JP2002191903A - Extraction method and apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an extraction method and apparatus capable of efficiently performing extraction and hydrothermal reaction, capable of efficiently treating extraction residue at a low cost by a simple device and easily adjusting the heat value of the extraction residue. SOLUTION: The substance to be treated such as a fermentation liquid or the like obtained in a fermentation tank 1 is supplied to an extractor 2 and brought into contact with the organic solvent supplied from a solvent storage tank 8 to extract a useful component and a solvent is separated from the extract in a solvent separator 6. If necessary, the solvent is separated from the extraction residue in a solvent recovering device 9 and, thereafter, the extraction residue is treated by hydrothermal reaction in a hydrothermal reactor 3. At this time, the organic solvent is supplied to the hydrothermal reactor 3 as fuel from the solvent storage tank 8 at least at the time of rising of the hydrothermal reactor 3 to be burnt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an extraction method for extracting useful components from an object to be treated such as a fermentation liquor using an organic solvent.

[0002]

2. Description of the Related Art It is useful when industrially producing useful components such as foods such as amino acids and nucleic acids or pharmaceuticals such as crude drugs and fat-soluble antibiotics by fermentation processes utilizing microorganisms such as bacteria and yeasts. Extraction and purification steps are generally required to separate the components. In this extraction step, an organic solvent such as water, alcohol (such as methanol), or acetone is used as the extract. In many cases, methanol or the like is selected because the operation is easy and the cost of the solvent is not so high. By this extraction step, an extract containing a useful component and an extraction residue from which the useful component has been removed are generated. An extract containing a useful component is separated into a useful component from a solvent by back extraction or the like to obtain a product. At this time, the separated organic solvent is circulated and used again for extraction. The extracted slag is disposed of as waste.

[0003] The extracted slag contains a residue of the substance to be treated and a part of the organic solvent, but when the fermented liquor is to be treated, it is discharged as an organic waste liquid containing a large amount of water. Conventionally, there is a biological treatment method as a method for treating extraction slag. In this case, however, there has been a problem that an organic solvent that cannot be completely recovered has an adverse effect on biological treatment, and stable treated water quality cannot be obtained. In addition, there is a method of dehydrating the extracted slag and then incinerating it, or a method of recovering the volatile organic solvent and then dehydrating and incinerating it. In this case, since a process of concentrating and dehydrating to a water content that can be incinerated is required, there has been a problem that the apparatus becomes large and initial investment is required.

On the other hand, as a method of treating organic waste liquid such as sewage sludge, a treatment method by a hydrothermal reaction has been proposed. In this method, an oxidizing reaction is caused by reacting an oxidizing agent with a reactant containing organic matter in a supercritical or subcritical state of water, and the organic matter in the reactant is almost completely decomposed in a short time. Can be. However, in the case of the hydrothermal reaction, when starting up or when the calorific value of the object to be treated is insufficient, it is necessary to supply an auxiliary fuel, and equipment for this is also required. In addition, when the extracted slag is treated by a hydrothermal reaction, there is a problem that it is difficult to adjust the amount of heat.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an extraction method and an apparatus which can efficiently perform extraction and hydrothermal reaction, and which can efficiently process extraction slag at a low cost with a simple apparatus. That is. Another object of the present invention is to obtain an extraction method and an apparatus that can easily adjust the calorific value of an extraction slag.

