JPH0920698A - Method for producing organic substance having affinity for hydrophilic medium - Google Patents
Method for producing organic substance having affinity for hydrophilic mediumInfo
- Publication number
- JPH0920698A JPH0920698A JP7169952A JP16995295A JPH0920698A JP H0920698 A JPH0920698 A JP H0920698A JP 7169952 A JP7169952 A JP 7169952A JP 16995295 A JP16995295 A JP 16995295A JP H0920698 A JPH0920698 A JP H0920698A
- Authority
- JP
- Japan
- Prior art keywords
- water
- organic substance
- acid
- molecular weight
- soluble organic
- 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
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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Sludge (AREA)
Abstract
(57)【要約】
【課題】 ギ酸や酢酸等のカルボン酸類やメタノール類
を中心とする低分子有機物、また界面活性剤として利用
可能な高分子水溶性有機酸といった水溶性有機物を、従
来とは全く異なる製法で、簡単に製造することを目的と
する。且つ従来において燃料等にしか用途がなかった石
炭やバイオマスといった高分子固体有機物を化学原料と
して有効に利用することを目的とする。
【解決手段】 高分子固体有機物を低級アルコールや水
の存在の下に置く。酸化剤を加えて酸化する。固液分離
を行って抽出液中に水溶性有機物を得る。
(57) 【Abstract】 PROBLEM TO BE SOLVED BY THE INVENTION Conventionally, a low molecular weight organic compound centered on carboxylic acids such as formic acid and acetic acid and methanol, and a water soluble organic compound such as a polymer water soluble organic acid usable as a surfactant are It aims to be easily manufactured by a completely different manufacturing method. Moreover, it is an object of the present invention to effectively use, as a chemical raw material, a polymer solid organic material such as coal or biomass which has been conventionally used only as a fuel. A polymer solid organic substance is placed in the presence of a lower alcohol or water. Add an oxidizing agent to oxidize. Solid-liquid separation is performed to obtain a water-soluble organic substance in the extract.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、石炭やバイオマス
等の固体有機物を原料として、親水性媒体に親和性を示
す有機物（以下、親水性有機物と称す）の製造方法に関
するものであり、特に親水性媒体に水を用いた場合に水
溶性有機物、例えばギ酸、酢酸、マロン酸、グリコール
酸、マレイン酸、リンゴ酸、コハク酸、メチルマロン
酸、ベンゼンカルボン酸といったカルボン酸類や、メタ
ノール、エタノールといったアルコール類等の低分子有
機物、更には分子量約７００以下の水溶性高分子有機物
を製造する方法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing an organic substance (hereinafter referred to as a hydrophilic organic substance) having an affinity for a hydrophilic medium from a solid organic substance such as coal or biomass as a raw material, and particularly to a hydrophilic method. When water is used as the organic medium, water-soluble organic matter, for example, formic acid, acetic acid, malonic acid, glycolic acid, maleic acid, malic acid, succinic acid, methylmalonic acid, carboxylic acids such as benzenecarboxylic acid, and alcohols such as methanol and ethanol. The present invention relates to a method for producing a low molecular weight organic substance such as a class of compounds, and further a water-soluble high molecular weight organic substance having a molecular weight of about 700 or less.
【０００２】[0002]
【従来の技術】カルボン酸類やアルコール類は、多くの
種類があり、現在の化学工業における製品として、また
他の化学製品の原料として重要な位置を占める物質であ
る。例えば、ギ酸は、種々の有機薬品の合成原料、溶
剤、試薬として、また織物の染色や皮革製品のなめし加
工等に広く用いられている。酢酸は、これらの用途に加
えて、酢酸繊維素や酢酸ビニル等の原料として大量に使
用され、またアミノ酸調味料の原料として用いられてい
る。また、マロン酸、グリコール酸、リンゴ酸、コハク
酸、メチルマロン酸等の有機酸はそれぞれ植物体中に含
まれていることが知られており、これらは食品添加物、
香料、医薬品、染料等の原料として利用価値の高いもの
である。BACKGROUND OF THE INVENTION There are many kinds of carboxylic acids and alcohols, which are important substances as products in the current chemical industry and as raw materials for other chemical products. For example, formic acid is widely used as a raw material for synthesizing various organic chemicals, a solvent, a reagent, and also for dyeing textiles and tanning leather products. In addition to these applications, acetic acid is used in large quantities as a raw material for fibrin acetate, vinyl acetate, etc., and is also used as a raw material for amino acid seasonings. Further, it is known that organic acids such as malonic acid, glycolic acid, malic acid, succinic acid, and methylmalonic acid are contained in plants, respectively, and these are food additives,
It is highly useful as a raw material for fragrances, pharmaceuticals, dyes, etc.
【０００３】また、メタノールは多くの化成品の原料と
して大量に使用され、更に近年においては、ガソリンの
代替え用或いは混合用に用い、内燃機関の燃料としての
用途が期待されている。エタノールは、飲料用はもとよ
り、溶剤や化成品原料また燃料に用いる等、メタノール
と同様に、幅広い用途に多量に使用されている。Methanol is used in large quantities as a raw material for many chemical products, and in recent years, it has been expected to be used as a fuel for an internal combustion engine by replacing or mixing gasoline. Ethanol is used not only for beverages but also for solvents, raw materials for chemical products and fuels, and is used in large amounts in a wide range of applications, similar to methanol.
【０００４】カルボン酸類やアルコール類の製造法とし
ては、従来より種々の方法が知られている。酢酸の合成
法としては、石油ナフサの部分酸化を行って得る方法、
ＮｉやＣｏを触媒としてメチルアルコールと一酸化炭素
から合成する方法、アセトアルデヒドを空気酸化するこ
とによって得る方法等が知られている。他に、酢酸はア
ルコールの醗酵によっても製造され、また木材乾留によ
っても製造される。As a method for producing carboxylic acids and alcohols, various methods have been conventionally known. As a method for synthesizing acetic acid, a method obtained by partially oxidizing petroleum naphtha,
Known methods include a method of synthesizing methyl alcohol and carbon monoxide using Ni or Co as a catalyst, a method of obtaining acetaldehyde by air oxidation, and the like. In addition, acetic acid is also produced by fermentation of alcohol and also by carbonization of wood.
