JPH02172942A - Production of p-hydroxybenzaldehyde - Google Patents
Production of p-hydroxybenzaldehydeInfo
- Publication number
- JPH02172942A JPH02172942A JP63327148A JP32714888A JPH02172942A JP H02172942 A JPH02172942 A JP H02172942A JP 63327148 A JP63327148 A JP 63327148A JP 32714888 A JP32714888 A JP 32714888A JP H02172942 A JPH02172942 A JP H02172942A
- Authority
- JP
- Japan
- Prior art keywords
- methanol
- hydroxybenzaldehyde
- water
- added
- 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
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 122
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 239000011541 reaction mixture Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 11
- 239000011707 mineral Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 150000002931 p-cresols Chemical class 0.000 claims abstract description 10
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 7
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 abstract description 19
- 239000000706 filtrate Substances 0.000 abstract description 10
- 238000001816 cooling Methods 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000011369 resultant mixture Substances 0.000 abstract 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 235000010755 mineral Nutrition 0.000 description 8
- -1 parahydroxybenzyl methyl ether Chemical compound 0.000 description 7
- 238000011084 recovery Methods 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 5
- 229930003836 cresol Natural products 0.000 description 5
- 239000011269 tar Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- WZWGGYFEOBVNLA-UHFFFAOYSA-N sodium;dihydrate Chemical compound O.O.[Na] WZWGGYFEOBVNLA-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical group CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Chemical group COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 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)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、ｐ−クレゾール又はｐ−クレゾール含有混合
物（以下ｐ−クレゾール類という）を酸素又は酸素含有
ガスで酸化して得られる反応混合ｔｉからｐ−ヒドロキ
シベンズアルデヒドを分離・ｆｉｔ製するｐ−ヒドロキ
シベンズアルデヒドの製造法に関する。Detailed Description of the Invention <Industrial Application Field> The present invention relates to a reaction mixture obtained by oxidizing p-cresol or a p-cresol-containing mixture (hereinafter referred to as p-cresols) with oxygen or an oxygen-containing gas. This invention relates to a method for producing p-hydroxybenzaldehyde by separating and fitting p-hydroxybenzaldehyde from.
〈従来の技術〉
ｐ−ヒドロキシベンズアルデヒドは、有機化学工業にお
ける原料として重要で、染料、医薬品、農薬等の製造に
広く使用されている。<Prior Art> p-Hydroxybenzaldehyde is important as a raw material in the organic chemical industry, and is widely used in the production of dyes, pharmaceuticals, agricultural chemicals, and the like.
従来、ｐ−ヒドロキシベンズアルデヒドの製造法として
は、ｐ−クレゾールをメタノール中で水酸化ナトリウム
およびコバルト化合物を含む触媒の存在下で酸素または
酸素含有ガスで酸化する方法が知られている（特開昭５
５−１１１１ｓ３２号、特開昭６３２６４４３５号公報
）。そしてかかる方法による反応混合物からｐ−ヒドロ
キシベンズアルデヒドヲ単離する方法としては、ｐ−ヒ
ドロキシベンズアルデヒドをナトリウム塩として晶析・
分離する精製方法が知られている（特開昭６２−２２
’７４０号公報、特開昭６３−２１６８３９号公報）。Conventionally, as a method for producing p-hydroxybenzaldehyde, a method is known in which p-cresol is oxidized in methanol with oxygen or an oxygen-containing gas in the presence of a catalyst containing sodium hydroxide and a cobalt compound (Japanese Patent Application Laid-open No. 5
5-1111s32, Japanese Unexamined Patent Publication No. 63264435). As a method for isolating p-hydroxybenzaldehyde from the reaction mixture by such a method, p-hydroxybenzaldehyde is crystallized as a sodium salt.
There is a known purification method for separating
'740, JP-A-63-216839).
〈発明が解決しようとする課題〉
しかし、これ等公知の方法は未反応のタレゾール類や、
反応で副生ずるパラヒドロキシベンジルメチルエーテル
、タール状物質などとの分離が悪く、パラヒドロキシベ
ンズアルデヒドの回収率が低いことや、純度が悪い等の
問題があった。<Problem to be solved by the invention> However, these known methods produce unreacted talesols,
There were problems such as poor separation of parahydroxybenzyl methyl ether, tar-like substances, etc. produced as by-products in the reaction, a low recovery rate of parahydroxybenzaldehyde, and poor purity.
