JPH01213255A - Production of carboxylic acid - Google Patents
Production of carboxylic acidInfo
- Publication number
- JPH01213255A JPH01213255A JP63040307A JP4030788A JPH01213255A JP H01213255 A JPH01213255 A JP H01213255A JP 63040307 A JP63040307 A JP 63040307A JP 4030788 A JP4030788 A JP 4030788A JP H01213255 A JPH01213255 A JP H01213255A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- oxide
- carboxylic acid
- water
- composite oxide
- 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract 5
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 239000002131 composite material Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000737 periodic effect Effects 0.000 abstract description 5
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 abstract description 4
- 239000010937 tungsten Substances 0.000 abstract description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003317 industrial substance Substances 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- 150000001735 carboxylic acids Chemical class 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- -1 chloro compound Chemical class 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- MLMQPDHYNJCQAO-UHFFFAOYSA-N 3,3-dimethylbutyric acid Chemical compound CC(C)(C)CC(O)=O MLMQPDHYNJCQAO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- ZAIDIVBQUMFXEC-UHFFFAOYSA-N 1,1-dichloroprop-1-ene Chemical compound CC=C(Cl)Cl ZAIDIVBQUMFXEC-UHFFFAOYSA-N 0.000 description 1
- QMQRQQASVUFJGS-UHFFFAOYSA-N 2,2-dichloro-3,3-dimethylbutane Chemical compound CC(C)(C)C(C)(Cl)Cl QMQRQQASVUFJGS-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical class [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 238000005406 washing Methods 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明はカルボン酸の製造方法に関し、詳しくは酸化タ
ングステンと周期律表第４Ａ族元素の酸化物との複合酸
化物の存在下に気相でクロル化合物を加水分解すること
によるカルボン酸の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing carboxylic acid, and more specifically to a process for producing carboxylic acid in a gas phase in the presence of a composite oxide of tungsten oxide and an oxide of Group 4A element of the periodic table. The present invention relates to a method for producing carboxylic acid by hydrolyzing a chloro compound.
〈従来の技術〉
カルボン酸は農薬、医薬、化成品等の種々の分野で使用
される工業用原料であり、クロル化合物を発煙硝酸、濃
硫酸などの鉱酸中で加水分解することにより得られるこ
とも知られている（例えばＢｕｌｌ。Ｃｈｅｍ、Ｓａｃ
、Ｊｐｎ、、 ３９４８０（Ｉ９６６）、Ｏｒｇ、５ｙ
ｎｔｈ、。<Prior art> Carboxylic acids are industrial raw materials used in various fields such as agricultural chemicals, medicines, and chemical products, and are obtained by hydrolyzing chloro compounds in mineral acids such as fuming nitric acid and concentrated sulfuric acid. It is also known (e.g. Bull. Chem, Sac
, Jpn, 39480 (I966), Org, 5y
nth,.
Ｖ、９３（Ｉ９７３） 、Ｂｅｒ、 １００．９８（Ｉ
９６７））。V, 93 (I973), Ber, 100.98 (I
967)).
〈発明が解決しようとする課題〉
しかしながら、上記の加水分解による方法では、取扱い
に注意を要する発煙硝酸、濃硫酸などを多量使用すると
いう問題、更には多量の廃酸、廃水が副生ずるという問
題等の工業上の種々の欠点があった。<Problems to be Solved by the Invention> However, the above hydrolysis method has the problem of using large amounts of fuming nitric acid, concentrated sulfuric acid, etc., which must be handled with care, and furthermore, the problem of producing large amounts of waste acid and waste water as by-products. There were various industrial drawbacks such as.
本発明者らは、これ等の問題点を解決すべく、クロル化
合物の加水分解によるカルボン酸の製造方法についてて
鋭意検討を重ねた結果、特定の複合酸化物が加水分解触
媒として有効であり、この複合酸化物を用いれば気相下
で加水分解反応を進行させることができ、上記公知方法
の諸問題を一挙に解決し得ることを見出すとともに、種
々の検討を加え本発明を完成した。In order to solve these problems, the present inventors have conducted intensive studies on a method for producing carboxylic acids by hydrolyzing chlorine compounds, and have found that a specific composite oxide is effective as a hydrolysis catalyst. The inventors discovered that by using this composite oxide, the hydrolysis reaction could proceed in the gas phase, and that the problems of the above-mentioned known methods could be solved all at once, and after various studies, the present invention was completed.