【０００５】ギ酸の合成法としては、１２０〜１５０
℃，６〜８気圧の条件で、水酸化ナトリウムに一酸化炭
素を作用させてギ酸ナトリウムを合成し、これを硫酸で
処理して製造する方法等が知られている。また、ギ酸
は、酢酸を石油ナフサの部分酸化法で合成する際の副産
物としても得られる。As a method for synthesizing formic acid, there are 120 to 150
There is known a method in which carbon monoxide is allowed to act on sodium hydroxide to synthesize sodium formate under conditions of 6 ° C. and 6 ° C., and the sodium formate is treated with sulfuric acid to produce. Formic acid can also be obtained as a by-product when synthesizing acetic acid by the partial oxidation method of petroleum naphtha.
【０００６】ベンゼンカルボン酸は、石炭にアルカリ水
を添加し、加圧下で１２０〜２００℃で酸化することに
よって得ることができるが、二酸化炭素の生成量が多
く、目的とする生成物の収率が低くなって、経済的でな
い。尚、褐炭等の低炭化度炭をアルカリ水で処理するこ
とにより、フミン酸等の高分子の有機酸を得ることがで
きるが、これらは通常分子量が１０００以上のものであ
り、あまり用途がない。その他、マロン酸等を製造する
には、それぞれ特定の原料から、更に複雑な工程を経て
合成する必要がある。Benzenecarboxylic acid can be obtained by adding alkaline water to coal and oxidizing it at 120 to 200 ° C. under pressure. However, a large amount of carbon dioxide is produced and the yield of the desired product is high. Is low and not economical. It should be noted that a high-molecular organic acid such as humic acid can be obtained by treating a low-carbon coal such as brown coal with alkaline water, but these usually have a molecular weight of 1,000 or more and are not very useful. . In addition, in order to produce malonic acid and the like, it is necessary to synthesize them from specific raw materials through more complicated steps.
【０００７】メタノールの製造方法としては、一酸化炭
素と水素よりなる混合ガスを原料とし、Ｎｉ系触媒を用
いて、１５〜３０気圧、８５０〜９５０℃で合成する方
法が一般的である。この原料である合成ガスは、石炭や
コークスをガス化したもの、また天然ガスや石油ナフ
サ，ＰＬＧをメタン源としてメタン分解法で製造された
もの等が知られており、現在では天然ガスを原料として
一般的に用いられている。As a method for producing methanol, a method of synthesizing a mixed gas of carbon monoxide and hydrogen as a raw material and using a Ni-based catalyst at 15 to 30 atm and 850 to 950 ° C. is generally used. Syngas, which is a raw material for this, is known to be gasified coal or coke, natural gas, petroleum naphtha, or PLG produced by a methane decomposition method using methane as a methane source. Currently, natural gas is used as a raw material. Is commonly used as.
【０００８】エタノールは、糖類やデンプン質を原料と
し発酵法により製造する方法、またエチレンと水を原料
としてリン酸系触媒を用いて直接水和法で製造する方法
等が知られている。[0008] Ethanol is known to be produced by a fermentation method using sugars and starches as raw materials, and a direct hydration method using ethylene and water as raw materials and a phosphoric acid catalyst.
【０００９】他方、石炭はコークス原料や燃料に用いら
れ、化成品の原料としてはガス化して用いることはあっ
ても、直接原料として利用されることはほとんどない。
殊に低品位炭は燃料としての用途も限られており、新し
い用途の開発が強く望まれている。また食品およびその
製造時の副産物等のバイオマスも用途が限られており、
農林業廃棄物や活性汚泥は現在廃棄物として処理されて
おり、環境上の問題という観点からも有効利用が強く望
まれている。On the other hand, coal is used as a raw material for coke and as a fuel, and although it may be gasified and used as a raw material for chemical products, it is rarely used directly as a raw material.
In particular, low-grade coal has limited applications as a fuel, and development of new applications is strongly desired. In addition, the use of food and biomass such as by-products during its production is limited,
Agricultural and forestry wastes and activated sludge are currently treated as wastes, and their effective use is strongly desired from the viewpoint of environmental problems.
【００１０】[0010]
【発明が解決しようとする課題】カルボン酸類やアルコ
ール類は前述の様に製造されているが、本発明は従来と
は全く異なる製法によって、ギ酸や酢酸等のカルボン酸
類やメタノール類を中心とする低分子有機物、また界面
活性剤として利用可能な高分子水溶性有機酸といった水
溶性有機物、或いは親水性有機物を、簡単な手法で製造
すると共に、従来において燃料等にしか用途がなかった
石炭やバイオマスといった高分子固体有機物を、化学原
料として有効に利用するという方法を提供することを目
的とする。Although the carboxylic acids and alcohols are produced as described above, the present invention mainly focuses on carboxylic acids such as formic acid and acetic acid and methanol by a completely different production method from the conventional one. Low molecular weight organic substances, water-soluble organic substances such as high molecular weight water-soluble organic acids that can be used as surfactants, or hydrophilic organic substances are produced by a simple method, and coal and biomass that have traditionally been used only as fuel etc. It is an object of the present invention to provide a method for effectively utilizing such a polymer solid organic substance as a chemical raw material.
【００１１】[0011]
【課題を解決するための手段】本発明に係る親水性有機
物の製造方法は、高分子固体有機物を親水性媒体の存在
の下に酸化剤を加えて酸化し、親水性有機物を製造する
ことを要旨とする。The method for producing a hydrophilic organic substance according to the present invention comprises producing a hydrophilic organic substance by oxidizing a polymer solid organic substance by adding an oxidizing agent in the presence of a hydrophilic medium. Use as a summary.
