CN118026426A - Membrane-free efficient electrochemical coupling process descaling system and method - Google Patents
Membrane-free efficient electrochemical coupling process descaling system and method Download PDFInfo
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Abstract
The invention discloses a membrane-free efficient electrochemical coupling process descaling system and a method, wherein the system comprises an electrochemical descaling system and a scale separation system which are connected; the electrochemical descaling system comprises an electrolytic tank; an anode is arranged in the electrolytic tank, the anode is connected with the positive electrode of the direct current power supply, a cathode porous filter element is connected with the negative electrode of the direct current power supply, and a cathode porous filter element is arranged in the anode; the top of the porous filter element is connected with a scale separation system through a water pump. The invention takes the conductive cathode porous filter element as an electrochemical descaling cathode, and is connected with a scale separation system through a water pump at the top of the cathode porous filter element, and adopts a method of pumping high-concentration OH ‑ water body near the cathode porous filter element by the water pump, so that the separation of high-efficiency H + and OH ‑ can be realized without any membrane material, and the removal of hardness ions in water is greatly promoted. The flocculant precipitation system or the filtration crystallization system is used as a scale separation system, so that the use of a membrane material for scale separation is avoided, and the method has strong operation stability and economy.
Description
Technical Field
The invention belongs to the technical field of industrial descaling, and particularly relates to a membrane-free efficient electrochemical coupling process descaling system and method, namely, the electrochemical descaling efficiency is improved under the condition that no membrane is adopted in the electrochemical descaling process.
Background
Any pipe and machinery in industrial production can produce scale caused by supersaturation of CaCO 3 or Mg (OH) 2 over time in contact with aqueous solutions, resulting in reduced plant efficiency and plugging of the pipe, creating economic losses and explosion risks. Therefore, the purpose of saving water resources can be greatly realized by removing Ca 2+、Mg2+ and other hardness ions in the industrial water such as circulating cooling water, mine water, sea water desalination and the like.
The methods commonly adopted at present are a scale inhibitor method, a chemical precipitation method, an ion exchange method, a reverse osmosis method and the like. Most of commonly used scale inhibitors are phosphorus organic scale inhibitors, and P element is introduced into circulating cooling water in the treatment process to cause secondary pollution. Meanwhile, the scale inhibitor can not remove hardness ions from water, and can only play a role in delaying precipitation. Chemical precipitation requires the addition of a large amount of chemicals to the circulating cooling water to raise the pH in the water, thereby promoting CaCO 3 or Mg (OH) 2 precipitation. However, the high cost of chemical agents, the subsequent neutralization treatment of water quality and sludge disposal are all problematic. Ion exchange processes require regeneration of the resin with large amounts of high salinity water after treatment, and large amounts of high salinity wastewater are discharged during the process, which places a significant burden on the environment. The core component of the reverse osmosis treatment method is a membrane, and a large amount of scale can be generated on the reverse osmosis membrane along with the progress of the reaction, so that the membrane is blocked, the energy consumption is increased, the cost for replacing the reverse osmosis membrane is high, and the large-scale application is difficult to realize. Therefore, there is a need to explore alternative techniques to achieve efficient scale removal in aqueous solutions.
Electrochemical precipitation is an active hardness removal technology, and has the advantages of high efficiency, environmental friendliness, low cost, easiness in operation and the like. In the electrochemical descaling process, OH - generated by the cathode can react with Ca 2+ and Mg 2+ in the solution to generate CaCO 3 and Mg (OH) 2 precipitate respectively, so that hardness ions are removed. However, there are two points that limit the descaling efficiency of electrochemical methods. One is that most of OH - generated by the cathode can be subjected to a composite reaction with H + generated by the anode in the electrochemical process, so that the utilization rate of OH - is low, and the hardness ion removal rate is low. The main solution to the problem is to separate the cathode and the anode by adopting an ion exchange membrane, but the problems of membrane pollution, membrane replacement and the like can be generated after long-term use, which is not beneficial to practical use. Secondly, under the dominant of heterogeneous nucleation, hardness ions in circulating cooling water can only be removed through the formation of cathode precipitation, and a large amount of time is consumed in a spontaneous homogeneous precipitation process, and generated scale still exists in a water body, so that the method is difficult to apply in practical production. In order to solve the problem, the method of membrane filtration and the like is mainly adopted to carry out solid-liquid separation on the homogeneous crystallization product, and the method also has the disadvantages of membrane pollution, high price and the like.