本発明者らはこれ等の問題点を解決すべ（、鋭意研究を
続けた結果、本発明を完成するに至ったものである。The inventors of the present invention have continued intensive research to solve these problems, and as a result have completed the present invention.
く課題を解決するための手段〉
本発明は、ｐ−クレゾール類をメタノール中で水酸化ナ
トリウムおよびコバルト化合物を含む触媒の存在下で酸
素または酸素含有ガスで酸化して得られる反応混合物か
らｐ−ヒドロキシベンズアルデヒドを単離するにあたり
、上記反応混合物にメタノールを加え、生じたタール分
等を濾別し、次いで水を加え、加熱してメタノールを溜
去し、次いで冷却してｐ−ヒドロキシベンズアルデヒド
をナトリウム塩の形で晶析・分離することを特徴とする
ｐ−ヒドロキシベンズアルデヒドの製造法である。所望
により分離したナトリウム塩の結晶を水に溶解し、必要
により濾過し、鉱酸で中和してｐ−ヒドロキシベンズア
ルデヒドを晶析・分離させることことを特徴とするｐ−
ヒドロキシベンズアルデヒドの製造法である。Means for Solving the Problems> The present invention provides p-cresols from a reaction mixture obtained by oxidizing p-cresols with oxygen or an oxygen-containing gas in the presence of a catalyst containing sodium hydroxide and a cobalt compound in methanol. To isolate hydroxybenzaldehyde, methanol is added to the above reaction mixture, the resulting tar and other substances are filtered off, water is then added and methanol is distilled off by heating, and then p-hydroxybenzaldehyde is purified by cooling. This is a method for producing p-hydroxybenzaldehyde, which is characterized by crystallizing and separating it in the form of a salt. The p-hydroxybenzaldehyde is characterized by dissolving the separated sodium salt crystals in water, filtering if necessary, and neutralizing with mineral acid to crystallize and separate p-hydroxybenzaldehyde.
This is a method for producing hydroxybenzaldehyde.
更に本発明の他の方法は、ｐ−クレゾール類をメタノー
ル中で水酸化ナトリウムおよびコバルト化合物を含む触
媒の存在下で酸素または酸素含有ガスで酸化して得られ
る反応混合物からｐ−ヒドロキシベンズアルデヒドを単
離するにあたり、上記反応混合物にメタノールを加え、
生じたタール分等を濾別し、次いで水を加え、加熱して
メタノールを溜去し、次いで鉱酸で中和し、冷却してｐ
−ヒドロキシベンズアルデヒドを結晶の形で晶析・分離
することを特徴とするｐ−ヒドロキシベンズアルデヒド
の製造法である。所望により分離したｐ−ヒドロキシベ
ンズアルデヒドの結晶を水に溶解し、必要により濾過し
、冷却して晶析・分離することを特徴とするｐ−ヒドロ
キシベンズアルデヒドの製造法である。Still another method of the present invention is to oxidize p-cresols in methanol with oxygen or an oxygen-containing gas in the presence of a catalyst containing sodium hydroxide and a cobalt compound to obtain p-hydroxybenzaldehyde. To separate, add methanol to the above reaction mixture,
The generated tar etc. are filtered off, water is added, heated to distill off methanol, then neutralized with mineral acid, cooled and p
- A method for producing p-hydroxybenzaldehyde, which is characterized by crystallizing and separating hydroxybenzaldehyde in the form of crystals. This is a method for producing p-hydroxybenzaldehyde, which is characterized by dissolving p-hydroxybenzaldehyde crystals separated if desired in water, filtering if necessary, and cooling to crystallize and separate.
本発明においてｐ−クレゾール類の酸化は従来公知の方
法が適用されるが、具体的には例えば、前記公知の方法
により容易に実施することができる。In the present invention, p-cresols are oxidized by conventionally known methods, and specifically, for example, the oxidation can be easily carried out by the above-mentioned known methods.
本発明において出発原料として用いられるｐ−クレゾー
ル類は、ｐ−クレゾール又はｐ−クレゾール含を混合物
であり、該混合物とは、具体的にはｍ−クレゾール、０
−クレゾール等を含有する合成りレゾールあるいはコー
ルタールより分留されるクレゾール酸類等ｐ−クレゾー
ルを含有するクレゾール混合物であっても良いが、混合
物を使用する場合はｐ−クレゾール含量が高い程好まし
い。たとえば、ｍ／ｐ混合クレゾールを使用する場合、
ｍ／ｐ比４０／６０〜０．１／９９．９の混合クレゾー
ルを用いることが好ましい。The p-cresols used as starting materials in the present invention are p-cresol or a mixture containing p-cresol, and the mixture specifically includes m-cresol, 0
A cresol mixture containing p-cresol, such as a synthetic resol containing -cresol or cresylic acids fractionated from coal tar, may be used, but when a mixture is used, the higher the p-cresol content, the better. For example, when using m/p mixed cresol,
It is preferable to use a mixed cresol with an m/p ratio of 40/60 to 0.1/99.9.
