JPS63122641A - Production of methacrolein and methacrylic acid - Google Patents
Production of methacrolein and methacrylic acidInfo
- Publication number
- JPS63122641A JPS63122641A JP61266549A JP26654986A JPS63122641A JP S63122641 A JPS63122641 A JP S63122641A JP 61266549 A JP61266549 A JP 61266549A JP 26654986 A JP26654986 A JP 26654986A JP S63122641 A JPS63122641 A JP S63122641A
- Authority
- JP
- Japan
- Prior art keywords
- methacrylic acid
- methacrolein
- group
- element selected
- oxygen
- 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.)
- Granted
Links
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 13
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 8
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 3
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical group [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical group [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 18
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000012808 vapor phase Substances 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229910052745 lead Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229940082569 selenite Drugs 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
Abstract
Description
【発明の詳細な説明】
上
〔産業ρ利用分野〕
本発明はイソブチレン又は三級ブタノールを分子状酸素
により気相接触酸イヒして、メタクロレイン及びメタク
リル酸を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing methacrolein and methacrylic acid by subjecting isobutylene or tertiary butanol to gas phase catalytic acidification with molecular oxygen.
インブチレノ又は三級ブタノールを高温気相下で接触酸
化してメタクロレイン及びメタクリル酸を製造する際に
用いられる触媒に関して数多（の提案がなされている。Many proposals have been made regarding catalysts used when producing methacrolein and methacrylic acid by catalytically oxidizing imbutylene or tertiary butanol in a high-temperature gas phase.
しかし、この反応に用いられる触媒は、一般に触媒活性
、メタクロレイン及びメタクリル酸の選択性、触媒寿命
等の触媒性能の点で工業的見地から改良が望まれている
。However, the catalyst used in this reaction is generally desired to be improved from an industrial standpoint in terms of catalytic performance such as catalytic activity, selectivity for methacrolein and methacrylic acid, and catalyst life.
本発明は、一般式
％式％
（式中Ｍｏ、Ｂｉ、Ｓｂ、 Ｆｅ、 Ｃｒ、 Ｓｅ及び
Ｏはツレぞれモリブデン、ビスマス、アンチモン、鉄、
クロム、セレン及び酸素、Ａはニッケル及びコバルトか
ら成る群より選ばれた少なくとも１種の元素、又はカリ
ウム、ルビジウム、セシウム及びタリウムから成る群よ
り選ばれた少なくとも１種の元素、Ｙはマグネシウム、
亜鉛、カドミウム、鉛、バリウム及び錫からなる群より
選ばれた少なくとも１種の元素、Ｚはリン、硼素、タン
グステン、硫黄、塩素、珪素及びセリウムからなる群よ
り選ばれた少な（とも１種の元素、ａ、ｂ、ｃ、ｄ、ｅ
、ｆ、ｇ、ｈ、ｉ、Ｊ及びｋは各元素の原子比率を示２
し、ａ＝１２のとき１）＝０．０１〜３、ｃ＝０．０１
〜６、ｄ＝０゜５〜４、ｅ ＝ ０．０１〜３、ｆ＝０
．０１〜３、ｇ＝１〜１２、ｈ＝０．［３１〜２、ｉ
＝ ０．０１〜５、ｊ＝ｏ〜７であり、ｋは前記各成分
の原子価を満足するのに必要な酸素原子数である）で表
わされる組成を有する触媒の存在下に、インブチレン又
は三級ブタノールを分子状酸素を用いて気相接触酸化す
ることを特徴とする、メタクロレイン及びメタクリル酸
の製造法である。The present invention is based on the general formula % (wherein Mo, Bi, Sb, Fe, Cr, Se and O are molybdenum, bismuth, antimony, iron,
Chromium, selenium and oxygen, A is at least one element selected from the group consisting of nickel and cobalt, or at least one element selected from the group consisting of potassium, rubidium, cesium and thallium, Y is magnesium,
At least one element selected from the group consisting of zinc, cadmium, lead, barium and tin; Z is at least one element selected from the group consisting of phosphorus, boron, tungsten, sulfur, chlorine, silicon and cerium; elements, a, b, c, d, e
, f, g, h, i, J and k indicate the atomic ratio of each element2
and when a=12, 1)=0.01~3, c=0.01
~6, d=0°5~4, e=0.01~3, f=0
．． 01-3, g=1-12, h=0. [31-2, i
= 0.01 to 5, j = o to 7, and k is the number of oxygen atoms necessary to satisfy the valence of each component. Alternatively, it is a method for producing methacrolein and methacrylic acid, which is characterized by subjecting tertiary butanol to gas phase catalytic oxidation using molecular oxygen.
