CN100482336C - Method for producing product decomposed with subcritical water and apparatus for decomposition treatment with subcritical water - Google Patents

Method for producing product decomposed with subcritical water and apparatus for decomposition treatment with subcritical water Download PDF

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Publication number
CN100482336C
CN100482336C CNB2005800048052A CN200580004805A CN100482336C CN 100482336 C CN100482336 C CN 100482336C CN B2005800048052 A CNB2005800048052 A CN B2005800048052A CN 200580004805 A CN200580004805 A CN 200580004805A CN 100482336 C CN100482336 C CN 100482336C
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subcritical water
reaction vessel
water
treated
subcritical
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CN1917941A (en
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吉田弘之
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Osaka Prefecture University
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Osaka Industrial Promotion Organization
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    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Abstract

A method for producing a product decomposed with a subcritical water, which comprises pulverizing a material to be treated in advance into particles, mixing the particles with water to prepare a slurry, pressurizing the slurry with a pressing means (1), heating the pressurized slurry with a heating means (2) to form a slurry in a subcritical state, introducing the slurry in a subcritical state from an introduction port (8) to the bottom of a reaction vessel (3), to form, from the bottom, a fixed layer, a fluidized layer and a layer being dissolved in a subcritical water respectively, and taking out a layer being dissolved in a subcritical water from anyone of the discharge ports (101) to (106) provided at upper and side portions of the reaction vessel (3), wherein the selection of an appropriate port from the above discharge ports allows the adjustment of the residence time of the subcritical water, resulting in the adjustment of the reaction time of the decomposition with the subcritical water.

Description

The production method of subcritical water resolution process thing and subcritical water resolution process thing process units
Technical field
The present invention relates to the production method and the subcritical water resolution process thing process units of subcritical water resolution process thing.
Background technology
As the method that from castoff, culled wood the like waste, reclaims the known use subcritical water of the method supercritical water hydrolysis of useful thing.For example, utilize the subcritical water supercritical water that the cellulose that contains in a large number in the biomass, starch etc. are carried out decomposition reaction, be decomposed into monosaccharide, oligosaccharides, the method that their are reclaimed.Gained monosaccharide, oligosaccharides further carry out alcohol fermentation or methane fermentation, are transformed to the ethanol, the methane gas (with reference to patent documentation 1) that are more prone to utilize thus.By this method, in advance the timber the like waste is pulverized, corpusculed, with itself and water mixed serumization, utilize the subcritical water supercritical water to carry out decomposition reaction then.
But this method is difficult to control decomposition reaction.React excessive, then resolve into carbon dioxide and water, can't reclaim useful thing.On the contrary, decompose inadequate words, reaction residues is too much, the treatment effeciency variation.Think that thus reason that this method is difficult to control decomposition reaction is owing to utilize the hydrolysis of subcritical water etc. to carry out on the solid formation branch surface of discarded object.For example, in the cellulose decomposition reaction that utilizes subcritical water or supercritical water to carry out, as the decomposition reaction velocity of the monose of analyte or oligosaccharides decomposition reaction velocity faster than cellulose itself.Therefore, monose or oligosaccharides are broken down into organic acid, carbon dioxide or water, perhaps polymerization carbonization mutually.
As the method that addresses this problem, following method (with reference to patent documentation 2) has been proposed.At first, cellulose powder is placed on two ends is equipped with in the pipe of sintering filter of aperture 5 μ m, the water of continuous flow subcritical state is extracted in the cellulose powder surface with subcritical water simultaneously and decomposes the oligosaccharides that generates.Then, the quenching subcritical water is fetched into outside the reactor simultaneously, prevents side reactions such as oligosaccharides decomposition thus.But,, be unsuitable for large-scale production because this method is an intermittent reaction.And the pore with sintering filter is by multiple product blocking problem.
In addition, proposed the use supercritical water, on the fluidized bed of special shape, decomposed and can dissolve e-machine chip, waste plastics etc., separates inorganic solid form minute after, utilize high-pressure reactor to be decomposed into the method (with reference to patent documentation 3) of gas and inorganic salts fully.The device of Shi Yonging is to be made of the cylindric fluidized bed reactor with vertical isolation wall in the method, and from reactor lower part pressurized delivered supercritical water, the crushed material that is pressed into discarded object from reactor top is dispersed in the slurries the supercritical water.As a result, contain the discarded object of organic principle in case behind the vertical wall part bottom that in reactor, descends, dives, also flow into the opposition side of reaction vessel.At this moment, therefore organic principle flows out from reactor top owing to be dissolved in the supercritical water.And then in high-pressure reactor, adding oxidant, the organic principle that is dissolved in supercritical water is decomposed into gas and inorganic salts such as carbon dioxide fully.In addition, the inorganic powders such as pottery that contain in discarded object are discharged from fluidized bed reactor top.In this method, at discarded object during comprise that certain stream in the fluidized bed reactor moves, organic matter is decomposed and can dissolve by supercritical water. because conduct reaction and extraction solvent use the water of the little supercriticality of density, therefore this method is suitable for the pottery that density is big, waste plastics etc. and is decomposed into gas and inorganic salts fully, perhaps decomposes inorganic solid content matter.
But, become the density that approaches supercritical water owing to contain the organic waste that the high solid formation of moisture content divides, therefore in order to control decomposition reaction or to obtain aspect the specific analyte with high yield, this method also has problem.In addition, therefore this method is installed shape and is become complicated owing to be that supercritical water is pressed in the fluidized bed from different input ports with organic waste, for be pressed into need at least 2 costlinesses high pressure press-in device (pressue device).And, for the corrosivity of resistant to supercritical water, must use the material of costlinesses such as the anti-corrosion Langaloy of haas troy, dilval as the material of reactor.Therefore has the problem that installation cost uprises.
In addition, proposed to be directed into the reaction vessel method of resolution process organic waste (patent documentation 4) by the mixed serum of subcritical water and organic waste being sprayed from the top of resistance to pressure reaction vessel.But, also be difficult to control the decomposition of organic waste by this method.
Patent documentation 1: TOHKEMY 2001-262162 communique
Patent documentation 2: Japanese kokai publication hei 10-327900 communique
Patent documentation 3: TOHKEMY 2002-210348 communique
Patent documentation 4: TOHKEMY 2001-246239 communique
Summary of the invention
Invent technical problem to be solved
Therefore, the method and apparatus of the object of the present invention is to provide in the subcritical water resolution process continuously, efficient being produced useful thing well.
Other purposes of the present invention are to be provided in the continuous subcritical water resolution process of the object being treated that contains solid content; can control object being treated decomposition reaction, can change on a large scale and then can reduce installation cost, optionally with the method and apparatus of the required useful thing of high efficiency production.
The method of technical solution problem
The inventor etc. investigate the decomposition development principle of the solid content of subcritical state in order to solve the problems of the technologies described above, and found that following method and apparatus.That is, the present invention is as described below.
Under the subcritical state of water,, decompose and sharply carry out though also be not under the supercriticality.The object being treated that is supplied to from introducing port reaction vessel with the water of subcritical state in case contact, then decompose through the time carry out.That is, with corresponding degraded carrying out of holdup time.If the decomposition of object being treated is excessively carried out, then organic matter is broken down into carbonic acid gas and water, becomes to be collected in useful things such as decomposing the stage obtains in the way organic acid, amino acid.Therefore, in order to collect useful thing, must decompose the moment that is broken down into required useful thing by appropriateness, the liquid that will contain analyte takes out from reaction vessel.The liquid that decomposition is proceeded to suitable decomposing state from reaction vessel takes out, and returns to common state from subcritical state, and then the dissolving power of water descends.Therefore, the low composition of hydrophily in oil reservoir, composition that hydrophily is high separates by layering in water layer, can reclaim useful thing efficiently.
Among the present invention, the liquid that will contain analyte takes out from one or more export mouths continuously, forms stable or pseudo-stable CONCENTRATION DISTRIBUTION in reaction vessel.The holdup time of object being treated is by the distance and the flow velocity decision of distance introducing port.That is, the CONCENTRATION DISTRIBUTION of required useful thing is corresponding with the distance apart from introducing port.By formation of the present invention,, therefore can efficient reclaim useful thing well from the export mouth of being located at the high position of required analyte concentration because above-mentioned required analyte is taken out.It should be noted that also to have and do not form the situation that steady concentration distributes.For example, when decomposing the organic matter attached to mud or sand, undecomposed sand, mud are put aside in the tower bottom as fixed bed or fluidized bed.For fear of this situation, the solid conveying end is set at the bottom of tower, when above-mentioned situation takes place, can from here solids be taken out off and on.
