JPH0132813B2 - - Google Patents
Info
- Publication number
- JPH0132813B2 JPH0132813B2 JP56018318A JP1831881A JPH0132813B2 JP H0132813 B2 JPH0132813 B2 JP H0132813B2 JP 56018318 A JP56018318 A JP 56018318A JP 1831881 A JP1831881 A JP 1831881A JP H0132813 B2 JPH0132813 B2 JP H0132813B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- water
- oxyisobutyric
- acetone cyanohydrin
- added
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 45
- 239000002253 acid Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 claims description 22
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 21
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 21
- 230000002378 acidificating effect Effects 0.000 claims description 20
- 238000000605 extraction Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 239000012071 phase Substances 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000008346 aqueous phase Substances 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 21
- 239000007788 liquid Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- -1 but in this process Chemical compound 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- NTQWADDNQQUGRH-UHFFFAOYSA-N hydrogen sulfate;2-methylprop-2-enoylazanium Chemical compound OS(O)(=O)=O.CC(=C)C(N)=O NTQWADDNQQUGRH-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 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
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明はアセトンシアンヒドリン、硫酸及び水
を反応させたのち加水分解して得たα−オキシイ
ソ酪酸、酸性硫酸アンモニウム及び場合により遊
離の硫酸を含有する反応液からα−オキシイソ酪
酸を分離する方法に関する。
α−オキシイソ酪酸は触媒存在下に加熱、脱水
することにより容易にメタクリル酸になる。メタ
クリル酸は従来アセトンシアンヒドリンを濃硫酸
と混合し、アミド化反応を経て加水分解によりメ
タクリル酸となるが、この過程においては中間体
としてアミド硫酸、メタクリロアミドの硫酸塩を
生成し、高粘度の反応液が生成する。この方法で
メタクリル酸の収率を向上させるには反応液の急
速な加熱、冷却が必要であるが、反応液の粘度が
高い為急速な熱移動を行なわせることが困難であ
り、この為アミド化工程、加水分解工程と経過す
るたびに副反応の生起、反応生成物の分解等が起
り目的とするメタクリル酸の収率は原料アセトン
シアンヒドリンに対し70％程度に低下する。これ
に対しアセトンシアンヒドリン、硫酸及び水を反
応させたのち加水分解してα−オキシイソ酪酸を
得、これを加熱脱水してメタクリル酸とする方法
はアセトンシアンヒドリンから収率良くメタクリ
ル酸を得ることが出来すぐれた方法であるが、α
−オキシイソ酪酸と同時に酸性硫酸アンモニウム
が副生し、これの共存下に加熱脱水反応を行なう
ときはα−オキシイソ酪酸の分解を起しメタクリ
ル酸の収率を低下させるので、α−オキシイソ酪
酸と酸性硫酸アンモニウムは加水分解反応の後直
ちに分離することが必要である。しかしα−オキ
シイソ酪酸は水溶性が非常に大であり、共存する
酸性硫酸アンモニウムの塩析効果を利用した分液
分離は困難であり、又仮りに分液分離しても得ら
れる有機相中には酸性硫酸アンモニウムの混入量
が大となり次工程に悪影響を与える。
本発明はかゝる問題点を解消したα−オキシイ
ソ酪酸と酸性硫酸アンモニウムの分離方法に関す
るもので、アセトンシアンヒドリン、硫酸及び水
を反応させた後、水を加えて加水分解して得たα
