WO2018072280A1 - Extracting device for fulvic acid dissolved in fresh water body and preparation method therefor - Google Patents

Abstract

An extracting device for fulvic acid dissolved in a fresh water body. The extracting device comprises a raw water supply unit, a pretreatment unit, a reverse osmosis concentration unit, a pH adjustment unit, a water tank (9), a general control system (5), a filtration and purification unit and a fulvic acid extracting unit. Further disclosed is a method for extracting fulvic acid dissolved in a fresh water body. The method comprises the following steps: separating purified water from concentrated water by means of the reverse osmosis concentration unit, letting the concentrated water enter into the water tank (9) once again for circulation and concentration until the concentration ratio is suitable, and closing the concentrating system; achieving automatic pH adjustment of the water body after concentration by means of the pH adjustment unit, which not only saves labor and reduces production costs, but also has a higher accuracy for the pH adjustment; separating fulvic acid from insoluble impurities by means of the filtration and purification unit, and then concentrating and purifying fulvic acid by means of the fulvic acid extracting unit to obtain a solution with a high concentration of fulvic acid.

Description

Dissolved fulvic acid extraction device in fresh water body and preparation method thereof Technical field

The invention relates to the field of concentration technology, in particular to a solution for dissolving fulvic acid in fresh water body and a preparation method thereof.

Background technique

Dissolved organic matter is a natural macromolecular organic mixture that can pass through a 0.45 μm pore size membrane. It is derived from animal and plant secretions and their residue decomposition products. The composition and structure vary from time to time and source. Dissolved organic matter plays an important ecological and environmental role in freshwater bodies. Dissolved organic matter mainly includes acidic substances such as fulvic acid and humic acid, as well as small molecules such as polypeptides, polysaccharides and amino acids. Among them, small molecules such as polypeptides, polysaccharides, and amino acids have a small proportion and are easily decomposed by the use of aquatic organisms. Acidic substances such as fulvic acid have large molecular weights and are difficult to degrade, and are the main components in the dissolution of organic matter in fresh water, and have been widely concerned. Fulvic acid is widely distributed in various natural water bodies. It can be dissolved under any pH adjustment and has strong migration. It has an important influence on the migration and transformation of metal ions and organic pollutants in water and the formation of disinfection by-products in water treatment. Therefore, research on fulvic acid can help to understand its environmental behaviors on heavy metals and toxic and harmful pollutants, and it has very important theoretical and practical significance for further improvement of water treatment process. The concentration of fulvic acid in freshwater water is low, generally 1-10 mg/L, which is difficult to separate and enrich. The establishment of fulvic acid extraction methods and devices in freshwater bodies is one of the bottlenecks in fulvic acid research.

Reverse osmosis technology is based on the osmotic pressure of the solution, according to the macromolecular substances can not pass through the semi-permeable membrane to leave these substances and moisture. The membrane pore size of the reverse osmosis membrane is very small, so that dissolved salts, colloids, microorganisms, organic matter, and the like in the water can be effectively removed. Reverse osmosis has the advantages of high salt rejection, high mechanical strength, long service life and strong chemical or biochemical tolerance. At present, the extraction of dissolved fulvic acid in organic matter is mainly based on experimental methods, mainly relying on manual operation. There is no complete device to achieve the separation of fulvic acid in natural water, and the extraction and purification of fulvic acid. Poorly implementable, in addition, the concentration of fulvic acid extracted from the laboratory is low, which cannot meet the current demand for fulvic acid concentration.

Summary of the invention

In order to realize separation of high-purity fulvic acid from water, the present invention provides a solution for dissolving fulvic acid in a fresh water body and a preparation method thereof, wherein the dissolved fulvic acid extraction device can conveniently and efficiently extract a desired fulvic acid solution.

In order to solve the above technical problems, the present invention provides a dissolved fulvic acid extraction device in a fresh water body, comprising a raw water supply unit, a pretreatment unit, a reverse osmosis concentration unit, a pH adjustment unit, a water tank, a total control system, a filtration purification unit, and fulvic acid. Extraction unit

The fulvic acid extraction unit includes an alkali solution tank, a rinsing device, an adsorption enrichment device, and an ion exchange device; an inlet of the adsorption enrichment device and an outlet of the lye reagent tank, and an outlet of the rinsing device Connecting, the outlet of the adsorption-enrichment device is connected to the inlet of the ion exchange device, and the bottom is provided with a waste liquid discharge switch; the outlet of the rinse device is connected to the inlet of the ion exchange device;

An outlet of the raw water supply unit is connected to an inlet of the pretreatment unit, an outlet of the pretreatment unit is connected to the water tank; and an inlet of the reverse osmosis concentration unit and the pH adjustment unit is connected to the water tank An outlet of the water tank is connected to an inlet of the filtration purification unit, and an outlet of the filtration purification unit is connected to an inlet of the fulvic acid extraction unit;

The raw water supply unit, the reverse osmosis concentration unit, and the pH adjustment unit are all connected to the control system;

The adsorption and enrichment device comprises an adsorption column and a filler, wherein the filler is disposed in the adsorption column, and the filler is one or more of XAD-8 resin, DAX-8 resin and XAD-7 resin; The ion exchange apparatus includes an adsorption column and a filler, and the filler is disposed in the adsorption column, and the filler is a hydrogen type cation exchange resin.

Preferably, the fulvic acid extraction unit comprises an organic chemical tank, a rinsing device and an adsorption and enrichment device; an inlet of the sorption and enrichment device is connected to an outlet of the organic chemical tank, an outlet of the rinsing device, and is absorbing rich a liquid discharge switch is arranged at the bottom of the collecting device;

The adsorption-enrichment device includes an adsorption column and a filler, and the filler is disposed in the adsorption column, and the filler is one or more of XAD-8 resin, DAX-8 resin, and XAD-7 resin.

Preferably, the fulvic acid extraction unit comprises an organic chemical tank, a leaching device, a first-stage adsorption and enrichment device, and a second-stage adsorption and enrichment device; an inlet of the first-stage adsorption and enrichment device and an outlet of the organic chemical agent tank The outlet of the rinsing device and the outlet of the liquid storage device are connected to the outlet of the rinsing device, the outlet of the organic chemical tank, and the outlet of the first-stage adsorption and enrichment device;

The bottom of the first-stage adsorption enrichment device and the second-stage adsorption and enrichment device are provided with a liquid discharge switch;

The first-stage adsorption and enrichment device includes an adsorption column and a filler, and the filler is disposed in the adsorption column, and the filler is one or more of XAD-8 resin, DAX-8 resin and XAD-7 resin. The secondary adsorption-enrichment device comprises an adsorption column and a filler, the filler is disposed in the adsorption column, and the filler is XAD-4 resin.

Preferably, the fulvic acid extraction unit comprises a first-stage adsorption and enrichment device, a first ion exchange device, a second-stage adsorption and enrichment device, a second ion exchange device, a leaching device and a dosing device, and the first-stage adsorption rich device Set device inlet and liquid storage The outlet of the reservoir, the outlet of the leaching device, and the outlet connection of the dosing device, and the outlet of the first-stage adsorption and enrichment device are respectively connected to the inlet of the first ion exchange device and the inlet of the second-stage adsorption and enrichment column device;

The inlet of the secondary adsorption enrichment device is connected to the outlet of the elution device, the outlet of the dosing device, and the outlet of the secondary adsorption enrichment device is connected to the inlet of the second ion exchange device;

An outlet of the rinsing device is connected to an inlet of the first ion exchange device and an inlet of the second ion exchange device;

a waste liquid discharge switch is respectively arranged at the bottom of the first-stage adsorption and enrichment device, the second-stage adsorption and enrichment device, the first ion exchange device and the second ion exchange device;

The first-stage adsorption and enrichment device includes an adsorption column and a filler, and the filler is disposed in the adsorption column, and the filler is one or more of XAD-8 resin, DAX-8 resin and XAD-7 resin. The first ion exchange device includes an adsorption column and a filler, the filler is disposed in the adsorption column, and the filler is a hydrogen type cation exchange resin;

The secondary adsorption enrichment device comprises an adsorption column and a filler, the filler is disposed in the adsorption column, the filler is XAD-4 resin; the second ion exchange device comprises an adsorption column and a filler, the filler Located in the adsorption column, the filler is a hydrogen type cation exchange resin.

