JP2020062581A - Recovery method and recovery apparatus of humin substance - Google Patents

Abstract

To provide a recovery method and a recovery apparatus of a humin substance capable of realizing both operation efficiency and quantitation.SOLUTION: A recovery method and a recovery apparatus of a humin substance of this invention recover the humin substance by fractionating the humin substance from mixed water acquired from a lake, a river, etc. using a column encasing resin. The recovery apparatus includes a flow passage switching unit that switches over flow directions of a supplied material that flows through a column pipe connected to a column unit. The recovery method includes: a first water passing step of acquiring a non-adsorbed substance by passing a mixture of the mixed water and an acidic solution from one side to the other side of the column; and a second water passing step of acquiring the humin substance, after the first water passing step, by passing an alkaline solution from the other side to the one side of the column.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method and apparatus for fractionating mixed water obtained from lakes and rivers, and in particular, a method and apparatus for collecting humic substances by fractionating and collecting humic substances from lake water, river water, etc. Regarding

  In some lakes, rivers, etc., it has been observed that chemical oxygen demand (COD), which is an index of organic matter in water, tends to increase, although measures for improving domestic wastewater have been taken in recent years. ing. One of the causes for this is the water pollution phenomenon caused by the accumulation of some dissolved organic matter in lake water, river water, and the like.

  Such dissolved organic substances are roughly classified into five types: humic substances, hydrophobic neutral substances, basic substances, hydrophilic acids, and hydrophilic neutral substances. Among them, humic substances are classified into soil humin and water humin. Among them, the aqueous humin is composed of hydrophobic organic acids (humic acid and fulvic acid), is hardly decomposed, and is said to occupy most of the dissolved organic matter (about 30 to 80%). It is a cause of environmental pollution.

  Since these humic substances react with chlorine added in water purification treatment, they are also known as precursors of disinfection by-products such as trihalomethane. Therefore, it is required to separate and collect humic substances from lake water and river water containing sludge.

  As a method for separating and recovering such a humic substance, for example, in Patent Document 1, after mixing mud obtained from the bottom of an aqueous system with water glass (sodium silicate), the mixture is solidified by firing at a predetermined temperature. Then, a method of separating and recovering the humic substance is disclosed, in which the solidified product is immersed in water to transfer the humic substance to water to generate a solution of the humic substance. According to this method, it is said that humic substances in water can be effectively used by simple work.

JP, 2006-306733, A

  The method for separating and recovering the humic substance described in Patent Document 1 is to selectively solidify the humic substance from the mud by leaching the humic substance into water after the humic substance is once solidified with water glass. Although it can be separated and collected, it is unclear how much of the humic substances contained in the sample mud can be separated and collected.Therefore, when conducting a water quality survey of lakes and rivers, etc. Evaluation is difficult. Further, since it is necessary to perform the firing step and the dipping step in order to separate and collect the humic substance, there is a problem that human intervention is unavoidable in each step and it is difficult to improve the work efficiency.

  Therefore, an object of the present invention is to provide a humic substance recovery method and a recovery device that enable both efficient work and quantification.

  In order to solve the above problems, according to the present invention, using a resin-encapsulated column, a method for recovering a humic substance by fractionating and recovering a humic substance from a mixed water obtained from a lake or a river is A first water-passing step for obtaining a non-adsorbed substance through a mixture of the mixed water and an acidic solution from one side to the other side; and, after the first water-passing step, from the other side of the column to the one side. A second water-passing step for obtaining a humic substance by passing an alkaline solution toward the water.

  According to such an invention, using a column in which a resin is enclosed, a non-adsorbed substance is obtained by passing mixed water from one side of the column to the other side thereof, and then an alkali is passed from the other side of the column to the one side. By performing the operation of passing the aqueous solution, the humic substance can be separated and recovered only by switching the flow direction of the feed substance flowing through the column, so that the work efficiency and the quantification can be compatible.

