KR100914444B1 - The hybrid recovery of iron and phosphate with interaction between gypsum released sulfur and cork impregnated ferrooxidans - Google Patents

Abstract

A hybrid recovery method of iron and phosphorus with interaction between gypsum releasing sulfur and carrier in which the iron oxide microorganism is dipped is provided to reduce environmental load due to the mining of the phosphate rock. A hybrid recovery device of iron and phosphorus with interaction between gypsum releasing sulfur and carrier in which the iron oxide microorganism is dipped comprises a reaction tub(1), a carrier(10) and a gypsum(9). The reaction tub includes an inlet port(12) and an outlet port(8). The reaction tub has a shape of a tank. The reaction tub comprises an oxygen supply device(7). The oxygen supply device supplies oxygen to the carrier. A dry ice(11) adheres to the carrier. The dry ice supplies carbon dioxide to the carrier. The carrier is a cork dipped with the iron oxide microorganism. The carrier is fixed with a stator. The gypsum is arranged at left and right sides of the carrier. The gypsum is a sulfur supply source arranged around the carrier. The inlet port and the outlet port are connected by fluid with lake and the circulation is possible. An auxiliary device is fixed to the outside of the reaction tub.

Description

The hybrid recovery of Iron and Phosphate with interaction between Gypsum released sulfur and Cork impregnated ferrooxidans}

The present invention relates to iron and phosphorus in a lake using the interaction of a carrier typified by Cork impregnated with ferrooxidases and a gib island for sulfur discharge (Gypsum: hereinafter referred to as 'gib island'). To the simultaneous recovery method and the device,

More specifically, the present invention relates to a method and an apparatus for simultaneously recovering iron divalent (Fe 2+) and inorganic phosphorus (Pi; hereinafter referred to as phosphorus).

In more detail, iron divalent is converted to iron trivalent in a carrier using a cork impregnated with Leptospirillum Ferrooxidnas, a kind of iron oxide microorganism, and the reaction of phosphorus with phosphorus (CaSO ₄ )) By discharging sulfur and supplying it to the cork carrier, it provides a method and a completely mixed treatment apparatus for allowing iron trivalent ions to react with sulfur to form pyrite (FeS ₂ ).

Iron cannot be recovered because it is combined with phosphorus in the soil of ordinary land. However, it is well known that iron and bivalent cations are present in sediments in lakes and rivers, and methods for recovering them have been established.

Phosphorus treatment technology which elutes from the bottom material of the lake generally used adopts a method of fixing the phosphorus eluted to the gimbsome through capping in the reservoir.

The current state of capping technology using Gibbsum is studied by the Korea Institute of Construction Technology in Paldang Lake, but it does not provide the technology to prevent phosphorus elution.

Existing static treatment method by Gibb's Island capping has incomplete point of preventing the continuous dissolution of phosphorus, and there is a limit to reduction of eutrophication in the lake because the controllable area is limited to the low quality in the lake. In particular, it does not provide a solution for recovering useful metals that are eluted simultaneously with phosphorus during the summer.

Accordingly, the present invention has been made in view of the above-described problems of the existing technology, and it is possible to continuously remove and recover phosphorus in the lake, obtain a recoverable phosphorus resource in the form of poly-P, and at the same time, Its purpose is to recover iron as pyrite (Pyrite: FeS ₂ )) using sulfur supplied by the reaction of phosphorus.

In addition, another object of the present invention is to drive the iron ore and phosphate ore in a simple manner from the cork carrier and the phosphorus scaled gibbs of the pyrite (FeS ₂ ), but for the operation of the power supply other than the power of the secondary supply device A separate power source is needed to enable operation with unnecessary power.

In particular, it is easy to ensure economic feasibility because the whole process is made of biochemical reactions by microorganisms during the recovery of phosphite.

Solution to Problem The present invention for achieving the above object is as follows.