−オキシイソ酪酸及び酸性硫酸アンモニウムを含
有する反応液に、メタクリル酸、メタクリル酸エ
ステル、これらと炭化水素類との混合物、エーテ
ル類、ケトン類からなる群より選ばれた抽剤を加
え、α−オキシイソ酪酸を抽剤相に抽出し、酸性
硫酸アンモニウムを水相に残存せしめる方法、ア
セトンシアンヒドリン、硫酸及び水を反応させた
のち加水分解して得たα−オキシイソ酪酸、酸性
硫酸アンモニウム及び遊離の硫酸を含有する反応
液にアルカリ及び抽剤を加え、遊離の硫酸を中和
すると共にα−オキシイソ酪酸を抽剤相に抽出
し、酸性硫酸アンモニウムを水相に残存せしめる
方法、及び上記の方法において抽出塔の中段付近
に上記加水分解後の反応液を導入し、塔底部より
抽剤を導入し、且つ塔頂濃縮部より水又はアルカ
リ水溶液を導入して向流抽出を行なう方法であ
る。
本発明においてアセトンシアンヒドリン、硫酸
及び水を反応させてα−オキシイソ酪酸を得るに
は、アセトンシアンヒドリンに対する硫酸のモル
比0.5〜2.0、好ましくは0.9〜1.2、アセトンシア
ンヒドリンに対する水のモル比0.2〜1.0好ましく
は0.4〜0.6、反応温度０〜80℃、好ましくは40〜
60℃の条件下反応させたのち、温度60〜130℃、
好ましくは80〜120℃でアセトンシアンヒドリン
に対し２倍モル以上、好ましくは３〜８倍モルの
水を加え加水分解すれば良い。
本発明においては以上の反応により得られたα
−オキシイソ酪酸及び酸性硫酸アンモニウムを含
有する反応液に抽剤を加え、α−オキシイソ酪酸
を抽剤相に抽出し、酸性硫酸アンモニウムを水相
に残存せしめることによりα−オキシイソ酪酸を
反応液から分離する。又反応液中に遊離の硫酸を
含有する場合には反応液にアルカリ及び抽剤を加
え遊離の硫酸を中和すると共にα−オキシイソ酪
酸を抽剤相に抽出し、酸性硫酸アンモニウムを水
相にに残存せしめる事によりα−オキシイソ酪酸
を反応液から分離する。即ち反応液中に遊離離の
硫酸が含まれている場合には遊離の硫酸のアンモ
ニヤあるいは無機のアルカリ性物質により中和す
る事により、α−オキシイソ酪酸の抽剤相中への
分配係数は飛躍的に増大する。中和の方法として
はあらかじめ反応液をアルカリ処理後抽出操作を
行なつても良く、又抽出時にアルカリ性水溶液を
加え、抽出操作とアルカリ洗滌操作を同時に行な
つても良い。
本発明において使用し得る抽剤は水性相からα
−オキシイソ酪酸を選択的に抽出し得るものであ
り、これらを例示すればメタクリル酸、メタクリ
ル酸エステル、あるいはこれらとベンゼン、トル
エン、キシレン等の芳香族炭化水素、シクロヘキ
サン等の脂環式炭化水素、ｎ−ブタン、ｎ−ヘキ
サン等の脂肪族炭化水素との混合物、エチル、プ
ロピル、ブチル、アミル等の低級炭化水素を有す
るエーテル類及びケトン類、等であり、特にメタ
クリル酸、メタクリル酸エステル、炭化水素とメ
タクリル酸の混合物、メチルエチルケトン及びメ
チルイソブチルケトンのケトンが分配係数が大き
く好ましい。
本発明におけるα−オキシイソ酪酸の抽出は温
度０〜100℃で反応液中のα−オキシイソ酪酸に
対し0.5〜２重量倍の割合で抽剤を接触させるこ
とにより行なう。
本発明における抽出操作は回分式でも行なうこ
とが出来るが向流抽出塔を用い連続式で行なうこ
とが好ましい。抽出塔としてはRDC塔（Rotary
Disc Contactor）、往復回転式抽出塔、交互流動
多孔板式抽出塔、ミキサーセトラー型抽出器等の
抽出装置を使用することが出来、塔の中段付近よ
り反応液を、塔底部より抽剤を導入して向流抽出
を行なうが、特に塔頂付近（濃縮部）より水又は
アルカリ水溶液を添加するのがα−オキシイソ酪
酸と酸性硫酸アンモニウムの分離効率を高める上
で好適である。この場合の水の添加割合は抽出相
に対し0.05〜0.5重量倍程度が好ましい。
本発明によればアセトンシアンヒドリン、硫酸
及び水を反応させたのち加水分解して得たα−オ
キシイソ酪酸及び酸性硫酸アンモニウムを含有す
る反応液からα−オキシイソ酪酸を選択的に分離
することが可能であり、α−オキシイソ酪酸を経
由するメタクリル酸の製造法の工業化に極めて有
用である。
実施例 １
撹拌機、温度センサーおよび還流冷却器を備え
た500c.c.の４つ口フラスコに、98％H2SO454.3ｇ
を仕込む。
フラスコ内容物を撹拌しながら、アセトンシア
ンヒドリン42.5ｇ、H2O5.4ｇ（H2O／ACHモル
比＝0.6）の混合物を徐々に滴下する。フラスコ
外部を冷水で冷却し、反応器内部温度を55±５℃
に保ちつつ、50分で滴下終了後、40分間55±５℃
で更に撹拌を続ける。次にフラスコに水80.7ｇを
投入し、フラスコ内液温を110℃に加熱して、60
分撹拌し、その後室温まで冷却する。
これにより得られた反応液100ｇ（α−オキシ
イソ酪酸28wt％、酸性硫酸アンモニウム31wt％、
硫酸2.7wt％）に、第１表に示した抽剤各46ｇを
添加し、大気圧下温度70℃で充分振盪した後静置
し抽出相と水相とに相分離した。
この液を分析しα−オキシイソ酪酸および酸性
硫酸アンモニウムの量を求めそれぞれの分配係数
を調べた処、第１表の如くであつた。