[0006]

The present invention is the following extracting method and apparatus. (1) An extraction step of extracting a useful component from an object to be treated using an organic solvent, a solvent separation step of separating the useful component and the organic solvent from the organic solvent containing the useful component, and an extraction residue generated in the extraction step is washed with water. A hydrothermal reaction step of treating by a thermal reaction,
A fuel supply step of supplying at least a part of the organic solvent obtained in the solvent separation step as fuel to the hydrothermal reaction step at least at the start-up of the hydrothermal reaction step. (2) The method according to the above (1), comprising a solvent recovery step of separating an organic solvent from the extracted residue. (3) an extractor that extracts a useful component by contacting the object to be treated with an organic solvent, a solvent separator that separates the useful component and the organic solvent from the organic solvent containing the useful component, and an extraction residue generated by the extractor. A hydrothermal reactor for processing by a hydrothermal reaction, a solvent supply system for supplying an organic solvent to the extractor, and an extraction slag supply system for supplying extraction slag from the extractor to the hydrothermal reactor were separated by a solvent separator. A fuel supply system for supplying at least a part of the organic solvent to the hydrothermal reactor as fuel. (4) The apparatus according to the above (3), further comprising a solvent recovery device for separating the organic solvent from the extraction residue.

[0007] In the present invention, the object to be treated is a substance containing useful substances as foods, pharmaceuticals and the like or raw materials thereof in a state that can be extracted with an organic solvent. As such a substance to be treated, there is an arbitrary substance such as a natural product or a synthetic product. The fermented liquid obtained by performing fermentation (culture) using microorganisms such as bacteria and yeast using these as a medium is treated according to the present invention. Suitable for.

[0008] The medium for fermentation includes a carbon source such as molasses, glucose and sucrose, a nitrogen source such as ammonia and ammonium sulfate, an organic nitrogen source such as peptone and meat extract, calcium salts and phosphates. And the like mixed with an inorganic salt. Depending on the type of useful substance to be produced, a precursor of an antibiotic or an inducer of an enzyme can be added. As microorganisms used for fermentation,
Mold, yeast, bacteria and the like. Useful substances produced by fermentation include fermented foods, pharmaceuticals, physiologically active substances, organic acids, fuel substances, enzymes, bacterial proteins, and the like.

In the present invention, in the step of extracting such an object to be treated, an organic solvent is used to extract useful components. Any organic solvent may be used as long as a useful component can be extracted from the material to be treated, and methanol, ethanol,
A volatile solvent such as acetone is preferred. The extraction is carried out by bringing the object to be treated into contact with an organic solvent, and the useful components are transferred to the organic solvent to obtain an extract. As the extractor, a known extractor such as a rotating disk type, a fence type, etc., for contacting an object to be treated with an organic solvent, particularly a solution contacting device can be used, and the organic solvent is supplied to the extractor. Contact the solvent supply system. It is preferable that the organic solvent is continuously supplied from the solvent supply system including the solvent storage tank to the extractor to perform extraction.

The extract from which the useful components have been extracted is introduced into a solvent separator in a solvent separation step, the organic solvent is separated by distillation, back extraction, membrane separation, etc., circulated to a solvent supply system, and the concentrate is purified. Thus, useful components can be obtained as products.

The extracted residue generated in the extraction step is subjected to an intermediate treatment such as solvent separation or the like, and then a hydrothermal reaction is performed in a hydrothermal reaction step to oxidatively decompose organic substances and other oxidizable substances. The hydrothermal reactor is configured to oxidatively decompose the extraction residue in a supercritical or subcritical state of water by a hydrothermal reaction in the presence of an oxidizing agent. Here, the hydrothermal reaction is a reaction in which a concentrate is oxidatively decomposed by an oxidation reaction in the presence of high-temperature, high-pressure water and an oxidizing agent in a supercritical or subcritical state. The supercritical state is a state of not less than 374 ° C. and not less than 22 MPa. The subcritical state is, for example, 374 ° C. or higher, 2.5 MPa or higher2
A state of less than 2 MPa or 374 ° C. or less, 22 MPa or more, or a state of 374 ° C. or less and less than 22 MPa but a high-temperature and high-pressure state close to a critical point.

