JPS5939413B2 - Method for producing methacrolein and methacrylic acid - Google Patents
Method for producing methacrolein and methacrylic acidInfo
- Publication number
- JPS5939413B2 JPS5939413B2 JP50042565A JP4256575A JPS5939413B2 JP S5939413 B2 JPS5939413 B2 JP S5939413B2 JP 50042565 A JP50042565 A JP 50042565A JP 4256575 A JP4256575 A JP 4256575A JP S5939413 B2 JPS5939413 B2 JP S5939413B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- catalyst
- methacrylic acid
- added
- nickel
- 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
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)
Description
【発明の詳細な説明】
本発明は、第3級ブチルアルコールもしくはイソブテン
から気相接触酸化法でメタクロレインとメタクリル酸を
製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing methacrolein and methacrylic acid from tertiary butyl alcohol or isobutene by a gas phase catalytic oxidation method.
第3級ブチルアルコールからメタクロレインおよびメタ
クリル酸を製造する方法に関し、本発明者らは先にPW
MoTesb系の触媒を用いる方法を提案した(特願昭
48−96948号)。Regarding the method for producing methacrolein and methacrylic acid from tertiary butyl alcohol, the present inventors previously reported that PW
A method using a MoTesb-based catalyst was proposed (Japanese Patent Application No. 96948/1983).
そこに示された触媒の反応成績は非常に良好であり、メ
タクロレインとメタクリル酸の単流収率は80モル%に
も達するが、反応温度が比較的高いという欠点があつた
。反応温度が高いと触媒の寿命を短くするのみならず、
反応操作上も好ましくないため出来るだけ低く保つこと
が有利である。本発明者らは、上記触媒の活性増加につ
いて鋭意検討した結果、上記の触媒にマグネシウム、マ
ンガンおよび(または)タルクを添加することにより、
反応温度を下げうると共にメタクロレインとメタクリル
酸の収率も向上するという新しい事実を発見した。Although the reaction performance of the catalyst shown therein was very good, and the single-stream yield of methacrolein and methacrylic acid reached as much as 80 mol%, it had the drawback that the reaction temperature was relatively high. High reaction temperatures not only shorten the life of the catalyst, but also
Since it is also unfavorable in terms of reaction operation, it is advantageous to keep it as low as possible. As a result of intensive studies on increasing the activity of the above catalyst, the present inventors discovered that by adding magnesium, manganese and/or talc to the above catalyst,
A new fact was discovered that the reaction temperature can be lowered and the yields of methacrolein and methacrylic acid can also be improved.
さらに本触媒はイソブテンの酸化反応にも有効であり、
メタクロレインとメタクリル酸を高収率で生成すること
を発見し、本発明に到達した。すなわち本発明の方法は
第3級ブチルアルコールまたはイソブテンと酸素を含む
混合ガスを一般式がPawbMOOTedSbOSnf
AgBhCiDjOk〔但し、式中P,.W,.MO,
.Te,.Sb,.SnおよびOはそれぞれリン、タン
グステン、テルル、アンチモンスズおよび酸素をあられ
しAは(a)ニツケルとコバルトの2種、(b)ニツケ
ルと鉄の2種、(c)ニツケルとコバルト(ビスマスの
3種もしくは(d)ニツケルと鉄とビスマスの3種の組
合わせをあられし、Bはカリウム、ルビジウムおよび(
または)セシウムをあられし、Cはマグネシウムおよび
(または)マンガンをあられし、Dはタルクをあられす
。Furthermore, this catalyst is also effective in the oxidation reaction of isobutene.
The present invention was achieved by discovering that methacrolein and methacrylic acid can be produced in high yield. That is, the method of the present invention uses a mixed gas containing tertiary butyl alcohol or isobutene and oxygen with the general formula PawbMOOTedSbOSnf.
AgBhCiDjOk [However, in the formula, P, . W,. MO,
.. Te,. Sb,. Sn and O represent phosphorus, tungsten, tellurium, antimony tin, and oxygen, respectively. seeds or (d) three combinations of nickel, iron and bismuth, B is potassium, rubidium and (
or) cesium, C hails magnesium and/or manganese, and D hails talc.