The present invention relates to a method for separating α-oxyisobutyric acid from a reaction solution containing α-oxyisobutyric acid obtained by reacting acetone cyanohydrin, sulfuric acid, and water and then hydrolyzing it, acidic ammonium sulfate, and optionally free sulfuric acid. . α-oxyisobutyric acid is easily converted to methacrylic acid by heating and dehydration in the presence of a catalyst. Methacrylic acid is conventionally produced by mixing acetone cyanohydrin with concentrated sulfuric acid, undergoing an amidation reaction, and then being hydrolyzed to produce methacrylic acid, but in this process, amidosulfuric acid and methacryloamide sulfate are produced as intermediates, resulting in high A viscous reaction liquid is produced. In order to improve the yield of methacrylic acid using this method, it is necessary to rapidly heat and cool the reaction solution, but the high viscosity of the reaction solution makes it difficult to perform rapid heat transfer. Each time the oxidation process and the hydrolysis process occur, side reactions occur, decomposition of the reaction product, etc. occur, and the yield of the desired methacrylic acid decreases to about 70% based on the raw material acetone cyanohydrin. On the other hand, a method in which acetone cyanohydrin, sulfuric acid, and water are reacted and then hydrolyzed to obtain α-oxyisobutyric acid, which is heated and dehydrated to produce methacrylic acid, is a method that produces methacrylic acid in a high yield from acetone cyanohydrin. This is an excellent method for obtaining α
-Acidic ammonium sulfate is produced as a by-product at the same time as oxyisobutyric acid, and when a heating dehydration reaction is performed in the coexistence of this, α-oxyisobutyric acid decomposes and the yield of methacrylic acid decreases, so α-oxyisobutyric acid and acidic ammonium sulfate are It is necessary to separate immediately after the hydrolysis reaction. However, α-oxyisobutyric acid is extremely highly water-soluble, and it is difficult to perform liquid separation using the salting-out effect of coexisting acidic ammonium sulfate. The amount of acidic ammonium sulfate mixed in becomes large and has an adverse effect on the next process. The present invention relates to a method for separating α-oxyisobutyric acid and acidic ammonium sulfate that solves these problems.