〈課題を解決するための手段〉
すなわち本発明は酸化タングステンと周期律表第４Ａ族
元素の酸化物との複合酸化物の存在下に、気相で一般式
（Ｉ）および／または一般式（ＩＩ）ＲＣＨ＝ ＣＣｌ
２ （Ｉ ）Ｒ’−ＣＨ２−ＣＣＩｓ
（ｎ）（式中、Ｒは水素原子もしくは低級アルキル基
を表す。）
で示されるクロル化合物と水とを反応させることを特徴
とする一般式（Ｉ［［）
（式中、Ｒは前記と同じ意味を表す。）で示されるカル
ボン酸の優れた製造方法を提供するものである。<Means for Solving the Problems> In other words, the present invention provides a method for preparing general formula (I) and/or general formula ( II) RCH=CCl
2 (I) R'-CH2-CCIs
(n) (wherein R represents a hydrogen atom or a lower alkyl group) The general formula (I[[) (wherein R represents the above-mentioned The present invention provides an excellent method for producing carboxylic acids represented by the following formulas.
本発明は触媒として、酸化タングステンと周期律表４Ａ
族元素の酸化物との複合酸化物を用いるものであるが、
その調製方法は多くのテキスト、文献等たとえば「金属
酸化物と複合酸化物」 （講談社すイエンテイフィク１
９７８年４月２０日発行）などに記載の方法が適用でき
る。The present invention uses tungsten oxide and 4A of the periodic table as a catalyst.
Although it uses a composite oxide with an oxide of a group element,
The preparation method is described in many texts and literature, such as "Metal oxides and composite oxides" (Kodansha Enteifiku 1)
(published on April 20, 1978) can be applied.
具体的には例えばタングステン酸塩と第４Ａ族元素の塩
類の水溶液を用いる共沈法、酸化物どう 。Specifically, for example, a coprecipitation method using an aqueous solution of a tungstate salt and a salt of a Group 4A element, or an oxide method.
しまたは一方の酸化物ともう一方の水酸化物を混合する
ことによる混練法等により先駆体を得、次いでこれ等の
混合物を４００〜７００ ℃の温度下、空気々流中で数
時間焼成する方法等が挙げられる。A precursor is obtained by a kneading method, etc. by mixing one oxide and the other hydroxide, and then the mixture is calcined for several hours at a temperature of 400 to 700 °C in a stream of air. Examples include methods.
周期律表第４Ａ族元素としては、チタン１、ジルコニウ
ム、ハフニウムが挙げられるが、好ましくはチタン、ジ
ルコニウムである。Examples of the Group 4A elements of the periodic table include titanium 1, zirconium, and hafnium, with titanium and zirconium being preferred.
本発明に使用される複合参加物は、タングステンの第４
Ａ族元素に対する原子比が通常０．０１〜９であり、酸
強度開数ＨＯが通常＋３．３以下、好ましくは＋１．５
以下である。The composite particulate used in the present invention is made of tungsten quaternary
The atomic ratio to the A group element is usually 0.01 to 9, and the acid strength numerical aperture HO is usually +3.3 or less, preferably +1.5.
It is as follows.
本発明で使用されるクロル化合物としては例えば−クキ
（Ｉ）および（ＩＩ）
ＲＣＨ＝ＣＣ１＊ （Ｉ）
ＲＣＨＣＣｌ３ （Ｉｔ）
（式中、Ｒは水素原子もしくは低級アルキル基を表わす
。）
で示される化合物が挙げられ、置換基Ｒとしては例えば
、水素原子、メチル、エチル、ｎ−プロピル、ｌ−プロ
ピル、ｎ−ブチル、ｌ−ブチル、５ｅｃ−フｆル、ｔ−
ブチル、ｎ−ペンチル、ｌ−ペンチル、ｎ−ヘキシル、
シクロヘキシル等の低級アルキル基などが挙げられる。Examples of the chlorine compounds used in the present invention include -Kuki (I) and (II) RCH=CC1* (I) RCHCCl3 (It) (wherein R represents a hydrogen atom or a lower alkyl group) Examples of the substituent R include hydrogen atom, methyl, ethyl, n-propyl, l-propyl, n-butyl, l-butyl, 5ec-fur, t-
Butyl, n-pentyl, l-pentyl, n-hexyl,
Examples include lower alkyl groups such as cyclohexyl.
