JPS63216839A - Production of p-hydroxybenzaldehyde - Google Patents
Production of p-hydroxybenzaldehydeInfo
- Publication number
- JPS63216839A JPS63216839A JP62048757A JP4875787A JPS63216839A JP S63216839 A JPS63216839 A JP S63216839A JP 62048757 A JP62048757 A JP 62048757A JP 4875787 A JP4875787 A JP 4875787A JP S63216839 A JPS63216839 A JP S63216839A
- Authority
- JP
- Japan
- Prior art keywords
- methanol
- hydroxybenzaldehyde
- oxygen
- water
- cresol
- 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.)
- Pending
Links
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 9
- 239000011541 reaction mixture Substances 0.000 claims abstract description 6
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 abstract description 9
- 238000001816 cooling Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000004821 distillation Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- 239000000203 mixture Substances 0.000 abstract 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000005749 Copper compound Substances 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
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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)
- 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−クレゾールを酸素で酸化して、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分離
・取得する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 oxidizing p-cresol with oxygen and separating and obtaining p-hydroxybenzaldehyde from the resulting reaction mixture.
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、農薬の製造に広
く使用されている。p-Hydroxybenzaldehyde is important as a raw material in the organic chemical industry and is widely used in the production of dyes, pharmaceuticals, and agricultural chemicals.
ｐ−ヒドロキシベンズアルデヒドの製造方法としては、
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、所望により銅化合物の存在下で酸素
または、酸素含有ガスで酸化する方法が知られ℃いる。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 sodium hydroxide and a cobalt compound, optionally a copper compound.
（特開昭５５−８１８！１２号、特開昭６１−２４５６
５号公報）、また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を分離スル方法としては、
ｐ−ヒドロキシベンズアルデヒドをナトリウム塩として
晶出・分離する方法が知られている。（特開昭６２−２
２７４０号公報）
〔本発明が解決しようとする問題点〕
本発明は、酸化反応混合物中にタール成分、触媒成分、
水酸化ナトリウム更には、メタールと共存するｐ−ヒド
ロキシベンズアルデヒドを効率よく分離する方法で、特
にタール分の製品への混入を回避することに成功した方
法である。(JP-A-55-818!12, JP-A-61-2456
5), and p-
The method for separating hydroxybenzaldehyde is as follows:
A method of crystallizing and separating p-hydroxybenzaldehyde as a sodium salt is known. (Unexamined Japanese Patent Publication No. 62-2
No. 2740) [Problems to be solved by the present invention] The present invention solves the problem that tar components, catalyst components,
This method efficiently separates p-hydroxybenzaldehyde, which coexists with sodium hydroxide, and metal, and has been particularly successful in avoiding the mixing of tar into products.
本発明は、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
合物に水を加え、生じた液を加熱して、メタノールを溜
去し、次いでＩの液を冷却し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出させ、これを分離する
方法であり、所望により分離した結晶を水に溶解しこれ
を濾過し、涙液を鉱酸で中和してｐ−ヒドロキシベンズ
アルデヒドを晶出させることもできる。The present invention provides a method for isolating p-hydroxybenzaldehyde from a reaction mixture obtained by oxidizing p-cresol with oxygen or an oxygen-containing gas in the presence of sodium hydroxide and a cobalt compound in methanol. is added, the resulting liquid is heated to distill off methanol, and then the liquid in I is cooled to crystallize p-hydroxybenzaldehyde in the form of sodium salt, which is then separated. It is also possible to crystallize p-hydroxybenzaldehyde by dissolving the crystals in water, filtering it, and neutralizing the lachrymal fluid with mineral acid.
本発明の前提となるｐ−クレゾールの酸素酸化は、前記
特開昭５５−８１８３２号、特開昭６１−２４５３５号
公報に記載の方法と諸条件の適用により容易に実施する
ことができる。Oxygen oxidation of p-cresol, which is a premise of the present invention, can be easily carried out by applying the method and conditions described in JP-A-55-81832 and JP-A-61-24535.