- To the reaction solution containing oxyisobutyric acid and acidic ammonium sulfate, add an extractant selected from the group consisting of methacrylic acid, methacrylic esters, mixtures of these with hydrocarbons, ethers, and ketones, and add α-oxyisobutyric acid Contains α-oxyisobutyric acid, acidic ammonium sulfate, and free sulfuric acid obtained by reacting acetone cyanohydrin, sulfuric acid, and water and then hydrolyzing it. A method in which an alkali and an extractant are added to the reaction solution to neutralize free sulfuric acid and extract α-oxyisobutyric acid into the extractant phase, leaving acidic ammonium sulfate in the aqueous phase; In this method, the reaction solution after hydrolysis is introduced nearby, an extractant is introduced from the bottom of the column, and water or aqueous alkaline solution is introduced from the top concentration section to perform countercurrent extraction. In the present invention, in order to obtain α-oxyisobutyric acid by reacting acetone cyanohydrin, sulfuric acid, and water, the molar ratio of sulfuric acid to acetone cyanohydrin is 0.5 to 2.0, preferably 0.9 to 1.2, and the molar ratio of sulfuric acid to acetone cyanhydrin is 0.5 to 2.0, preferably 0.9 to 1.2. Molar ratio 0.2-1.0 preferably 0.4-0.6, reaction temperature 0-80℃, preferably 40-80℃
After reacting at 60℃, the temperature is 60-130℃,
Preferably, the hydrolysis may be carried out at 80 to 120°C by adding water in an amount of 2 times or more, preferably 3 to 8 times, mole of acetone cyanohydrin. In the present invention, α obtained by the above reaction
- Adding an extractant to a reaction solution containing oxyisobutyric acid and acidic ammonium sulfate, extracting α-oxyisobutyric acid into the extractant phase, and allowing acidic ammonium sulfate to remain in the aqueous phase, thereby separating α-oxyisobutyric acid from the reaction solution. If the reaction solution contains free sulfuric acid, add an alkali and an extractant to the reaction solution to neutralize the free sulfuric acid, extract α-oxyisobutyric acid to the extractant phase, and add acidic ammonium sulfate to the aqueous phase. α-oxyisobutyric acid is separated from the reaction solution by allowing it to remain. In other words, if free sulfuric acid is contained in the reaction solution, by neutralizing the free sulfuric acid with ammonia or an inorganic alkaline substance, the distribution coefficient of α-oxyisobutyric acid into the extractant phase can be dramatically increased. increases to As a neutralization method, the reaction solution may be treated with an alkali in advance and then subjected to an extraction operation, or an alkaline aqueous solution may be added during extraction to perform the extraction operation and the alkali washing operation at the same time. The extracting agent that can be used in the present invention is α
- Oxyisobutyric acid can be selectively extracted, and examples thereof include methacrylic acid, methacrylic acid ester, or these and aromatic hydrocarbons such as benzene, toluene, and xylene, alicyclic hydrocarbons such as cyclohexane, Mixtures with aliphatic hydrocarbons such as n-butane and n-hexane, ethers and ketones containing lower hydrocarbons such as ethyl, propyl, butyl, amyl, etc., especially methacrylic acid, methacrylic esters, carbonized A mixture of hydrogen and methacrylic acid, and ketones such as methyl ethyl ketone and methyl isobutyl ketone are preferred because they have a large distribution coefficient. The extraction of α-oxyisobutyric acid in the present invention is carried out at a temperature of 0 to 100°C by contacting the extracting agent at a ratio of 0.5 to 2 times the weight of α-oxyisobutyric acid in the reaction solution. Although the extraction operation in the present invention can be carried out batchwise, it is preferably carried out continuously using a countercurrent extraction column. The extraction tower is RDC tower (Rotary
Extraction devices such as disc contactor), reciprocating rotary extraction tower, alternating flow perforated plate extraction tower, and mixer-settler type extractor can be used.The reaction liquid is introduced near the middle of the tower and the extractant is introduced from the bottom of the tower. Countercurrent extraction is carried out, and it is particularly preferable to add water or an aqueous alkali solution near the top of the column (concentrating section) in order to increase the efficiency of separating α-oxyisobutyric acid and acidic ammonium sulfate. In this case, the ratio of water added is preferably about 0.05 to 0.5 times the weight of the extraction phase. According to the present invention, it is possible to selectively separate α-oxyisobutyric acid from a reaction solution containing α-oxyisobutyric acid and acidic ammonium sulfate obtained by reacting acetone cyanohydrin, sulfuric acid, and water and then hydrolyzing the mixture. Therefore, it is extremely useful for industrializing the method for producing methacrylic acid via α-oxyisobutyric acid. Example 1 54.3 g of 98% H 2 SO 4 was added to a 500 c.c. four-necked flask equipped with a stirrer, temperature sensor, and reflux condenser.
Prepare. While stirring the contents of the flask, a mixture of 42.5 g of acetone cyanohydrin and 5.4 g of H 2 O (H 2 O/ACH molar ratio = 0.6) is gradually added dropwise. Cool the outside of the flask with cold water and keep the reactor internal temperature at 55±5℃.
55±5℃ for 40 minutes after finishing the drop in 50 minutes.
