CN113277602A - Device and method for continuously removing cations in water for hydrogen conductivity measurement - Google Patents

Device and method for continuously removing cations in water for hydrogen conductivity measurement Download PDF

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CN113277602A
CN113277602A CN202110753403.3A CN202110753403A CN113277602A CN 113277602 A CN113277602 A CN 113277602A CN 202110753403 A CN202110753403 A CN 202110753403A CN 113277602 A CN113277602 A CN 113277602A
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water
ammonia
electric
deamination device
chamber
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张贺
胡鉴耿
徐浩然
冯向东
陈彪
付晓靖
金水玉
金可勇
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Zhejiang Energy Group Research Institute Co Ltd
Hangzhou Water Treatment Technology Development Center Co Ltd
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Zhejiang Energy Group Research Institute Co Ltd
Hangzhou Water Treatment Technology Development Center Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
    • G—PHYSICS
    • G01—MEASURING; TESTING
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    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/4005—Concentrating samples by transferring a selected component through a membrane
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
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    • G01N1/40—Concentrating samples
    • G01N1/4005—Concentrating samples by transferring a selected component through a membrane
    • G01N2001/4011—Concentrating samples by transferring a selected component through a membrane being a ion-exchange membrane
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N2001/4038—Concentrating samples electric methods, e.g. electromigration, electrophoresis, ionisation

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Abstract

The invention relates to a device for continuously removing cations in water for hydrogen conductivity measurement, which comprises: the device comprises a conductivity meter, a PH meter, a pure water tank, an ammonia-containing water tank, an electric deamination device, a power supply, a power water pump and a flowmeter; the electric deamination device comprises an ammonia removal compartment, a positive electrode chamber and a negative electrode chamber; the anode chamber and the cathode chamber are respectively positioned at the left side and the right side of the electric deamination device, and an anode chamber water distribution plate is arranged between the anode chamber and the ammonia removal compartment. The invention has the beneficial effects that: the optimization is carried out on the structure of the electrodeionization method, and the device for continuously removing cations in water for hydrogen conductivity measurement is designed, so that ammonia water can be efficiently removed. The cation exchange membrane is selected, so that anions can be prevented from entering the ammonia removal compartment, and anion pollution is avoided; the ammonia removal device is provided with the anode chamber and the cathode chamber which are used for providing a direct current electric field, strong acid type ion exchange resin is arranged in the ammonia removal compartment, the chemical balance type ammonia water transfer efficiency to the ammonia radical ions is improved, and the removal efficiency is improved.

Description

Device and method for continuously removing cations in water for hydrogen conductivity measurement
Technical Field
The invention belongs to the field of boiler water deamination, and particularly relates to a device and a method for continuously removing cations in water for hydrogen conductivity measurement.
Background
At present, the main steam pressure of a coal-fired power generating unit with the power of 300MW and above reaches the supercritical and ultra-supercritical state, and the requirement on the quality of water vapor in the system is very strict in order to prevent equipment and pipelines from being corroded.
When the boiler steam sample water contains ammonia, its quality of water PH changes, because the characteristic of aqueous ammonia, forms certain chemical equilibrium with the form of molecule, ion coexistence in aqueous, sees following chemical equilibrium formula:
NH3+H 2 0＝＝＝NH3·H2o (reversible reaction)
NH3·H2O＝＝＝NH4 ++ OH-the reversible reaction
With a portion of the ammonia molecules reacting with water to form NH4 +Ammonium ion and OH-hydroxide ion, water is easily weakly alkaline. The pure water in the boiler contains 1-5mg/L of ammonia, the ammonia content is low, the ammonia is not easy to remove, and the difficulty is high.
Electrodeionization (EDI) is a pure water production technique that combines ion exchange technology, ion exchange membrane technology, and ion electromigration technology. The anion and cation in the water are directionally migrated under the action of the direct current electric field through the permselectivity of the anion and cation exchange membrane to the anion and cation and the exchange action of the anion and cation exchange resin to the ions in the water, so that the deep desalination of the water is realized. Hydrogen ions H produced simultaneously by electrolysis of water+And hydroxyl ion OH-to continuously regenerate the cation and anion exchange resin. The principle schematic of the electrodeionization process is shown in FIG. 1.
