CN114890591A - Water treatment system and method without reducing ion content - Google Patents
Water treatment system and method without reducing ion content Download PDFInfo
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- CN114890591A CN114890591A CN202210353769.6A CN202210353769A CN114890591A CN 114890591 A CN114890591 A CN 114890591A CN 202210353769 A CN202210353769 A CN 202210353769A CN 114890591 A CN114890591 A CN 114890591A
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- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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Abstract
The invention relates to a water treatment system and a method without reducing ion content, wherein the water treatment system comprises a first filtering unit, a second filtering unit and a control unit, the control unit can perform coordinated regulation and control on at least monitoring data of water inlet/outlet characteristic parameters of the first filtering unit and/or the second filtering unit based on a sampling assembly, so that when the configuration mode and/or working conditions of any one filtering unit are changed, other units can be adaptively regulated and controlled, and the regulation and control mode comprises but is not limited to using a secondary flow channel with the flow direction opposite to that of a main flow channel; the water treatment method comprises the following steps executed by a control unit: the control unit can carry out coordinated type regulation to the monitoring data of the business turn over/play water characteristic parameter of different filter unit based on the sampling subassembly, and wherein, the control unit can guarantee reverse osmosis process's steady operation at least through adjusting the connected mode to each level of concentrated subassembly in the second filter unit.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a water treatment system and a water treatment method without reducing ion content.
Background
Lithium is widely used in the battery, ceramic, glass, lubricant, refrigerant fluid, nuclear industry and photovoltaic industry. With the development of electronic products such as computers, mobile phones, digital cameras, mobile electric tools and the like, particularly with the vigorous national advance of the development of new energy automobile industry and the construction of large-scale 5G communication base stations, the new energy industry of lithium batteries has become the largest lithium consumption field, and the demand for lithium salt products such as lithium carbonate, lithium hydroxide and the like is huge. Therefore, the lithium ions in different forms in the wastewater need to be efficiently recovered to meet the huge use requirements. For example:
CN212954701U discloses lithium waste water recovery system, including interconnect's preheater, homogeneity water tank, lithium carbonate crystallization separation unit, decarbonization unit and evaporation concentration unit in proper order, lithium waste water passes through waste water inlet pipe and preheater intercommunication, be equipped with crystallization mother liquor back flow between evaporation concentration unit and the homogeneity water tank. The utility model discloses a lithium waste water recovery system that contains utilizes the solubility product difference of lithium carbonate and lithium sulfate, retrieves the lithium salt through lithium carbonate crystallization separation unit when lithium ion concentration is higher and obtains the lithium carbonate product, remains the lithium carbonate and turns into lithium sulfate through the decarbonization unit, improves lithium ion concentration through the evaporation concentration unit, and the lithium is retrieved again in the crystallization mother liquor backward flow, and lithium ion obtains fully retrieving, has advantages such as lithium ion rate of recovery height.
In order to better fill up the gap of lithium salt supply, a recovery method needs to be further optimized to improve the recovery efficiency of lithium ions in lithium-containing wastewater, and the situation that the ion content, especially the lithium ion content, is possibly reduced by arranging an excessively complicated process flow while the recovery method is optimized is avoided as much as possible. Therefore, it is desirable to provide a water treatment system and method without reducing the ion content, and to perform specific periodic sampling of the ion content in the water entering and exiting from different devices during the water treatment process, so as to facilitate the real-time regulation and control of the water treatment system.
Furthermore, on the one hand, due to the differences in understanding to the person skilled in the art; on the other hand, since the applicant has studied a great deal of literature and patents when making the present invention, but the disclosure is not limited thereto and the details and contents thereof are not listed in detail, it is by no means the present invention has these prior art features, but the present invention has all the features of the prior art, and the applicant reserves the right to increase the related prior art in the background.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a water treatment system and a water treatment method without reducing the ion content, so as to solve the problems in the prior art.
The invention discloses a water treatment system without reducing ion content, which comprises: a first filtering unit and a second filtering unit which are configured differently from each other and are used for separating different components in the lithium-containing wastewater according to different filtering modes, a control unit, is used for regulating and controlling at least the first filtering unit and/or the second filtering unit, and based on the configuration mode of the first filtering unit and the second filtering unit, such that the first filter unit can be positioned in the water treatment system relatively upstream of the primary flow passage relative to the second filter unit, wherein, the control unit can perform linkage regulation and control on the monitoring data of at least the water inlet/outlet characteristic parameters of the first filtering unit and/or the second filtering unit based on the sampling component, when the configuration mode and/or the working condition of any one of the filtering units are changed, other units can be adaptively regulated and controlled, and the regulation and control mode includes but is not limited to the use of a secondary flow channel with the flow direction opposite to that of the main flow channel.
The water treatment system can arrange an adsorption tower filled with adsorption resin on a main flow passage, wherein the adsorption tower can remove hardness and other partial ions not containing lithium ions in lithium-containing wastewater based on different types of the filled adsorption resin.
The second filtering unit comprises a plurality of concentrating components which are connected in series and/or in parallel, wherein the control unit can control the configuration mode of the second filtering unit in a mode of adjusting the connection relation among the plurality of concentrating components.