【００１２】更に、前記酸化剤として、過酸化水素、オ
ゾン、重クロム酸、過マンガン酸、硝酸よりなる群から
選択される一種以上を用いることが好ましい。その他、
酸化剤としてはＫＭｎＯ4 ，ＭｎＯ2 ，Ｍｎ（ＣＨ3 Ｃ
Ｏ2 ）3 ，ＣｒＯ3 ，ＮａＣｒ2 Ｏ7 ，ＨＮＯ2 ，Ｎ2
Ｏ3 ，Ｎ2 Ｏ4 ，Ｏ2 ，Ｎａ2 Ｏ2 ，（Ｃ6 Ｈ5 ＣＯ）
2 Ｏ2 ，ＣＨ3 ＣＯ3 Ｈ、Ｃ6 Ｈ5 ＣＯ3 Ｈ，Ｋ2 Ｓ2
Ｏ8 を用いても良い。また、前記親水性媒体が水または
アルコールであることが望ましい。特に、高分子固体有
機物を水の存在の下に酸化剤を加えて酸化して水溶性有
機物を製造すると良い。加えて、前記高分子固体有機物
を予め低級アルコールに膨潤させることがより好まし
い。Further, as the oxidizing agent, it is preferable to use one or more selected from the group consisting of hydrogen peroxide, ozone, dichromic acid, permanganic acid and nitric acid. Other,
As the oxidizer, KMnO 4 , MnO 2 , Mn (CH 3 C
O 2 ) 3 , CrO 3 , NaCr 2 O 7 , HNO 2 , N 2
O 3, N 2 O 4, O 2, Na 2 O 2, (C 6 H 5 CO)
2 O 2 , CH 3 CO 3 H, C 6 H 5 CO 3 H, K 2 S 2
O 8 may be used. Further, it is desirable that the hydrophilic medium is water or alcohol. In particular, it is preferable to produce a water-soluble organic substance by oxidizing a polymer solid organic substance by adding an oxidizing agent in the presence of water. In addition, it is more preferable to swell the high molecular weight solid organic material with a lower alcohol in advance.
【００１３】[0013]
【発明の実施の形態】以下に、親水性媒体として水を用
い、親水性有機物として水溶性有機物を製造する場合を
代表として主に説明する。前記本発明によれば、高分子
固体有機物を湿式で穏やかな条件として、二酸化炭素の
発生を抑制しつつ、徐々に酸化することになる。これに
より原料の高分子固体有機物が有機酸やアルコールに酸
化分解されて抽出される。即ち、湿式で緩やかな条件で
酸化することによって、高分子固体有機物にカルボキシ
ル基、または水酸基、或いはこれら両者を導入すると共
に、高分子固体有機物を分解し、水溶性のアルコールや
カルボン酸を主成分とする低分子有機物や、分子量約７
００以下の高分子水溶性有機物といった水溶性有機物を
生成させるのである。これら生成した水溶性有機物は水
に溶出されるので、これを固液分離して回収する。尚、
二酸化炭素の発生を抑制することのできる穏やかな条件
としては、処理温度を低くする、また酸化剤の濃度を低
くする等の方法が挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the case of using water as a hydrophilic medium and producing a water-soluble organic substance as a hydrophilic organic substance will be mainly described as a representative. According to the present invention, the solid polymer organic material is gradually wetted under a wet and mild condition while suppressing the generation of carbon dioxide. As a result, the high-molecular solid organic material as a raw material is oxidatively decomposed into organic acid or alcohol and extracted. That is, by introducing a carboxyl group, a hydroxyl group, or both into the polymer solid organic material by oxidizing it under wet conditions under mild conditions, the polymer solid organic material is decomposed, and the water-soluble alcohol or carboxylic acid is the main component. Low molecular weight organic substances and molecular weight of about 7
A water-soluble organic substance such as a high molecular weight water-soluble organic substance of 00 or less is produced. These water-soluble organic substances produced are eluted in water, and are separated by solid-liquid separation and collected. still,
Examples of mild conditions that can suppress the generation of carbon dioxide include methods such as lowering the treatment temperature and lowering the concentration of the oxidizing agent.
【００１４】一方、湿式で酸化剤を用いるといった本発
明の方法ではなく、空気中の酸素を用いた気相酸化によ
る場合では、低温での酸化速度が著しく遅くなるという
問題がある。そこで酸化速度を上げるために処理温度を
上げると、導入された酸素が固体有機物の架橋構造を形
成し、更に酸化を進めると二酸化炭素となる為、上記カ
ルボン酸はほとんど生成しないことになる。また、湿式
酸化であっても、アルカリ下あるいは加圧下で１２０〜
２００℃程度の厳しい条件で酸化した場合は、二酸化炭
素の生成量が増加し、有機酸の収率が著しく低下する。On the other hand, in the case of the gas phase oxidation using oxygen in the air instead of the method of the present invention using an oxidizing agent in a wet manner, there is a problem that the oxidation rate at a low temperature is remarkably slowed. Therefore, when the treatment temperature is raised to increase the oxidation rate, the introduced oxygen forms a crosslinked structure of a solid organic matter, and further oxidation turns into carbon dioxide, so that the carboxylic acid is hardly produced. In addition, even in the case of wet oxidation, 120 to 120
When oxidized under a severe condition of about 200 ° C., the amount of carbon dioxide produced increases and the yield of organic acid significantly decreases.
【００１５】尚、本発明で言う水溶性有機物とは、ギ
酸、酢酸、マロン酸、グリコール酸、マレイン酸、リン
ゴ酸、コハク酸、メチルマロン酸、ベンゼンカルボン酸
等のカルボン酸類や、メタノール、エタノール等のアル
コール類、またカルボキシル基及び／または水酸基を有
する分子量約７００以下の水溶性高分子有機物を指す。The water-soluble organic substances referred to in the present invention include carboxylic acids such as formic acid, acetic acid, malonic acid, glycolic acid, maleic acid, malic acid, succinic acid, methylmalonic acid and benzenecarboxylic acid, and methanol and ethanol. And alcohols, and water-soluble polymer organic substances having a carboxyl group and / or a hydroxyl group and having a molecular weight of about 700 or less.
【００１６】本発明における酸化処理の温度は特に限定
されるものではないが、親水性媒体の沸点以下であれば
大気圧で処理できることから、親水性媒体が水の場合は
１００℃以下が望ましく、より望ましくは４０〜８０℃
である。The temperature of the oxidation treatment in the present invention is not particularly limited, but since it can be treated at atmospheric pressure as long as it is not higher than the boiling point of the hydrophilic medium, it is preferably 100 ° C. or lower when the hydrophilic medium is water, More desirably 40 to 80 ° C
It is.