Continue stirring. Next, put 80.7g of water into the flask, heat the liquid temperature in the flask to 110℃, and
Stir for 1 minute, then cool to room temperature. 100 g of the reaction solution obtained (α-oxyisobutyric acid 28 wt%, acidic ammonium sulfate 31 wt%,
46 g of each extractant shown in Table 1 was added to sulfuric acid (2.7 wt%), thoroughly shaken at a temperature of 70° C. under atmospheric pressure, and then allowed to stand to separate into an extraction phase and an aqueous phase. This liquid was analyzed to determine the amounts of α-oxyisobutyric acid and acidic ammonium sulfate, and the distribution coefficients were as shown in Table 1.
【表】
実施例 ２
実施例１と同じ反応液に第２表に示した抽剤を
添加し、大気圧下温度50℃で実施例１と同様に分
配係数を調べた。
その結果を次に示す。[Table] Example 2 The extractant shown in Table 2 was added to the same reaction solution as in Example 1, and the partition coefficient was examined in the same manner as in Example 1 at a temperature of 50° C. under atmospheric pressure. The results are shown below.
【表】
実施例 ３
実施例１の反応液100ｇに25％アンモニア水溶
液２ｇを添加し遊離の硫酸を中和したのち、第３
表に示した抽剤46ｇを添加し、温度50℃で充分振
盪した後静置し、抽剤相と水相とに相分離した。
この液を分析しα−オキシイソ酪酸および酸性硫
酸アンモニウムの量を求めその分配係数を調べた
処、次の如くであつた。[Table] Example 3 After adding 2 g of 25% ammonia aqueous solution to 100 g of the reaction solution of Example 1 to neutralize free sulfuric acid,
46 g of the extractant shown in the table was added, and the mixture was sufficiently shaken at a temperature of 50°C and then allowed to stand to separate into an extractant phase and an aqueous phase.
This liquid was analyzed to determine the amounts of α-oxyisobutyric acid and acidic ammonium sulfate, and the distribution coefficient was determined as follows.
【表】
実施例 ４
それぞれ撹拌機を有する連続４段槽型合成装置
の第１槽に98％硫酸およびアセトンシアンヒドリ
ンと水の混合物を連続的に供給し、反応液は第２
槽を経て第３槽へ導き、ここで加水分解のための
水を加え、更に第４槽へ導くと云う工程でα−オ
キシイソ酪酸の連続合成反応を行つた。各槽の反
応条件は第４表の通りである。[Table] Example 4 A mixture of 98% sulfuric acid, acetone cyanohydrin and water was continuously supplied to the first tank of a continuous four-stage synthesis apparatus each having a stirrer, and the reaction liquid was fed to the second tank.
Continuous synthesis reaction of α-oxyisobutyric acid was carried out in the following steps: the mixture was led to a third tank through a tank, water was added there for hydrolysis, and the mixture was further led to a fourth tank. The reaction conditions for each tank are shown in Table 4.
【表】
これにより得られた反応液６Kg／Ｈ（α−オキ
シイソ酪酸33wt％、酸性硫酸アンモニウム
36.5wt％、水30.5wt％）を向流多段抽出塔（回収
部18段、濃縮部８段）の中段に、メチルイソブチ
ルケトン６Kg／Ｈをこの抽出塔の塔底部に、水
1.02Kg／Ｈを塔頂部に供給し、塔頂より抽剤相、
塔底より抽残相（水相）を抜き出し向流抽出を行
つた結果は次の如くであつた。[Table] 6 kg/H of the reaction solution obtained (α-oxyisobutyric acid 33 wt%, acidic ammonium sulfate
36.5 wt%, water 30.5 wt%) in the middle stage of a countercurrent multistage extraction column (18 stages of recovery section, 8 stages of concentration section), 6 kg/H of methyl isobutyl ketone at the bottom of this extraction tower, and water.
1.02Kg/H is supplied to the top of the column, and the extractant phase,
The raffinate phase (aqueous phase) was extracted from the bottom of the column and subjected to countercurrent extraction, and the results were as follows.
【表】
比較例 １
実施例１における反応液に、次の抽剤を用いて
実施例１と同様の操作で分配係数を調べた。その
結果を次に示す。[Table] Comparative Example 1 The partition coefficient was examined in the same manner as in Example 1 using the following extractant in the reaction solution in Example 1. The results are shown below.