本発明の工程は、■反応混合物に水を加える工程、■こ
れを加熱してメタノールを溶去する工程、■メタノール
溶去液を冷却しｐ−ヒドロキシベンズアルデヒドをナト
リウム塩の形で晶出させる工程、■晶出した結晶を分離
する工程より成っでいる。The steps of the present invention are: (1) adding water to the reaction mixture, (2) heating it to elute methanol, and (2) cooling the methanol eluate to crystallize p-hydroxybenzaldehyde in the form of sodium salt. , 2. The process consists of the step of separating the crystals that have crystallized.
更にｐ−ヒドロキシベンズアルデヒドを非ナトリウム塩
として取得する工程は、■第４工程で得られた結晶を水
に溶解する工程、■この溶液を濾過する工程、■Ｆ液を
鉱酸で中和しｐ−ヒドロキシベンズアルデヒドな晶出・
分離する工程から成る。Furthermore, the steps of obtaining p-hydroxybenzaldehyde as a non-sodium salt include: (1) dissolving the crystals obtained in the fourth step in water, (2) filtering this solution, and (2) neutralizing the F solution with mineral acid. -Hydroxybenzaldehyde crystallization
It consists of a process of separation.
夫々の工程の実施にあたっては、第１工程では、メタノ
ール溶去後の苛性ソーダ濃度が５〜４０重量％になるよ
う、更に好ましくは、１０〜２０重量％になるよう水を
添加するのが好ましい。In implementing each step, in the first step, water is preferably added so that the concentration of caustic soda after methanol elution is 5 to 40% by weight, more preferably 10 to 20% by weight.
又第７エ程の濾液をこの目的に使用することもできる。The filtrate from step 7 can also be used for this purpose.
第２工程のメタノール溜去は、５０°Ｃ〜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。The methanol distillation in the second step is preferably carried out at a temperature of 50°C to 100°C, and temperatures exceeding 100°C should be avoided since they result in a decrease in yield.
第６エ程の晶出は、液温０〜５０℃の範囲内で、更に好
ましくは、５〜２０℃の範囲で行うのが好ましい。第４
工程の分離は通常の分離機が使用できる。所望により稀
薄苛性ソーダ水溶液で洗滌することも結晶の純度向上に
効果がある。The crystallization in the sixth step is preferably carried out at a liquid temperature of 0 to 50°C, more preferably 5 to 20°C. Fourth
A normal separator can be used for separation in the process. If desired, washing with a dilute aqueous caustic soda solution is also effective in improving the purity of the crystals.
所望工程を実施にあたってｐ−ヒドロキシベンズアルデ
ヒドのナトリウム塩を溶解した水溶液の中和は、鉱酸例
えば硫酸を用いて液のｐＨが４〜乙になるよう液性を見
ながら添加するのが好ましい。ｐ−ヒドロキシベンズア
ルデヒドの結晶分離は、格別の方法を必要としない。To neutralize the aqueous solution in which the sodium salt of p-hydroxybenzaldehyde is dissolved in carrying out the desired process, it is preferable to add a mineral acid such as sulfuric acid while monitoring the liquid properties so that the pH of the solution becomes 4 to O. Crystal separation of p-hydroxybenzaldehyde does not require any special method.
かかる工程の結合により、反応で生成したｐ−ヒドロキ
シベンズアルデヒドをナトリウムの形で収率８０チ以上
で、又ｐ−ヒドロキシベンズアルデヒドを収率７７％で
収得することができる。By combining these steps, p-hydroxybenzaldehyde produced in the reaction can be obtained in the form of sodium at a yield of 80% or more, and p-hydroxybenzaldehyde can be obtained at a yield of 77%.