It should be noted that owing to be not subcritical state, therefore decomposition stops if will containing the liquid of analyte from reaction vessel takes out. still, during stopping fully, decompose in the reality and all carrying out until decomposition.Therefore, the liquid that preferably will contain analyte from following position takes out, and described position is compared with the position that required useful substrate concentration becomes the peak, a little near introducing port.In addition, often decomposing certain being decomposed during thing, export mouth is fixed on the optimum position in advance and gets final product; When the processing difference is decomposed thing, can consider position, taking-up amount, the crushing of export mouth, suitably set.
Maximum of the present invention is characterized as, in order fully to decompose object being treated, until the solid content of object being treated decompose fully or in the solid content that constitutes by inorganic matter and organic matter as bone contained organic matter all disappear, above-mentioned solid content is stayed in the reaction vessel; On the other hand, for the composition excessive decomposition that suppresses to dissolve the object being treated in subcritical water or suppress the carbonization that thermal decomposition causes, can adjust subcritical water arbitrarily and be trapped in time in the reaction vessel.The present invention is the proportion that utilizes gravity and solid content, in fixed bed, fluidized bed and subcritical water dissolving layer (piston fluid layer) three layers, form above-mentioned fluidized bed and subcritical water solution layer at least by this order, with regard to above-mentioned subcritical water dissolving layer, flow through distance and flow velocity by adjusting it, make the holdup time of holdup time of above-mentioned solid content and subcritical water different, adjustment can be dissolved the degree of decomposition of the composition in the above-mentioned object being treated of subcritical water, reclaims the production method of target resolution process thing.
That is, decompose inadequate solid content and stay on fixed bed and the fluidized bed, accept decomposition reaction by subcritical water.On the other hand, the composition that produces by this decomposition is dissolved in the subcritical water, is positioned at subcritical water layer.This subcritical laminar flow is to the downstream direction of reaction vessel.Therefore, flow through distance and flow velocity, can adjust the time of decomposition reaction by adjusting it.Take out from reaction vessel if will flow through part or all of subcritical water dissolving layer of suitable distance, stop decomposition reaction, then more decomposition can not take place, can take out the target analyte.For example, as bone etc., be not organic matter when solid content but when containing organic inorganic matter, can dissolve by the decomposition that subcritical water carries out in the bone, particle is cut apart thus, particle diameter diminishes, and finally becomes calcium phosphate powder.In this process, form by particle diameter and begin the fixed bed that the particle of particle diameter constitutes greater than liquidation; Begin the fluidized bed that the particle of particle diameter constitutes by particle diameter less than liquidation; And further corpusculed, become identical speed, be the state of piston flow with subcritical water, contain 3 layers of subcritical water dissolving layer of powdered calcium phosphate.With regard to this subcritical water dissolving layer, by adjusting the distance that this laminar flow is crossed, can adjust organic degree of decomposition, can reclaim the target analyte.Even if it should be noted that when organic matter in the above-mentioned bone is toxicants such as pathogenicity prion or pathogenicity material, also they can be decomposed by this decomposable process.In addition, as plastics, when broken particle itself diminishes owing to subcritical water decomposes,, form the zone of fixed bed, fluidized bed and piston flow with above-mentioned same.By this method, can be better than step continous way with efficient and handle.
Concrete grammar of the present invention, the device as follows.
The production method of subcritical water resolution process thing of the present invention is situated between by the introducing port on the reaction vessel that is located at the subcritical state that is maintained at water in the container for (1), be supplied to object being treated in the reaction vessel continuously, (2) liquid that will contain analyte takes out from being located at export mouths one or more on the above-mentioned reaction vessel continuously, adjust the holdup time of the liquid that contains above-mentioned analyte in reaction vessel, the position of described export mouth is different with the set position of introducing port.
The production method of subcritical water resolution process thing of the present invention is situated between by the introducing port on the reaction vessel that is located at the subcritical state that is maintained at water in the container for (1), be supplied to object being treated in the reaction vessel continuously, (2) liquid that will contain analyte takes out from being located at export mouths one or more on the above-mentioned reaction vessel continuously, the steady concentration that produces required analyte in reaction vessel distributes, the position of described export mouth is different with the set position of introducing port, (3) in above-mentioned one or more export mouths, above-mentioned required analyte is taken out from the export mouth of being located at the high position of required analyte concentration.It should be noted that here " continuously " contain the interrupted meaning.
The production method of subcritical water resolution process thing of the present invention is following carries out, promptly (1) is situated between by the introducing port on the vertical response container that is located at the subcritical state that is maintained at water in the container, it is slow to contain the decomposition rate that is undertaken by subcritical water, the object being treated that proportion is different from the solid content of subcritical water is supplied in the reaction vessel continuously, (2) in being located at one or more export mouths of above-mentioned reaction vessel, adjust the position and the derived quantity thereof that derive the liquid that contains analyte, in the subcritical water that remains static, make opposite with the sedimentation of above-mentioned solid content or the direction of floating, wait a moment in its sinking speed or float the stationary flow of speed, described export mouth is located on the position different with the set height of introducing port, (3) in aforementioned stable stream, at least form from the above-mentioned solid content in upstream of liquid stream and decomposed by above-mentioned subcritical water, corpusculed, product that fluidized bed that this particulate flows in liquid stream and above-mentioned object being treated further become corpusculed or complete liquefiable product and the subcritical water dissolving layer that flows with subcritical water, (4) and then, kind according to object being treated, form the fixed bed that rests on certain position according to above-mentioned liquid stream solid content in the upstream of above-mentioned fluidized bed, (5) any in the above-mentioned one or more export mouths of use, the liquid that will contain required analyte from above-mentioned subcritical water dissolving layer takes out from reaction vessel.
In addition, the production method of subcritical water resolution process thing of the present invention also can followingly be carried out, promptly (1) is in the subcritical water of inactive state, the mixture of the object being treated that contains solid content and subcritical water is flowed along the direction in contrast to above-mentioned solid content moving direction, (2) in above-mentioned liquid stream, at least form from the above-mentioned solid content in upstream of liquid stream and decomposed by above-mentioned subcritical water, corpusculed, product that fluidized bed that this particulate flows in liquid stream and above-mentioned object being treated further become corpusculed or complete liquefiable product and the subcritical water dissolving layer that flows with subcritical water, (3) and then, kind according to object being treated, form the fixed bed that rests on certain position according to above-mentioned liquid stream solid content in the upstream of above-mentioned fluidized bed, (4) adjust the distance that flows through of above-mentioned subcritical water dissolving layer, make the holdup time of holdup time of above-mentioned solid content and above-mentioned subcritical water different, adjustment can be dissolved in the degree of decomposition of the composition of the above-mentioned object being treated of subcritical water, obtains target resolution process thing.
In this constitutes, same with said method, also can take out the target analyte.
With regard to aforementioned production method, the sedimentation in the mixture that remains static of above-mentioned solid content, said mixture flows to can be opposite with gravity direction, suspends in the mixture that remains static, and the flow direction of said mixture can be a gravity direction.Among the present invention, during sedimentation, the flow direction of said mixture is preferably opposite with gravity direction in the said mixture of inactive state for above-mentioned solid content.In addition, when above-mentioned solid content suspended in the said mixture of inactive state, the flow direction of said mixture was preferably gravity direction.
In aforementioned production method, the flow velocity of said mixture needs only smaller or equal to the sinking speed of said mixture in the mixture that remains static or floats speed.
Said mixture is as long as be slurries.
In the aforementioned production method, the reaction temperature of subcritical water hydrolysis is that 130～374 ℃ of scopes, reaction pressure get final product more than or equal to the Saturated water vapor pressure in reaction temperature.
Can use supercritical water to replace subcritical water with subcritical water among the present invention.Above-mentioned subcritical water is 134～374 ℃ of pressure 0.3～100MPa of temperature for example, is preferably 150～350 ℃ of pressure 0.5～100MPa of temperature, is more preferably 170～300 ℃ of pressure 0.8～100MPa of temperature.