The control unit sets the start-stop control of a plurality of separation elements configured in the concentration assembly in a mode of not exchanging the order sequence of the separation elements, so that the lithium-containing wastewater flows along a specific trend direction in each stage of concentration assembly of the second filtering unit, wherein the trend direction is the same as the flow direction of the main flow channel.
The first filtered fresh water separated by the first filtering unit can be separated in the second filtering unit as the inlet water of the second filtering unit, wherein the nanofiltration membrane arranged in the first filtering unit can at least partially intercept impurities in the lithium-containing wastewater so as to ensure the inlet water quality of the second filtering unit.
The second filtering unit is provided with a reverse osmosis membrane, and can perform the separation of solute and solvent in a manner of pressurizing one side of the reverse osmosis membrane, so that the content of solute on the pressurizing side is obviously higher than that on the opposite side, and the side with relatively less solute can be further recycled and processed as second filtered fresh water to obtain purified water with higher purity.
The second filtered concentrated water obtained by the second filtering unit at the pressurizing side and having relatively more solute can be further concentrated by the third filtering unit to improve the content of lithium ions in the solution, wherein the third filtered concentrated water obtained by the concentration of the third filtering unit can enable the lithium ions to be recovered in the form of lithium chloride crystals according to different solubilities at different temperatures.
The third filtering unit can be configured with an electrically driven membrane to make the charged ions in the inlet water of the third filtering unit perform directional migration based on an externally applied electric field, so that the content of lithium ions in the third filtered concentrated water reaches the set concentration for recycling.
The third filtered fresh water from the third filter unit can be returned to the relatively upstream side of the water treatment system through one of the circulation pipes of the secondary flowpath, so that the third filtered fresh water can flow along the primary flowpath to the relatively downstream side of the water treatment system again.
The invention discloses a water treatment method without reducing ion content, which adopts the water treatment system of any one of the preceding claims, wherein a control unit of the water treatment system can execute the following steps: the control unit can carry out coordinated type regulation to the monitoring data of the business turn over/play water characteristic parameter of different filter unit based on the sampling subassembly, and wherein, the control unit can guarantee reverse osmosis process's steady operation at least through adjusting the connected mode to each level of concentrated subassembly in the second filter unit.
The control unit can accurately monitor the water inlet/outlet characteristic parameters of each filtering unit based on the sampling assembly, realize linkage adjustment of a plurality of units at least comprising the second filtering unit, and remove the hardness of water based on the adsorption resin which is filled in the adsorption tower and does not reduce the content of other main ions, thereby ensuring that the content of lithium ions in the concentrated water after separation and impurity removal reaches the predetermined concentration for recycling.
Drawings
FIG. 1 is a schematic diagram of a simplified module connection relationship based on a primary flow channel in a preferred embodiment of the present invention;
FIG. 2 is a graph showing the variation of the amount of water in the second filter unit in a preferred embodiment of the present invention;
FIG. 3 is a graph showing the change in pH of the second filtration unit in a preferred embodiment of the present invention;
FIG. 4 is a graph of the change in conductivity of a second filter element in a preferred embodiment of the invention;
fig. 5 is a graph showing the change in lithium content of the second filter unit in a preferred embodiment of the present invention.
List of reference numerals
100: a primary unit; 200: a pre-processing unit; 300: a first filter unit; 400: a second filter unit; 410: a first concentration component; 420: a secondary concentration component; 500: a third filtering unit; 600: a control unit; 610: and a sampling component.
Detailed Description
The following detailed description is made with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of a simplified module connection relationship based on a primary flow channel in a preferred embodiment of the present invention; fig. 2 is a diagram illustrating a variation in the amount of water in the second filter unit 400 according to a preferred embodiment of the present invention; FIG. 3 is a graph showing the change in pH of the second filter unit 400 in a preferred embodiment of the present invention; FIG. 4 is a graph of the change in conductivity of a second filter unit 400 in a preferred embodiment of the present invention; fig. 5 is a graph showing the change in the lithium content of the second filter unit 400 according to a preferred embodiment of the present invention.
Example 1
The invention provides a water treatment system without reducing the ion content, which at least comprises a first filtering unit 300, a second filtering unit 400 and a third filtering unit 500, wherein different filtering units can bear different separation tasks. Preferably, the first filtering unit 300, the second filtering unit 400 and the third filtering unit 500 can be connected in sequence, so that the lithium-containing wastewater can gradually increase the recovery degree of lithium ions when passing through the three filtering units in sequence, and the byproducts are separated and then discharged and/or recycled. Further, based on the sequential connection of the three filter units, the lithium-containing wastewater can directionally flow along the main flow channel in the water treatment system, wherein the main flow channel is set to be a flow direction in which the lithium-containing wastewater flows from the first filter unit 300 to the third filter unit 500 through the second filter unit 400, that is, along the directional flow direction of the main flow channel, the first filter unit 300 is located relatively upstream of the main flow channel, the third filter unit 500 is located relatively downstream of the main flow channel, and the lithium-containing wastewater located in the main flow channel can flow along the directional flow direction of the main flow channel. Preferably, since the main flow passage has a directional flow direction, the first filter unit 300, the second filter unit 400, and the third filter unit 500 connected in sequence can be configured in such a manner that the degree of separation is gradually increased. Alternatively, the first filtering unit 300 may perform the separation of the nanofiltration process through a nanofiltration membrane, the second filtering unit 400 may perform the separation of the reverse osmosis process through a reverse osmosis membrane, and the third filtering unit 500 may perform the separation of the electrodialysis process through an electrically driven membrane, so as to improve the overall recovery rate of lithium ions through the separation of different degrees.