In the process of monitoring the water vapor quality of each power plant, sample water of each system usually passes through a cation resin exchange column, cations in the sample water are removed, and then the conductivity of the sample water is measured, so that the content of harmful anions in reaction water changes, the measured conductivity value is called as hydrogen conductivity, the conductivity of the sample water is generally 3-10 mu S/cm, the content of ammonia is 1-5mg/L, and the pH value is about 9-10. The cation resin exchange column has the defects that the resin in the hydrogen ion exchange column can often lose efficacy (cations penetrate through the resin layer), the lost resin needs to be replaced and regenerated for recycling, the labor cost and the economic cost are lost, the hydrogen electric derivative data is displayed inaccurately during replacement of the lost resin and during flushing after replacement of the resin, the water quality cannot be monitored accurately, the data accuracy can be influenced by the regeneration level of the resin, and the operation safety is indirectly influenced. Therefore, it is necessary to develop a convenient and effective technology for removing ammonia from water.
Disclosure of Invention
The object of the present invention is to overcome the disadvantages of the prior art and to provide a device and a method for continuous removal of cations from water for hydrogen conductivity measurement.
The device for continuously removing cations in water for hydrogen conductivity measurement comprises: the device comprises a conductivity meter, a PH meter, a pure water tank, an ammonia-containing water tank, an electric deamination device, a power supply, a power water pump and a flowmeter;
the electric deamination device comprises an ammonia removal compartment, a positive electrode chamber and a negative electrode chamber; the positive electrode chamber and the negative electrode chamber are respectively positioned at the left side and the right side of the electric deamination device, a positive electrode chamber water distribution plate is arranged between the positive electrode chamber and the ammonia removal compartment, and a negative electrode chamber water distribution plate is arranged between the negative electrode chamber and the ammonia removal compartment; the anode chamber is internally provided with an anode material, and the cathode chamber is internally provided with a cathode material; the anode chamber water distribution plate and the cathode chamber water distribution plate are fixedly clamped with the ammonia removal compartment through screw fixing devices (stainless steel bolts); strong acid type ion exchange resin is filled in the ammonia removal compartment, two sides in the ammonia removal compartment are sealed and isolated by a cation exchange membrane and a water distribution plate of the anode chamber and a water distribution plate of the cathode chamber, and the cation exchange membrane can prevent anions from entering the ammonia removal compartment and avoid anion pollution; the positive electrode chamber and the negative electrode chamber provide a direct current electric field, so that the ammonia ions can migrate to the negative electrode chamber under the action of the electric field and are discharged out of the ammonia removal compartment; the strong acid type ion exchange resin in the ammonia removal compartment and the cation exchange membranes on the two sides improve the chemical balance type of the ammonia water to transfer to the ammonia ions, and improve the removal efficiency;
the two power water pumps are respectively connected with the pure water tank and the ammonia-containing water tank; the power water pump connected with the pure water tank is connected with the anode water inlet and the cathode water inlet of the electric deamination device; a power water pump connected with the ammonia-containing water tank is connected with a water inlet of an ammonia removal compartment of the ammonia removal device; flow meters are arranged on connecting pipelines of the two power water pumps and the electric deamination device, and the flow of the connecting pipelines can be adjusted through the flow meters on the pipelines; the electrode wiring of the electric deamination device is connected with the positive and negative terminals of the power supply; a pipeline connected with an outlet of an ammonia removal compartment in the electric deamination device is provided with a conductivity meter and a PH meter, and the conductivity meter and the PH meter are used for detecting the water quality change condition of produced water; the electric deamination device is also provided with a positive water outlet and a negative water outlet for discharging polar water.
Preferably, the electric deamination device is connected with positive and negative terminals of a power supply through positive and negative terminals respectively led out from the positive and negative chambers.
Preferably, the cathode material, the cathode chamber water distribution plate, the anode material and the anode chamber water distribution plate are titanium iridium-coated electrode materials.
The working method of the device for continuously removing the positive ions in the water for measuring the hydrogen conductivity comprises the following steps:
step 1, preparing a NaOH solution, wherein the NaOH solution flows into an ammonia removal compartment for soaking;
step 2, washing the NaOH solution in the electric deamination device by using pure water in a pure water tank until the conductivity of the effluent of the electric deamination device is less than a set value;
step 3, preparing an HCl solution, wherein the HCl solution flows into an ammonia removal compartment for soaking;
step 4, washing the HCl solution in the electric deamination device by using pure water in a pure water tank until the conductivity of the effluent of the electric deamination device is less than a set value;
step 5, introducing pure water into an ammonia removal compartment, a positive electrode compartment and a negative electrode compartment of the electric deamination device, adding 15-20V direct-current voltage, operating the electric deamination device for 45-60 minutes, finishing operating the electric deamination device when the direct-current voltage is 0.00-0.05A, and finishing initialization of the electric deamination device;
step 6, detecting ammonia water by adopting a direct neutralization titration method, and simultaneously proving the removal effect of the electric deamination device on the ammonia water by adopting an indirect method: and detecting the pH value change (the pH value is reduced) of the effluent of the electric deamination device through a pH meter on line, detecting the conductivity value change (the conductivity is reduced) of the effluent of the electric deamination device through a conductivity meter, and judging the removal effect of the ammonia water.
