JP2847150B2 - Method for producing acrolein or methacrolein - Google Patents
Method for producing acrolein or methacroleinInfo
- Publication number
- JP2847150B2 JP2847150B2 JP2306141A JP30614190A JP2847150B2 JP 2847150 B2 JP2847150 B2 JP 2847150B2 JP 2306141 A JP2306141 A JP 2306141A JP 30614190 A JP30614190 A JP 30614190A JP 2847150 B2 JP2847150 B2 JP 2847150B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- catalyst component
- methacrolein
- compound
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はプロピレン、二級プロパノール、イソブチレ
ン又は三級ブタノールを分子状酸素を用いて気相接触酸
化してアクロレインまたはメタクロレインを製造する方
法に関する。The present invention relates to a process for producing acrolein or methacrolein by subjecting propylene, secondary propanol, isobutylene or tertiary butanol to gas-phase catalytic oxidation using molecular oxygen. .
プロピレン、二級プロパノール、イソブチレン又は三
級ブタノールを分子状酸素により気相接触酸化としてア
クロレインまたはメタクロレインを製造する際に用いら
れる触媒に関して、従来から数多くの提案がなされてい
る。Numerous proposals have been made on catalysts used for producing acrolein or methacrolein by gas phase catalytic oxidation of propylene, secondary propanol, isobutylene or tertiary butanol with molecular oxygen.
しかし、触媒活性、選択性、触媒の安定性、触媒寿命
などの触媒性能が触媒調製のロット毎に異なり再現性の
良い触媒調製法とはいえず、その点の改良が望まれてい
た。However, catalyst performance such as catalyst activity, selectivity, catalyst stability, and catalyst life varies from lot to lot of catalyst preparation, and cannot be said to be a catalyst preparation method with good reproducibility, and improvement in that point has been desired.
本発明の目的は、触媒活性、メタクロレイン選択性、
触媒の安定性に優れた触媒の再現性の良い調製方法を提
供することにある。The object of the present invention is to provide catalytic activity, methacrolein selectivity,
An object of the present invention is to provide a method for preparing a catalyst having excellent catalyst stability and good reproducibility.
本発明者らは、プロピレン、二級プロパノール、イソ
ブチレン又は三級ブタノールを分子状酸素により気相接
触酸化してアクロレイン又はメタクロレインを製造する
際に用いられる触媒、特に、Mo、BiおよびFeを必須成分
として含有し、且つNiおよびCoの中から選ばれる１種以
上の元素、並びにＫ、Rb、CsおよびTlの中から選ばれる
１種以上の元素を必須成分として含有する触媒につい
て、アクロレイン又はメタクロレインの収率および選択
性、安定性に優れた触媒を開発すべく、触媒成分、組
成、調製法について鋭意検討を進めた。The present inventors require a catalyst used in the production of acrolein or methacrolein by gas phase catalytic oxidation of propylene, secondary propanol, isobutylene or tertiary butanol with molecular oxygen, particularly Mo, Bi and Fe. Acrolein or methacrolein for a catalyst containing, as an essential component, one or more elements selected from Ni and Co, and one or more elements selected from K, Rb, Cs and Tl. In order to develop a catalyst with excellent yield, selectivity and stability of rhein, the catalyst components, composition, and preparation method were studied diligently.
その結果、触媒調製の際、これら触媒成分を二種類以
上に分割し、溶液とした後、それぞれの溶液を短時間に
混合し、熟成することなく直ちに噴霧乾燥して得られる
乾燥粉を原料として触媒を調製することにより、アクロ
レイン又はメタクロレインの収率および選択性などの触
媒性能が向上し、またその再現性も向上し、さらに触媒
活性の安定性が大きく向上することを見出し本発明の方
法を完成させるに至った。As a result, at the time of catalyst preparation, these catalyst components are divided into two or more types, and after being made into a solution, each solution is mixed in a short time, and a dried powder obtained by spray drying immediately without aging is used as a raw material. By preparing the catalyst, it was found that the catalyst performance such as the yield and selectivity of acrolein or methacrolein was improved, the reproducibility was improved, and the stability of the catalyst activity was greatly improved. Was completed.