  In the above-mentioned invention, a washing step of washing the resin enclosed in the column with an acidic solution may be further included after the second water passing step. According to such an invention, it is possible to repeat the above-mentioned first water passing step after the washing step as it is, so that it is possible to further improve the efficiency of the work and also to cope with automatic operation.

  On the other hand, according to the present invention, a humic substance recovery device for fractionating and recovering humic substances from mixed water obtained from lakes, rivers, etc. using a resin-encapsulated column is a supply containing the mixed water. A supply unit having a supply tank for each substance, the column and a column unit holding the column, a recovery unit having a recovery tank for recovering the substance that has passed through the column, and a supply flowing through a column pipe connected to the column unit. A flow path switching unit connected to a recovery pipe for switching to the flow direction of the substance and connected to a recovery pipe, and a recovery destination of the substance which is provided between the flow path switching unit and the recovery unit and which flows through the recovery pipe And a control unit for controlling the operation of all the units included in the recovery device. And wherein the door.

  According to such an invention, with respect to the column in which the resin is sealed, the flow path switching unit has a function of switching the flow direction of the feed substance flowing through the column pipe, and therefore, the flow direction of the feed substance flowing through the column can be simply switched. Since the humic substances can be separated and recovered, work efficiency and quantification can both be achieved.

  In the above invention, a supply source selection unit may be provided between the supply unit and the flow path switching unit to selectively switch the supply flow path of the supply substance supplied from the supply unit. . According to this invention, the pump for supplying the supply substance to the flow path switching unit can be made common (becomes one), so that the device configuration can be further simplified.

  Further, in the above invention, a plurality of column units connected to the flow path switching unit may be provided in parallel. According to such an invention, it is possible to improve the fractionation capability of the entire apparatus and, for example, to prepare (set up) another column unit while using one column unit.

It is a schematic diagram which shows the outline of the collection | recovery apparatus of the humic substance by a typical example of this invention. It is a side view which shows the outline of the supply unit shown in FIG. It is a partial top view which shows the outline | summary of the supply source selection unit shown in FIG. It is a partial top view which shows the outline of the flow-path switching unit shown in FIG. It is a schematic diagram of the column unit shown in FIG. 1, and FIG. 5 (a) is a plan view and FIG. 5 (b) is a right side view. It is a partial top view which shows the outline | summary of the collection | recovery destination selection unit shown in FIG. FIG. 6 is a schematic diagram showing an operation of a preparatory step in the method for recovering a humic substance according to a representative example of the present invention. It is a schematic diagram which shows operation | movement of the 1st water-passing process in the recovery method of the humic substance by a typical example of this invention. It is a schematic diagram which shows operation | movement of the 1st water-passing process in the recovery method of the humic substance by a typical example of this invention. It is a schematic diagram which shows operation | movement of the acid adjustment process in the recovery method of the humic substance by a typical example of this invention. It is a schematic diagram which shows operation | movement of the 2nd water-passing process in the recovery method of the humic substance by a typical example of this invention. It is a schematic diagram which shows operation | movement of the 2nd water-passing process in the recovery method of the humic substance by a typical example of this invention. It is a schematic diagram which shows operation | movement of the washing | cleaning process in the recovery method of the humic substance by the modification of this invention. It is a schematic diagram which shows operation | movement of the washing | cleaning process in the recovery method of the humic substance by the modification of this invention.

  Hereinafter, a concrete outline of a method for recovering a humic substance and a recovery apparatus thereof according to the present invention will be described with reference to the drawings. In addition, in this specification, "mixed water acquired from lakes and rivers" means not only lake water and river water, but also all fresh water including water and sewerage.

