispersed dispersion or slurry. The molybdenum content in the B liquid is preferably 20 to 80% by mass. The molybdenum-containing liquid (liquid B) may contain a metal other than molybdenum, but it is preferable that a metal salt that is unnecessary or hardly soluble in the medium is contained in liquid B rather than liquid A.
このようなモリブデン含有液（Ｂ液）は、モリブデン塩の所定量を媒体に加え、加熱攪拌して調製することができる。加熱温度は、４０〜１００℃が好ましく、５０〜８０℃がさらに好ましい。 Such a molybdenum-containing liquid (liquid B) can be prepared by adding a predetermined amount of molybdenum salt to a medium and heating and stirring. The heating temperature is preferably 40-100 ° C, more preferably 50-80 ° C.
本発明の金属含有触媒の製造方法においては、次いでＡ液とＢ液を混合して金属含有液を調製する工程を有する。Ａ液とＢ液の混合方法は特に限定されず、Ａ液にＢ液を投入してもよいし、Ｂ液にＡ液を投入してもよいし、Ａ液とＢ液を同時に混合してもよい。混合の際には、Ａ液、Ｂ液ともに攪拌しておくことが好ましい。Ａ液とＢ液を混合する際の液温度は、Ａ液及びＢ液を調製した温度、４０〜１００℃が好ましく、５０〜８０℃がさらに好ましい。Ａ液とＢ液の混合によって得られた触媒前駆体スラリーは、混合後、８０〜１０５℃の温度で、少なくとも０．５時間以上加熱攪拌することが均質化した触媒構造を有する優れた触媒性能の触媒が得られるため、好ましい。混合後の金属含有液のｐＨは２〜５が好ましい。 In the manufacturing method of the metal containing catalyst of this invention, it has the process of mixing A liquid and B liquid then, and preparing a metal containing liquid. The mixing method of A liquid and B liquid is not specifically limited, B liquid may be thrown into A liquid, A liquid may be thrown into B liquid, and A liquid and B liquid are mixed simultaneously. Also good. In mixing, it is preferable to stir both liquid A and liquid B. The liquid temperature at the time of mixing A liquid and B liquid, the temperature which prepared A liquid and B liquid, 40-100 degreeC is preferable and 50-80 degreeC is more preferable. The catalyst precursor slurry obtained by mixing the A liquid and the B liquid has excellent catalyst performance having a homogenized catalyst structure that is heated and stirred at a temperature of 80 to 105 ° C. for at least 0.5 hours after mixing. Since the catalyst of this is obtained, it is preferable. The pH of the metal-containing liquid after mixing is preferably 2-5.
上記II価金属含有液（Ａ液）とモリブデン含有液（Ｂ液）の混合割合としては、Ａ液、Ｂ液中の各金属の含有割合から上記金属含有触媒が得られるような混合比であればよいが、例えば、Ａ液とＢ液の容積比が、Ａ液：Ｂ液として１．０：０．２〜１．０：０．５等を挙げることができる。 The mixing ratio of the II-valent metal-containing liquid (liquid A) and the molybdenum-containing liquid (liquid B) should be such that the metal-containing catalyst can be obtained from the content ratio of each metal in liquid A and liquid B. For example, the volume ratio of the A liquid and the B liquid may be 1.0: 0.2 to 1.0: 0.5 as the A liquid: B liquid.