本発明に用いられる触媒を調製する場合の元素の原料と
しては、酸化物あるいは強熱することにより酸化物にな
り得る塩化物、硫酸塩、硝酸塩、炭酸塩又はそれらの混
合物が好ましい。When preparing the catalyst used in the present invention, the elemental raw material is preferably an oxide or a chloride, sulfate, nitrate, carbonate, or a mixture thereof that can be converted into an oxide by ignition.
触媒の調製に際しては、蒸発乾固法、沈殿法、酸化物混
合法等の既知の方法を用いることができる。触媒成分は
担体に担持させて用いることもできる。担体としては、
例えばシリカ、アルミナ、シリカ−アルミナなどが用い
られる。In preparing the catalyst, known methods such as evaporation to dryness method, precipitation method, oxide mixing method, etc. can be used. The catalyst component can also be supported on a carrier. As a carrier,
For example, silica, alumina, silica-alumina, etc. are used.
本発明を実施するに際しては、原料のインブチレン又は
三級ブタノールに分子状酸素を加え、前記の触媒の存在
下に気相接触酸化を行う。インブチレン又は三級ブタノ
ール対酸素のモル比はｉ：ｏ、ｓ〜３が好ましい。原料
ガスは不活性ガスで金沢して用いることが好ましい。酸
化に用いられる分子状酸素は純酸素ガスでも空気でもよ
いが、工業的には空気が有利である。反応圧力は常圧な
いし数気圧まで用いられる。反応温度は２５０〜４５０
°Ｃの範囲が好ましく、反応は流動床でも固定床でも行
うことができる。In carrying out the present invention, molecular oxygen is added to imbutylene or tertiary butanol as a raw material, and gas phase catalytic oxidation is performed in the presence of the above catalyst. The molar ratio of inbutylene or tertiary butanol to oxygen is preferably i:o, s~3. It is preferable to use an inert gas as the raw material gas. The molecular oxygen used for oxidation may be pure oxygen gas or air, but air is industrially advantageous. The reaction pressure used is from normal pressure to several atmospheres. Reaction temperature is 250-450
A range of 0.degree. C. is preferred and the reaction can be carried out in either a fluidized bed or a fixed bed.
本発明の方法によれば、インブチレン又は三級ブタノー
ルからメタクロレイン及びメタクリル酸を工業的に有利
に得ることができる。According to the method of the present invention, methacrolein and methacrylic acid can be industrially advantageously obtained from inbutylene or tertiary butanol.
下記実施例及び比較例中の部は重量部を意味し、分析は
ガスクロマトグラフィにより行った。In the Examples and Comparative Examples below, parts mean parts by weight, and the analysis was performed by gas chromatography.
またインブチレン又は三級ブタノールの反応率、生成さ
れるメタクロレイン及びメタクリル酸の選択率、単流収
率は下記のように定義される。Further, the reaction rate of inbutylene or tertiary butanol, the selectivity of methacrolein and methacrylic acid produced, and the single flow yield are defined as follows.
インブチレン又は三級ブタノールの反応率（％）メタク
ロレインの選択率（％）
メタクリル酸の選択率（％）
（メタクロレイン＋メタクリル酸）の単流収率（％）実
施例１
水１０００部にモリブデン酸アンモニウム５００部、亜
セレン酸９１部及び硝酸セシウム２６．０部を加え加熱
攪拌した（Ａ液）。別に水８５０部に６０％硝酸２５０
部を加え、均一にしたのち、硝酸ビスマス５７．２部を
加え溶解した。Reaction rate of inbutylene or tertiary butanol (%) Selectivity of methacrolein (%) Selectivity of methacrylic acid (%) Single flow yield (%) of (methacrolein + methacrylic acid) Example 1 To 1000 parts of water 500 parts of ammonium molybdate, 91 parts of selenite and 26.0 parts of cesium nitrate were added and stirred with heating (Liquid A). Separately, add 250 parts of 60% nitric acid to 850 parts of water.
57.2 parts of bismuth nitrate was added and dissolved.
