JPH1157476A - Preparation of catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acid - Google Patents
Preparation of catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acidInfo
- Publication number
- JPH1157476A JPH1157476A JP9228307A JP22830797A JPH1157476A JP H1157476 A JPH1157476 A JP H1157476A JP 9228307 A JP9228307 A JP 9228307A JP 22830797 A JP22830797 A JP 22830797A JP H1157476 A JPH1157476 A JP H1157476A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- dried
- hot air
- parts
- wet
- 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.)
- Pending
Links
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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】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(以後TBAと略
す)またはメチル第三級ブチルエーテル(以後MTBE
と略す)を分子状酸素を用いて気相接触酸化し、不飽和
アルデヒドおよび不飽和カルボン酸を合成する際に使用
する触媒の湿式賦形を伴う製造方法、該製造方法により
得られた触媒、および該触媒を用いて不飽和アルデヒド
および不飽和カルボン酸を製造する方法に関する。The present invention relates to propylene, isobutylene, tertiary butyl alcohol (hereinafter abbreviated as TBA) or methyl tertiary butyl ether (hereinafter MTBE).
Abbreviated as) in the gas phase using molecular oxygen to produce an unsaturated aldehyde and an unsaturated carboxylic acid, the production method involving wet shaping of the catalyst, the catalyst obtained by the production method, And a method for producing an unsaturated aldehyde and an unsaturated carboxylic acid using the catalyst.
【0002】[0002]
【従来の技術】プロピレンを気相接触酸化してアクロレ
インおよびアクリル酸を製造する際に用いられる触媒
や、イソブチレン、TBAまたはMTBEを気相接触酸
化してメタクロレインおよびメタクリル酸を製造する際
に用いられる触媒を製造する際に、触媒前駆体を湿式賦
形する方法は公知である。2. Description of the Related Art A catalyst used for producing acrolein and acrylic acid by gas-phase catalytic oxidation of propylene and a catalyst used for producing methacrolein and methacrylic acid by gas-phase catalytic oxidation of isobutylene, TBA or MTBE. In producing the resulting catalyst, a method for wet-shaping the catalyst precursor is known.
【0003】このような従来の方法では、湿式賦形体を
熱風により乾燥していたが、得られる触媒の性能が十分
でなく、より高性能な触媒を製造する方法が望まれてい
た。[0003] In such a conventional method, the wet shaped body is dried by hot air. However, the performance of the obtained catalyst is not sufficient, and a method of producing a higher performance catalyst has been desired.
【0004】[0004]
【発明が解決しようとする課題】従って本発明の目的
は、プロピレン、イソブチレン、TBAまたはMTBE
を分子状酸素を用いて気相接触酸化し、不飽和アルデヒ
ドおよび不飽和カルボン酸を有利に合成できる触媒の製
造方法を提供することにある。Accordingly, an object of the present invention is to provide propylene, isobutylene, TBA or MTBE.
Is to provide a process for producing a catalyst which can advantageously synthesize unsaturated aldehydes and unsaturated carboxylic acids by gas-phase catalytic oxidation using molecular oxygen.
【0005】[0005]
【課題を解決するための手段】本発明者らは鋭意研究を
重ねた結果、焼成物を湿式賦形した湿式賦形体をマイク
ロ波および熱風を併用して乾燥することにより、高性能
な触媒が得られることを見出し、本発明を完成するに至
った。Means for Solving the Problems As a result of intensive studies, the present inventors have found that a high-performance catalyst can be obtained by drying a wet-formed body obtained by wet-shaping a fired product by using both microwaves and hot air. The inventors have found that the present invention can be obtained, and have completed the present invention.
【0006】すなわち本発明は、プロピレン、イソブチ
レン、第三級ブチルアルコールおよびメチル第三級ブチ
ルエーテルを分子状酸素を用いて気相接触酸化し、不飽
和アルデヒドおよび不飽和カルボン酸を合成する際に用
いられる触媒の製造方法おいて、少なくともモリブデ
ン、ビスマスおよび鉄を含む触媒の製造において、触媒
成分を含む水性スラリーを乾燥し、次いで焼成し、得ら
れた焼成物を湿式賦形した湿式賦形体をマイクロ波およ
び熱風を併用して乾燥することを特徴とする触媒の製造
方法である。That is, the present invention provides a method for synthesizing unsaturated aldehydes and unsaturated carboxylic acids by subjecting propylene, isobutylene, tertiary butyl alcohol and methyl tertiary butyl ether to gas-phase catalytic oxidation using molecular oxygen. In the method for producing a catalyst according to the present invention, in the production of a catalyst containing at least molybdenum, bismuth and iron, an aqueous slurry containing a catalyst component is dried and then calcined. This is a method for producing a catalyst, characterized by drying using both waves and hot air.
【0007】[0007]
【発明の実施の形態】本発明の方法において製造される
触媒は、少なくともモリブデン、ビスマスおよび鉄を含
むものであればとくに限定されないが、一般式 MoaBibFecMdXeYfZgSihOi (式中、Mo、Bi、Fe、SiおよびOはそれぞれモ
リブデン、ビスマス、鉄、ケイ素および酸素を示し、M
はコバルトおよびニッケルからなる群より選ばれた少な
くとも1種の元素を示し、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、タンタルおよび亜鉛からなる群より選ばれた少なく
とも1種の元素を示し、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、アンチモンおよ
びチタンからなる群より選ばれた少なくとも1種の元素
を示し、Zはリチウム、ナトリウム、カリウム、ルビジ
ウム、セシウムおよびタリウムなる群より選ばれた少な
くとも1種の元素を示す。a、b、c、d、e、f、
g、hおよびiは各元素の原子比を表し、a=12の時
b=0.01〜3、c=0.01〜5、d=1〜12、e=
0〜8、f=0〜5、g=0.001〜2、h=0〜20
であり、iは前記各成分の原子価を満足するのに必要な
酸素の原子比である)で表される組成のものが好まし
い。Catalyst prepared in the method of the embodiment of the present invention contains at least molybdenum is not particularly limited as long as it contains bismuth and iron, the general formula Mo a Bi b Fe c M d X e Y f Z g Si h O i (wherein, Mo, Bi, Fe, Si and O represent molybdenum, bismuth, iron, silicon and oxygen, respectively;
Represents at least one element selected from the group consisting of cobalt and nickel, and X represents chromium, lead, manganese,
Y represents at least one element selected from the group consisting of calcium, magnesium, niobium, silver, barium, tin, tantalum and zinc, and Y represents phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony and titanium. Z represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and thallium. a, b, c, d, e, f,
g, h and i represent the atomic ratio of each element, and when a = 12, b = 0.01 to 3, c = 0.01 to 5, d = 1 to 12, and e =
0-8, f = 0-5, g = 0.1-2, h = 0-20
And i is the atomic ratio of oxygen necessary to satisfy the valence of each component described above.)