  FIG. 1 is a schematic diagram showing an outline of a humic substance recovery apparatus according to a representative example of the present invention. As shown in FIG. 1, a humic substance recovery apparatus 100 according to a representative example of the present invention has a supply tank having a supply tank for each supply substance containing mixed water obtained from a lake or a river, which is an object to be fractionated. A unit 110, a column unit 150 including a resin-encapsulated column C, a recovery unit 170 having a recovery tank for recovering a substance after passing water through the column C, and a supply substance supplied from the supply unit 110. A source selection unit 120 that selects a flow path, a liquid feed pump 130 that sucks a feed substance from a feed tank and pushes it out to a downstream flow, and a column unit 150 that will be described later to feed the feed substance supplied from the liquid feed pump 130. Of the flow path switching unit 140 and the flow path switching unit 140 and the recovery unit 170, which switches the flow path to send to the collection unit 170. Disposed includes a recovery destination selection unit 160 to switch the recovery destination of material after the water passage, and a control unit 180 for controlling the operation of all units contained in the collecting apparatus 100, a.

  FIG. 2 is a side view showing an outline of the supply unit 110 shown in FIG. As shown in FIG. 2, the supply unit 110 includes, for example, a supply base 111, a mixed water tank 112 that stores mixed water SS acquired from a measurement target such as a lake or a river, and hydrochloric acid (HCl), for example. A low-concentration acid tank 113 and a high-concentration acid tank 114 for respectively storing aqueous solutions of the above with a predetermined concentration, and an alkali tank 115 for storing an aqueous solution of, for example, sodium hydroxide (NaOH) with a predetermined concentration are included.

  Here, as an example of the supplied substance, the mixed water SS is adjusted to have a pH of 2 by adding a predetermined acid after removing large dusts contained in water obtained from lakes and rivers by filtering. Use the one adjusted to. On the other hand, regarding the HCl aqueous solutions LA and HA stored in the low-concentration acid tank 113 and the high-concentration acid tank 114, the low-concentration acid LA is 0.01M and the high-concentration HA is 0.1M (M = mol / L). The alkali aqueous solution AL stored in the alkali tank 115 is adjusted to 0.1M.

  The mixed water tank 112, the low-concentration acid tank 113, the high-concentration acid tank 114, and the alkali tank 115 are provided with supply pipes 112a, 113a, 114a, and 115a connected to a supply source selection unit 120 described later, respectively. And is sucked and supplied by the suction pressure from the liquid feed pump 130. Further, as shown in FIG. 2, the mixed water tank 112 is preferably mounted on a weighing machine such as a weight scale 116.

  Here, the weighing scale 116 is connected to, for example, a communication line 181 that measures the weight of the mixed water tank 112 and transmits an output signal to the control unit 180. Thereby, the supply amount of the mixed water SS can be adjusted by weight (for example, automatic control such as stopping the supply when the supply amount decreases by a predetermined amount becomes possible).

  FIG. 3 is a partial plan view showing an outline of the supply source selection unit 120 shown in FIG. In FIG. 3, the inside of the supply source selection unit 120 is visible as a cutaway view of a part of the housing. As shown in FIG. 3, the supply source selection unit 120 includes, for example, a substantially hollow box-shaped casing 121, a supply pipe switching mechanism 122 provided inside the casing 121, and the supply pipe switching mechanism 122. A supply pipe 123 connected to a liquid delivery pump 130 described later is attached to the housing 121, and a communication line 182 for exchanging signals with the control unit 180 is connected to the housing 121.

  The supply pipe switching mechanism 122 is connected to the above-described supply pipes 112a, 113a, 114a and 115a, and has a function of selectively switching the supply pipes 112a to 115a and the downstream supply pipe 123 therein. Have As a result, since the plurality of supply tanks 112 to 115 and the liquid feed pump 130 are connected in a one-to-one correspondence, the liquid feed pump 130 is shared (becomes one), thereby further simplifying the apparatus configuration. In addition, the feed materials are not mixed and supplied at the same time.

  Here, as the liquid feed pump 130, for example, a diaphragm pump, a rotary pump, or the like can be exemplified, but a peristaltic tube type pump is particularly preferable. Further, as shown in FIG. 1, the liquid feed pump 130 is connected to a communication line 183 that receives a signal such as an output command from the control unit 180.