The hydrothermal reactor supplies and burns an auxiliary fuel to bring it to a supercritical or subcritical state. In the present invention, at least a part of the organic solvent obtained in the solvent separation step is passed through a fuel supply system. It is configured to be supplied to the hydrothermal reactor and burned. Thus, the auxiliary fuel supply system can be omitted, and the hydrothermal reaction can be performed with a simple device and at low cost. It is preferable to supply an organic solvent to adjust the calorific value even when the calorific value of the extraction residue is insufficient. If organic solvents are circulated in the extraction process, impurities will accumulate,
It is necessary to withdraw each part, but if this extraction solvent is supplied to the hydrothermal reaction step as a waste solvent, the adjustment of the amount of heat in the hydrothermal reaction and the treatment of the waste solvent can be performed simultaneously, and the auxiliary fuel is also omitted. Can be. The organic solvent supplied to the hydrothermal reaction is not limited to the used waste solvent obtained from the extractor, and an unused organic solvent may be supplied from the solvent supply system of the extractor together with the waste solvent. it can.
Also in this case, the auxiliary fuel supply system for the hydrothermal reaction can be omitted.

In the extraction step, the organic solvent and the extraction conditions are generally selected so that the organic solvent moves to the extract side and almost no organic solvent remains on the extract residue side. When the amount of the extraction slag moves to a large amount, the heat of the extraction slag may be too high. In such a case, it is preferable to provide a solvent recovery unit in the extraction slag supply system to the hydrothermal reactor to separate and recover the organic solvent, and to adjust the calorific value. The recovered organic solvent can be circulated to the solvent supply system of the extractor.

The hydrothermal reaction is carried out in a hydrothermal reactor with the extraction slag mixed with an oxidizing agent, and these mixtures undergo a hydrothermal reaction inside the reactor. The oxidizing agents include air, oxygen, liquid oxygen, hydrogen peroxide, nitric acid, nitrous acid, nitrate,
Nitrite and the like can be used. The oxidizing agent may be supplied by being mixed with the extraction slag, or may be supplied as a multi-layer flow by using a double-hole nozzle at the supply port. If necessary, a catalyst, a neutralizing agent, and the like may be added. These may be mixed with the extraction slag or supplied separately to the reactor.

[0015] The hydrothermal reactor used in the present invention is formed of a heat-resistant, pressure-resistant material and a substantially vertical cylindrical reactor so as to perform a hydrothermal reaction in a supercritical or subcritical state. . When the supercritical or subcritical state is not reached only by the heat of reaction, an external heating means can be provided. The shape of the reactor may be a cylinder, an ellipsoid, or a polygonal cylinder, and the lower end may have a cone shape. When a hydrothermal reaction is performed in a supercritical or subcritical state using such a hydrothermal reactor, the organic substance to be reacted is oxidized by an oxidizing agent and is finally decomposed into water and carbon dioxide, or is reduced by hydrolysis. It is molecularized, and the inorganic substances are separated in a solid or molten state. After separating the solid, the reaction product is cooled, decompressed, and separated into a gas component and a liquid component.

As the above-mentioned hydrothermal reactor, those conventionally used for hydrothermal reactions can be used as they are, but as disclosed in JP-A-11-156186,
A mixed reaction zone with a backflow in the upper part, a substantially vertical reactor forming a plug-shaped flow reaction zone in the lower part, and a mixed flow of the reactant and the oxidant from the supply device provided in the upper part in a downward flow To form a mixed flow with backflow in the upper mixing reaction zone and perform a hydrothermal reaction, and form a parallel downward plug flow in the lower plug-like reaction zone to perform additional hydrothermal reaction Structures are preferred.

The material of the hydrothermal reactor is not limited, but a corrosion-resistant material such as Hastelloy, Inconel or stainless steel is preferable. Preferably, the hydrothermal reactor is provided with a corrosion resistant liner. The corrosion-resistant liner is not particularly limited, and a corrosion-resistant liner having a gap between the corrosion-resistant liner and the pressure load wall as disclosed in JP-A-11-156186 can be used. .