Disclosure of Invention
Aiming at the problems that the electrochemical descaling efficiency is improved by adopting a membrane material at present, the solid-liquid separation process of homogeneous crystallization products has membrane pollution and high price, scale particles in water bodies are difficult to collect after electrochemical descaling, the homogeneous precipitation effect of scale forming ions is difficult to utilize, and the like, the invention aims to provide a membrane-free efficient electrochemical coupling process descaling system and a membrane-free efficient electrochemical coupling process descaling method.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
A membrane-free efficient electrochemical coupling process descaling system comprises an electrochemical descaling system and a scale separating system which are connected;
the electrochemical descaling system comprises a direct-current power supply, an electrolytic tank and a water pump;
an anode is arranged in the electrolytic tank, the anode is connected with the positive electrode of the direct current power supply, a cathode porous filter element is connected with the negative electrode of the direct current power supply, and a cathode porous filter element is arranged in the anode;
The top of the cathode porous filter element is connected with a scale separation system through a water pump;
the scale separation system is a filtration crystallization system comprising a flocculant precipitation system or a porous adsorption packing.
Further, the device also comprises a water inlet tank, wherein the water inlet tank is connected with the inlet of the electrolytic tank, and the outlet at the top of the electrolytic tank is also connected with the inlet of the water inlet tank.
Further, the electrolytic tank is cylindrical; the anode is a cylindrical reticular electrode.
Further, the cathode porous filter element is made of nickel plating copper powder sintered filter element, titanium filter element or stainless steel filter element.
Further, the cathode porous filter element is cylindrical, the inside is of a cavity structure, the outer wall is of a porous structure, the top is provided with a pumping water outlet, and the pumping water outlet is connected with a water pump.
Further, the anode is made of carbon electrode, boron doped diamond electrode, noble metal oxide coating electrode, lead dioxide coating electrode or titanium dioxide coating electrode.
Further, the filtering crystallization system comprises a filtering crystallization column, a porous adsorption filler is arranged in the filtering crystallization column, an inlet is arranged at the top of the filtering crystallization column, and an outlet is arranged at the bottom of the filtering crystallization column;
The flocculant precipitation system comprises a flocculation sedimentation tank, a stirring rod is arranged in the flocculation sedimentation tank, a sludge bucket is arranged at the lower end of the flocculation sedimentation tank, and a sewage outlet is arranged at the bottom of the sludge bucket.
Further, the porous adsorption filler is artificial zeolite, molecular sieve, activated carbon, adsorption resin, corundum or quartz sand.
Further, a flocculating agent and a coagulant aid are added in the flocculation sedimentation tank, wherein the flocculating agent comprises polyacrylamide and polyaluminium chloride, and the coagulant aid comprises aluminum sulfate, calcium chloride, activated silicic acid and bone glue.
The descaling method of the membraneless high-efficiency electrochemical coupling process comprises the following steps:
The water to be treated is pumped out of the electrolytic tank through the cathode porous filter core pump, and then enters a scale separation system for homogeneous precipitation and solid-liquid separation.
Compared with other methods, the invention has the following beneficial effects:
The invention takes the conductive cathode porous filter element as the electrochemical descaling cathode for the first time, and is connected with the scale separation system through the water pump by arranging the top of the cathode porous filter element, and adopts the method of pumping high-concentration OH - water body near the cathode porous filter element by the water pump, so that the high-efficiency separation of H + and OH - can be realized without adopting any membrane material, the complex reaction of OH - and H + generated by an anode is prevented, the utilization rate of OH - is improved, and the removal of hardness ions in water is greatly promoted. At this time, OH - reacts with HCO 3 - in the solution to generate CO 3 2-, and then combines with Ca 2+ to generate CaCO 3 precipitate; and Mg 2+ also generates Mg (OH) 2 under the condition that the pH is more than 10, so that the high-efficiency removal of hardness ions is realized. The electrochemical system is coupled with the filtration crystallization system, the porous adsorption filler in the filtration crystallization system not only can filter and intercept scale particles in the effluent of the electrochemical descaling system, but also can provide a large number of deposition sites for homogeneous deposition of CaCO 3 and Mg (OH) 2, and induce rapid crystallization and deposition of scale forming ions in the effluent of the electrochemical descaling system, so that the homogeneous deposition time is greatly shortened. The porous adsorption material provided by the invention has low price and can be repeatedly used, so that the use of a membrane material for separating scale is avoided, and the porous adsorption material has strong operation stability and economy.
