JP6216856B1 - Useful resource recovery apparatus and method for recovering useful resources from an eluate from which useful resources are eluted - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus and a method for separating and recovering useful resources from an eluate from which useful resources are eluted. SOLUTION: PVDF immersion membrane (for MBR) module 3, PVDF hollow fiber (MF membrane) module 4, PVDF hollow fiber (UF membrane) module 5, nanofiltration membrane (NF membrane) module 6, reverse osmosis membrane (RO membrane) ) The useful resources adsorbed and separated in the module 7 are forcibly backwashed and separated using the backwashing water tank 9, the backwashing water pump 10, and the air compressor 11, which are backwashing devices, and the recovered resource tank I (Reference numeral 13) and the recovered resource tank II (reference numeral 14) are sent into the crystallizing device 18. While adding crystal nuclei and controlling the temperature in the crystallization tank 19 of the crystallization device 18 by supplying temperature adjustment water from the temperature adjustment water inlet 26 according to the measured temperature of the temperature measuring element 29, the recovered resource agitator By stirring the inside of the crystallizing tank 19 of the crystallizing device 18 by using, useful resources can be rapidly crystallized. [Selection] Figure 1

Description

  The present invention relates to a recovery apparatus and method for efficiently recovering useful resources (such as three elements of fertilizer) contained in carbides and other inorganic substances (such as heavy metals) by efficient adsorption filtration, and crystallization of useful resources. Relates to the device.

  So far, regarding the method of recovering useful water-soluble resources (three elements of fertilizers) and other inorganic substances (mineral components, heavy metals, salts) contained in carbides, the pH is adjusted using chemicals, and the flocculant After agglomerating using a method, there are a method of dehydrating and solidifying, a method of separating by using a separation chemical and adsorbing it to calcium carbonate, etc., and a method of separating and recovering using an electrode, etc. The conventional apparatus for separating and recovering inorganic substances has a large-scale and complicated structure and requires an engineer with specialized knowledge. In addition, it is not suitable for medium-scale or small-scale useful resource recovery equipment, and it is necessary to operate and manage it by an engineer with specialized knowledge, and it is cost-effective when manufacturing high-value-added products. It has been difficult to manufacture products that cannot be expected to be effective and to disseminate the harmless business from the viewpoints of economy and environmental impact.

  Currently, the HAP method, the MAP method, the ash alkali extraction method, the electrode separation method, and the like are used, but they are not widespread due to low cost effectiveness and high maintenance costs. Even if implemented, most devices are operating at the expense of cost effectiveness to reduce environmental impact.

  That is, the conventional HAP method, MAP method, and ash alkali extraction method are methods of separation and recovery using acids and alkalis, and the electrode separation method consumes a lot of energy. In the conventional HAP method, MAP method, ash alkali extraction method, and electrode separation method, it is difficult to separate and recover heavy metals and salts even though it is possible to recover useful resources in one line. is there. In order to collect useful resources (three elements of fertilizer, etc.) and other inorganic substances (mineral components, heavy metals, salts) in a single line, the facility scale becomes large and the maintenance management becomes complicated. The adoption of each device and method is a cause of not widespread use.

Japanese Patent Application No. 2006-197772

  A facility that separates, recovers, and crystallizes useful resources and other inorganic materials according to the prior art requires a large amount of eluate to be separated and recovered in order to be profitable. In addition to this, engineers with specialized knowledge are required, and it is difficult to install and manage each facility from the viewpoint of cost effectiveness. Therefore, the present invention is to provide a recovery apparatus and a recovery method that are low in facility installation cost, facility maintenance management cost, and facility operation management cost, are simple in maintenance management and operation management, and can reduce environmental burden. Objective.

  The present invention provides an apparatus for efficiently separating and recovering useful resources (three elements of fertilizer, etc.) eluted from a carbide from an eluate without using chemicals, electrodes and the like. For the method for preparing the eluate and the method for concentrating, refer to the co-pending Patent Document 1.