Ａ液とＢ液を混合して調製された金属含有液は、次いで乾燥、焼成することができる。金属含有液の乾燥方法は、例えば、スプレードライヤー、スラリードライヤー、ドラムドライヤーを用いる方法や、蒸発乾固して塊状の乾燥物を粉砕する方法等を適用することができる。中でも、乾燥と同時に粒子が得られる点、得られる金属含有粒子の形状が触媒として好適な球形である点から、スプレー乾燥機を用いて乾燥球状粒子を得ることが好ましい。乾燥条件は乾燥方法により異なるが、スプレー乾燥機を用いる場合、入口温度は、例えば１００〜５００℃、出口温度は例えば１００℃以上、好ましくは１０５〜２００℃等とすることができる。 The metal-containing liquid prepared by mixing the A liquid and the B liquid can then be dried and fired. As a method for drying the metal-containing liquid, for example, a method using a spray dryer, a slurry dryer, or a drum dryer, a method of pulverizing a lump-like dried product by evaporation to dryness, or the like can be applied. Especially, it is preferable to obtain dry spherical particles using a spray dryer from the point that particles are obtained simultaneously with drying and the shape of the obtained metal-containing particles is a suitable spherical shape as a catalyst. Although the drying conditions vary depending on the drying method, when a spray dryer is used, the inlet temperature can be, for example, 100 to 500 ° C, and the outlet temperature can be, for example, 100 ° C or higher, preferably 105 to 200 ° C.
このようにして得られた乾燥粒子を焼成してもよい。乾燥粒子は金属塩等に由来する硝酸等が残留する場合があり、焼成してこれらの残留塩を分解除去し、金属含有粒子を金属酸化物の焼成粒子とすると、触媒として成形した成形体において強度を有し、取り扱いが容易なことから好ましい。焼成条件は例えば２００〜６００℃の温度範囲で行うことができ、焼成時間は目的とする触媒によって適宜選択される。 The dry particles thus obtained may be fired. In the dried particles, nitric acid or the like derived from metal salts or the like may remain, and when fired to decompose and remove these residual salts, the metal-containing particles are fired particles of metal oxide. It is preferable because it has strength and is easy to handle. The calcination conditions can be performed in a temperature range of 200 to 600 ° C., for example, and the calcination time is appropriately selected depending on the target catalyst.
更に、焼成粒子を触媒成形体に成形してもよい。焼成粒子は担持体に担持させた後成形してもよい。焼成粒子を担持体に担持させるには、焼成粒子と担体成分とを必要に応じて加熱、混合して形成することができる。担体成分としては、シリカ、アルミナ、シリカ−アルミナ、マグネシア、チタニア等を用いることができる。 Furthermore, the fired particles may be formed into a catalyst molded body. The fired particles may be molded after being supported on a support. In order to carry the fired particles on the carrier, the fired particles and the carrier component can be heated and mixed as necessary. As the carrier component, silica, alumina, silica-alumina, magnesia, titania and the like can be used.
更に、触媒成形体を製造する際、その他の添加剤として、例えば、ポリビニルアルコール、カルボキシメチルセルロース等の有機化合物、グラファイトやケイソウ土等の無機化合物、ガラス繊維、セラミックファイバーや炭素繊維等の無機ファイバーを添加してもよい。 Furthermore, when manufacturing a catalyst molded body, as other additives, for example, organic compounds such as polyvinyl alcohol and carboxymethyl cellulose, inorganic compounds such as graphite and diatomaceous earth, inorganic fibers such as glass fibers, ceramic fibers and carbon fibers. It may be added.
触媒成形体を成形する方法としては、上記焼成粒子或いは、これを担持体に担持させた焼成粒子と、必要に応じて添加する添加物とを混合し、打錠成型機、押出成形機、転動造粒機等の粉体用成形機を用いて、球状、リング状、円柱状、星型状等の任意の形状に成形する方法を挙げることができる。上記のようにして得られた触媒の成形体を再度焼成してもよい。焼成は、例えば、通常２００〜６００℃の温度範囲で行うことができる。 As a method for forming a catalyst molded body, the above-mentioned calcined particles or the calcined particles carried on a carrier and the additives to be added as necessary are mixed, and a tableting molding machine, an extrusion molding machine, a rolling machine are mixed. Examples thereof include a method of forming into an arbitrary shape such as a spherical shape, a ring shape, a cylindrical shape, or a star shape using a powder molding machine such as a dynamic granulator. The molded article of the catalyst obtained as described above may be fired again. Firing can be performed, for example, in a temperature range of usually 200 to 600 ° C.