本発明はかかるクロル化合物と水とを前記複合酸化物の
存在下に反応させるものであるが、水のクロル化合物に
対するモル比は通常０．５〜１００、好ましくは１〜３
０、より好ましくは２〜１０である。In the present invention, the chlorine compound and water are reacted in the presence of the composite oxide, and the molar ratio of water to the chlorine compound is usually 0.5 to 100, preferably 1 to 3.
0, more preferably 2-10.
また反応温度は通常１００〜６００ ℃であり、好まし
くは１５０〜４５０ ℃、より好ましくは２００〜４０
０℃である。圧力は特に限定はなく減圧下、常圧下、加
圧下いずれでも良い。The reaction temperature is usually 100 to 600°C, preferably 150 to 450°C, more preferably 200 to 40°C.
It is 0°C. The pressure is not particularly limited and may be under reduced pressure, normal pressure, or increased pressure.
本発明は通常、複合酸化物触媒床上にクロル化合物と水
の気相混合物を連続的にフィードすることにより実施さ
れる。この場合、窒素などの不活性ガスの共存下で実施
するのが好ましい。The present invention is typically carried out by continuously feeding a gas phase mixture of chlor compound and water over a bed of complex oxide catalyst. In this case, it is preferable to carry out in the coexistence of an inert gas such as nitrogen.
生成したカルボン酸は反応マスを蒸留等の分離手段を用
いることにより単離することができる。The produced carboxylic acid can be isolated by using a separation means such as distillation of the reaction mass.
〈発明の効果〉
本発明によれば、公知法で多量使用され、取扱に注意を
要する発煙硝酸、濃硫酸の使用をなしにすることができ
る、のみならず多量副生ずる廃酸、廃水の処理問題も解
消し得る。<Effects of the Invention> According to the present invention, it is possible not only to eliminate the use of fuming nitric acid and concentrated sulfuric acid, which are used in large quantities in known methods and require careful handling, but also to treat waste acids and wastewater, which are produced in large quantities as by-products. The problem can also be solved.
そのうえ、工程の簡素化、反応装置の簡略化もなし得る
ので、・本発明はカルボン酸の工業的製法として極めて
有利である。Furthermore, the present invention is extremely advantageous as an industrial method for producing carboxylic acids, since it is possible to simplify the steps and the reaction apparatus.
〈実施例〉
以下、実施例により本発明を更に詳細に説明するが、本
発明はこれらに限定されるものではない。<Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
尚、Ｗ／Ｆ 、反応率、選択率は下式により算出した。In addition, W/F, reaction rate, and selectivity were calculated by the following formula.
クロル化合物供給速度
参考例１
チタンテトライソプロポキシド１２７．９ ｇを水６０
〇−中に滴下加水分解した後、濃硝酸１１０−を加えて
均一溶液にした。次いでこの溶液と三酸化タングステン
１１．５９ｇと２８％アンモニア水３００−からなる均
一溶液を混合して沈澱を生成せしめた。Chlor compound supply rate reference example 1 127.9 g of titanium tetraisopropoxide was added to 60 g of water
After hydrolysis by dropping into 〇-, concentrated nitric acid 110- was added to make a homogeneous solution. Next, this solution was mixed with a homogeneous solution consisting of 11.59 g of tungsten trioxide and 300 g of 28% aqueous ammonia to form a precipitate.