In one embodiment of the present invention, a predetermined amount of eluate containing useful resources and other inorganic substances is supplied to the useful resource recovery apparatus of the present invention under a predetermined pressure. First, using the MBR (Membrane Bioreactor) for PVDF (poly (vinylidene fluoride)) manufactured by submerged membrane module as a prefilter, a material of mineral components such as the 8μm or more dimensions in the eluate was adsorbed filtration, subsequent PVDF hollow yarn M F Makumo joules, to reduce the suction-filtered load in PVDF hollow fiber U F Makumo joules. Then, after suction filtered through stepwise slow useful resources more dimensions 0.1μm using PVDF hollow fiber M F Makumo Joule and PVDF hollow fiber U F Makumo Joule, PVDF hollow fiber M from each of the F Makumo Joule 4 and PVDF hollow fiber U F Makumo Joule, forcibly disengaged useful resources from the membrane using air from backwash water and air compressor, is recovered as a useful resource of the water-soluble . In one embodiment, the heavy metal concentration remaining in the filtrate in after flowing through the reverse osmosis membrane (RO membrane) module measures the salt concentration, depending on the value of the measurement, PVDF manufactured submerged membrane for the MBR motor further comprising module, a control unit capable of controlling the supply pressure and supply amount of eluate into the PVDF hollow fiber M F Makumo Joule and the PVDF hollow fiber U F Makumo joules. In addition, the recovered eluate containing water-soluble useful resources is sent to the crystallizer, added with crystal nuclei, and then stirred while maintaining a temperature suitable for the crystallization temperature. An apparatus and a method for efficiently crystallizing and recovering useful resources are provided.

  Using a nanofiltration membrane (NF membrane) module, heavy metals with a size of 0.001 μm or more are adsorbed and filtered to reduce environmental impact and increase safety. In one embodiment of the present invention, in order to effectively use the filtrate, the filtrate is close to pure water after a salt having a size of 0.003 μm or more is adsorbed and filtered using a reverse osmosis membrane (RO membrane) module 7. Is provided with a conduit in fluid communication with the elution water reservoir so that it can be reused as elution water for eluting useful resources from the high-temperature carbide.

In another embodiment of the present invention, there is provided a recovery method for separating and recovering useful resources from an eluate containing useful resources (three elements of fertilizer) eluted in elution water, wherein the recovery method is performed under a predetermined pressure. in, supplied from the eluate reservoir tank that stored the eluate containing useful resources, the eluate filtered process amounts in PVDF manufactured dipping Makumo joules for MBR to PVDF manufactured dipping Makumo joules for MBR, the MBR recovering the predetermined or more minerals dimensions and other inorganic material was filtered using a use PVDF manufactured immersion Makumo joules fluidly communicatively disposed downstream of the PVDF manufactured dipping Makumo joules for MBR using PVDF hollow fiber M F Makumo joules, the steps of the filtrate after flowing through the PVDF manufactured dipping Makumo joules for the MBR further filtered to recover more useful resource predetermined size, P Using fluidly communicatively-arranged PVDF hollow fiber U F Makumo Joule downstream of the hollow fiber M F membrane module manufactured by DF, further filtrate after flowing through the PVDF hollow fiber M F film recovering the more useful resources predetermined dimensions by filtration, fluidly communicatively-arranged nanofiltration membrane (NF membrane) downstream of PVDF hollow fiber U F Makumo joules using a module, PVDF a step to no further cations of the above predetermined size is filtered filtrate after flowing through the manufacturing hollow fiber U F film recovering heavy metals, fluidly communicating the downstream of the nanofiltration membrane (NF membrane) using the placed reverse osmosis membrane (RO membrane) module, to recover the nanofiltration membrane (NF membrane) to no further anions or a predetermined size is filtered filtrate after flowing through the salt such steps Through the reverse osmosis membrane (RO membrane) module And a step of reusing the filtrate after flowing as the elution water.

Using a mineral component adsorbed with the PVDF manufactured dipping Makumo joules for MBR, and nanofiltration membrane (NF membrane) through cation adsorbed with modules heavy metals, a reverse osmosis membrane (RO membrane) module adsorbed anions (chloride ions, sulfate ions, etc.) for a to no salt such, as well as pumping periodically backwash water using backwash water pump, forced by supplying air from the air compressor The module membrane is washed and the adsorption filtration capacity of each module membrane is maintained. Furthermore, for inorganic substances (mineral components, heavy metals, salts, etc.) recovered by each module, after sending them to the reaction tank, add a flocculant, etc., dehydrate with a filter press etc. (not shown) and reduce the amount, Appropriate treatment is performed to reduce environmental impact.