The flocculation precipitation system is coupled behind the electrochemical system, and the flocculant in the flocculation precipitation system not only can flocculate and precipitate scale particles in the water discharged from the electrochemical descaling system, but also can provide a large number of deposition sites for homogeneous precipitation of CaCO 3 and Mg (OH) 2, so that the homogeneous precipitation time is greatly shortened. Furthermore, because the flocculant and the coagulant aid in the invention are low in price and the related application is very mature in the field of water treatment, the separation of scale by adopting a membrane material is avoided, and the method has strong operation stability and economy.
Drawings
Advantages of the present invention will be further understood by reading the following description of the drawings, the illustrative embodiments of the invention and their descriptions are used to explain the invention and are not to be construed as unduly limiting the invention. In the drawings:
FIG. 1 is a schematic view of a descaling process of an electrochemical coupling filtration crystallization system;
In the figure, 1 is a water inlet tank, 2 is a direct current power supply, 3 is an electrolytic tank, 4 is an anode, 5 is a cathode porous filter element, 6 is a water pump, 7 is a filtering crystallization column, 8 is a porous adsorption filler, 9 is a first water outlet tank, 10 is a flocculation sedimentation tank, 11 is a stirring rod, 12 is a sludge hopper, 13 is a sewage outlet, and 14 is a second water outlet tank.
FIG. 2 is a schematic diagram of an electrochemical descaling system according to the present invention;
FIG. 3 is a schematic diagram of the structure and principle of the filtration crystallization system of the present invention;
FIG. 4 is a schematic diagram of the structure and principle of action of the flocculation precipitation system of the present invention;
FIG. 5 is an illustration of the effect of increasing the pH of a pumped water body using the electrochemical system of the present invention in an example;
Fig. 6 is an effect of removing hardness and alkalinity of circulated cooling water using the electrochemical system of the present invention in the example.
FIG. 7 is an OH-separation efficiency, current efficiency and energy consumption effect using a pumped and non-pumped scale removal scheme.
FIG. 8 is a graph of OH - separation efficiency versus current density.
Fig. 9 is a graph of theoretical fraction of Ca 2+、Mg2+ as a function of pH, where (a) is theoretical fraction of Ca 2+ and (b) is theoretical fraction of Mg 2+.
FIG. 10 is an illustration of the effect of using the electrochemical system of the present invention to remove mine water hardness and alkalinity in an example.
FIG. 11 shows the effect of removing hardness and alkalinity of circulated cooling water using the electrochemical coupling filtration crystallization system and the flocculation precipitation system of the present invention in examples.
Detailed Description
The present invention will be more clearly, fully and thoroughly explained below by way of examples in order to enable a person skilled in the relevant art to understand the present invention. However, the phenomena and results in the described embodiments are only a part of the present invention, and the embodiments do not represent all cases, so the embodiments do not limit the scope of the disclosure of the present invention.
In addition, an element in the present disclosure may be referred to as being "fixed" or "disposed" on another element or being directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like are used herein for illustrative purposes only and are not meant to be the only embodiment.
Referring to fig. 1, a membraneless high-efficiency electrochemical coupling process descaling system mainly comprises an electrochemical descaling system and a scale separating system.
Wherein, electrochemical descaling system includes: a direct current power supply 2, an electrolytic tank 3, a cathode porous filter element 5, a net-shaped anode 4 and a water pump 6. In the electrochemical process, a water pump is adopted to pump alkaline water body rich in OH - near the cathode porous filter core at a certain flow rate. The electrolytic tank 3 is connected with a water inlet tank 1, an anode 4 is arranged in the electrolytic tank 3, a cathode porous filter element 5 is arranged in the anode 4, the anode 4 is connected with the positive electrode of the direct current power supply 2, and the cathode porous filter element 5 is connected with the negative electrode of the direct current power supply 2. The outlet of the top of the electrolytic tank 3 is also connected with the inlet of the water inlet tank 1, and the water to be treated in the electrolytic tank 3 overflows into the water inlet tank 1.
Specifically, the electrolytic tank 3 is cylindrical. The cathode porous filter element 5 is made of nickel-plated copper powder sintered filter element, titanium filter element or stainless steel filter element (nickel-plated copper powder sintered filter element manufacturer: kunshanbo method new material science and technology Co., ltd.), and the cathode porous filter element 5 is used for pumping boundary layer solution around the filter element by adopting a water pump while conducting electricity; preferably, the cathode porous filter element 5 is cylindrical, the inside is of a cavity structure, the outer wall is of a porous structure, the top is of a pumping water outlet, the aperture is 10-90 mu m, the pumping water outlet is connected with the water pump 6, and an opening is arranged at the top of the electrolytic tank 3 and used for connecting the pumping water outlet with the water pump 6; the anode 4 is a cylindrical mesh electrode suitable for electrochemical water treatment, and the materials include, but are not limited to, a carbon electrode, a boron-doped diamond electrode, a noble metal electrode or a metal oxide coating electrode (noble metal oxide coating electrode (titanium ruthenium iridium coating electrode), a lead dioxide coating electrode, a titanium dioxide coating electrode, etc.); further, the distance between the anode 4 and the cathode porous filter element 5 is 1cm-10cm, so that the generated scale can cause short circuit due to contact of the anode and the cathode, and the too far distance can cause too high voltage and too high energy consumption.