【００１７】用いる酸化剤としては、特に限定されるも
のではないが、過酸化水素水、オゾン、重クロム酸、過
マンガン酸、硝酸等は水中で酸化作用を有するので好ま
しい。特に過酸化水素水あるいはオゾンを用いた場合
は、二酸化炭素の発生を抑え、水溶性有機物を高収率で
得ることができるからより望ましい。その他の酸化剤と
して上記の様に種々のものが使用でき、生成物への残留
の問題から、重金属ではなくまた毒性のない物が推奨さ
れる。添加する酸化剤は、これらの酸化剤を二種類以上
組合せて用いることも可能である。尚、酸化剤として酸
素（Ｏ2 ）を用いることもでき、この場合は水中に酸素
を溶存させて用い、この際には溶存酸素量を大きくする
為、加圧下で処理することが望ましく、また前記水溶性
の酸化剤と組合せる様にしても良い。The oxidizing agent to be used is not particularly limited, but hydrogen peroxide solution, ozone, dichromic acid, permanganic acid, nitric acid and the like are preferable because they have an oxidizing effect in water. In particular, the use of hydrogen peroxide water or ozone is more preferable because the generation of carbon dioxide can be suppressed and the water-soluble organic substance can be obtained in a high yield. Various other oxidants can be used as described above, and non-heavy metals and non-toxic ones are recommended due to the problem of residue in the product. The oxidizing agent to be added may be a combination of two or more kinds of these oxidizing agents. It is also possible to use oxygen (O 2 ) as an oxidant. In this case, oxygen is dissolved in water to be used, and in this case, it is desirable to treat under pressure in order to increase the amount of dissolved oxygen. You may make it combine with the said water-soluble oxidizing agent.
【００１８】高分子固体有機物としては、石炭、ピー
ト、および木材、農業廃棄物、活性汚泥、食品廃棄物、
パルプ／食品製造工程で生成する副産物／廃棄物等のバ
イオマスが挙げられる。尚、炭素含有量の大きな石炭
は、芳香族環が発達し単位構造の分子量が大きくなる
為、本発明で行っている温和な酸化条件では、低分子化
できず、低分子有機酸は生成しなくなる。従って、石炭
としては、有機物（無水無灰物）の全量に対して炭素含
有量が８０％以下ものが好ましい。より好ましくは７０
％以下の褐炭や泥炭といった低品位炭である。The polymer solid organic matter includes coal, peat, and wood, agricultural waste, activated sludge, food waste,
Examples include biomass such as by-products / wastes generated in pulp / food manufacturing processes. In addition, since the aromatic ring develops and the molecular weight of the unit structure becomes large in coal with a large carbon content, it is not possible to reduce the molecular weight under the mild oxidation conditions performed in the present invention, and a low molecular weight organic acid is generated. Disappear. Therefore, the coal preferably has a carbon content of 80% or less with respect to the total amount of organic matter (anhydrous ashless matter). More preferably 70
% Low-grade coal such as brown coal and peat.
【００１９】これら高分子固体有機物は、塊状の石炭等
の場合では数ｍｍ以下、好ましくは１ｍｍ以下に粉砕し
て処理することが望ましく、微細化することにより親水
性媒体（水）および酸化剤と効率良く接触させることが
できる。尚、数ｍｍ以下の粒状あるいは細かい繊維状の
有機物はそのまま処理でき、また水分を多量に含んだ状
態でも処理可能であることは言うまでもない。In the case of lumpy coal or the like, it is desirable that these high molecular weight solid organic substances are pulverized to a size of several mm or less, preferably 1 mm or less, and then treated, and when they are made finer, they become a hydrophilic medium (water) and an oxidizing agent. The contact can be made efficiently. Needless to say, granular or fine fibrous organic matter having a size of several mm or less can be treated as it is, and can be treated even in a state of containing a large amount of water.
【００２０】メタノールやエタノール等の低級アルコー
ルは、親水性媒体として水を用いる場合には、上記高分
子固体有機物を膨潤させるから、後の酸化工程における
高分子固体有機物と酸化剤の接触効率を上げることがで
き、加えて酸化剤を必要な部位に選択的に作用させるこ
とができる。When water is used as the hydrophilic medium, lower alcohols such as methanol and ethanol swell the above-mentioned polymer solid organic matter, so that the contact efficiency between the polymer solid organic matter and the oxidizing agent in the subsequent oxidation step is increased. In addition, the oxidizing agent can be selectively acted on the required site.
【００２１】このとき、低級アルコールの処理効率を上
げる為に、該固体有機物を脱水しても良い。尚、用いた
アルコールは酸化処理後、水溶性有機生成物と共に、回
収することができる。At this time, the solid organic matter may be dehydrated in order to improve the treatment efficiency of the lower alcohol. The alcohol used can be recovered together with the water-soluble organic product after the oxidation treatment.
【００２２】以上の説明において親水性媒体として主に
水を挙げて述べたが、他の親水性媒体を用いた場合に
は、当該親水性媒体に親和性を有する有機物が製造され
る。該親水性有機物としては、カルボン酸類やアルコー
ル類といった低分子有機物、また分子量約７００以下の
高分子有機物が挙げられる。In the above description, water was mainly mentioned as the hydrophilic medium, but when another hydrophilic medium is used, an organic substance having an affinity for the hydrophilic medium is produced. Examples of the hydrophilic organic substance include low molecular weight organic substances such as carboxylic acids and alcohols, and high molecular weight organic substances having a molecular weight of about 700 or less.
【００２３】親水性媒体（例えば水）は高分子固体有機
物に対し１〜２０倍量（重量）用いることが推奨され、
酸化により生成されて親水性媒体に溶出してきた親水性
有機物を、固液分離を施すことにより回収することがで
きる。It is recommended that the hydrophilic medium (for example, water) is used in an amount of 1 to 20 times (weight) with respect to the solid polymer organic material.
The hydrophilic organic substance generated by oxidation and eluted in the hydrophilic medium can be recovered by solid-liquid separation.
【００２４】図１は本発明に係る水溶性有機物（親水性
有機物）の製造方法の一例を示すフロー図である。以下
に、高分子固体有機物が塊状であった場合の本発明の製
造方法について説明する。FIG. 1 is a flow chart showing an example of a method for producing a water-soluble organic substance (hydrophilic organic substance) according to the present invention. The production method of the present invention when the polymer solid organic material is in the form of lumps will be described below.
【００２５】まず、高分子固体有機物を数ｍｍ以下に粉
砕し、予備処理工程で低級アルコール（例えばメタノー
ル）と接触させる。このとき、用いるアルコール量は高
分子固体有機物がアルコールに浸り、アルコールを十分
吸収できる程度であれば良い。尚、この予備処理工程は
省略することが可能であり、特に高分子固体有機物が多
量の水分を含む（約３０wt％以上の水分を含む）場合は
必要がない。First, the polymer solid organic material is pulverized to several mm or less and brought into contact with a lower alcohol (eg methanol) in a pretreatment step. At this time, the amount of alcohol used may be such that the solid polymer organic material can be immersed in the alcohol and can absorb the alcohol sufficiently. This pretreatment step can be omitted, and is not particularly necessary when the polymer solid organic substance contains a large amount of water (containing about 30 wt% or more water).