Provided is a method for simultaneously recovering iron and phosphorus by using iron oxide microorganisms eluted in summer in the lake or river bed and available in the field soluble iron and phosphorus ions present in water-soluble; The iron oxide microorganism cultured in a carrier represented by a sterile, pore-enlarged cork was impregnated and maintained, and a natural gibbs Island having a relatively high sulfur content as compared to other gibbs is used as a source of sulfur. ,

Performing oxygen supply between the cork carrier and the gib island.

By providing a carbon source represented by dry ice as a source of carbon dioxide (CO ₂ ),

The iron oxide microorganism oxidizes iron divalent to iron trivalent, and the iron trivalent reacts with sulfur supplied from the gibb island to grow into crystallized particles of pyrite (FeS2) on the surface of the carrier,

After the iron ore, which is the grown pyrite (FeS ₂ ) form, was taken out of the intestine as a raw material, pyrite was obtained by centrifugation to recover iron,

In order to recover the phosphorus of the gib island changed from CaSO ₄ to CaPO ₄ after the discharge of sulfur in the form of poly-P, phosphoric acid phosphate (PSM: Phosphate Solublizing Microorganism) was used to form calcium phosphate (CaPO _4). ) Is dissolved in water to separate Ca and PO ₄ to convert the phosphorous in the form of Pi to the form of Poly-P to recover the phosphorus.

In addition, the configuration as a main device,

Tank-shaped reactor having inlet and outlet as flow path,

A carrier represented by a cork impregnated with iron oxide microorganisms and fixed to a stator to maintain its position,

Gibseom, which is a source of sulfur excreted to maintain a position fixed to the stator around the carrier,

An oxygen supply device for supplying oxygen to the carrier,

Having dry ice supplied as a carbon supply source,

The inlet and outlet are configured to circulate in fluid connection with the lake.

Simultaneous recovery method of iron and phosphorus in the lake using the interaction of cork carrier and sulfur discharge Gippsum impregnated with Ferrooxidnas, in particular Leptospirillum Ferrooxidnas According to the adopted device,

The recovered phosphorus can be used as a resource to replace phosphorus, which has been mainly supplied through the mining of phosphate ores. Therefore, there is a double environmental effect that improves the environmental performance of the lake and reduces the environmental load due to mining. .

In particular, it can be newly used as a factor required in the chemical industry and widely used as a phosphate fertilizer material. Therefore, it is efficient in terms of resource use, and at the same time, phosphorus in the lake can be removed simultaneously. It has a high effect on the improvement of environmental system by reducing eutrophication in lake by phosphorus.

According to the present invention, the recovered iron also uses the iron ore recovered by the microorganisms can reduce the various environmental and economic costs in the process of mining the iron ore from the mine.

As a result, new iron resources will be supplied to the iron ore processing industry. In particular, considering the situation in Korea where iron ore is imported entirely from abroad, iron ore can be partially self-procured, thus reducing the logistics costs associated with iron ore imports. In addition, import imports have increased by more than 65% due to the current unstable supply of iron ore.

1 is a schematic diagram of a complete mixed batch device for simultaneous recovery of iron and phosphorus according to an embodiment of the present invention.

2 is an explanatory diagram showing the leaching of iron and phosphorus in a lake to which the technique of the present invention is applied;

3 is a graph showing the change of iron divalent in a lake to which the technique of the present invention is applied.

Figure 4 is a component analysis table of the components of the Gibsum to which the technique of the present invention is applied.

Fig. 5 is a graph showing the recovery rate of phosphorus of gib island to which the technique of the present invention is applied.

Figure 6 is a micrograph showing the release of sulfur after the reaction of gibsome and phosphorus according to the present invention.

7 is a micrograph showing the growth of microorganisms in a carrier to which the technique of the present invention is applied.

8 is a micrograph showing the conversion from iron divalent to iron trivalent according to the present invention.

9 is a graph of the production and conversion of iron trivalent according to the present invention.

Figure 10 is a micrograph showing the attachment of the microorganism, pyrite, carrier according to the present invention.

11 is a graph showing a change in concentration of sulfur in effluents according to the present invention.

12 is an explanatory diagram of a chemical formula illustrating a theoretical principle to which the technique of the present invention is applied.

13 is an explanatory diagram of an actual reaction scheme after the technique of the present invention is applied.