Preferably, the filter purification unit comprises a filter, a liquid reservoir and a vacuum pump, an inlet of the filter being connected to an outlet of the water tank, an outlet of the filter being connected to an inlet of the liquid reservoir; the vacuum pump and The liquid reservoir is connected, and an outlet of the liquid reservoir is connected to an inlet of the adsorption enrichment device;

The filter comprises an impurity chamber, a filter membrane and a sand core, the filter membrane is disposed in the impurity chamber and supported by the sand core; the filter membrane has a pore diameter ranging from 0.1 to 0.7 μm.

Preferably, the pH adjustment unit includes a pH sensor, a stirrer, a metering dosing pump, a first acid solution tank, and a second acid solution tank; the pH sensor is disposed in a water tank, the first acid solution The medicine tank and the second acid liquid medicine tank are arranged side by side; the metering dosing pump is disposed between the first acid liquid medicine tank, the second acid liquid medicine tank and the water tank, and the metering dosing pump inlet and the first acid liquid respectively The outlet of the medicament box, the outlet connection of the second acid solution tank, and the outlet of the metering dosing pump are connected to the water tank.

Preferably, the water tank is made of an acid-resistant material, and has a sealing cover on the upper end, a funnel shape at the lower end, a stirrer, a liquid level sensor and a pH sensor; the end surface of the sealing cover is provided with at least 5 through holes; The pipe between the water tank and the filter extends into the water tank, the top of the pipe is a sealing structure, and the wall of the water pipe is provided with a plurality of holes having a diameter of 50 μm, and the minimum height of the hole is controlled at 1/100 of the height of the water tank. At -1/10, a filter cover is disposed outside the water inlet pipe, and the filter cover has a hole diameter of 100 μm.

Preferably, the reverse osmosis concentration unit comprises a reverse osmosis unit, a high pressure pump, a first conductivity probe and a second conductivity probe; wherein the reverse osmosis unit comprises a reverse osmosis membrane and a stainless steel membrane shell, and the pore size of the reverse osmosis membrane is taken The value is 0.1 nm;

The first conductivity probe is disposed at the concentrated water outlet of the reverse osmosis unit, and the second conductivity probe is disposed between the pure water outlet of the reverse osmosis concentration unit and the rinsing device; by comparing two conductivity probes By detecting the value, it can be judged whether the working state of the reverse osmosis membrane is good.

Preferably, the reverse osmosis unit is provided with a liquid inlet, a concentrated water outlet and a pure water outlet; the liquid inlet is connected to the water tank through a high pressure pump, and the concentrated water outlet is connected to the water tank, the pure water outlet and the leaching device Connecting; the reverse osmosis unit concentrated water and pure water outlet are provided with a security valve; in the raw water concentration process, when the difference between the pure water and the concentrated water conductivity of the reverse osmosis unit is less than a preset value, the security valve is opened, indicating that The system is unable to perform reverse osmosis concentration.

Preferably, the raw water supply unit is supplied by a self-priming pump, and the raw water is mainly fresh water bodies such as rivers, lakes and groundwater, and the turbidity of the raw water is within 1000 NTU, and the value of dissolved organic carbon is within 1000 mg/L, and the conductivity is taken as a value. Within 30000 μS/cm; the front end of the self-priming pump is provided with a filter bag having a pore size of 10 μm.

Preferably, the raw water supply unit comprises a self-priming pump; the pre-processing unit comprises a first-stage precision microfiltration filter, a secondary precision microfiltration filter and a three-stage precision microfiltration filter, and a first-stage precision microfiltration filter. The precision of the medium-precision filter element is 5μm, the diameter of the precision filter element in the second-stage precision microfiltration filter is 1μm, and the diameter of the precision filter element in the three-stage precision microfiltration filter is 0.45μm; the entrance of the first-stage precision microfiltration filter Connected to the outlet of the self-priming pump, the outlet of the first-stage precision microfiltration filter is connected to the inlet of the secondary precision microfiltration filter, the outlet of the secondary precision microfiltration filter and the inlet of the tertiary precision microfiltration filter Connection, the outlet of the three-stage precision microfiltration filter is connected to the water tank.

Preferably, the first, second and third precision filter elements are all made of polypropylene filter elements, and the precision filter elements need to be replaced in time to avoid clogging and excessive contaminant accumulation to breed microorganisms.

Preferably, the overall control system comprises a control unit and a touch screen, the control unit is connected to a touch screen, and the control unit is connected with a self-priming pump, a liquid level sensor, a pH sensor, a metering dosing pump and a high pressure pump. The pH sensor is provided with a lifting platform, and if necessary, the pH sensor is raised outside the water tank.

Preferably, the water tank is provided with a liquid level sensor whose water level is controlled at 1/5-4/5 of the height of the water tank.

The invention provides a method for dissolving fulvic acid extraction by using a fulvic acid extraction device, which comprises the following steps:

(1) Start the total power start button of the total control system;

(2) Start the self-priming pump start button, the self-priming pump draws the raw water through the pipeline, and the raw water is pre-filtered by the filter bag at the front end of the self-priming pump, and the raw water after the preliminary filtration enters the pretreatment unit through the supercharging of the self-priming pump. Precision microfiltration filter pair The raw water is filtered once, and the primary filtered water enters the secondary precision microfiltration filter for secondary filtration. The primary filtered water enters the tertiary precision microfiltration filter for three times of filtration; the filtered raw water enters the water tank through the pipeline. When the water level in the water tank reaches the height of 4/5 tank, the self-priming pump stops working;

(3) The raw water in the water tank is pressurized by the high-pressure pump and enters the reverse osmosis concentration unit through the pipeline. The reverse osmosis membrane can concentrate the dissolved salt and the naturally dissolved organic matter in the raw water to obtain pure water and concentrated water; after passing through the reverse osmosis membrane Pure water is directly discharged into the leaching device for storage, and the concentrated water is circulated into the water tank. When the dissolved organic carbon content measured by the dissolved organic carbon on-line measuring device in the water tank reaches a preset value, the concentration is stopped; the reverse osmosis membrane will treat the rivers and lakes and Freshwater water such as groundwater is separated into pure water and concentrated water. The higher the ratio of pure water, the higher the salt content and organic matter concentration of concentrated water, but the excessively high proportion of pure water causes damage to the reverse osmosis membrane. Therefore, the reverse osmosis membrane is discharged. The ratio of the amount of pure water to the amount of concentrated water discharged is 1:9-9:1, preferably 1:2-2:1;

(4) Starting the pH adjustment unit, the metering dosing pump receives the pH sensor signal to start the acid addition procedure, and extracts the acid solution from the first acid solution tank into the water tank through the first acid-resistant pipeline, and simultaneously injects the non-oxidizing acid solution into the water tank. The agitation motor is started to uniformly mix the acid solution and the concentrated water until the preset pH value is reached, and the first acid addition program of the dosing dosing pump stops working;

The metering dosing pump extracts hydrofluoric acid from the second acid solution tank, and injects hydrofluoric acid into the water tank through the second acid-proof pipeline until the preset hydrofluoric acid concentration is reached, and the metering dosing pump and the water tank stirring motor stop. jobs;

(5) Open the outlet valve of the water tank, start the vacuum pump at the same time, apply pressure by the vacuum pump, the concentrated water in the water tank flows into the liquid reservoir through the filter, the acid insoluble impurities are removed by the filter membrane, and the crude fulvic acid solution flows through the filter membrane. In a liquid reservoir;