【００２６】次に、この高分子固体有機物を１００℃以
下の一定温度に保った酸化槽に送り、撹拌によって水中
に分散させてスラリー化すると共に酸化させる。尚、酸
化槽では酸化剤が連続的に供給されている。Next, the high molecular solid organic material is sent to an oxidation tank kept at a constant temperature of 100 ° C. or lower, and dispersed in water by stirring to be slurried and oxidized. The oxidizing agent is continuously supplied in the oxidizing tank.
【００２７】その後、酸化処理の終わったスラリーを、
酸化槽より抜き出し、濾過もしくは遠心分離等の方法に
よって固液分離を行い、残渣と抽出液に分離する。尚、
固液分離に際し、沈降槽を設け、酸化槽から抜き出した
スラリーを沈降槽に導入し上澄みと濃縮スラリーに分離
した後、濃縮スラリーを濾過や遠心分離によって固液分
離しても良く、また沈降槽を設けずに、酸化槽において
スラリーを静置して上澄みと濃縮スラリーに分離し、上
澄みを回収した後、上記濃縮スラリーを濾過や遠心分離
によって固液分離する様にしても良い。After that, the slurry after the oxidation treatment is
It is extracted from the oxidation tank, and solid-liquid separation is performed by a method such as filtration or centrifugation to separate it into a residue and an extract. still,
Upon solid-liquid separation, a sedimentation tank is provided, and the slurry extracted from the oxidation tank may be introduced into the sedimentation tank to separate the supernatant and the concentrated slurry, and then the concentrated slurry may be subjected to solid-liquid separation by filtration or centrifugation. Alternatively, the slurry may be allowed to stand in an oxidizing tank to separate it into a supernatant and a concentrated slurry, and after collecting the supernatant, the concentrated slurry is subjected to solid-liquid separation by filtration or centrifugation.
【００２８】図２は酸化槽と沈降槽の組合わせを２段と
した場合の製造フローを示す図である。酸化槽を１段と
し、そこで長時間酸化を続けると、生成した水溶性有機
物の酸化が一層進み、ＣＯ2 まで分解してしまうことが
あるが、図２に示す様に酸化槽を２段とし、１段目で生
成した水溶性有機物を収集し、残る濃縮スラリーの高分
子固体有機物を２段目の酸化槽で更に酸化剤を加えて酸
化し、水溶性有機物を生成させる様にすれば、先に生成
した水溶性有機物がＣＯ2 まで酸化分解されることな
く、水溶性有機物を多く得ることができる。酸化槽、或
いは酸化槽と沈降濃縮槽の組合わせは、１段や２段に限
るものではなく、３段以上であっても良い。尚、酸化剤
が十分であれば２段目以降の酸化槽への新たな酸化剤の
供給を省略する場合もあり、また分離した上澄み液を上
流側の酸化槽に循環する場合もある。FIG. 2 is a diagram showing a manufacturing flow when the combination of the oxidation tank and the sedimentation tank is two stages. If the oxidation tank is set to one stage and the oxidation is continued for a long time there, the generated water-soluble organic matter may be further oxidized and CO 2 may be decomposed. However, as shown in FIG. By collecting the water-soluble organic matter generated in the first step and oxidizing the remaining solid polymer organic matter of the concentrated slurry by further adding an oxidant in the second-stage oxidation tank to generate the water-soluble organic matter, A large amount of water-soluble organic matter can be obtained without oxidative decomposition of the water-soluble organic matter generated previously to CO 2 . The oxidation tank or the combination of the oxidation tank and the sedimentation and concentration tank is not limited to one stage or two stages, and may be three stages or more. If the oxidizing agent is sufficient, the supply of new oxidizing agent to the second and subsequent oxidation tanks may be omitted, and the separated supernatant may be circulated to the upstream oxidation tank.
【００２９】尚、処理時間については、例えば生成物と
して分子量の小さいものを得たい場合には酸化処理時間
を長く、分子量の大きいものを得たい場合には処理時間
を短くする等して、調整すると良い。The treatment time is adjusted by, for example, increasing the oxidation treatment time to obtain a product having a small molecular weight and shortening the treatment time to obtain a product having a large molecular weight. Good to do.
【００３０】この様にして得られた抽出液を、更に減圧
蒸留等によって処理し、アルコールや水といった媒体と
親水性有機物（水溶性有機生成物）を分離，回収する。
尚、有機生成物がギ酸等の様に低沸点生成物の場合は、
減圧蒸留による精留によって回収する方法が利用でき、
高分子有機物等の様に高沸点生成物の場合は、濃縮後の
晶析等の分離法が利用できる。また、晶析を利用するに
あたって、アルカリ塩として分離することも有効であ
る。回収されたアルコールや水また残存酸化剤は循環使
用することができ、経済性がよい。The extract thus obtained is further treated by vacuum distillation or the like to separate and collect a medium such as alcohol or water and a hydrophilic organic substance (water-soluble organic product).
If the organic product is a low boiling point product such as formic acid,
A method of collecting by rectification by vacuum distillation is available,
In the case of a high boiling point product such as a high molecular weight organic substance, a separation method such as crystallization after concentration can be used. Further, when utilizing crystallization, it is also effective to separate it as an alkali salt. The recovered alcohol, water or residual oxidant can be reused and is economical.
【００３１】尚、生成物の分離精製およびアルコールの
回収、更には酸化剤の回収および処理は、用いる酸化剤
によって異なるため、それに応じてそれぞれ最適な方法
を採用する。Since the separation and purification of the product, the recovery of alcohol, and the recovery and treatment of the oxidizing agent differ depending on the oxidizing agent used, an optimum method is adopted accordingly.
【００３２】[0032]
【実施例】次に本発明の実施例を示すが、本発明はもと
より下記実施例によって制限を受けるものではなく、本
発明の趣旨に適合し得る範囲において適宜変更を加えて
実施することも可能であって、それらはいずれも本発明
の技術的範囲に含まれる。EXAMPLES Next, examples of the present invention will be shown, but the present invention is not limited by the following examples and can be carried out by appropriately modifying within a range compatible with the gist of the present invention. However, all of them are included in the technical scope of the present invention.