14 is a micrograph of the growth diameter of a microorganism according to the present invention.

Experimental example of a method and apparatus for the simultaneous recovery of iron and phosphorus in the lake using the interaction of the cork carrier impregnated with the lepttospirilum-iron oxide microorganisms and the sulfur discharge Gibbom of the present invention for achieving the above object with reference to the accompanying drawings and Best Mode for Carrying Out the Preferred Embodiments

First, a method for simultaneously recovering iron and phosphorus in a lake using the interaction of a cork carrier impregnated with Leptospirillum Ferrooxidnas and sulfur discharge Gippsum and a leptospirilum-iron acid employed in the apparatus Brief description of Leptospirillum Ferrooxidnas will be given.

Leptospirillum Ferrooxidnas, which is employed in the present invention as iron oxide microorganisms, is a microorganism that is widely known in the industry and easily collected at a specific site, and converts insoluble metals into water-soluble bioleaching. ) And a type of iron oxidizing bacteria that play an important industrial role in biooxidation, which extracts metals from minerals.

It was initially found separately in industrial continuous-flow biooxidation tanks and is a major factor in the acid mine drainage process.

The activity of this microorganism can be judged by the ratio of iron divalent and trivalent, because it absorbs carbon dioxide as a carbon source and converts it into iron trivalent as a by-product. In other words, carbon is obtained from carbon dioxide for metabolism, and carbon is fixed using iron divalent ions.

Bio-oxidation, not bio-reaching, converts iron trivalent by supplying carbon dioxide using microorganisms that selectively absorb only iron divalent ions among the minerals contained in the lake water. Based on the principle

The iron oxide microorganisms described above may of course increase the yield of iron and phosphorus through proper genetic manipulation.

The present invention relates to a device for treating this on the premise that the bioriching in the lake is made first. In addition, in the case of phosphorus, there is phosphorus dissolved in water, and there is phosphorus present without dissolving in water. It is very difficult to make phosphorus from insoluble to water-soluble, and the recovery of phosphorus in the present invention has various effects described above.

The present invention also pays attention to the phenomenon shown in FIG. 2, wherein iron ions and phosphorus ions are present in a form in which they do not melt until they reach summer until the summer in the lake.

This can be easily seen from the biochemical gradients in the lake of FIG.

In particular, as shown in the graph of Figure 3 the amount of iron divalent in the summer lake water is continuously increasing.

The method of the present invention and the apparatus to which the method is applied will be described together with the apparatus of the embodiment.

[Corkdam]

Various kinds of carriers may be employed, but the present invention uses corks used for bottle caps and various plates of wine.

Air washing removes the impurities in the pores of cork and sterilizes them in autoclave for 15 minutes at 121 degrees Celsius to remove other microorganisms that may be in the carrier. And after drying, it is cooled to 50 degrees Celsius to shrink the pores in the carrier.

Then, heated again to 160 degrees Celsius to expand the pores again, and then rapidly cooled to maintain the enlarged pores to reach 55 degrees Celsius when the above-mentioned leptospirilum cultured in LB agar medium (agar) medium Iron oxide microorganisms (Leptospirillum Ferrooxidnas) are impregnated into the cork carrier. The temperature is then kept at 30 degrees Celsius.

In the present invention, the cork carrier used in the present invention is low in density and has excellent buoyancy in the lake, can be supplied in large quantities at low cost, and is easily adapted to allow microorganisms to be initially impregnated by easily adjusting the pore size.

Gibbs Island

As a source of salary, Gibseom is employed here. In the case of Gibseom, it is important to contain a large amount of sulfur among various kinds, so it is important to increase the discharge of sulfur using a natural Gibseom.

As shown in FIG. 4, in the case of a natural gib island, sulfur content is higher than that of a phospho group or a ferro group, and it is about 75 g / kg according to a conventional analysis.

The principle of the recovery of iron and phosphorus in the lake and the reaction according to the present invention, the cork carrier and the gibsum is adopted, the arrangement of the cork carrier in the center and the left and right gibseom of the cork carrier, respectively, the device so that the interaction occurs do.