【0008】本発明の触媒製造方法において、触媒成分
を含む水性スラリーを製造する方法としては、特殊な方
法に限定する必要はなく、成分の著しい偏在を伴わない
限り、従来からよく知られている沈殿法、酸化物混合法
等の種々の方法を用いることができる。触媒成分の原料
としては、各触媒元素の酸化物、硫酸塩、硝酸塩、炭酸
塩、水酸化物、アンモニウム塩、ハロゲン化物等を組み
合わせて使用することができる。例えば、モリブデンの
原料としてはパラモリブデン酸アンモニウム、三酸化モ
リブデン等が使用できる。In the method for producing a catalyst of the present invention, the method for producing an aqueous slurry containing a catalyst component does not need to be limited to a special method, and is well known insofar as the component is not significantly unevenly distributed. Various methods such as a precipitation method and an oxide mixing method can be used. As the raw material of the catalyst component, oxides, sulfates, nitrates, carbonates, hydroxides, ammonium salts, halides, and the like of the respective catalyst elements can be used in combination. For example, as a raw material of molybdenum, ammonium paramolybdate, molybdenum trioxide and the like can be used.
【0009】触媒成分を含む水性スラリーを乾燥する方
法は特に限定されないが、より高性能な触媒を得るため
にはスプレー乾燥機を用いて乾燥することが好ましい。
スプレー乾燥により得られる乾燥粉は球状粒子であり、
これを用いて湿式賦形することにより、球状粒子に囲ま
れた空隙が形成され、触媒反応に有効な細孔構造をより
多く発現させることができる。スプレー乾燥により得ら
れる球状粒子の平均粒子径は30〜100μmが好まし
く、特に35〜90μmが好ましい。水性スラリーを蒸
発乾固法等により乾燥した場合には、塊状の乾燥物が得
られる場合があるが、この場合は適宜粉砕して粉体状と
することが好ましい。The method of drying the aqueous slurry containing the catalyst component is not particularly limited, but it is preferable to dry the slurry using a spray drier in order to obtain a higher performance catalyst.
Dry powder obtained by spray drying is spherical particles,
By performing wet shaping using this, voids surrounded by spherical particles are formed, and a more effective pore structure for the catalytic reaction can be expressed. The average particle diameter of the spherical particles obtained by spray drying is preferably from 30 to 100 μm, particularly preferably from 35 to 90 μm. When the aqueous slurry is dried by the evaporation to dryness method or the like, a lump-shaped dried product may be obtained. In this case, it is preferable to appropriately pulverize the aqueous slurry to obtain a powder.
【0010】次いで、このようにして得られた乾燥粉を
焼成する。焼成条件としては特に限定はなく、公知の焼
成条件を適用することができる。通常、焼成は200〜
600℃の温度範囲で行われ、焼成時間は目的とする触
媒によって適宜選択される。Next, the thus obtained dried powder is fired. The firing conditions are not particularly limited, and known firing conditions can be applied. Usually firing is 200 ~
The calcination is performed in a temperature range of 600 ° C., and the calcination time is appropriately selected depending on the target catalyst.
【0011】続いて、得られた焼成物に水を添加して湿
式賦形する。湿式賦形の方法および形状は特に限定され
るものではなく、押出成形機、転動造粒機等の一般的な
湿式成形機を用いて、球状、リング状、円柱状、星型状
等の任意の形状に賦形することができる。賦形の際に添
加する水の量は、触媒焼成物100重量部に対して15
〜40重量部の範囲が好ましい。この際には、従来公知
の添加剤、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を必要に応じて添加することもでき
る。更には、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。Subsequently, water is added to the obtained fired product to perform wet shaping. The method and shape of the wet shaping are not particularly limited, and a general wet molding machine such as an extruder, a rolling granulator, and the like, may be used, such as a sphere, a ring, a column, and a star. It can be shaped into any shape. The amount of water added at the time of shaping is 15 parts per 100 parts by weight of the baked catalyst.
A range of 4040 parts by weight is preferred. At this time, conventionally known additives, for example, polyvinyl alcohol, carboxymethyl cellulose, and the like can be added as necessary. Further, inorganic compounds such as graphite and diatomaceous earth, and inorganic fibers such as glass fiber, ceramic fiber and carbon fiber may be added.
【0012】次いで得られた湿式賦形体を乾燥する。乾
燥の際にはマイクロ波および熱風を併用して乾燥させる
ことが重要である。一般に、工業用途で加熱に用いられ
ているマイクロ波は、2,450MHz、915MHz
の2バンドのものであり、装置の入手が容易であること
から、このマイクロ波を発生させることが出来る乾燥機
の使用が好ましいが、必ずしもこれに限定されるもので
はない。Next, the obtained wet shaped body is dried. It is important to use microwaves and hot air in combination for drying. Generally, microwaves used for heating in industrial applications are 2,450 MHz and 915 MHz.
The use of a dryer capable of generating microwaves is preferred, but is not necessarily limited to this.