また式中A.b.c.d.e.f.g、H.iおよびk
はそれぞれの元素の原子数を示し、b+c=1としたと
き、Asdおよびeはoを含まない1以下の数、fはO
〜1の範囲、gは各元素の合計で0.01〜2、それぞ
れの金属では0.02〜1の範囲、hは0〜0.6、b
とcとの比は0.01〜100.kは存在する金属酸化
物の標準の原子価から自然に決まる値であり、iはO〜
6の範囲でj=0のときiは0.01以上である。jは
触媒の全重量に占める重量百分率を示しO〜50重量%
の範囲でありi=0のときjは1重量%以下である。〕
であられされる触媒と高温の気相で接触させることを特
徴とするメタクロレインとメタクリル酸の製造方法であ
る。本発明において用いる触媒中のマグネシウム又はマ
ンガンは目的物の収率を向上させると共に反応温度を低
下させる効果を有し、触媒寿命も一層延長することがで
きる。In addition, A. b. c. d. e. f. g, H. i and k
indicates the number of atoms of each element, and when b+c=1, Asd and e are numbers less than or equal to 1 not including o, and f is O
-1 range, g is 0.01-2 for each element in total, 0.02-1 for each metal, h is 0-0.6, b
The ratio between and c is 0.01 to 100. k is a value naturally determined from the standard valence of existing metal oxides, and i is O~
6 and when j=0, i is 0.01 or more. j represents the weight percentage in the total weight of the catalyst, O ~ 50% by weight
When i=0, j is 1% by weight or less. ]
This is a method for producing methacrolein and methacrylic acid, which is characterized by contacting the catalyst in a high temperature gas phase. Magnesium or manganese in the catalyst used in the present invention has the effect of improving the yield of the target product and lowering the reaction temperature, and can further extend the life of the catalyst.
またタルクはシリカゲル、シリカアルミナなどの担体と
異り、マグネシウム又はマンガンと同様の効果を有する
。本発明に用いる触媒の存在状態に関しては特別の制限
はなく、例えばリンならびにそれぞれの金属元素の混合
物であつてもよく、またこれらの元素が何らかの状態で
結合したものの酸化物であつ斗てもよい。Furthermore, unlike carriers such as silica gel and silica alumina, talc has an effect similar to that of magnesium or manganese. There are no particular restrictions on the state of the catalyst used in the present invention; for example, it may be a mixture of phosphorus and each metal element, or it may be an oxide of these elements combined in some way. .
本発明に用いる触媒はシリカゲル、シリカアルミナ、コ
ランダム、シリコンカーバイト等の良く知られた担体と
共に使用することもできる。The catalyst used in the present invention can also be used with well known supports such as silica gel, silica alumina, corundum, silicon carbide and the like.
触媒の調製にあたつては、従来から知られた触媒調製法
を比較的自由に用いることができ、特別の手段を必要と
しない。調製方法の1例を示せば、触媒原料の水溶液ま
たは懸濁液を蒸発乾固し、空気中で焼成する方法を挙げ
ることができる。In preparing the catalyst, conventionally known catalyst preparation methods can be used relatively freely, and no special means are required. One example of the preparation method is a method in which an aqueous solution or suspension of the catalyst raw material is evaporated to dryness and then calcined in air.
触媒原料としては、金属、その酸化物、塩化物、または
酸、アンモニウム塩、硝酸塩の如く強熱することにより
、酸化物となる化合物が好ましい。The catalyst raw material is preferably a metal, its oxide, chloride, or a compound that becomes an oxide when ignited, such as an acid, an ammonium salt, or a nitrate.
またリンモリブデン酸アンモニウム、スズモリブデン酸
の如くリンならびに金属元素が化学的に結合した原料を
用いることもできる。触媒の焼成は250〜700℃、
好ましくは350〜600℃で行うと良い。反応は任意
の適当な方法、例えば固定床法または流動床法で行うこ
とができる。It is also possible to use raw materials in which phosphorus and metal elements are chemically combined, such as ammonium phosphomolybdate and tin molybdate. Calcination of catalyst is 250-700℃,
Preferably it is carried out at 350 to 600°C. The reaction can be carried out in any suitable manner, such as a fixed bed method or a fluidized bed method.