Specifically, the water pump 6 for the alkaline water body with the suction cathode rich in OH - can be a centrifugal pump, a self-priming pump, a plunger pump, a screw pump, a peristaltic pump or the like.
Specifically, the DC power supply 2 can provide a voltage in the range of 0-36V and a current in the range of 0-1000A.
The scale separation system comprises a filtering crystallization system and a flocculating agent precipitation system.
The filtering crystallization system mainly comprises a filtering crystallization column 7, wherein a porous adsorption filler 8 is arranged in the filtering crystallization column, and the bottom of the filtering crystallization column 7 is connected with a first water outlet tank 9. The water flows through the filtration crystallization column 7 in a top-down manner. The packing of the adsorption material (porous adsorption packing 8) in the filtration crystallization column 7 plays the following two roles: firstly, particles in the water discharged from the electrochemical descaling system are filtered and trapped, and secondly, the adsorption material or the adsorption material with the surface covered with the scale is used as a crystal nucleus to induce scale forming ions in the water discharged from the electrochemical descaling system to be further crystallized. The hardness and alkalinity of the water to be treated can be further reduced by the two functions, and the overall treatment effect of the system is improved.
Specifically, the porous adsorption filler 8 is artificial zeolite, molecular sieve, activated carbon, adsorption resin, corundum or quartz sand, etc. Further, the particle size of the adsorbent material may be appropriately selected according to the object to be treated.
The flocculant precipitation system mainly comprises a flocculation precipitation tank 10, wherein a stirring rod 11 is arranged in the flocculation precipitation tank 10, a second water outlet tank 14 is arranged at the bottom of the flocculation precipitation tank 10, a sludge bucket 12 is arranged at the lower end of the flocculation precipitation tank 10, and a sewage outlet 13 is arranged at the bottom of the sludge bucket 12. The main body of the flocculation sedimentation tank 10 adopts the method of adding flocculant and coagulant aid into the solution to accelerate the homogeneous sedimentation process. Wherein the flocculant is used for aggregating micro scale particles suspended in water into larger flocculent aggregates, thereby being convenient for removing by physical methods such as sedimentation or filtration. Coagulant aids are chemical agents that assist the action of a flocculant, and they often do not have flocculation function themselves or are weak in flocculation ability. The main function of the coagulant aid is to change the water quality condition (such as pH value) or provide micro flocculation, thereby enhancing the effect of the flocculant.
Specifically, the flocculant includes Polyacrylamide (PAM) and polyaluminum chloride (PAC), and the common coagulant aids include aluminum sulfate, calcium chloride, activated silicic acid and bone glue. The stirring in the invention is mechanical stirring by arranging the stirring rod, and can also adopt methods such as magnetic stirring, pneumatic stirring or vibration stirring.
As shown in FIG. 1, in the invention, circulating cooling water firstly enters an electrolytic tank 3, water flow is divided into two parts after electrochemical treatment, one part of the water flow is sucked out of the electrolytic tank 3 from the top end of a cathode porous filter element 5, then the water flow is injected into a filtering crystallization column 7 from the top end, and the whole treatment process is finished after the water flow is discharged from the bottom end. The other part overflows from the side of the electrolytic tank 3 and flows back to the water inlet tank 1.
As shown in fig. 2, the principle of the present invention is that: by adopting a mode of pumping water near the cathode porous filter element 5, OH - generated by the cathode is sucked out along with water flow of a cathode boundary layer in the electrolysis process, so that the OH - and H + generated by the anode are prevented from undergoing a composite reaction, and the utilization rate of OH - is improved. At this time, OH - reacts with HCO 3 - in the solution to generate CO 3 2-, and then combines with Ca 2+ to generate CaCO 3 precipitate; and Mg 2+ also generates Mg (OH) 2 under the condition that the pH is more than 10, so that the high-efficiency removal of hardness ions is realized. In the process, the pH of the solution remained in the electrolytic tank 3 is slightly reduced under the action of H +, and the hardness of the solution is basically unchanged, so that overflowed water flows back to the water inlet tank 1 to be mixed with raw water.