Preferably, the mass fraction of the NaOH solution in step 1 is 1%, and the length of time for soaking the ammonia removal compartment with the NaOH solution is 12 hours.
Preferably, the conductivity set value of the water discharged from the deamination device in the step 2 is 0.3 mu S/cm.
Preferably, the mass fraction of the HCl solution in step 3 is 1%, and the length of time for which the HCl solution flows into the ammonia removal compartment for soaking is 12 hours.
Preferably, the conductivity set value of the effluent of the electro-deamination device in step 4 is 0.3. mu.S/cm.
The invention has the beneficial effects that: the invention optimizes the structure of the electrodeionization method, designs the device for continuously removing cations in water for measuring the hydrogen conductivity, and can efficiently remove ammonia water. The cation exchange membrane is selected, so that anions can be prevented from entering the ammonia removal compartment, and anion pollution is avoided; the ammonia removal device is provided with the anode chamber and the cathode chamber which are used for providing a direct current electric field, strong acid type ion exchange resin is arranged in the ammonia removal compartment, the chemical balance type ammonia water transfer efficiency to the ammonia radical ions is improved, and the removal efficiency is improved.
Drawings
FIG. 1 is a schematic diagram of the principle of Electrodeionization (EDI);
FIG. 2 is a schematic diagram of the electric ammonia removal principle of the present invention;
FIG. 3 is a schematic structural view of an electric ammonia removal device according to the present invention;
FIG. 4 is a process flow diagram of the present invention;
FIG. 5 is a graph of the effect of operating voltage on effluent conductivity versus pH;
FIG. 6 is a graph of effluent conductivity versus pH over time under non-energized conditions;
FIG. 7 is a process flow diagram of the cyclic operation of the present invention;
FIG. 8 is a graph showing the change of the conductivity and pH of effluent water when the reactor is operated for 1 hour under the conditions of 10V and 0V electrification;
FIG. 9 is a graph of the change in conductivity and pH of the polar and effluent waters;
FIG. 10 is a graph of effluent conductivity versus pH change at different operating voltages after resin exchange saturation;
FIG. 11 is a graph of the effect of different flow rates on the conductivity and pH of produced water at 10V.
Description of reference numerals: the device comprises a positive water outlet 1, a positive water inlet 2, a positive terminal 3, a negative terminal 4, a positive chamber 5, a negative chamber 6, an ammonia removal compartment 7, a conductivity meter 8, a PH meter 9, a pure water tank 10, an ammonia-containing water tank 11, an electric deamination device 12, a power supply 13, a positive water distribution plate 14, a negative water distribution plate 15, a power water pump 16, a flowmeter 17, a negative water outlet 18, a negative water inlet 19, an ammonia removal compartment water inlet 20 and a screw fixing device 21.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are set forth merely to aid in the understanding of the invention. It should be noted that, for a person skilled in the art, several modifications can be made to the invention without departing from the principle of the invention, and these modifications and modifications also fall within the protection scope of the claims of the present invention.
As shown in fig. 2, the principle of the electric ammonia removal technology adopted by the present invention is similar to that of EDI, and is also a technology combining an electrodialysis technology and an ion exchange technology, but for the characteristics of ammonia water, a strong acid cation exchange resin (hydrogen type ion exchange resin), a cation exchange membrane and positive and negative electrodes are selected. Introducing ammonia-containing pure water into the cavity containing hydrogen-type ion exchange resin between the anode membrane and the cathode membrane, and collecting NH in the ammonia water4 +The radical ions being exchangeable with hydrogen ion exchange resins, H+The ions can combine with OH-to form water to promote the chemical equilibrium reaction of ammonia water to NH4 +Radical ion conversion, NH3·H2O and NH3The content of the active carbon is reduced,
NH4 ++OHˉ+RˉH＝RˉNH4+H2O
under the action of DC electric field, NH4 +The ions migrate to the negative electrode and penetrate through the anode film to reach the water side of the negative electrode, and can combine with OH-generated by the negative electrode to form a new chemical equilibrium system, and hydrogen ions H generated by the electrolysis of water at the positive electrode+Under the action of electric field, the cation membrane and regenerated exchange resin adsorbing ammine radical ion exchange resin can be continuously used.