【0013】熱風の温度は、50〜200℃が好まし
く、特に60〜150℃が好ましい。熱風の温度が50
℃未満の場合、マイクロ波乾燥中に発生する水蒸気が乾
燥室内で結露し、マイクロ波が結露した水に吸収されて
しまうためエネルギー効率が低下するので好ましくな
い。また、熱風の温度が200℃を超えた場合、熱風に
より外表面の乾燥速度が内部の乾燥速度に比べて相対的
に増大するため、湿式賦形体の外表面の細孔が閉塞する
恐れがあり好ましくない。[0013] The temperature of the hot air is preferably from 50 to 200 ° C, particularly preferably from 60 to 150 ° C. Hot air temperature is 50
If the temperature is lower than 0 ° C., water vapor generated during microwave drying is condensed in the drying chamber, and the microwave is absorbed by the condensed water. Further, when the temperature of the hot air exceeds 200 ° C., since the drying speed of the outer surface is relatively increased by the hot air as compared with the inner drying speed, there is a possibility that pores on the outer surface of the wet-type shaped body may be blocked. Not preferred.
【0014】マイクロ波および熱風を併用した乾燥時間
は、目的とする乾燥賦形体の含水率や乾燥速度等にもよ
るが、通常10秒〜30分間程度である。マイクロ波と
熱風は常に併用して使用する必要はなく、例えば、マイ
クロ波と熱風とを併用して乾燥を開始し、湿式賦形体の
含水率が15重量%未満に達した時点で熱風だけの乾燥
に切り替えるといったことも可能である。The drying time using microwaves and hot air together is usually about 10 seconds to 30 minutes, though it depends on the water content, drying speed, etc. of the desired dried shaped body. It is not necessary to always use the microwave and the hot air together, for example, the drying is started by using the microwave and the hot air together, and only the hot air is used when the moisture content of the wet shaped body reaches less than 15% by weight. It is also possible to switch to drying.
【0015】従来の熱風だけを用いた乾燥方法では、湿
式賦形体の表面から加熱されるため、まず外表面に近い
部分の水分が急激に蒸発し、続いて相対的に移動可能な
状態にある湿式賦形体内部の微細粒子が外表面付近に移
動して乾燥するため、外表面付近の細孔が閉塞するもの
と推定される。In the conventional drying method using only hot air, since the wet shaped body is heated from the surface, first, the water near the outer surface evaporates rapidly, and is in a relatively movable state. It is presumed that the fine particles inside the wet excipient moved to the vicinity of the outer surface and dried, so that pores near the outer surface were closed.
【0016】本発明においては、マイクロ波を照射する
ことにより、湿式賦形体の内部の乾燥速度を外部の乾燥
速度に近づけることで、内部の微細粒子の移動が抑制さ
れ、外表面の細孔の閉塞が抑制されたものと推定され
る。しかしながら、マイクロ波だけを用いて乾燥させる
と、マイクロ波の照射位置により湿式賦形体に乾燥むら
が生じやすく、均一に乾燥させることが困難となるた
め、熱風を併用して乾燥させる必要がある。In the present invention, by irradiating the microwave, the internal drying speed of the wet type shaped body is made closer to the external drying speed, whereby the movement of the internal fine particles is suppressed, and the pores on the external surface are reduced. It is estimated that the blockage was suppressed. However, when drying is performed using only microwaves, unevenness in drying tends to occur in the wet-shaped shaped body depending on the irradiation position of the microwaves, and it is difficult to dry uniformly. Therefore, it is necessary to use hot air in combination for drying.
【0017】このように湿式賦形体を乾燥して得られた
乾燥賦形体は、触媒としてこのまま反応に使用してもよ
いが、再度焼成しても構わない。再度焼成する場合の焼
成温度は、通常200〜600℃である。The dried shaped body obtained by drying the wet shaped body as described above may be used as it is as a catalyst in the reaction, or may be fired again. The firing temperature for firing again is usually 200 to 600 ° C.
【0018】本発明の方法により製造された触媒は、プ
ロピレン、イソブチレン、TBAまたはMTBEを気相
接触酸化して不飽和アルデヒドおよび不飽和カルボン酸
を合成するために使用される触媒である。具体的には、
プロピレンからアクロレインおよびアクリル酸を合成
し、イソブチレン、TBAまたはMTBEからメタクロ
レインおよびメタクリル酸を合成するために使用される
触媒である。The catalyst produced by the method of the present invention is a catalyst used for synthesizing unsaturated aldehydes and unsaturated carboxylic acids by subjecting propylene, isobutylene, TBA or MTBE to gas phase catalytic oxidation. In particular,
It is a catalyst used to synthesize acrolein and acrylic acid from propylene and to synthesize methacrolein and methacrylic acid from isobutylene, TBA or MTBE.
【0019】この触媒を用いて不飽和アルデヒドおよび
不飽和カルボン酸を合成する際の反応は、通常固定床反
応器で行われる。このときの反応条件は、従来から知ら
れている通常の条件が適用できるが、プロピレン、イソ
ブチレン、TBAまたはMTBE対酸素の好ましいモル
比は1:0.5〜3である。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
化した空気も用いうる。原料ガスは窒素等の不活性ガス
で希釈して用いることが好ましく、水蒸気や炭酸ガス等
を含んでもよい。The reaction for synthesizing unsaturated aldehydes and unsaturated carboxylic acids using this catalyst is usually carried out in a fixed-bed reactor. As the reaction conditions at this time, conventionally known ordinary conditions can be applied, but the preferred molar ratio of propylene, isobutylene, TBA or MTBE to oxygen is 1: 0.5 to 3. It is economical to use air as the molecular oxygen source, but if necessary, air enriched with pure oxygen can also be used. The raw material gas is preferably used after being diluted with an inert gas such as nitrogen, and may contain steam, carbon dioxide gas, or the like.
【0020】反応圧力は常圧から数気圧までがよい。反
応温度は200〜450℃の範囲で選ぶことができる
が、特に250〜400℃の範囲が好ましい。また、固
定床反応器中において、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担体で希釈されていてもよ
い。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 is particularly preferably in the range of 250 to 400 ° C. In the fixed bed reactor, the catalyst may be diluted with an inert carrier such as silica, alumina, silica-alumina, silicon carbide, ceramic balls, and stainless steel.