The water body sucked by the pump is rich in OH -, so that the water body has stronger homogeneous precipitation effect, and the homogeneous precipitation process of hardness ions can be accelerated and the descaling efficiency can be further improved by coupling the scale separation system after the electrochemical descaling system. Specifically, the descaling efficiency of the conventional electrochemical descaling process is 15-25%. The descaling rate of the pumping electrochemical process adopted by the invention is about 70%, and the descaling efficiency can reach about 92% at the highest through the coupling scale separation system.
Specifically, as shown in fig. 3, in the filtration crystallization system using porous material as porous adsorption filler, the porous adsorption filler 8 not only can adsorb and filter the formed scale particles, but also can provide sufficient crystallization sites for homogeneous crystallization of CaCO 3 and Mg (OH) 2, so that the homogeneous crystallization process is accelerated, and the scale removal efficiency of the produced water is further improved.
Specifically, as shown in fig. 4, a flocculant precipitation system using a flocculant and a coagulant aid as dosing agents, wherein the flocculant aggregates particles into larger agglomerates by neutralizing the surface charge of suspended scale particles (reducing repulsive forces between particles) and/or bridging (connecting a plurality of particles through a portion of the polymer chain) and adsorption and entanglement. The coagulant aid can enable the flocculant to interact with suspended particles more effectively, or provide more 'joints' for bridging action of the flocculant by forming tiny coagulated particles, so that flocculation effect is improved, flocculation precipitation process of scale is enhanced, and hardness removal efficiency is increased.
A descaling method for a membraneless high-efficiency electrochemical coupling process comprises the following steps:
(1) Electrolyte flows in from the lower end of the side edge of the electrolytic tank 3, when the electrolytic tank 3 is filled with water, a part of water overflows from the upper end of the side edge of the electrolytic tank 3, and a part of water is pumped out from the top of the cathode porous filter element 5 by the water pump 6.
(2) The pH of the overflowed water is slightly reduced because the part of water body containing OH - is pumped out, and the hardness ion concentration is hardly changed, but the alkalinity is reduced due to the effect of H +, and the overflowed water is further returned to the water inlet tank 1 for mixing treatment with raw water.
(3) The pump discharges water into the filtration crystallization system, water flows in from the upper end of the filtration crystallization column 7, and water flows out from the lower end of the filtration crystallization column, so that the discharged water is treated low-hardness water, and the water can be subjected to subsequent treatment or discharged. Or (b)
The pumped water flows in from the upper part of the side surface of the flocculation sedimentation tank 10, the lower part flows out, the flocculate is collected by the lower sludge hopper 12, and the discharged water is the treated low-hardness water which can be processed or discharged later.
The specific parameters of the size of the electrolytic tank, the size of the porous cathode, the size of the anode, the size of the filtering crystallization column, the size of the flocculation sedimentation tank 10, the size of the stirrer and the like related to the method can be optimized according to the flow of the actual treated water sample.
Parameters related to the method, such as current density, water inflow, pumping flow, flocculant consumption, coagulant aid consumption, stirring frequency and the like, can be optimized according to different water quality conditions.
Example 1 Using a pumping scheme
(1) The electrolyte is 0.8g/L Na 2SO4 solution;
(2) The anode adopts a titanium-coated ruthenium iridium electrode, the cathode adopts nickel-plated copper powder to sinter the filter element, the current density is 8mA/cm 2, and the electrolysis time is 1h;
(3) Electrolyte flows in from the lower end of the side edge of the electrolytic tank 3, is electrolyzed in the electrolytic tank 3, after the water body is filled in the electrolytic tank 3, a part of electrolyte overflows from the upper end of the side edge of the electrolytic tank 3, a part of electrolyte is pumped out from the top of the cathode porous filter element 5 by the water pump 6, and overflowed water flows back to the water inlet tank 1 to be mixed with raw water. At this time, the water inflow rate of the electrolytic bath 3 was 1200mL/h, the pumping rate of the water pump 6 was 600mL/h, and the pH of the water discharged from the pump was measured.
Comparative example 1 Using the pumping-free protocol
The difference from example 1 is that (3) the electrolyte flowed in from the lower side of the electrolytic cell 3 and electrolyzed in the electrolytic cell 3, and when the electrolyte was filled in the electrolytic cell 3, the whole electrolyte overflowed from the upper side of the electrolytic cell 3, and the inflow rate of the electrolytic cell 3 was 600mL/h, and the pH of the overflowed water was measured.