即ち、本発明の方法は、一般式 Moa Bib Fec Xd Ye Zf Og （式中、ＸはNiおよびCoの中から選ばれる１種以上の元
素であり、ＹはK,Rb,CsおよびTlの中から選ばれる１種
以上の元素であり、ＺはW,Be,Mg,S,Ca,Sr,Ba,Te,Se,Ce,
Ge,Mn,Zn,Cr,Ag,Sb,Pb,As,B,P,Nb,Cu,Cd,Sn,Al,Zr,Tiお
よびSiの中から選ばれる１種以上の元素を表わす。a,b,
c,d,e,f,gは各元素の原子比率を表わし、ａを基準にと
り、ａ＝12としたとき、ｂ＝0.1〜10、ｃ＝0.1〜20、ｄ
＝２〜20、ｅ＝0.01〜２、ｆ＝０〜４であり、ｇは前記
各成分の原子価を満足するに必要な酸素の原子数であ
る。）で示される組成物を含有する触媒の存在下に、分
子状酸素を用いて気相接触酸化してアクロレインまたは
メタクロレインを製造するに際し、該触媒成分を二種類
以上に分割し、溶液とした後、それぞれの溶液を短時間
に混合し熟成することなく直ちに噴霧乾燥して得られる
乾燥粉を原料とする触媒を用いることを特徴とするアク
ロレインまたはメタクロレインの製造方法である。That is, the method of the present invention uses the general formula Moa Bib Fec Xd Ye Zf Og (where X is one or more elements selected from Ni and Co, and Y is K, Rb, Cs and Tl). At least one element selected from the group consisting of W, Be, Mg, S, Ca, Sr, Ba, Te, Se, Ce,
It represents one or more elements selected from Ge, Mn, Zn, Cr, Ag, Sb, Pb, As, B, P, Nb, Cu, Cd, Sn, Al, Zr, Ti and Si. a, b,
c, d, e, f, and g represent the atomic ratio of each element. Based on a, when a = 12, b = 0.1-10, c = 0.1-20, d
= 2 to 20, e = 0.01 to 2, f = 0 to 4, and g is the number of oxygen atoms necessary to satisfy the valence of each component. In the presence of a catalyst containing the composition represented by the formula (1), when producing acrolein or methacrolein by gas phase catalytic oxidation using molecular oxygen, the catalyst component was divided into two or more types to form a solution. Thereafter, a method for producing acrolein or methacrolein is characterized by using a catalyst starting from a dry powder obtained by mixing the respective solutions in a short time and immediately spray-drying without aging.
本発明の方法で用いるMo−Bi−Fe系複合酸化物触媒は
アリル位酸化触媒としてのこの分野で多様されている
が、従来の方法では、例えば特開昭59−46132号などに
開示されているように、通常、触媒成分を含む二種類以
上の水溶液を滴下混合し、加熱撹拌下で濃縮乾固し、つ
いで焼成して調製される。The Mo-Bi-Fe-based composite oxide catalyst used in the method of the present invention is diversified in this field as an allylic oxidation catalyst, but the conventional method is disclosed in, for example, JP-A-59-46132. Usually, two or more kinds of aqueous solutions containing a catalyst component are dropped and mixed, concentrated to dryness under heating and stirring, and then calcined.
従来の方法の、滴下混合し、加熱撹拌下で濃縮乾固す
る過程では、脱水重合、核生成、吸着、沈殿、再溶解と
いった複雑な液相内あるいは固液相反応が併発的に起こ
っていると思われる。これらは混合する溶液の濃度、温
度、pH、混合順序、滴下速度、撹拌速度、沈殿槽の大き
さ、形状、加熱撹拌時の温度履歴、撹拌強度、濃縮速
度、濃縮時のバス温などにより、それぞれの素反応の速
度が変化するため、調製条件の少しの違いが得られる無
機縮重合物の化学的、物理的性質を大きく変える結果と
なり、ひいては触媒性能のばらつきを生んでいるものと
考えられる。In the conventional method of drop-mixing and concentrating to dryness under heating and stirring, complicated in-liquid or solid-liquid phase reactions such as dehydration polymerization, nucleation, adsorption, precipitation, and re-dissolution occur concurrently. I think that the. These are determined by the concentration of the solution to be mixed, the temperature, the pH, the mixing order, the dropping speed, the stirring speed, the size and shape of the precipitation tank, the temperature history during heating and stirring, the stirring intensity, the concentration speed, the bath temperature during concentration, etc. Because the rate of each elementary reaction changes, slight differences in the preparation conditions result in significant changes in the chemical and physical properties of the inorganic condensation polymer, which in turn is thought to result in variations in catalyst performance. .
