CN107115793B - Purification and concentration system and method for magnesium-containing lithium liquid - Google Patents
Purification and concentration system and method for magnesium-containing lithium liquid Download PDFInfo
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- CN107115793B CN107115793B CN201710341078.3A CN201710341078A CN107115793B CN 107115793 B CN107115793 B CN 107115793B CN 201710341078 A CN201710341078 A CN 201710341078A CN 107115793 B CN107115793 B CN 107115793B
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Abstract
The invention relates to the field of lithium liquid purification, and discloses a purification and concentration system and method for magnesium-containing lithium liquid. The system comprises a stock solution tank, a pretreatment unit, a primary filtering unit, a secondary filtering unit, a tertiary filtering unit and a quaternary filtering unit; the pretreatment unit comprises a delivery pump and a self-cleaning filter; the first-stage filtering unit comprises a plurality of first-stage ultrafiltration membranes; the second-stage filtering unit comprises a second-stage water production tank, a second-stage delivery pump, a second-stage security filter, a second-stage high-pressure pump and a second-stage composite membrane filtering component; the three-stage filtering unit comprises a three-stage water production tank, a three-stage delivery pump, a three-stage security filter, a three-stage high-pressure pump and a three-stage composite membrane filtering assembly; the four-stage filtering unit comprises a four-stage water production tank, a four-stage delivery pump, a four-stage security filter, a four-stage high-pressure pump and a four-stage composite membrane filtering component. The method can purify and concentrate the magnesium-containing lithium liquid, has low energy consumption, no pollution and high efficiency, and the obtained lithium liquid has low impurity content and high lithium concentration.
Description
Technical Field
The invention relates to the field of lithium liquid purification, in particular to a system and a method for purifying and concentrating magnesium-containing lithium liquid.
Background
In the current practical production process, the purification and concentration of the lithium liquid mainly adopt evaporation concentration or precipitation, and the two methods have respective defects. Wherein, the evaporation concentration needs to consume a large amount of energy consumption, the cost is high, and the concentration efficiency is lower; meanwhile, precipitation purification adds new impurities to the lithium solution, and the efficiency is low. For example, granted chinese patent application No. CN200910042883.1 discloses a method for extracting lithium salt from salt lake brine with low mg/li ratio by calcium circulation solid phase conversion, which uses salt lake brine with low mg/li ratio as raw material, and adopts the process flows of brine concentration, lime milk magnesium removal and desulfurization, lithium carbonate calcium separation, sodium carbonate lithium extraction, calcium carbonate thermal decomposition, quicklime hydration to form milk and the like to extract lithium carbonate product. The main technical points are based on anions (OH-, CO)3 2-) By the principle of solid phase conversion of Ca (OH)2→Mg(OH)2、Li2CO3→Ca(OH)2And CaCO3→CaO→Ca(OH)2The solid phase conversion of the brine realizes the demagging, calcium removal and lithium salt purification of the brine and the closed cycle of calcium. The method comprehensively utilizes the magnesium and lithium resources in the salt lake, and has the characteristics of high magnesium removal efficiency, good lithium salt purification effect, high lithium and magnesium recovery rate, low energy consumption, low cost, closed calcium circulation, low project engineering investment and the like. The whole process is simple, clean and environment-friendly. The invention is especially suitable for large-scale industrial production.
The evaporation and concentration method adopted in the above patent has the disadvantages of high energy consumption, high cost and low efficiency. The membrane separation process is a physical separation process without phase change and low energy consumption, has the characteristics of high efficiency, energy conservation, no pollution, convenient operation, wide application and the like, and is one of the most advanced chemical separation technologies recognized in the present generation.
However, for the purification and concentration of lithium liquid in the prior art, the application of membrane separation to the purification and concentration of lithium liquid also has obvious technical problems: the purity and concentration of the lithium liquid after membrane separation are not high enough, and evaporation and precipitation are generally matched to be carried out together in practical application, while the purification and concentration of the lithium liquid through membrane separation in the whole process cannot be realized in the prior art.