According to a preferred embodiment, the water treatment system may further include a primary unit 100 and a pretreatment unit 200, wherein the primary unit 100 and the pretreatment unit 200 can be disposed upstream of the main flow channel of the whole of the first, second and third filter units 300, 400 and 500 to perform a preliminary conditioning treatment on the untreated lithium-containing wastewater through the primary unit 100 and the pretreatment unit 200, thereby preventing suspended contaminants included in the lithium-containing wastewater from blocking and/or damaging membranes in the respective filter units located relatively downstream, and at least ensuring the quality of the inlet water entering the first filter unit 300.
Preferably, the primary unit 100 may be configured as a primary sedimentation tank for accommodating untreated raw lithium-containing wastewater and adjusting and buffering the raw lithium-containing wastewater, wherein the raw lithium-containing wastewater may be high-salt lithium-containing wastewater with high total hardness and lithium ion content of less than or equal to 0.5g/L, and the water treatment system can at least realize raw water treatment capacity of more than or equal to 5 m 3 H is used as the reference value. Optionally, boron extraction treatment can be performed in the adjusting tank to remove boron in the original lithium-containing wastewater, so as to improve the quality of the effluent of the primary sedimentation tank, wherein a boron selective ion exchange resin method, a sulfuric acid sedimentation method, an activated carbon adsorption method, a lime sedimentation method, an electrocoagulation method or an aluminum hydroxide adsorption method can be selected. Preferably, sulfuric acid is added to the primary sedimentation tank to form a precipitate at least containing boric acid, and the precipitate is removed by a solid-liquid separation method, so that the effluent of the primary sedimentation tank is acidic, and simultaneously, sulfate dissolved in the effluent of the primary sedimentation tank can be removed by a subsequent separation process, for example, at least by a nanofiltration process of the first filtration unit 300.
Preferably, the pretreatment unit 200 may be configured with a security filter assembly, so as to intercept at least part of the micro suspended matters, bacteria and other impurities flowing from the primary unit 100 to the first filter unit 300 by a tubular filter element such as a PP melt-blown, wire-fired, folded, titanium filter element or activated carbon filter element configured in the security filter assembly, so that the quality of the outlet water of the security filter assembly at least meets the inlet water quality requirement of the first filter unit 300.
Preferably, the pretreatment unit 200 may further be provided with an activated carbon adsorption module relatively downstream of the main flow channel of the security filter module, so as to further improve the capability of the pretreatment unit 200 to separate impurities, so that the activated carbon adsorption module may adsorb impurities escaping from the security filter module, thereby ensuring the quality of the inlet water of the first filter unit 300.
Further, a first storage tank for temporarily storing the effluent of the pretreatment unit 200 may be disposed between the pretreatment unit 200 and the first filtration unit 300, so that the effluent of the pretreatment unit 200 flowing through the first storage tank may flow into the first filtration unit 300 as the influent of the first filtration unit 300 at an adjustable flow rate to perform a nanofiltration process.
According to a preferred embodiment, a circulation pipeline can be configured among the primary unit 100, the pretreatment unit 200, the first filtration unit 300, the second filtration unit 400 and/or the third filtration unit 500 to construct a secondary flow channel with a flow direction opposite to the directional flow direction of the main flow channel through the circulation pipeline, so that the effluent of the at least part of units can flow to other units relatively upstream through the secondary flow channel, wherein the effluent of the at least part of units can comprise filtered concentrated water and/or filtered fresh water of the corresponding unit for the first filtration unit 300, the second filtration unit 400 and the third filtration unit 500, and the filtered concentrated water and/or filtered fresh water returned to relatively upstream through the secondary flow channel can be mixed with lithium-containing wastewater in the corresponding unit of the main flow channel to complete the directional flow of the main flow channel again.
According to a preferred embodiment, the water treatment system can be provided with a control unit 600 for comprehensively controlling the units, the control unit 600 can monitor the water inlet and outlet characteristic parameters of the units based on the sampling component 610, the configuration modes of the units are adjusted in a linkage way and/or the flow rate of the liquid flowing to the relative upstream through the circulating pipeline is adjusted in a linkage way, wherein, the linkage type adjustment means that when the connection relation of any unit occurs and/or the operation parameters are changed, the control unit 600 may adapt the connection relationships and/or operating parameters of the other units based on the conditions under which the changes occur, the condition for changing can be normal alternation between components, isolation or replacement after component failure, or adjustment caused by real-time change of related parameters such as flow rate and water quality of original lithium-containing wastewater.