これに対し、本発明の方法は出来るだけ短時間で混合
し直ぐ噴霧乾燥し、ついで焼成するところにその特徴が
ある。On the other hand, the method of the present invention is characterized in that it is mixed in a short time as possible, spray-dried immediately, and then calcined.
本発明の方法は、液相の関与する緩慢な併発反応を除
外し、且つ反応を出来るだけ単純にするため、反応を短
時間で完結させることを基本的な技術思想としている。
即ち触媒成分を含む二種類以上の溶液を出来るだけ短時
間で混合し直ぐ噴霧乾燥することで、脱水重合、吸着、
再溶解といった液相の関与する緩慢な併発反応を除外
し、且つ核生成脱水、乾燥も連続的に一定条件で行える
噴霧乾燥で一気に行うことで、履歴を実質的に排除して
いる。The basic idea of the method of the present invention is to complete the reaction in a short time in order to eliminate the slow concurrent reaction involving the liquid phase and to make the reaction as simple as possible.
That is, by mixing two or more types of solutions containing a catalyst component in the shortest possible time and immediately spray-drying, dehydration polymerization, adsorption,
The history is substantially eliminated by excluding a slow concurrent reaction involving the liquid phase such as re-dissolution, and by performing nucleation, dehydration, and drying all at once by spray drying that can be performed under constant conditions.
本発明の方法で使用する触媒成分を含む溶液は、例え
ば次のような方法で調製することができる。The solution containing the catalyst component used in the method of the present invention can be prepared, for example, by the following method.
適当なモリブデン酸塩例えばモリブデン酸アンモンを
純水に加熱溶解し、Ｋ、Rb、CsおよびTlから選ばれる少
なくとも一種の塩、例えば硝酸塩を加え、第一の原料溶
液とする。また、シリカゾルをこの溶液に加えてもよ
い。Fe、CoおよびNiの中から選ばれる１種以上の元素の
化合物、例えば硝酸塩を純水に溶解して第二の原料溶液
とする。ビスマスの化合物、例えば硝酸塩を純水に溶解
して第三の原料溶液とする。A suitable molybdate such as ammonium molybdate is dissolved in pure water by heating, and at least one salt selected from K, Rb, Cs and Tl, such as nitrate, is added to obtain a first raw material solution. Also, a silica sol may be added to this solution. A second raw material solution is obtained by dissolving a compound of at least one element selected from Fe, Co and Ni, for example, nitrate, in pure water. A third raw material solution is obtained by dissolving a bismuth compound, for example, a nitrate, in pure water.
本発明の方法で用いる原料溶液は、それぞれの原料溶
液が溶液調製時あるいは、溶液保存時に脱水重合、核生
成、吸着、沈殿、再溶解といった反応が起こらないよう
な原料化合物の組合せから成っている。従って溶液の数
は通常２つ以上であり、その数には特に制限はない。The raw material solution used in the method of the present invention is composed of a combination of raw material compounds such that each raw material solution does not undergo a reaction such as dehydration polymerization, nucleation, adsorption, precipitation, and re-dissolution during solution preparation or solution storage. . Therefore, the number of solutions is usually two or more, and the number is not particularly limited.
本発明の触媒は必要に応じてＺ成分としてBe,Mg,S,C
a,Sr,Ba,Te,Se,Ce,Ge,Mn,Zn,Cr,Ag,Sb,Pb,As,B,P,Nb,C
u,W,Cd,Sn,Al,ZrおよびTiの中から選ばれる１種以上の
元素の化合物を加えることができる。The catalyst of the present invention may contain Be, Mg, S, C
a, Sr, Ba, Te, Se, Ce, Ge, Mn, Zn, Cr, Ag, Sb, Pb, As, B, P, Nb, C
Compounds of one or more elements selected from u, W, Cd, Sn, Al, Zr and Ti can be added.
