JPS6039055B2 - Manufacturing method of resorcinol - Google Patents
Manufacturing method of resorcinolInfo
- Publication number
- JPS6039055B2 JPS6039055B2 JP51057253A JP5725376A JPS6039055B2 JP S6039055 B2 JPS6039055 B2 JP S6039055B2 JP 51057253 A JP51057253 A JP 51057253A JP 5725376 A JP5725376 A JP 5725376A JP S6039055 B2 JPS6039055 B2 JP S6039055B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- temperature
- present
- acidic
- hydrogen
- 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
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
【発明の詳細な説明】
本発明はｍ−ジニトロベンゼンからしゾルシソを製造す
る方法の改良に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvements in the process for producing m-dinitrobenzene mustard solciso.
更に詳しくはｍ−ジニトロベンゼンのニトロ基を水酸基
に変えることによりレソルシンを製造する方法に関する
。本発明者らはさきにｏ，ｍまたはｐ−ジニトロベンゼ
ンなどの芳香族ニト。化合物を酸性硫酸アルカリ金属塩
、硫酸アルカリ金属塩、酸性硫酸アンモニウム塩および
硫酸アンモニウム塩からなる群から選ばれた１種または
２種以上の塩の存在下に水と反応させることにより種々
のフェノール類を製造し得ることを見出しこの方法を提
供した。しかし乍らこの反応は、例えばｏ，ｍまたはｐ
ージニトロベンゼンの何れのニトロ化合物を用いた場合
においてもｏ−ジヒドロキシベンゼン（力７コール）お
よびｐ一ジヒドロキシベンゼン（ハイドロキノン）が優
先的に生成され、ｍ−ジヒドロキシベンゼン（レゾルシ
ン）は優先的に生成されるｏ−ジヒドロキシベンゼソま
たはｐ−ジヒドロキシベンゼンの例えば１０分の１量に
も満たない程度にしか生成し難いことを見出した。本発
明者らは上記した実情に鑑み、ｍ−ジニトロベンゼンよ
りｍ−ジヒドロキシベンゼンを高収率で得る方法につい
て鋭意検討した結果、通常用いられる水素添加用触媒の
存在下に反応系に水素を添加することが極めて有効であ
ることを見出し、この方法をも提供した。More specifically, the present invention relates to a method for producing resorcin by changing the nitro group of m-dinitrobenzene to a hydroxyl group. The present inventors first prepared aromatic nitrites such as o, m or p-dinitrobenzene. Various phenols are produced by reacting a compound with water in the presence of one or more salts selected from the group consisting of acidic alkali metal sulfates, acidic ammonium sulfates, and ammonium sulfates. We found that it can be done and proposed this method. However, this reaction can be performed for example o, m or p
- When any nitro compound of dinitrobenzene is used, o-dihydroxybenzene (power 7 call) and p-dihydroxybenzene (hydroquinone) are preferentially produced, and m-dihydroxybenzene (resorcinol) is preferentially produced. It has been found that it is difficult to produce, for example, less than one-tenth of the amount of o-dihydroxybenzeso or p-dihydroxybenzene. In view of the above-mentioned circumstances, the present inventors conducted intensive studies on a method for obtaining m-dihydroxybenzene from m-dinitrobenzene in high yield, and found that hydrogen was added to the reaction system in the presence of a commonly used hydrogenation catalyst. We have also provided this method.
しかし乍ら、この方法による場合にし、おてもなおター
ル様乃至は炭素様副生物が若干生成し、目的とするレゾ
ルシンの収率を低下せしめる傾向にあった。本発明者ら
はこの点の改善について深く検討を進めた結果、特定触
媒の存在下に反応を２段に進めることによって上記の問
題を極めて効果的に解決し得ることを見出し本発明に到
達した。即ち、本発明は酸性硫酸塩および水素添加用触
媒の存在下にｍ−ジニトロベンゼンを水素還元し、しか
る後、加熱昇温するレゾルシンの製造方法である。上記
した本発明の方法は酸性硫酸塩の存在下に比較的低温で
水素還元し、次いで比較的高温で反応を完結せしめる点
において特徴的である。However, when using this method, some tar-like or carbon-like by-products are produced, which tends to reduce the yield of the desired resorcinol. The inventors of the present invention have conducted deep studies to improve this point, and have discovered that the above problem can be solved extremely effectively by proceeding the reaction in two stages in the presence of a specific catalyst, resulting in the present invention. . That is, the present invention is a method for producing resorcinol, which involves reducing m-dinitrobenzene with hydrogen in the presence of an acidic sulfate and a hydrogenation catalyst, and then heating and raising the temperature. The method of the present invention described above is distinctive in that hydrogen reduction is carried out at a relatively low temperature in the presence of an acidic sulfate, and then the reaction is completed at a relatively high temperature.