As shown in FIG. 5, after 1h treatment, the pH of the effluent water pumped in the example 1 is obviously improved, the pH of the effluent water reaches 11.8, the high-efficiency OH - separation efficiency is achieved, and the pH of the effluent water is basically unchanged when the effluent water is not pumped in the comparative example 1.
Example 2
(1) The hardness of the circulating water is 350mg/L, and the alkalinity is 230mg/L.
(2) The anode adopts a titanium-coated ruthenium iridium electrode, the cathode adopts nickel-plated copper powder to sinter the filter element, the current density is 8mA/cm 2, and the electrolysis time is 1h;
(3) The pumping scheme is adopted: electrolyte flows in from the lower end of the side edge of the electrolytic tank 3, is electrolyzed in the electrolytic tank 3, after the electrolytic tank 3 is filled with the electrolyte, a part of the electrolyte overflows from the upper end of the side edge of the electrolytic tank 3, a part of the electrolyte is pumped out from the top of the cathode porous filter element 5 by the water pump 6, and overflowed water flows back to the water inlet tank 1 to be mixed with raw water. At this time, the water inflow rate of the electrolytic tank 3 was 1200mL/h, the pumping flow rate of the water pump 6 was 600mL/h, and the hardness of the pumped water was measured after the pumped water was allowed to stand for 3 hours.
Comparative example 2 Using the pumping-free protocol
The difference from example 2 is that (1) the electrolyte flowed in from the lower end of the side of the electrolytic cell 3, and when the electrolytic cell 3 was filled with the electrolyte, the whole electrolyte overflowed from the upper end of the side of the electrolytic cell 3, and the inflow rate was 600mL/h, and the hardness of the overflowed water was measured after standing for 3h.
As a result, as shown in FIG. 6, it was found that the hardness removal rate of the pumped water in example 2 was high, and it was 90% in 5 minutes, whereas the hardness removal rate was only 30% in comparative example 2 when not pumped.
OH - separation efficiency, current efficiency and total hardness removal energy consumption calculation:
The OH - separation efficiency (formula 1), the current efficiency (formula 2) and the total hardness removal energy consumption (formula 3) of the pump-out water in example 2 were calculated.
The OH - separation efficiency (formula 1), the current efficiency (formula 2) and the total hardness removal energy consumption (formula 3) of the overflow water in comparative example 2 were calculated.
The OH - separation efficiency has a formula shown in the formula (1)
Wherein ζ is OH - separation efficiency (%); n is OH - concentration (mol); v is the solution volume (L); f is Faraday constant (96485C/mol), I is current (A); t is the reaction time(s).
The current efficiency calculation formula is shown as (2)
Wherein CE is current efficiency; c in and cout is the hardness of water inlet and outlet (g CaCO 3/L) (after stable reaction); q is the process flow (L/s); f is Faraday constant (96485C/mol); m CaCO3 is CaCO 3 relative molecular mass (g/mol); m Mg(OH)2 is Mg (OH) 2 relative molecular mass (g/mol); i is the current (A).
The total hardness removal energy consumption calculation formula is shown as (3):
Wherein E is the total hardness energy consumption (kWh (kg CaCO 3)-1), U is the voltage (V), t is the reaction time (h), I is the current (A), and Δm is the mass (kg) of the total hardness removed, expressed as CaCO 3.
The results of example 2 and comparative example 2 are shown in fig. 7, after 1H treatment, by comparing the OH - separation efficiency, the current efficiency and the energy consumption by adopting the pumping (example 2) and the non-pumping descaling scheme (comparative example 2), it can be found that the non-pumping descaling scheme has almost no OH - separation capacity, the current efficiency is only 27.7%, the energy consumption is as high as 22.22kwh/kg CaCO 3, the pumping descaling scheme OH - separation efficiency is 85.35%, the efficient separation of OH - and H + is realized, the current efficiency is 86.6%, and the energy consumption is 7.19kwh/kg CaCO 3, and the purpose of high efficiency and energy saving is really achieved.
Example 3
(1) The hardness of the circulating water is 350mg/L, and the alkalinity is 230mg/L.
(2) The anode adopts a titanium-coated ruthenium iridium electrode, the cathode adopts nickel-plated copper powder to sinter the filter core, and the surface area of the cathode is 16cm 2.