Above-mentioned object being treated can be to be selected from food, livestock products, agricultural product, aquatic products, timber, natural organic matter, plastics, organochlorine compounds, rubber, fiber and their discarded object, following at least a in water treatment discarded object and the wastewater treatment discarded object.
The production method of above-mentioned subcritical water resolution process thing can be used with lower device and implement.
Subcritical water decomposing processor of the present invention possesses: use subcritical water to decompose the reaction vessel of object being treated, in order to form the heater that the subcritical state of keeping water heats the mixture that is made of water and above-mentioned object being treated, the pressue device that pressurizes, be used for above-mentioned object being treated is imported to the gatherer of reaction vessel, be used for above-mentioned object being treated is directed into the introducing port of reaction vessel, the export mouth that the mixture of analyte and water is derived from reaction vessel; Above-mentioned export mouth is arranged on the position different with the set position of above-mentioned introducing port, can adopt a plurality of positions.
In addition, subcritical water decomposing processor of the present invention possesses: use subcritical water to decompose the vertical response container of object being treated, in order to form the heater that the subcritical state of keeping water heats the mixture that is made of water and above-mentioned object being treated, the pressue device that pressurizes, be used for above-mentioned object being treated is imported to the gatherer of reaction vessel, be used for above-mentioned object being treated is directed into the introducing port of reaction vessel, the export mouth that the mixture of analyte and water is derived from reaction vessel; Above-mentioned reaction vessel perpendicular is provided with, above-mentioned introducing port is located at the upper end of above-mentioned reaction vessel and at least one place of bottom, in being in the subcritical water of static situation, make the mixture of the object being treated that is imported into and subcritical water flow to the opposite direction of above-mentioned solid content moving direction, in above-mentioned liquid stream, form at least and decomposed corpusculed by above-mentioned subcritical water from the above-mentioned solid content in upstream of liquid stream, the fluidized bed that this particulate moves in liquid stream, and the above-mentioned object being treated subcritical water dissolving layer that becomes the product of further corpusculed or can dissolve product fully and flow with subcritical water, and then form the fixed bed that stops at certain position according to liquid stream solid content in the upstream of above-mentioned fluidized bed according to object being treated, simultaneously the subcritical water dissolving layer is derived, can set the desired location of described export mouth, so that can adjust the distance that flows through of subcritical water dissolving layer.
Above-mentioned export mouth can be formed on the above-mentioned sidewall of reactor along a plurality of positions of above-mentioned liquid flow path direction.Above-mentioned export mouth can also be can be along the mobile continuously export mouth of above-mentioned flow direction.
Above-mentioned vertical response container can possess can observe inner finder.In addition, above-mentioned vertical response container is a cylindrical container, and above-mentioned introducing port is circular, and the internal diameter of this introducing port is that 1/5～1/15 times scope of above-mentioned vertical cylinder shape inside diameter of vessel gets final product.
Said apparatus also can be the device that possesses a plurality of above-mentioned vertical response containers.
In addition, above-mentioned subcritical water decomposing processor possesses the cylindric secondary response container of the circulation cast that is connected in above-mentioned reaction vessel export mouth, and the internal diameter of the cylindric secondary response container of above-mentioned circulation cast is that 1～1/5 times scope of above-mentioned vertical cylinder shape inside diameter of vessel gets final product.
The cylindric secondary response container of above-mentioned circulation cast is a plurality of, as long as can be connected in series and/or be connected in parallel between the cylindric secondary response container of these circulation casts.
The heating-cooling device that preferably can possess the reaction temperature in the cylindric secondary response container of the above-mentioned circulation cast of control.
On above-mentioned vertical response container, be provided with counterbalance valve, use this counterbalance valve can control the interior reaction pressure of above-mentioned vertical response container.
The dead ahead of above-mentioned counterbalance valve possesses cooling tube.
The invention effect
Production method and subcritical water decomposing processor by subcritical water resolution process thing of the present invention, by adjusting the holdup time of subcritical water dissolving layer, set the reaction time of solid content and the reaction time of dissolved matter arbitrarily but can in reaction vessel, distinguish.As a result, can easily control the decomposition reaction of object being treated.In addition, because the production method and the subcritical water decomposing processor of subcritical water resolution process thing of the present invention can be handled object being treated continuously, therefore be suitable for extensiveization.And, compare with supercriticality, because subcritical state is to react, therefore can reduce installation cost under more stable condition.By adjusting the holdup time of subcritical water dissolving layer, can be optionally with the required useful thing of high produced in yields.
Description of drawings
[Fig. 1] Fig. 1 is the outline pie graph that is used to illustrate subcritical water decomposing processor one example of the present invention.
[Fig. 2] Fig. 2 is the outline pie graph that is used to illustrate other examples of subcritical water decomposing processor of the present invention.
[Fig. 3] Fig. 3 is the outline pie graph that is used to illustrate other examples of subcritical water decomposing processor of the present invention.
[Fig. 4] Fig. 4 is the outline pie graph that is used to illustrate other examples of subcritical water decomposing processor of the present invention.
[Fig. 5] Fig. 5 is with respect to the chart of each phase yield of holdup time in expression one embodiment of the invention.
[Fig. 6] Fig. 6 is with respect to the chart of the aqueous phase organic acid yield of holdup time in expression one embodiment of the invention.
[Fig. 7] Fig. 7 is with respect to the chart of the aqueous phase amino acid yield of holdup time in expression one embodiment of the invention.
[Fig. 8] Fig. 8 is with respect to the chart of the aqueous phase organic acid yield of holdup time in the expression other embodiments of the invention.
[Fig. 9] Fig. 9 is with respect to the chart of the aqueous phase amino acid yield of holdup time in the expression other embodiments of the invention.
[Figure 10] Figure 10 be expression the present invention in addition among other embodiment with respect to the chart of the aqueous phase organic acid yield of holdup time.
[Figure 11] Figure 11 be expression the present invention in addition among other embodiment with respect to the chart of the aqueous phase amino acid yield of holdup time.
[Figure 12] Figure 12 be expression the present invention in addition among other embodiment with respect to the chart of the aqueous phase organic acid yield of holdup time.
[Figure 13] Figure 13 be expression the present invention in addition among other embodiment with respect to the chart of the aqueous phase amino acid yield of holdup time.
[Figure 14] Figure 14 be expression the present invention in addition among other embodiment with respect to the chart of the aqueous phase organic acid yield of holdup time.
[Figure 15] Figure 15 be expression the present invention in addition among other embodiment with respect to the chart of the aqueous phase amino acid yield of holdup time.
Symbol description
1 pressue device
2 heaters
3 reaction vessels
4 cooling tubes
5 counterbalance valves
The thing recycling can is finished in 6 reactions
7 effluent recycling cans
8 introducing ports
9 outlets
10 cooling tubes
11 counterbalance valves
12 secondary response containers
13 finders
14 pliability pipes
15 suction portions
16 chains
17 groove internal gears
101,102,103,104,105,106,107,108 export mouths
201,202,203 export mouths
The specific embodiment
[object being treated]
Object being treated by the production method of subcritical water resolution process thing of the present invention and subcritical water decomposing processor resolution process is natural organic matter and their discarded objects such as livestock products, agricultural product, aquatic products, xylplant, food and castoff, the synthesis of organic substance that contains plastics, organochlorine compounds, rubber, fiber and their discarded object, and contain following water treatment discarded object, wastewater treatment discarded object of activated sludge, excess sludge etc.These object being treateds can be a kind of solid contents, also can be the mixtures of multiple solid content.In addition, these object being treateds can also contain water.
As above-mentioned object being treated; for example can enumerate the meat, bone, brain, skin, internal organ, fat, meat meal tankage, pathogenicity prion etc. of animals such as internal organ, fish-bone, ox or horse of internal organ, the oyster of black intestines bag, the scallop of internal organ, the scallop of fish offal, cuttlefish; the core of edible wild herbs disintegrating slag, corn, straw etc.; the trunk or the bark of wood, bamboo; big sawdust, culled wood etc., activated sludge, excess sludge, animal wastes etc.When object being treated contains very hard solid content such as bone, owing to reason such as the used pump of size, the pressurization of device introducing port, pipeline or need to shorten the reaction time, object being treated normally pulverized or fragmentation after again for decomposing in subcritical water.