【0021】[0021]
【実施例】以下、本発明による触媒の製造例、および得
られた触媒を用いた反応例について具体的に説明する。
実施例および比較例において「部」は重量部を意味す
る。反応生成物の分析はガスクロマトグラフィーにより
行った。原料オレフィン、TBAまたはMTBEの反応
率(以下、原料の反応率という)、生成する不飽和アル
デヒドおよび不飽和カルボン酸の選択率は以下のように
定義される。 原料の反応率(%)=B/A×100 不飽和アルデヒドの選択率(%)=C/B×100 不飽和カルボン酸の選択率(%)=D/B×100 ここでAは供給した原料オレフィン、TBAまたはMT
BEのモル数、Bは反応した原料オレフィン、TBAま
たはMTBEのモル数、Cは生成した不飽和アルデヒド
のモル数、Dは生成した不飽和カルボン酸のモル数を示
す。EXAMPLES Hereinafter, production examples of the catalyst according to the present invention and reaction examples using the obtained catalyst will be specifically described.
In the examples and comparative examples, “parts” means parts by weight. The reaction product was analyzed by gas chromatography. The reaction rate of the starting olefin, TBA or MTBE (hereinafter referred to as the reaction rate of the starting material) and the selectivity of the unsaturated aldehyde and unsaturated carboxylic acid to be formed are defined as follows. Reaction rate (%) of raw material = B / A × 100 Selectivity of unsaturated aldehyde (%) = C / B × 100 Selectivity of unsaturated carboxylic acid (%) = D / B × 100 Here, A was supplied. Raw olefin, TBA or MT
The number of moles of BE, B is the number of moles of the reacted starting olefin, TBA or MTBE, C is the number of moles of the unsaturated aldehyde generated, and D is the number of moles of the unsaturated carboxylic acid generated.
【0022】[実施例1]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6.2部、硝酸カリウム1.4部、三酸化アン
チモン27.5部および三酸化ビスマス66.0部を加
え加熱攪拌した(A液)。別に純水1000部に硝酸第
二鉄114.4部、硝酸コバルト288.4部および硝
酸亜鉛35.1部を順次加え溶解した(B液)。A液に
B液を加え水性スラリーとした後、該水性スラリーをス
プレー乾燥機を用いて乾燥球状粒子(平均粒子径72.
2μm)を得た後、得られた乾燥球状粒子を300℃で
1時間焼成を行い触媒焼成物を得た。このようにして得
られた触媒焼成物500部に純水160部を混合し、ニ
ーダーにて混練りした後、押出成形して外径5mm、内
径2mm、平均長さ5mmのリング状の湿式賦形体を得
た。この湿式賦形体500gに対して1KWのマイクロ
波(2,450MHz)と100℃の熱風を併用して7
分間乾燥を行い乾燥賦形体を得た。この乾燥賦形体を5
10℃で3時間再度焼成を行い、以下の組成(酸素を除
く、以下同じ)の触媒を得た。 Mo12W0.1Bi1.2Fe1.2Sb0.8Co4.2Zn0.5K
0.06 Example 1 500 parts of ammonium paramolybdate, 6.2 parts of ammonium paratungstate, 1.4 parts of potassium nitrate, 27.5 parts of antimony trioxide and 66.0 parts of bismuth trioxide in 1000 parts of pure water Was added and stirred with heating (Solution A). Separately, 114.4 parts of ferric nitrate, 288.4 parts of cobalt nitrate and 35.1 parts of zinc nitrate were sequentially added and dissolved in 1000 parts of pure water (solution B). After the solution B is added to the solution A to form an aqueous slurry, the aqueous slurry is dried using a spray dryer to form dried spherical particles (average particle diameter of 72.
2 μm), the obtained dried spherical particles were calcined at 300 ° C. for 1 hour to obtain a calcined catalyst product. 500 parts of the catalyst fired product thus obtained was mixed with 160 parts of pure water, kneaded in a kneader, and extruded to form a ring-shaped wet application having an outer diameter of 5 mm, an inner diameter of 2 mm, and an average length of 5 mm. Obtained the form. A microwave (2,450 MHz) of 1 KW and hot air of 100 ° C. are used in combination with 500 g of the wet shaped body to obtain 7 g.
After drying for a minute, a dried excipient was obtained. 5
Recalcination was performed at 10 ° C. for 3 hours to obtain a catalyst having the following composition (excluding oxygen, the same applies hereinafter). Mo 12 W 0.1 Bi 1.2 Fe 1.2 Sb 0.8 Co 4.2 Zn 0.5 K
0.06
【0023】この触媒をステンレス製反応管に充填し、
プロピレン5%、酸素12%、水蒸気10%および窒素
73%(容量%)の原料ガスを接触時間3.6秒にて触
媒層を通過させ、310℃で反応させた。その結果、プ
ロピレンの反応率99.1%、アクロレインの選択率9
1.1%、アクリル酸の選択率6.5%であった。This catalyst is filled in a stainless steel reaction tube,
A raw material gas of propylene 5%, oxygen 12%, steam 10% and nitrogen 73% (vol%) was passed through the catalyst layer for a contact time of 3.6 seconds, and reacted at 310 ° C. As a result, the conversion of propylene was 99.1% and the selectivity of acrolein was 9
1.1% and selectivity of acrylic acid was 6.5%.
【0024】[比較例1]実施例1において、湿式賦形
体を1kWのマイクロ波(2,450MHz)だけで7
分間乾燥し、熱風を併用しなかった点以外は実施例1と
同様にして触媒を製造した。この触媒を用いて実施例1
と同じ条件で反応を行った結果、プロピレンの反応率9
9.0%、アクロレインの選択率90.7%、アクリル
酸の選択率6.3%であった。[Comparative Example 1] In Example 1, the wet-type shaped body was irradiated with only 1 kW microwave (2,450 MHz).