これらのＺ成分の化合物は、均一溶液となるようにい
ずかの溶液に加えられるか、あるいは独立の溶液として
調製される。These compounds of the Z component may be added to any solution so as to be a homogeneous solution, or may be prepared as independent solutions.
本発明の触媒の原料は、触媒調製過程で酸化物の形に
分解される化合物が望ましい。そのような化合物として
は、例えば硝酸塩、アンモニウム塩、有機酸塩、水酸化
物、酸化物、金属酸、金属酸アンモニウム塩などであ
る。The raw material of the catalyst of the present invention is preferably a compound that is decomposed into an oxide in the course of preparing the catalyst. Such compounds include, for example, nitrates, ammonium salts, organic acid salts, hydroxides, oxides, metal acids, ammonium metal salts and the like.
また、シリカの原料としては、シリカゾル、シリカゲ
ル、珪酸エステル、珪酸塩などが用いられる。Further, as a raw material of silica, silica sol, silica gel, silicate ester, silicate and the like are used.
また、これらの溶液に硝酸を加え、原料溶液を混合し
た時の混合液のpHを５以下とすると、脱水縮合が起こり
難くなるので、触媒調製の再現性を高める上でより好ま
しい。Further, when nitric acid is added to these solutions and the pH of the mixed solution when the raw material solutions are mixed is adjusted to 5 or less, dehydration and condensation hardly occur, so that it is more preferable to enhance reproducibility of catalyst preparation.
また、これら溶液に増粘剤を加え、原料溶液を混合し
た時の混合液の粘度を高め、噴霧乾燥して得られる粉体
の粒度を制御することもできる。In addition, a thickener may be added to these solutions to increase the viscosity of the mixture when the raw material solutions are mixed, and the particle size of the powder obtained by spray drying can be controlled.
本発明の方法では、これら触媒成分を含む二種類以上
の溶液を出来るだけ短時間で混合し直ぐ噴霧乾燥する。In the method of the present invention, two or more kinds of solutions containing these catalyst components are mixed in the shortest possible time and spray-dried immediately.
混合の方法は通常用いられる撹拌混合、超音波混合、
ラインミキサー、スタティックミキサーなどによる方法
が採用される。混合時間は、短時間であるほど望まし
い。混合時の温度にもよるが、通常、数分、長くても数
十分の範囲である。Mixing method is commonly used stirring mixing, ultrasonic mixing,
A method using a line mixer, a static mixer, or the like is employed. The shorter the mixing time, the better. Although it depends on the temperature at the time of mixing, it is usually within a range of several minutes or at most several tens of minutes.
混合時の温度は、特に制限はないが、通常、常温前後
である。The temperature during mixing is not particularly limited, but is usually around room temperature.
混合液は直ちに噴霧乾燥される。噴霧乾燥の方法およ
び条件は、この分野で通常用いられるものがそのまま適
用でき、特に制限はない。The mixture is spray dried immediately. The method and conditions for spray drying can be directly applied to those commonly used in this field, and are not particularly limited.
噴霧乾燥粉は、仮焼し、必要に応じて成形し、400〜7
50℃の温度範囲で１〜20時間程度焼成する。Spray-dried powder is calcined, molded as needed, 400-7
Bake for about 1 to 20 hours at a temperature of 50 ° C.
触媒は粒状または成形体として固定床で使用される
が、移動床あるいは流動床にも使用できる。The catalysts are used in fixed beds as granules or shaped bodies, but can also be used in moving or fluidized beds.
本発明による接触気相酸化反応は原料ガス組成として
１〜10容量％のプロピレン、二級プロパノール、イソブ
チレンまたは三級ブタノール、３〜20容量％の分子状酸
素および70〜90容量％の希釈ガスからなる混合ガスを前
記した触媒上に250〜450℃の温度範囲および常圧〜10気
圧の圧力下、空間速度300〜5000/hrで導入することで実
施される。The catalytic gas phase oxidation reaction according to the present invention comprises, as a raw material gas composition, 1 to 10% by volume of propylene, secondary propanol, isobutylene or tertiary butanol, 3 to 20% by volume of molecular oxygen and 70 to 90% by volume of a diluent gas. This is carried out by introducing a mixed gas into the above-mentioned catalyst at a space velocity of 300 to 5000 / hr under a temperature range of 250 to 450 ° C. and a pressure of normal pressure to 10 atm.