本発明の分離・精製工程は、反応混合物にメタノールを
加える工程■、濾過をしてタールを分離する工程■、濾
液に水を加える工程■、これを加熱してメタノールを溜
去する工程■を主要部とし、一方の方法は次いでメタノ
ール溶去後の液を冷却してｐ−ヒドロキシベンズアルデ
ヒドをナトリウム塩の形で晶析・分離する工程■、所望
により、分離した結晶を水に溶解し■、必要により濾過
し、鉱酸で中和し■、冷却してｐ−ヒドロキシベンズア
ルデヒドを晶析・分離する工程■から成り、また、他の
方法は、前記メタノールを漏失後の液を鉱酸により中和
し■、冷却してｐ−ヒドロキシベンズアルデヒドを結晶
の形で晶析・分離する工程＠から成り、所望により、分
離した結晶を水に溶解し■、必要により濾過し、冷却し
てｐ−ヒドロキシベンズアルデを晶析・分離する工程■
からなっている。The separation and purification process of the present invention includes a step (1) of adding methanol to the reaction mixture, a step (2) of filtering to separate tar, a step (2) of adding water to the filtrate, and a step (4) of distilling off methanol by heating it. The main part is the step of cooling the liquid after methanol has been eluted and crystallizing and separating p-hydroxybenzaldehyde in the form of sodium salt. If desired, the separated crystals are dissolved in water. It consists of a step (2) of filtering if necessary, neutralizing it with a mineral acid, and cooling it to crystallize and separate p-hydroxybenzaldehyde.Another method is to neutralize the liquid after the methanol has leaked out with a mineral acid. The process consists of (1) cooling and crystallizing/separating p-hydroxybenzaldehyde in the form of crystals; if desired, dissolving the separated crystals in water (2), filtering if necessary, and cooling to form p-hydroxybenzaldehyde. Process of crystallizing and separating benzalde■
It consists of
以下、本発明の各工程について詳述する。Each step of the present invention will be explained in detail below.
先ず、反応混合物にメタノールを加える工程■は、ｐ−
クレゾール類に対して０．２〜２０重量部、好ましくは
１〜ｌＯ重量部になるようにメタノールを添加する。First, step (2) of adding methanol to the reaction mixture is p-
Methanol is added in an amount of 0.2 to 20 parts by weight, preferably 1 to 10 parts by weight, based on the cresols.
次に、濾過をしてタールを分離する工程■では生じたメ
タノール溶液を必要によって例えば３０〜１００℃の温
度に加熱し、主としてタール成分、触媒成分、シ二−酸
ソーダ等を濾過して分離する。Next, in the step (2) of filtering and separating tar, the resulting methanol solution is heated to a temperature of, for example, 30 to 100°C as necessary, and mainly tar components, catalyst components, sodium cindia acid, etc. are filtered and separated. do.
分離機は通常のものが使用でき、この場合所望により濾
過助材を添加することも可能である。A conventional separator can be used, and in this case, it is also possible to add a filter aid if desired.
次に濾液に水を加える工程■では、ｐ−クレゾール類に
対して０．２〜２０重量部、好ましくは１〜１０重量部
の水を加える。この際、ｐ−ヒドロキシベンズアルデヒ
ドの結晶を晶析・分離した後の濾液をこの目的のために
使用することもできる。Next, in step (2) of adding water to the filtrate, 0.2 to 20 parts by weight, preferably 1 to 10 parts by weight of water is added to the p-cresol. At this time, the filtrate obtained after crystallizing and separating p-hydroxybenzaldehyde crystals can also be used for this purpose.
更に、メタノールを溶去する工程■は、通常温度５０℃
〜１００℃で行うのが好ましく、１００℃を超える温度
は収率の低下をもたらすため避けるべきである。Furthermore, the step (2) of eluting methanol is usually carried out at a temperature of 50°C.