(6) After the filtration is completed, the outlet valve of the water tank is closed, the outlet valve of the liquid reservoir is opened, the liquid in the liquid reservoir flows into the adsorption enrichment device, and the fulvic acid is adsorbed on the resin;

(7) After the adsorption is completed, the switch between the leaching device and the adsorption enrichment device is turned on, and the waste liquid discharge switch of the adsorption and enrichment device is turned on, and the pure water in the leaching device is injected into the adsorption and enrichment device through the pipeline to adsorb The enrichment device performs rinsing, and the rinsing waste liquid is directly discharged from the waste liquid outlet; the switch between the leaching device and the ion exchange device is opened, and the pure water in the rinsing device rinses the ion exchange device to remove impurities, and the rinsing liquid is directly discharged. ;

(8) After the flushing is completed, the switch between the eluent device and the adsorption enrichment device and the waste liquid discharge valve are closed, the outlet valve of the alkali solution tank is opened, and the alkali solution tank is injected into the adsorption enrichment device through the alkali-resistant pipeline. The lye, the fulvic acid adsorbed by the resin is desorbed by the action of the alkali solution, and the desorbed solution is discharged through the ion exchange device, and the discharged solution is the fulvic acid solution to be extracted.

Preferably, the first acid-resistant pipe is required to withstand 10 mol/L of non-oxidizing acid; the second acid-resistant pipe is required to withstand 6 mol/L of hydrofluoric acid; the mixed acid concentration in the water tank ranges from 0.001 to 1 mol. / L non-oxidizing strong acid and 0.1-0.5 mol / L hydrofluoric acid; the pH is preset to a value of 0.5 - 3; the lye in the dosing device is a strong base of 0.1 - 6 mol / L; Alkali-resistant pipes are required to withstand 6 mol/L of strong alkali.

Preferably, the reverse osmosis unit has a speed regulating valve disposed on the discharge pipe of the pure water, and the speed oscillating valve is arranged on the pipeline connected to the water tank by the reverse osmosis unit, and the pure water discharged by the reverse osmosis membrane and the concentrated water discharged The ratio is 1:9-9:1.

Preferably, the reverse osmosis membrane is not dry to store, and it is necessary to ensure that there is water in the membrane shell. If the equipment is idle for more than 70 hours, the reverse osmosis membrane should be immersed in clean water. If it is left unused for a long time, it must be stored in the storage mode required by the reverse osmosis membrane.

Preferably, the total control system adopts low-voltage power distribution, the voltage level of the power supply and distribution equipment is 22a0aVAC, and the low-voltage power distribution cabinet is provided to supply power to the process system power equipment; the power switch and the electric control cabinet door interlock protection in the control system, It can achieve dustproof, fast heat dissipation and easy installation.

Preferably, the front end of the high-pressure pump is provided with a pressure gauge and a security valve. When the pressure of the high-pressure pump is greater than a preset value in the raw water concentration process, the security valve is opened to avoid damage of the high-pressure pump and bursting of the pipeline.

Preferably, the front end of the self-priming pump is provided with a safety valve, and the water tank is provided with a liquid level sensor. When the water level is in the water tank of the water tank 4/5, the safety valve is opened, the self-priming pump stops running, and the water tank is avoided. The water level is too high.

The beneficial effects produced by the present invention over the prior art are:

(1) The present invention provides a method for dissolving fulvic acid in a fresh water body with simple structure, high degree of automation, convenient operation, convenient and effective separation of fulvic acid from other impurities, extraction of a large amount of fulvic acid, and research and application of fulvic acid. Provide sample protection;

(2) The first-order precision filter element has a pore size of 5 μm in the present invention, a secondary precision filter element has a pore size of 1 μm, and a three-stage precision filter element has a pore size of 0.45 μm, which more effectively filters out impurities such as suspended matter of larger particles in water, thereby avoiding Scratches, clogging and high pressure impact on the film caused by particulate matter;

(3) The whole process of pH adjustment by the pH adjustment unit is fully automatic, saving labor, reducing production cost, and preparing the pH value with high accuracy; the first acid solution tank and the second acid solution tank share one Metering dosing pump reduces production costs;

(4) The ratio of the amount of pure water discharged from the reverse osmosis unit to the amount of concentrated water discharged in the reverse osmosis concentration unit is 2:1-1:2, thereby avoiding damage to the membrane caused by excessive or too little pure water outflow. Or equipment efficiency is reduced;

(5) The bottom of the water tank is in the shape of a funnel, and a filter cover is arranged outside the pipeline extending into the water tank, which is beneficial not only for the outflow of concentrated water but also for the precipitation of impurities in the concentrated water; after the pH adjustment is completed, the concentrated water passes through the filter membrane. Filtration can remove acid-insoluble impurities such as humic acid in concentrated water; the resin in the adsorption and concentration device further removes impurities in the concentrated water.

DRAWINGS

Figure 1 is a schematic view showing the structure of a first embodiment of the present invention;

Figure 2 is a schematic view showing the structure of a second embodiment of the present invention;

Figure 3 is a schematic structural view of a third embodiment of the present invention;

Figure 4 is a schematic view showing the structure of a fourth embodiment of the present invention.

detailed description

The embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

The dissolved fulvic acid extraction device in the fresh water body provided by the invention comprises a raw water supply unit, a pretreatment unit, a reverse osmosis concentration unit, a pH adjustment unit, a water tank 9, a total control system 5, a filtration purification unit and a fulvic acid extraction unit; wherein the raw water supply The unit comprises a self-priming pump 1; the pre-processing unit comprises a first-stage precision microfiltration filter 2, a second-stage precision microfiltration filter 3, a three-stage precision microfiltration filter 4; the reverse osmosis concentration unit comprises a reverse osmosis membrane and a stainless steel membrane shell The pH adjustment unit comprises a pH sensor, a dosing pump 6, a first acid solution tank 7 and a second acid solution tank 8; the filter purification unit comprises a liquid reservoir 17, a filter, a vacuum pump 15, wherein the filter comprises an impurity chamber 18. The filter membrane 16 and the sand core 19, the filter membrane 16 is located in the impurity chamber 18, and is supported by the sand core 19; the total control system 5 is mainly controlled by automatic control, wherein the centralized control operation is uniformly performed in the control cabinet, so that the whole The system implements automatic control operations and manual operations.

Wherein, the inlet of the first-stage precision microfiltration filter 2 is connected to the outlet of the self-priming pump 1, and the outlet of the first-stage precision microfiltration filter 2 is connected to the inlet of the second-stage precision microfiltration filter 3, and the second-stage precision microfiltration filter The outlet of the device 3 is connected to the inlet of the tertiary precision microfiltration filter 4, the outlet of the tertiary precision microfiltration filter 4 is connected to the water tank 9; the pH sensor is located in the water tank 9, the first acid solution tank 7 and the second acid The liquid medicine tanks 8 are arranged side by side, and the dose dosing pump 6 is disposed between the water tank 9 and the first acid liquid medicine tank 7 and the second acid liquid medicine tank 8, and the inlets of the metering dosing pump 6 and the first acid liquid medicine tank respectively The outlet of 7 and the outlet of the second acid solution tank 8 are connected, the outlet of the dosing pump 6 is connected to the water tank 9; the reverse osmosis unit 11 is provided with a liquid inlet, a concentrated water outlet and a pure water outlet; the liquid inlet is passed through the high pressure pump 10 Connected to the water tank 9, the concentrated water outlet is connected to the water tank 9, the pure water outlet is connected to the rinsing device 14, the inlet of the liquid reservoir 17 is connected to the filter outlet, the inlet of the filter is connected to the outlet of the water tank 9, and the suction of the vacuum pump 15 The gas port is placed in the cavity of the liquid reservoir 17; the liquid reservoir Export with fulvic acid The inlet of the extraction unit is connected; the total control system 5 comprises a control unit and a touch screen, the control unit is connected with the touch screen, the control unit and the self-priming pump 1, the liquid level sensor, the pH sensor, the metering dosing pump 6, the high pressure pump 10 It is connected to the vacuum pump 15 for control.