これに硝酸第二鉄２８６．０部、硝敢クロム９４部、硝
酸ニッケル４１１．８部及び硝酸マグネシウム９０．８
部を順次加え溶解した（Ｂ液）。Ａ液にＢｉを加えスラ
リー状としたのち、三酸化アンチモン３４．４部を加え
加熱攪拌し、水の大部分を蒸発させた。To this, 286.0 parts of ferric nitrate, 94 parts of chromium nitrate, 411.8 parts of nickel nitrate, and 90.8 parts of magnesium nitrate.
were added and dissolved in order (liquid B). After adding Bi to liquid A to form a slurry, 34.4 parts of antimony trioxide was added and stirred while heating to evaporate most of the water.
得られたケーキ状物質を１２０℃で乾燥させたのち、５
００℃で６時間焼成して成形した。After drying the obtained cake-like substance at 120°C,
It was molded by firing at 00°C for 6 hours.
こうして得られた触媒の組成は次式
％式％
る。酸素の原子比率には他の元素の原子価により自然に
決まる値であるので以下省略する。The composition of the catalyst thus obtained is given by the following formula: Since the atomic ratio of oxygen is a value naturally determined by the valences of other elements, the following description is omitted.
この触媒をステンレス製反応管に充填し、インブチレン
５％、酸素１２％、水蒸気１０％及び窒素７６％の原料
混合ガスを接触時間３．６秒で触媒層を通過させ、３６
０°Ｃで反応させた。This catalyst was packed in a stainless steel reaction tube, and a raw material mixed gas of 5% inbutylene, 12% oxygen, 10% water vapor, and 76% nitrogen was passed through the catalyst layer for a contact time of 3.6 seconds.
The reaction was carried out at 0°C.
その結果、イソブチレンの反応率９６％、メタクロレイ
ンの選択率８８．０％、メタクリル酸の選択率４．２％
、（メタクロレイン＋メタクリル酸）の単流収率は８８
．５％であった。As a result, the reaction rate of isobutylene was 96%, the selectivity of methacrolein was 88.0%, and the selectivity of methacrylic acid was 4.2%.
, the single flow yield of (methacrolein + methacrylic acid) is 88
．． It was 5%.
実施例２〜９ 実施例１に準じて下記の触媒を調製した。Examples 2-9 The following catalyst was prepared according to Example 1.
実施例２ ”、 Ｍｏ （２ＢＩＯ，５Ｓ ｂＩＦｅ３
Ｃｒｏ、 １Ｓｅ６．３ Ｃ０６Ｋ。、４Ｚ１１４．
５” ３：ＭｏＨＢｉＩＳｂ、Ｆｅ５Ｃｒｏ４Ｓ
ｅｏ、３Ｎｉ４Ｃｏ３Ｋｏ、２Ｃｓ、）、Ｃｄ、）、５
Ｐｏ、、）ｓｔｔ ４：Ｍｏ１２ＢｉＩＳｂＩＦｅ３
Ｃｒ（、，３Ｓｅ（、，２Ｎｉ４Ｃｏ３Ｒｂ（１，４Ｐ
ｂ、１．５Ｂ（、，５／’ ５：Ｍｏ、２Ｂｘ、５ｂ
１ＦｅｓＣｒｏ、５Ｓｅｏ、４Ｎ１ａＴｌｏ！Ｂａｏ、
３Ｗｏ、、Ｓｏ、ａ” ６’、Ｍｏ、２Ｂｉ、Ｓｂ、
Ｆｅ３Ｃｒ、）、ｌ５ｅ（、，３Ｎ１４Ｃｏ３Ｔｌｏ、
２Ｓｎ、）、５Ｃ１（、，４〃７ ：Ｍｏ１２Ｂ１．５
ｂＩＦｅ４Ｃｒ（１４ＳｅＯ，３Ｎｉ５Ｃ０２，５Ｔ１
ｏ、２ＭｇＢ、５Ｓｉ５〃８ ＋、 Ｍｏ １２ Ｂ
Ｉ ＩＳｂ ＨＦＱ３ Ｃｒ６．、Ｓｅｏ、３Ｎ １６
Ｃ０２Ｔ１ｏ、２ＭｇＬ５Ｗ（１，ＩＣｅｏ、２”
９：Ｍｏ１２Ｂ１、Ｓｂ、Ｆｅ５ＣｒＯ，ｌ５ｅ６，
３Ｃｏ６Ｃｓ０４Ｔ１０４Ｍｇ、、Ｚｎ（１，５これら
の触媒を用いて反応温度を変え、その他は実施例１と同
様にして反応を行った。その結果を第１表に示す。Example 2 ”, Mo (2BIO,5S bIFe3
Cro, 1Se6.3 C06K. , 4Z114.