(3) The pumping scheme is adopted: electrolyte flows in from the lower end of the side edge of the electrolytic tank 3, is electrolyzed in the electrolytic tank 3, after the electrolytic tank 3 is filled with the electrolyte, a part of the electrolyte overflows from the upper end of the side edge of the electrolytic tank 3, a part of the electrolyte is pumped out from the top of the cathode porous filter element 5 by the water pump 6, and overflowed water flows back to the water inlet tank 1 to be mixed with raw water. The water inflow rate of the electrolytic tank 3 is 1200mL/h, and the pumping flow rate of the water pump 6 is 600mL/h;
the pump-out water pH at this time can be calculated from the applied current density as shown in formula (4).
Wherein phi pH is the pH of the pump outlet water; zeta is OH - separation efficiency (%); v is the pump suction water volume (L); f is Faraday constant (96485C/mol), I is current (A); t is the reaction time(s).
Under the condition that the current density is 4mA/cm 2、6mA/cm2、8mA/cm2、10mA/cm2、12mA/cm2、14mA/cm2, a pumping experiment is carried out, the separation efficiency of OH - is calculated, the relation between the separation efficiency zeta of OH - and the current density is shown in figure 8, the pH of pumped water can be calculated through different current densities, and the regulation and control of the pH of the water can be realized through controlling the current density of the electrolytic tank 3.
Theoretical fraction of Ca 2+、Mg2+ as pH varies:
(1) The theoretical fractions of calcium and magnesium are calculated as a function of pH by the Hydroa-Medusa software according to the acid-base ionization balance and solid solution balance theory.
(2) The input parameters are based on simulated circulating water, [ Ca 2+]＝3.1mmol/L;[Mg2+]＝0.5mmol/L;[HCO3 - ] = 6.0mmol/L;25 ℃.
As a result, as shown in FIGS. 9 (a) and (b), when the pH exceeds 11.4, ca 2+ is completely precipitated as CaCO 3, and Mg 2+ is also gradually changed to Mg (OH) 2 precipitate. This indicates that most of the Ca 2+ hardness and Mg 2+ hardness in the solution will be removed when the pH of the solution reaches 11.4. In the invention, by adopting a pumping scheme, the pumped water can easily reach about 11.4, and the sediment removal requirement of Ca 2+、Mg2+ hardness is completely met.
Example 4
(1) The hardness of mine water is 1610mg/L, and the alkalinity is 652mg/L.
(2) The anode adopts a titanium-coated ruthenium iridium electrode, the cathode adopts nickel-plated copper powder to sinter the filter element, the current density is 40mA/cm 2, and the electrolysis time is 1h;
(3) The pumping scheme is adopted: electrolyte flows in from the lower end of the side edge of the electrolytic tank 3, is electrolyzed in the electrolytic tank 3, after the electrolytic tank 3 is filled with the electrolyte, a part of water overflows from the upper end of the side edge of the electrolytic tank 3, a part of electrolyte is pumped out from the top of the cathode porous filter element 5 by the water pump 6, and overflowed water flows back to the water inlet tank 1 to be mixed with the initial electrolyte. At this time, the inflow rate of the electrolytic bath 3 was 1200mL/h, the pumping rate of the water pump 6 was 600mL/h, and the hardness change of the pumped water was measured after the pumped water was allowed to stand for 3 hours.
As a result, as shown in FIG. 10, after 1 hour of treatment, it was found that the pump-out water hardness removal rate was high, and the hardness removal rate was 98.4%.
Example 5
(1) The hardness of the circulating water is 350mg/L, and the alkalinity is 230mg/L.
(2) The anode adopts a titanium-coated ruthenium iridium electrode, the cathode adopts nickel-plated copper powder to sinter the filter element, the current density is 8mA/cm 2, and the electrolysis time is 1h; the water inflow rate is 1200mL/h, and the pumping flow rate is 600mL/h;
(3) Electrolyte flows in from the lower end of the side edge of the electrolytic tank 3, is electrolyzed in the electrolytic tank 3, after the electrolytic tank 3 is filled with the electrolyte, a part of the electrolyte overflows from the upper end of the side edge of the electrolytic tank 3, a part of the electrolyte is pumped out from the top of the cathode porous filter element 5 by the water pump 6, and overflowed water flows back to the water inlet tank 1 to be mixed with raw water.
(4) And pumping out water, introducing the water into a filtering crystallization system, wherein the filler is activated carbon, water flows in from the upper end of the filtering crystallization column 7, and flows out from the lower end of the filtering crystallization column, so that the water body after the outflow is treated low-hardness water, and measuring the hardness and alkalinity change of the water.
Example 6
The difference from example 5 is that (4) pump discharge water is introduced into flocculation precipitation system, 100mg/L PAC is added, stirring is carried out for 2min, then 1mg/L PAM is added, stirring is carried out for 2min, electrolyte flows in from upper side of flocculation precipitation tank 10, and then flows out from lower side, flocculate is collected by lower sludge hopper 12, and the discharged electrolyte is treated low hardness water, and water hardness and alkalinity change are measured.