本発明において用いられる水素添加用紙煤としては、パ
ラジウム、白金、ニッケルまたはこれらの酸化物であり
、一種または二種以上の混合物として使用することもで
きる。本発明で使用される前記水素添加用触媒の使用量
に関しても特に制限はないが、その使用量が増大するほ
ど反応速度が増大する傾向にあり、通常、ｍ−ジニトｏ
ベンゼン１モル（１６８夕）に対して０．００１〜１０
０夕の範囲である。本発明の方法において用いられるも
う一つの触媒成分である酸性硫酸塩としては酸性硫酸ナ
トリウムまたは酸性硫酸アンモニウムが用いられる。The hydrogenated paper soot used in the present invention is palladium, platinum, nickel, or oxides thereof, and they can be used alone or as a mixture of two or more. There is no particular restriction on the amount of the hydrogenation catalyst used in the present invention, but as the amount used increases, the reaction rate tends to increase.
0.001 to 10 per mole of benzene (168 molar)
It is in the range of 0 evening. Acidic sodium sulfate or acidic ammonium sulfate is used as the acidic sulfate, which is another catalyst component used in the method of the present invention.
本発明の方法で採用される酸性硫酸塩触媒の濃度に関し
ては特に制限がないが、触媒の種類及び温度によって生
成するレゾルシンの収率及び選択率に影響があるので、
触媒活性及び経済性を考慮して適宜選択されるが、通常
、０．０１〜１０モ／その範囲で用いられる。本発明に
よる反応の反応条件は、反応速度、収率、選択率等を考
慮して選ぶ事ができる。Although there are no particular limitations on the concentration of the acidic sulfate catalyst employed in the method of the present invention, the yield and selectivity of the resorcinol produced are affected by the type and temperature of the catalyst.
It is appropriately selected in consideration of catalytic activity and economical efficiency, but is usually used in the range of 0.01 to 10 mo/s. The reaction conditions for the reaction according to the present invention can be selected in consideration of reaction rate, yield, selectivity, etc.
まづｐＨに関しては特に制限はないが、ｐＨＯ〜７好ま
しくは０〜５の範囲で適当に選ぶ事ができる。First, there is no particular restriction on the pH, but it can be appropriately selected within the range of pH 7 to 7, preferably 0 to 5.
即ち、硫酸、酸性硫酸アンモニウム、硫酸アンモニウム
、酸性硫酸ナトリウム、硫酸ナトリウム、アンモニア、
アンモニア水、水酸化ナトリウムの一種または二種以上
を混合し任意に調製する事ができる。本発明において採
用される反応温度条件に閣しては、ｍ−ジニトロベンゼ
ンの水素還元を行う低温反応と加熱昇温して行なう高温
反応とに分けて明示する必要がある。Namely, sulfuric acid, acidic ammonium sulfate, ammonium sulfate, acidic sodium sulfate, sodium sulfate, ammonia,
It can be arbitrarily prepared by mixing one or more of aqueous ammonia and sodium hydroxide. Regarding the reaction temperature conditions employed in the present invention, it is necessary to clearly specify the low-temperature reaction in which m-dinitrobenzene is reduced with hydrogen and the high-temperature reaction in which the temperature is increased by heating.
本発明における低温反応を実施する温度範囲は、通常、
０〜１００ｏｏ、好ましくは１０〜７０００である。一
方、加熱昇温して行なう高温反応の温度範囲は１５０〜
３００ｑ○、好ましくは１８０〜２７０ｏｏである。低
温反応における反応圧力に関しては特に制限はないが、
常圧または高圧の水素雰囲気で実施することができ、好
ましい水素圧は０〜２００ｋ９／ｃ柊の範囲である。ま
た、水素と窒素の如き不活性ガスとの混合気体を用いる
こともできる。本発明における高温反溢を実施する際の
反応雰囲気は、水素、窒素、一酸化炭素、二酸化炭素、
ヘリウム等の不活性雰囲気または還元雰囲気が好ましい
。The temperature range for carrying out the low-temperature reaction in the present invention is usually
0-100oo, preferably 10-7000. On the other hand, the temperature range for high-temperature reactions carried out by heating is 150~
300q○, preferably 180 to 270oo. There are no particular restrictions on the reaction pressure in low-temperature reactions, but
It can be carried out in a hydrogen atmosphere at normal pressure or high pressure, and the preferred hydrogen pressure is in the range of 0 to 200 k9/c Hiiragi. Furthermore, a gas mixture of hydrogen and an inert gas such as nitrogen can also be used. The reaction atmosphere when carrying out the high-temperature reflow in the present invention includes hydrogen, nitrogen, carbon monoxide, carbon dioxide,
An inert or reducing atmosphere such as helium is preferred.