  FIG. 4 is a partial plan view showing an outline of the flow path switching unit 140 shown in FIG. Note that, also in FIG. 4, as in the case of FIG. 3, the inside of the flow path switching unit 140 is visible as a cutaway view of a part of the housing. As shown in FIG. 4, the flow path switching unit 140 includes, as an example, a substantially hollow box-shaped housing 141, a flow path selection mechanism 142 provided inside the housing 141, and a first flow direction switching mechanism. 143 and a second flow direction switching mechanism 144, and a communication line 184 for exchanging signals with the control unit 180 is connected to the housing 141.

  The flow path selection mechanism 142 is connected to the feed pipe 131 from the liquid feed pump 130 on the inlet side and is connected to the first internal pipe 142a and the second internal pipe 142b on the outlet side. Then, the flow path selecting mechanism 142 has a function of switching the flow path so that the supply substance sent from the supply pipe 131 communicates with only one of the first internal pipes 142a and 142b.

  The first flow switching mechanism 143 is connected to the first internal pipe 142a on the inlet side and is connected to the first column pipe 143a and the first recovery pipe 143b on the outlet side. Then, the first flow switching mechanism 143 is connected so as to send the feed substance flowing through the first internal pipe 142a to the first column pipe 143a, or the column water flow flowing from the first column pipe 143a. It has a function of connecting the latter substance so as to be sent to the first recovery pipe 143b or switching it to be one of the flow paths.

  Similarly, the second flow switching mechanism 144 is connected to the second internal pipe 142b on the inlet side and is connected to the second column pipe 144a and the second recovery pipe 144b on the outlet side. Then, the second flow switching mechanism 144 is connected so as to send the feed substance flowing through the second internal pipe 142b to the second column pipe 144a, or the column water flow flowing through the second column pipe 144a. It has a function of connecting the latter substance so as to be sent to the second recovery pipe 144b or switching it to be one of the flow paths.

  5A and 5B are schematic diagrams of the column unit 150 shown in FIG. 1. FIG. 5A is a plan view and FIG. 5B is a right side view. As shown in FIG. 5, the column unit 150 includes, as an example, a support member 151 extending in the vertical direction, a pair of gripping members 152 provided on the support member 151, and a column gripped by the pair of gripping members 152. Including C and.

  The column C applied to the humic substance recovery apparatus 100 according to the present invention includes a cylindrical column main body C1, a pair of lid members C2 that closes both ends of the column main body C1 to form an internal space, and the above-mentioned internal space. And a resin RC to be housed. Here, as the resin RC to be encapsulated, a nonionic XAD-8 (or DAX-8) resin having a MR structure (giant network structure) which is a copolymer of acrylic and divinylbenzene is applied.

  The first column pipe 143a from the flow path switching unit 140 is connected to one of the pair of lid members C2, and the second column pipe 144a is connected to the other of the lid members C2. ing. Therefore, when the mixed water SS described above is flowed from one side of the column C to the resin RC made of the XAD-8 (or DAX-8) resin, the hydrophobic substance containing the humic substance is adsorbed on one side of the resin RC. It

  The pair of gripping members 152 are attached to the support member 151 via a hinge 153, and are configured to rotate about a shaft 153a. Here, the gripping member 152 is preferably a latch slide type clamp. As a result, it becomes possible to deal with columns C of various sizes (thicknesses).

  Referring to FIG. 4 and FIG. 5 together, the flow path selection unit 140, which is one of the major features of the humic substance recovery apparatus according to the present invention, receives a command from the control unit 180, for example, from the feed pipe 131. First, the flow path selection mechanism 142 selects the direction of the first internal pipe 142a or the second internal pipe 142b for the supplied supply substance. Here, when the first internal pipe 142a is selected, the first internal pipe 142a and the first column pipe 143a are communicated with each other in the first flow switching mechanism 143, and the first recovery pipe 143b is closed. To be done. As a result, the feed material flowing through the first internal pipe 142a is supplied to the column C from the upper side in the drawing of FIG. 5 through the first column pipe 143a.