【００３３】＜実施例１＞無水無灰炭基準で６４．８重
量％の炭素を含有する褐炭を、２００メッシュ以下に粉
砕後、乾燥し、メタノールに浸す。該褐炭及びメタノー
ルに、この１０倍量の３０％過酸化水素水を加え、撹拌
しつつ６０℃で２時間保持した後、濾過を行って固液を
分離し、濾液中に水溶性有機物を得た。該濾液中の水溶
性有機物の分析結果を、表１及び表２に示す。Example 1 Brown coal containing 64.8% by weight of carbon based on anhydrous ashless coal was pulverized to 200 mesh or less, dried, and immersed in methanol. To the brown coal and methanol, 10 times the amount of 30% hydrogen peroxide solution was added, and the mixture was maintained at 60 ° C. for 2 hours while stirring, and then filtered to separate solid and liquid to obtain a water-soluble organic substance in the filtrate. It was The analysis results of the water-soluble organic substances in the filtrate are shown in Tables 1 and 2.
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【表２】 [Table 2]
【００３６】表１，２から分かる様に、褐炭中の炭素の
３０．１％が水溶性有機物に転化し、低分子有機物とし
て酢酸，ギ酸，マロン酸を主成分とする有機酸が生成し
た。また多くのメタノールも得られた。上記水溶性有機
物中の炭素量３０．１％のうち、約１３％が分子量３０
０〜７００の高分子有機物であった。これは生成した水
溶性有機物中の炭素量を１００％とすると、その約４５
％に相当する。As can be seen from Tables 1 and 2, 30.1% of the carbon in the brown coal was converted into a water-soluble organic substance, and an organic acid containing acetic acid, formic acid, and malonic acid as main components was produced as a low molecular weight organic substance. A lot of methanol was also obtained. Of the carbon content of 30.1% in the water-soluble organic matter, about 13% has a molecular weight of 30.
It was a high molecular weight organic substance of 0 to 700. This is about 45% of the amount of carbon in the water-soluble organic matter produced.
%.
【００３７】＜実施例２＞６０℃に保持する時間を２４
時間とする以外は上記実施例１と同様の処理を行った。
濾液中の水溶性有機物の分析結果を、上記表１及び表２
に示す。表１，２から分かる様に、有機酸生成量は褐炭
中炭素の６２．２％に達しており、特に低分子有機酸の
生成量ではギ酸やマロン酸の収率が増加し、副生成物と
してメタノール、グリコール酸、マレイン酸、メチルマ
ロン酸、コハク酸、リンゴ酸、分子量７００以下の水溶
性高分子有機物も多く生成した。上記水溶性有機物中の
炭素量６２．２％のうち約３０％が分子量３００〜７０
０の高分子有機物であり、これは生成した水溶性有機物
中の炭素量を１００％とすると、その約５２％に相当す
る。<Example 2> The time for holding at 60 ° C was 24
The same process as in Example 1 was performed except that the time was changed.
The analysis results of the water-soluble organic matter in the filtrate are shown in Tables 1 and 2 above.
Shown in As can be seen from Tables 1 and 2, the amount of organic acids produced reached 62.2% of the carbon in brown coal, and especially the amount of low-molecular organic acids produced increased the yield of formic acid and malonic acid and caused by-products. As a result, methanol, glycolic acid, maleic acid, methylmalonic acid, succinic acid, malic acid, and a large amount of water-soluble polymer organic substances having a molecular weight of 700 or less were also produced. About 30% of the carbon amount of 62.2% in the above water-soluble organic matter has a molecular weight of 300 to 70.
It is a high molecular weight organic substance of 0, which corresponds to about 52% of the carbon content in the produced water-soluble organic substance.
【００３８】＜実施例３＞水分６２重量％を含む褐炭
（無水無灰炭基準での炭素含有量：６４．８重量％）を
１ｍｍ以下に粉砕し、これに１０倍量の３０％過酸化水
素を加えて混合し、６０℃で２４時間処理した。その
後、濾過によって固液を分離し、濾液中に水溶性有機物
を得た。該濾液中の水溶性有機物の分析結果を表３，４
に示す。<Example 3> Lignite containing 62% by weight of water (carbon content based on anhydrous ashless coal: 64.8% by weight) was crushed to 1 mm or less, and 10 times amount of 30% peroxide was added thereto. Hydrogen was added and mixed, and the mixture was treated at 60 ° C. for 24 hours. Then, the solid-liquid was separated by filtration to obtain a water-soluble organic substance in the filtrate. The analysis results of the water-soluble organic substances in the filtrate are shown in Tables 3 and 4.
Shown in
【００３９】[0039]
【表３】 [Table 3]
【００４０】[0040]
【表４】 [Table 4]
【００４１】表３，４から分かる様に、褐炭中の有機炭
素の５４．８％が水溶性有機物に転化し、メタノール、
ギ酸、酢酸等が得られた。これらの分子量１３０以下の
低分子有機物に転化した炭素量は１５．７％であり、残
りは分子量１３０〜７００の水溶性高分子有機物であっ
た。これらの水溶性高分子有機物は、生成液を著しく発
泡させており、界面活性剤として利用できる化合物であ
ることが分かった。As can be seen from Tables 3 and 4, 54.8% of the organic carbon in the brown coal was converted into water-soluble organic matter, and methanol,
Formic acid, acetic acid, etc. were obtained. The carbon amount converted into these low molecular weight organic substances having a molecular weight of 130 or less was 15.7%, and the rest was a water-soluble polymer organic substance having a molecular weight of 130 to 700. It was found that these water-soluble high molecular weight organic compounds foamed the produced liquid remarkably and could be used as a surfactant.
【００４２】＜実施例４＞酸化剤として５％過酸化水素
を用いる以外は、上記実施例３と同様の処理を行った。
濾液中の水溶性有機物の分析結果を表３，４に示す。表
３，４から分かる様に、褐炭中の有機炭素の１８．８％
が水溶性有機物に転化し、量は少ないものの、メタノー
ルがほとんどなかった以外は実施例３と同様の水溶性有
機物が得られた。分子量１３０以下の低分子有機物に転
化した炭素量は６．９％であり、残りは分子量１３０〜
７００の水溶性有機物であった。<Example 4> The same treatment as in Example 3 was carried out except that 5% hydrogen peroxide was used as the oxidizing agent.
Tables 3 and 4 show the analysis results of water-soluble organic substances in the filtrate. As can be seen from Tables 3 and 4, 18.8% of organic carbon in brown coal
Was converted into a water-soluble organic substance, and although the amount was small, the same water-soluble organic substance as in Example 3 was obtained except that almost no methanol was present. The amount of carbon converted to a low molecular weight organic substance having a molecular weight of 130 or less is 6.9%, and the rest is a molecular weight of 130-
It was 700 water-soluble organic matter.