また、本発明の高温反応における反応圧力に関しては特
に制限はないが、常圧乃至高圧下、好ましくは常圧乃至
は１００た‘／地のような圧力下に実施される。The reaction pressure in the high-temperature reaction of the present invention is not particularly limited, but the reaction is carried out under normal pressure to high pressure, preferably normal pressure to 100 m/m.
本発明において採用される反応装置に関しては、特に制
限はなく、一般に回分式または連続式の液相用の反応装
置が用いられる。There are no particular limitations on the reaction apparatus employed in the present invention, and generally a batch-type or continuous-type liquid phase reaction apparatus is used.
連続式では本発明による触媒を含む水溶液とｍ一ジニト
ロベンゼンとを水素雰囲気下で並流または同流で接触せ
しめた後、反応液をそのま）高温反応装置に送り込むか
、或は水素添加触媒を除去した後、反応液を高温反応装
置に送り込むなどの方法によって実施する事ができる。
而して後者の方法による場合は水素添加用触媒を高温状
態に保持する必要がないことから触媒活性を保つ上にお
いて好ましい方法としていまいま採用される。一方、低
温反応時における酸性硫酸塩の存在量は前記した量的範
囲内の比較的少量とし高温反応の開始に先立って追加す
ることもできる。また反応器から排出した反応液は、通
常、レゾルシンを蒸留分離したのち、残液を反応器に循
環することにより触媒系を再使用することもできる。本
発明による利点は次のようである。In a continuous system, an aqueous solution containing the catalyst of the present invention and m-dinitrobenzene are brought into contact with each other in parallel flow or in the same flow under a hydrogen atmosphere, and then the reaction solution is directly fed into a high-temperature reactor, or a hydrogenation catalyst is added to the reaction solution. This can be carried out by a method such as sending the reaction solution into a high-temperature reactor after removing .
Since the latter method does not require keeping the hydrogenation catalyst at a high temperature, it is currently being adopted as a preferred method in order to maintain catalyst activity. On the other hand, the amount of acidic sulfate present during the low-temperature reaction may be a relatively small amount within the quantitative range described above, and the acidic sulfate may be added prior to the start of the high-temperature reaction. Further, the reaction liquid discharged from the reactor is usually distilled to separate resorcin, and then the residual liquid is recycled to the reactor so that the catalyst system can be reused. The advantages of the present invention are as follows.
第１に本発明を実施する際に、タール様物質や炭素様物
質が殆ど生成しない事である。即ち、ｍ−フェニレンジ
アミン、ｍ−ニト。アニリン、ｍ−ニトロフェノール等
を酸性硫酸塩の存在下で加熱昇溢し、レゾルシンを得る
べく反応させた際には、多量のタール様物質乃至は炭素
様物質が創生する。従ってこのようなタール様物質や炭
素様物質が生成する場合にはしゾルシンの分離精製を困
難にし、装置の閉塞の原因となる。しかし乍ら、本発明
のように、酸性硫酸塩の存在下にｍ−ジニトロベンゼン
を水素還元し、しかる後、加熱昇塩してレゾルシンを生
成せしめる場合には殆どタール様物質や炭素様物質の創
生は認められないのである。第２にタール様物質や炭素
様物質等の副生が殆どないので、生成するレゾルシンの
収率が大変高いことである。次に実施例により本発明を
さらに説明する。First, when carrying out the present invention, almost no tar-like substances or carbon-like substances are generated. Namely, m-phenylenediamine, m-nit. When aniline, m-nitrophenol, etc. are heated in the presence of acidic sulfate and reacted to obtain resorcinol, a large amount of tar-like or carbon-like substances are created. Therefore, when such tar-like substances and carbon-like substances are produced, it becomes difficult to separate and purify zorcin, and this causes clogging of the apparatus. However, as in the present invention, when m-dinitrobenzene is hydrogen-reduced in the presence of acidic sulfate and then heated and salted to produce resorcinol, most tar-like substances and carbon-like substances are produced. Creation is not recognized. Second, since there are almost no by-products such as tar-like substances or carbon-like substances, the yield of resorcinol produced is very high. Next, the present invention will be further explained by examples.