[Recovery Method and Theoretical Basis]

The oxygen supply device is installed vertically in the form of a rod between the cork carrier and the gib island as described above to continuously supply oxygen to the water.

Then, phosphorus, which is eluted from the low quality in the lake and soluble in water below the level of reducing acid in the lake, reacts with Gibbsum (CaSO ₄ ), and as shown in FIG. ₄ ) and recovered from the photomicrograph of FIG. 6, it can be seen that SO ₄ was discharged by the substitution reaction with PO ₄ to continuously supply sulfur to the cork carrier.

The above-described leptospiryllum-iron oxide microorganism of the cork carrier impregnated with a leptospiryllum-oxidase containing carbon dioxide (CO ₂ ),

As can be seen in Figure 7, it can be seen that the growth continues in the carrier,

As shown in FIG. 8, when iron divalent is oxidized to iron trivalent, as shown in FIG. A, iron divalent is present in the form of dots around the microorganism, but since the oxidation has not yet proceeded, the color appears relatively bright. As shown in Fig. B, when oxidation progresses and the iron trivalent is changed, it can be clearly seen that a black spot appears. As shown in Fig. 9, the reaction time for the highest production and conversion rate from iron divalent to trivalent is 0.1 to 0.12. It can be seen that it is time.

As shown in FIG. 10, when iron trivalent reacts with sulfur supplied from Gibb Island and grows into crystallized particles of pyrite (FeS ₂ ) in the form of cork carrier, the microorganism is attached to the carrier in FIG. Figure B shows an enlarged image of the microorganisms attached to the carrier, showing that pyrite (FeS ₂ ) is annularly surrounded by the microorganisms.

In addition, as shown in Figure 11 as a result of the continuous reaction of iron trivalent and sulfur, it can be seen that the concentration of sulfur in the effluent continues to decrease.

This grown pyrite (FeS ₂ ) form of iron ore was taken out of the market as a raw material, and then centrifuged to move the small cork carrier to the top and the high density of pyrite to the bottom. It can be recovered by separating pyrite.

In addition, the discharge of Gibbs, which has been discharged from sulfur, has already been changed from GiSum (CaSO ₂ ) to calcium phosphate (CaPO ₄ ), where Phosphate Solublizing Microorganism is used to recover phosphorus in the form of Poly-P. Dissolve the calcium phosphate (CaPO ₄ ) in water in water and then separate Ca and PO ₄ ,

Phosphorus microorganisms (e.g., PhoU mutant E. coli.) Selected from various types are used to convert the Pi-type phosphorus into the form of Poly-P (phenyleneterephthalate), and For example, when PhoU mutant E. coli. Is heated at 70 degrees Celsius for 1 hour, poly-P-type phosphorus is released into the water so that it can be recovered as a phosphorus resource. Shown.

[Theoretical Basis of Recovery Unit]

Based on the recovery method described above, the proposed fully mixed crystallization reactor having excellent field applicability in the proposed lake of the present invention will be composed of a tank-like body having a circular or polygonal cross section.

When the lake water taken in below the redox level of the lake flows into the lower part of the reactor, the pretreatment process is performed to solve various problems that occur during the operation of the reactor by securing a space for precipitate of large humic substances. From here, iron and phosphorus are recovered.

At this time, the cork carrier and Gibseom start the reaction by the upflow by the hydraulic pressure, as shown in Figure 14, the hydraulic retention time (HRT) is preferably about 1 to 1.02 hours. This is because the biological reaction time is 0.1 to 0.12 hours as shown in FIG. 9 and the physicochemical reaction time is about 0.5 for sulfur emission, as shown in FIG.

If this time elapses, the treated water recovered from the iron and phosphorus is quickly flowed back into the lake by the natural drainage system in the reactor, thereby promoting circulation in the lake and increasing the water level in the lake again. In the reactor proposed in the present invention, since the sulfur generated when the phosphorus reacts with the Gibbsum is used to form pyrite (FeS ₂ ), a proper pH is maintained. This is because the supply of sulfur is in the form of SO ₄ .