The fulvic acid extraction device is provided in the freshwater water body provided by the invention, wherein the raw water source is fresh water body such as rivers and lakes and groundwater, and the water quality requirement of the raw water is that the turbidity of the water is within 1000 NTU, and the value of dissolved organic carbon is 1000 mg/L. Inside, the conductivity is within 30,000 μS/cm; the front end of the self-priming pump is provided with a filter bag having a pore size of 10 μm.

The total control system uses low-voltage power distribution, the voltage level of the power supply and distribution equipment is 22a0aVAC, and the low-voltage power distribution cabinet is provided to supply power to the process system power equipment. In addition, the control system is equipped with an independent operation of the control cabinet, as well as electrical switches and electrical components are concentrated in the control cabinet, the power switch and the electronic control cabinet door interlock protection, can achieve dust, heat dissipation and easy to install.

Embodiment 1

1 is a schematic view showing the structure of a first embodiment of a solution for dissolving fulvic acid in a fresh water body according to the present invention; in FIG. 1, the fulvic acid extraction unit includes a rinsing device 14 and a lye agent. a tank 20a, an adsorption enrichment device 21a and an ion exchange device 22a; wherein an outlet of the liquid reservoir 17 is connected to an inlet of the adsorption enrichment device 21a, and an outlet of the adsorption enrichment device 21a is connected to an inlet of the ion exchange device 22a, and ion exchange The inlet of the device 22a is also connected to the outlet of the rinsing device 14.

The process of fulvic acid extraction using the dissolved fulvic acid extraction apparatus shown in Figure 1 is as follows:

Firstly, the main power supply and the start button are turned on to make the whole system in working state. The self-priming pump 1 draws raw water through the pipeline, and the raw water is initially filtered through a filter bag located at the front end of the self-priming pump. The pore size of the filter bag is 10 μm, and the raw water after preliminary filtration The primary water is filtered once by the supercharging pump's pressurization into the first-stage precision microfiltration filter 2 in the pretreatment unit, and the primary filtered water enters the secondary precision microfiltration filter 3 for secondary filtration, twice The filtered raw water enters the three-stage precision microfiltration filter 4 for three times of filtration, wherein the filter element of the first-stage precision microfiltration filter 2 has a pore size of 5 μm, and the filter element of the second-stage precision microfiltration filter 3 has a pore size of 1 μm, three stages. The filter element in the precision microfiltration filter 4 has a pore size of 0.45 μm. Due to the large amount of suspended solids in the fresh water body, the three-stage precision microfiltration filter is connected in series, and the diameter of the filter element can better filter out larger particles in the water. Impurities such as suspended solids improve water quality and more effectively avoid scratches, clogging and high-pressure impact on the membrane caused by particulate impurities. In addition, precision filter cartridges need to be replaced in time to avoid clogging and excessive contaminants accumulating breeding microorganisms.

The raw water filtered by the three-stage precision filtering device enters the water tank 9 through the connecting pipe, and the liquid level sensor in the water tank 9 detects the water level in the water tank. When the water level reaches 4/5 of the volume of the water tank, the liquid level sensor reaches the total control system. Transmitting liquid The bit signal, after receiving the liquid level signal, the total control system sends a control signal to the self-priming pump to stop the operation, that is, stop injecting water into the water tank.

The water tank is made of acid-resistant material, and has a sealing cover on the upper side and a funnel shape on the lower end, and a stirrer and a pH sensor are arranged therein; and the end surface of the sealing cover is provided with at least five through holes.

The raw water in the water tank 9 is pressurized by the high pressure pump 10 into the reverse osmosis membrane in the reverse osmosis unit 11, and the reverse osmosis membrane can intercept inorganic salts and dissolved organic matter in fresh water such as surface water, ground water and tap water, and the sodium ions are removed. The rate is about 96%, and the highest can reach 98%; the pure water discharged through the reverse osmosis membrane is directly discharged into the rinsing device 14, and the speed regulating valve is arranged on the connecting pipe of the reverse osmosis unit 11 and the rinsing device 14, which can be adjusted. The speed of pure water flowing out of the reverse osmosis membrane is adjusted to a range of 0-20a0L/h; after the system is finished, the reverse osmosis membrane can be washed and washed by pure water in the leaching device 14; the concentrated water passing through the reverse osmosis membrane passes through The pipeline is returned to the water tank 9, and a speed regulating valve is arranged on the pipeline connecting the reverse osmosis unit 11 and the water tank 9, and the speed of the concentrated water flowing out of the reverse osmosis membrane can be adjusted, and the speed adjustment range is 0-20a0L/h; The speed of the permeable membrane and the velocity of the concentrated water flowing out of the reverse osmosis membrane are set within an appropriate range, so that the ratio of the amount of pure water discharged from the reverse osmosis membrane to the amount of concentrated water discharged is 1:9-9:1, thereby avoiding Because the speed of pure water flowing out is too fast or too Slow damage to the reverse osmosis membrane or reduced equipment efficiency. The concentrated water inlet tank can be circulated and concentrated. In this way, the water in the raw water tank is less and less, the concentration of salt and organic matter is getting higher and higher, and the dissolved organic carbon determined by the dissolved organic carbon on-line measuring device located in the water tank. When the content reaches the preset value, the concentration is stopped and the concentration system is turned off.

In the process of concentration of raw water, try to avoid the concentration ratio is too high, the higher the concentration ratio, the higher the salt content and the organic matter concentration, and the excessive concentration will cause damage to the reverse osmosis membrane. Therefore, the organic matter content in the concentrated water is controlled at 10000 mg. /L below.

A first conductivity probe 13 is disposed at the concentrated water outlet of the reverse osmosis concentration unit, and a second conductivity probe 12 is disposed between the reverse osmosis unit and the rinsing device 14 by comparing the first conductivity probe 13 with the second conductivity probe 12 The value of the detection can determine whether the reverse osmosis membrane leaks; that is, if the values detected by the first conductivity probe 13 and the second conductivity probe 12 are equal, it can be determined that the reverse osmosis membrane leaks. There is also a security valve at the outlet of the reverse osmosis unit concentrated water and pure water. When the difference between the conductivity of the reverse osmosis unit concentrated water and pure water is less than the preset value during the raw water concentration process, the security valve is opened and the system stops running. .

The front end of the high pressure pump 10 is provided with a security valve. During the concentration process, when the water level is lower than 1/5 of the water tank, the security valve is opened and the high pressure pump 10 is stopped, thereby avoiding the high pressure pump burning when the high pressure pump is idling. Phenomenon; the front end of the high-pressure pump is also equipped with a pressure gauge. When the pressure before the high-pressure pump is greater than the preset value, the safety valve is opened to avoid the damage of the high-pressure pump and the bursting of the pipeline.

After the concentration of the raw water is completed, the pH adjustment unit is activated. The desired pH value is set in the total control system 5, and the set pH range is 0.5-3. The pH sensor transmits the pH signal to the metering dosing pump 6, and the metering dosing pump starts the acid addition procedure. The first acid solution tank 7 draws the acid solution into the water tank through the first acid-proof pipeline, and the non-oxidizing acid liquid is injected into the water tank, and the stirring motor in the water tank 9 is started, so that the acid liquid and the concentrated water are uniformly mixed, and the pH is adjusted until the pH is adjusted. The value reaches the preset value, and the first dosing process of the dosing pump stops working; the dosing pump extracts hydrofluoric acid from the second acid solution tank 8, and injects hydrogen into the water tank 9 through the second acid-resistant pipe. Fluoric acid, until the preset hydrofluoric acid concentration is reached, the metering dosing pump and the tank agitator motor stop working.