分子状酸素としては通常空気が使用されるが、純酸素
を使用してもよい。Air is usually used as molecular oxygen, but pure oxygen may be used.
希釈ガスとしては窒素、炭酸ガスなどの不活性ガスが
使用される。また、反応ガスに含まれる非凝縮性ガスの
一部を循環して使用してもよい。An inert gas such as nitrogen or carbon dioxide is used as the diluent gas. Further, a part of the non-condensable gas contained in the reaction gas may be circulated and used.
希釈ガスとして水蒸気を併せて使用することが活性、
選択性を高める上で好ましい。その場合、原料ガス中の
水蒸気は通常60容量％まで添加される。It is active to use water vapor as a diluent gas,
It is preferable to increase selectivity. In that case, the water vapor in the source gas is usually added up to 60% by volume.
実施例および比較例によって本発明をさらに詳細に説
明する。The present invention will be described in more detail with reference to Examples and Comparative Examples.
実施例１ 水12000mlを加熱撹拌しつつ、モリブデン酸アンモン1
272g、次いで硝酸セシウム43gを溶解し、更に20wt％濃
度のシリカゾル1110gを加えＡ液とした。Example 1 While heating and stirring 12,000 ml of water, ammonium molybdate 1
272 g and then 43 g of cesium nitrate were dissolved, and 1110 g of silica sol having a concentration of 20 wt% was further added to prepare solution A.
水1800mlに硝酸コバルト1396g、硝酸第二鉄702gを溶
解しＢ液とした。A solution B was prepared by dissolving 1396 g of cobalt nitrate and 702 g of ferric nitrate in 1800 ml of water.
60％硝酸150mlと水1500mlとからなる硝酸水溶液に硝
酸ビスマス571.4gを溶解しＣ液とした。571.4 g of bismuth nitrate was dissolved in a nitric acid aqueous solution consisting of 150 ml of 60% nitric acid and 1500 ml of water to obtain a liquid C.
Ａ液を1200ml/min、Ｂ液を180ml/min、Ｃ液を165ml/m
inでラインミキサーに供給し、連続的に混合し、ライン
ミキサー出口の混合溶液をそのまま噴霧乾燥した。Solution A 1200ml / min, Solution B 180ml / min, Solution C 165ml / m
The mixture was supplied to the line mixer at "in", continuously mixed, and the mixed solution at the outlet of the line mixer was spray-dried as it was.
乾燥粉を仮焼し、直径および高さが共に5mmの円柱状
に成形し、550℃で10時間空気中で焼成して、Mo/Bi/Fe/
Co/Cs原子比が12/2.0/3.0/8.0/0.4なる酸化物の混合物9
0重量％と10重量％のシリカとからなる触媒を得た。The dried powder is calcined, formed into a cylinder having a diameter and height of 5 mm, and fired in air at 550 ° C. for 10 hours to obtain Mo / Bi / Fe /
Mixture 9 of oxides with Co / Cs atomic ratio of 12 / 2.0 / 3.0 / 8.0 / 0.4
A catalyst consisting of 0% by weight and 10% by weight of silica was obtained.
得られた触媒40mlを3/4インチの鋼鉄製反応管に充填
し、イソブチレン６容量％、酸素12容量％、水蒸気15容
量％、残り67重量％が窒素という原料ガス組成、反応器
バス温度350℃、空間速度1000/hrという標準条件で反応
を行い、触媒の初期性能を評価した。The obtained catalyst (40 ml) was charged into a 3/4 inch steel reaction tube, and a raw material gas composition comprising 6% by volume of isobutylene, 12% by volume of oxygen, 15% by volume of steam, and the remaining 67% by weight of nitrogen, and a reactor bath temperature of 350% The reaction was carried out under standard conditions of 1000C and space velocity of 1000 / hr, and the initial performance of the catalyst was evaluated.