5” 3:MoHBiISb, Fe5Cro4S
eo, 3Ni4Co3Ko, 2Cs, ), Cd, ), 5
Po,, ) stt 4:Mo12BiISbIFe3
Cr(,,3Se(,,2Ni4Co3Rb(1,4P
b, 1.5B(,,5/' 5:Mo, 2Bx, 5b
1FesCro, 5Seo, 4N1aTlo! Bao,
3Wo,,So,a''6',Mo,2Bi,Sb,
Fe3Cr,), l5e(,,3N14Co3Tlo,
2Sn,), 5C1(,,4〃7:Mo12B1.5
bIFe4Cr(14SeO,3Ni5C02,5T1
o, 2MgB, 5Si5〃8 +, Mo 12 B
I ISb HFQ3 Cr6. , Seo, 3N 16
C02T1o, 2MgL5W (1, ICeo, 2”
9: Mo12B1, Sb, Fe5CrO, l5e6,
3Co6Cs04T104Mg, , Zn (1,5) Using these catalysts, the reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed. The results are shown in Table 1.
実施例１０〜１２
それぞれ実施例１〜６の触媒を用い、原料を三級ブタノ
ールに変え、その他は実施例１と同様にして反応を行っ
た。その結果を第２表に示す。Examples 10 to 12 Reactions were carried out in the same manner as in Example 1 except that the catalysts of Examples 1 to 6 were used, and tertiary butanol was used as the raw material. The results are shown in Table 2.
比較例１
亜−レン酸９１部及び硝酸クロム９４部を除き、その他
は実施例１と同様にして次式％式％
で表わされる組成の触媒を得た。＝＃陰≠≠捧六斗この
触媒を用い、実施例１と同様にして反応を行ったところ
、イソブチレンの反応率９０６．７１メタクロレインの
選択率８６．５％、メタクリル酸の選択率５．７％、（
メタクロレイン＋メタクリル酸）の単流収率８３．０％
であった。Comparative Example 1 A catalyst having a composition represented by the following formula % was obtained in the same manner as in Example 1 except that 91 parts of lenous acid and 94 parts of chromium nitrate were used. = #Yin≠≠RokutoKen When a reaction was carried out in the same manner as in Example 1 using this catalyst, the reaction rate of isobutylene was 906.71, the selectivity of methacrolein was 86.5%, and the selectivity of methacrylic acid was 5. 7%, (
Single flow yield of methacrolein + methacrylic acid) 83.0%
Met.
比較例２
比較例１の触媒を用い、実施例１０と同様にして反応を
行ったところ、三級ブタノールの反応率１００％、メタ
クロレインの選択率７９５％、メタクリル酸の選択率４
．０％、（メタクロレイン＋メタクリル酸）の単流収率
８３．５％であった。Comparative Example 2 A reaction was carried out in the same manner as in Example 10 using the catalyst of Comparative Example 1. The reaction rate of tertiary butanol was 100%, the selectivity of methacrolein was 795%, and the selectivity of methacrylic acid was 4.
．． 0%, and the single flow yield of (methacrolein + methacrylic acid) was 83.5%.
Claims (1)
＿ｇＸ＿ｈＹ＿ｉＺ＿ｊＯ＿ｋ（式中Ｍｏ、Ｂｉ、Ｓｂ
、Ｆｅ、Ｃｒ、Ｓｅ及びＯはそれぞれモリブデン、ビス
マス、アンチモン、鉄、クロム、セレン及び酸素、Ａは
ニツケル及びコバルトからなる群より選ばれた少なくと
も１種の元素、Ｘはカリウム、ルビジウム、セシウム及
びタリウムからなる群より選ばれた少なくとも１種の元
素、Ｙはマグネシウム、亜鉛、カドミウム、鉛、バリウ
ム及び錫からなる群より選ばれた少なくとも１種の元素
、Ｚはリン、硼素、タングステン、硫黄、塩素、珪素及
びセリウムからなる群より選ばれた少なくとも１種の元
素、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈ、ｉ、ｊ及びには
各元素の原子比率を示し、ａ＝１２のときｂ＝０．０１
〜３、ｃ＝０．０１〜３、ｄ＝０．５〜４、ｅ＝０、０
１〜３、ｆ＝０．０１〜３、ｇ＝１〜１２、ｈ＝０．０
１〜２、ｉ＝０．０１〜５、ｊ＝０〜７であり、ｋは前
記各成分の原子価を満足するのに必要な酸素原子数であ
る）で表わされる組成を有する触媒の存在下に、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
触酸化することを特徴とする、メタクロレイン及びメタ
クリル酸の製造法。[Claims] General formula Mo_aBi_bSb_cFe_dCr_eSe_fA
_gX_hY_iZ_jO_k (Mo, Bi, Sb
, Fe, Cr, Se and O are molybdenum, bismuth, antimony, iron, chromium, selenium and oxygen, A is at least one element selected from the group consisting of nickel and cobalt, X is potassium, rubidium, cesium and At least one element selected from the group consisting of thallium; Y is at least one element selected from the group consisting of magnesium, zinc, cadmium, lead, barium, and tin; Z is phosphorus, boron, tungsten, sulfur; At least one element selected from the group consisting of chlorine, silicon, and cerium, a, b, c, d, e, f, g, h, i, and j, and the atomic ratio of each element is shown, a = When 12, b=0.01
~3, c=0.01~3, d=0.5~4, e=0, 0
1-3, f=0.01-3, g=1-12, h=0.0