  According to the present invention, in order to recover and recycle useful resources contained in organic sludge that has not been sufficiently reused, it is possible to recover and recycle useful resources from the high-temperature carbide. it can. The present invention can also reduce the equipment cost of the apparatus as compared to the conventional apparatus.

The figure which shows the whole useful resource collection | recovery apparatus of this invention. The side view which shows one Example of the useful resource crystallization apparatus of this invention. The top view which shows one Example of the useful resource crystallization apparatus of this invention. The figure which shows one Example of the rotation part of the useful resource crystallization apparatus of this invention in detail.

FIG. 1 shows the entire useful resource recovery apparatus of the present invention. In one embodiment, under a predetermined pressure, useful resources eluting and concentrating device from the eluate tank 1 containing the eluted and concentrated with (see Patent Document 1) solution, manufactured by MBR for PVDF immersed Makumo Joule 3 in minerals delivered over the eluent supply port, equal to or greater than the predetermined dimension PVDF manufactured dipping Makumo joules for MBR filtration process amounts of the eluate dipping steel MBR for PVDF Makumo Joule 3 and other inorganic The product is recovered by filtration. Then, the filtrate after being filtered through MBR for PVDF manufactured immersed Makumo joules 3, through a PVDF hollow fiber M F Makumo Joule 4 filtrate supply port, PVDF hollow fiber M F Makumo Joules 4 is supplied. Subsequently, the filtrate after being filtered through a PVDF hollow fiber M F Makumo Joules 4, PVDF hollow fiber U F Makumo Joule 5 filtrate PVDF hollow fiber U F Makumo Joule through the supply port supplying to 5, by filtration through a PVDF hollow fiber U F Makumo joules 5, it is possible to efficiently adsorb recover useful resources.

In one embodiment, the elution water after being filtered processed in PVDF hollow fiber M F Makumo Joules 4 and PVDF hollow fiber U F Makumo Joule 5 useful resources are adsorptive separation, nanofiltration membrane (NF Membrane) is sent to the module 6 and adsorbs heavy metals with restricted release in the filtrate and heavy metals (including various metal ions) that impede reuse. Subsequently, it is sent to a reverse osmosis membrane (RO membrane) module 7 to adsorb various anions or salts in the filtrate. The filtrate after passing through the reverse osmosis membrane (RO membrane) module has a water quality close to that of pure water, and can be reused as elution water for eluting useful resources from the carbide.

  In the useful resource recovery apparatus shown in FIG. 1, useful resources are mainly recovered in the recovered resource tank I and the recovered resource tank II. After the items recovered in the recovered resource tank I and the recovered resource tank II are sent to the crystallizer 18 through the inspection / confirmation port 30, a small amount of crystal nuclei are added and stirred using the recovered resource agitator 21. To do. In order to efficiently perform the crystallization reaction of the recovered resources, the temperature adjustment water is supplied from the temperature adjustment water inlet 26 to the jacket portion of the crystallization tank 19, drained from the temperature adjustment water outlet 28, and the side temperature body 29 is used. The temperature may be controlled while measuring the temperature in the crystallization tank 19.

  2 to 4 show an embodiment of the crystallizing device 18 according to the present invention. 2 is a side view of the crystallizing device 18, FIG. 3 is a plan view of the crystallizing device 18, and FIG. 4 is a diagram showing in detail the rotating part of the crystallizing device 18. Since the operation of the crystallizing device 18 other than the resource crystallizing stand is constantly controlled in a wet state, it is desirable that the crystallizing device 18 is made of SUS304 or SUS310. The material of the stirring shaft and the stirring blade of the recovered resource stirrer 21 is desirably SUS304 or SUS310. It is desirable that the resource crystallization tank rotating shaft 23 of the crystallization apparatus 18 is formed of SS400 or FC200 to FC300 that has been subjected to corrosion resistance.

  Further, by measuring the concentration of heavy metals and the concentration of salts in the eluate using the metal concentration measuring device 16 and the salt concentration measuring device 17, the PVDF immersion membrane (for MBR) module 3, the nanofiltration membrane (NF It may be determined whether the adsorption / filtration capability of the membrane) module 6 and the reverse osmosis membrane (RO membrane) module 7 is reduced.

  In order to maintain the adsorption filtration capacity of the PVDF immersion membrane (for MBR) module 3, the nanofiltration membrane (NF membrane) module 6 and the reverse osmosis membrane (RO membrane) module 7, periodically use a reverse washing water pump. It is preferable to remove the remaining inorganic substances by pumping back washing water and supplying air from an air compressor to wash each module membrane.