But the object being treated that uses in the production method of subcritical water resolution process thing of the present invention and treating apparatus is not limited only to contain the object being treated of solid content.For example, can with in subcritical water for slightly solubility, in subcritical water, be into phase liquid, have in subcritical water suspend or the liquid of sedimentation character as object being treated.By the present invention, also can adjust the reaction time of liquid and the reaction time of decomposing the subcritical water dissolved matter of this liquid respectively for this liquid.In addition, if use method of the present invention or device, even if the object being treated that is made of the liquid that is dissolved in the subcritical water also can be selected the condition of suitable subcritical water decomposition reaction.As a result, even if only be the object being treated of the class I liquid I of PCB (polybiphenyl), also can carry out resolution process.This object being treated can also be to contain organic inorganic matter.
In addition, the object being treated that uses in the production method of subcritical water resolution process thing of the present invention and treating apparatus can also contain the indissoluble inorganic matter of subcritical water.For example can enumerate the mud that contains stone, sand or sheet metal as this object being treated, contain the FEP (fiber-reinforced plastic) of glass fibre etc.As described later, device of the present invention uses the vertical response container.Above-mentioned indissoluble inorganic matter is trapped in the bottom of reaction vessel.Therefore, by discharging the inorganic matter that is trapped in reaction container bottom at any time, can carry out resolution process continuously.
Among the present invention, be included in " solid content " in the object being treated and be preferably and contain organic solid content.In this solid content, the hydrolysis, the thermal decomposition that are caused by subcritical water take place on the solid content surface.Therefore, decomposed fully until solid content and needed certain hour.When this solid content decomposes, become the reason that eyelet stops up in existing continous way device.In addition, when this solid content decomposes, be dissolved in the solid content composition excessive decomposition of subcritical water at first or because thermal decomposition and charing in the batch (-type) device, not the energy efficiency useful thing of productive target well.
The density that the density of above-mentioned solid content (proportion) is greater than or less than subcritical water gets final product.Its reason is, the decomposition that the subcritical water that the present invention relates to causes utilizes the sedimentation or the come-up of contained solid content in the mixture of object being treated and subcritical water.
[production method of subcritical water resolution process thing]
The production method of subcritical water resolution process thing of the present invention preferably uses subcritical water decomposing processor of the present invention to carry out.The production method of subcritical water resolution process thing is described in the explanation device therefore.
[subcritical water decomposing processor]
(embodiment 1)
Fig. 1 is for showing the notion pie graph of reaction unit one example that embodiment of the present invention 1 relates to.As shown in the drawing, this device possesses reaction vessel 3, pressue device 1, heater 2, cooling tube 4, counterbalance valve 5, reacts and finish thing recycling can 6 and effluent recycling can 7.In the device of Fig. 1, heater 1 also is a mixture introducing apparatus simultaneously.This reaction vessel 3 is vertical, cylindric, the perpendicular setting.Be provided with introducing port 8 and outlet 9 in the bottom of this reaction vessel 3.On above-mentioned introducing port 8, be connected with pressue device 1 and heater 2 by pipe.In addition, effluent recycling can 7 Jie are connected in outlet 9 by cooling tube and counterbalance valve 11.On the head of reaction vessel 3 and sidewall, be provided with export mouth.In the example of Fig. 1, be provided with 8 outlets 101～106 altogether.Outlet 101～106 is situated between and is connected in reaction by separately pipe and finishes thing recycling can 6.
Use following the carrying out of resolution process of the object being treated of Fig. 1 device.At first, pulverize object being treated in advance and make it become particle, with water hybrid modulation slurries.These slurries are sent to pressue device 1 pressurization by pipe.Then, pressurized slurries are sent to heater 2 heating, become subcritical state.The slurries of subcritical state are fed to the bottom of reaction vessel 3 by introducing port 8.In this reaction vessel 3, by under begin to form respectively fixed bed, fluidized bed and subcritical water dissolving layer.Any taking-up from the export mouth 101～106 that is located at reaction vessel 3 tops and sidepiece of subcritical water dissolving layer.The subcritical water dissolving layer that is removed is situated between by cooling tube 4 and counterbalance valve 5, is recycled to reaction and finishes in the thing recycling can 6.
(heater pressue device)
Above-mentioned heater 1 is not particularly limited and can uses known heater.For example, can enumerate electric heater, induction heating device, the heating by hot coal profit steam etc.As above-mentioned pressue device 2, can use force (forcing) pump etc.
(gatherer)
Above-mentioned gatherer is the device that the mixture of water and object being treated is directed into reaction vessel 3.Be not particularly limited as gatherer, for example can utilize high pressure press-in device etc.Among the present invention, be directed in the reaction unit after preferably the mixture of object being treated and subcritical water being made slurries.Like this, above-mentioned pressue device 1 can also be used as gatherer.As a result, there is the high pressure press-in device (pressue device) of 1 costliness to get final product, can reduces installation cost.When pressue device 1 is also used as gatherer, as following, object being treated is directed in the reaction vessel 3.With pulverize in advance, solid content in the object being treated of corpusculed mixes with water, makes pulpous state.Then, after this paste mixture heated in heater 1, by pressue device 2 in introducing port 8 is directed into reaction vessel 3. subcritical water decomposing processor of the present invention can also have the corpusculed device that the solid content that is used for pulverizing in advance object being treated carries out corpusculed.
In the device of the present invention, the decomposition of object being treated preferably uses subcritical water to carry out.The water of supercritical water and liquid than have strong oxidizing force, diffusion coefficient is big, therefore is excellent reaction dissolvent.But supercritical water almost is decomposed into carbon dioxide with all object being treateds.The oxidizing force of subcritical water is weaker than supercritical water, but has the abundant hydrolysis power that is used to obtain useful thing and to the abundant extraction power of oil and aliphatic acid etc.In addition, subcritical water is compared with supercritical water, and is little to the corrosivity of metal etc.As a result, can not use expensive material such as the anti-corrosion Langaloy of haas troy, dilval, and use the mild steel (carbon steel) etc. of the cheapness of in common pressure vessel, using as the material of reaction unit.Even if than under the conditions of higher, also can use the material of comparing cheap a lot of SUS316 degree with the anti-corrosion Langaloy of haas troy, dilval etc. in the corrosivity that generates organic acid and so on.It should be noted that among the present invention, can and use subcritical water and supercritical water as required.In addition, can also in water, add acid, alcohol etc. as subcritical water.
(reaction vessel)
In the device of the present invention, the shape of reaction vessel 3 is not particularly limited, but is preferably cylindric.In at least one place of the upper end of this reaction vessel 3 or bottom, be provided with introducing port 8.Object being treateds such as above-mentioned slurries are situated between and are fed in the reaction vessel by this introducing port 8.The internal diameter of introducing port 8 as mentioned above, needs only 1/5～1/15 times scope at above-mentioned vertical cylinder shape inside diameter of vessel.If the internal diameter of introducing port 8 is as described below in above-mentioned scope, then can control the flow velocity of the object being treated in the reaction vessel 3.For example, if, slurries are directed in the reaction vessel 3 from introducing port 8 with transporting velocity or more than or equal to the speed of transporting velocity, then since the internal diameter in the reaction vessel 3 greater than the internal diameter of introducing port, the flow velocity that therefore is fed to the slurries in the container is slack-off.The result, because the flow velocity of slurries is adjusted to more than the liquidation commencing speed (transporting velocity) of particle, therefore can in reaction vessel 3, form the solid-liquid fluidized bed. here, if so-called transporting velocity is meant particle sedimentation or speed of floating in static fluid. subcritical water is crossed in the reaction vessel 3 with the velocity flow more than the transporting velocity, then is included in solid content in the object being treated also all along with liquid stream flows.As a result, the reaction time between solid content and the subcritical water dissolved matter becomes and does not have difference.If subcritical water is crossed in the reaction vessel 3 with the velocity flow below the liquidation commencing speed, then solid content does not move, if form fixed bed. subcritical water is crossed in the reaction vessel 3 with the velocity flow more than the liquidation commencing speed, and then solid content forms fluidized bed.That is, formed the solid-liquid fluidized bed.