上記方法により製造された金属含有触媒の存在下、原料のプロピレン、イソブチレン、ＴＢＡ又はＭＴＢＥを分子状酸素と気相接触反応させることにより不飽和アルデヒド及び不飽和カルボン酸を製造することができる。かかる気相接触反応は、触媒を充填した管式反応器を使用することが好ましく、多管式反応器を用いることができる。 Unsaturated aldehydes and unsaturated carboxylic acids can be produced by subjecting raw material propylene, isobutylene, TBA or MTBE to gas phase catalytic reaction with molecular oxygen in the presence of the metal-containing catalyst produced by the above method. For this gas phase contact reaction, it is preferable to use a tubular reactor filled with a catalyst, and a multitubular reactor can be used.
原料ガスの分子状酸素としては、空気を用いるのが工業的に有利であるが、必要に応じて純酸素を混合して用いることもできる。原料ガスは、窒素、炭酸ガス等の不活性ガス、水蒸気等で希釈して使用することが経済的である。原料ガス中のプロピレン等の濃度は広い範囲で変えることができ、例えば、１〜２０容量％とすることができ、好ましくは３〜１０容量％である。原料ガス中のプロピレン等と分子状酸素のモル比は１：０．５〜３の範囲が好ましい。原料ガス中のプロピレン等と分子状酸素のモル比は１：０．５〜３の範囲が好ましい。反応器中に充填する上記金属含有触媒は、シリカ、アルミナ、シリカ−アルミナ、シリコンカーバイト、セラミックボールやステンレス鋼等の不活性物質で希釈して用いることもできる。反応圧力は常圧から数気圧までがよい。反応温度は２００〜４５０℃の範囲で選択することができるが、特に、２５０〜４００℃の範囲が好ましい。原料ガスと触媒との接触時間は０．５〜１０秒が好ましく、より好ましくは１〜５秒である。 Although it is industrially advantageous to use air as the molecular oxygen of the source gas, pure oxygen can be mixed and used as necessary. It is economical to use the source gas diluted with an inert gas such as nitrogen or carbon dioxide, water vapor or the like. The concentration of propylene or the like in the raw material gas can be varied within a wide range, and can be, for example, 1 to 20% by volume, preferably 3 to 10% by volume. The molar ratio between propylene and the like in the source gas and molecular oxygen is preferably in the range of 1: 0.5-3. The molar ratio between propylene and the like in the source gas and molecular oxygen is preferably in the range of 1: 0.5-3. The metal-containing catalyst filled in the reactor can be diluted with an inert substance such as silica, alumina, silica-alumina, silicon carbide, ceramic balls, and stainless steel. The reaction pressure is preferably from normal pressure to several atmospheres. The reaction temperature can be selected in the range of 200 to 450 ° C., but the range of 250 to 400 ° C. is particularly preferable. The contact time between the raw material gas and the catalyst is preferably 0.5 to 10 seconds, more preferably 1 to 5 seconds.
このような気相接触反応により、原料ガスとしてプロピレンを用いた場合は、アクロレイン及びアクリル酸を、原料ガスとしてイソブチレン、ＴＢＡ、ＭＴＢＥを用いた場合、メタクロレイン及びメタクリル酸を高収率で合成することができる。 By such a gas phase contact reaction, when propylene is used as the raw material gas, acrolein and acrylic acid are synthesized, and when isobutylene, TBA, and MTBE are used as the raw material gas, methacrolein and methacrylic acid are synthesized in a high yield. be able to.
以下、本発明の金属含有触媒の製造方法による触媒の製造例及びその触媒を用いた反応例を具体的に説明する。以下実施例において、「部」は「質量部」を示す。 Hereinafter, a catalyst production example by the method for producing a metal-containing catalyst of the present invention and a reaction example using the catalyst will be specifically described. In the following examples, “part” means “part by mass”.