  Various inorganic substances (mineral components, heavy metals, salts) collected in the immersion water tank 12 and the heavy metal / salt tank 15 are solidified by adding a flocculant after being sent to the inorganic solidification device. Reduce the amount by dehydrating with a filter press or the like (not shown) and properly process.

  A method for producing crystal nuclei will be described. The eluate containing useful resources is added to a Soxhlet extraction cylindrical filter paper and subjected to Soxhlet extraction with purified water for 24 hours. After washing the extract with an organic solvent such as hexane to remove impurities such as organic matter, and concentrating under reduced pressure, the solids containing useful resources become a mixture with components such as calcium, potassium, chlorine and nitrogen. can get. When this solid is used as a crystal nucleus, a useful resource can be recovered at a high yield of 98% or more using the crystallization device 18. Since a small amount of crystal nuclei may be added, it is produced by a small scale batch type Soxhlet extraction method. The concentrated resource-containing eluate is added to a cylindrical filter paper for Soxhlet extraction, and Soxhlet extraction is performed using purified water. The extract is washed with hexane to remove a small amount of impurities, and then a solid substance concentrated by decompression is used as a crystal nucleus.

  In the crystallization device 18, in order to separate the water after the recovered resources are crystallized from the crystal content, the water is preferably passed through the drainage filter 25 via the drainage gate valve 24. The dehydrated crystals are tilted by using the crystallization tank rotating shaft 23 of the crystallization device 18, the crystallization tank 19 of the crystallization device 18 is tilted, the management cover 22 of the crystallization device 18 is opened, and the crystals are taken out. Efficiently collect and recycle. In another embodiment, instead of the management lid 22 of the crystallizing device 18, there is a case where an outlet exclusively for the crystal is provided.

  Using the useful resource recovery device and the crystallization device 18 shown in each figure, the filtrate after the useful resources are adsorbed and filtered from the eluate from which the useful resources are eluted, and after crystallization by the crystallization device 18 Analysis was conducted. In [Table 1], the upper row is the analysis value when the apparatus of the present invention is used, and the lower row is the analysis value when the conventional method (extracted from the incinerated ash by the alkali extraction method) is used.

  [Table 2] shows a predetermined amount of eluate concentrated using a useful resource elution / concentration device (see Patent Document 1), and a filtrate after filtration using the useful resource recovery device of the present invention ( Results of recovery analysis (including useful resources) are shown. In the present example, the recovery rate of useful resources from the high-temperature carbide eluate is 98% or more, whereas the conventional ash-alkali extraction method has only a recovery rate of about 71%. It is effective from the viewpoint of Therefore, the useful resource recovery device of the present invention has a high removal rate of 98% or more of inorganic substances (mineral components, heavy metals, salts, etc.) other than useful resources, and can be said to be a device / equipment with a low environmental load.

1 ... Eluent tank
2 ... Eluate pump 3 ... PVDF immersion membrane (for MBR) module
4 ... PVDF hollow fiber (MF membrane) module 5 ... PVDF hollow fiber (UF membrane) module
6 ... Nanofiltration membrane (NF membrane) module
7 ... Reverse osmosis membrane (RO membrane) module 8 ... Adsorption / filtrate (backwash water, elution water)
9 ... Backwash water tank 10 ... Backwash water pump
11 ... Backwash air compressor
12 ... Immersion water tank 13 ... Recovery resource tank I
14 ... Recovery tank II
DESCRIPTION OF SYMBOLS 15 ... Tank for heavy metals and salts 16 ... Heavy metal concentration measuring device 17 ... Salt concentration measuring device 18 ... Crystallizing device 19 ... Crystallizing tank 20 ... Eluate / crystallization inlet 21 ... Stirrer 22 ... Crystallizing device management Lid 23 ... Crystallization tank rotary shaft 24 ... Crystal water discharge port gate valve 25 ... Crystal water filtration filter 26 ... Temperature control water inlet 27 ... Crystallizer mount 28 ... Temperature control water outlet 29 ... Temperature measuring element 30 ... Inspection / Confirmation port

Claims (6)