【００４３】＜実施例５＞酸化剤として１５％過酸化水
素を用いる以外は、上記実施例３と同様の処理を行っ
た。濾液中の水溶性有機物の分析結果を表３，４に示
す。表３，４から分かる様に、褐炭中の有機炭素の４
４．８％が水溶性有機物に転化し、実施例３と同様の水
溶性有機物が得られた。分子量１３０以下の低分子有機
物に転化した炭素量は１２．１％であり、残りは分子量
１３０〜７００の水溶性有機物であった。Example 5 The same treatment as in Example 3 was carried out except that 15% hydrogen peroxide was used as the oxidizing agent. Tables 3 and 4 show the analysis results of water-soluble organic substances in the filtrate. As can be seen from Tables 3 and 4, 4 of organic carbon in brown coal
4.8% was converted to a water-soluble organic substance, and the same water-soluble organic substance as in Example 3 was obtained. The amount of carbon converted to a low molecular weight organic substance having a molecular weight of 130 or less was 12.1%, and the rest was a water-soluble organic substance having a molecular weight of 130 to 700.
【００４４】＜実施例６＞酸化処理の条件を８０℃、１
時間とする以外は、上記実施例３と同様の処理を行っ
た。濾液中の水溶性有機物の分析結果を表３，４に示
す。表３，４から分かる様に、褐炭中の有機炭素の４
２．７％が水溶性有機物に転化し、実施例３と同様の水
溶性有機物が得られた。分子量１３０以下の低分子有機
物に転化した炭素量は８．５％であり、残りは分子量１
３０〜７００の水溶性有機物であった。<Embodiment 6> The conditions of the oxidation treatment are 80 ° C. and 1
The same process as in Example 3 was performed except that the time was changed. Tables 3 and 4 show the analysis results of water-soluble organic substances in the filtrate. As can be seen from Tables 3 and 4, 4 of organic carbon in brown coal
2.7% was converted to a water-soluble organic matter, and the same water-soluble organic matter as in Example 3 was obtained. The amount of carbon converted to low molecular weight organic matter having a molecular weight of 130 or less is 8.5%, and the rest is molecular weight 1
It was a water-soluble organic matter of 30 to 700.
【００４５】＜実施例７＞酸化処理の条件を４０℃、２
４時間とする以外は、上記実施例３と同様の処理を行っ
た。濾液中の水溶性有機物の分析結果を表３，４に示
す。表３，４から分かる様に、褐炭中の有機炭素の２
２．０％が水溶性有機物に転化し、実施例３と同様の水
溶性有機物が得られた。分子量１３０以下の低分子有機
物に転化した炭素量は１１．１％であり、残りは分子量
１３０〜７００の水溶性有機物であった。<Embodiment 7> The conditions of the oxidation treatment are 40 ° C. and 2
The same treatment as in Example 3 was performed except that the time was 4 hours. Tables 3 and 4 show the analysis results of water-soluble organic substances in the filtrate. As can be seen from Tables 3 and 4, 2 of organic carbon in brown coal
2.0% was converted to a water-soluble organic substance, and the same water-soluble organic substance as in Example 3 was obtained. The carbon amount converted to a low molecular weight organic substance having a molecular weight of 130 or less was 11.1%, and the rest was a water-soluble organic substance having a molecular weight of 130 to 700.
【００４６】＜実施例８＞無水無灰炭基準で７４．５重
量％の炭素を含有する石炭を粉砕乾燥後、１０倍量の３
０％過酸化水素と混合し、６０℃で２４時間処理した。
処理後、濾過によって固液を分離し、濾液中に水溶性有
機物を得た。該濾液中の水溶性有機物の分析結果を表
３，４に示す。Example 8 Coal containing 74.5% by weight of carbon based on anhydrous ashless coal was pulverized and dried, and then 10 times amount of 3 was added.
It was mixed with 0% hydrogen peroxide and treated at 60 ° C. for 24 hours.
After the treatment, solid-liquid was separated by filtration to obtain a water-soluble organic substance in the filtrate. Tables 3 and 4 show the results of analysis of water-soluble organic substances in the filtrate.
【００４７】表３，４から分かる様に、石炭中の有機炭
素の３７．２％が水溶性有機物に転化し、ギ酸、酢酸等
が得られた。これらの分子量１３０以下の低分子有機物
に転化した炭素量は１７．９％であり、残りは分子量１
３０〜７００の水溶性高分子有機物であり、これらの水
溶性高分子有機物は、実施例３と同様に該生成液を著し
く発泡させ、界面活性剤として利用できる化合物である
ことが分かった。As can be seen from Tables 3 and 4, 37.2% of the organic carbon in coal was converted to water-soluble organic matter, and formic acid, acetic acid, etc. were obtained. The amount of carbon converted to these low molecular weight organic substances having a molecular weight of 130 or less is 17.9%, and the rest is a molecular weight of 1
It was found that they are water-soluble high molecular weight organic compounds of 30 to 700, and these water soluble high molecular weight organic compounds are compounds which can foam the product liquid remarkably in the same manner as in Example 3 and can be used as a surfactant.
【００４８】＜実施例９＞無水無灰炭基準で６９．５重
量％の炭素を含有する石炭を用いて、上記実施例８と同
様の処理を行った。濾液中の水溶性有機物の分析結果を
表３，４に示す。表３，４から分かる様に、褐炭中の有
機炭素の４４．１％が水溶性有機物に転化し、グリコー
ル酸を除いて実施例３と同様の水溶性有機物が得られ
た。分子量１３０以下の低分子有機物に転化した炭素量
は１３．６％であり、残りは分子量１３０〜７００の水
溶性高分子有機物であった。Example 9 The same treatment as in Example 8 was performed using coal containing 69.5% by weight of carbon based on anhydrous ashless coal. Tables 3 and 4 show the analysis results of water-soluble organic substances in the filtrate. As can be seen from Tables 3 and 4, 44.1% of the organic carbon in the brown coal was converted into the water-soluble organic matter, and the same water-soluble organic matter as in Example 3 was obtained except for glycolic acid. The carbon content converted to a low molecular weight organic material having a molecular weight of 130 or less was 13.6%, and the rest was a water-soluble polymer organic material having a molecular weight of 130 to 700.