原料ガス及び生成物の分析はガスクロマトグラフィーによる。ｐＨ測定には、堀場製作所製Ｄ−２１ｐＨメーターを使用した。 Source gas and product analysis is by gas chromatography. A D-21 pH meter manufactured by Horiba, Ltd. was used for pH measurement.
原料オレフィン、ＴＢＡ又はＭＴＢＥの反応率、生成する不飽和アルデヒド及び不飽和カルボン酸の選択率、生成する不飽和アルデヒド及び不飽和カルボン酸の合計収率（以下、合計収率という。）は次式により算出した。 The reaction rate of the raw material olefin, TBA or MTBE, the selectivity of the unsaturated aldehyde and unsaturated carboxylic acid produced, and the total yield of the unsaturated aldehyde and unsaturated carboxylic acid produced (hereinafter referred to as the total yield) are: Calculated by
反応率（％）＝（Ｍｒ／Ｍｓ）×１００
不飽和アルデヒドの選択率（％）＝（Ｐａ／Ｍｒ）×１００
不飽和カルボン酸の選択率（％）＝（Ｐｃ／Ｍｒ）×１００
合計収率（％）＝｛（Ｐａ＋Ｐｃ）／Ｍｓ｝×１００。
Reaction rate (%) = (Mr / Ms) × 100
Selectivity of unsaturated aldehyde (%) = (Pa / Mr) × 100
Selectivity of unsaturated carboxylic acid (%) = (Pc / Mr) × 100
Total yield (%) = {(Pa + Pc) / Ms} × 100.
式中、Ｍｒは反応したプロピレン、イソブチレン、ＴＢＡ、ＭＴＢＥのモル数、Ｍｓは供給したプロピレン、イソブチレン、ＴＢＡ、ＭＴＢＥのモル数、Ｐａは生成した不飽和アルデヒドのモル数、Ｐｃは生成した不飽和カルボン酸のモル数である。
〔実施例１〕
［触媒の調製］
室温の純水１０００部に、硝酸第二鉄２０９．８部、硝酸ニッケル７５．５部、硝酸コバルト４５３．３部、硝酸鉛３１．３部及び８５％リン酸５．６部を順次加え、溶解した。さらに、２８％アンモニア水１２．０部を加え、ｐＨ１．５に調整し、II価金属含有液（Ａ液）を調製した。
これとは別に、６０℃の純水１０００部に、パラモリブデン酸アンモニウム５００部、パラタングステン酸アンモニウム１２．４部、硝酸セシウム２３．０部、三酸化アンチモン２７．４部及び三酸化ビスマス３３．０部を加え、攪拌し、モリブデン含有液（Ｂ液）を調製した。このとき、Ｂ液のｐＨは５．８であった。
調製したＡ液とＢ液とを混合し金属含有液を得た。この金属含有液のｐＨは３．８であった。
その後、この金属含有液を９５℃に加熱、攪拌しながら１．５時間熱処理し、回転円板型遠心アトマイザーを備えたスプレー乾燥機にて噴霧乾燥した。このとき、スプレー乾燥機のアトマイザーの回転数は１１０００ｒｐｍであり、入口温度は１６５℃であり、出口温度は１２５℃であった。
このようにして得た乾燥球状粒子をロータリーキルンを用いて空気雰囲気下３００℃で1時間焼成を行い触媒焼成粉とし、加圧成型した。その後再び空気雰囲気下５００℃で６時間焼成し、金属含有触媒を得た。得られた金属含有触媒の組成を測定した。金属含有触媒の酸素原子以外の原子の組成は、Ｍｏ12Ｗ0.2Ｂｉ0.6Ｆｅ2.2Ｓｂ0.8Ｎｉ1.1Ｃｏ6.6Ｐｂ0.4Ｐ0.2Ｃｓ0.5であった。
In the formula, Mr is the number of moles of reacted propylene, isobutylene, TBA, MTBE, Ms is the number of moles of propylene, isobutylene, TBA, MTBE supplied, Pa is the number of moles of unsaturated aldehyde produced, and Pc is the unsaturated produced. The number of moles of carboxylic acid.