As shown in FIG. 11, it can be found that the homogeneous precipitation process can be greatly accelerated by the coupling filtration crystallization system in the embodiment 5, the removal rate of the hardness of the effluent can reach 92% rapidly, and the removal rate of the alkalinity can reach 69%. In the embodiment 6, the solid-liquid separation process of scale particles can be greatly accelerated through the coupling flocculation precipitation system, the hardness removal rate of the effluent can reach 88 percent rapidly, and the alkalinity removal rate can reach 50 percent. The turbidity of the effluent of the coupling process is obviously reduced.
The spontaneous homogeneous precipitation must reach more than 3 hours to achieve the best effect, so the scale separation system is arranged in the invention, and aims to accelerate the homogeneous precipitation and separate scale particles after the electrochemical reaction in a short time.
The foregoing is illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary. It is intended that all such variations as fall within the scope of the appended claims.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Claims (10)
1. The descaling system of the membraneless high-efficiency electrochemical coupling process is characterized by comprising an electrochemical descaling system and a scale separating system which are connected;
The electrochemical descaling system comprises a direct-current power supply (2), an electrolytic tank (3) and a water pump (6);
An anode (4) is arranged in the electrolytic tank (3), the anode (4) is connected with the positive electrode of the direct current power supply (2), a cathode porous filter element (5) is connected with the negative electrode of the direct current power supply (2), and a cathode porous filter element (5) is arranged in the anode (4);
the top of the cathode porous filter element (5) is connected with a scale separation system through a water pump (6);
the scale separation system is a filtration crystallization system comprising a flocculant precipitation system or a porous adsorption packing.
2. The membrane-free efficient electrochemical coupling process descaling system according to claim 1, further comprising a water inlet tank (1), wherein the water inlet tank (1) is connected with an inlet of the electrolytic tank (3), and an outlet at the top of the electrolytic tank (3) is further connected with the inlet of the water inlet tank (1).
3. The membrane-free efficient electrochemical coupling process descaling system according to claim 1, wherein the electrolyzer (3) is cylindrical; the anode (4) is a cylindrical reticular electrode.
4. The membrane-free efficient electrochemical coupling process descaling system according to claim 1, wherein the cathode porous filter element (5) is made of nickel-plated copper powder sintered filter element, titanium filter element or stainless steel filter element.
5. The membrane-free efficient electrochemical coupling process descaling system according to claim 1, wherein the cathode porous filter element (5) is cylindrical, the inside is of a cavity structure, the outer wall is of a porous structure, the top is provided with a pumping water outlet, and the pumping water outlet is connected with the water pump (6).
6. The membrane-free efficient electrochemical coupling process descaling system according to claim 1, wherein the anode (4) is made of carbon electrode, boron doped diamond electrode, noble metal oxide coated electrode, lead dioxide coated electrode or titanium dioxide coated electrode.
7. The membrane-free efficient electrochemical coupling process descaling system according to claim 1, wherein the filtration crystallization system comprises a filtration crystallization column (7), a porous adsorption filler (8) is arranged in the filtration crystallization column (7), an inlet is arranged at the top of the filtration crystallization column (7), and an outlet is arranged at the bottom of the filtration crystallization column;
The flocculant sedimentation system comprises a flocculation sedimentation tank (10), a stirring rod (11) is arranged in the flocculation sedimentation tank (10), a sludge bucket (12) is arranged at the lower end of the flocculation sedimentation tank (10), and a sewage outlet (13) is arranged at the bottom of the sludge bucket (12).
8. The membrane-free efficient electrochemical coupling process descaling system according to claim 7, wherein the porous adsorption filler (8) is artificial zeolite, molecular sieve, activated carbon, adsorption resin, corundum or quartz sand.
9. The membrane-free efficient electrochemical coupling process descaling system according to claim 7, wherein a flocculating agent and a coagulant aid are added in the flocculation sedimentation tank (10), the flocculating agent comprises polyacrylamide and polyaluminum chloride, and the coagulant aid comprises aluminum sulfate, calcium chloride, activated silicic acid and bone glue.
10. A method for descaling a membraneless high-efficiency electrochemical coupling process based on a system according to any one of claims 1-9, characterized by comprising the following steps:
the water to be treated is pumped out of the electrolytic tank (3) through the cathode porous filter element (5), and then enters a scale separation system for homogeneous precipitation and solid-liquid separation.
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