共沈法で生成したヒドロゲルを濾過、水洗、乾燥後、空
気々流中５００℃で３時間焼成して淡黄色のＷＯ，−Ｔ
ｉＯ，複合酸化物４７ｇを得た。The hydrogel produced by the coprecipitation method was filtered, washed with water, dried, and then calcined in a stream of air at 500°C for 3 hours to form a pale yellow WO,-T.
47 g of iO, composite oxide was obtained.
このもののチタンに対するタングステンの比率は原子比
で０．１であり、酸強度関数を指示薬法で求めたところ
Ｈａ が−３以下であった。The ratio of tungsten to titanium in this material was 0.1 in terms of atomic ratio, and when the acid strength function was determined by the indicator method, the Ha was -3 or less.
このものの粒径を２４〜４８メツシニに揃え、反応に供
した。The particle size of this product was adjusted to 24 to 48 mesh, and it was used for reaction.
実施例１
参考例１で調製したＮＯ，−Ｔｉｅ２複合酸化物を長さ
３２ｃ＋ａ、内径１ ｃｍの石英ガラス反応管中に所定
量充填し、窒素気流下３００℃で１時間予熱処理した。Example 1 A predetermined amount of the NO, -Tie2 composite oxide prepared in Reference Example 1 was filled into a quartz glass reaction tube with a length of 32c+a and an inner diameter of 1 cm, and preheated at 300° C. for 1 hour under a nitrogen stream.
次いで、１．１−ジクロル−３，３−ジメチルブテン−
１（以下、ＤＤＢと略称する）を１．４４ｇ／ｈｒ、水
を０．７１ｇ／ｈｒ 、窒素Ｑ、３１／ｈｒで３００℃
に保温された熔融アルミナ充填気化器を通して、３００
℃に保温された反応管に導入した。Then, 1,1-dichloro-3,3-dimethylbutene-
1 (hereinafter abbreviated as DDB) at 1.44 g/hr, water at 0.71 g/hr, nitrogen Q at 31/hr at 300°C.
Passed through a vaporizer filled with molten alumina kept at a temperature of 300
The mixture was introduced into a reaction tube kept at ℃.
反応管を出た反応マスは氷冷してトラップし、これをガ
スクロマトグラフにより分析した。結果を表１に示した
。The reaction mass leaving the reaction tube was ice-cooled and trapped, and analyzed by gas chromatography. The results are shown in Table 1.
表 １
＊ｔ−ブチル酢酸選択率
参考例２
タングステン酸ソーダ（ＮａＪＯｎ ・２ Ｈａ０）
２４．８ ｇと水２５０ ｍｌ！からなる溶液とオキシ
塩化ジルコニウム（２ｒＯＣ１ｚ ・８ＬＯ）１２．
１ｇと水１２５ Ｗｄ！からなる溶液を混合した後、濃
塩酸１２５艷を加えて沈澱物を熟成させた。Table 1 *T-Butylacetic acid selectivity reference example 2 Sodium tungstate (NaJOn 2 Ha0)
24.8 g and 250 ml of water! A solution consisting of zirconium oxychloride (2rOC1z .8LO)12.
1g and water 125Wd! After mixing the solution, 125 liters of concentrated hydrochloric acid was added to ripen the precipitate.
沈澱物を濾過、希塩酸洗浄、乾燥後、空気々流中４５０
℃で７時間焼成して淡黄色の１１０．−Ｚｒ０２！！１
合酸化物２１．５ｇを得た。After filtering the precipitate, washing with diluted hydrochloric acid, and drying, the precipitate was heated at 450 °C in a stream of air.
Baked at ℃ for 7 hours to give a light yellow color of 110. -Zr02! ! 1
21.5 g of combined oxide was obtained.
このもののジルコニウムに対するタングステンの原子比
は２であり、酸強度関数Ｈｏは−３，０以下であった。The atomic ratio of tungsten to zirconium in this product was 2, and the acid strength function Ho was -3.0 or less.
参考例１と同様にメッシユを揃えて反応に供した。Similar to Reference Example 1, meshes were prepared and subjected to reaction.