Preferably, it is carried out at ~100°C; temperatures above 100°C should be avoided as they result in reduced yields.
次にｐ−ヒドロキシベンズアルデヒドの晶析−分離工程
■は、液温−２０〜５０℃の範囲内で、更に好ましくは
、０〜２０℃の範囲で行うのが好ましい。この工程の分
離は通常の分離機が使用でき、また、稀薄苛性ソーダ水
溶液や冷水で洗滌することも結晶の純度向上に効果的で
ある。Next, the p-hydroxybenzaldehyde crystallization-separation step (2) is preferably carried out at a liquid temperature of -20 to 50°C, more preferably 0 to 20°C. A normal separator can be used for separation in this step, and washing with a dilute aqueous caustic soda solution or cold water is also effective in improving the purity of the crystals.
なふ、ここで原料として混合クレゾールを用いる場合は
、濾液を鉱酸で中和し、溶媒で抽出してｍ−クレゾール
を回収することもできる。If mixed cresol is used as a raw material here, m-cresol can also be recovered by neutralizing the filtrate with mineral acid and extracting with a solvent.
ここで抽出溶媒としては、エチレンジクロライド、トリ
クロルエチレン等の脂肪族のハロゲン化炭化水ｓ 類、
モノクロルベンゼン、ジクロルペンチルイソプロピルケ
トン等の脂肪族ケント類、ベンゼン、トルエン、キシレ
ン等の芳香族炭化水素類ｓｍ−プロピルエーテル、イソ
プロピルエーテル、セカンダリ−ブチルエーテル等の脂
肪族エーテル類、酢酸メチル、酢酸エチル、酢酸ブチル
等の脂肪酸エステル類を用いることができる。これ等の
抽出溶媒は単独又は２種以上を混合して用いることが可
能である。Here, as the extraction solvent, aliphatic halogenated hydrocarbons such as ethylene dichloride and trichlorethylene,
Aliphatic compounds such as monochlorobenzene and dichloropentyl isopropyl ketone, aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic ethers such as sm-propyl ether, isopropyl ether, and secondary butyl ether; methyl acetate and ethyl acetate. , fatty acid esters such as butyl acetate can be used. These extraction solvents can be used alone or in combination of two or more.
次に、分離した結晶の水への溶解■は、ｐ−クレゾール
に対して０．２〜２０重量部、好ましくは１〜１０重量
部の水を加え、必要により３０℃〜１００℃に加温し、
例えば活性炭等を加えて濾過する。Next, to dissolve the separated crystals in water, add 0.2 to 20 parts by weight, preferably 1 to 10 parts by weight of water to p-cresol, and if necessary, heat to 30 to 100 degrees Celsius. death,
For example, add activated carbon or the like and filter.
また、鉱酸での中和の工程■は、例えば硫酸又は塩酸を
用いて液のｐＨが１〜８、好ましくは３〜７になるよう
液性を見ながら添加する。Further, in the step (2) of neutralization with a mineral acid, for example, sulfuric acid or hydrochloric acid is added while monitoring the liquid properties so that the pH of the liquid becomes 1 to 8, preferably 3 to 7.
更にｐ−ヒドロキシベンズアルデヒドの晶析・分離の工
程■は格別の方法を必要としない。Furthermore, step (2) of crystallizing and separating p-hydroxybenzaldehyde does not require any special method.
本発明の他の方法、すなわち前記メタノールを漏失後の
液を鉱酸により中和する工程■は、鉱酸例えば硫酸又は
塩酸を用いて液のｐＨが１〜８、好ましくは３〜７にな
るように行なわれる。Another method of the present invention, that is, step (2) of neutralizing the liquid after methanol leakage with a mineral acid, uses a mineral acid such as sulfuric acid or hydrochloric acid to adjust the pH of the liquid to 1 to 8, preferably 3 to 7. It is done like this.
ここでのｐ−ヒドロキシベンズアルデヒドの晶析・分離
の工程＠も格別の方法を必要としない。The step of crystallizing and separating p-hydroxybenzaldehyde here also does not require any special method.
分離したｐ−ヒドロキシベンズアルデヒドの結晶の水へ
の溶解■は、３０〜１００℃で行われ、必要により、加
熱し、活性炭等を加えて熱濾過することもできる。Dissolution of the separated p-hydroxybenzaldehyde crystals in water is carried out at 30 to 100 DEG C. If necessary, heating may be performed, and activated carbon or the like may be added for hot filtration.