原料ガス中の第3級ブチルアルコールまたはイソブテン
と酸素の濃度はそれぞれおよそ1〜20容量%の広い範
囲で変えることができる。The concentrations of tertiary butyl alcohol or isobutene and oxygen in the feed gas can each be varied over a wide range of about 1 to 20% by volume.
第3級ブチルアルコール、イソブテン、ならびに酸素の
稀釈にあたつては、例えば窒素炭酸ガス、水蒸気または
それらの混合物を稀釈剤として使用できる。For diluting tertiary butyl alcohol, isobutene, and oxygen, nitrogen carbon dioxide, water vapor, or a mixture thereof can be used as a diluent, for example.
反応温度は200〜500℃とくに250〜400℃に
することが好ましく、接触時間は0.5〜10秒が好ま
しい。The reaction temperature is preferably 200 to 500°C, particularly 250 to 400°C, and the contact time is preferably 0.5 to 10 seconds.
以下実施例および比較例を示して本発明の内容を具体的
に説明する。EXAMPLES The content of the present invention will be specifically explained below with reference to Examples and Comparative Examples.
なお部は重量部をあられし、メタクロレインとメタクリ
ル酸の単流収率(%)は次の如く定義する。Note that parts are parts by weight, and the single flow yield (%) of methacrolein and methacrylic acid is defined as follows.
実施例 1
パラタングステン酸アンモニウム2.25部を水50部
に溶解させ、これにパラモリブデン酸アンモニウム35
.3部を水200部に溶解させた溶液を加え、これにシ
リコンカーバイト100部と酸化アンチモン4.9部と
を加え、さらに硝酸第2鉄20.2部、硝酸ニツケル4
3.7部および硝酸マグネシウム5.1部を水500部
に溶解させた混合溶液および硝酸カリウム0.257部
と硝酸セシウム0.5部とを水10部に溶解させたもの
を添加し、次いで硝酸ビスマス16.2部を10%硝酸
50部に溶解させた溶液と塩化第1錫3.8部を水50
部に溶解させた溶液を加え最後に85%リン酸0.95
部を添加した。Example 1 2.25 parts of ammonium paratungstate was dissolved in 50 parts of water, and 35 parts of ammonium paramolybdate was dissolved in the solution.
.. A solution of 3 parts dissolved in 200 parts of water was added, 100 parts of silicon carbide and 4.9 parts of antimony oxide were added, and further 20.2 parts of ferric nitrate and 4 parts of nickel nitrate were added.
A mixed solution of 3.7 parts of magnesium nitrate and 5.1 parts of magnesium nitrate dissolved in 500 parts of water and a solution of 0.257 parts of potassium nitrate and 0.5 parts of cesium nitrate dissolved in 10 parts of water were added, and then nitric acid A solution of 16.2 parts of bismuth dissolved in 50 parts of 10% nitric acid and 3.8 parts of stannous chloride in 50 parts of water
85% phosphoric acid (0.95%)
part was added.
この混合物を攪拌しながら,ε加熱蒸発乾固させ、つい
で空気流通下500℃で5時間焼成しこの焼成物に二酸
化テルル5.35部を加え、良く攪拌したのち成型し触
媒とした。この触媒の組成比は原子比でであつた。This mixture was evaporated to dryness by ε heating while stirring, and then calcined at 500° C. for 5 hours under air circulation. 5.35 parts of tellurium dioxide was added to the calcined product, and after stirring well, it was molded into a catalyst. The composition ratio of this catalyst was in atomic ratio.
容量で第3級ブチルアルコール5%、酸素12%、水蒸
気30%および窒素53%の組成の混合ガスを350℃
に保持した触媒層に導入し、接触時間3.6秒で反応を
行つた。A mixed gas with a composition of 5% tertiary butyl alcohol, 12% oxygen, 30% water vapor, and 53% nitrogen by volume was heated at 350°C.
was introduced into a catalyst layer maintained at a temperature of 3.5 seconds, and the reaction was carried out for a contact time of 3.6 seconds.