Preferably, when there is a case where the quality of the effluent water is affected by a decrease or insufficiency of the filtering capacity among the factors triggering a change of the occurrence condition, the control unit 600 can circulate the solution circulating at least in the above-mentioned abnormal filtering time range back to the corresponding unit where the filtering capacity problem occurs and has been restored in a flow metering manner to perform filtering again, based on a delay of data acquisition and transmission and/or a time taken for restoration of the filtering capacity of the corresponding unit. Further, when the corresponding unit with the filtering capability problem restores the filtering capability by triggering the change occurrence condition, other related units can also be adaptively adjusted, so that the returned solution is not necessarily separated according to the previous filtering manner. Preferably, the control unit 600 is capable of counting abnormal filtering times and estimating the flow of the solution to be returned based on factors such as the flow rate of the solution and the filtering capacity of each unit downstream, so that the circulation valve is opened at the corresponding node to return the solution substantially equal to the estimated flow through the circulation line.
According to a preferred embodiment, the first filtering unit 300 can receive the effluent from the pre-treating unit 200 and filter the effluent by using a nanofiltration membrane filled in the first filtering unit, so that most of sulfate and magnesium ions are separated in the first filtered concentrated water, and the first filtered fresh water with low lithium-magnesium ratio is transmitted to the second storage tank as the effluent, and the first filtered concentrated water generated by the first filtering unit 300 can be discharged to an energy recovery device for recycling and/or introduced into the first storage tank through a circulating pipeline. Optionally, the first filtered concentrated water generated by the first filtering unit 300 can be adjusted and controlled by the control unit 600 to realize the adjustment of the discharge amount and the circulation amount, so as to control the input and output of the liquid of the first filtering unit 300, and ensure the reasonable use of the first filtered concentrated water. The first filtered concentrated water distribution ratio may be adaptively adjusted based on real-time conditions of lithium contents in the inlet water, the outlet water, and the concentrated water of the first filtering unit 300, and the configuration and operation conditions of the first filtering unit 300. Further, the distribution ratio of the first filtered concentrated water may be substantially in the range of 1: 1 so that part of the lithium ions mixed in the first filtered concentrated water can pass through the first filtering unit 300 again to enter the first filtered concentrated water, and prevent the excessive first filtered concentrated water from returning to the first filtering unit 300 again to reduce the nanofiltration efficiency and effect.
Preferably, the operating pressure of the first filtering unit 300 can be controlled within the range of 2.8-4.0 MPa, so as to improve the effect of magnesium-lithium separation based on high pressure, and improve the content of lithium ions in the effluent water of the first filtering unit 300, so that more than 90% of magnesium ions and sulfate radicals are intercepted in a non-phase-change manner, and the effluent water with low lithium-magnesium ratio of the first filtering unit 300 is obtained.
Preferably, the nanofiltration membrane has a higher rejection rate for high-valence ions compared with low-valence ions based on the south-of-the-way effect, monovalent ions such as sodium ions, lithium ions and the like with a lower rejection rate can pass through the nanofiltration membrane, and sulfate ions, calcium ions, magnesium ions and the like which easily cause the hardness of water to be high are more easily intercepted by the nanofiltration membrane, so that the non-phase-change separation of at least part of ions is realized based on the different rejection rates of the nanofiltration membrane for the monovalent ions and the high-valence ions.
According to a preferred embodiment, the outlet water of the first filtering unit 300 entering the second storage tank can be used as the inlet water of the second filtering unit 400 to perform concentration and separation under the selective permeability of the reverse osmosis membrane filled in the second filtering unit 400, wherein the second filtering unit 400 can be configured with a plurality of concentrating modules connected in series and/or in parallel, and different connecting modes can enable the second filtering unit 400 to complete different reverse osmosis concentration and separation tasks. The concentration component can apply external pressure at least greater than osmotic pressure of corresponding solution on one side of the concentration component, so that concentrated solution containing more solute can be obtained on the side where the pressure is applied, and penetrating fluid containing more solvent can be obtained on the opposite side where the pressure is applied by the reverse osmosis membrane, thereby realizing separation of the solute and the solvent and achieving the purpose of improving the relative content of lithium ions. Preferably, the second filter unit 400 may be configured with at least a primary concentrating component 410 and a secondary concentrating component 420, wherein the primary concentrating component 410 and the secondary concentrating component 420 can adopt the same or different structural configurations. Further, when the second filtering unit 400 is configured in series, the front module may be configured as a concentration module for performing medium-pressure reverse osmosis, and the rear module may be configured as a concentration module for performing high-pressure reverse osmosis, and the concentration of lithium ions is completed under different separation conditions, that is, when both the concentration module for medium-pressure reverse osmosis and the concentration module for high-pressure reverse osmosis are configured, the concentration module for medium-pressure reverse osmosis can be configured upstream of the concentration module for high-pressure reverse osmosis, and the configuration position of the concentration module for medium-pressure reverse osmosis can be closer to the first filtering unit 300, which does not refer to a geographical position, but is a position in the process flow, wherein the rear module can perform a high-pressure reverse osmosis process using GTR4 equipment; when the second filtering unit 400 is formed in parallel, the first-stage concentration component 410 and the second-stage concentration component 420 can adopt the same equipment configuration, so that the quality of the outlet water of the two concentration components is not greatly different. Further, when the two concentration components are configured in the same equipment, switching between a series connection mode and a parallel connection mode can be completed, so that the central control unit can adjust the configuration mode of the second filtering unit 400 based on different concentration and separation tasks, wherein switching of the connection mode can be realized by adopting a switching valve and the like.