RˉNH4+H+＝RˉH+NH4 +
Under the condition that the hydrolysis voltage is sufficient, the water discharged from the positive electrode cavity can be used as the water inlet of the negative electrode cavity.
Comparing the structure of the electrodeionization unit with the EDI structure, the following points can be found:
1. in the aspect of using the ion exchange resin, the EDI uses the anion-cation exchange resin, but the strong acid ion exchange resin is selected for the purpose of removing ammonia by the electric ammonia removal technology;
2. in the aspect of ion exchange membrane use, EDI needs two kinds of anion and cation exchange membranes for use, but the cation exchange membrane is selected for the electric ammonia removal technology, only in order to remove ammonia ions, hydrogen ions selectively permeate, and other anions are prevented from entering;
3. as shown in fig. 1, the device for EDI on the cavity contains two paths of fresh water and concentrated water, the electric ammonia removal device comprises an electrolysis water path on two sides of the positive electrode and the negative electrode and an ammonia removal cavity containing ion exchange resin, and comparing the device for EDI with the electric ammonia removal device, the fresh water path of the device for EDI has a function similar to the water path containing ion exchange resin in the electric ammonia removal device, and the water path of the positive electrode and the negative electrode of the electric ammonia removal device is similar to the concentrated water path of EDI.
In conclusion, the electric ammonia removal device is special EDI ammonia removal equipment which is adopted according to the characteristics of ammonia water.
Example 1:
as shown in fig. 3, an apparatus for continuously removing cations in water for hydrogen conductivity measurement, comprising: the device comprises a conductivity meter 8, a PH meter 9, a pure water tank 10, an ammonia-containing water tank 11, an electric deamination device 12, a power supply 13, a power water pump 16 and a flowmeter 17;
wherein the electric deamination device 12 comprises an ammonia removal compartment 7, a positive electrode chamber 5 and a negative electrode chamber 6; the anode chamber 5 and the cathode chamber 6 are respectively positioned at the left side and the right side of the electric deamination device 12, an anode chamber water distribution plate 14 is arranged between the anode chamber 5 and the ammonia removal compartment 7, and a cathode chamber water distribution plate 15 is arranged between the cathode chamber 6 and the ammonia removal compartment 7; a positive electrode material is arranged in the positive electrode chamber 5, and a negative electrode material is arranged in the negative electrode chamber 6; the anode chamber water distribution plate 14 and the cathode chamber water distribution plate 15 are fixedly clamped with the ammonia removal compartment 7 through screw fixing devices 21 (stainless steel bolts); strong acid type ion exchange resin is filled in the ammonia removal compartment 7, two sides in the ammonia removal compartment 7 are sealed and isolated from the anode chamber water distribution plate 14 and the cathode chamber water distribution plate 15 through cation exchange membranes, and the cation exchange membranes can prevent anions from entering the ammonia removal compartment and avoid anion pollution; the positive electrode chamber and the negative electrode chamber provide a direct current electric field, so that the ammonia ions can migrate to the negative electrode chamber under the action of the electric field and are discharged out of the ammonia removal compartment; the strong acid type ion exchange resin in the ammonia removal compartment and the cation exchange membranes on the two sides improve the chemical balance type of the ammonia water to transfer to the ammonia ions, and improve the removal efficiency; the two power water pumps 16 are respectively connected with the pure water tank 10 and the ammonia-containing water tank 11; a power water pump 16 connected with the pure water tank 10 is connected with a positive water inlet 2 and a negative water inlet 19 of the electric deamination device 12; a power water pump 16 connected with the ammonia-containing water tank 11 is connected with a water inlet 20 of an ammonia removal compartment of the electric deamination device 12; flow meters 17 are arranged on connecting pipelines of the two power water pumps 16 and the electric deamination device 12, and the flow of the connecting pipelines can be adjusted through the flow meters on the pipelines; the electrode wiring of the electric deamination device 12 is connected with the positive and negative terminals of the power supply 13; a pipeline connected with an outlet of an ammonia removal compartment 7 in the electric deamination device 12 is provided with a conductivity meter 8 and a PH meter 9, and the conductivity meter and the PH meter are used for detecting the water quality change condition of produced water; the electric deamination device 12 is also provided with a positive water outlet 1 and a negative water outlet 18 for discharging polar water.