The hydrothermal reactor can be provided with cooling means for cooling the reaction mixture before discharging it from the outlet. The cooling means is not particularly limited, but water can be introduced into the reactor to cool it, and the inorganic salt can be dissolved to facilitate its discharge. In addition, water containing an acid or an alkali can be introduced into the reactor and cooled to neutralize the alkali or the acid. If the solid is very sticky, a mechanical removal device for removing the solid attached to the inner wall of the reactor can be provided. The mechanical removal device for removing solids is not particularly limited, but a substantially cylindrical scraper including a cutout window portion disclosed in Japanese Patent Application Laid-Open No. H11-156186 is preferred.

A separating means for separating solids in the reaction fluid discharged from the hydrothermal reactor can be provided. In particular,
In the supercritical reaction fluid, the inorganic salts are not dissolved but are contained as solids. Therefore, separation of the insolubilized inorganic material facilitates reuse of the treated water. The solids separating means is not particularly limited, and a container provided with an inlet for introducing a reaction fluid from the hydrothermal reactor and an outlet for discharging a fluid from which solids have been removed, and a container provided in the container and having the reaction fluid One provided with a means for removing and discharging the solid contained therein can be used. In the steps of cooling and depressurization, means for solid separation or gas-liquid separation may be included.

The means for initiating the reaction by the hydrothermal reactor is not particularly limited. Usually, the reactor is preheated to near a predetermined reaction temperature at the start of the reaction. The preheating can be carried out by providing a heating device in the reactor, or by introducing heated water or air provided in the workpiece and / or the oxidant supply passage. Also, usually, water or oxidizing agent is supplied to the reactor,
The pressure is increased to a predetermined pressure by a normally provided pressure regulating valve. After being adjusted to a predetermined temperature and pressure, a fluid containing mixed sludge, which is a reactant, is supplied to start a hydrothermal reaction.
Organic substances are decomposed by the reaction, and heat of reaction is generated. If a mixing reaction zone with a backflow is provided in the upper part of the hydrothermal reactor (upper part of the reactor), the reactant, oxidizing agent, reactor contents, etc. are sufficiently mixed by the mixing action with the backflow. The temperature of the fluid increases. As a result, the supplied reactant immediately starts a hydrothermal reaction, and a stable reaction is continued. The reaction fluid moves downward in the reactor, continuously reacts in the plug flow reaction zone, and is discharged from the outlet.
The length: diameter ratio of the reactor is preferably from 1: 1 to 100: 1.

The reaction fluid exiting the hydrothermal reactor is cooled and decompressed and separated into gas and liquid without separating the solid or after separating the solid. When a liquid is generated by cooling in the reactor, the liquid is separated from the liquid together with the solid upon exiting the reactor, and if necessary, further cooling and gas-liquid separation are performed. The water, gas, and solids finally produced are recovered as they are, reused as a substance, or discarded as they are or additionally processed.

[0022]

According to the present invention, efficient extraction and hydrothermal reaction can be carried out by supplying at least part of the organic solvent obtained in the solvent separation step as fuel at the start of the hydrothermal reaction step. The extraction slag can be efficiently treated with a simple apparatus and at low cost. In addition, the use of an organic solvent for adjusting the amount of heat or the separation of excess organic solvent from the extraction slag facilitates the adjustment of the amount of heat of the extraction slag.

[0023]

Embodiments of the present invention will be described below with reference to the drawings. 1 and 2 are flowcharts showing the extraction device of the embodiment.

1 and 2, 1 is a fermenter, 2 is an extractor, and 3 is a hydrothermal reactor. The fermenter 1 is connected to a seed culture tank 4 and a medium storage tank 5 by supply paths L1 and L2. A fermentation liquid supply path L3 from the fermenter 1 communicates with the upper part of the extractor 2.