After drying for a minute, a catalyst was produced in the same manner as in Example 1 except that hot air was not used in combination. Example 1 using this catalyst
As a result of carrying out the reaction under the same conditions as in
9.0%, acrolein selectivity was 90.7%, and acrylic acid selectivity was 6.3%.
【0025】[比較例2]実施例1において、マイクロ
波を使用せず、湿式賦形体を100℃の熱風だけを用い
て7分間乾燥したところ、乾燥が不十分であったので1
00℃の熱風だけを用いてさらに15分間乾燥を行った
以外は実施例1と同様にして触媒を製造した。この触媒
を用いて実施例1と同じ条件で反応を行った結果、プロ
ピレンの反応率98.9%、アクロレインの選択率9
0.6%、アクリル酸の選択率6.2%であった。[Comparative Example 2] In Example 1, the wet shaped body was dried for 7 minutes using only 100 ° C. hot air without using microwaves.
A catalyst was produced in the same manner as in Example 1 except that drying was performed for another 15 minutes using only hot air at 00 ° C. Using this catalyst, the reaction was carried out under the same conditions as in Example 1. As a result, the conversion of propylene was 98.9% and the selectivity of acrolein was 9
The selectivity for acrylic acid was 0.6% and the acrylic acid selectivity was 6.2%.
【0026】[実施例2]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6.2部、硝酸カリウム1.4部、三酸化アン
チモン27.5部および三酸化ビスマス66.0部を加
え加熱攪拌した(A液)。別に純水1000部に硝酸第
二鉄95.3部、硝酸コバルト267.8部および硝酸
亜鉛35.1部を順次加え溶解した(B液)。A液にB
液を加え水性スラリーとした後、該水性スラリーをドラ
ムドライヤーを用いて乾燥粒子(平均粒子径40.1μ
m)を得た後、得られた乾燥粒子を300℃で1時間焼
成を行い触媒焼成物を得た。このようにして得られた触
媒焼成物500部に純水160部を混合し、ニーダーに
て混練りした後、押出成形して外径5mm、内径2m
m、平均長さ5mmのリング状の湿式賦形体を得た。こ
の湿式賦形体500gに対して1kWのマイクロ波
(2,450MHz)と130℃の熱風を併用して6分
間乾燥を行い乾燥賦形体を得た。この乾燥賦形体を51
0℃で3時間再度焼成を行い、以下の組成の触媒を得
た。 Mo12W0.1Bi1.2Fe1.0Sb0.8Co3.9Zn0.5K
0.06 Example 2 500 parts of ammonium paramolybdate, 6.2 parts of ammonium paratungstate, 1.4 parts of potassium nitrate, 27.5 parts of antimony trioxide and 66.0 parts of bismuth trioxide in 1000 parts of pure water Was added and stirred with heating (Solution A). Separately, 95.3 parts of ferric nitrate, 267.8 parts of cobalt nitrate and 35.1 parts of zinc nitrate were sequentially added and dissolved in 1000 parts of pure water (solution B). A to B
After adding the liquid to form an aqueous slurry, the aqueous slurry was dried with a drum dryer (average particle diameter of 40.1 μm).
After obtaining m), the obtained dried particles were fired at 300 ° C. for 1 hour to obtain a fired catalyst product. To 500 parts of the fired catalyst product thus obtained, 160 parts of pure water was mixed, kneaded with a kneader, and extruded to form an outer diameter of 5 mm and an inner diameter of 2 m.
m, a ring-shaped wet shaped body having an average length of 5 mm was obtained. Drying was performed for 6 minutes using a microwave (2,450 MHz) of 1 kW and hot air of 130 ° C. in combination with 500 g of the wet shaped body to obtain a dried shaped body. This dried excipient is placed in 51
The mixture was calcined again at 0 ° C. for 3 hours to obtain a catalyst having the following composition. Mo 12 W 0.1 Bi 1.2 Fe 1.0 Sb 0.8 Co 3.9 Zn 0.5 K
0.06
【0027】この触媒をステンレス製反応管に充填し、
プロピレン5%、酸素12%、水蒸気10%および窒素
73%(容量%)の原料ガスを接触時間3.6秒にて触
媒層を通過させ、310℃で反応させた。その結果、プ
ロピレンの反応率98.7%、アクロレインの選択率9
0.7%、アクリル酸の選択率6.3%であった。This catalyst is filled in a stainless steel reaction tube,
A raw material gas of propylene 5%, oxygen 12%, steam 10% and nitrogen 73% (vol%) was passed through the catalyst layer for a contact time of 3.6 seconds, and reacted at 310 ° C. As a result, the conversion of propylene was 98.7% and the selectivity of acrolein was 9
0.7% and selectivity for acrylic acid were 6.3%.
【0028】[比較例3]実施例2において、湿式賦形
体を1kWのマイクロ波(2,450MHz)だけで7
分間乾燥し、熱風を併用しなかった点以外は実施例2と
同様にして触媒を製造した。この触媒を用いて実施例2
と同じ条件で反応を行った結果、プロピレンの反応率9
8.6%、アクロレインの選択率90.1%、アクリル
酸の選択率6.1%であった。[Comparative Example 3] In Example 2, the wet extruded body was subjected to a 7 kW microwave (2,450 MHz) alone.
After drying for 2 minutes, a catalyst was produced in the same manner as in Example 2 except that hot air was not used in combination. Example 2 using this catalyst
As a result of carrying out the reaction under the same conditions as in
8.6%, acrolein selectivity was 90.1%, and acrylic acid selectivity was 6.1%.
【0029】[比較例4]実施例2において、マイクロ
波を使用せず、湿式賦形体を130℃の熱風だけを用い
て6分間乾燥したところ、乾燥が不十分であったので1
30℃の熱風だけを用いてさらに15分間乾燥を行った
以外は実施例2と同様にして触媒を製造した。この触媒
を用いて反応を行った結果、プロピレンの反応率98.
4%、アクロレインの選択率90.1%、アクリル酸の
選択率6.0%であった。[Comparative Example 4] In Example 2, the wet shaped body was dried for 6 minutes using only 130 ° C. hot air without using microwaves.