In a useful resource recovery system for separating and recovering useful resources from eluate containing three elements and other useful resources fertilizer eluted in elution water,
And PVDF manufactured dipping Makumo Joules for MBR for collecting a predetermined size or more minerals and other inorganic matter was filtered the eluate,
Fluidly is communicatively disposed downstream of the PVDF manufactured dipping Makumo joules for the MBR, the MBR for PVDF manufactured immersed Makumo Joule was further filtered and the filtrate after flowed useful than a predetermined dimension resources a PVDF hollow fiber M F Makumo joules for collecting,
Fluidly it is communicatively disposed downstream of the PVDF hollow fiber M F Makumo joules, the PVDF hollow fiber M F film was further filtered and the filtrate after flowed useful than a predetermined dimension resources a PVDF hollow fiber U F Makumo joules for collecting,
Fluidly is communicatively disposed downstream of the PVDF hollow fiber U F Makumo joules, the PVDF hollow fiber U F film was further filtered filtrate after flowing through the predetermined size or more cations to a nanofiltration Makumo joules for recovering heavy metals,
Fluidly communicatively disposed downstream of the nanofiltration membrane module, reverse for to no further anions or a predetermined size is filtered filtrate after flowing through the nano-filtration membrane to recover the salt compound and penetration Makumo Jules,
A useful resource recovery device. Heavy metal concentration remaining in the filtrate in after flowing through the reverse osmosis Makumo joules, depending on the value of measurement of salinity, the MBR for PVDF manufactured immersion Makumo joules, the PVDF hollow fiber M F Makumo Joules and useful resource recovery apparatus of claim 1 further comprising a control device capable of controlling the supply pressure and supply amount of eluate into the PVDF hollow fiber U F Makumo joules. To claim 1, characterized in that it comprises an elution water reservoir fluidly communicatively conduit to the filtrate after flowing through the reverse osmosis Makumo Joule can be reused as the eluting water The useful resource recovery device described. A recovery method for separating and recovering useful resources from eluate containing three elements and other useful resources fertilizer eluted in elution water,
Under a predetermined pressure, supplied from the eluate reservoir tank that stored the eluate containing useful resources, the eluate filtered process amounts in PVDF manufactured dipping Makumo joules for MBR to PVDF manufactured dipping Makumo Joules for MBR and a step of then filtered to recover the predetermined or more minerals dimensions and other inorganic material using a PVDF manufactured dipping Makumo joules for the MBR,
Using fluidly communicatively-arranged PVDF hollow fiber M F Makumo Joule downstream of PVDF manufactured dipping Makumo joules for the MBR, filtration of after flowing through the PVDF manufactured dipping Makumo joules for the MBR Further filtering the liquid to recover useful resources over a predetermined size;
Using fluidly communicatively-arranged PVDF hollow fiber U F Makumo Joule downstream of the PVDF hollow fiber M F Makumo joules, filtered after flowed the PVDF hollow fiber M F film Further filtering the liquid to recover useful resources over a predetermined size;
Using fluidly communicatively-arranged nanofiltration Makumo Joules downstream of the PVDF hollow fiber U F Makumo Joule, further filtering the filtrate after flowing through the PVDF hollow fiber U F film recovering the heavy metals to free cations above a predetermined size and,
Using fluidly communicatively disposed inverse osmosis Makumo Joule downstream of the nanofiltration membrane module, a filtrate after flowing through the nanofiltration membrane was further filtered over a predetermined dimension anion to recovering the salt compound,
A step of reusing the filtrate after flowing through the reverse osmosis Makumo Joule as the eluting water,
A recovery method including: With the backwash water pump, as well as pumping the backwashing water to the PVDF hollow fiber M F Makumo Joule and the PVDF hollow fiber U F Makumo Joule, forcibly supplying air from the air compressor The recovery method according to claim 4, further comprising a step of causing the useful resources to leave the membrane and sending back wash water containing the detached useful resources to each of the recovery resource tanks. After supplying each effluent stored in each recovery resource tank into the crystallization tank of the crystallization apparatus, adding a small amount of crystal nuclei and then stirring with the agitator of the crystallization apparatus;
Maintaining a temperature suitable for crystallization by supplying temperature adjustment water into the crystallization device while measuring the temperature in the crystallization tank using a side temperature body;
In order to remove moisture from the crystals crystallized by the crystallizer, dewatering through a drainage filter;
The recovery method according to claim 5, further comprising:

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