Disclosure of Invention
In order to solve the technical problems, the invention provides a system and a method for purifying and concentrating magnesium-containing lithium liquid. The system and the method for purifying and concentrating the magnesium-containing lithium liquid can purify and concentrate the magnesium-containing lithium liquid, are low in energy consumption, pollution-free and high in efficiency, and the obtained lithium liquid is low in impurity content and high in lithium liquid concentration, so that the system and the method are suitable for practical application.
The specific technical scheme of the invention is as follows: a purification and concentration system for magnesium-containing lithium liquid comprises a stock solution tank, a pretreatment unit, a primary filtering unit, a secondary filtering unit, a tertiary filtering unit and a quaternary filtering unit which are sequentially connected in series; the pretreatment unit comprises a delivery pump and a self-cleaning filter which are sequentially connected in series; the first-stage filtering unit comprises a plurality of first-stage ultrafiltration membranes connected in parallel; the secondary filtering unit comprises a secondary water production tank, a secondary delivery pump, a secondary security filter, a secondary high-pressure pump and a secondary composite membrane filtering component which are sequentially connected in series; the three-stage filtering unit comprises a three-stage water production tank, a three-stage delivery pump, a three-stage security filter, a three-stage high-pressure pump and a three-stage composite membrane filtering assembly which are sequentially connected in series; the four-stage filtering unit comprises a four-stage water production tank, a four-stage delivery pump, a four-stage security filter, a four-stage high-pressure pump and a four-stage composite membrane filtering component which are sequentially connected in series; and a concentrated lithium liquid collecting pipe is arranged on the four-stage composite membrane filtering component.
Compared with the prior art, the first-stage ultrafiltration membrane is matched with the third-stage composite membrane filtering component, and the purification and concentration of the magnesium-containing lithium liquid are realized by adopting a full-process membrane separation method. The invention has the advantages that: 1. the whole process adopts membrane separation, and has low energy consumption, no pollution and high efficiency. 2. Through the specific arrangement of each stage of membrane separation, the finally obtained lithium concentrated solution has low impurity content and high lithium solution concentration, is suitable for practical application, and overcomes the defects of more impurities and low concentration in the membrane separation concentrated solution.
The self-cleaning filter is used for pre-filtering to remove large-particle impurities in the magnesium-containing lithium liquid mother liquor and prevent the filtering membrane from being blocked.
Each guard filter is used for safe filtration of wastewater before entering the membrane module, and the purpose of the filter is to intercept visible particles entering the circulation pipe bucket due to previous improper operation.
Preferably, the second-stage composite membrane filtering assembly, the third-stage composite membrane filtering assembly and the fourth-stage composite membrane filtering assembly are composed of a plurality of composite membranes, inlets and outlets of the composite membranes are sequentially connected, and the outlet of the first composite membrane is further connected with the outlet of the last composite membrane.
Preferably, the first-stage ultrafiltration membrane is made of PVDF.
Preferably, the design pressure of the first-stage ultrafiltration membrane is 2.5-3.5 Bar.
Preferably, the composite film is made of PA material.
Preferably, the design pressure of the composite membrane of the secondary composite membrane filtration assembly is 17-19 Bar; the design pressure of a composite membrane of the three-stage composite membrane filtering assembly is 34-36 Bar; the design pressure of the composite membrane of the four-stage composite membrane filtration assembly is 64-66 Bar.
The invention strictly sets the materials and the design pressure of the ultrafiltration membrane and the composite membrane, and obtains the lithium concentrated solution with high concentration of lithium ions and low content of magnesium and other impurities in the concentrated solution under the mutual matching of the design pressure values through the setting and matching of the specific design pressure values at all levels. Because the relation between the design pressure value of each stage of filtering membrane and the lithium concentration and magnesium concentration in the obtained lithium liquid does not have strong regularity, the design pressure values of each stage of the filtering membrane are obtained by combining a great deal of research for a long time with self experience of the inventor, and on the premise of lacking obvious regularity, a person skilled in the art cannot easily obtain a specific numerical value of the filtering membrane through limited tests, so the technical scheme of the invention is creative.