A catalyst was produced in the same manner as in Example 2, except that drying was performed for another 15 minutes using only hot air at 30 ° C. As a result of performing a reaction using this catalyst, the conversion of propylene was 98.
4%, acrolein selectivity was 90.1%, and acrylic acid selectivity was 6.0%.
【0030】[実施例3]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6.2部、硝酸セシウム23.0部、三酸化ア
ンチモン27.5部および三酸化ビスマス33.0部を
加え加熱攪拌した(A液)。別に純水1000部に硝酸
第二鉄190.7部、硝酸ニッケル68.6部、硝酸コ
バルト446.4部、硝酸鉛39.1部および85%リ
ン酸2.7部を順次加え溶解した(B液)。A液にB液
を加え水性スラリーした後、該水性スラリーをスプレー
ドライヤーを用いて乾燥球状粒子(平均粒子径65.3
μm)を得た後、得られた乾燥粒子を300℃で1時間
焼成を行い触媒焼成物を得た。このようにして得られた
触媒焼成物500部に純水160部を混合した後、ニー
ダーにて混練りし、押出成形して外径5mm、内径2m
m、平均長さ5mmのリング状の湿式賦形体を得た。こ
の湿式賦形体500gに対して1kWのマイクロ波
(2,450MHz)と100℃の熱風を併用して7分
間乾燥を行い乾燥賦形体を得た。この乾燥賦形体を51
0℃で3時間再度焼成を行い、以下の組成の触媒を得
た。Mo12W0.1Bi0.6Fe2Sb0.8Ni1Co6.5Pb
0.5P0.1Cs0.5 Example 3 500 parts of ammonium paramolybdate, 6.2 parts of ammonium paratungstate, 23.0 parts of cesium nitrate, 27.5 parts of antimony trioxide and 33.0 parts of bismuth trioxide in 1000 parts of pure water The mixture was heated and stirred (Solution A). Separately, 190.7 parts of ferric nitrate, 68.6 parts of nickel nitrate, 446.4 parts of cobalt nitrate, 39.1 parts of lead nitrate and 2.7 parts of 85% phosphoric acid were sequentially added to 1000 parts of pure water and dissolved. B liquid). Liquid B was added to Liquid A to form an aqueous slurry, and the aqueous slurry was dried using a spray drier to obtain dried spherical particles (average particle diameter of 65.3).
μm), the obtained dried particles were fired at 300 ° C. for 1 hour to obtain a fired catalyst product. After mixing 160 parts of pure water with 500 parts of the catalyst fired product thus obtained, the mixture is kneaded with a kneader, and extruded to form an outer diameter of 5 mm and an inner diameter of 2 m.
m, a ring-shaped wet shaped body having an average length of 5 mm was obtained. Drying was performed for 7 minutes using a microwave (2,450 MHz) of 1 kW and hot air of 100 ° C. in combination with 500 g of the wet shaped body to obtain a dried shaped body. This dried excipient is placed in 51
The mixture was calcined again at 0 ° C. for 3 hours to obtain a catalyst having the following composition. Mo 12 W 0.1 Bi 0.6 Fe 2 Sb 0.8 Ni 1 Co 6.5 Pb
0.5 P 0.1 Cs 0.5
【0031】この触媒をステンレス製反応管に充填し、
イソブチレン5%、酸素12%、水蒸気10%および窒
素73%(容量%)の原料ガスを接触時間3.6秒にて
触媒層を通過させ、340℃で反応させた。その結果、
イソブチレンの反応率97.9%、メタクロレインの選
択率89.9%、メタクリル酸の選択率4.0%であっ
た。The catalyst is filled in a stainless steel reaction tube,
A raw material gas containing 5% of isobutylene, 12% of oxygen, 10% of water vapor and 73% of nitrogen (volume%) was passed through the catalyst layer for a contact time of 3.6 seconds, and reacted at 340 ° C. as a result,
The conversion of isobutylene was 97.9%, the selectivity of methacrolein was 89.9%, and the selectivity of methacrylic acid was 4.0%.
【0032】[比較例5]実施例3において、湿式賦形
体を1kWのマイクロ波(2,450MHz)だけで7
分間乾燥し、熱風を併用しなかった点以外は実施例3と
同様にして触媒を製造した。この触媒を用いて実施例3
と同じ条件で反応を行った結果、イソブチレンの反応率
97.7%、メタクロレインの選択率89.5%、メタ
クリル酸の選択率3.8%であった。[Comparative Example 5] In Example 3, the wet shaped body was subjected to 7 MW only with a 1 kW microwave (2,450 MHz).
A catalyst was produced in the same manner as in Example 3 except that the catalyst was dried for a minute and hot air was not used in combination. Example 3 using this catalyst
As a result, the reaction was 97.7% for isobutylene, 89.5% for methacrolein, and 3.8% for methacrylic acid.
【0033】[比較例6]実施例3において、マイクロ
波を使用せず湿式賦形体を100℃の熱風だけを用いて
7分間乾燥したところ、乾燥が不十分であったので10
0℃の熱風だけを用いてさらに15分間乾燥を行った点
以外は実施例3と同様にして触媒を製造した。この触媒
を用いて実施例3と同じ条件で反応を行った結果、イソ
ブチレンの反応率97.5%、メタクロレインの選択率
89.4%、メタクリル酸の選択率3.7%であった。[Comparative Example 6] In Example 3, the wet shaped body was dried for 7 minutes using only hot air at 100 ° C without using microwaves.
A catalyst was produced in the same manner as in Example 3, except that drying was performed for another 15 minutes using only hot air at 0 ° C. The reaction was carried out under the same conditions as in Example 3 using this catalyst. As a result, the conversion of isobutylene was 97.5%, the selectivity of methacrolein was 89.4%, and the selectivity of methacrylic acid was 3.7%.