初期性能評価後、イソブチレン10重量％、酸素25容量
％、水蒸気20容量％、残り45容量％が窒素という原料ガ
ス組成、反応器バス温度420℃、空間速度30000/hrとい
う強制劣化条件で２日間反応を行った後、標準条件に戻
して反応を行い、触媒の安定性を評価した。After initial performance evaluation, 2 days under the conditions of forced gas degradation of 10 wt% isobutylene, 25 vol% oxygen, 20 vol% steam, and the remaining 45 vol% nitrogen, raw material gas composition, reactor bath temperature 420 ° C, space velocity 30,000 / hr. After the reaction, the reaction was returned to the standard conditions, and the stability of the catalyst was evaluated.
評価結果を表１に示した。 Table 1 shows the evaluation results.
実施例２ 触媒性能にばらつきのないことを確かめるために、実
施例１と同様の方法で触媒を調製し、性能を評価した。
結果を表１に示した。Example 2 In order to confirm that there was no variation in catalyst performance, a catalyst was prepared in the same manner as in Example 1, and the performance was evaluated.
The results are shown in Table 1.
比較例１〜５ 従来法による触媒性能のばらつきを明らかにするた
め、実施例１と同じ組成のＡ液、Ｂ液およびＣ液を調製
した。Ａ液にＢ液とＣ液を順次滴下し、60℃で５時間、
撹拌下熟成した後、噴霧乾燥した他は実施例１と同様の
方法で触媒を調製し、性能を評価した。結果を表１に示
した。Comparative Examples 1 to 5 Liquids A, B and C having the same composition as in Example 1 were prepared in order to clarify the variation in catalyst performance by the conventional method. Solution B and Solution C are sequentially dropped into Solution A, and the mixture is added at 60 ° C. for 5 hours.
After aging under agitation, a catalyst was prepared in the same manner as in Example 1 except for spray drying, and the performance was evaluated. The results are shown in Table 1.
実施例３〜５ 表２に示した原子比の酸化物の混合物とシリカからな
る触媒を実施例１と同様の方法で調製し、性能を評価し
た。結果を表２に示した。Examples 3 to 5 Catalysts composed of a mixture of oxides having the atomic ratios shown in Table 2 and silica were prepared in the same manner as in Example 1, and the performance was evaluated. The results are shown in Table 2.
比較例６〜８ 表１に示した原子比の酸化物の混合物とシリカからな
る触媒を比較例１と同様の方法で調製し、性能を評価し
た。結果を表２に示した。Comparative Examples 6 to 8 A catalyst comprising a mixture of oxides having the atomic ratios shown in Table 1 and silica was prepared in the same manner as in Comparative Example 1, and the performance was evaluated. The results are shown in Table 2.
実施例６ 表１に示した原子比の酸化物の混合物とシリカからな
る触媒を実施例１と同様の方法で調製し、性能評価時の
原料ガス中のイソブテンをプロピレンに変え、反応器バ
ス温度を320℃とした他は実施例１と同様に操作した。
結果を表２に示した。Example 6 A catalyst composed of a mixture of oxides having the atomic ratios shown in Table 1 and silica was prepared in the same manner as in Example 1, and the isobutene in the raw material gas at the time of performance evaluation was changed to propylene. The operation was performed in the same manner as in Example 1 except that the temperature was changed to 320 ° C.
The results are shown in Table 2.
比較例９ 表１に示した原子比の酸化物の混合物とシリカからな
る触媒を比較例１と同様の方法で調製し、 性能評価時の原料ガス中のイソブテンをプロピレンに変
え、反応器バス温度を320℃とした他は比較例１と同様
に操作した。結果を表２に示した。Comparative Example 9 A catalyst comprising a mixture of oxides having the atomic ratios shown in Table 1 and silica was prepared in the same manner as in Comparative Example 1. The same operation as in Comparative Example 1 was carried out except that the isobutene in the raw material gas at the time of performance evaluation was changed to propylene, and the reactor bath temperature was changed to 320 ° C. The results are shown in Table 2.
以上の実施例および比較例の結果から、つぎのような
ことが判る。From the results of the above Examples and Comparative Examples, the following can be understood.