When having the bigger unreacted solid content of granularity in a large number in reaction vessel 3, the introducing port in reaction vessel upper end or bottom is provided with the part place becomes the state of fixed bed (fixed bed).Bigger, the unreacted solid content of granularity then is subjected to the reaction of subcritical water, and particle diameter diminishes.The particle that particle diameter diminishes to the diffluence of the downstream of reaction vessel, forms solid-liquid fluidized bed (fluidized bed) by flowing of subcritical water.The useful thing that decomposition reaction by subcritical water generates is dissolved in the subcritical water, Yi Bian form piston flow (subcritical water dissolving layer), Yi Bian move to the downstream direction of reaction vessel 3.In reaction vessel 3, be provided with to be provided with on the side of introducing port and stir the broken device that forms the solid content of said fixing phase.Thus, can promote decomposition reaction more efficiently.
Export mouth is located on the position different with above-mentioned introducing port 8 set positions.Export mouth can be on a plurality of positions on the downstream side of the set position of introducing port.In the example of Fig. 1, above-mentioned export mouth is formed on to a plurality of positions on the above-mentioned reaction vessel sidewall (101～108) along above-mentioned liquid flow path direction.By a plurality of export mouths are set like this, piston flow can be taken out from reaction vessel 3.Specifically, can be corresponding to the holdup time that is dissolved in the object being treated in the subcritical water, be the subcritical water resolving time of processed composition, the subcritical water flow direction in the reaction vessel 3 is set the position of export mouth.In the example of Fig. 1, can be chosen in any in the export mouth (101～108) that forms on a plurality of positions, piston flow is taken out. like this,, can adjust the subcritical water decomposition reaction time by from any export mouth, piston flow being taken out.3
Being located at the introducing port 8 of reaction vessel 3 and the position of export mouth determines according to the density of solid content in the object being treated and the density of subcritical water.For example, if the solid content density in the object being treated that imports greater than the density of subcritical water, then introducing port 8 is located at the bottom of reaction vessel 3, export mouth is located at the top of the set position of above-mentioned introducing port.On the contrary, if the solid content density in the object being treated that imports less than the density of subcritical water, then introducing port 8 is located at the upper end of reaction vessel 3, export mouth is located at the bottom of the set position of above-mentioned introducing port.Perhaps, when the solid content density in the object being treated that imports is to mix when depositing greater than the density of subcritical water with less than the density of subcritical water, introducing port 8 can be located at the upper end and the bottom of reaction vessel 3.At this moment, can lay respectively at 2 export mouths of desired location or from same export mouth, the subcritical water solution layer is taken out from upper and lower end parts.In addition, when in the solid content of density, containing a small amount of density, can be only introducing port be set on the bottom of reaction vessel, being used to more than one be set in reaction vessel suppressing the filter that the little solid content of above-mentioned density swims less than the solid content of subcritical water greater than subcritical water.
The solid content of object being treated rests in fixed bed or the solid-liquid fluidized bed, is decomposed by subcritical water from the surface of solid content.In addition, when as bone etc., solid content is that the organic matter in the bone is decomposed and can dissolve by subcritical water when containing organic inorganic matter, and the solid content particle that becomes bone is cut apart thus, particle diameter diminishes, and finally becomes the powder of calcium phosphate.The fluidized bed that in the reaction vessel, in the process of decomposing, formed the fixed bed that constitutes by the particle that begins particle diameter greater than liquidation, constitutes by the particle that begins particle diameter less than liquidation and further powdered become identical speed, be 3 layers of the subcritical water dissolving layer that contains powdered calcium phosphate of plug flow regime with subcritical water.For this subcritical water dissolving layer, by adjusting the distance that flows through of subcritical water dissolving layer, can adjust organic degree of decomposition, reclaim the target analyte.Even if when organic matter pathogenicity prion toxicants such as (abnormal prions) in the bone or pathogenicity material,, also they can be decomposed, not have and poison by above-mentioned resolution process process.
When being pressed and delivered to the slurries pipe arrangement in the reaction vessel 3, the flow velocity of slurries is preferably transporting velocity or its above speed of solid content.Speed during the pipe arrangement pressurized delivered is when transporting velocity is following, and the solid content composition that is contained in the slurries is deposited in the pipe arrangement bottom, becomes the reason of pipe plug plug.
The density of subcritical water and viscosity are 887kg/m down at 178 ℃ (1MPa saturation waters) 3, 0.541kg/mhr, be down 778kg/m at 364 ℃ (5MPa saturation waters) 3, 0.359kg/mhr, be down 688kg/m at 311 ℃ (10MPa saturation waters) 3, 0.294kg/mhr. for example because the subcritical water wood powder density of soaking into is about 1000kg/m 3, therefore, can form fluidized bed by with suitable flow rate subcritical water.
When the density of contained solid content was greater than the density of subcritical water in the object being treated, transporting velocity can be calculated by the relation of solid content and particle diameter according to the physics value of subcritical water.Liquidation commencing speed (Umf) can be calculated with the Wen formula. and on the other hand, transporting velocity (Ut) can be calculated by the formula of fluid resistance.Liquidation commencing speed (Umf) is meant the fluid resistance that acts on particle and the flow velocity of gravity balance.By with the above flow velocity pressurized delivered subcritical water of liquidation commencing speed (Umf), can form the solid-liquid fluidized bed.In addition, during with the flow velocity pressurized delivered subcritical water more than the transporting velocity (Ut), as mentioned above, solid content flows out from the export mouth of reaction vessel.
Gu the true specific gravity of shape particle (dividing Gu form) is 1500kg/m 3The time, be shown in following table 1 with respect to the liquidation commencing speed (Umf) of each particle diameter (mm) that calculates with the saturation water of 1MPa, 5MPa, 10MPa, transporting velocity (Ut) and than (Ut/Umf).
Table 1
As shown in Table 1, the solid content that is contained in the object being treated that is hydrolyzed is ground into suitable size, makes slurries, can transfer with above-mentioned solid content non-settling abundant speed in conveying thus, can heat slurries, in reaction vessel, obtain the abundant flow regime of slurries.For example, when making particle diameter be the object being treated slurry reaction of 0.1mm in the 5MPa saturation water, transporting velocity (Ut) is 0.022m/s.Afterwards, if carry slurries with its 0.22m/s of 10 times, then slurries can fully be carried, be heated.When these slurries are fed in the reaction vessel with 10 times of internal diameters of introducing port, empty tube speed becomes 1/100. result, the empty tube speed of the subcritical water in the solid-liquid fluidized bed becomes 0.0022m/s, can form speed about 4 times to the solid-liquid fluidized bed of liquidation commencing speed (Umf).Here, so-called empty tube speed is meant the speed that the subcritical water fluid moves in reaction vessel 3.
By table 1 also as can be known, the liquidation commencing speed (Umf) of solids is different with the particle diameter of solids with transporting velocity (Ut).Particle diameter is big more, and it is big that then liquidation commencing speed (Umf) and transporting velocity (Ut) become simultaneously.Therefore, when with certain empty tube speed the different object being treated crushed material of particle diameter being risen in reaction vessel 3, the solids that particle diameter is big does not form the solid-liquid fluidized bed, but fixed bed is formed on the bottom in reaction vessel 3.Formed also hydrolysis of the big solids of the particle diameter of fixed bed by causing by subcritical water, analyte from the surface of solids begin dissolving, particle diameter diminishes, and rises formation solid-liquid fluidized bed reaction vessel 3 in.It should be noted that when the object being treated that contains the particle diameter solid content composition more consistent with true specific gravity being carried out the subcritical water decomposition,, then often can not form fixed bed (fixed bed) if its particle diameter begins particle diameter less than liquidation.
Like this, in the present invention,, can set powder liquor ratio and reaction time in a wide range by density, particle diameter and the reaction temperature of the solid content that reacts.Flow can pass through pressue device, gatherer control.Can be when for example, using force (forcing) pump by its rotation number control flow.