Preferably, the second filtered concentrated water separated by the second filter unit 400 can flow to the third filter unit 500 along the directional flow direction of the main flow channel, and the second filtered fresh water separated by the second filter unit 400 can be collected in the third storage tank to be further processed to obtain high-purity purified water.
According to a preferred embodiment, the second filtered concentrated water can be used as the inlet water of the third filtering unit 500, under the action of the external electric field applied by the third filtering unit 500, and the electrically driven membrane as the ion selective membrane makes the charged solute particles at least including the charged ions in the inlet water of the third filtering unit 500 migrate through the membrane, so as to realize the secondary concentration of the inlet water of the third filtering unit 500, thereby obtaining the third filtered concentrated water and the third filtered fresh water. Preferably, the third filter unit 500 can include several electrically driven membrane separation components to ensure flexibility and adjustability of the configuration of the third filter unit 500 while achieving efficient concentration through a multi-stage, multi-stage configuration.
Preferably, the third filtered fresh water can be refluxed into the primary sedimentation tank of the primary unit 100 to be mixed with the original lithium-containing wastewater introduced into the primary sedimentation tank to enter the pretreatment unit 200 after being buffer-conditioned.
Preferably, the third filtered concentrated water can recover lithium ions in the form of lithium chloride crystals according to different solubilities at different temperatures, so that the lithium ions can be reused.
According to a preferred embodiment, each stage of the concentrating assembly of the second filtering unit 400 can be formed by connecting a plurality of segmented separating elements in series, and at least one separating element which does not perform separating operation synchronously with other separating elements is arranged in the same concentrating assembly, so that when any separating element performing separating operation is in a fault or blockage state, and other abnormal conditions which may affect the separating effect, the abnormal separating element can be replaced by the separating element which is not in the working state, and the normal operation of the concentrating assembly is ensured.
The inlet and outlet arrangement orientation based on the concentration assembly can enable a plurality of separation elements connected in series to have corresponding arrangement sequence, the separation element closer to the inlet of the concentration assembly can have a previous position sequence, the separation element closer to the outlet of the concentration assembly can have a subsequent position sequence, and once the series connection relationship in the concentration assembly is constructed, the circulation direction of the water flow in the concentration assembly is determined, namely the water flow flowing in from the inlet of the concentration assembly can flow out from the outlet of the concentration assembly after the separation element in the previous position sequence flows through the separation element in the subsequent position sequence.
Preferably, the inlet and outlet of the concentration assembly can be in communication with a plurality of separation elements for controllable opening and closing and/or in communication between the inlet and outlet of different separation elements for cross-position subsequence communication, so that part of the separation elements can be selectively opened and closed under the condition of not changing the general flow direction of water flow in the concentration assembly, and accordingly, the corresponding separation elements can be started and stopped particularly under the condition of adjustment or failure of concentration and separation tasks of the second filtering unit 400.
Furthermore, the activation and deactivation of the separation elements does not affect the order sequence of other separation elements in the working state when the concentration assembly is configured, that is, the water flow can still flow from the previous order sequence to the next order sequence, and when the separation elements in the deactivated state are encountered in the flow process, the water flow can directly flow from the separation elements in the previous order sequence to the separation elements in the next order sequence through the communication of the cross order sequence, so that the allocation of the separation elements is realized without affecting the flow direction.
The establishment of the separation element deployment mode enables the separation elements which are not in the working state in the concentration assembly to be put into the concentration separation work in time, and correspondingly, at least one separation element which is in the working state can be deactivated in the separation elements which are in the working state currently, so that the concentration assembly can still keep at least one separation element out of the working state simultaneously with other separation elements. Generally, the separation elements in the previous subsequence are contacted with more impurities in the water flow, so that the situation of reverse osmosis membrane blockage or breakage and the like are more likely to occur, and the concentration efficiency is influenced, therefore, the separation elements which are not in the working state can be replaced by the separation elements which need to be stopped in the reverse osmosis working process, wherein the separation elements which need to be stopped can be the separation elements which are positioned at the forefront of the subsequence in the plurality of separation elements in the working state currently or the separation elements in the working state currently and have continuous working time reaching the preset working time threshold, namely the separation elements can be stopped based on the influence factors such as the sampling result of effluent, the operation pressure monitoring data and/or the preset working time threshold.