Preferably, the last composite membrane of the secondary composite membrane filtering assembly is connected with a concentrated magnesium liquid recovery pipe; and a weak liquid recovery pipe is arranged on the last composite membrane of the three-stage composite membrane filtering assembly and the four-stage composite membrane filtering assembly.
Preferably, the online cleaning device comprises a cleaning medicine box, a plurality of flushing pumps and a cartridge filter which are connected in series in sequence; the cartridge filter is respectively connected with the ultrafiltration membrane, the second-stage composite membrane filtering component, the third-stage composite membrane filtering component and the fourth-stage composite membrane filtering component; and the ultrafiltration membrane, the second-level composite membrane filtering component, the third-level composite membrane filtering component and the fourth-level composite membrane filtering component are respectively provided with a cleaning water return pipe and connected with a cleaning medicine box.
The invention provides a cleaning scheme according to the actual running state, so as to ensure the long-term and stable running of the system.
Preferably, the water inlet surface of the first-stage ultrafiltration membrane is coated with a macroporous anti-blocking coating, and the preparation method comprises the following steps: preparing 50-60wt% of titanium dioxide colloidal solution according to a conventional method, adding cellulose, N-methyl perfluorohexane sulfonamide ethyl methacrylate and an adhesive into the silicon dioxide colloidal solution, and uniformly stirring to obtain a coating; and coating the coating on a concentrated liquid surface of the first-stage ultrafiltration membrane, aging at normal temperature for 8-12h, and completely drying to obtain the macroporous anti-blocking coating. The addition amount of the cellulose, the [ N-methyl perfluorohexane sulfonamide ] ethyl methacrylate and the adhesive is 3-5%, 1-3% and 0.5-1.5% of the mass of the titanium dioxide colloid solution.
After the first-stage ultrafiltration membrane is filtered for a long time, pores of the first-stage ultrafiltration membrane are gradually blocked by impurities, so that the filtering efficiency is gradually reduced. If the common coating is coated on the surface of the first-stage ultrafiltration membrane, the filtration efficiency of the first-stage ultrafiltration membrane is seriously influenced. Therefore, the coating has good porosity and larger pore size, and cannot greatly influence the original filtering efficiency of the primary ultrafiltration membrane. Wherein, the titanium dioxide sol can form a loose and porous coating after being cured, and the high porosity and the larger aperture of the coating are ensured. In addition, the titanium dioxide has higher photocatalytic activity, and after the titanium dioxide is used for a certain time, when a large amount of organic impurities are adsorbed in the coating, organic matters attached to the coating can be degraded only by illuminating the coating, so that self-cleaning is realized, and the titanium dioxide can be repeatedly used. In addition, the [ N-methyl perfluorohexane sulfonamide ] ethyl methacrylate has very low surface energy, and when impurities attached to the coating cannot be effectively removed through photocatalysis, the impurities can be quickly washed away and separated from the coating through backwashing. The cellulose has the function of complexing insoluble substances in the solution and preventing the insoluble substances from contacting the surface of the primary ultrafiltration membrane.
Preferably, the thickness of the macroporous anti-blocking coating is 5-10 microns. Porosity is 70-80%, and average pore diameter is 0.5-2 μm.
A purification and concentration method for magnesium-containing lithium liquid comprises the following steps:
(1) pre-filtering the magnesium-containing lithium liquid;
(2) filtering the pre-filtered magnesium-containing lithium liquid in a first-stage ultrafiltration membrane; the design pressure of the first-stage ultrafiltration membrane is 2.5-3.5 Bar;
(3) filtering the magnesium-containing lithium liquid by a cartridge filter, then concentrating and separating the magnesium-containing lithium liquid in a secondary composite membrane filtering assembly, and collecting separated concentrated magnesium liquid; the design pressure of the secondary composite membrane filtering component is 17-19 Bar;
(4) filtering the concentrated lithium liquid obtained in the step (3) by a cartridge filter, then, entering a three-stage composite membrane filtering assembly for concentration and separation, and collecting separated light liquid, wherein the design pressure of the three-stage composite membrane filtering assembly is 34-36 Bar;
(5) filtering the concentrated lithium liquid obtained in the step (4) by a cartridge filter, then concentrating and separating the concentrated lithium liquid in a four-stage composite membrane filtering assembly, and collecting separated light liquid, wherein the design pressure of the four-stage composite membrane filtering assembly is 64-66 Bar; and collecting concentrated lithium liquid.