Though it should be noted that among Fig. 1 not provide, preferably be provided with in the reaction vessel 3 that the present invention relates to can observing response container 3 internal states finder.Be not particularly limited as finder, for example can enumerate window, glass etc. are set on the reaction vessel sidewall.When window is set, can also merges the window that daylighting is used is set.In addition, when using glass, also lighting device can be set as required.By finder is set like this, mixture color, particle size, turbidity, the length of fixed bed, the flow regime of fluidized bed and the length of this layer etc. in observation or the assaying reaction container can confirm whether reaction is undertaken by setting.The finder quantity that is provided with is not particularly limited, and for example can be provided with at certain intervals to the lower end from reaction vessel 3 upper ends.Particularly, when on reaction vessel 3 sidewalls, a plurality of export mouth being set, can finder be set corresponding export mouth.
Outlet 9 can also be set in the bottom of reaction vessel 3.The density of the inorganic matter that is not dissolved in subcritical water that is contained in the object being treated, carbide etc. forms the density of branch admittedly greater than organic property.If outlet 9 is set, then can be easily the inorganic matter, carbide etc. that are deposited in the bottom be discharged from outlet 9 in the bottom of reaction vessel 3.
Among the present invention, the reaction temperature of reaction vessel 3 can be by the heater adjustment.Its temperature is preferably 130～374 ℃ scope, more preferably 150～350 ℃ scope, more preferably 170～300 ℃ scope.If reaction temperature is more than 150 ℃, then the reaction time can be not long.On the other hand, if reaction temperature below 300 ℃, then decomposition reaction can excessively not carried out, and can also prevent the corrosion of reaction vessel 3 in addition.Waiting with insulation is purpose, can also on the periphery of reaction vessel heating and heat-insulating device be set.Safety devices such as safety valve can also be set.
In the subcritical water decomposing processor of the present invention, in the reaction time can not become extreme long scope, preferably under lower temperature, carry out decomposition reaction.Its reason be to prevent useful thing thermal decomposition, can reduce operating cost.For example, when the starch that volume contains in the hydrolysis leftovers obtains glucose, oligosaccharides, can under 150～220 ℃, be hydrolyzed.Its reason is the more acceptant hydrolysis of starch, perhaps easily causes carbonization by thermal decomposition.For example, when the cellulose that is contained in the hydrolysis soybean residue obtains glucose, oligosaccharides, preferably under 170～250 ℃, be hydrolyzed.Its reason is that cellulose is compared with starch, and hydrolysis rate is slow.The protein that in the hydrolysis fish offal, is contained, amino acid and organic acid and oil are extracted when reclaiming simultaneously, can under 150～250 ℃, be hydrolyzed.
Among the present invention,, can use employed catalyst in subcritical water decomposes usually in order to promote reaction and to suppress thermal decomposition.As catalyst system therefor, for example can enumerate acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, base catalysts such as NaOH, sodium carbonate, metal oxide-type catalyst such as manganese oxide, cupric oxide, rare-earth oxide class catalyst such as rhodium, ruthenium, palladium, precious metal catalyst such as gold, platinum etc.The adding method of catalyst is not particularly limited, and for example can be added in the slurries in advance.
In the device of the present invention, can be by adjusting the aperture control reaction pressure of counterbalance valve 11.In addition, cooling tube 10 can also be set in the dead ahead of counterbalance valve 11.If possess cooling tube 10, then can safely reaction be finished thing and be recovered to reaction and finish in the thing recycling can etc.Finish in the thing jar in this reaction, when target product is water miscible oligosaccharides, monosaccharide, amino acid, organic acid, peptide etc., reclaim with the state that is dissolved in the water; When being water-insoluble materials such as oil, fat, reclaim with the state that is trapped in aqueous solution top.
The subcritical water resolution process thing that uses production method of the present invention to produce can be finished the thing from above-mentioned reaction and reclaim.It is the mixture that contains water, oil phase, solid phase that thing is finished in this reaction.These mutually can be by separation such as natural separation or centrifugations.The kind of gained resolution process thing is difference with the kind of temperature, pressure, reaction time or object being treated.
For example, object being treated is during from the bone of ox or meat etc., contains organic acid, phosphoric acid, amino acid, ammonia and sugar etc. at aqueous phase.The gained organic acid is lower fatty acids (material that has carboxyl) such as pyroglutamic acid, lactic acid, acetate, formic acid, butanedioic acid, pyruvic acid, propionic acid.Gained amino acid for example is histidine, glycine, alanine, glutamine, aspartic acid, leucine, isoleucine, phenylalanine, valine, taurine etc.Gained sugar is glucose, fructose etc.In addition, contain aliphatic acid etc. in the oil phase.Can enumerate oleic acid, palmitic acid, stearic acid, palmitoleic acid etc. as aliphatic acid.Also contain calcium phosphate that derives from bone etc. in the solid phase.
For example, when object being treated comes from timber etc., contain organic acid, sugar etc. at aqueous phase.As the gained organic acid, can enumerate glycolic, lactic acid, acetate, formic acid, levulic acid, propionic acid, malic acid and butanedioic acid etc.Can enumerate cellotriose (being combined with 3 glucose), cellobiose (being combined with 2 glucose), glucose, fructose and erythrose (catabolite of glucose) etc. as gained sugar.Contain tarry oily mater in the oil phase.And, contain low density carbon material in the solid phase with vesicular structure.
And when object being treated came from the black intestines bag etc. of scallop in mollusk source, aqueous phase contained organic acid, phosphoric acid and amino acid etc.Can enumerate pyroglutamic acid, lactic acid, acetate, formic acid, butanedioic acid, pyruvic acid etc. as the gained organic acid. in oil phase, contain aliphatic acid etc.Can enumerate eicosapentaenoic acid (EPA), DHA (DHA), oleic acid, palmitic acid, palmitoleic acid, myristic acid, stearic acid, eicosenoic acid, docosenoic acid etc. as gained aliphatic acid.
Be not particularly limited for the method for decomposing these catabolites respectively, can utilize in the past known method to carry out.For example, can enumerate ion-exchange, membrane separation process, crystallization method and their recombination process etc. as the method for separating each catabolite from aqueous phase.In addition, can enumerate vacuum evaporation etc. as the method for from oil phase, separating each catabolite.
(embodiment 2)
Embodiment 2 is embodiments that the secondary response container further is set on the reaction unit of embodiment 1.Fig. 2 is the outline pie graph that is used to illustrate other example of subcritical water decomposing processor of the present invention.Among Fig. 2, on the position identical, have prosign with Fig. 1.As shown in Figure 2, secondary response container 12 Jie are connected in the export mouth 101 of reaction vessel 3 by pipe.Secondary response container 12 is connected by pipe respectively.On each pipe, be provided with transfer valve.Secondary response container 12 is by the switching of valve, can freely switch to be connected in series, to be connected in parallel.These secondary response containers 12 are connected in cooling tube by pipe, and then are connected with counterbalance valve 5.Be provided with reaction in the front portion of counterbalance valve 5 and finish thing recycling can 6.In the example of this figure, on the sidewall of reaction vessel 3, be provided with finder 13.
Shown in present embodiment, device of the present invention can also possess the secondary response container 12 that Jie is connected by export mouth 101～108 on the basis of reaction vessel 3.Constitute by this, can carry out the decomposition reaction of subcritical water mediation more for a long time.As this secondary response container 12, be preferably the cylindric secondary response container of circulation cast.
Above-mentioned secondary response container 12 preferably has heater.In addition, preferably on ingress pipe that is connected in the secondary response container and delivery line, has transfer valve respectively.
Reaction vessel 3 and secondary response container 12 are connected in series, can utilize a pressue device to adjust its flow.At this moment, in order to prevent the boiling in the container, the reaction pressure and the reaction temperature of less reacting condition container 3 and secondary response container 12 are better.Therefore, in the secondary response container 12, the flow velocity of speed dependent in subcritical water reached in reaction, promptly depends on the internal diameter of secondary response container 12, and the holdup time depends on the length of secondary response container 12.
The reaction of liquid phase is reached speed dependent in object being treated and reaction temperature.In order suitably to keep the reaction of liquid phase to reach speed, the internal diameter that can make secondary response container 12 is in 1～1/5 scope of the internal diameter of reaction vessel 3.
In order to prolong the reaction time, can use the tube connector parallel connection and/or be connected in series a plurality of secondary response containers 12.By such connection, can guarantee the suitable holdup time.In addition, transfer valve can also be set on tube connector.By each transfer valve of suitable switching, select used secondary response container, can adjust the reaction time.