The extractor 2 is composed of a rotating disk type liquid-liquid contacting device, and a multi-stage rotating disk 2b is arranged between the fence steps 2a provided on the inner periphery in multiple stages. An extract extraction path L4 is connected to a solvent separator 6 such as a distillation apparatus at the upper part of the extractor 2. A useful component extraction path L5 is connected to the outside from the lower part of the solvent separator 6 and a solvent extraction path L6 is connected to the upper part. Communicates with the solvent storage tank 8 via the cooler 7. From the lower part of the solvent storage tank 8, the solvent supply path L7 communicates with the lower part of the extractor 2, and the fuel supply path L8 communicates with the upper part of the hydrothermal reactor 3. A solvent supply path L9 communicates with the solvent supply path L7. In FIG. 2, the extraction residue supply path L11 is connected directly to the upper part of the hydrothermal reactor 3 from the bottom of the extractor 2 through the solvent recovery unit 9 such as a distillation apparatus and the separation residue supply path L12 in FIG. From the upper part of the solvent recovery unit 9, a solvent extraction path L <b> 13 communicates with the upper part of the solvent storage tank 8 via the cooler 11.

An oxidizing agent supply path L14 is connected to the upper part of the hydrothermal reactor 3 from the oxidizing agent storage tank 11. From the lower part of the hydrothermal reactor 3, a reaction fluid outlet passage L <b> 15 communicates with the gas-liquid separator 13 via the cooler 12. A gas outlet L16 communicates with the upper part of the gas-liquid separator 13 and a liquid outlet L1 with the lower part.
7 is in contact. L21, 22, and 23 are cooling channels, P
1 to P4 are pumps.

The extraction method using the above-described apparatus is performed as follows. First, the seed microorganisms cultured in the seed culture tank 4 are supplied to the fermentation tank 1 from the supply path L1.
Fermentation (cultivation) is performed by supplying a medium through 2 to produce useful components by the action of microorganisms. The fermentation liquor is supplied from the fermentation liquor supply line L3 to the upper part of the extractor 2 as a substance to be treated.
Perform the extraction.

In the extractor 2, an organic solvent is supplied from the solvent storage tank 8 through the solvent supply path L7 while flowing the fermentation liquid in a downward flow, and while rotating the rotating disk 2b, the fermentation liquid is caused to flow in the upward flow, thereby causing liquid-liquid contact. Transfer the useful component to the organic solvent. At this time, a new solvent can be supplied from the solvent supply path L9. The extract collected at the upper part of the extractor 2 is taken out from the extract outlet L4 to the solvent separator 6, where the solvent is separated by distillation or the like, and the separated solvent is cooled and condensed by the cooler 7, and the solvent is stored in the solvent storage tank. Cycle to 8. The concentrated liquid from which the solvent has been separated is taken out from the useful component take-out path L5 as a useful component and sent to the purification step.

The extracted slag collected at the lower portion of the extractor 2 is taken out from the extracted slag supply line L11, and is directly connected to the hydrothermal reactor 3 in FIG. 2 and the solvent recovery unit 9 and the separated slag supply line L12 in FIG. Supplied at the top. FIG. 2 is suitable for treating an extraction slag with a small amount of the organic solvent mixed therein, and FIG. 1 is suitable for processing an extraction slag having a large amount of the organic solvent mixture.
In FIG. 1, the extraction slag entering the solvent recovery unit 9 separates and recovers an organic solvent by distillation or the like, and the recovered solvent is passed through a solvent extraction path L13.
And cooled by the cooler 11 and circulated to the solvent storage tank 8. The separated slag is supplied to the hydrothermal reactor 3 from the separated slag supply path L12. In this case, the amount of heat of the extraction slag is adjusted by removing the organic solvent from the extraction slag.

In the hydrothermal reactor, the extraction slag is supplied from the separation slag supply passage L12 or the extraction slag supply passage L11.
By supplying the oxidizing agent from the oxidizing agent storage tank 11 through the oxidizing agent supply passage L14, a hydrothermal reaction is performed in a supercritical or subcritical state, and organic substances and other oxidizable substances in the extraction slag are oxidatively decomposed.