The first-stage ultrafiltration membrane is matched with the third-stage composite membrane filtering component, and the purification and concentration of the magnesium-containing lithium liquid are realized by adopting a full-process membrane separation method. The invention has the advantages that: 1. the whole process adopts membrane separation, and has low energy consumption, no pollution and high efficiency. 2. Through the specific arrangement of each stage of membrane separation, the finally obtained lithium concentrated solution has low impurity content and high lithium solution concentration, is suitable for practical application, and overcomes the defects of more impurities and low concentration in the membrane separation concentrated solution.
Preferably, in the steps (1) to (5), the liquid temperature is controlled to be 5 to 35 ℃ and the pH value is controlled to be 6 to 9.
The invention strictly sets the materials and the design pressure of the ultrafiltration membrane and the composite membrane, and obtains the lithium concentrated solution with high concentration of lithium ions and low content of magnesium and other impurities in the concentrated solution under the mutual matching of the design pressure values through the setting and matching of the specific design pressure values at all levels. Because the relation between the design pressure value of each stage of filtering membrane and the lithium concentration and magnesium concentration in the obtained lithium liquid does not have strong regularity, the design pressure values of each stage of the filtering membrane are obtained by combining a great deal of research for a long time with self experience of the inventor, and on the premise of lacking obvious regularity, a person skilled in the art cannot easily obtain a specific numerical value of the filtering membrane through limited tests, so the technical scheme of the invention is creative.
Compared with the prior art, the invention has the beneficial effects that: the system and the method for purifying and concentrating the magnesium-containing lithium liquid can purify and concentrate the magnesium-containing lithium liquid, are low in energy consumption, pollution-free and high in efficiency, and the obtained lithium liquid is low in impurity content and high in lithium liquid concentration, so that the system and the method are suitable for practical application.
Drawings
FIG. 1 is a schematic diagram of a structure of the present invention.
The reference signs are: the device comprises a stock solution tank 1, a delivery pump 2, a self-cleaning filter 3, a first-stage ultrafiltration membrane 4, a second-stage water production tank 5, a second-stage delivery pump 6, a second-stage cartridge filter 7, a second-stage high-pressure pump 8, a second-stage composite membrane filtering component 9, a third-stage water production tank 10, a third-stage delivery pump 11, a third-stage cartridge filter 12, a third-stage high-pressure pump 13, a third-stage composite membrane filtering component 14, a fourth-stage water production tank 15, a fourth-stage delivery pump 16, a fourth-stage cartridge filter 17, a fourth-stage high-pressure pump 18, a fourth-stage composite membrane filtering component 19, a concentrated lithium liquid collecting pipe 20, a concentrated magnesium liquid recovery pipe 21, a fresh liquid.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
As shown in figure 1, a purification and concentration system for magnesium-containing lithium liquid comprises a stock solution tank 1, a pretreatment unit, a first-stage filtering unit, a second-stage filtering unit, a third-stage filtering unit, a fourth-stage filtering unit and an online cleaning device which are sequentially connected in series.
The pretreatment unit comprises a delivery pump 2 and a self-cleaning filter 3 which are sequentially connected in series; the first-stage filtering unit comprises four first-stage ultrafiltration membranes 4 (made of PVDF and with the design pressure of 3Bar) connected in parallel; the secondary filtering unit comprises a secondary water production tank 5, a secondary delivery pump 6, a secondary security filter 7, a secondary high-pressure pump 8 and a secondary composite membrane filtering component 9 which are sequentially connected in series; the three-stage filtering unit comprises a three-stage water production tank 10, a three-stage delivery pump 11, a three-stage cartridge filter 12, a three-stage high-pressure pump 13 and a three-stage composite membrane filtering component 14 which are sequentially connected in series; the four-stage filtering unit comprises a four-stage water production tank 15, a four-stage delivery pump 16, a four-stage cartridge filter 17, a four-stage high-pressure pump 18 and a four-stage composite membrane filtering component 19 which are sequentially connected in series; and a concentrated lithium liquid collecting pipe 20 is arranged on the four-stage composite membrane filtering component.