Secondary response container 12 is connected in reaction vessel 3.Therefore, for the reaction temperature that makes both is equal substantially, preferably adjust the temperature of secondary response container 12.By adstante febres such as hydrolysis, preferably cool off secondary response container 12 and equate substantially until reaction temperature with reaction vessel 3.On the other hand, when the endothermic reaction, heat release take place, preferably heat secondary response container 12 and equate substantially until reaction temperature with reaction vessel 3.
If when the reaction temperature of secondary response container 12 became below 150 ℃, the reaction speed of hydrolysis etc. was slack-off.Therefore, length that sometimes must significant prolongation secondary response container 12.In addition, when reaction temperature surpassed 300 ℃, it is big that the pyrolysis speed of hydrolysate becomes.Therefore, be difficult to reclaim target product, corrode secondary response container 12 simultaneously sometimes with high yield.
When only on secondary response container 12, utilizing above-mentioned catalyst, the inlet of catalyst can be set in the importing of secondary response container 12 on tube connector, inject thus.
The device that embodiment 2 relates to is effective when thing is finished in the reaction of desiring further decomposition derivation from reaction vessel 3.Be situated between from any subcritical water analyte of being located at any taking-up the export mouth 101～108 of reaction vessel 3 and be fed in the secondary response container 12 by pipe.In the example of Fig. 2, secondary response container 12 has 4.By being connected, can connect these secondary response devices 12 respectively in 4 the secondary response containers 12 of switching, serial or parallel connection or their combination of the transfer valve of these secondary response containers 12.By the combination of this connection, can adjust decomposition reaction.The analyte that in secondary response container 12, obtains from secondary response container 12 via pipe, be situated between by cooling tube 4 and counterbalance valve 5, be recycled to reaction and finish thing recycling can 6.Here, counterbalance valve 5 is the devices that are used to adjust reaction vessel 3 and secondary response container 12 both sides or either party's container inner pressure.The unreacted reactant that is deposited in reaction vessel 3 bottoms is situated between and is recycled in the effluent recycling can 7 by outlet 9, cooling tube 10 and counterbalance valve 11.
(embodiment 3)
Fig. 3 is the outline pie graph that is used to illustrate other examples of subcritical water decomposing processor of the present invention.Among Fig. 3, the position identical with Fig. 1 has prosign.As shown in Figure 3, in the device of present embodiment, being provided with can be along the mobile continuously export mouth of subcritical water flow direction in the reaction vessel 3.
Movably export mouth be by pliability pipe 14, be positioned at the chain 16 of the suction portion 15 that its front end sucks required subcritical water dissolving layer, the above-mentioned pliability pipe 14 of slinging, the groove internal gear 17 that can roll or put down chain 16 constitutes.Suction portion 15 can be fixed on the desired location by the length of adjusting chain 16.
In the example of this figure, pliability pipe 14 has the formation of inserting from reaction vessel 3 upper ends, but also can have the formation of inserting from the bottom of reaction vessel 3.
(embodiment 4)
Fig. 4 is the outline pie graph that is used to illustrate other examples of subcritical water decomposing processor of the present invention.Among Fig. 4, the position identical with Fig. 1 has prosign.As shown in Figure 4, reaction vessel 3 is situated between by any of export mouth 101～108, utilizes pipe to engage with secondary response container 12.On this secondary response container 12, be formed with 3 export mouths 201～203.Export mouth 201～203 is independent respectively, and Jie is connected in reaction by cooling tube 4 and counterbalance valve 5 and finishes thing recycling can 6.By this formation, from reaction vessel 3, be removed, import to the subcritical water dissolving layer of secondary response container 12, even if when reducing owing to temperature, also can from a plurality of export mouths of being located at secondary response container 12, target be reclaimed mutually according to formation layers such as water, oil phase, solid phases.
Embodiment 1
Below, enumerate embodiment and describe the present invention in detail.The present invention is not subjected to any restriction of these embodiment.
(embodiment 1)
Use the subcritical water decomposing processor of Fig. 1, carry out the subcritical water of fish-bone (Ji is rubbed the back) and handle.The internal diameter that the internal diameter of introducing port 8 is made as 15mm, reaction vessel 3 is made as 128mm, highly is made as 3m.At this moment, the internal diameter of introducing port 8 is about 1/9 times of reaction vessel 3 internal diameters.Flow velocity is made as 1 liter/min, and 2 processes of 200 ℃ of reaction temperatures and 260 ℃ of carrying out are handled.The results are shown in Fig. 5,6 chart under 200 ℃ of the reaction temperatures, the chart that the results are shown in Fig. 8, Fig. 9 under 260 ℃ of the reaction temperatures.The longitudinal axis that it should be noted that the chart of Fig. 5 is the yield (kg/kg-dried feed) of each phase, and the chart of Fig. 6～9 is that the transverse axis of yield (kg/kg-dried feed), Fig. 5～9 of each material of aqueous phase is the holdup time (reaction time) in the reaction vessel 3.The holdup time of reaction vessel 3 (reaction time) changes by any that select to be located at a plurality of export mouths 101～107 on reaction vessel 3 short transverses.The holdup time (reaction time) under export mouth 101～107 each positions is represented on the transverse axis top of Fig. 5～9.Amino acid among Fig. 7,9 is called for short as follows.
The ASP aspartic acid
The THR threonine
The SER serine
The GLU glutamine
The PRO proline
The GLY glycine
The ALA alanine
The CYS cysteine
The VAL valine
The MET methionine
The ILE isoleucine
The LUE leucine
TYR tyrosine
The PHE phenylalanine
LYS lysine
The HIS histidine
The ARG arginine
(embodiment 2)
Use the subcritical water decomposing processor of Fig. 1 to carry out the subcritical water processing of the excess sludge of activated sludge.The internal diameter that the internal diameter of introducing port 8 is made as 15mm, reaction vessel 3 is made as 128mm, highly is made as 3m.At this moment, the internal diameter of introducing port 49 is about 1/9 times of reaction vessel 3 internal diameters.Flow velocity is made as 1 liter/min, and 3 processes of 160 ℃ of reaction temperatures, 200 ℃ and 240 ℃ of carrying out are handled.The results are shown in Figure 10,11 chart under 160 ℃ of the reaction temperatures, the chart that the results are shown in Figure 12, Figure 13 under 200 ℃ of the reaction temperatures the results are shown in Figure 14,15 chart under 240 ℃ of the reaction temperatures.The longitudinal axis that it should be noted that the chart of Figure 10～15 is the yield (kg/kg-dried feed) of water, and transverse axis is the holdup time (reaction time) in reaction vessel 3.The holdup time of reaction vessel 3 (reaction time) changes by any that select to be located at a plurality of export mouths 101～107 on reaction vessel 3 short transverses.The holdup time (reaction time) under export mouth 101～107 each positions is represented on the transverse axis top of Figure 10～15.Amino acid abbreviation among Figure 11,13,15 is called for short identical with the amino acid shown in Fig. 7,9 of embodiment 1.
As shown in Figure 5, when carrying out the subcritical processing of fish-bone under 200 ℃, the yield of residual solid is even if at short export mouth 107 places of reaction time, also be below 0.05 (the kg/kg-dried feed).Along with the increase of holdup time, the yield of residual solid does not almost change.This is because the decomposition of fish-bone is fully carried out, and only becomes calcium phosphate.In addition, as shown in figure 11 as can be known, when under 160 ℃, carrying out the subcritical processing of the excess sludge of activated sludge,, can reclaim methionine with high yield by selecting export mouth 103.
Industrial applicability
In sum, by the present invention can resource through the discarded object of burning disposal. As a result, The present invention is useful in establishment of environmental resource, zero-discharge technology etc. In addition, the present invention also The useful things such as the organic acid that contains in can the resource discarded object, amino acid. If use acetic acid Use Deng the raw material of organic acid as methane fermentation, then the methane fermentation of the high digestibility of high speed becomes May, can quantize also to become possibility with high efficiency. By the present invention, can also not have poison and Resource has and contains the dangerous meat meal tankage such as pathogenicity prion (abnormal prion) etc. As a result, The present invention is useful for the depollution of environment. And, can also be beyond the discarded object by the present invention Produce useful subcritical water resolution process thing in the organic matter raw material.