実施例 １〜１０内容２００の‘の擬拝機つきチタン製
オートクレーブ中にｍ−ジニトロベンゼン８．４９下表
に示すような種および量の水素添加触媒、塩触媒、およ
び水９０夕を入れ、オートクレープ中の空気を窒素ガス
で置換し、水素を初圧３５ｋ９／ｃ虎となるように封入
した後、低温で、２時間オートクレープを裾拝した。Examples 1 to 10 Into a titanium autoclave equipped with a 200 ml m-dinitrobenzene 8.49 m-dinitrobenzene hydrogenation catalyst of the type and amount as shown in the table below, a salt catalyst, and 90 ml of water, After replacing the air in the autoclave with nitrogen gas and sealing in hydrogen to an initial pressure of 35k9/c, the autoclave was kept at a low temperature for 2 hours.
次いで未反応水素凝圧を除去し、窒素を２０ｋｇ／塊に
なる迄封入した後、加熱昇温し、下表に示すような反応
温度で２時間反応を行ないその結果を下表に示した。Next, unreacted hydrogen condensation pressure was removed, and nitrogen was sealed until the amount was 20 kg/lump.Then, the temperature was increased and the reaction was carried out for 2 hours at the reaction temperature shown in the table below.The results are shown in the table below.
但し、酸性硫酸ナトリウムは重硫酸ソーダとして、酸性
硫酸アンモニウムは重硫安＊として示した。※ 低温
反応終了後高温反応に先立って添加した。However, acidic sodium sulfate is shown as sodium bisulfate, and acidic ammonium sulfate is shown as ammonium bisulfate*. *Added after low temperature reaction and prior to high temperature reaction.
※※ 反応中の最高圧力を示した。参考例
内容２００の‘の澄洋機つきチタン製オートクレープ中
に、原料、塩触媒、および水１００夕を入れ、オートク
レープ中の空気を窒素で置換し、窒素または水素を封入
した後、郷拝しながら加熱昇温し、下表に示す反応温度
で２時間反応を行ない結果を下表に示した。※※ Indicates the highest pressure during the reaction. Reference example Contents: Raw materials, salt catalyst, and water are placed in a titanium autoclave with a 200 mm diameter clearing machine, the air in the autoclave is replaced with nitrogen, and nitrogen or hydrogen is sealed. The temperature was raised while heating, and the reaction was carried out for 2 hours at the reaction temperature shown in the table below, and the results are shown in the table below.
Claims (1)
パラジウム、白金またはニツケル含有触媒の存在下にｍ
−ジニトロベンゼンを水素還元し、しかる後に、加熱昇
温することを特徴とするレゾルシンの製造方法。1 m in the presence of acidic sodium sulfate or acidic ammonium sulfate and a palladium-, platinum- or nickel-containing catalyst.
- A method for producing resorcinol, which comprises reducing dinitrobenzene with hydrogen and then heating and raising the temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51057253A JPS6039055B2 (en) | 1976-05-20 | 1976-05-20 | Manufacturing method of resorcinol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51057253A JPS6039055B2 (en) | 1976-05-20 | 1976-05-20 | Manufacturing method of resorcinol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS52142025A JPS52142025A (en) | 1977-11-26 |
| JPS6039055B2 true JPS6039055B2 (en) | 1985-09-04 |
Family
ID=13050355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP51057253A Expired JPS6039055B2 (en) | 1976-05-20 | 1976-05-20 | Manufacturing method of resorcinol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6039055B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62115478A (en) * | 1985-11-15 | 1987-05-27 | Canon Inc | Image forming device |
| JPS62116970A (en) * | 1985-11-18 | 1987-05-28 | Canon Inc | Image forming device |
| JPH01210978A (en) * | 1988-02-18 | 1989-08-24 | Canon Inc | Image forming device |
-
1976
- 1976-05-20 JP JP51057253A patent/JPS6039055B2/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62115478A (en) * | 1985-11-15 | 1987-05-27 | Canon Inc | Image forming device |
| JPS62116970A (en) * | 1985-11-18 | 1987-05-28 | Canon Inc | Image forming device |
| JPH01210978A (en) * | 1988-02-18 | 1989-08-24 | Canon Inc | Image forming device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52142025A (en) | 1977-11-26 |
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