Claims (1)
0.2〜1.0の条件下40〜60℃で、アセトンシアンヒ
ドリン、硫酸及び水を反応させた後、水を加えて
原料のアセトンシアンヒドリンに対する水のモル
比を2.0以上とし、80〜120℃で加水分解して得た
α−オキシイソ酪酸及び酸性硫酸アンモニウムを
含有する反応液に、メタクリル酸、メクタリル酸
エステル、これらと炭化水素類との混合物、エー
テル類、ケトン類からなる群より選ばれた抽剤を
加え、α−オキシイソ酪酸を抽剤相に抽出し、酸
性硫酸アンモニウムを水相に残存せしめることを
特徴とするα−オキシイソ酪酸の分離法。 ２ アセトンシアンヒドリンに対する水のモル比
0.2〜1.0の条件下40〜60℃で、アセトンシアンヒ
ドリン、硫酸及び水を反応させた後、水を加えて
原料のアセトンシアンヒドリンに対する水のモル
比を2.0以上とし、80〜120℃で加水分解して得た
α−オキシイソ酪酸、酸性硫酸アンモニウム及び
遊離の硫酸を含有する反応液に、アルカリ及び、
メタクリル酸、メタクリル酸エステル、これらと
炭化水素類との混合物、エーテル類、ケトン類か
らなる群より選ばれた抽剤を加え、遊離の硫酸を
中和すると共ににα−オキシイソ酪酸を抽剤相に
抽出することを特徴とするα−オキシイソ酪酸の
分離法。 ３ アセトンシアンヒドリンに対応する水のモル
比0.2〜1.0の条件下40〜60℃で、アセトンシアン
ヒドリン、硫酸及び水を反応させた後、水を加え
て原料のアセトンシアンヒドリンに対する水のモ
ル比を2.0以上とし、80〜120℃で加水分解して得
たα−オキシイソ酪酸及び酸性硫酸アンモニウム
及び場合によつて遊離の硫酸を含有する反応液
に、メタクリル酸、メクタリル酸エステル、これ
らと炭化水素類との混合物、エーテル類、ケトン
類からなる群より選ばれた抽剤を加え、α−オキ
シイソ酪酸を抽出分離する方法において、抽出塔
の中段付近より上記反応液を導入し、塔底部より
上記抽剤を導入し、且つ塔頂濃縮部より水又はア
ルカリ水溶液を導入して向流抽出を行うことを特
徴とするα−オキシイソ酪酸の分離法。[Claims] 1. Molar ratio of water to acetone cyanohydrin
After reacting acetone cyanohydrin, sulfuric acid and water at 40 to 60°C under conditions of 0.2 to 1.0, water is added to make the molar ratio of water to acetone cyanohydrin of the raw material 2.0 or more, and the mixture is heated at 80 to 120°C. An extract selected from the group consisting of methacrylic acid, methacrylic acid ester, mixtures of these with hydrocarbons, ethers, and ketones is added to the reaction solution containing α-oxyisobutyric acid and acidic ammonium sulfate obtained by hydrolysis. 1. A method for separating α-oxyisobutyric acid, which comprises adding an agent, extracting α-oxyisobutyric acid into an extractant phase, and allowing acidic ammonium sulfate to remain in an aqueous phase. 2 Molar ratio of water to acetone cyanohydrin
After reacting acetone cyanohydrin, sulfuric acid and water at 40 to 60°C under conditions of 0.2 to 1.0, water is added to make the molar ratio of water to acetone cyanohydrin of the raw material 2.0 or more, and the mixture is heated at 80 to 120°C. An alkali and a reaction solution containing α-oxyisobutyric acid obtained by hydrolysis with
An extractant selected from the group consisting of methacrylic acid, methacrylic acid esters, mixtures of these with hydrocarbons, ethers, and ketones is added to neutralize free sulfuric acid and extract α-oxyisobutyric acid into the extractant phase. A method for separating α-oxyisobutyric acid, which is characterized by extracting α-oxyisobutyric acid. 3. After reacting acetone cyanohydrin, sulfuric acid, and water at 40 to 60°C under conditions with a molar ratio of water corresponding to acetone cyanohydrin of 0.2 to 1.0, water is added to the water relative to the raw material acetone cyanohydrin. methacrylic acid, methacrylic acid ester, and a reaction solution containing α-oxyisobutyric acid obtained by hydrolysis at 80 to 120°C, acidic ammonium sulfate, and optionally free sulfuric acid, with a molar ratio of 2.0 or more. In the method of extracting and separating α-oxyisobutyric acid by adding an extractant selected from the group consisting of mixtures with hydrocarbons, ethers, and ketones, the above reaction liquid is introduced near the middle of the extraction column, and the mixture is added to the bottom of the column. 1. A method for separating α-oxyisobutyric acid, which comprises introducing the above-mentioned extractant from the top of the column and introducing water or an aqueous alkali solution from the top concentration section to carry out countercurrent extraction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56018318A JPS57131736A (en) | 1981-02-10 | 1981-02-10 | Isolation of alpha-oxyisobutyric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56018318A JPS57131736A (en) | 1981-02-10 | 1981-02-10 | Isolation of alpha-oxyisobutyric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57131736A JPS57131736A (en) | 1982-08-14 |