生成ガスをガスクロマトグラフイ一で分析した結果、メ
タクロレインおよびメタクリル酸の合計単流収率は85
.6%であつた。比較例 1
実施例1において硝酸マグネシウムを添加しないことだ
けが異なる触媒を調製し、反応温度を370℃にする以
外は、実施例1と同様に反応させた。As a result of analyzing the produced gas using gas chromatography, the total single flow yield of methacrolein and methacrylic acid was 85.
.. It was 6%. Comparative Example 1 A catalyst was prepared that differed from Example 1 in that no magnesium nitrate was added, and the reaction was carried out in the same manner as in Example 1, except that the reaction temperature was 370°C.
メタクロレインとメタクリル酸の合計単流収率は84.
2%であつた。実施例 2
パラタングステン酸アンモニウム27.0部を水600
部に溶解させ、これに酸化アンチモン4.9部を添加し
、さらにパラモリブデン酸アンモニウム35.3部を水
200部に溶解させた溶液と硝酸第2鉄13.5部硝酸
ニツケル4.9部および硝酸マグネシウム3.9部を水
100部に溶解させた混合溶液を添加し、ついで硝酸ビ
スマス32.3部を10%硝酸150部に溶解させた溶
液と硝酸カリウム1.54部を水20部に溶解させた溶
液と85%リン酸3.8部を添加した。The total single stream yield of methacrolein and methacrylic acid was 84.
It was 2%. Example 2 27.0 parts of ammonium paratungstate and 600 parts of water
A solution of 35.3 parts of ammonium paramolybdate dissolved in 200 parts of water and 13.5 parts of ferric nitrate and 4.9 parts of nickel nitrate were added. Then, a mixed solution of 3.9 parts of magnesium nitrate dissolved in 100 parts of water was added, and then a solution of 32.3 parts of bismuth nitrate dissolved in 150 parts of 10% nitric acid and 1.54 parts of potassium nitrate were added to 20 parts of water. The dissolved solution and 3.8 parts of 85% phosphoric acid were added.
この混合物を攪拌しながら加熱蒸発乾固させついで空気
流通下に500℃で5時間焼成し、この焼成物に二酸化
テルル5.6部を添加し、良く混合したのち成型した。
この成型品の組成は原子比でであつた。This mixture was heated and evaporated to dryness while stirring, and then calcined at 500° C. for 5 hours under air circulation. 5.6 parts of tellurium dioxide was added to this calcined product, mixed well, and then molded.
The composition of this molded article was in atomic ratio.
これを触媒として用い、触媒層の温度を335℃とし、
その他の条件は実施例1と同様にして反応した結果、メ
タクロレインとメタクリル酸の合計単流収率は79.3
%であつた。比較例 2実施例2において、硝酸マグネ
シウムを添加しないことだげが異なる触媒を調製し、反
応温度を350℃にする以外は実施例1と同様に反応さ
せた。Using this as a catalyst, the temperature of the catalyst layer was set to 335°C,
Other conditions were the same as in Example 1. As a result, the total single flow yield of methacrolein and methacrylic acid was 79.3.
It was %. Comparative Example 2 A different catalyst was prepared in Example 2 except that magnesium nitrate was not added, and the reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 350°C.
メタクロレインとメタクリル酸の合計単流収率は76%
であつた。実施例 3
パラタングステン酸アンモニウム4.5部を水100部
に溶解させ、これにシリコンカーバイト:100部と酸
化アンチモン4.9部を加え、さらにパラモリブデン酸
アンモニウム35.3部を水200部に溶解させた溶液
と硝酸コバルト4.8部、硝酸ニツケル19.4部およ
び硝酸マンガン6.2部を水100部に溶解させた混合
溶液と塩化ルビジウム0.6部と硝酸セシウム1.0部
を水20部に溶解させた溶液を加え、ついで硝酸ビスマ
ス8.1部を10%硝酸60部に溶解させた溶液と85
%リン酸1.0部を添加し、さらに酸化第2錫2.5部
と二酸化テルル0.8部を添加し、攪拌しながら加熱蒸
発乾固させ、130℃で16時間乾燥後成型し、空気流
通下で500゜Cで5時間焼成し、触媒とした。Total single stream yield of methacrolein and methacrylic acid is 76%
It was hot. Example 3 4.5 parts of ammonium paratungstate was dissolved in 100 parts of water, 100 parts of silicon carbide and 4.9 parts of antimony oxide were added thereto, and further 35.3 parts of ammonium paramolybdate was dissolved in 200 parts of water. A mixed solution of 4.8 parts of cobalt nitrate, 19.4 parts of nickel nitrate, and 6.2 parts of manganese nitrate dissolved in 100 parts of water, 0.6 parts of rubidium chloride, and 1.0 parts of cesium nitrate. A solution of 8.1 parts of bismuth nitrate dissolved in 60 parts of 10% nitric acid was added, followed by a solution of 8.1 parts of bismuth nitrate dissolved in 60 parts of 10% nitric acid.