  Then, the feed material sent to the column C passes through the resin RC and then flows into the second flow switching mechanism 144 through the second column pipe 144a. At this time, in the second flow switching mechanism 144, the second column pipe 144a and the second recovery pipe 144b are communicated with each other, and the second internal pipe 142b is closed. As a result, the substance that has passed through the column C is sent to the recovery destination selection unit 160 from the second recovery pipe 144b.

  On the other hand, when the flow path selection mechanism 142 selects the second internal pipe 142b, the second flow switching mechanism 144 connects the second internal pipe 142b and the second column pipe 144a with each other, and The recovery pipe 144b is closed. As a result, the feed material flowing through the second internal pipe 142b is supplied to the column C from the lower side in the drawing of FIG. 5 through the second column pipe 144a.

  Then, the supply substance sent to the column C passes through the resin filter RC and then flows into the first flow switching mechanism 143 through the first column pipe 143a. At this time, in the 1st flow switching mechanism 143, the 1st column piping 143a and the 1st recovery piping 143b are open for free passage, and the 1st internal piping 142a is closed. As a result, the substance that has passed through the column is sent to the recovery destination selection unit 160 from the first recovery pipe 143b.

  FIG. 6 is a partial plan view showing the outline of the collection destination selection unit 160 shown in FIG. Note that, also in FIG. 6, as in the case of FIG. 3, the inside of the recovery destination selection unit 160 is visible as a cutaway view of a part of the housing. As shown in FIG. 6, the collection destination selection unit 160 includes, for example, a substantially hollow box-shaped housing 161, a confluence mechanism 162 and a collection destination selection mechanism 163 provided inside the housing 161. A communication line 185 for exchanging signals with the control unit 180 is connected to the housing 161.

  The merging mechanism 162 is connected to the first recovery pipe 143b and the second recovery pipe 144b from the flow path selection unit 140 on the inlet side, and is connected to the merging pipe 162a on the outlet side. Then, the merging mechanism 162, based on a command from the control unit 180, when a supply substance or a substance that has passed through the column C flows from either one of the first recovery pipe 143b and the second recovery pipe 144b. , Has the function of closing the connection to the other pipe to prevent backflow.

  The recovery destination selection mechanism 163 is connected to the merging pipe 162a on the inlet side, and is connected to the acid recovery pipe 163a, the alkali recovery pipe 163b, the non-adsorbed substance recovery pipe 163c, the humic substance recovery pipe 163d, and the drain pipe 163e on the outlet side. ing. Further, referring also to FIG. 1, the acid recovery pipe 163a, the alkali recovery pipe 163b, the non-adsorbed substance recovery pipe 163c, the humic substance recovery pipe 163d, and the drain pipe 163e include an acid recovery tank 171, an alkali recovery tank 172, and a non-adsorption tank. The substance recovery tank 173, the humic substance recovery tank 174, and the drain recovery tank 175 are respectively connected.

  Then, the recovery destination selection mechanism 163, on the basis of the command from the control unit 180, causes the substance flowing from the merging pipe 162a to collect an acid recovery pipe 163a, an alkali recovery pipe 163b, a non-adsorbed substance recovery pipe 163c, and a humic substance recovery pipe. It has a function of switching the pipe connected to the recovery destination tank so as to flow into any one of the 163d and the drain pipe 163e.

  Here, at least the non-adsorbed substance recovery tank 173 and the humic substance recovery tank 174 are provided with lids, and it is preferable that the lids be provided with valves that can be opened and closed. This makes it possible to suppress so-called dead volume and prevent contamination of the collected substance from the outside.

  Next, a specific operation of the method for recovering a humic substance according to a representative example of the present invention will be described with reference to FIGS.