In contrast, as shown in FIG. 11, when the supply of sulfur is in the form of HS, Ph decreases due to the increase of hydrogen ions, and acidification in the reactor proceeds, making the reaction difficult. Therefore, no action is required, but it is also possible to configure the stability of the continuous reaction by checking the concentration of sulfur and oxygen using an external sensor attached to the reactor.

Cork and Gibsum used in the reaction tank of the present invention, since the apparent volume of the particle itself continues to increase more than several times after a certain period of operation, it should be discharged out of the intestine when it grows to a size of resource value.

On the other hand, the sulfur discharged by the substitution reaction by phosphorus during the operation period is continuously supplied to the cork carrier to improve the efficiency of iron recovery, and the supply of carbon dioxide and oxygen is essential for the continuous stabilization of leptospiryl-iron oxide microorganisms, The carbon dioxide is supplied in the form of dry ice to be used as a carbon source of the leptospirum-iron oxide microorganism, and the oxygen supply is preferably provided by continuously supplying a vertical rod type feeder in the reactor.

In addition, in the case of the conventional Fenton oxidation method, it is not only necessary to use a large amount of hydrogen peroxide catalyst for the recovery of iron, but also the cost is very high. Therefore, according to the method of the present invention, it is possible to economically recover iron at low cost by using leptospiryl-iron oxide microorganisms.

[Example of Recovery Device]

The recovery device of the present invention will be described in more detail with reference to FIG. 1 as follows.

1 is a cross-sectional view of a batch system for simultaneous recovery of iron and phosphorus according to an embodiment of the present invention, which is employed as a tank-shaped crystallization reactor 1 of circular or polygonal cross section.

The inlet pipe 12 and the discharge pipe 8 are provided in the reactor 1 as a tubular flow path.

The reactor 1 is supplied with oxygen to the cork carrier 10 through the oxygen supply device 7, and carbon dioxide is attached to the dry ice 11 attached to the cork carrier 10.

The baffle and the gibsum stator 2 fix the gibsum 9 and suppress the swirl flow along the circulation. Although the shape of the gimbs 9 is made into the shape of the fin which protrudes as shown in the figure in order to facilitate the discharge | release of sulfur, it is a matter of course that it can employ | adopt what kind of thing which increases the contact area.

In addition, when the dry ice 11 and the oxygen supply device 7 are stopped, various corrosive substances 13 settle by gravity into moisture, and then the treated water is temporarily discharged, and the inflow water is filled again to restart the operation. You have a pattern.

In order to secure economical efficiency of the reaction tank of the present invention, minimization of circulating energy is required in the operation of the reaction tank (1). For this, the shape of the reaction tank is circular or rectangular, and in the cross-section, it is made into an egg shape, a half egg type, or a polygon corresponding thereto. It will be possible to design various types of fluid circulation energy.

The hydraulic residence time of the batch reactor 1 is suitable for 1 hour.

As a driving factor of the pyrite formation reaction by sulfur, it is very important to maintain the pH in the reactor 1 from 7 to 7.5, and the adjustment of the pH is made using a ready-made automatic pH control device (3).

Other major operating factors for determining pyrite formation in reactor 1 include the concentration of sulfur ions in the reactor 1, the concentration of corrosives, and the water temperature, which are typically practically negligible in the recovery process.

Although the size of the reaction tank 1 in this invention is not specifically limited, It can select suitably according to the processing conditions, such as the amount of inflow of water from a lake, the amount of oxygen supply, the site situation, etc. It is good to divide three or more tanks, and to install as a double tank.

For example, a plurality of sets of devices can be provided around the lake, respectively. If the size of the lake is large, using a plurality of reactors, the diameter and depth of each unit reactor is increased, it is also possible to employ a way to install a plurality of oxygen supply device.

Installation of the batch reactor 1 shown in FIG. 1 is a circular or square reactor in a single reactor, and the gib islet 9 attached to the inner edge of the reactor continuously reacts with phosphorus to release sulfur, thereby producing leptospirilum-iron oxide microorganisms. It is important to continuously form pyrite in this impregnated cork carrier 10.