[Example 1]
[Preparation of catalyst]
To 1000 parts of pure water at room temperature, 209.8 parts of ferric nitrate, 75.5 parts of nickel nitrate, 453.3 parts of cobalt nitrate, 31.3 parts of lead nitrate, and 5.6 parts of 85% phosphoric acid were sequentially added. Dissolved. Furthermore, 12.0 parts of 28% ammonia water was added to adjust the pH to 1.5 to prepare a II-valent metal-containing liquid (A liquid).
Separately from this, 1000 parts of pure water at 60 ° C., 500 parts of ammonium paramolybdate, 12.4 parts of ammonium paratungstate, 23.0 parts of cesium nitrate, 27.4 parts of antimony trioxide and 33. 0 parts was added and stirred to prepare a molybdenum-containing liquid (liquid B). At this time, pH of the B liquid was 5.8.
The prepared liquid A and liquid B were mixed to obtain a metal-containing liquid. The pH of this metal-containing liquid was 3.8.
Thereafter, this metal-containing liquid was heated to 95 ° C. and heat-treated for 1.5 hours with stirring, and spray-dried with a spray dryer equipped with a rotating disk centrifugal atomizer. At this time, the rotation speed of the atomizer of the spray dryer was 11000 rpm, the inlet temperature was 165 ° C., and the outlet temperature was 125 ° C.
The dry spherical particles thus obtained were calcined for 1 hour at 300 ° C. in an air atmosphere using a rotary kiln to obtain a catalyst calcined powder, which was pressure-molded. Thereafter, it was again fired at 500 ° C. for 6 hours in an air atmosphere to obtain a metal-containing catalyst. The composition of the obtained metal-containing catalyst was measured. The composition of atoms other than oxygen atoms in the metal-containing catalyst was Mo 12 W 0.2 Bi 0.6 Fe 2.2 Sb 0.8 Ni 1.1 Co 6.6 Pb 0.4 P 0.2 Cs 0.5 .
［不飽和アルデヒド及び不飽和カルボン酸の調製］
得られた触媒をステンレス製反応管に充填し、これにイソブチレン５容量％、分子状酸素１２容量％、水蒸気１０容量％及び窒素７３容量％の原料ガスを供給し、常圧下、接触時間３．６秒、反応温度３４０℃の条件で反応させ、イソブチレンを分子状酸素により気相接触酸化した。その結果、イソブチレンの反応率９５．３％、メタクロレインの選択率８９．９％、メタクリル酸の選択率２．６％、合計収率８８．２％であった。
〔実施例２〕
実施例１において、Ａ液の調製時に２８％アンモニア水１２．０部に替え９．０部を加え、ｐＨ０．８に調整した以外は、実施例１と同様にして触媒を製造し、同様の条件で不飽和アルデヒド及び不飽和カルボン酸を製造した。
[Preparation of unsaturated aldehyde and unsaturated carboxylic acid]
The obtained catalyst is filled in a stainless steel reaction tube, and a raw material gas of 5% by volume of isobutylene, 12% by volume of molecular oxygen, 10% by volume of water vapor, and 73% by volume of nitrogen is supplied to the reaction tube. The reaction was carried out for 6 seconds at a reaction temperature of 340 ° C., and isobutylene was vapor-phase contact oxidized with molecular oxygen. As a result, the reaction rate of isobutylene was 95.3%, the selectivity of methacrolein was 89.9%, the selectivity of methacrylic acid was 2.6%, and the total yield was 88.2%.