【0034】[実施例4]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6.2部、硝酸セシウム23.0部、三酸化ア
ンチモン27.5部および三酸化ビスマス33.0部を
加え加熱攪拌した(A液)。別に純水1000部に硝酸
第二鉄209.8部、硝酸ニッケル54.9部、硝酸コ
バルト446.4部および85%リン酸2.7部を順次
加え溶解した(B液)。A液にB液を加え水性スラリー
した後、該水性スラリーをスプレードライヤーを用いて
乾燥球状粒子(平均粒子径48.3μm)を得た後、得
られた乾燥粒子を300℃で1時間焼成を行い触媒焼成
物を得た。このようにして得られた触媒焼成物500部
に純水160部を混合した後、ニーダーにて粘土状にな
るまで混合した後、押出成形して外径5mm、内径2m
m、平均長さ5mmのリング状の湿式賦形体を得た。こ
の湿式賦形体500gに対して1kWのマイクロ波
(2,450MHz)と75℃の熱風を併用して9分間
乾燥を行い乾燥賦形体を得た。この乾燥賦形体を510
℃で3時間再度焼成を行い、以下の組成の触媒を得た。 Mo12W0.1Bi0.6Fe2.2Sb0.8Ni0.8Co6.5P
0.1Cs0.5 Example 4 500 parts of ammonium paramolybdate, 6.2 parts of ammonium paratungstate, 23.0 parts of cesium nitrate, 27.5 parts of antimony trioxide and 33.0 parts of bismuth trioxide in 1000 parts of pure water The mixture was heated and stirred (Solution A). Separately, 209.8 parts of ferric nitrate, 54.9 parts of nickel nitrate, 446.4 parts of cobalt nitrate and 2.7 parts of 85% phosphoric acid were sequentially added and dissolved in 1000 parts of pure water (solution B). After the aqueous slurry was added to the liquid A to obtain the aqueous slurry, the aqueous slurry was dried using a spray drier to obtain dried spherical particles (average particle diameter: 48.3 μm), and the obtained dried particles were calcined at 300 ° C. for 1 hour. This was performed to obtain a fired catalyst product. After mixing 160 parts of pure water with 500 parts of the catalyst calcined product thus obtained, mixing the mixture with a kneader until the mixture becomes clay-like, and then extruding the mixture to form an outer diameter of 5 mm and an inner diameter of 2 m.
m, a ring-shaped wet shaped body having an average length of 5 mm was obtained. Drying was performed for 9 minutes using a microwave (2,450 MHz) of 1 kW and hot air of 75 ° C. in combination with 500 g of the wet shaped body to obtain a dried shaped body. This dried excipient is added to 510
The mixture was calcined again at 3 ° C. for 3 hours to obtain a catalyst having the following composition. Mo 12 W 0.1 Bi 0.6 Fe 2.2 Sb 0.8 Ni 0.8 Co 6.5 P
0.1 Cs 0.5
【0035】この触媒をステンレス製反応管に充填し、
イソブチレン5%、酸素12%、水蒸気10%および窒
素73%(容量%)の原料ガスを接触時間3.6秒にて
触媒層を通過させ、340℃で反応させた。その結果、
イソブチレンの反応率97.9%、メタクロレインの選
択率89.9%、メタクリル酸の選択率4.1%であっ
た。This catalyst is filled in a stainless steel reaction tube,
A raw material gas containing 5% of isobutylene, 12% of oxygen, 10% of water vapor and 73% of nitrogen (volume%) was passed through the catalyst layer for a contact time of 3.6 seconds, and reacted at 340 ° C. as a result,
The conversion of isobutylene was 97.9%, the selectivity of methacrolein was 89.9%, and the selectivity of methacrylic acid was 4.1%.
【0036】[比較例7]実施例4において、湿式賦形
体を1kWのマイクロ波(2,450MHz)だけで9
分間乾燥し、熱風を併用しなかった点以外は実施例4と
同様にして触媒を製造した。この触媒を用いて実施例4
と同じ条件で反応を行った。その結果、イソブチレンの
反応率97.6%、メタクロレインの選択率89.6
%、メタクリル酸の選択率3.8%であった。[Comparative Example 7] In Example 4, the wet shaped body was subjected to 9 microwaves only with 1 kW microwave (2,450 MHz).
A catalyst was produced in the same manner as in Example 4 except that the catalyst was dried for a minute and hot air was not used in combination. Example 4 using this catalyst
The reaction was carried out under the same conditions as described above. As a result, the conversion of isobutylene was 97.6% and the selectivity of methacrolein was 89.6.
%, And the selectivity of methacrylic acid was 3.8%.
【0037】[比較例8]実施例4において、マイクロ
波を使用せず、湿式賦形体を75℃の熱風だけを用いて
9分間乾燥したところ、乾燥が不十分であったので75
℃の熱風だけを用いてさらに15分間乾燥を行った点以
外は実施例4と同様にして触媒を製造した。この触媒を
用いて実施例4と同じ条件で反応を行った結果、イソブ
チレンの反応率97.5%、メタクロレインの選択率8
9.5%、メタクリル酸の選択率3.7%であった。[Comparative Example 8] In Example 4, the wet shaped body was dried for 9 minutes using only hot air at 75 ° C without using microwaves.
A catalyst was produced in the same manner as in Example 4, except that drying was performed for another 15 minutes using only hot air at ° C. The reaction was carried out under the same conditions as in Example 4 using this catalyst. As a result, the conversion of isobutylene was 97.5% and the selectivity of methacrolein was 8
The selectivity of 9.5% and methacrylic acid was 3.7%.
【0038】[実施例5]実施例3において製造した触
媒を用いて、原料のイソブチレンをTBAに変えた以外
は実施例3と同じ条件で反応を行った結果、TBAの反
応率100%、メタクロレインの選択率88.8%、メ
タクリル酸の選択率3.1%であった。Example 5 Using the catalyst prepared in Example 3, the reaction was carried out under the same conditions as in Example 3 except that the raw material isobutylene was changed to TBA. The selectivity for rain was 88.8% and the selectivity for methacrylic acid was 3.1%.