Preferably, the deactivated separation elements are capable of regeneration, replacement or isolation. The reverse osmosis membrane of the separation element can be quickly backwashed by water entering the water producing side to realize the regeneration of the separation element, so that impurities trapped on the reverse osmosis membrane are removed, and the filtration capability of the separation element is recovered in a short time. For a separation element in which a reverse osmosis membrane has been damaged or otherwise structurally damaged and which cannot be restored by regeneration or the like, it is possible to replace the other separation element in a removable condition, so that the concentration assembly can regain substantially the same filtration capacity as before. For example, for a separation element which has reached a predetermined working time threshold, in particular in the case of a relatively late ranking of the separation element, most of the impurities are filtered by the other separation elements preceding the ranking, so that the separation element can be deactivated as a function of the reaching of the predetermined working time threshold without regeneration or replacement operations being required, and the reverse osmosis operation can be resumed in subsequent iterations, while also reducing the frequency of the backwashing operation in order to save costs and reduce resource consumption; as a further example, for separating elements with reduced filtering capacity, in particular in the relatively early bit subsequences, if the separation effect is affected by the continued use of parameters which may affect the operating pressure of other separation elements connected in series therewith in the event that regeneration or replacement cannot be effected, it is possible to temporarily isolate the separation element and to put it back into use when the filtration capacity of the other separation elements in the concentration assembly also drops to a corresponding degree, to maintain the stability of the operation of the entire thickening assembly, but the overall filtration capacity of the thickening assembly may be reduced, the concentration component can be subjected to the pre-reverse osmosis process in a series mode by adjusting the connection relation of the concentration component and other stages of concentration components, and the other stages of concentration components receive the effluent water to perform the subsequent re-reverse osmosis, thereby ensuring the quality of the outlet water of the second filtering unit 400 by a multi-stage multi-section reverse osmosis mode.
According to a preferred embodiment, the alternation of the separation elements in each stage of concentration assembly is not a simple cycle alternation, but is performed based on the common regulation and control of a plurality of influence factors, such as the conditions of concentration and separation tasks, the connection relationship between concentration assemblies of different stages, the start-stop ratio of the separation elements in each stage of concentration assembly, a preset working time threshold value, and the like, and the plurality of influence factors have mutual influence rather than independent control, so that the plurality of influence factors need to be reasonably planned to realize the normal operation of the second filtering unit 400. For example, different connection relationships of the concentration components can be adopted for different concentration and separation tasks, the connection relationships can also affect the start-stop ratio of the separation elements in each stage of concentration components, the preset working time threshold can be correspondingly adjusted according to different start-stop ratios, and in addition, the preset working time threshold can be adaptively adjusted based on the position sequence of different separation elements, namely, the preset working time threshold set for the separation elements before the position sequence is smaller, and conversely, the preset working time threshold set for the separation elements after the position sequence is larger, so that the separation elements in different position sequences can have corresponding gradient distinction based on the degree of separating impurities, and the corresponding preset working time threshold can be set according to the gradient, thereby ensuring that the separation elements before the position sequence can be timely deactivated for regeneration or replacement, and the waste of cost and resources caused by frequent deactivation of the separating element behind the bit sequence is avoided.
According to a preferred embodiment, the water treatment system can be provided with a sampling component 610 for dynamically monitoring each separation and recovery process in real time, wherein the sampling component can monitor at least the water inlet and outlet conditions of the second filtering unit 400 with high precision so as to obtain the operation conditions of the second filtering unit 400.
Preferably, the sampling component 610 may perform data transmission based on a certain data transmission time interval after acquiring the monitoring data, so as to avoid the increase of load caused by frequent data transmission, which may cause the delay of feedback adjustment due to the generation of delay. The data transmission time interval may be varied based on a preset fluctuation value, and particularly, when the ion content in the second filtered concentrated water and/or the second filtered fresh water is monitored, the preset fluctuation value is a preset content fluctuation value, wherein the content at least includes the lithium ion content.
As can be seen from fig. 2-4, during the normal operation of the water treatment system, the overall water amount of the second filter unit 400 is stable and has no attenuation; the overall pH change is stable; the overall conductance varies with the inlet water of the second filter unit 400, and thus it can be seen that the operation process of the second filter unit 400 is stable.
As can be seen from fig. 5, during the operation of the second filter unit 400, the content of lithium ions in the effluent of the second filter unit 400 changes with the content of the influent, and the overall data is relatively stable. Even if the lithium content fluctuates, the second filtering unit 400 can also perform regulation and control based on each stage of concentration component, so that the lithium ion content can fluctuate in a small amplitude around the average value, and the operation stability of the second filtering unit 400 is ensured.
Further, the data transmission rule of the sampling component 610 is set based on whether a preset content fluctuation value is reached, wherein the preset content fluctuation value may be set as an initial value based on experience or a database, and then flexibly adjusted based on the association relationship between the real-time data and the preset content fluctuation value. The preset content fluctuation value is set in a desired time period, the content of the corresponding ions in the time period is in a set threshold range, and when the content of the corresponding ions exceeds the threshold range, the actual time period can be compared with the desired time period to judge the running state of the equipment. In other words, the real-time content data is judged by using the preset content fluctuation value set in the above manner, the time is counted from the starting point of the time period and the starting content is recorded, when the variation value of the real-time content data relative to the starting content exceeds the preset content fluctuation value, the variation value is recorded as the end point of the time period, the time period from the starting point of the time period to the end point of the time period is the actual time period, and the actual time period is compared with the expected time period to judge the operation condition of the corresponding device.
Generally, the shorter the actual time period compared to the desired time period, the lower the operational stability of the second filter unit 400 when comparing the actual time period to the desired time period; conversely, the longer the actual time period compared to the desired time period, the higher the operational stability of the second filter unit 400.