Example 2:
on the basis of example 1, the effect of removing ammonia water after the operation of the apparatus for continuously removing cations from water for hydrogen conductivity measurement shown in fig. 4 was judged:
1. the specification of the ammonia removal equipment in the test is a CEDI-200 model developed by Hangzhou water treatment technology research and development center, wherein the strong acid ion resin is 001 multiplied by 7 strong acid cation resin of the optical corporation, and the filling density of the equipment is 1.25 g/m. The equipment is initialized, and the initialization process is as follows:
step 1, preparing about 1% NaOH solution, flowing into an ammonia removal compartment, and soaking for 12 hours;
step 2, washing the 1% NaOH solution in the equipment by using pure water until the conductivity is less than 0.3 muS/cm;
step 3, preparing about 1% HCl solution, flowing into an ammonia removal compartment, and soaking for 12 hours;
step 4, washing the 1% HCl solution in the equipment by using pure water until the conductivity is less than 0.3 mu S/cm;
and 5, introducing pure water into the ammonia removal equipment, the ammonia removal compartment and the polar water compartment, adding 15-20V of direct current voltage, operating the equipment for 45-60 minutes, and finishing the initialization of the equipment when the direct current is 0.00-0.05A.
The ammonia water detection method adopts a direct neutralization titration method and an indirect method to prove the ammonia water removal effect, namely, the ammonia water removal effect is judged by detecting the change of pH value (the pH value is reduced) and the change of conductivity value (the conductivity is reduced) of a conductivity instrument on line through the pH instrument.
The device carries out test comparison of different flow under different voltage conditions, tests the ammonia removal performance, inspects the ammonia removal change of the device along with time under the condition of no power on according to the effect of the ammonia removal device, and explores the ammonia removal mechanism. The conductivity of the pure water in the test is 1-5 un/cm, the conductivity of the water of the ammonia-containing boiler is about 50un/cm, and the pH value is about 10.4.
2. Results and discussion
2.1 influence on the effluent conductivity and PH value under different operating voltages
The experimental apparatus CEDI-200, after the initialization was completed, had the following experimental operating conditions: the flow rate of the extreme water is 3L/h, the water inflow rate of the ammonia-containing boiler is 4L/h, and the water outlet operation of the equipment is carried out once. Tests under different voltages are carried out, and after stable operation is carried out for 30min, the pH value and the conductivity value of the produced water are detected, as shown in figure 5. As shown in FIG. 5, at operating voltages of 0V, 6V, 10V, 15V, 20V, 25V, 30V and 40V, respectively, the conductivity of the produced water is substantially 3-4un/cm, and the pH is about 5.2. Compared with the water sample entering the equipment, the conductivity of which is 50un/cm and the pH value of which is 10.4, the pH value is changed from alkalinity to acidity, and the conductivity is reduced to the RO pure water level. The ammonia water is alkaline solution, and the effluent shows acidity, which indicates that the ammonia water is not pure, and the desalting rate is more than 92%. Ammonia water in the solution was detected by neutralization titration, and the result showed no detection. The ammonia removal effect is obvious. As shown by the conductivity value and the pH value of the operation voltage of 0V in FIG. 5, compared with the ammonia-removing raw water, the ammonia-removing effect is obvious, and the strongly acidic ion exchange resin can realize the exchange of the ammonia ions. Meanwhile, compared with the operation voltages of 6V, 10V, 15V, 20V, 25V, 30V and 40V, the effect is basically consistent and no obvious change exists.
The test device CEDI-200 is charged under the condition of no voltage, the exchange capacity of the strong acid ion exchange resin in the ammonia removal compartment is limited, and NH is added4 +After the ion exchange is saturated, the CEDI-200 will lose the effect of removing ammonia from the equipment, and the equipment is developed as shown in FIG. 6And the PH meter and the conductivity instrument track the change of the monitoring data during long-term continuous operation. As shown in FIG. 6, after 650min of operation, the pH value and the conductivity value are obviously increased, indicating that the exchange capacity of the strongly acidic ion exchange resin is saturated and the exchange function is lost.