% phosphoric acid was added, 2.5 parts of stannic oxide and 0.8 parts of tellurium dioxide were added, and the mixture was heated and evaporated to dryness with stirring, dried at 130°C for 16 hours, and then molded. The mixture was calcined at 500°C for 5 hours under air circulation to obtain a catalyst.
この触媒の組成は原子比でであつた。The composition of this catalyst was in atomic ratios.
触媒層の温度を345℃とし、実施例1と同じ条件で反
応を行つた結果、メタクロレインおよびメタクリル酸の
合計単流収率は84.0%であつた。The temperature of the catalyst layer was set at 345° C. and the reaction was carried out under the same conditions as in Example 1. As a result, the total single-stream yield of methacrolein and methacrylic acid was 84.0%.
比較例 3実施例3において硝酸マンガンを添加しない
ことだけが異なる触媒を調製し、反応温度を370℃と
する以外は実施例1と同様に反応させた。Comparative Example 3 A catalyst was prepared that differed from Example 3 in that no manganese nitrate was added, and the reaction was carried out in the same manner as in Example 1, except that the reaction temperature was 370°C.
メタクロレインとメタクリル酸の合計単流収率は82.
5%であつた。実施例 4
パラタングステン酸アンモニウム38.5部を水600
部に加えて煮沸溶解させ、これに酸化アンチンモン7.
3部とシリコンカーバイト50部を加え、さらにパラモ
リブデン酸アンモニウム35.3部を水200部に溶解
させた溶液と硝酸第2鉄33.7部、硝酸ニツケル8.
3部、硝酸マグネシウ)ム4.4部および硝酸マンガン
9.9部を水200部に溶解させた混合液と硝酸カリウ
ム0.257部、硝酸ルビジウム0.3部および硝酸セ
シウム0.5部を水10部に溶解させた溶液を添加し、
ついで85%リン酸6.6部を加え最後に塩化第1スズ
7.5部を水100部に溶解させた溶液を加え、攪拌し
ながら加熱蒸発乾固する。The total single stream yield of methacrolein and methacrylic acid was 82.
It was 5%. Example 4 38.5 parts of ammonium paratungstate and 600 parts of water
7. parts of antimony oxide and dissolved in boiling water.
A solution of 35.3 parts of ammonium paramolybdate dissolved in 200 parts of water, 33.7 parts of ferric nitrate, and 8.0 parts of nickel nitrate were added.
A mixture of 3 parts of magnesium nitrate, 4.4 parts of magnesium nitrate, and 9.9 parts of manganese nitrate dissolved in 200 parts of water, and 0.257 parts of potassium nitrate, 0.3 parts of rubidium nitrate, and 0.5 parts of cesium nitrate were dissolved in water. Add a solution dissolved in 10 parts,
Next, 6.6 parts of 85% phosphoric acid are added, and finally a solution of 7.5 parts of stannous chloride dissolved in 100 parts of water is added, and the mixture is heated and evaporated to dryness while stirring.
ついで空気流通下500℃で5時間焼成し、この焼成物
に二酸化テルル6.8部を添加し、良く混合したのち、
成型し、これを触媒として用いた。この触媒の組成は原
子比でであつた。Then, it was fired at 500°C for 5 hours under air circulation, and 6.8 parts of tellurium dioxide was added to this fired product and mixed well.
It was molded and used as a catalyst. The composition of this catalyst was in atomic ratios.