Preferably, the preset content fluctuation value set in the next period can be adjusted based on the comparison result between the actual time period and the expected time period in the previous period and the operation state of the corresponding device. The operation condition of the corresponding device can comprise continuous operation time, adjustment condition of configuration mode, adjustment condition of processes in the upstream and downstream of the process, and the like.
For example, for the second filter unit 400, when the operation stability of the second filter unit 400 is reduced to be out of the defined range, the corresponding separation element needs to be deactivated, regenerated, replaced or isolated. Preferably, the preset content fluctuation value can be adjusted based on a plurality of influencing factors, including at least the task progress of the second filter unit 400, the operating conditions of the separation element, etc. The preset content fluctuation value can be reduced along with the advance of the reverse osmosis task process; the preset content fluctuation value can be adaptively reduced based on the deactivation or isolation of the separation element, and can be adaptively increased based on the regeneration or replacement of the separation element, wherein the adaptive increase is adjusted according to the actual situation, and the influence of the overlarge preset content fluctuation value on the monitoring precision is avoided.
Besides the preset content fluctuation value, the sampling unit 610 may also transmit in the above manner when monitoring other characteristic parameters, and compared with a transmission manner in which a fixed or variable time period is used as a data transmission time interval, the above manner may improve the sampling accuracy of the sampling unit 610, which may not only avoid setting an excessively large time interval to cause delayed transmission or missed transmission of data, thereby affecting the operation stability of the second filtering unit 400; it is also possible to avoid setting a too small time interval, which may cause too much data to be transmitted, stored, calculated, and/or analyzed, which may cause too much load on hardware and software and processing delay of data, which may also affect the operation stability of the first filter unit 300.
Preferably, the effluent quality can be circularly returned to the relative upstream of the outlet when the water quality requirement is not met so as to be separated again, wherein when the water quality is monitored to be abnormal, besides returning part of the effluent after the abnormal point monitoring, the delay conditions of data transmission, data processing and the like can be settled so as to obtain the actual abnormal point position before the abnormal point monitoring, and the effluent circulating between the two point positions can be returned to the relative upstream so as to avoid that part of the effluent which does not meet the water quality requirement directly enters the relative downstream of the process flow due to data delay, thereby influencing the overall treatment efficiency and effect of the water treatment system.
According to a preferred embodiment, the water treatment system is capable of removing hardness from water by a highly effective adsorbent resin in a manner that does not reduce the content of other major ions. The resin adsorption can not only ensure that the content of lithium ions in water is kept stable without the tendency of attenuation, but also can control the total hardness of the water to be less than 20mg/L, thereby meeting the requirement of recovery.
Alternatively, the adsorption resin may be a boron adsorption resin, so that at least a middle partial region within the adsorption tower may be filled with the boron adsorption resin, and the adsorption tower filled with the boron adsorption resin may be disposed relatively downstream of the second filter unit 400. Preferably, the water treatment system may be configured with at least two adsorption towers filled with resin to facilitate simultaneous adsorption and regeneration processes, thereby improving adsorption efficiency based on the use of cyclic alternation. Preferably, the period of alternation of the regeneration process and the adsorption process is generally controlled between 9h and 11h to ensure continuous production. Further, the loaded adsorption resin can be regenerated by using 1-5% by mass of hydrochloric acid solution as a regeneration liquid, wherein the regeneration process needs to control the flow rate and the regeneration time of the regeneration liquid according to the filling condition of the adsorption tower.
According to a preferred embodiment, after the original lithium-containing wastewater with the lithium content of about 350mg/L (i.e. less than or equal to 500mg/L) and high total hardness is subjected to operations such as separation and extraction of a water treatment system, the lithium ion content in the third filtered concentrated water is more than or equal to 8.5g/L, and the comprehensive recovery rate of the water treatment system on lithium ions is more than or equal to 90 percent; the contents of iron, aluminum and silicon in the third filtered concentrated water are respectively about 0.18mg/L, 0.31mg/L and 2.87mg/L, and all meet the requirement of less than or equal to 10 mg/L; in the continuous operation of resin adsorption, the adsorption effect is good, and the total hardness is less than or equal to 20mg/L (CaCO) 3 And the lithium ions are not lost, so that the water treatment system can complete the recovery of the lithium ions while treating the lithium-containing wastewater. Further, recovered to obtainThe lithium ions substantially in the form of lithium carbonate can be reused by the lithium salt preparation process.
Example 2
This embodiment is a further improvement of embodiment 1, and repeated contents are not described again.
The invention also provides a water treatment method without reducing the ion content, which adopts the water treatment system device in the embodiment 1 to realize the regulation and control of other functional units through the control unit 600, thereby recycling the lithium ions in the lithium-containing wastewater while performing water treatment on the lithium-containing wastewater to obtain purified water.
The water treatment method at least comprises the following steps:
the control unit 600 can perform coordinated adjustment on the acquisition of the inlet/outlet characteristic parameters of the first filtering unit 300, the second filtering unit 400 and/or the third filtering unit 500 based on the sampling component 610, wherein the control unit 600 can ensure stable operation of the reverse osmosis process at least by adjusting the connection mode of each stage of concentration components in the second filtering unit 400.