2.2 discussion of the Ammonia removal mechanism test of resin regeneration
According to the CEDI-200 test device, after a water inlet sample runs under the condition of no electricity, when strong-acid ion exchange resin is saturated with ammonia water in an exchange manner, the operation condition is changed, and the following condition tests are carried out:
500ml of ammonia-containing water is taken, the conductivity of the ammonia-containing water is about 50un/cm, the pH value is about 10.4, an outlet of the electric ammonia removal pipeline is connected back to the ammonia-containing water tank after the pH meter and the conductivity, a circulating pipeline is formed, and the polar water pipeline is still directly discharged. The circulation flow is 4L/h, the polar water flow is 3L/h, and the steady-current direct-current voltage is set to be 10V. The flow chart is shown in FIG. 7.
Two sets of tests were carried out, i.e. the conductivity value of the ammonia removal water line was compared with the pH value during the operation of 1h with 10V and 1h without electricity. As shown in FIG. 8, under the condition of no power supply, after the strong acid ion exchange resin is saturated with the ammonia water, the ammonia removal effect of the equipment is basically disabled, the change of the pH value is not obvious, and the conductivity is reduced to some extent due to the concentration difference diffusion of the pure water in the polar water chamber and the ammonia water in the ammonia removal chamber. Under the condition of applying a 10V direct current electric field, the pH value is reduced to below 5 from 10 along with the increase of time, and the conductivity is reduced to 5un/cm and is close to the conductivity of RO pure water. The strong acid ion exchange resin in the device CEDI-200 is saturated with ammonia water, so that deamination can not be realized, but water molecules on the surface of the strong acid ion exchange resin can be hydrolyzed under a certain direct current electric field to exchange ammonia ions, so that the ammonia ions are transferred to a negative electrode chamber under the action of the electric field, and a system is removed.
In order to verify that the resin exchange adsorbed ammonia ions can migrate to the polar water chamber through the resin interface under the action of the direct current electric field, the following tests were carried out: after the strong acid ion exchange resin in the test device CEDI-200 is saturated with ammonia water in an exchange manner, pure water is used for washing the ammonia water solution in the ammonia removal compartment of the device, the conductivity of the outlet water meets the condition when the conductivity of the pure water is the conductivity of the pure water, 500ml of pure water is taken and filled into an ammonia-containing water tank, the outlet of an electric ammonia removal pipeline is connected back to the ammonia-containing water tank after a PH meter and the conductivity, a circulating pipeline is formed, and a polar water pipeline is still directly discharged. The circulation flow is 4L/h, the polar water flow is 3L/h, and the steady-flow direct-current voltage is set to be 20V. And detecting the pH value and the conductivity of the outlet water of the polar water. The flow chart is as shown in the above figure. The conductivity versus PH change is shown in fig. 9. In FIG. 9, the conductivity of pure water after passing through the ammonia removal compartment remained substantially unchanged from the pH value and did not change much from the initial value of the feed water, with a conductivity of 3.4un/cm and a pH of 5.6. The inlet water of the polar water is pure water, but after the polar water enters ammonia removal equipment, the conductivity of the polar water is more than 40un/cm, the pH value of the polar water is more than 10, and the ammonia-containing component of the outlet water of the solution is detected and can be detected to be 0.8 mg/L. It is considered that the strongly acidic ion exchange resin, when energized at 20V, adsorbs the ammonia ions not dissolved in the pure aqueous solution discharged from the apparatus but migrates to the outside of the apparatus through the resin surface to the negative electrode compartment.
In the device CEDI-200, after strong acid ion exchange resin and ammonia water are exchanged and saturated, pure water of an ammonia-containing boiler is introduced into an ammonia removal compartment, water is directly discharged for one time, test methods of different operating voltages are carried out, and after the water is discharged for 30min, the change of the pH value and the conductivity value of the discharged water is detected. As shown in FIG. 10, after the strong acid ion exchange resin is saturated with ammonia water, the strong acid ion exchange resin is still electrified, the conductivity value of the effluent is obviously reduced, certain value fluctuation of the conductivity and the pH value is not large along with the increase of the voltage, but the conductivity value cannot be reduced to the level of 5.0un/cm of the conductivity of pure water, and the pH is not obviously reduced and still shows alkalinity. The result shows that when the ammonia removal test is carried out after the strong-acid ion exchange resin and the ammonia water are subjected to exchange saturation, the ammonia water cannot be completely removed after the voltage is applied, and only the ammonia water can be partially removed effectively.
The experiments verify that the ammonia removal mechanism of the ammonia removal device CEDI-200 is that the ammonia is removed from the system through the exchange action of the strong acid ion exchange resin and the ammonia radical ion, and the ammonia is removed from the system under the action of the direct current electric field, and the strong acid ion exchange resin and the ammonia radical ion are organically combined and interact with each other to realize the continuous regeneration function of the equipment. One function of the single aspect cannot fully realize the ammonia removal regeneration function.