[Example 2]
In Example 1, a catalyst was produced in the same manner as in Example 1 except that 9.0 parts was added in place of 12.0 parts of 28% aqueous ammonia at the time of preparation of solution A and the pH was adjusted to 0.8. Under the conditions, an unsaturated aldehyde and an unsaturated carboxylic acid were produced.
その結果、イソブチレンの反応率９５．２％、メタクロレインの選択率８９．４％、メタクリル酸の選択率２．６％、合計収率８７．７％であった。 As a result, the reaction rate of isobutylene was 95.2%, the selectivity of methacrolein was 89.4%, the selectivity of methacrylic acid was 2.6%, and the total yield was 87.7%.
〔実施例３〕
実施例１において、Ａ液の調製時に２８％アンモニア水１２．０部に替え２４．０部を加え、ｐＨ３．２に調整した以外は、実施例１と同様にして触媒を製造し、同様の条件で不飽和アルデヒド及び不飽和カルボン酸を製造した。
Example 3
In Example 1, a catalyst was produced in the same manner as in Example 1 except that 14.0 parts of 28% aqueous ammonia was added and 24.0 parts were added to adjust the pH to 3.2. Under the conditions, an unsaturated aldehyde and an unsaturated carboxylic acid were produced.
その結果、イソブチレンの反応率９５．１％、メタクロレインの選択率８９．５％、メタクリル酸の選択率２．６％、合計収率８７．６％であった。 As a result, the reaction rate of isobutylene was 95.1%, the selectivity of methacrolein was 89.5%, the selectivity of methacrylic acid was 2.6%, and the total yield was 87.6%.
〔比較例１〕
実施例１において、Ａ液の調製時にアンモニア水を加えない以外は、実施例１と同様にして触媒を製造し、同様の条件で不飽和アルデヒド及び不飽和カルボン酸を製造した。Ａ液のｐＨは０．１であった。
[Comparative Example 1]
In Example 1, a catalyst was produced in the same manner as in Example 1 except that ammonia water was not added at the time of preparing the liquid A, and an unsaturated aldehyde and an unsaturated carboxylic acid were produced under the same conditions. The pH of the liquid A was 0.1.
その結果、イソブチレンの反応率９５．１％、メタクロレインの選択率８８．８％、メタクリル酸の選択率２．５％、合計収率８６．８％であった。 As a result, the reaction rate of isobutylene was 95.1%, the selectivity of methacrolein was 88.8%, the selectivity of methacrylic acid was 2.5%, and the total yield was 86.8%.
〔比較例２〕
実施例１において、Ａ液の調製時に２８％アンモニア水１２．０部に替え３４．０部を加え、ｐＨ４．０に調整した以外は、実施例１と同様にして触媒を製造し、同様の条件で不飽和アルデヒド及び不飽和カルボン酸を製造した。
[Comparative Example 2]
In Example 1, a catalyst was produced in the same manner as in Example 1 except that 34.0 parts were added instead of 12.0 parts of 28% aqueous ammonia at the time of preparing the liquid A, and the pH was adjusted to 4.0. Under the conditions, an unsaturated aldehyde and an unsaturated carboxylic acid were produced.
その結果、イソブチレンの反応率９４．７％、メタクロレインの選択率８９．０％、メタクリル酸の選択率２．１％、合計収率８６．３％であった。 As a result, the reaction rate of isobutylene was 94.7%, the selectivity of methacrolein was 89.0%, the selectivity of methacrylic acid was 2.1%, and the total yield was 86.3%.