When the hydrothermal reactor 3 is started, an auxiliary fuel is usually injected. In the present invention, a part of the organic solvent in the solvent storage tank 8 is supplied to the hydrothermal reactor 3 from the fuel supply passage L8 as fuel. It can be burned to a supercritical or subcritical state, and auxiliary fuel and fuel supply equipment can be omitted. Even when the amount of heat of the extracted slag is insufficient, the fuel supply path L8
When the organic solvent is supplied from, the calorific value of the extraction slag as the reactant can be adjusted. Since the organic solvent used for extraction in the extractor 2 accumulates impurities, it is necessary to extract a part of the organic solvent and discharge it to the outside of the system. However, since such a waste solvent can be used as fuel, the hydrothermal reaction can be efficiently performed. It can be carried out.

The reaction fluid generated by the hydrothermal reaction in the hydrothermal reactor 3 is taken out from the reaction fluid outlet passage L15, and
2 to produce a liquid, gas-liquid separation is performed by the gas-liquid separator 13, gas is taken out from the gas take-out path L16, and liquid is taken out from the liquid take-out path L17. Or collected and used effectively.

In the above method, a part of the organic solvent used in the extractor 2 is supplied as a fuel at least when the hydrothermal reactor 3 is started up, so that the extraction and the hydrothermal reaction can be performed efficiently and the simple process can be performed. The extraction slag can be efficiently treated with the apparatus and at low cost. In addition, the use of an organic solvent for adjusting the amount of heat or the separation of excess organic solvent from the extraction slag facilitates the adjustment of the amount of heat of the extraction slag. In addition, when used for adjustment of extraction slag, even if there is a fluctuation in the amount of heat
By using the solvent storage tank 8, an amount of the organic solvent that can withstand the fluctuation can be held.

[Brief description of the drawings]

FIG. 1 is a flowchart of an extraction apparatus according to an embodiment.

FIG. 2 is a flowchart of an extraction device according to another embodiment.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Fermentation tank 2 Extractor 3 Hydrothermal reactor 4 seed culture tank 5 Medium storage tank 6 Solvent separator 8 Solvent storage tank 9 Solvent recovery unit 13 Gas-liquid separator

 ──────────────────────────────────────────────────続 き Continued on the front page (71) Applicant 598124412 General Atomics Inc. San Diego, California, USA General Atomics Coat 3550 (72) Inventor Hironori Kaku 3-4-7 Nishishinjuku, Shinjuku-ku, Tokyo No. Kurita Kogyo Co., Ltd. F-term (reference) 4B029 AA02 BB02 BB07 BB08 CC01 DG10 4D056 AB12 AC01 BA16 CA22 DA01 DA02

Claims (4)

[Claims] 1. An extraction step of extracting a useful component from an object to be treated using an organic solvent, a solvent separation step of separating the useful component and the organic solvent from the organic solvent containing the useful component, and an extraction residue generated in the extraction step And a fuel supply step of supplying at least a part of the organic solvent obtained in the solvent separation step as fuel to the hydrothermal reaction step at least at the time of startup of the hydrothermal reaction step. Including extraction methods. 2. The method according to claim 1, further comprising a solvent recovery step of separating an organic solvent from the extracted residue. 3. An extractor for extracting a useful component by contacting an object to be treated with an organic solvent, a solvent separator for separating the useful component and the organic solvent from the organic solvent containing the useful component, and an extraction produced by the extractor A hydrothermal reactor for treating the slag by a hydrothermal reaction, a solvent supply system for supplying an organic solvent to the extractor, an extraction slag supply system for supplying the extraction slag from the extractor to the hydrothermal reactor, and a solvent separator. A fuel supply system for supplying at least a part of the separated organic solvent as fuel to the hydrothermal reactor. 4. The apparatus according to claim 3, further comprising a solvent recovery device for separating an organic solvent from the extraction slag.