実施例２
参考例２で調製した１１０．−ＺｒＯ□複合酸化物を用
い、反応温度３５０℃、ＤＤＥに対する水のモル比を２
．４．６、に変化させ、実施例１と同様に反応、分析し
た。結果を表２に示した。Example 2 110. prepared in Reference Example 2. - Using ZrO□ composite oxide, the reaction temperature was 350°C, and the molar ratio of water to DDE was 2.
．． 4.6, and the reaction and analysis were carried out in the same manner as in Example 1. The results are shown in Table 2.
表 ２
実施例３
実施例１に右いて、ＤＤＢの代わりに１．１゜１−）ジ
クロロ−３，３−ジメチルブタン（以下、ＴＤＢと略称
する）を用い、供給速度０．８０２ｇ／ｈｒ 。Table 2 Example 3 Same as Example 1, 1.1°1-) dichloro-3,3-dimethylbutane (hereinafter abbreviated as TDB) was used instead of DDB, and the feed rate was 0.802 g/hr.
水のＴＤＢに対するモル比を５．８に、反応温度を２０
０℃にする以外は実施例１に準拠して反応、分析した。The molar ratio of water to TDB was 5.8, and the reaction temperature was 20
The reaction and analysis were conducted in accordance with Example 1 except that the temperature was 0°C.
結果を表３に示した。The results are shown in Table 3.
表３
実施例４
実施例１において、ＤＤＥの代わりに１．１−ジクロル
プロペン（以下ＤＣＰと略称する）を用い、供給速度０
．８２ｇ／ｈｒ 、水のＤＣＰに対するモル比を４に、
反応温度を３００℃にする以外は実施例１に準拠して反
応、分析した。結果を第４表に示した。Table 3 Example 4 In Example 1, 1,1-dichloropropene (hereinafter abbreviated as DCP) was used instead of DDE, and the feed rate was 0.
．． 82 g/hr, the molar ratio of water to DCP was 4,
The reaction and analysis were conducted in accordance with Example 1 except that the reaction temperature was 300°C. The results are shown in Table 4.
表 ４
＊ プロピオン毀選択率
実施例５
実施例１において、ＤＤＥの代わりに１．１゜１−トリ
クロルエタン（以下、ＴＣＥと略称する）を用い、供給
速度０．３３ｇ／ｈｒ 、水のＴＣＥに対するモル比を
６に反応温度を表５に示す以外は実施例１に準拠して反
応、分析した。結果を表５にしめ（Ｗ／Ｆ ＝４５０）
＊ ＴＣＥ転化率
＊ 酢酸選択率
＊（酢酸＋塩化ビニリデン）選択率
手続補正書（自発）
昭和６３年 ４月７３日
１、事件の表示
昭和６３年特許願第 ４０３０７ 号２、発明の名
称
カルボン酸の製造方法
３、補正をする者
事件との関係 特許出願人
住 所 大阪市東区北浜５丁目１５番地明細書の発明
の詳細な説明の欄
６、補正の内容
（Ｉ）明細書筒１２頁６〜７行目に「・・・にしめした
、」とあるを、「・・・に示した。」と補正する。Table 4 *Propion dissipation selectivity Example 5 In Example 1, 1.1°1-trichloroethane (hereinafter abbreviated as TCE) was used instead of DDE, the supply rate was 0.33 g/hr, and the ratio of water to TCE was The reaction and analysis were carried out in accordance with Example 1 except that the molar ratio was 6 and the reaction temperature was shown in Table 5. The results are shown in Table 5 (W/F = 450) * TCE conversion rate * Acetic acid selectivity * (acetic acid + vinylidene chloride) Selectivity procedure amendment (voluntary) April 73, 1988 1, Incident display 1988 Patent Application No. 40307 2, Name of the invention: Process for producing carboxylic acid 3, Relationship with the case of the person making the amendment Patent applicant address: 5-15 Kitahama, Higashi-ku, Osaka City Detailed explanation of the invention in the specification 6 , Details of the amendment (I) On page 12 of the specification, lines 6-7, the phrase "shown..." is corrected to "shown...".
（２）同第１２頁最下行の次に下記を加入する。(2) Add the following to the bottom line of page 12.