触媒調製ロット間のばらつきは本発明の方法による触
媒の方が小さかった。（実施例1,2、比較例１〜５） 同一組成の触媒の初期性能および強制劣化後の性能を
比較すると、本発明の方法による触媒の方が優れてい
た。（実施例1,2と比較例１〜５、実施例３と比較例
６、実施例４と比較例７、実施例５と比較例８、実施例
６と比較例９） 〔発明の効果〕 触媒活性、アクロレインまたはメタクロレイン選択
性、触媒の安定性に優れた触媒を再現性よく調製でき
る。The variation between catalyst preparation lots was smaller for the catalyst according to the method of the present invention. (Examples 1, 2 and Comparative Examples 1 to 5) Comparing the initial performance and the performance after forced deterioration of the catalysts having the same composition, the catalyst according to the method of the present invention was superior. (Examples 1, 2 and Comparative Examples 1 to 5, Example 3 and Comparative Example 6, Example 4 and Comparative Example 7, Example 5 and Comparative Example 8, Example 6 and Comparative Example 9) [Effect of the Invention] A catalyst having excellent catalytic activity, acrolein or methacrolein selectivity, and excellent catalyst stability can be prepared with good reproducibility.
フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０７Ｃ 45/37 Ｃ０７Ｃ 45/37 47/22 47/22 Ｊ // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (58)調査した分野(Int.Cl.6，ＤＢ名) C07C 47/22 C07C 45/35 - 45/39 B01J 23/88 B01J 27/04 - 27/18 C07B 61/00 ＷＰＩ／Ｌ（ＱＵＥＳＴＥＬ)Continued on the front page (51) Int.Cl. 6 Identification symbol FI C07C 45/37 C07C 45/37 47/22 47/22 J // C07B 61/00 300 C07B 61/00 300 (58) Investigated field (Int. .Cl. 6 , DB name) C07C 47/22 C07C 45/35-45/39 B01J 23/88 B01J 27/04-27/18 C07B 61/00 WPI / L (QUESTEL)
Claims (6)
レン又は三級ブタノールを、一般式 Moa Bib Fec Xd Ye Zf Og （式中、ＸはNiおよびCoの中から選ばれる１種以上の元
素であり、ＹはK,Rb,CsおよびTlの中から選ばれる１種
以上の元素であり、ＺはW,Be,Mg,S,Ca,Sr,Ba,Te,Se,Ce,
Ge,Mn,Zn,Cr,Ag,Sb,Pb,As,B,P,Nb,Cu,Cd,Sn,Al,Zr,Tiお
よびSiの中から選ばれる１種以上の元素を表わす。a,b,
c,d,e,f,gは各元素の原子比率を表わし、ａを基準にと
り、ａ＝12としたとき、ｂ＝0.1〜10、ｃ＝0.1〜20、ｄ
＝２〜20、ｅ＝0.01〜２、ｆ＝０〜４であり、ｇは前記
各成分の原子価を満足するに必要な酸素の原子数であ
る。）で示される組成物を含有する触媒の存在下に、分
子状酸素を用いて気相接触酸化してアクロレインまたは
メタクロレインを製造するに際し、該触媒成分を二種類
以上に分割し、溶液とした後、それぞれの溶液を短時間
に混合し熟成することなく直ちに噴霧乾燥して得られる
乾燥粉を原料とする触媒を用いることを特徴とするアク
ロレインまたはメタクロレインの製造方法。1. A method according to claim 1, wherein propylene, secondary propanol, isobutylene or tertiary butanol is represented by the general formula: Moa Bib Fec Xd Ye Zf Og (where X is at least one element selected from Ni and Co; Is one or more elements selected from K, Rb, Cs and Tl, and Z is W, Be, Mg, S, Ca, Sr, Ba, Te, Se, Ce,
It represents one or more elements selected from Ge, Mn, Zn, Cr, Ag, Sb, Pb, As, B, P, Nb, Cu, Cd, Sn, Al, Zr, Ti and Si. a, b,
c, d, e, f, and g represent the atomic ratio of each element. Based on a, when a = 12, b = 0.1-10, c = 0.1-20, d
= 2 to 20, e = 0.01 to 2, f = 0 to 4, and g is the number of oxygen atoms necessary to satisfy the valence of each component. In the presence of a catalyst containing the composition represented by the formula (1), when producing acrolein or methacrolein by gas phase catalytic oxidation using molecular oxygen, the catalyst component was divided into two or more types to form a solution. Thereafter, a method for producing acrolein or methacrolein, comprising using a catalyst obtained by using a dry powder obtained by spray-drying immediately without mixing and aging the respective solutions, as a raw material.