  FIG. 7 is a schematic diagram showing the operation of the preparatory step in the method for recovering a humic substance according to a representative example of the present invention. First, the control unit 180 drives the liquid feed pump 130 in a state where the supply source selection unit 120 selects communication with the high-concentration acid tank 114 as preparation for carrying out the humic substance recovery method according to the present invention. To supply the high-concentration acid HA to the flow path switching unit 140 (preparation step).

  When carrying out this preparatory step, the control unit 180 repeats the flow path switching in the flow path switching unit 140 so that the high-concentration acid HA becomes the first column pipe 143a and the second column pipe 144a, The column unit 150 and the first recovery pipe 143b and the second recovery pipe 144b are supplied so as to be distributed over each of them. At this time, since it is often unknown what kind of residual substance was present in each flow path before the preparation step, the supplied high-concentration acid HA is drained through the drain pipe 163e in the recovery destination selection unit 160. It is led to the recovery tank 175. These operations prevent air from remaining in various pipes when fractionation is performed.

  8 and 9 are schematic diagrams showing the operation of the first water passing step in the method for recovering a humic substance according to a representative example of the present invention. Next, as shown in FIG. 8, the control unit 180 drives the liquid feed pump 130 and selects the flow path switching unit for the mixed water SS in a state where the supply source selection unit 120 selects the communication with the mixed water tank 112. Supply to 140.

  At this time, the control unit 180 switches the flow path in the flow path switching unit 140 so that the mixed water SS is supplied from the first column pipe 143a (see FIG. 4) to the column C, and the recovery destination selection unit 160. At, a command is issued to select the drain recovery tank 175 as the recovery destination. As a result, the mixed water SS supplied from the mixed water tank 112 was passed from one side (upper side in FIG. 5) of the column C through the first column pipe 143a, and was present in the pipe in the preparation step. The high-concentration acid HA is discharged from the second recovery pipe 144b to the drain recovery tank 175 via the recovery destination selection unit 160.

  Then, as shown in FIG. 9, the control unit 180 issues a command in the recovery destination selection unit 160 to select the non-adsorbed substance recovery tank 173 as the recovery destination, and continues the supply of the mixed water SS (No. 1 water flow step). At this time, the mixed water SS is supplied at a supply rate of 1 ml / min as an example. As a result, the non-adsorbed substance of the mixed water SS that has passed through the column C is recovered in the non-adsorbed substance recovery tank 173, and the resin RC of the column C adsorbs the hydrophobic substance of the mixed water SS.

  FIG. 10 is a schematic view showing the operation of the acid adjusting step in the method for recovering a humic substance according to a representative example of the present invention. Next, the control unit 180 drives the liquid feed pump 130 to supply the low-concentration acid LA to the flow path switching unit 140 in a state where the supply source selection unit 120 selects the communication with the low-concentration acid tank 113.

  At this time, the control unit 180 causes the low concentration acid LA to be supplied to the column C from the first column pipe 143a (see FIG. 5) in the flow path switching unit 140, as in the case shown in FIG. While switching the flow paths, the recovery destination selection unit 160 issues a command to select the drain recovery tank 175 as the recovery destination. As a result, the low-concentration acid LA supplied from the low-concentration acid tank 113 is passed from one side (upper side in FIG. 5) of the column C through the first column pipe 143a, and the pipe is used in the first water passing step. The mixed water SS existing therein is discharged from the second recovery pipe 144b to the drain recovery tank 175 via the recovery destination selection unit 160 (acid adjusting step).

  11 and 12 are schematic views showing the operation of the second water passing step in the method for fractionating a humic substance according to a representative example of the present invention. Next, as shown in FIG. 11, the control unit 180 drives the liquid feed pump 130 to select the flow path switching unit 140 by driving the liquid feed pump 130 in a state where the supply source selection unit 120 selects communication with the alkali tank 115. Supply to.