In particular, it is most important that the formed pyrite is attached to the cork carrier 10 through the leptospiryl-iron oxide microorganism. This is because centrifugation is used later to recover pyrite.

In the case of Gibsum (9), it is important to supply sulfur in the form of SO4 because the substitution reaction of phosphorus and sulfur occurs continuously.

In FIG. 1, reference numeral 5 denotes a sulfuric acid solution tank, 4 is a caustic soda solution tank, and 6 is a sulfur automatic control device.

Hereinafter, the present invention will be described in more detail based on the experimental examples.

Experimental Example

The reactor of the simultaneous recovery of iron and phosphorus in the lake using the interaction of the cork carrier impregnated with the leptospirilum-iron oxide microorganism of the present invention with the above-described structure and the sulfur discharge Gibbom was operated.

As a result of microscopic photographs of cork carrier and Gibsum, pyrite was attached to cork carrier with Leptospirilum-iron oxide microorganism in the middle, as shown in the micrograph of FIG.

As shown in the micrograph of FIG. 6, in the case of Gibsom, it was observed that SO ₄ ions originally contained were replaced by PO ₄ ions and SO ₄ was discharged.

Claims (5)

Oxygen and carbon dioxide in the iron and phosphorus ions that are soluble in the lake or stream at the bottom of the redox level in the summer using iron oxide microorganisms represented by Leptospirillum Ferrooxidnas. In the method for recovering iron and phosphorus at the same time using iron oxide microorganisms capable of supplying CO ₂ ) and collecting on-site and power saving; The method; Impregnated and maintained in the iron oxide microorganism cultured in a carrier represented by sterile, pore enlarged cork, As a source of sulfur, by employing a natural gib island, which is relatively high in sulfur content as compared to other gimb islands, is disposed apart from the carrier, The iron oxide microorganism oxidizes the iron divalent to iron trivalent, and the iron trivalent reacts with sulfur supplied from the gibb island to grow into crystallized particles of pyrite (FeS ₂ ) in the surface of the carrier, After the iron ore, which is the grown pyrite (FeS ₂ ) form, was taken out of the intestine as a raw material, pyrite was obtained by centrifugation to recover iron, In order to recover the phosphorus of the gib isoform changed from calcium (CaSO ₄ ) to calcium phosphate (CaPO ₄ ) 4 in the form of Poly-P after the discharge of sulfur, phosphoric acid in an insoluble form using Phosphate Solublizing Microorganism (PSM) Impregnated with iron oxide microorganisms, which is a method of improving the degree of recovery by dissolving calcium (CaPO ₄ ) in water, separating Ca and PO ₄ , converting the phosphorus in the Pi form into the poly-P form, and recovering the phosphorus. Recovery of Iron and Phosphorus in Lakes Using the Interactions of Carriers with Sulfur-Emitted Gibbs. delete Oxygen and carbon dioxide in the iron and phosphorus ions that are soluble in the lake or stream at the bottom of the redox level in the summer using iron oxide microorganisms represented by Leptospirillum Ferrooxidnas. In the device of the constitution to recover the iron and phosphorus simultaneously using iron oxide microorganisms capable of supplying CO ₂ ) and harvesting on-site and power saving; The device, Tank-shaped reactor having inlet and outlet as flow path, A carrier represented by a cork impregnated with iron oxide microorganisms and fixed to a stator to maintain its position, It includes a gibseom that is a sulfur source is excreted to maintain a position fixed to the stator around the carrier, The carbon source is dry ice, and the inlet and the outlet are connected to the lake in fluid communication with the iron oxide microorganisms impregnated, characterized in that the carrier and the recovery of iron and phosphorus in the lake using the sulfur discharge Gibbseom . The method of claim 3, wherein The lake using the interaction of the iron oxide microorganism-impregnated carrier and the sulfur discharge Gibsum, characterized in that the sulfuric acid solution tank and the sulfur automatic control device and the caustic soda solution tank fixed to the outside of the reaction tank can be further provided as an auxiliary device. Recovery device for iron and phosphorus. delete