次に、前記液を冷却してｐ−ヒドロキシベンズアルデヒ
ドの晶析・分離０は通常の方法によって行われる。Next, the liquid is cooled, and p-hydroxybenzaldehyde is crystallized and separated by a conventional method.
〈発明の効果〉
本発明の方法によれば、以上の工程の結合により、反応
で生成したｐ−ヒドロキシベンズアルデヒドをす） Ｉ
Ｊウムの形で回収率９５．０％以上で、又ｐ−ヒドロキ
シベンズアルデヒドを回収率９０゜０％以上で収得する
ことができる。<Effects of the Invention> According to the method of the present invention, by combining the above steps, p-hydroxybenzaldehyde produced in the reaction can be
It is possible to obtain Jium with a recovery rate of 95.0% or more, and p-hydroxybenzaldehyde with a recovery rate of 90.0% or more.
以下実施例によって本発明を説明するが、本発明は、こ
れに限定されるものではない。The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.
〈実施例〉
実施例−１（酸化反応／分離工程）
酸化反応
ガス導入管、温度計及び攪拌機を備えた１１のオートク
レーブでｍ／ｐ−混合クレゾール（ｍ／ｐ比＝３／７）
１８０．５ｇ、水酸化ナトリウム１３２．６ｇ、酢酸コ
バルト四水塩０．１２ｇ及びメタノール２８１．６ｇか
ら成る溶液を、７５℃及び１１０００ｒｐで空気によっ
て７ ｋｇ ／ ｃｔｌ Ｇの圧力で酸化した。１０時
間後に酸化をやめた。<Example> Example-1 (oxidation reaction/separation step) m/p-mixed cresol (m/p ratio = 3/7) in 11 autoclaves equipped with an oxidation reaction gas introduction tube, a thermometer, and a stirrer.
A solution consisting of 180.5 g, 132.6 g of sodium hydroxide, 0.12 g of cobalt acetate tetrahydrate and 281.6 g of methanol was oxidized with air at a pressure of 7 kg/ctl G at 75 °C and 11000 rpm. Oxidation stopped after 10 hours.
ｐ−クレゾールの変換率は、９９．８％、ｐ−ヒドロキ
シベンズアルデヒドの生成収率は８０．０％であり、メ
タクレゾール回収率は９５．３％であった。The conversion rate of p-cresol was 99.8%, the production yield of p-hydroxybenzaldehyde was 80.0%, and the recovery rate of metacresol was 95.3%.
分離工程
酸化反応混合物にメタノール７５０ｇを加えて濾過をし
た。この濾液に水３５０ｇを加え、液温か１００℃に達
する迄加熱してメタノールを溜去した。メタノールの漏
失後に残った溶液を１０℃に冷却し、析出したｐ−ヒド
ロキシベンズアルデヒドのナトリウム塩の結晶を濾取し
、乾燥した。Separation Step: 750 g of methanol was added to the oxidation reaction mixture and filtered. 350 g of water was added to this filtrate and heated until the liquid temperature reached 100°C to distill off methanol. The solution remaining after the leakage of methanol was cooled to 10° C., and the precipitated crystals of sodium salt of p-hydroxybenzaldehyde were collected by filtration and dried.
ｐ−ヒドロキシベンズアルデヒドのナトリウム塩２水和
物の収量１６３．７ｇ、純度９８．８％であった。The yield of sodium salt dihydrate of p-hydroxybenzaldehyde was 163.7 g, and the purity was 98.8%.
次にナトリウム塩を水２５０ｇで溶解し、濾過した。濾
液に３５％塩酸をゆっくり加えて、液のｐＨを６に調整
し、ｐ−ヒドロキシベンズアルデヒドを遊離させ、これ
を１０℃に冷却して晶析させ、濾取し、水洗した後乾燥
した。目的物の収量１０３．３ｇ、純度９９．５％であ
った。The sodium salt was then dissolved in 250 g of water and filtered. 35% hydrochloric acid was slowly added to the filtrate to adjust the pH of the liquid to 6 to liberate p-hydroxybenzaldehyde, which was cooled to 10°C to crystallize, collected by filtration, washed with water, and then dried. The yield of the target product was 103.3 g, and the purity was 99.5%.
前記す） ＋７ウム塩晶析濾液に３５％塩酸を加えてｐ
Ｈ＝７に中和し、メチルイソブチルケトン１３０ｇを加
えて、２回ｍ−クレゾールを抽出すると、回収率９８．
５％でｍ−クレゾールが回収された。Add 35% hydrochloric acid to the +7um salt crystallization filtrate and
Neutralize to H=7, add 130 g of methyl isobutyl ketone, and extract m-cresol twice, yielding a recovery rate of 98.