【００４９】[0049]
【発明の効果】以上の様に、本発明に係る親水性有機物
の製造方法によれば、安価で大量に存在する褐炭やバイ
オマス等の高分子固体有機物を原料として、ギ酸、酢
酸、マロン酸等の低分子有機酸及びメタノールなどの低
級アルコール、更には界面活性剤等への広用が可能と考
えられる水溶性高分子有機物といった親水性有機物を、
効率良く且つ容易に製造することができる。加えて、本
発明の製造方法により、石炭や低品位炭、農林業廃棄
物、活性汚泥、バイオマス等を化学原料として有効利用
することができ、これらを資源として有効活用すること
ができる。As described above, according to the method for producing a hydrophilic organic substance according to the present invention, formic acid, acetic acid, malonic acid, etc. are prepared from a large amount of inexpensive solid polymer organic substance such as brown coal or biomass. Hydrophilic organic substances such as low molecular weight organic acids and lower alcohols such as methanol, and water-soluble high molecular weight organic substances that are considered to be widely applicable to surfactants,
It can be manufactured efficiently and easily. In addition, according to the production method of the present invention, coal, low-grade coal, agricultural and forestry waste, activated sludge, biomass and the like can be effectively used as chemical raw materials, and these can be effectively used as resources.
【図１】本発明に係る水溶性有機物の製造フローの一例
を示す図。FIG. 1 is a diagram showing an example of a production flow of a water-soluble organic substance according to the present invention.
【図２】本発明に係る水溶性有機物の製造フローの他の
例を示す図。FIG. 2 is a diagram showing another example of the manufacturing flow of the water-soluble organic substance according to the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 57/145 Ｃ０７Ｃ 57/145 59/06 9450−4Ｈ 59/06 59/245 9450−4Ｈ 59/245 (72)発明者 大隈 修 兵庫県神戸市西区高塚台１丁目５番５号 株式会社神戸製鋼所神戸総合技術研究所内 (72)発明者 清水 孝浩 兵庫県神戸市西区高塚台１丁目５番５号 株式会社神戸製鋼所神戸総合技術研究所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C07C 57/145 C07C 57/145 59/06 9450-4H 59/06 59/245 9450-4H 59 / 245 (72) Inventor Osamu Okuma 1-5-5 Takatsukadai, Nishi-ku, Kobe-shi, Hyogo Prefecture Kobe Steel Co., Ltd. Kobe Research Institute (72) Inventor Takahiro Shimizu 1-5-5 Takatsukadai, Nishi-ku, Kobe-shi, Hyogo Prefecture Kobe Steel Co., Ltd.Kobe Research Institute
Claims (5)
下に酸化剤を加えて酸化して、親水性媒体に親和性を示
す有機物を製造することを特徴とする親水性媒体に親和
性を示す有機物の製造方法。1. An affinity for a hydrophilic medium, characterized in that an organic substance having an affinity for a hydrophilic medium is produced by oxidizing a polymer solid organic substance by adding an oxidizing agent in the presence of the hydrophilic medium. Showing a method for producing an organic substance.
ン、重クロム酸、過マンガン酸、硝酸よりなる群から選
択される一種以上を用いる請求項１に記載の製造方法。2. The method according to claim 1, wherein one or more selected from the group consisting of hydrogen peroxide, ozone, dichromic acid, permanganic acid, and nitric acid is used as the oxidizing agent.
ある請求項１または２に記載の製造方法。3. The method according to claim 1, wherein the hydrophilic medium is water or alcohol.
剤を加えて酸化して水溶性有機物を製造する請求項１〜
３のいずれかに記載の製造方法。4. A water-soluble organic substance is produced by oxidizing a polymer solid organic substance by adding an oxidizing agent in the presence of water.
3. The manufacturing method according to any one of 3 above.
ールに膨潤させる請求項１〜４のいずれかに記載の製造
方法。5. The method according to claim 1, wherein the polymer solid organic material is swollen in a lower alcohol in advance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16995295A JP3864432B2 (en) | 1995-07-05 | 1995-07-05 | Method for producing organic substance having affinity for hydrophilic medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16995295A JP3864432B2 (en) | 1995-07-05 | 1995-07-05 | Method for producing organic substance having affinity for hydrophilic medium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0920698A true JPH0920698A (en) | 1997-01-21 |
| JP3864432B2 JP3864432B2 (en) | 2006-12-27 |
Family
ID=15895909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16995295A Expired - Lifetime JP3864432B2 (en) | 1995-07-05 | 1995-07-05 | Method for producing organic substance having affinity for hydrophilic medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3864432B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7090768B2 (en) * | 2002-06-25 | 2006-08-15 | Page Pat | Surfactant for bitumen separation |
| JP2007039368A (en) * | 2005-08-02 | 2007-02-15 | Kyoto Univ | Organic acid and process for producing the same |
| EA017562B1 (en) * | 2006-11-03 | 2013-01-30 | Биджам Байосайенсиз Прайвет Лимитед | Production of functionally effective organic molecules from lignite cleavage |
| CN112919678A (en) * | 2021-01-29 | 2021-06-08 | 江苏集萃托普索清洁能源研发有限公司 | Acetic acid production wastewater treatment process |
| WO2025183161A1 (en) * | 2024-02-29 | 2025-09-04 | 国立大学法人京都大学 | Biomass composition and production method for same |
-
1995
- 1995-07-05 JP JP16995295A patent/JP3864432B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7090768B2 (en) * | 2002-06-25 | 2006-08-15 | Page Pat | Surfactant for bitumen separation |
| JP2007039368A (en) * | 2005-08-02 | 2007-02-15 | Kyoto Univ | Organic acid and process for producing the same |
| EA017562B1 (en) * | 2006-11-03 | 2013-01-30 | Биджам Байосайенсиз Прайвет Лимитед | Production of functionally effective organic molecules from lignite cleavage |
| CN112919678A (en) * | 2021-01-29 | 2021-06-08 | 江苏集萃托普索清洁能源研发有限公司 | Acetic acid production wastewater treatment process |
| CN112919678B (en) * | 2021-01-29 | 2023-04-18 | 江苏集萃托普索清洁能源研发有限公司 | Acetic acid production wastewater treatment process |
| WO2025183161A1 (en) * | 2024-02-29 | 2025-09-04 | 国立大学法人京都大学 | Biomass composition and production method for same |
| WO2025182032A1 (en) * | 2024-02-29 | 2025-09-04 | 国立大学法人京都大学 | Biomass composition and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3864432B2 (en) | 2006-12-27 |
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