2.3 influence on effluent conductivity and PH value under different operation flows
Because the device CEDI-200 is one-time water inlet and outlet in the process flow, different water inlet flows show that the amount of ammonia-containing raw water to be treated by the equipment in unit time is changed, the ammonia removal effect of the device CEDI-200 under different flows is analyzed, and the test process is as follows: the operation voltage is 10V, the water inlet operation flow rates are respectively selected to be 1L/h, 2L/h, 3L/h, 4L/h and 5L/h, the polar water flow rate is 3L/h, and the conductivity and the PH value are compared and analyzed after running for 60 min. As shown in FIG. 11, the pH of the effluent from the CEDI-200 apparatus was found to be acidic at an operating voltage of 10V, and remained substantially constant as the flow rate increased, and the ammonia content of the effluent was detected as undetected. The conductivity value is increased along with the increase of the flow, but the increased value is not large, the conductivity is still in the conductivity value range of the common RO pure water, and the RO pure water can be used as the RO pure water. Therefore, the experimental device CEDI-200 can effectively remove ammonia water in ammonia-containing wastewater within the flow range of 1L/h to 5L/h under the operation voltage of 10V (when the water quality conductivity is 50un/cm, and the PH is 10). The adjustable operation range of the equipment is ideal.
3. Small knot
The present embodiment provides a method for removing pure water containing ammonia from a boiler, and discusses the principle of ammonia removal, aiming at the device CEDI-200. Tests prove that the function of key components of the equipment is realized, namely the exchange adsorption function of strong acid ion exchange resin and ammonia ions and the function of direct current electric field, the ammonia ions can permeate the anode membrane to migrate to the cathode side of the polar chamber through the surface of the resin, and the continuous renewable ammonia removal function is realized. The ammonia removal effect test under different voltage conditions and different flow rates is preliminarily developed. The ammonia removal mechanism of the ammonia removal device CEDI-200 is considered to be that the strong acid ion exchange resin and the ammonia radical ion exchange function are utilized, and the ammonia radical ion exchange resin are moved out of the system under the action of the direct current electric field, and the strong acid ion exchange resin and the ammonia radical ion exchange resin are organically combined and interact to realize the continuous regeneration function of the equipment, so that the continuous regeneration function cannot be effectively realized by unilateral operation. According to the CEDI-200 device, the operation flow can be regulated and controlled within the operation range of 1L/h to 5L/h, the operation voltage is 6V to 40V, the effect of removing ammonia can be achieved, and the detection values are all undetected.
The invention adopts an electric ammonia removal technology, and aims at the characteristics of ammonia water, an Electrodeionization method (EDI) is used for reference, the optimization is carried out on the structure of the Electrodeionization method, the ammonia water is efficiently removed, a cation exchange membrane is selected, the ammonium ions are removed, the hydrogen ions selectively permeate, and the entering of other anions is avoided; by utilizing the exchange adsorption action of strong acid ion exchange resin and ammonia radical ions and under the action of a direct current electric field, the ammonia radical ions can permeate an anode film to migrate to the negative side of an electrode chamber through the surface of the resin, and the continuous renewable ammonia removal action is realized.

Claims (8)

1. An apparatus for continuously removing cations from water for hydrogen conductivity measurement, comprising: the device comprises a conductivity meter (8), a PH meter (9), a pure water tank (10), an ammonia-containing water tank (11), an electric deamination device (12), a power supply (13), a power water pump (16) and a flowmeter (17);
wherein the electric deamination device (12) comprises an ammonia removal compartment (7), a positive electrode chamber (5) and a negative electrode chamber (6); the anode chamber (5) and the cathode chamber (6) are respectively positioned at the left side and the right side of the electric deamination device (12), an anode chamber water distribution plate (14) is arranged between the anode chamber (5) and the ammonia removal compartment (7), and a cathode chamber water distribution plate (15) is arranged between the cathode chamber (6) and the ammonia removal compartment (7); a positive electrode material is arranged in the positive electrode chamber (5), and a negative electrode material is arranged in the negative electrode chamber (6); the ammonia removal compartment (7) is fixedly clamped by the anode chamber water distribution plate (14) and the cathode chamber water distribution plate (15) through screw fixing devices (21); strong acid type ion exchange resin is filled in the ammonia removal compartment (7), and two sides in the ammonia removal compartment (7) are sealed and isolated from the anode chamber water distribution plate (14) and the cathode chamber water distribution plate (15) through cation exchange membranes;
the two power water pumps (16) are respectively connected with the pure water tank (10) and the ammonia-containing water tank (11); a power water pump (16) connected with the pure water tank (10) is connected to the anode water inlet (2) and the cathode water inlet (19) of the electric deamination device (12); a power water pump (16) connected with an ammonia-containing water tank (11) is connected to a water inlet (20) of an ammonia removal compartment of an electric deamination device (12); flow meters (17) are arranged on connecting pipelines of the two power water pumps (16) and the electric deamination device (12); the electrode wiring of the electric deamination device (12) is connected with the positive and negative terminals of the power supply (13); a pipeline connected with the outlet of an ammonia removal compartment (7) in the electric deamination device (12) is provided with a conductivity meter (8) and a PH meter (9); the electric deamination device (12) is also provided with a positive water outlet (1) and a negative water outlet (18).