The entire pH adjustment process is fully automated, saving labor, reducing production costs, and the pH of the prepared pH is relatively high, and the process efficiency of the preparation is also high. During the pH adjustment process, the agitator motor is turned on to cause the agitator to agitate the water in the water tank 9, so that the acid solution flowing therein is uniformly dissolved in the water, and the local pH value is prevented from being high or low.

After the pH adjustment is completed, the concentrated water in the water tank 9 is allowed to stand for 24 hours. Since the water tank 9 is made of acid-resistant material and has a sealing cover thereon, the end surface of the sealing cover is provided with at least five through holes; the lower end is in the shape of a funnel, which is favorable for The output of concentrated water; it is equipped with a stirrer and pH sensor; the pH sensor is equipped with a lifting platform. After the pH adjustment is completed, the lifting platform can raise the pH sensor above the water surface to prevent the hydrofluoric acid from eroding the probe.

The pipe between the water tank and the filter extends into the water tank. The top of the pipe is a sealed structure. The wall of the water pipe is provided with a plurality of holes with a diameter of 50 μm. The minimum height of the hole is controlled at 1/100-1/10 of the height of the water tank. Wherein, the filter cover is provided with a filter cover outside the pipeline, and the filter cover has a pore diameter of 100 μm, which is more favorable for precipitating acid-insoluble impurities such as humic acid in the concentrated water.

The outlet valve of the water tank 9 is opened, and the vacuum pump 15 is started, and the pressure is applied by the vacuum pump 15. The concentrated water in the water tank 9 flows into the liquid reservoir 17 through the filter, and the acid-insoluble impurities are removed by the filter membrane 16 to be removed, and the crude fulvic acid solution is removed. The filter membrane flows into the liquid reservoir 17.

After the filtration is completed, the outlet valve of the water tank 9 is closed, the outlet valve of the liquid reservoir 17 is opened, and the waste liquid discharge switch of the adsorption enrichment device 21a is opened, and the liquid in the liquid reservoir 17 flows into the adsorption enrichment device 21a, and the fulvic acid is Adsorbed on the resin; after the adsorption is completed, the switch between the elution device 14 and the adsorption and enrichment device 21a is opened, and the pure water in the eluent device 14 is injected into the adsorption and enrichment device 21a through the pipeline to rinse the adsorption and enrichment device 21a. The flushing waste liquid is directly discharged from the waste liquid outlet. Opening the switch between the rinsing device 14 and the ion exchange device 22a, the pure water in the rinsing device 14 is flushed to the ion exchange device 22a to remove impurities, and the rinsing liquid is directly discharged;

After the flushing is completed, the switch between the eluent device 14 and the adsorption enrichment device 21a and the waste liquid discharge valve are closed, the outlet valve of the alkali solution tank 20a is opened, and the alkali solution tank 20a passes through the alkali-resistant pipe to the adsorption enrichment device 21a. Injecting lye, The fulvic acid adsorbed by the resin is desorbed by the action of the alkali solution, and the desorbed solution flows into the ion exchange device 22a, and is discharged through the hydrogen-type cation exchange resin in the ion exchange device, and the discharged solution is the desired extracted Fuli. The acid solution is freeze-dried to obtain a fresh water body fulvic acid solid powder.

Embodiment 2

2 is a schematic view showing the structure of a second embodiment of a solution for dissolving fulvic acid in a fresh water body according to the present invention; in FIG. 2, the fulvic acid extraction unit includes a rinsing device 14 and an organic chemical tank. 20b, an adsorption enrichment device 21b; wherein the outlet of the liquid reservoir 17 is connected to the inlet of the adsorption enrichment device 21b, and the inlet of the adsorption enrichment device 21b is also connected to the outlet of the organic liquid chemical tank 20b and the outlet of the eluent device 14. The bottom of the adsorption-concentrating device 21b is provided with a liquid discharge switch.

In the present embodiment, the concentration, filtration and crude extraction of fulvic acid in the present embodiment are the same as in the examples, except that the fulvic acid extraction unit is different. In the second embodiment, the extraction process of fulvic acid is as follows: fulvic acid after the crude The solution is stored in the liquid reservoir, the outlet valve of the liquid reservoir 17 is opened, the liquid in the liquid reservoir flows into the adsorption enrichment device 21b, and the fulvic acid is adsorbed on the resin; after the adsorption is completed, the elution device 14 is opened and the adsorption is rich The switch between the collecting devices 21b simultaneously opens the waste liquid discharge switch of the adsorption and enrichment device 21b, and the pure water in the elution device is injected into the adsorption and enrichment device 21b through the pipe, and the adsorption and enrichment device 21b is flushed, and the waste after the flushing The liquid is discharged directly from the liquid outlet;

After the flushing is completed, the switch and the liquid discharge valve between the elution device 14 and the adsorption and enrichment device 21b are closed, the outlet valve of the organic chemical tank 20b is opened, and the organic chemical tank 20b is injected into the adsorption and enrichment device 21b through the organic-resistant pipe. The polar organic solvent, the fulvic acid adsorbed by the resin is desorbed by the action of the non-polar organic solvent, and the discharged solution is a fulvic acid solution, and the fulvic acid solid dissolved in the fresh water body is obtained by rotary evaporation and nitrogen blowing. powder.

In the second embodiment, the reverse osmosis concentration unit further comprises an ion exchange device 22b. The ion exchange device 22b is provided between the reverse osmosis unit concentrated water outlet and the water tank, and the packing in the ion exchange device is a hydrogen type cation exchange resin, and the reverse osmosis concentration is During the process, the cations such as metal ions in the water are simultaneously concentrated, and the hydrogen-type cation exchange resin can effectively remove the cations such as metal ions in the concentrated water during the reverse osmosis concentration process, thereby effectively preventing the flocculation and precipitation existing in the concentration process of the raw water.

Embodiment 3

Referring to FIG. 3, FIG. 3 is a schematic structural view of a third embodiment of a solution for dissolving fulvic acid in a freshwater body according to the present invention; in FIG. 3, the fulvic acid extraction unit includes a rinsing device 14 and an organic chemical tank. 20c, a first-stage adsorption and enrichment device 21c, and a second-stage adsorption and enrichment device 22c; wherein the outlet of the liquid reservoir 17 is connected to the inlet of the first-stage adsorption and enrichment device 21c, and the inlet of the first-stage adsorption and enrichment device 21c is also organic The outlet of the liquid medicine tank 20c and the outlet of the rinsing device 14 Connecting; the outlet of the first-stage adsorption and enrichment device 21c is connected to the inlet of the second-stage adsorption and enrichment device 22c, and the inlet of the second-stage adsorption and enrichment device 22c is also connected to the outlet of the organic liquid chemical tank 20c and the outlet of the rinsing device 14; A liquid discharge switch is provided at the bottom of each of the primary adsorption enrichment device 21c and the secondary adsorption enrichment device 22c.