触媒層の温度を330℃とし、その他の条件は実施例1
と同様にして反応させた結果、メタクロレインおよびメ
タクリル酸の合計単流収率84.5%が得られた。比較
例 4
実施例4において硝酸マグネシウムおよび硝酸マンガン
を添加しないことだけが異なる触媒を調製し、反応温度
を360℃にする以外は実施例1と同様にして反応させ
た。The temperature of the catalyst layer was 330°C, and the other conditions were as in Example 1.
As a result of the reaction in the same manner as above, a total single-stream yield of methacrolein and methacrylic acid of 84.5% was obtained. Comparative Example 4 A catalyst was prepared that differed from Example 4 in that magnesium nitrate and manganese nitrate were not added, and the catalyst was reacted in the same manner as in Example 1 except that the reaction temperature was 360°C.
メタクロレインとメタクリル酸の合計単流収率は83.
0%であつた。実施例 5パラタングステン酸アンモニ
ウム38.5部を水600部に加えて煮沸して溶解させ
、これにシリコンカーバイト100部と酸化アンチモン
0.69>部とを加え、さらにパラモリブデン酸アンモ
ニウム5部を水200部に溶解させた溶液と硝酸コバル
ト27部および硝酸ニツケル2.8部を水100部に溶
解させた混合溶液と硝酸セシウム0.23部を水10部
に溶解させた溶液を添加し、ついで85%リン酸5.0
部を加え、さらに塩化第1錫1.58部を水50部に溶
解させた溶液を加え、最後にタルク12.0部を水50
部に懸濁させたものを加え、攪拌しながら加熱蒸発乾固
させた。The total single stream yield of methacrolein and methacrylic acid was 83.
It was 0%. Example 5 Add 38.5 parts of ammonium paratungstate to 600 parts of water, boil and dissolve, add 100 parts of silicon carbide and 0.69 parts of antimony oxide, and further add 5 parts of ammonium paramolybdate. A mixed solution of 27 parts of cobalt nitrate and 2.8 parts of nickel nitrate dissolved in 100 parts of water, and a solution of 0.23 parts of cesium nitrate dissolved in 10 parts of water were added. , then 85% phosphoric acid 5.0
A solution of 1.58 parts of stannous chloride dissolved in 50 parts of water was added, and finally 12.0 parts of talc was dissolved in 50 parts of water.
The suspension was added to the suspension and heated and evaporated to dryness while stirring.
ついで、空気流通下、500℃で5時間焼成し、この焼
成物に二酸化テルル4.1部を添加し、よく混合したの
ち、成型し、これを触媒として用いた。この触媒の組成
は原子比でであつた。Then, it was calcined at 500° C. for 5 hours under air circulation, and 4.1 parts of tellurium dioxide was added to the calcined product, mixed well, and then molded and used as a catalyst. The composition of this catalyst was in atomic ratios.
触媒層の温度を330℃とし、その他の条件は実施例1
と同様にして反応させた結果、メタクロレインおよびメ
タクリル酸の合計単流収率82.2%が得られた。The temperature of the catalyst layer was 330°C, and the other conditions were as in Example 1.
As a result of the reaction in the same manner as above, a total single-stream yield of methacrolein and methacrylic acid of 82.2% was obtained.
比較例 5
実施例5においてタルクを添加しないことのみが異なる
触媒を調製し、反応温度を350℃とする以外は実施例
1と同様に反応させた。Comparative Example 5 A catalyst different from Example 5 except that talc was not added was prepared, and the reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 350°C.
メタクロレインとメタクリル酸の合計単流収率は80.
6%であつた。実施例 6
実施例5において硝酸ニツケルの次に硝酸マンガン8.
6部を加えることと塩化第1錫の添加後にタルク6.0
部を水25部に懸濁させたものを加えることのみが異な
る触媒を調製し反応温度を325℃とし、その他の条件
は実施例1と同様にして反応させた結果、メタクロレイ
ンとメタクリル酸の合計単流収率は82.9%であつた
。The total single stream yield of methacrolein and methacrylic acid was 80.
It was 6%. Example 6 In Example 5, nickel nitrate was followed by manganese nitrate8.