  At this time, the control unit 180 switches the flow path in the flow path switching unit 140 so that the alkaline aqueous solution AL is supplied to the column C from the second column pipe 144a (see FIG. 4), and the recovery destination selection unit 160. At, a command is issued to select the drain recovery tank 175 as the recovery destination. As a result, the alkaline aqueous solution AL supplied from the alkaline tank 115 is passed from the other side of the column C (the lower side in FIG. 5) through the second column pipe 144a, and enters the pipe and the column C in the acid adjusting step. The existing low-concentration acid LA is discharged from the first recovery pipe 143b to the drain recovery tank 175 via the recovery destination selection unit 160.

  Subsequently, as shown in FIG. 12, the control unit 180 issues a command in the recovery destination selection unit 160 to select the humic substance recovery tank 174 as the recovery destination and continues the supply of the alkaline aqueous solution AL (second). Water flow process). At this time, the alkaline aqueous solution AL is supplied at a supply rate of 0.3 ml / min, for example. As a result, the humic substance among the hydrophobic substances adsorbed on the resin RC is eluted together with the alkaline aqueous solution AL flowing in the column C in the reverse direction, and is recovered in the humic substance recovery tank 174.

  With such a configuration and operation, the humic substance recovery method and the humin substance recovery device according to the present invention have a flow path switching unit with respect to a resin-encapsulated column that has a function of switching the flow direction of the feed material flowing through the column pipe. By the passage switching unit, the non-adsorbed substance is obtained by passing the mixed water from one side to the other side of the column, and then the humic substance is obtained by passing the alkaline aqueous solution from the other side of the column to the one side. Since the humic substance can be fractionated and collected by simply switching the flow direction of the feed substance flowing through the column, it is possible to achieve both efficient work and quantification.

  Next, with reference to FIGS. 13 and 14, a specific operation of the method for fractionating a humic substance according to a modification of the present invention will be described.

  13 and 14 are schematic diagrams showing the operation of the washing step in the method for fractionating a humic substance according to a modification of the present invention. In the method for fractionating a humic substance according to a modification of the present invention, in order to remove the feed substance remaining in the column C and various pipes of the recovery device, following the second water passing step shown in FIGS. 11 and 12 described above. The cleaning step of is carried out. That is, as shown in FIG. 13, the control unit 180 drives the liquid sending pump 130 to switch the flow path of the high-concentration acid HA in a state where the supply source selection unit 120 selects the communication with the high-concentration acid tank 114. Supply to the unit 140.

  At this time, the control unit 180 switches the flow path in the flow path switching unit 140 so that the high-concentration acid HA is supplied from the first column pipe 143a to the column C, and then from the second recovery pipe 144b. In the recovery destination selection unit 160, a command is issued to select the drain recovery tank 175 as the recovery destination. As a result, the high-concentration acid HA supplied from the high-concentration acid tank 114 is passed through the first column pipe 143a from one side of the column C, and the first column pipe 143a and the second recovery pipe 144b are supplied. The supply material (particularly, the alkaline aqueous solution AL) existing in (1) is discharged to the drain recovery tank 175 via the recovery destination selection unit 160.

  Subsequently, as shown in FIG. 14, in the flow path switching unit, the control unit 180 supplies the high-concentration acid HA to the column C from the second column pipe 144a, and then selects the recovery destination from the first recovery pipe 143b. The flow path is switched so as to flow to the unit 160, and a command is issued to continue the supply of the high-concentration acid HA. Thereby, the high-concentration acid HA supplied from the high-concentration acid tank 114 is passed through the second column pipe 144a from the other side of the column C, and the second column pipe 144a and the first recovery pipe 143b are supplied. The supplied substance existing in the above is discharged to the drain recovery tank 175 via the recovery destination selection unit 160. Then, if the state directly shifts from this state to the preparation step shown in FIG. 7, the recovery method according to the present invention can be repeated and performed again.

  By such an operation, according to the humic substance recovery method according to the modified example of the present invention, it is possible to repeat the first water passing step and the subsequent steps after the washing step as it is, so that the work efficiency can be further improved. At the same time, it becomes possible to support automatic driving.