In the present embodiment, the concentration, filtration and crude extraction of fulvic acid are the same as in the examples, except that the fulvic acid extraction unit is different. In the third embodiment, the extraction process of fulvic acid is as follows: fulvic acid after the crude The solution is stored in the liquid reservoir, and the switch between the liquid reservoir 17 and the primary adsorption enrichment device 21c is opened, and the switch between the primary adsorption enrichment device 21c and the secondary adsorption enrichment device 22c is opened, and the liquid is stored. The crude fulvic acid solution in the device 17 sequentially flows into the first-stage adsorption and enrichment device 21c, the second-stage adsorption and enrichment device 22c, the first-stage adsorption and enrichment device 21c, and the second-stage adsorption and enrichment device 22c to carry out the fulvic acid solution. After the adsorption is completed, the switch between the liquid reservoir 17 and the first-stage adsorption and enrichment device 21c is closed, and the switch between the first-stage adsorption and enrichment device 21c and the second-stage adsorption and enrichment device 22c is closed;

Opening the switch between the rinsing device 14 and the first-stage adsorption and enrichment device 21c, and simultaneously opening the liquid discharge switch of the first-stage adsorption and enrichment device 21c, and the pure water in the rinsing device 14 is injected into the first-stage adsorption and enrichment device 21c through the pipeline. , the adsorption and enrichment device 21c is flushed, and the flushing waste liquid is directly discharged from the liquid discharge switch; the switch between the elution device 14 and the first-stage adsorption and enrichment device 21c is turned off, and the elution device 14 and the second-stage adsorption and enrichment device are turned on. The switch between the 22c simultaneously opens the liquid discharge switch of the secondary adsorption enrichment device 22c, and the pure water in the elution device 14 is injected into the secondary adsorption and enrichment device 22c through the pipeline to flush the secondary adsorption and enrichment device 22c. Flushing waste liquid is directly discharged from the liquid discharge switch;

After the rinsing is completed, the switch between the rinsing device 14 and the first-stage adsorption and enrichment device 21c and the second-stage adsorption and enrichment device 22c is turned off, and the switch between the first-stage adsorption and enrichment device 21c and the second-stage adsorption and enrichment device 22c is turned off. Opening the outlet valve of the organic chemical tank 20c, the organic chemical tank 20c injects a volatile organic solvent into the first-stage adsorption and enrichment device 21c through the organic-resistant pipeline, and the fulvic acid adsorbed by the resin is desorbed by the volatile organic solvent. After being discharged through the liquid discharge switch, labeled as fulvic acid organic solution 1;

The switch between the organic chemical tank 20c and the primary adsorption enrichment device 21c is closed, the switch between the organic chemical tank 20c and the secondary adsorption enrichment device 22c is opened, and the liquid outlet valve of the organic chemical tank 20c is opened, and the organic chemical tank 20c The volatile organic solvent is injected into the second-stage adsorption and enrichment device 22c through the organic-resistant pipeline, and the fulvic acid adsorbed by the resin is desorbed by the action of the volatile organic solvent, and is discharged as an organic solution 2 of fulvic acid;

The fulvic acid organic solution 1 and the fulvic acid organic solution 2 are combined, and the solid powder of the fulvic acid dissolved in the fresh water body is obtained by rotary evaporation and nitrogen blowing.

Embodiment 4

4 is a schematic view showing the structure of a fourth embodiment of a solution for dissolving fulvic acid in a fresh water body according to the present invention; in FIG. 4, the fulvic acid extraction unit includes a rinsing device 14 and a lye agent. a tank 20d, a first-stage adsorption and enrichment device 21d, a first ion exchange device 22d, a second-stage adsorption and enrichment device 23d, and a second ion exchange device 24d; wherein, the outlet of the liquid reservoir 17 and the inlet of the first-stage adsorption and enrichment device 21d connection, the inlet of the first-stage adsorption and enrichment device 21d is also connected to the outlet of the lye reagent tank 20d and the outlet of the rinsing device 14; the outlet of the first-stage adsorption and enrichment device 21d and the inlet of the first ion exchange device 22d, The stage of the adsorption-concentration device 23d is connected; the outlet of the second-stage adsorption-enrichment device is connected to the second ion exchange device 24d; the first-stage adsorption and enrichment device 21d, the second-stage adsorption and enrichment device 23d, the first ion exchange device 22d, and the second A waste liquid discharge switch is provided at the bottom of the ion exchange unit 24d.

In the present embodiment, the concentration, filtration and crude extraction of fulvic acid in the present embodiment are the same as in the examples, except that the fulvic acid extraction unit is different. In the third embodiment, the extraction process of fulvic acid is as follows: after the filtration is completed, the water tank is closed. The outlet valve of 9 opens the outlet valve of the liquid reservoir 17, and the liquid in the liquid reservoir sequentially flows into the first-stage adsorption and enrichment device 21d and the second-stage adsorption and enrichment device 23d, and the fulvic acid is adsorbed on the resin;

After the adsorption is completed, the communication valve between the primary adsorption device 21d and the secondary adsorption and concentration device 23d is closed, and the communication valve between the primary adsorption enrichment device 21d and the first ion exchange device 22d is closed, and the elution device 14 is opened. The communication valve with the first-stage adsorption and enrichment device 21d opens the waste liquid discharge switch at the bottom of the first-stage adsorption and enrichment device 21d, and the pure water in the rinse device 14 is flushed through the pipeline to the first-stage adsorption and enrichment device 21d, and the waste is washed. The liquid is discharged through the waste liquid discharge switch, completes the flushing of the first-stage adsorption and enrichment device 21d, closes the waste liquid discharge switch at the bottom of the first-stage adsorption and enrichment device 21d, and closes between the elution device 14 and the first-stage adsorption and enrichment device 21d. Connecting valve

Opening the communication valve between the rinsing device 14 and the first ion exchange device 22d, opening the waste liquid discharge switch at the bottom of the first ion exchange device 22d, and the pure water in the rinsing device 14 flushes the first ion exchange device 22d through the pipe. The flushing waste liquid is discharged through the waste liquid discharge switch, completes the flushing of the first ion exchange device 22d, closes the waste liquid discharge switch at the bottom of the first ion exchange device 22d, and closes the communication between the rinse device 14 and the first ion exchange device 22d. valve;

The communication valve between the secondary adsorption enrichment device 23d and the second ion exchange device 24d is closed, and the communication valve between the elution device 14 and the secondary adsorption and enrichment device 23d is opened to open the bottom of the secondary adsorption and enrichment device 23d. The waste liquid discharge switch, the pure water in the elution device 14 is flushed through the pipeline to the secondary adsorption and enrichment device 23d, and the flushing waste liquid is discharged through the waste liquid discharge switch to complete the flushing of the secondary adsorption and enrichment device 23d, and the secondary adsorption rich is closed. The waste liquid discharge switch at the bottom of the collecting device 23d closes the communication valve between the eluting device 14 and the secondary adsorption enriching device 23d;

Opening the communication valve between the rinsing device 14 and the second ion exchange device 24d, opening the waste liquid discharge switch at the bottom of the second ion exchange device 24d, the pure water in the rinsing device is flushed through the pipeline to the second ion exchange device 24d, and rinsed The waste liquid is discharged through the waste liquid discharge switch, completes the flushing of the second ion exchange device 24d, closes the waste liquid discharge switch at the bottom of the second ion exchange device 24d, and closes the communication valve between the rinse device 14 and the second ion exchange device 24d. ;

After the flushing is completed, the communication valve between the primary adsorption device 21d and the secondary adsorption and concentration device 23d is closed, and the communication valve between the alkali solution tank 20d and the first-stage adsorption and enrichment device 21d is opened to open the first-stage adsorption and enrichment. The communication valve between the device 21d and the first ion exchange device 22d, the alkali solution tank 20d injects the alkali solution into the first-stage adsorption and enrichment device 21d through the alkali-resistant pipe, and the fulvic acid adsorbed by the resin occurs under the action of the alkali solution. Desorbing, the desorbed effluent is discharged through the hydrogen-type cation exchange resin in the first ion exchange unit 22d, and the hydrogen-type cation exchange resin in the first ion exchange unit 22d is ensured to be activated in a sufficient amount or in time to be discharged. The liquid is labeled as a first-stage adsorption enrichment liquid;

Closing the communication valve between the lye reagent tank 20d and the primary adsorption enrichment device 21d, opening the communication valve between the lye reagent tank 20d and the secondary adsorption enrichment device 23d, opening the secondary adsorption enrichment device 23d and the The communication valve between the two ion exchange devices 24d, the alkali solution tank 20d injects the alkali solution into the secondary adsorption and enrichment device 23d through the alkali-resistant pipeline, and the fulvic acid adsorbed by the resin is desorbed by the action of the alkali solution, and after desorption The effluent is discharged through the hydrogen-type cation exchange resin in the second ion exchange unit 24d, and the hydrogen-type cation exchange resin in the second ion exchange unit 24d is ensured to be activated in a sufficient amount or in time, and the discharged liquid is marked as two. Stage adsorption enrichment liquid;

The first-stage adsorption enrichment liquid and the second-stage adsorption enrichment liquid are combined, and after lyophilization, the high-purity fresh water body fulvic acid powder solid is obtained.