The second-level composite membrane filtering assembly, the third-level composite membrane filtering assembly and the fourth-level composite membrane filtering assembly are composed of 3-4 composite membranes (PA materials), the inlets and the outlets of the composite membranes are sequentially connected, and the outlet of the first composite membrane is also connected with the outlet of the last composite membrane. Wherein the design pressure of the composite membrane of the secondary composite membrane filtration assembly is 18 Bar; the design pressure of a composite membrane of the three-stage composite membrane filtering assembly is 35 Bar; the design pressure of the composite membrane of the four-stage composite membrane filtering assembly is 65 Bar. The last composite membrane of the secondary composite membrane filtering component is connected with a concentrated magnesium liquid recovery pipe 21; and a weak liquid recovery pipe 22 is arranged on the last composite membrane of the three-stage composite membrane filtering component and the four-stage composite membrane filtering component.
The online cleaning device comprises a cleaning medicine box 23, a plurality of flushing pumps 24 and a security filter 25 which are connected in series in sequence; the cartridge filter is respectively connected with the ultrafiltration membrane, the second-stage composite membrane filtering component, the third-stage composite membrane filtering component and the fourth-stage composite membrane filtering component; and the ultrafiltration membrane, the second-level composite membrane filtering component, the third-level composite membrane filtering component and the fourth-level composite membrane filtering component are respectively provided with a cleaning water return pipe 26 connected with the cleaning medicine box.
A purification and concentration method for magnesium-containing lithium liquid comprises the following steps:
(1) pre-filtering the magnesium-containing lithium liquid;
(2) filtering the pre-filtered magnesium-containing lithium liquid in an ultrafiltration membrane; the design pressure of the ultrafiltration membrane is 3 Bar;
(3) filtering the magnesium-containing lithium liquid by a cartridge filter, then concentrating and separating the magnesium-containing lithium liquid in a secondary composite membrane filtering assembly, and collecting separated concentrated magnesium liquid; the design pressure of the secondary composite membrane filtering component is 18 Bar;
(4) filtering the concentrated lithium liquid obtained in the step (3) by a cartridge filter, then, entering a three-stage composite membrane filtering assembly for concentration and separation, and collecting separated light liquid, wherein the design pressure of the three-stage composite membrane filtering assembly is 35 Bar;
(5) filtering the concentrated lithium liquid obtained in the step (4) by a cartridge filter, then concentrating and separating the concentrated lithium liquid in a four-stage composite membrane filtering assembly, and collecting separated light liquid, wherein the design pressure of the four-stage composite membrane filtering assembly is 65 Bar; and collecting concentrated lithium liquid.
In each step, the temperature of the liquid is controlled to be 20 ℃, and the pH value is controlled to be 7-8.
Example 2
The utility model provides a purification concentrated system to magnesium lithium liquid that contains, includes stoste case 1, preprocessing unit, one-level filter unit, second grade filter unit, tertiary filter unit, level four filter unit and the online cleaning device who establishes ties in proper order.