1 to 2, i = 0.01 to 5, j = 0 to 7, and k is the number of oxygen atoms necessary to satisfy the valence of each component. Below, a method for producing methacrolein and methacrylic acid, which is characterized by subjecting isobutylene or tertiary butanol to gas phase catalytic oxidation using molecular oxygen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61266549A JPS63122641A (en) | 1986-11-11 | 1986-11-11 | Production of methacrolein and methacrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61266549A JPS63122641A (en) | 1986-11-11 | 1986-11-11 | Production of methacrolein and methacrylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63122641A true JPS63122641A (en) | 1988-05-26 |
| JPH0420418B2 JPH0420418B2 (en) | 1992-04-02 |
Family
ID=17432393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61266549A Granted JPS63122641A (en) | 1986-11-11 | 1986-11-11 | Production of methacrolein and methacrylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63122641A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5728894A (en) * | 1994-06-22 | 1998-03-17 | Ashahi Kasei Kogyo Kabushiki Kaisha | Method for producing methacrolein |
| US7012039B2 (en) | 2001-12-21 | 2006-03-14 | Asahi Kasei Chemicals Corporation | Oxide catalyst composition |
-
1986
- 1986-11-11 JP JP61266549A patent/JPS63122641A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5728894A (en) * | 1994-06-22 | 1998-03-17 | Ashahi Kasei Kogyo Kabushiki Kaisha | Method for producing methacrolein |
| US7012039B2 (en) | 2001-12-21 | 2006-03-14 | Asahi Kasei Chemicals Corporation | Oxide catalyst composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0420418B2 (en) | 1992-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0550489B2 (en) | ||
| JPS63122642A (en) | Production of methacrolein and methacrylic acid | |
| JP2841324B2 (en) | Method for producing methacrolein | |
| JPH03238051A (en) | Preparation of catalyst for preparing methacrylic acid | |
| WO1995035273A1 (en) | Process for producing methacrolein | |
| JPH0813332B2 (en) | Preparation of catalysts for the production of methacrolein and methacrylic acid | |
| JPH0753686B2 (en) | Method for producing methacrylic acid | |
| US5208371A (en) | Process for production of methacrolein and methacrylic acid | |
| JP2720215B2 (en) | Preparation of catalyst for methacrylic acid production | |
| US4083805A (en) | Preparation of methacrylic acid from methacrolein | |
| JP2657693B2 (en) | Preparation of catalysts for the production of methacrolein and methacrylic acid | |
| KR900002454B1 (en) | Process for producing methacrylic acid and catalysts for the process | |
| JPS63122641A (en) | Production of methacrolein and methacrylic acid | |
| JP3209778B2 (en) | Preparation of catalyst for methacrylic acid production | |
| JPH0662463B2 (en) | Method for producing methacrolein and methacrylic acid | |
| JPH0479697B2 (en) | ||
| JPH0459739A (en) | Production of methacrolein and methacrylic acid | |
| JPH1066874A (en) | Preparation of catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid | |
| JPH11179209A (en) | Catalyst for production of methacrylic acid and production of methacrylic acid using that | |
| JPS6154013B2 (en) | ||
| JP2747941B2 (en) | Method for producing acrolein and acrylic acid | |
| JPS6176436A (en) | Production of unsaturated carboxylic acid | |
| JPH0827089A (en) | Method for producing acrylonitrile | |
| JPH0320237A (en) | Production of methacrolein and methacrylic acid | |
| KR920003103B1 (en) | Production of methacrolein and methacrylic acid |