In the second embodiment, the reverse osmosis concentration unit further comprises an ion exchange device 4d. The ion exchange device 4d is provided with a reverse osmosis unit concentrated water outlet and a water tank, and the packing in the ion exchange device is a hydrogen type cation exchange resin, and the reverse osmosis concentration is performed. During the process, the cations such as metal ions in the water are simultaneously concentrated, and the hydrogen-type cation exchange resin can effectively remove the cations such as metal ions in the concentrated water during the reverse osmosis concentration process, thereby effectively preventing the flocculation and precipitation existing in the concentration process of the raw water.

After completing a working cycle, restart the self-priming pump and proceed to the next working cycle. When the organic matter content of the water body is low, the water can be fed through the self-priming pump 1 multiple times, so that the dissolved organic carbon concentration in the water tank 9 reaches a preset value, and then the pH adjustment is performed next.

After the fulvic acid extraction is finished, the valve between the water tank 9 and the filter is closed, the pure water in the rinsing device 14 is poured into the water tank, the concentration is started, the concentrated water valve is opened to the maximum, and the scouring of the membrane is reversed by the pure water. Cleaning of the permeable membrane. The reverse osmosis membrane is strictly prohibited from being stored dry. It is necessary to ensure that there is water in the membrane shell. If it is not used for more than 70 hours, the reverse osmosis membrane should be immersed in clean water. If it is left unused for a long time, it must be stored in the reverse osmosis membrane required storage mode. The pure water obtained in the fulvic acid extraction of fresh water body is stored in the leaching device 14, which provides water for the reverse osmosis membrane washing, and successfully solves the practical problem that the field pure water is difficult to obtain.

The filter purification unit uses a filter membrane as a disposable filter membrane, and the filter membrane needs to be able to withstand a strong acid of 0.2-0.4 mol/L, and the filter membrane is stored and used as required, but a silicon-containing filter membrane such as a glass fiber filter membrane cannot be used.

The positional arrangement of each part in the dissolved fulvic acid extraction device in the fresh water body provided by the invention can be adaptively adjusted according to the needs of the operator, and all the ways of disposing the positions of the parts in the fulvic acid extraction device are within the protection scope of the invention. .

The detailed descriptions of the foregoing are merely illustrative of the possible embodiments of the present invention, and are not intended to limit the scope of the present invention, which is within the knowledge of those skilled in the art Various changes made without departing from the spirit of the invention are within the scope of the invention.

Claims (13)