5% m-cresol was recovered.
実施例−２（酸化反応／分離工程）
酸化反応
ガス導入管、温度計及び攪拌機を備えた１１のオートク
レーブで、純度９９．７％のｐ−クレゾール１８１．０
ｇ、水酸化ナトリウム１３２．６ｇ１酢酸コバルト４水
塩０．１２ｇ及びメタノール２８１６ｇから成る溶液を
７５℃、１１０００ｒｐで空気によって７ｋｇ／ｃｄＧ
の圧力で酸化した。１０時間後に酸化をやめた、ｐ−ク
レゾールの変換率は９９．７％、ｐ−ヒドロキシベンズ
アルデヒドの生成収率は８０．５％であった。Example-2 (oxidation reaction/separation step) p-cresol 181.0 with a purity of 99.7% was produced in 11 autoclaves equipped with an oxidation reaction gas introduction tube, a thermometer, and a stirrer.
g, 132.6 g of sodium hydroxide, 1 cobalt acetate tetrahydrate 0.12 g, and methanol 2816 g at 75°C and 11000 rp with air at 7 kg/cdG.
oxidized at a pressure of Oxidation stopped after 10 hours, the conversion rate of p-cresol was 99.7%, and the production yield of p-hydroxybenzaldehyde was 80.5%.
分離工程
酸化した溶液にメタノール７４１．８ｇを加えて濾過を
した。次に水３９０ｇと混合し、液温か１００℃に達す
る迄加熱してメタノールを溜去した。メタノールの漏失
後に残った溶液を１０℃に冷却し、析出したｐ−ヒドロ
キシベンズアルデヒドのナトリウム塩の結晶を濾取し、
乾燥した。Separation Step: 741.8 g of methanol was added to the oxidized solution and filtered. Next, it was mixed with 390 g of water and heated until the liquid temperature reached 100° C. to distill off methanol. The solution remaining after the leakage of methanol was cooled to 10°C, and the precipitated crystals of sodium salt of p-hydroxybenzaldehyde were collected by filtration.
Dry.
ｐ−ヒドロキンベンズアルデヒドのナトリウム塩２水和
物の収量２３３．６ｇ、純度９９，０％であった。The yield of sodium salt dihydrate of p-hydroquine benzaldehyde was 233.6 g, and the purity was 99.0%.
次にこのナトリウム塩を水３６０ｇに溶解し、濾過し、
濾液に３５％塩酸をゆっくり加えて、液のｐＨを６にし
、ｐ−ヒドロキシベンズアルデヒドを遊離させた。これ
を１０℃に冷却後濾取し、水洗した後乾燥した。目的物
の収量１４８．５ｇ、純度９９．６％であった。Next, this sodium salt was dissolved in 360 g of water, filtered,
35% hydrochloric acid was slowly added to the filtrate to adjust the pH of the solution to 6, thereby liberating p-hydroxybenzaldehyde. This was cooled to 10°C, collected by filtration, washed with water, and then dried. The yield of the target product was 148.5 g, and the purity was 99.6%.
実施例３
酸化反応及び分離工程のメタノール置去までは実施例１
と同様に実施した。Example 3 Example 1 up to the oxidation reaction and removal of methanol in the separation process
It was carried out in the same way.
メタノールの漏失後に残った溶液を３５％塩酸をゆっく
り加えて１．液のｐＨ＝６に調整し、これを１０℃に冷
却して晶析し、析出したｐ−ヒドロキシベンズアルデヒ
ドの結晶を濾取した。1. Add 35% hydrochloric acid slowly to the solution remaining after methanol leakage. The pH of the solution was adjusted to 6, and the solution was cooled to 10° C. for crystallization, and the precipitated crystals of p-hydroxybenzaldehyde were collected by filtration.
次に濾取した結晶を水３００ｇに溶解し、これを１０℃
に冷却して再晶析させ、濾取し、水洗した後乾燥した。Next, the crystals collected by filtration were dissolved in 300 g of water, and the mixture was heated to 10°C.
The mixture was cooled to 50°C, recrystallized, collected by filtration, washed with water, and then dried.
目的物の収１１．０４．２ｇ、純度９９．０％であった
。The yield of the target product was 11.04.2 g, and the purity was 99.0%.