「参考例３゜
参考例１に於けるチタンテトライソプロポキシドを４２
．６２ ｇに代える以外は、参考例１に準じて触媒を調
製した。"Reference Example 3゜Titanium tetraisopropoxide in Reference Example 1 is 42
．． A catalyst was prepared according to Reference Example 1 except that 62 g was used.
得られた同３− Ｔｉｅ、複合酸化物は、Ｗ／Ｔｉ ＝
０．３３原子比で、ＨＯは一３以下の酸強度を示した。The obtained 3-Tie, composite oxide, W/Ti =
At an atomic ratio of 0.33, HO exhibited an acid strength of 13 or less.
参考例６゜
参考例３で調製°した−０５−ＴｉＯ１複合酸化物触媒
１．８４ｇ（Ｉ，６ｃｃ）を用い、実施例１に準じてＤ
ＤＢの加水分解反応を実施した。但し、フィード条件は
以下のとおりである。Reference Example 6 Using 1.84 g (I, 6 cc) of the -05-TiO1 composite oxide catalyst prepared in Reference Example 3, D was prepared according to Example 1.
A hydrolysis reaction of DB was carried out. However, the feed conditions are as follows.
ＤＤＢ＝０．８６ｇ／ｈｒ （Ｗ／Ｆ−３２８ｇ−
ｃａｔ −ｈｒ／５ｏｌｅ）水＝０．４１ｇ／ｈｒ、
Ｎｚキャリヤ＝０．８６ｊ！／ｈｒ反応開始後３時間
での反応結果を以下に示した。DDB=0.86g/hr (W/F-328g-
cat -hr/5ole) water = 0.41g/hr,
Nz carrier = 0.86j! /hrReaction results 3 hours after the start of the reaction are shown below.
ＤＤＢ反応率＝４１．０％
ｔ−ブチル酢酸収率＝３９．５％
ｔ−ブチル酢酸選択率＝９６．３％ 」以
上DDB reaction rate = 41.0% t-butylacetic acid yield = 39.5% t-butylacetic acid selectivity = 96.3%
Up
Claims (1)
複合酸化物の存在下に、気相で一般式（ I ）および／
または一般式（II） ▲数式、化学式、表等があります▼（ I ） ▲数式、化学式、表等があります▼（II） （式中、Ｒは水素原子もしくは低級アルキル基を表す。 ） で示されるクロル化合物と水とを反応せさることを特徴
とする一般式（III） ▲数式、化学式、表等があります▼ （III） （式中、Ｒは前記と同じ意味を表す。） で示されるカルボン酸の製造方法。[Claims] General formula (I) and /
Or general formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R represents a hydrogen atom or a lower alkyl group.) The general formula (III) is characterized by reacting a chlorine compound with water. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) (In the formula, R represents the same meaning as above.) Method for producing carboxylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63040307A JPH0813774B2 (en) | 1988-02-22 | 1988-02-22 | Method for producing carboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63040307A JPH0813774B2 (en) | 1988-02-22 | 1988-02-22 | Method for producing carboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01213255A true JPH01213255A (en) | 1989-08-28 |
| JPH0813774B2 JPH0813774B2 (en) | 1996-02-14 |
Family
ID=12576959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63040307A Expired - Lifetime JPH0813774B2 (en) | 1988-02-22 | 1988-02-22 | Method for producing carboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0813774B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014038489A1 (en) * | 2012-09-04 | 2014-03-13 | 旭硝子株式会社 | Method for producing unsaturated acid and/or unsaturated acid ester |
-
1988
- 1988-02-22 JP JP63040307A patent/JPH0813774B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014038489A1 (en) * | 2012-09-04 | 2014-03-13 | 旭硝子株式会社 | Method for producing unsaturated acid and/or unsaturated acid ester |
| US9238612B2 (en) | 2012-09-04 | 2016-01-19 | Asahi Glass Company, Limited | Method for producing unsaturated acid and/or unsaturated acid ester |
| JPWO2014038489A1 (en) * | 2012-09-04 | 2016-08-08 | 旭硝子株式会社 | Method for producing unsaturated acid and / or unsaturated acid ester |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0813774B2 (en) | 1996-02-14 |
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