It should be noted that the above-mentioned embodiments are exemplary, and that those skilled in the art, having benefit of the present disclosure, may devise various arrangements that are within the scope of the present disclosure and that fall within the scope of the invention. It should be understood by those skilled in the art that the present specification and figures are illustrative only and are not limiting upon the claims. The scope of the invention is defined by the claims and their equivalents. The present description contains several inventive concepts, such as "preferably", "according to a preferred embodiment" or "optionally", each indicating that the respective paragraph discloses a separate concept, the applicant reserves the right to submit divisional applications according to each inventive concept. Throughout this document, the features referred to as "preferably" are only an optional feature and should not be understood as necessarily requiring that such applicant reserves the right to disclaim or delete the associated preferred feature at any time.
Claims (10)
1. A water treatment system without reducing ion content, comprising:
a first filtering unit (300) and a second filtering unit (400) configured differently from each other for separating different components in the lithium-containing wastewater according to different filtering manners,
a control unit (600) for regulating at least the first filter unit (300) and/or the second filter unit (400),
it is characterized in that the preparation method is characterized in that,
based on the configuration of the first filter unit (300) and the second filter unit (400), the first filter unit (300) is arranged in the water treatment system in a manner that is relatively upstream of a main flow passage relative to the second filter unit (400), wherein,
the control unit (600) can perform coordinated regulation and control on at least monitoring data of water inlet/outlet characteristic parameters of the first filtering unit (300) and/or the second filtering unit (400) based on the sampling assembly (610), so that when the configuration mode and/or the working condition of any one filtering unit is changed, other units can be adaptively regulated and controlled, and the regulation and control mode includes but is not limited to the use of a secondary flow channel with the flow direction opposite to the main flow channel.
2. The water treatment system according to claim 1, wherein an adsorption tower filled with an adsorption resin is disposed in the main flow path, and wherein the adsorption tower is capable of removing hardness and ions of other portions not containing lithium ions from the lithium-containing wastewater based on a difference in the type of the filled adsorption resin.
3. The water treatment system according to claim 1 or 2, wherein the second filter unit (400) comprises several stages of concentration modules connected in series and/or in parallel, wherein the control unit (600) is capable of controlling the configuration of the second filter unit (400) in such a way that the connection relationship between the multi-stage concentration modules is adjusted.
4. The water treatment system according to any one of claims 1 to 3, wherein the start and stop control of the control unit (600) on the plurality of separation elements arranged in the concentration assembly is set in a manner of not exchanging the order sequence of the separation elements, so that the lithium-containing wastewater flows along a specific trend direction in each stage of the concentration assembly of the second filtering unit (400), wherein the trend direction is the same as the flow direction of the main flow channel.
5. The water treatment system according to any one of claims 1 to 4, wherein the first filtered fresh water separated by the first filtering unit (300) can be separated in the second filtering unit (400) as the inlet water of the second filtering unit (400), wherein the nanofiltration membrane arranged in the first filtering unit (300) can at least partially retain impurities in the lithium-containing wastewater so as to ensure the inlet water quality of the second filtering unit (400).
6. The water treatment system according to any one of claims 1 to 5, wherein the second filtering unit (400) is provided with a reverse osmosis membrane, and is capable of separating solute from solvent in a manner of pressurizing one side of the reverse osmosis membrane, so that the solute content on the pressurizing side is obviously higher than that on the opposite side, and the side with relatively less solute can be further recycled and processed as second filtered fresh water to obtain purified water with higher purity.
7. The water treatment system according to any one of claims 1 to 6, wherein the second filtered concentrated water obtained by the second filtering unit (400) at the pressurized side with relatively more solute can be further concentrated by the third filtering unit (500) to increase the content of lithium ions in the solution, wherein the third filtered concentrated water obtained by the concentration of the third filtering unit (500) can recover lithium ions in the form of lithium chloride crystals according to different solubilities at different temperatures.
8. The water treatment system according to any one of claims 1 to 7, wherein the third filtering unit (500) is configured with an electrically driven membrane to make the charged ions in the inlet water of the third filtering unit (500) perform directional migration based on an externally applied electric field, so that the content of lithium ions in the third filtered concentrated water reaches a set concentration for recycling.
9. The water treatment system according to any one of claims 1-8, wherein the third filtered fresh water obtained by the third filter unit (500) is returned to the relatively upstream of the water treatment system through one of the circulation pipes of the secondary flow passage, so that the third filtered fresh water can flow along the primary flow passage to the relatively downstream of the water treatment system again.
10. A water treatment method without reducing ion content, characterized in that the water treatment method employs a water treatment system according to any one of the preceding claims, wherein a control unit (600) of the water treatment system is capable of performing the following steps:
the control unit (600) can carry out coordinated type regulation to the monitoring data of the water inlet/outlet characteristic parameters of different filtering units based on the sampling assembly (610), wherein, the control unit (600) can guarantee the stable operation of the reverse osmosis process at least by regulating the connection mode of each level of concentration assemblies in the second filtering unit (400).
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