2. The apparatus for continuous removal of cations in water for hydrogen conductivity measurement according to claim 1, wherein: the electric deamination device (12) is connected with positive and negative terminals of a power supply (13) through a positive terminal (3) and a negative terminal (4) which are respectively led out from the positive chamber (5) and the negative chamber (6).
3. The apparatus for continuous removal of cations in water for hydrogen conductivity measurement according to claim 1, wherein: the anode material and the anode chamber water distribution plate (14) and the cathode material and the cathode chamber water distribution plate (15) are titanium ruthenium and iridium coated electrode materials.
4. A method of operating an apparatus for continuously removing cations from water for hydrogen conductivity measurement according to claim 1, comprising the steps of:
step 1, preparing NaOH solution, wherein the NaOH solution flows into an ammonia removal compartment (7) to be soaked;
step 2, using pure water in the pure water tank (10) to flush NaOH solution in the electric deamination device (12) until the conductivity of the effluent of the electric deamination device (12) is less than a set value;
step 3, preparing HCl solution, wherein the HCl solution flows into the ammonia removal compartment (7) to be soaked;
step 4, using pure water in the pure water tank (10) to flush the HCl solution in the electric deamination device (12) until the conductivity of the effluent of the electric deamination device (12) is less than a set value;
step 5, introducing pure water into an ammonia removal compartment (7), an anode chamber (5) and a cathode chamber (6) of the electric deamination device (12), adding 15-20V direct current voltage, operating the electric deamination device (12) for 45-60 minutes, finishing operating the electric deamination device (12) when the direct current shows that the direct current is 0.00-0.05A, and finishing initialization of the electric deamination device (12);
and 6, detecting the ammonia water by adopting a direct neutralization titration method, and simultaneously proving the removal effect of the electric deamination device (12) on the ammonia water by adopting an indirect method: the pH value change of the effluent of the electric deamination device (12) is detected through a pH meter (9) on line, and the removal effect of the ammonia water is judged through detecting the conductivity value change of the effluent of the electric deamination device (12) through a conductivity meter (8).
5. The operating method of the apparatus for continuously removing cations in water for hydrogen conductivity measurement according to claim 3, wherein: in the step 1, the mass fraction of the NaOH solution is 1%, and the time for soaking the ammonia removal compartment (7) by the NaOH solution is 12 hours.
6. The operating method of the apparatus for continuously removing cations in water for hydrogen conductivity measurement according to claim 3, wherein: the set value of the conductivity of the water discharged from the deamination device (12) in the step 2 is 0.3 mu S/cm.
7. The operating method of the apparatus for continuously removing cations in water for hydrogen conductivity measurement according to claim 3, wherein: the mass fraction of the HCl solution in the step 3 is 1 percent, and the time for the HCl solution to flow into the ammonia removal compartment (7) for soaking is 12 hours.
8. The operating method of the apparatus for continuously removing cations in water for hydrogen conductivity measurement according to claim 3, wherein: in the step 4, the set value of the conductivity of the effluent of the electric deamination device (12) is 0.3 mu S/cm.
CN202110753403.3A 2021-07-02 2021-07-02 Device and method for continuously removing cations in water for hydrogen conductivity measurement Pending CN113277602A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114477385A (en) * 2021-12-16 2022-05-13 华能南京燃机发电有限公司 Method and device for removing cations in steam water of power station

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114477385A (en) * 2021-12-16 2022-05-13 华能南京燃机发电有限公司 Method and device for removing cations in steam water of power station

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