  Although the embodiments according to the present invention and the modifications based on the embodiments have been described above, the present invention is not necessarily limited to these examples. Also, one of ordinary skill in the art will be able to find various alternatives and modifications without departing from the spirit of the invention or the scope of the appended claims.

  For example, in the specific example described above, a plurality of column units 150 connected to the flow path switching unit 140 may be provided in parallel. This makes it possible to improve the fractionation capability of the entire apparatus and, for example, to prepare (set up) another column unit while using one column unit.

  Further, in the above-described specific example, after performing the preparatory step shown in FIG. 7, high-concentration acid HA is passed from one side (upper side in FIG. 5) of the column C through the first column pipe 143a, The “preliminary organic substance measurement process” of discharging the acid from the second recovery pipe 144b to the acid recovery tank 171 via the recovery destination selection unit 160 may be performed. At this time, by analyzing the components of the recovered high-concentration acid HA, it is possible to grasp the components and the amount of the organic substances that have previously adhered to the resin RC enclosed in the column C.

  As in the case of the “preliminary organic substance measurement process” described above, after the second water-passing step shown in FIG. 12 is performed, the alkaline aqueous solution AL is supplied to one side of the column C (see FIG. 5) via the first column pipe 143a. The “post-treatment organic matter measurement process” may be performed in which water is supplied from above) and discharged from the second recovery pipe 144b to the alkali recovery tank 172 via the recovery destination selection unit 160. At this time, by analyzing the components of the recovered alkaline aqueous solution AL, it is possible to grasp the components and the amount of the organic substances attached to the resin RC after carrying out the method for recovering the humic substance according to the present invention.

100 Recovery Device 110 Supply Unit 112 Mixed Water Tank 113 Low Concentration Acid Tank 114 High Concentration Acid Tank 115 Alkaline Tank 120 Source Selection Unit 122 Supply Pipe Switching Mechanism 130 Liquid Delivery Pump 140 Flow Path Switching Unit 142 Flow Path Selection Mechanism 143 1st Flow direction switching mechanism 143a first column pipe 143b first recovery pipe 144 second flow direction switching mechanism 144a second column pipe 144b second recovery pipe 150 column unit 151 support member 152 gripping member 160 recovery destination selection Unit 162 Confluence mechanism 163 Recovery destination selection mechanism 170 Recovery unit 171 Acid recovery tank 172 Alkali recovery tank 173 Non-adsorbed substance recovery tank 174 Humic substance recovery tank 175 Drain recovery tank 180 Control unit

Claims (5)

A method for recovering a humic substance by fractionating and recovering a humic substance from a mixed water obtained from a lake, river, etc., using a column containing resin.
A first water-passing step of obtaining a non-adsorbed substance from the one side of the column toward the other side through the mixed water;
A second water-passing step of obtaining a humic substance by passing an alkaline solution from the other side of the column toward the one side after the first water-passing step;
A method for recovering a humic substance, which comprises:   The method for recovering a humic substance according to claim 1, further comprising a washing step of washing the resin encapsulated in the column with an acidic solution after the second water passing step. A humic substance recovery device for fractionating and recovering humic substances from mixed water obtained from lakes, rivers, etc. using a column containing resin.
A supply unit having a supply tank for each supply substance containing the mixed water;
A column unit for holding the column and the column,
A recovery unit having a recovery tank for recovering the substance passing through the column;
While switching the flow direction of the feed material flowing to the column pipe connected to the column unit, a flow path switching unit to which the recovery pipe toward the recovery unit is connected,
A recovery destination selection unit that is provided between the flow path switching unit and the recovery unit, and switches the recovery destination of the substance flowing through the recovery pipe,
A control unit for controlling the operation of all the units included in the recovery device;
A device for recovering humic substances, comprising:   The humic substance according to claim 3, further comprising: a source selection unit that selectively switches a supply flow path of the supply material supplied from the supply unit, between the supply unit and the flow path switching unit. Recovery device. The humic substance recovery apparatus according to claim 3, further comprising a plurality of the column units connected in parallel to the flow path switching unit.

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