【0039】[比較例9]比較例5において製造した触
媒を用いて、原料のイソブチレンをTBAに変えた以外
は比較例5と同じ条件で反応を行った結果、TBAの反
応率100%、メタクロレインの選択率88.3%、メ
タクリル酸の選択率2.9%であった。Comparative Example 9 Using the catalyst prepared in Comparative Example 5, the reaction was carried out under the same conditions as in Comparative Example 5 except that the raw material isobutylene was changed to TBA. The selectivity for rain was 88.3% and the selectivity for methacrylic acid was 2.9%.
【0040】[比較例10]比較例6において製造した
触媒を用いて、原料のイソブチレンをTBAに変えた以
外は比較例6と同じ条件で反応を行った結果、TBAの
反応率100%、メタクロレインの選択率88.0%、
メタクリル酸の選択率2.8%であった。Comparative Example 10 Using the catalyst prepared in Comparative Example 6, the reaction was carried out under the same conditions as in Comparative Example 6 except that the raw material isobutylene was changed to TBA. Rain selectivity 88.0%,
The selectivity of methacrylic acid was 2.8%.
【0041】[0041]
【発明の効果】本発明の方法によれば、プロピレン、イ
ソブチレン、TBAまたはMTBEを分子状酸素を用い
て気相接触酸化し、不飽和アルデヒドおよび不飽和カル
ボン酸を有利に合成できる触媒が得られる。According to the process of the present invention, a catalyst can be obtained which is capable of advantageously synthesizing unsaturated aldehydes and unsaturated carboxylic acids by subjecting propylene, isobutylene, TBA or MTBE to gas-phase catalytic oxidation using molecular oxygen. .
フロントページの続き (51)Int.Cl.6 識別記号 FI C07C 45/39 C07C 45/39 47/21 47/21 57/05 57/05 // C07B 61/00 300 C07B 61/00 300 (72)発明者 近藤 正英 広島県大竹市御幸町20番1号 三菱レイヨ ン株式会社中央技術研究所内 (72)発明者 黒田 徹 広島県大竹市御幸町20番1号 三菱レイヨ ン株式会社中央技術研究所内Continued on the front page (51) Int.Cl. 6 Identification code FI C07C 45/39 C07C 45/39 47/21 47/21 57/05 57/05 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Masahide Kondo 20-1, Miyuki-cho, Otake-shi, Hiroshima Prefecture, Central Research Laboratory of Mitsubishi Rayon Co., Ltd. (72) Inventor Toru Kuroda 20-1, Miyuki-cho, Otake City, Hiroshima Prefecture, Central Research Laboratory of Mitsubishi Rayon Co., Ltd.
Claims (3)
ルアルコールおよび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し、不飽和アルデヒドおよ
び不飽和カルボン酸を合成する際に用いられる触媒の製
造方法おいて、少なくともモリブデン、ビスマスおよび
鉄を含む触媒の製造において、触媒成分を含む水性スラ
リーを乾燥し、次いで焼成し、得られた焼成物を湿式賦
形した湿式賦形体をマイクロ波および熱風を併用して乾
燥することを特徴とする触媒の製造方法。1. A catalyst used for synthesizing unsaturated aldehydes and unsaturated carboxylic acids by subjecting propylene, isobutylene, tertiary butyl alcohol and methyl tertiary butyl ether to gas phase catalytic oxidation using molecular oxygen. In the production method, in the production of a catalyst containing at least molybdenum, bismuth and iron, an aqueous slurry containing a catalyst component is dried and then calcined, and the obtained calcined material is subjected to wet shaping by microwave and hot air. And drying the catalyst.
媒。2. A catalyst produced by the method of claim 1.
とする、プロピレン、イソブチレン、第三級ブチルアル
コールおよび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し、不飽和アルデヒドおよび不飽
和カルボン酸を製造する方法。3. An unsaturated aldehyde obtained by subjecting propylene, isobutylene, tertiary butyl alcohol and methyl tertiary butyl ether to gas-phase catalytic oxidation using molecular oxygen, using the catalyst according to claim 2. And a method for producing an unsaturated carboxylic acid.
Priority Applications (1)
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JP9228307A JPH1157476A (en) | 1997-08-25 | 1997-08-25 | Preparation of catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acid |
Applications Claiming Priority (1)
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JP9228307A JPH1157476A (en) | 1997-08-25 | 1997-08-25 | Preparation of catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acid |
Publications (1)
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JPH1157476A true JPH1157476A (en) | 1999-03-02 |
Family
ID=16874398
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JP9228307A Pending JPH1157476A (en) | 1997-08-25 | 1997-08-25 | Preparation of catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acid |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004085060A1 (en) * | 2003-03-26 | 2004-10-07 | Lg Chem Ltd. | Method for preparing catalysts for partial oxidation of propylene and iso-butylene |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63236766A (en) * | 1987-03-26 | 1988-10-03 | 松下電工株式会社 | Method of drying ceramics |
JPH09117664A (en) * | 1995-10-23 | 1997-05-06 | Mitsubishi Rayon Co Ltd | Preparation of catalyst for synthesis of unsaturated aldehyde and unsaturated carboxylic acid |
-
1997
- 1997-08-25 JP JP9228307A patent/JPH1157476A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63236766A (en) * | 1987-03-26 | 1988-10-03 | 松下電工株式会社 | Method of drying ceramics |
JPH09117664A (en) * | 1995-10-23 | 1997-05-06 | Mitsubishi Rayon Co Ltd | Preparation of catalyst for synthesis of unsaturated aldehyde and unsaturated carboxylic acid |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004085060A1 (en) * | 2003-03-26 | 2004-10-07 | Lg Chem Ltd. | Method for preparing catalysts for partial oxidation of propylene and iso-butylene |
US7329628B2 (en) | 2003-03-26 | 2008-02-12 | Lg Chem, Ltd. | Method for preparing catalysts for partial oxidation of propylene and iso-butylene |
CN100423837C (en) * | 2003-03-26 | 2008-10-08 | Lg化学株式会社 | Method for preparing catalysts for partial oxidation of propylene and iso-butylene |
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