〔比較例３〕
実施例１において、室温の純水１０００部に、パラタングステン酸アンモニウム１２．４部、硝酸セシウム２３．０部、三酸化アンチモン２７．４部および三酸化ビスマス３３．０部及び８５％リン酸５．６部を順次加え、溶解した。さらに、硝酸０．６部を加えｐＨ１．５に調整した（ａ液）。これとは別に、６０℃の純水１０００部に、パラモリブデン酸アンモニウム５００部、硝酸第二鉄２０９．８部、硝酸ニッケル７５．５部、硝酸コバルト４５３．３部、硝酸鉛３１．３部を加え、攪拌しモリブデン含有液を調製した（Ｂ液）。得られたａ液、Ｂ液とを混合した以外は実施例１と同様にして触媒を製造した。このときのＢ液のｐＨならびにａ液とＢ液とを混合した金属含有液のｐＨはそれぞれ１．６と２．０であった。得られた触媒を用いた他は実施例１と同様の条件で不飽和アルデヒド及び不飽和カルボン酸を製造した。 その結果、イソブチレンの反応率８７．９％、メタクロレインの選択率８９．５％、メタクリル酸の選択率２．４％、合計収率８２．４％であった。
[Comparative Example 3]
In Example 1, 12.4 parts of ammonium paratungstate, 23.0 parts of cesium nitrate, 27.4 parts of antimony trioxide, 33.0 parts of bismuth trioxide and 5% of 85% phosphoric acid were added to 1000 parts of pure water at room temperature. .6 parts were sequentially added and dissolved. Further, 0.6 parts of nitric acid was added to adjust the pH to 1.5 (solution a). Separately, in 1000 parts of pure water at 60 ° C., 500 parts of ammonium paramolybdate, 209.8 parts of ferric nitrate, 75.5 parts of nickel nitrate, 453.3 parts of cobalt nitrate, 31.3 parts of lead nitrate And stirred to prepare a molybdenum-containing liquid (liquid B). A catalyst was produced in the same manner as in Example 1 except that the obtained liquid a and liquid B were mixed. At this time, the pH of the liquid B and the pH of the metal-containing liquid obtained by mixing the liquid a and the liquid B were 1.6 and 2.0, respectively. An unsaturated aldehyde and an unsaturated carboxylic acid were produced under the same conditions as in Example 1 except that the obtained catalyst was used. As a result, the reaction rate of isobutylene was 87.9%, the selectivity of methacrolein was 89.5%, the selectivity of methacrylic acid was 2.4%, and the total yield was 82.4%.
結果からも、本発明の金属含有触媒の製造方法により得られる触媒を用いることにより、不飽和アルデヒド及び不飽和カルボン酸を高収率で得られることが明らかである。 From the results, it is clear that unsaturated aldehyde and unsaturated carboxylic acid can be obtained in high yield by using the catalyst obtained by the method for producing a metal-containing catalyst of the present invention.
Claims (1)
金属含有触媒を構成する前記ＩＩ価の金属を分散又は溶解し、アルカリを加えてｐＨを０．５〜３．５に調整してＩＩ価金属含有液（Ａ液）を調製する工程と、
少なくともモリブデンを分散又は溶解したモリブデン含有液（Ｂ液）を調製する工程と、
前記ＩＩ価金属含有液（Ａ液）と前記モリブデン含有液（Ｂ液）とを混合して、金属含有液を調製する工程とを有することを特徴とする金属含有触媒の製造方法。 Used in the synthesis of unsaturated aldehydes and carboxylic acids corresponding to propylene, isobutylene, tertiary butyl alcohol or methyl tertiary butyl ether by vapor phase catalytic oxidation with molecular oxygen. A process for producing a metal-containing catalyst comprising at least a molybdenum, bismuth , and a divalent metal selected from Fe, Co, Ni and Pb ,
Dispersing or dissolving the II valent metal constituting the metal-containing catalyst, the method comprising the steps of: preparing II valent metal-containing solution (A solution) to adjust the pH to 0.5 to 3.5 by adding an alkali,
Preparing a molybdenum-containing liquid (liquid B) in which at least molybdenum is dispersed or dissolved;
A method for producing a metal-containing catalyst, comprising the step of mixing the II-valent metal-containing liquid (liquid A) and the molybdenum-containing liquid (liquid B) to prepare a metal-containing liquid.
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