Talc 6.0 after addition of 6 parts and addition of stannous chloride
A catalyst was prepared with the only difference that 1 part suspended in 25 parts of water was added, the reaction temperature was 325°C, and the other conditions were the same as in Example 1. As a result, the reaction was carried out in the same manner as in Example 1. The total single stream yield was 82.9%.
実施例 7実施例1で調製した触媒を用い容量でイソブ
テン5%、酸素12%、水蒸気30%および窒素53%
の組成の原料混合ガスを350℃に保持した触媒層に導
入し、接触時間3.6秒で反応させた。Example 7 5% isobutene, 12% oxygen, 30% water vapor and 53% nitrogen by volume using the catalyst prepared in Example 1.
A raw material mixed gas having the composition was introduced into the catalyst layer maintained at 350°C, and reacted for a contact time of 3.6 seconds.
生成ガスをガスクロマトグラフイ一および化学分析法に
よつて分析した結果、メタクロレインとメタクリル酸の
合計単流収率は81.7%であつた。実施例 8実施例
2で調整した触媒を用い、反応温度335℃としたほか
は実施例7と同一条件で反応させた結果、メタクロレイ
ンとメタクリル酸の合計単流収率75.0%を得た。As a result of analyzing the produced gas by gas chromatography and chemical analysis, the total single flow yield of methacrolein and methacrylic acid was 81.7%. Example 8 Using the catalyst prepared in Example 2, the reaction was carried out under the same conditions as in Example 7 except that the reaction temperature was 335°C. As a result, a total single flow yield of methacrolein and methacrylic acid of 75.0% was obtained. Ta.
実施例 9
実施例6で調整した触媒を用い反応温度を325℃とし
たほかは実施例7と同一条件で反応させた結果、メタク
ロレインとメタクリル酸の合計単流収率78.7%を得
た。Example 9 The reaction was carried out under the same conditions as in Example 7, except that the catalyst prepared in Example 6 was used and the reaction temperature was 325°C. As a result, a total single flow yield of methacrolein and methacrylic acid of 78.7% was obtained. Ta.
実施例 10
実施例5において、シリコンカーバイトを添加しないこ
とのみが異なる触媒を調製し反応温度を320℃とし、
その他の条件は実施例1と同様にして反応させた。Example 10 A catalyst was prepared in Example 5 except that silicon carbide was not added, and the reaction temperature was 320°C.
The reaction was carried out under the same conditions as in Example 1 except for the following conditions.
メタクロレインとメタクリル酸の合計単流収率は82.
6%であつた。この結果によりシリコンカーバイトはタ
ルクと異り反応成績自体には殆ど影響を与えないことが
わかる。実施例 11実施例5において、シリコンカー
バイトの代りにアルミナ粉末50部を添加することのみ
が異なる触媒を調製し、反応温度を335℃としその他
の条件は実施例1と同様にして反応させた。The total single stream yield of methacrolein and methacrylic acid was 82.
It was 6%. This result shows that silicon carbide, unlike talc, has almost no effect on the reaction performance itself. Example 11 A catalyst was prepared in Example 5 except that 50 parts of alumina powder was added instead of silicon carbide, the reaction temperature was 335°C, and the other conditions were the same as in Example 1. .
メタクロレインとメタクリル酸の合計単流収率は82.
3%であつた。比較例 6
実施例5において、タルクとシリコンカーバイトの代り
にアルミナ粉末50部を添加することのみが異なる触媒
を調製し、反応温度を355℃とし、その他の条件は実
施例1と同様にして反応させた。The total single stream yield of methacrolein and methacrylic acid was 82.
It was 3%. Comparative Example 6 A catalyst was prepared in Example 5 except that 50 parts of alumina powder was added instead of talc and silicon carbide, the reaction temperature was 355°C, and the other conditions were the same as in Example 1. Made it react.
メタクロレインとメタクリル酸の合計単流収率は80.
1%であつた。The total single stream yield of methacrolein and methacrylic acid was 80.
It was 1%.