以下で実施例で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（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、ｐ−クレゾール１０８１、水酸化ナトリウム
１２０１、塩化コバルトろ水塩２．２６９−及びメタノ
ール５８０１から成る溶液を８０℃及び１１０００ｒｐ
で酸素によって１ｋｇ／ｃＩｆｔＧの圧力で酸化した。Example (oxidation reaction/separation step) In 11 autoclaves equipped with an oxidation reaction gas inlet tube, a thermometer, and a stirrer, p-cresol 1081, sodium hydroxide 1201, cobalt chloride filtrate 2.269- and methanol 5801 were used. The solution was heated at 80°C and 11,000 rpm.
oxidized with oxygen at a pressure of 1 kg/cIftG.
５時間後に酸化をやめた、ｐ−クレゾールの変換率は１
００％、ｐ−ヒドロキシベンズアルデヒドの生成収率は
８２チであった。Oxidation stopped after 5 hours, the conversion rate of p-cresol was 1
00%, and the production yield of p-hydroxybenzaldehyde was 82%.
分離工程
酸化した溶液を水５００？と混合し、液温か１００℃に
達する迄加熱してメタノールを留去した。メタノールの
留去後に残った溶液を１゜℃に冷却し、析出したｐ−ヒ
ドロキシペンズアルデヒドのナトリウム塩の結晶を戸数
し、乾燥させた。粗すｌ−ＩＪウム塩の収量１６１１、
純度８９６％
次にナトリウム塩を水６００ｙ−で溶解し、活性炭４１
を加えて３０分間攪拌した後ｐ過した。Separation process: Add oxidized solution to 500% water. The methanol was distilled off by heating until the liquid temperature reached 100°C. The solution remaining after methanol was distilled off was cooled to 1°C, and the precipitated crystals of sodium salt of p-hydroxypenzaldehyde were separated and dried. Yield of crude l-IJium salt 1611,
Purity: 896% Next, dissolve the sodium salt in 600 ml of water and add 41 ml of activated carbon.
was added, stirred for 30 minutes, and then filtered.
Ｐｉに硫１唆をゆっくり加えて、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。これを冷
却後戸数し、水洗した後乾燥させた。収量９４．１ ｊ
７、純度９９８％７％ ｉ−ｒ ＊ ｈ’！’−ノ・・
ラ じに、 ＩＴ。Slowly add 1 sulfur to Pi to bring the pH of the solution to 6.
-Hydroxybenzaldehyde was liberated. After cooling, it was washed with water and dried. Yield 94.1 j
7. Purity 998% 7% ir * h'! '-No...
Basically, IT.
Claims (1)
およびコバルト化合物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
に水を加え、生じた液を加熱してメタノールを溜去し、
次いでこの液を冷却し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出・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方法 ２、分離した結晶を水に溶解し、これを濾過し、濾液を
鉱酸で中和してｐ−ヒドロキシベンズアルデヒドを晶出
・分離する特許請求の範囲１の方法[Claims] 1. In isolating p-hydroxybenzaldehyde from a reaction mixture obtained by oxidizing p-cresol with oxygen or an oxygen-containing gas in the presence of sodium hydroxide and a cobalt compound in methanol, Water is added to the above reaction mixture, the resulting liquid is heated to distill off methanol,
Next, this liquid is cooled, and p-hydroxybenzaldehyde is crystallized and separated in the form of a sodium salt. Method 2 for producing p-hydroxybenzaldehyde, the separated crystals are dissolved in water, and this is filtered to obtain a filtrate. The method according to claim 1, wherein p-hydroxybenzaldehyde is crystallized and separated by neutralizing it with a mineral acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62048757A JPS63216839A (en) | 1987-03-05 | 1987-03-05 | Production of p-hydroxybenzaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62048757A JPS63216839A (en) | 1987-03-05 | 1987-03-05 | Production of p-hydroxybenzaldehyde |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63216839A true JPS63216839A (en) | 1988-09-09 |
Family
ID=12812151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62048757A Pending JPS63216839A (en) | 1987-03-05 | 1987-03-05 | Production of p-hydroxybenzaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63216839A (en) |
-
1987
- 1987-03-05 JP JP62048757A patent/JPS63216839A/en active Pending
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