A fulvic acid extraction device for freshwater water, comprising a raw water supply unit, a pretreatment unit, a reverse osmosis concentration unit, a pH adjustment unit, a water tank, a total control system, a filtration purification unit and a fulvic acid extraction unit; An outlet of the raw water supply unit is connected to an inlet of the pretreatment unit, an outlet of the pretreatment unit is connected to the water tank; and an inlet of the reverse osmosis concentration unit and the pH adjustment unit is connected to the water tank An outlet of the water tank is connected to an inlet of the filtration purification unit, and an outlet of the filtration purification unit is connected to an inlet of the fulvic acid extraction unit; The raw water supply unit, the reverse osmosis concentration unit, and the pH adjustment unit are all connected to the control system; The fulvic acid extraction unit includes an alkali solution tank, a rinsing device, an adsorption enrichment device, and an ion exchange device; an inlet of the adsorption enrichment device and an outlet of the lye reagent tank, and an outlet of the rinsing device Connecting, the outlet of the adsorption-enrichment device is connected to the inlet of the ion exchange device, and the bottom is provided with a waste liquid discharge switch; the outlet of the rinse device is connected to the inlet of the ion exchange device; The adsorption and enrichment device comprises an adsorption column and a filler, wherein the filler is disposed in the adsorption column, and the filler is one or more of XAD-8 resin, DAX-8 resin and XAD-7 resin; The ion exchange apparatus includes an adsorption column and a filler, and the filler is disposed in the adsorption column, and the filler is a hydrogen type cation exchange resin. The apparatus for extracting fulvic acid in a fresh water body according to claim 1, wherein the fulvic acid extraction unit comprises an organic chemical tank, a rinsing device, and an adsorption and enrichment device; and an inlet and an inlet of the adsorption and enrichment device. An outlet of the organic chemical tank, an outlet connection of the rinsing device, and a liquid discharge switch at the bottom of the adsorption and enrichment device; The adsorption-enrichment device includes an adsorption column and a filler, and the filler is disposed in the adsorption column, and the filler is one or more of XAD-8 resin, DAX-8 resin, and XAD-7 resin. The apparatus for extracting fulvic acid in a fresh water body according to claim 1, wherein the fulvic acid extraction unit comprises an organic chemical tank, a leaching device, a first-stage adsorption and enrichment device, and a second-stage adsorption and enrichment device; The inlet of the first-stage adsorption and enrichment device is connected to the outlet of the organic chemical tank, the outlet of the rinsing device, and the outlet of the liquid reservoir, and the inlet of the secondary adsorption-enrichment device and the outlet of the leaching device respectively , an outlet of the organic chemical tank, and an outlet connection of the first-stage adsorption and enrichment device; The bottom of the first-stage adsorption enrichment device and the second-stage adsorption and enrichment device are provided with a liquid discharge switch; The first-stage adsorption and enrichment device includes an adsorption column and a filler, and the filler is disposed in the adsorption column, and the filler is one or more of XAD-8 resin, DAX-8 resin and XAD-7 resin. The secondary adsorption-enrichment device comprises an adsorption column and a filler, the filler is disposed in the adsorption column, and the filler is XAD-4 resin. The apparatus for extracting fulvic acid in a fresh water body according to claim 1, wherein the fulvic acid extraction unit comprises a first-stage adsorption and enrichment device, a first ion exchange device, a second-stage adsorption and concentration device, and a second ion. The exchange device, the leaching device and the medicating device, the inlet of the first-stage adsorption and enrichment device is connected with the outlet of the liquid storage device, the outlet of the leaching device, and the outlet of the medicinal device, and the outlets of the first-stage adsorption and enrichment device are respectively An inlet of the first ion exchange device and an inlet connection of the secondary adsorption enrichment column device; The inlet of the secondary adsorption enrichment device is connected to the outlet of the elution device, the outlet of the dosing device, and the outlet of the secondary adsorption enrichment device is connected to the inlet of the second ion exchange device; An outlet of the rinsing device is connected to an inlet of the first ion exchange device and an inlet of the second ion exchange device; a waste liquid discharge switch is respectively arranged at the bottom of the first-stage adsorption and enrichment device, the second-stage adsorption and enrichment device, the first ion exchange device and the second ion exchange device; The first-stage adsorption and enrichment device includes an adsorption column and a filler, and the filler is disposed in the adsorption column, and the filler is one or more of XAD-8 resin, DAX-8 resin and XAD-7 resin. The first ion exchange device includes an adsorption column and a filler, the filler is disposed in the adsorption column, and the filler is a hydrogen type cation exchange resin; The secondary adsorption enrichment device comprises an adsorption column and a filler, the filler is disposed in the adsorption column, the filler is XAD-4 resin; the second ion exchange device comprises an adsorption column and a filler, the filler Located in the adsorption column, the filler is a hydrogen type cation exchange resin. A freshwater body water-dissolved fulvic acid extraction apparatus according to claim 1, wherein the filter purification unit comprises a filter, a liquid reservoir, and a vacuum pump, and an inlet of the filter is connected to an outlet of the water tank, the filter An outlet connected to the inlet of the liquid reservoir; the vacuum pump being coupled to the liquid reservoir, the outlet of the liquid reservoir being coupled to an inlet of the adsorption enrichment device; The filter comprises an impurity chamber, a filter membrane and a sand core, the filter membrane is disposed in the impurity chamber and supported by the sand core; the filter membrane has a pore diameter ranging from 0.1 to 0.7 μm. The apparatus for extracting fulvic acid in a fresh water body according to claim 1, wherein the pH adjusting unit comprises a pH sensor, a stirrer, a metering dosing pump, a first acid solution tank, and a second acid solution tank. The pH sensor is disposed in the water tank, and the first acid liquid medicine tank and the second acid liquid medicine tank are arranged side by side; the metering dosing pump is disposed in the first Between an acid solution tank, a second acid solution tank and a water tank, the inlet of the metering dosing pump is respectively connected with the outlet of the first acid solution tank and the outlet of the second acid solution tank, and the outlet of the dosing pump is metered Connected to the water tank. The freshwater body water-dissolved fulvic acid extraction device according to claim 1, wherein the water tank is made of an acid-resistant material, and has a sealing cover on the upper side and a funnel shape at the lower end, and is provided with a stirrer, a liquid level sensor and a pH therein. a sensor; the end surface of the sealing cover is provided with at least 5 through holes; a pipe between the water tank and the filter extends into the water tank, the top of the pipe is a sealing structure, and the wall of the pipe is inserted into the wall of the water tank to have a plurality of holes A 50 μm hole whose minimum height is controlled at 1/100 to 1/10 of the height of the water tank, and a filter cover is provided outside the water tank pipe, and the filter cover has a hole diameter of 100 μm. The freshwater water-dissolved fulvic acid extraction apparatus according to claim 1, wherein the reverse osmosis concentration unit comprises a reverse osmosis unit, a high pressure pump, a first conductivity probe and a second conductivity probe; wherein the reverse osmosis unit comprises a reverse osmosis membrane and a stainless steel membrane shell, the reverse osmosis membrane has a pore diameter of 0.1 nm; The first conductivity probe is disposed at the concentrated water outlet of the reverse osmosis unit, and the second conductivity probe is disposed between the pure water outlet of the reverse osmosis concentration unit and the rinsing device. The apparatus for extracting fulvic acid from fresh water according to claim 8, wherein said reverse osmosis unit is provided with a liquid inlet, a concentrated water outlet and a pure water outlet; said liquid inlet is connected to the water tank through a high pressure pump, said thick The water outlet is connected to the water tank, and the pure water outlet is connected to the rinsing device; the reverse osmosis unit concentrated water and the pure water outlet are provided with a security valve. The freshwater water body fulfilment acid extraction apparatus according to claim 1, wherein the raw water supply unit comprises a self-priming pump; and the pretreatment unit comprises a first-stage precision microfiltration filter and a second-stage precision microfiltration filter. And the three-stage precision microfiltration filter, the precision filter element of the first-stage precision microfiltration filter has a pore size of 5μm, the precision filter element of the second-stage precision microfiltration filter has a pore size of 1μm, and the precision filter element of the three-stage precision microfiltration filter The pore size is 0.45 μm; the inlet of the first-stage precision microfiltration filter is connected to the outlet of the self-priming pump, and the outlet of the first-stage precision microfiltration filter is connected with the inlet of the second-stage precision microfiltration filter, and the second-stage precision The outlet of the microfiltration filter is connected to the inlet of a three-stage precision microfiltration filter, and the outlet of the three-stage precision microfiltration filter is connected to the water tank. A freshwater water-dissolved fulvic acid extraction apparatus according to claim 1, wherein said total control system comprises a control unit and a touch panel, said control unit is connected to a touch panel, said control unit and a self-priming pump, The liquid level sensor, the pH sensor, the metering dosing pump and the high pressure pump are connected; the pH sensor is provided with a lifting platform. A method for dissolving fulvic acid extraction by using the freshwater water-dissolved fulvic acid extraction apparatus according to any one of claims 1 to 11, characterized in that it comprises the following steps: (1) Start the total power start button of the total control system; (2) Start the self-priming pump start button, the self-priming pump draws the raw water through the pipeline, and the raw water is pre-filtered by the filter bag at the front end of the self-priming pump, and the raw water after the preliminary filtration enters the pretreatment unit through the supercharging of the self-priming pump. The first-stage precision microfiltration filter filters the raw water once, and the primary filtered water enters the secondary precision microfiltration filter for secondary filtration. The secondary filtered crude water enters the tertiary precision microfiltration filter for three times of filtration; The raw water after entering the water tank through the pipeline, when the water level in the water tank reaches the height of 4/5 water tank, the self-priming pump stops working; (3) The raw water in the water tank is pressurized by the high-pressure pump and enters the reverse osmosis concentration unit through the pipeline. The reverse osmosis membrane can concentrate the dissolved salt and the naturally dissolved organic matter in the raw water to obtain pure water and concentrated water; after passing through the reverse osmosis membrane The pure water is directly discharged into the leaching device for storage, and the concentrated water is circulated into the water tank, and when the dissolved organic carbon content measured by the dissolved organic carbon on-line measuring device in the water tank reaches a preset value, the concentration is stopped; (4) Starting the pH adjustment unit, the metering dosing pump receives the pH sensor signal to start the acid addition procedure, and extracts the acid solution from the first acid solution tank into the water tank through the first acid-resistant pipeline, and simultaneously injects the non-oxidizing acid solution into the water tank. The agitation motor is started to uniformly mix the acid solution and the concentrated water until the preset pH value is reached, and the first acid addition program of the dosing dosing pump stops working; The metering dosing pump extracts hydrofluoric acid from the second acid solution tank, and injects hydrofluoric acid into the water tank through the second acid-proof pipeline until the preset hydrofluoric acid concentration is reached, and the metering dosing pump and the water tank stirring motor stop. jobs; (5) Open the outlet valve of the water tank, start the vacuum pump at the same time, apply pressure by the vacuum pump, the concentrated water in the water tank flows into the liquid reservoir through the filter, the acid insoluble impurities are removed by the filter membrane, and the crude fulvic acid solution flows through the filter membrane. In a liquid reservoir; (6) After the filtration is completed, the outlet valve of the water tank is closed, the outlet valve of the liquid reservoir is opened, the liquid in the liquid reservoir flows into the adsorption enrichment device, and the fulvic acid is adsorbed on the resin; (7) After the adsorption is completed, the switch between the leaching device and the adsorption enrichment device is turned on, and the waste liquid discharge switch of the adsorption and enrichment device is turned on, and the pure water in the leaching device is injected into the adsorption and enrichment device through the pipeline to adsorb The enrichment device performs rinsing, and the rinsing waste liquid is directly discharged from the waste liquid outlet; the switch between the leaching device and the ion exchange device is opened, and the pure water in the rinsing device rinses the ion exchange device to remove impurities, and the rinsing liquid is directly discharged. ; (8) After the flushing is completed, the switch between the eluent device and the adsorption enrichment device and the waste liquid discharge valve are closed, the outlet valve of the alkali solution tank is opened, and the alkali solution tank is injected into the adsorption enrichment device through the alkali-resistant pipeline. The lye, the fulvic acid adsorbed by the resin is desorbed by the action of the alkali solution, and the desorbed solution is discharged through the ion exchange device, and the discharged solution is the fulvic acid solution to be extracted. A method for extracting fulvic acid in a freshwater body according to claim 12, wherein said first acid-resistant pipe is capable of withstanding a non-oxidizing acid of 10 mol/L; said second acid-resistant pipe is capable of withstanding a hydrogen of 6 mol/L Fluoric acid; the mixed acid concentration in the water tank ranges from 0.001 to 1 mol/L non-oxidizing strong acid and 0.1-0.5 mol/L hydrofluoric acid; the pH is preset to 0.5-3; in the dosing device The alkali solution is a strong base of 0.1 to 6 mol/L; the alkali-resistant pipe is required to withstand a strong alkali of 6 mol/L.

Images