以下となるよう酸を該溶液に加える特許請求の範囲
（１）の方法。2. When the solution containing the catalyst component is mixed, the pH is 5
The method of claim (1) wherein an acid is added to said solution such that:
デン化合物とアルカリ金属化合物あるいはテルル化合物
を含む水溶液を用いる特許請求の範囲（１）または
（２）の方法。3. The method according to claim 1, wherein an aqueous solution containing a molybdenum compound and an alkali metal compound or a tellurium compound is used as one of the solutions containing the catalyst component.
物並びにコバルトおよびニッケルの中から選ばれる１種
以上の金属化合物を含む水溶液を用いる特許請求の範囲
（１）、（２）または（３）の方法。4. The method according to claim 1, wherein an aqueous solution containing an iron compound and one or more metal compounds selected from cobalt and nickel is used as one of the solutions containing the catalyst component. Method 3).
ス化合物を含む水溶液を用いる特許請求の範囲（１）、
（２）、（３）または（４）の方法。5. The method according to claim 1, wherein an aqueous solution containing a bismuth compound is used as one of the solutions containing the catalyst component.
The method of (2), (3) or (4).
の範囲（１）、（２）、（３）、（４）または（５）の
方法。6. The method according to claim 1, wherein silica sol is used as the Si component.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2306141A JP2847150B2 (en) | 1990-11-14 | 1990-11-14 | Method for producing acrolein or methacrolein |
| DE69109746T DE69109746T2 (en) | 1990-06-06 | 1991-06-05 | Process for the production of acrolein or methacrolein. |
| KR1019910009285A KR940002982B1 (en) | 1990-06-06 | 1991-06-05 | Method for preparing acrolein or methacrolein |
| EP91305074A EP0460932B1 (en) | 1990-06-06 | 1991-06-05 | Method for preparing acrolein or methacrolein |
| US07/711,032 US5144090A (en) | 1990-06-06 | 1991-06-06 | Method for preparing acrolein or methacrolein |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2306141A JP2847150B2 (en) | 1990-11-14 | 1990-11-14 | Method for producing acrolein or methacrolein |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04182449A JPH04182449A (en) | 1992-06-30 |
| JP2847150B2 true JP2847150B2 (en) | 1999-01-13 |
Family
ID=17953550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2306141A Expired - Lifetime JP2847150B2 (en) | 1990-06-06 | 1990-11-14 | Method for producing acrolein or methacrolein |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2847150B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013172414A1 (en) | 2012-05-18 | 2013-11-21 | 日本化薬株式会社 | Catalyst for use in production of methacrylic acid, method for producing said catalyst, and method for producing methacrylic acid using said catalyst |
| KR101462633B1 (en) * | 2011-01-05 | 2014-12-05 | 주식회사 엘지화학 | PROCESS FOR PREPARING Mo-Bi BASED MULTI-METAL OXIDE CATALYST |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014157040A1 (en) | 2013-03-28 | 2014-10-02 | 日本化薬株式会社 | Catalyst for methacrylic acid production, method for producing same, and method for producing methacrylic acid |
-
1990
- 1990-11-14 JP JP2306141A patent/JP2847150B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101462633B1 (en) * | 2011-01-05 | 2014-12-05 | 주식회사 엘지화학 | PROCESS FOR PREPARING Mo-Bi BASED MULTI-METAL OXIDE CATALYST |
| WO2013172414A1 (en) | 2012-05-18 | 2013-11-21 | 日本化薬株式会社 | Catalyst for use in production of methacrylic acid, method for producing said catalyst, and method for producing methacrylic acid using said catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04182449A (en) | 1992-06-30 |
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