| JPH0132813B2 true JPH0132813B2 (en) | 1989-07-10 |
Family
ID=11968259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56018318A Granted JPS57131736A (en) | 1981-02-10 | 1981-02-10 | Isolation of alpha-oxyisobutyric acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57131736A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007522156A (en) * | 2004-02-11 | 2007-08-09 | レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング | Process for producing α-hydroxycarboxylic acids and esters thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007050284A1 (en) | 2007-10-18 | 2009-04-23 | Evonik Röhm Gmbh | Process for amidation of nitriles in the presence of sulfuric acid |
| ES2935290T3 (en) | 2020-10-23 | 2023-03-03 | Roehm Gmbh | Optimized procedure for the preparation of alkyl methacrylate by reducing disturbing by-products |
| US20240010604A1 (en) | 2020-10-23 | 2024-01-11 | Röhm Gmbh | Optimized process for synthesizing methacrylic acid (maa) and/or alkyl methacrylate by reducing unwanted byproducts |
| WO2023169810A1 (en) | 2022-03-11 | 2023-09-14 | Röhm Gmbh | Process for producing alpha-hydroxyisobutyric acid methyl ester, and its use in the electronics industry |
-
1981
- 1981-02-10 JP JP56018318A patent/JPS57131736A/en active Granted
Non-Patent Citations (1)
| Title |
|---|
| ADVANCED ORGANIC CHEMISTRY=1977 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007522156A (en) * | 2004-02-11 | 2007-08-09 | レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング | Process for producing α-hydroxycarboxylic acids and esters thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57131736A (en) | 1982-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4644076A (en) | Continuous process for the synthesis of hexamethyldisilazane | |
| JPH0680023B2 (en) | Acetic anhydride recovery method | |
| JPH0132813B2 (en) | ||
| JP2001322968A (en) | Method for purifying methacrylic acid ester | |
| JPS6361932B2 (en) | ||
| US4354042A (en) | Process for making N,N,N',N'-tetraacetylethylenediamine | |
| US2533808A (en) | Manufacture of isopropyl alcohol | |
| CN109942357A (en) | A kind of low boiling point alcohol continuous esterification reaction rectification process | |
| CN110105239B (en) | Production method of 3-methyl-4-nitrobenzoic acid trichlorocyanobutyl ester | |
| US2776972A (en) | Recovery of morpholine from aqueous solutions thereof | |
| RU2282620C1 (en) | Method for preparing trifluoromethane sulfoacid anhydride | |
| JPS63303937A (en) | Manufacture of propynol | |
| JP2004529972A (en) | Method for treating an aqueous medium containing phosphate, cyclohexanone and cyclohexanone oxime | |
| JP2000159736A (en) | Production of n-(1,1-dimethyl-3-oxobutyl)acrylamide | |
| US3642889A (en) | Production of lactic acid | |
| CN117756625B (en) | Preparation method of o-ethoxybenzoyl chloride | |
| RU2208009C1 (en) | Method for preparing pentaerythritol with content of basic substance above 98 mass % and pentaerythritol enriched with dipentaerythritol in amount 5-20 mass % | |
| CN113511983A (en) | A kind of purification method of hydroxyethyl hydrazine nitrate crude product | |
| CN119455855B (en) | Device and method for producing oxamide | |
| JP2501603B2 (en) | Method for producing α-methylstyrene | |
| SU625387A1 (en) | Method of preparation of lower isocyanates | |
| JPH0730015B2 (en) | Method for producing perpropionic acid | |
| JPS5819665B2 (en) | Succinyl succinate diester | |
| JPS6220976B2 (en) | ||
| JPS6210975B2 (en) |