前記晶析濾液にメチルイソブチルケトン１００ｇを加え
て、２回ｍ−クレゾールを抽出すると、回収率９９，０
％でｍ−クレゾールが回収された。When m-cresol was extracted twice by adding 100 g of methyl isobutyl ketone to the crystallization filtrate, the recovery rate was 99.0.
% of m-cresol was recovered.
実施例４
酸化反応及び分離工程のメタノール漏失までは実施例２
と同様に実施した。Example 4 Example 2 until methanol leakage during oxidation reaction and separation process
It was carried out in the same way.
メタノールの漏失後に残った溶液を３５％塩酸をゆっく
り加えて、液のｐＨ＝６に調整し、これを１０℃に冷却
して晶析し、析出したｐ−ヒドロキシベンズアルデヒド
の結晶を濾取した。The pH of the solution remaining after methanol leaked was slowly added with 35% hydrochloric acid to adjust the pH of the solution to 6, which was cooled to 10°C to crystallize, and the precipitated crystals of p-hydroxybenzaldehyde were collected by filtration.
次に濾取した結晶を水３２０ｇに溶解し、これを１０℃
に冷却して再晶析させ、濾取し、水洗した後乾燥した。Next, the crystals collected by filtration were dissolved in 320 g of water, and this was heated to 10°C.
The mixture was cooled to 50°C, recrystallized, collected by filtration, washed with water, and then dried.
目的物の収量１４８．９ｇ、純度９９．２％であった。The yield of the target product was 148.9 g, and the purity was 99.2%.
（以下余白）(Margin below)
Claims (4)
ウムおよびコバルト化合物を含む触媒の存在下で酸素ま
たは酸素含有ガスで酸化して得られる反応混合物からｐ
−ヒドロキシベンズアルデヒドを単離するにあたり、上
記反応混合物にメタノールを加え、生じたタール分等を
濾別し、次いで水を加え、加熱してメタノールを溜去し
、次いで冷却してｐ−ヒドロキシベンズアルデヒドをナ
トリウム塩の形で晶析・分離することを特徴とするｐ−
ヒドロキシベンズアルデヒドの製造法。(1) From a reaction mixture obtained by oxidizing p-cresols with oxygen or an oxygen-containing gas in the presence of a catalyst containing sodium hydroxide and a cobalt compound in methanol,
- To isolate hydroxybenzaldehyde, methanol is added to the above reaction mixture, the generated tar etc. are filtered off, then water is added and methanol is distilled off by heating, then cooled to remove p-hydroxybenzaldehyde. p-, which is characterized by being crystallized and separated in the form of sodium salt.
Method for producing hydroxybenzaldehyde.
鉱酸で中和してｐ−ヒドロキシベンズアルデヒドを晶析
・分離することを特徴とする請求項１に記載のｐ−ヒド
ロキシベンズアルデヒドの製造法。(2) Dissolve the separated crystals in water, filter if necessary,
The method for producing p-hydroxybenzaldehyde according to claim 1, characterized in that p-hydroxybenzaldehyde is crystallized and separated by neutralization with a mineral acid.
ウムおよびコバルト化合物を含む触媒の存在下で酸素ま
たは酸素含有ガスで酸化して得られる反応混合物からｐ
−ヒドロキシベンズアルデヒドを単離するにあたり、上
記反応混合物にメタノールを加え、生じたタール分等を
濾別し、次いで水を加え、加熱してメタノールを溜去し
、次いで鉱酸で中和し、冷却してｐ−ヒドロキシベンズ
アルデヒドを結晶の形で晶析・分離することを特徴とす
るｐ−ヒドロキシベンズアルデヒドの製造法。(3) From a reaction mixture obtained by oxidizing p-cresols with oxygen or an oxygen-containing gas in the presence of a catalyst containing sodium hydroxide and a cobalt compound in methanol,
- To isolate hydroxybenzaldehyde, methanol is added to the above reaction mixture, the resulting tar content is filtered off, water is added, the methanol is distilled off by heating, the methanol is then neutralized with mineral acid, and the mixture is cooled. 1. A method for producing p-hydroxybenzaldehyde, which comprises crystallizing and separating p-hydroxybenzaldehyde in the form of crystals.