Claims (1)
含む混合ガスを下記の組成を有する触媒と高温の気相で
接触させることを特徴とするメタクロレインとメタクリ
ル酸の製造方法。 P_aW_bMo_cTe_dSb_eSn_fA_g
B_hC_iD_jO_k但し式中P、W、Mo、Te
、Sb、SnおよびOはそれぞれリン、タングステン、
モリブデン、テルル、アンチモン、スズおよび酸素をあ
らわし、Aは(a)ニッケルとコバルトの2種、(b)
ニッケルと鉄の2種、(c)ニッケルとコバルトとビス
マスの3種もしくは(d)ニッケルと鉄とビスマスの3
種の組合せをあらわし、Bはカリウム、ルビジウムおよ
び(または)セシウムをあらわし、Cはマグネシウムお
よび(または)マンガンをあらわし、Dはタルクをあら
わす。 また式中a、b、c、d、e、f、g、h、iおよびk
はそれぞれの元素の原子数を示しb+c=1としたとき
、a、dおよびeは0を含まない1以下の数、fは0〜
1の範囲、gは各元素の合計で0.08〜2それぞれの
金属では0.02〜1の範囲、hは0〜0.6、bとc
との比は0.01〜100、kは存在する金属酸化物の
標準の原子価から自然に決まる値でありiは0〜6の範
囲でj=0のときiは0.01以上である。jは触媒の
全重量に占める重量百分率を示し、0〜50重量%の範
囲でありi=0のときjは1重量%以上である。[Scope of Claims] 1. A method for producing methacrolein and methacrylic acid, which comprises bringing a mixed gas containing tertiary butyl alcohol or isobutene and oxygen into contact with a catalyst having the following composition in a high-temperature gas phase. P_aW_bMo_cTe_dSb_eSn_fA_g
B_hC_iD_jO_k However, in the formula, P, W, Mo, Te
, Sb, Sn and O are phosphorus, tungsten,
Represents molybdenum, tellurium, antimony, tin and oxygen, A is (a) two types of nickel and cobalt, (b)
Two types: nickel and iron, (c) three types: nickel, cobalt, and bismuth, or (d) three types: nickel, iron, and bismuth.
Represents a combination of species, B represents potassium, rubidium and/or cesium, C represents magnesium and/or manganese, and D represents talc. Also, in the formula a, b, c, d, e, f, g, h, i and k
indicates the number of atoms of each element, and when b+c=1, a, d, and e are numbers less than or equal to 1, not including 0, and f is 0 to
1 range, g is 0.08 to 2 in total for each element, 0.02 to 1 range for each metal, h is 0 to 0.6, b and c
The ratio is 0.01 to 100, k is a value naturally determined from the standard valence of existing metal oxides, and i is in the range of 0 to 6, and when j = 0, i is 0.01 or more. . j represents the weight percentage based on the total weight of the catalyst, and is in the range of 0 to 50% by weight, and when i=0, j is 1% by weight or more.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP50042565A JPS5939413B2 (en) | 1975-04-08 | 1975-04-08 | Method for producing methacrolein and methacrylic acid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP50042565A JPS5939413B2 (en) | 1975-04-08 | 1975-04-08 | Method for producing methacrolein and methacrylic acid |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS51118706A JPS51118706A (en) | 1976-10-18 |
JPS5939413B2 true JPS5939413B2 (en) | 1984-09-22 |
Family
ID=12639565
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP50042565A Expired JPS5939413B2 (en) | 1975-04-08 | 1975-04-08 | Method for producing methacrolein and methacrylic acid |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5939413B2 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4065507A (en) * | 1976-08-02 | 1977-12-27 | Standard Oil Company | Preparation of methacrylic derivatives from tertiary butyl-containing compounds |
JPH0699335B2 (en) * | 1984-02-01 | 1994-12-07 | 三菱レイヨン株式会社 | Method for producing methacrolein and methacrylic acid |
JPH0625084B2 (en) * | 1984-07-23 | 1994-04-06 | 三菱レイヨン株式会社 | Method for producing methacrolein and methacrylic acid |
JPH0625085B2 (en) * | 1984-07-24 | 1994-04-06 | 三菱レイヨン株式会社 | Method for producing methacrolein and methacrylic acid |
-
1975
- 1975-04-08 JP JP50042565A patent/JPS5939413B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
JPS51118706A (en) | 1976-10-18 |
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