Claims (22)

1. the production method of subcritical water resolution process thing, this method intermediary is by the introducing port on the reaction vessel that is arranged at the subcritical state that is maintained at water in the container, be supplied to object being treated in the reaction vessel continuously, the liquid that a plurality of export mouths on being located at described reaction vessel any will contain analyte takes out continuously, adjust the holdup time of the liquid that contains described analyte in reaction vessel, wherein said export mouth is located on the position that is different from the set position of introducing port.
2. the production method of subcritical water resolution process thing, this method intermediary is by the introducing port on the reaction vessel that is arranged at the subcritical state that is maintained at water in the container, be supplied to object being treated in the reaction vessel continuously, the liquid that will contain analyte the one or more export mouths on being located at described reaction vessel takes out continuously, described export mouth is located on the position that is different from the set position of introducing port, the steady concentration that produces required analyte in reaction vessel distributes, in described one or more export mouths, from be located at the high locational export mouth of required analyte concentration, described required analyte is taken out.
3. the production method of subcritical water resolution process thing is characterized in that,
Jie will be contained the decomposition rate that is mediated by subcritical water object being treated slow, that proportion is different from the solid content of subcritical water and will be supplied to continuously in the reaction vessel by the introducing port on the vertical response container that is arranged at the subcritical state that is maintained at water in the container,
In being arranged at one or more export mouths of described reaction vessel, adjust the position and the derived quantity thereof that derive the liquid that contains analyte, described export mouth is located on the position that is different from the set height of introducing port, in the subcritical water that remains static, the sedimentation of fabrication direction and described solid content or float direction opposite, wait a moment in its sinking speed or float the stationary flow of speed
In described stationary flow, form at least: from the described solid content in upstream of liquid stream by described subcritical water decomposes, corpusculed, this particulate is mobile fluidized bed in liquid stream; And described object being treated becomes the product or the complete liquefiable product of further corpusculed, the subcritical water dissolving layer that flows with subcritical water,
And then, according to the kind of object being treated, even if form because described liquid flows, and solid content also rests on the fixed bed of certain position in the upstream of described fluidized bed,
Use any in described one or more export mouth, the liquid that will contain required analyte is from described subcritical water dissolving layer, take out from reaction vessel.
4. the production method of subcritical water resolution process thing is characterized in that,
In the subcritical water that remains static, the object being treated that contains solid content is flowed along the direction opposite with described solid content moving direction with the mixture of subcritical water,
In described liquid stream, form at least: from the described solid content in upstream of liquid stream by described subcritical water decomposes, corpusculed, this particulate is mobile fluidized bed in liquid stream; And described object being treated becomes the product or the complete liquefiable product of further corpusculed, the subcritical water dissolving layer that flows with subcritical water,
And then, according to the kind of object being treated, even if form because described liquid flows, and solid content also rests on the fixed bed of certain position in the upstream of described fluidized bed,
Adjust the distance that flows through of described subcritical water dissolving layer, make the holdup time of holdup time of described solid content and described subcritical water different, adjustment can be dissolved the degree of decomposition of the composition of the described object being treated in subcritical water, obtains target resolution process thing.
5. the production method of subcritical water resolution process thing as claimed in claim 4, the sedimentation in the mixture that remains static of wherein said solid content, the flow direction of described mixture is opposite with gravity direction.
6. the production method of subcritical water resolution process thing as claimed in claim 4, wherein said solid content suspends in the mixture that remains static, and the flow direction of described mixture is identical with gravity direction.
7. as the production method of each described subcritical water resolution process thing in the claim 4～6, it is characterized in that, the flow velocity of described mixture in the mixture that remains static less than the sinking speed that equals described mixture or float speed.
8. as the production method of each described subcritical water resolution process thing in the claim 4～7, wherein said mixture is slurries.
9. as the production method of each described subcritical water resolution process thing in the claim 1～8, it is characterized in that the subcritical water hydrolysising reacting temperature is 130～374 ℃ a scope, reaction pressure is more than or equal to the Saturated water vapor pressure of reaction temperature.
10. as the production method of each described subcritical water resolution process thing in the claim 1～8, wherein said object being treated is to be selected from food, livestock products, agricultural product, aquatic products, timber, natural organic matter, plastics, organochlorine compounds, rubber, fiber and their discarded object, at least a in water treatment discarded object and the wastewater treatment discarded object down.
11. the subcritical water decomposing processor is characterized in that, possesses: use the reaction vessel of subcritical water decomposition object being treated,
In order to form the subcritical state of keeping water, heat the heater of the mixture that constitutes by water and described object being treated and the pressue device that pressurizes,
Be used for described object being treated is directed into gatherer in the reaction vessel,
Be used for described object being treated be directed in the reaction vessel introducing port and
Be used for export mouth that the mixture of analyte and water is derived from reaction vessel;
Described export mouth is located on the position that is different from the set position of described introducing port, can get a plurality of positions.
12. the subcritical water decomposing processor is characterized in that, possesses:
Use the vertical response container of subcritical water decomposition object being treated,
In order to form the subcritical state of keeping water, add the heater and the pressue device that pressurizes of the mixture of hot water and described object being treated,
Be used for described object being treated is directed into gatherer in the reaction vessel,
Be used for described object being treated be directed in the reaction vessel introducing port and
Be used for export mouth that the mixture of analyte and water is derived from reaction vessel;
Basic vertical setting of described reaction vessel, described export mouth is located at the upper end of described reaction vessel and at least one place of bottom, in the subcritical water that remains static, the object being treated of importing and the mixture of subcritical water are flowed along the direction opposite with described solid content moving direction
In described liquid stream, form at least: from the described solid content in upstream of liquid stream by described subcritical water decompose, corpusculed, the fluidized bed that this particulate flows in liquid stream, and described object being treated becomes the product or the complete liquefiable product of further corpusculed, with the mobile subcritical water dissolving layer of subcritical water
And then, according to object being treated, even if form because described liquid stream in the upstream of described fluidized bed, solid content also rests on the fixed bed of certain position, simultaneously the subcritical water dissolving layer is derived, can set the desired location of described export mouth, so that can adjust the distance that flows through of subcritical water dissolving layer.
13. subcritical water decomposing processor as claimed in claim 12, wherein said export mouth is formed on the described reaction vessel sidewall along a plurality of positions of described liquid flow path direction.
14. subcritical water decomposing processor as claimed in claim 12, wherein said export mouth can move continuously along the liquid flow path direction.
15., it is characterized in that described vertical response container possesses can observe inner finder as each described subcritical water decomposing processor in the claim 12～14.
16. as each described subcritical water decomposing processor in the claim 12～15, it is characterized in that, described vertical response container is a cylindrical container, and described introducing port is circular, and the internal diameter of this introducing port is 1/5～1/15 times a scope of described vertical cylinder shape inside diameter of vessel.
17., be characterised in that wherein that described device possesses a plurality of described vertical response containers as each described subcritical water decomposing processor in the claim 12～16.
18. as each described subcritical water decomposing processor in the claim 12～17, it is characterized in that, described subcritical water decomposing processor also possesses the cylindric secondary response container of the circulation cast that is connected in described reaction vessel export mouth, and the internal diameter of the cylindric secondary response container of described circulation cast is 1～1/5 times of scope of described vertical cylinder shape inside diameter of vessel.
19. as each described subcritical water decomposing processor in the claim 12～18, it is characterized in that, the cylindric secondary response container of described circulation cast is a plurality of, can be connected in series and/or be connected in parallel between the cylindric secondary response container of these circulation casts.
20., it is characterized in that to possess the heating-cooling device of the reaction temperature in the cylindric secondary response container of the described circulation cast of control as claim 18 or 19 described subcritical water decomposing processors.
21. as each described subcritical water decomposing processor in the claim 12～20, it is characterized in that described vertical response container is provided with counterbalance valve, use this counterbalance valve can control the interior reaction pressure of described vertical response container.
22. subcritical water decomposing processor as claimed in claim 21 is characterized in that, possesses cooling tube in the dead ahead of described counterbalance valve.
CNB2005800048052A 2004-02-13 2005-02-14 Method for producing product decomposed with subcritical water and apparatus for decomposition treatment with subcritical water Expired - Fee Related CN100482336C (en)

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