を水に溶解し、必要により濾過し、冷却して再晶析・分
離することことを特徴とする請求項３に記載のｐ−ヒド
ロキシベンズアルデヒドの製造法。(4) The method for producing p-hydroxybenzaldehyde according to claim 3, characterized in that the separated crystals of p-hydroxybenzaldehyde are dissolved in water, filtered if necessary, cooled, and recrystallized and separated. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63327148A JP2697056B2 (en) | 1988-12-23 | 1988-12-23 | Method for producing p-hydroxybenzaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63327148A JP2697056B2 (en) | 1988-12-23 | 1988-12-23 | Method for producing p-hydroxybenzaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02172942A true JPH02172942A (en) | 1990-07-04 |
| JP2697056B2 JP2697056B2 (en) | 1998-01-14 |
Family
ID=18195847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63327148A Expired - Lifetime JP2697056B2 (en) | 1988-12-23 | 1988-12-23 | Method for producing p-hydroxybenzaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2697056B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0725052A1 (en) * | 1995-02-01 | 1996-08-07 | Bayer Ag | Process for the purification of reaction mixtures containing 4-hydroxybenzaldehyde |
| JP2010202556A (en) * | 2009-03-02 | 2010-09-16 | Nagoya Industrial Science Research Inst | Method for producing aromatic aldehyde compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6222740A (en) * | 1985-07-19 | 1987-01-30 | ヘキスト アクチェンゲゼルシャフト | Isolation of p-hydroxybenzaldehyde |
| JPS63301843A (en) * | 1986-12-17 | 1988-12-08 | Sumitomo Chem Co Ltd | Method for purifying p-hydroxybenzaldehyde |
-
1988
- 1988-12-23 JP JP63327148A patent/JP2697056B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6222740A (en) * | 1985-07-19 | 1987-01-30 | ヘキスト アクチェンゲゼルシャフト | Isolation of p-hydroxybenzaldehyde |
| JPS63301843A (en) * | 1986-12-17 | 1988-12-08 | Sumitomo Chem Co Ltd | Method for purifying p-hydroxybenzaldehyde |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0725052A1 (en) * | 1995-02-01 | 1996-08-07 | Bayer Ag | Process for the purification of reaction mixtures containing 4-hydroxybenzaldehyde |
| JP2010202556A (en) * | 2009-03-02 | 2010-09-16 | Nagoya Industrial Science Research Inst | Method for producing aromatic aldehyde compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2697056B2 (en) | 1998-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0684332B2 (en) | Method for optical resolution of a-isopropyl-p-chlorophenylacetic acid | |
| US4772754A (en) | Process for the isolation of p-hydroxybenzaldehyde | |
| JPH02172942A (en) | Production of p-hydroxybenzaldehyde | |
| JP2697054B2 (en) | Method for producing p-hydroxybenzaldehyde | |
| JP2697055B2 (en) | Method for producing p-hydroxybenzaldehyde | |
| JPH0248543A (en) | Purification of p,p'-biphenol | |
| RU2130449C1 (en) | Method of synthesis of 3,4-dihydroxy-5-nitrobenzaldehyde | |
| JPS6023338A (en) | Production of high-purity p,p'-biphenol | |
| JPS61106535A (en) | Recovery of benzoic acid | |
| JP3291987B2 (en) | Purification method of O, S-dimethyl-N-acetylphosphoramidothioate | |
| JPH0460457B2 (en) | ||
| JPH0244821B2 (en) | ||
| US4202828A (en) | Process for separation of naphthoquinone and phthalic acid | |
| JPS62242644A (en) | Method for oxidizing alkylphenol or such | |
| JPH07206763A (en) | Production of purified 3,3',4,4',-biphenyltetracarboxylic acid or its acid dianhydride | |
| KR20120086012A (en) | Preparation of p-Chloromethylbenzoic acid and Benzoic acid from by-products in method for processing dimethyl terephthalate | |
| CN117924062A (en) | Method for purifying terephthalaldehyde by recrystallizing terephthalaldehyde crude product | |
| JPS5896035A (en) | Purification of phloroglucin | |
| JP2590206B2 (en) | Method for producing 8-hydroxyquinoline-7-carboxylic acid | |
| JPH01143847A (en) | Separation and purification of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid ester | |
| JPS6281341A (en) | Production of 2,5-di-tert-butylhydroquinone | |
| US1930753A (en) | Chlorination of cresidine | |
| JP2005187414A (en) | Method for producing 2-methyl-1,4-naphthoquinone | |
| JP2000198779A (en) | Purification of 3-alkylflavanol derivative | |
| JPH039107B2 (en) |