The pretreatment unit comprises a delivery pump 2 and a self-cleaning filter 3 which are sequentially connected in series; the first-stage filtering unit comprises a plurality of first-stage ultrafiltration membranes 4 (made of PVDF and designed with the pressure of 2.5Bar) connected in parallel; the secondary filtering unit comprises a secondary water production tank 5, a secondary delivery pump 6, a secondary security filter 7, a secondary high-pressure pump 8 and a secondary composite membrane filtering component 9 which are sequentially connected in series; the three-stage filtering unit comprises a three-stage water production tank 10, a three-stage delivery pump 11, a three-stage cartridge filter 12, a three-stage high-pressure pump 13 and a three-stage composite membrane filtering component 14 which are sequentially connected in series; the four-stage filtering unit comprises a four-stage water production tank 15, a four-stage delivery pump 16, a four-stage cartridge filter 17, a four-stage high-pressure pump 18 and a four-stage composite membrane filtering component 19 which are sequentially connected in series; and a concentrated lithium liquid collecting pipe 20 is arranged on the four-stage composite membrane filtering component.
The second-level composite membrane filtering assembly, the third-level composite membrane filtering assembly and the fourth-level composite membrane filtering assembly are composed of a plurality of composite membranes (PA materials), the inlets and the outlets of the composite membranes are sequentially connected, and the outlet of the first composite membrane is also connected with the outlet of the last composite membrane. Wherein the design pressure of the composite membrane of the secondary composite membrane filtration assembly is 17 Bar; the design pressure of a composite membrane of the three-stage composite membrane filtering assembly is 34 Bar; the design pressure of the composite membrane of the four-stage composite membrane filtration assembly is 64 Bar. The last composite membrane of the secondary composite membrane filtering component is connected with a concentrated magnesium liquid recovery pipe 21; and a weak liquid recovery pipe 22 is arranged on the last composite membrane of the three-stage composite membrane filtering component and the four-stage composite membrane filtering component.
The online cleaning device comprises a cleaning medicine box 23, a plurality of flushing pumps 24 and a security filter 25 which are connected in series in sequence; the cartridge filter is respectively connected with the ultrafiltration membrane, the second-stage composite membrane filtering component, the third-stage composite membrane filtering component and the fourth-stage composite membrane filtering component; and the ultrafiltration membrane, the second-level composite membrane filtering component, the third-level composite membrane filtering component and the fourth-level composite membrane filtering component are respectively provided with a cleaning water return pipe 26 connected with the cleaning medicine box.
Wherein, the concentrated liquid surface of the first-stage ultrafiltration membrane is also coated with a macroporous anti-blocking coating (the thickness is 8 microns, the porosity is 75 percent, and the average pore diameter is 1.5 microns), and the preparation method comprises the following steps: preparing 55 wt% of titanium dioxide colloidal solution according to a conventional method, adding cellulose, N-methyl perfluorohexane sulfonamide ethyl methacrylate and an adhesive into the silicon dioxide colloidal solution, and uniformly stirring to obtain a coating; and coating the coating on a concentrated liquid surface of the first-stage ultrafiltration membrane, aging at normal temperature for 10 hours, and completely drying to obtain the macroporous anti-blocking coating. The addition amount of the cellulose, the [ N-methyl perfluorohexane sulfonamide ] ethyl methacrylate and the binder is 4%, 2% and 1% of the mass of the titanium dioxide colloid solution.
A purification and concentration method for magnesium-containing lithium liquid comprises the following steps:
(1) pre-filtering the magnesium-containing lithium liquid;
(2) filtering the pre-filtered magnesium-containing lithium liquid in an ultrafiltration membrane; the design pressure of the ultrafiltration membrane is 2.5 Bar;
(3) filtering the magnesium-containing lithium liquid by a cartridge filter, then concentrating and separating the magnesium-containing lithium liquid in a secondary composite membrane filtering assembly, and collecting separated concentrated magnesium liquid; the design pressure of the secondary composite membrane filtering component is 17 Bar;
(4) filtering the concentrated lithium liquid obtained in the step (3) by a cartridge filter, then, entering a three-stage composite membrane filtering assembly for concentration and separation, and collecting separated light liquid, wherein the design pressure of the three-stage composite membrane filtering assembly is 34 Bar;
(5) filtering the concentrated lithium liquid obtained in the step (4) by a cartridge filter, then, entering a four-stage composite membrane filtering assembly for concentration and separation, and collecting separated light liquid, wherein the design pressure of the four-stage composite membrane filtering assembly is 64 Bar; and collecting concentrated lithium liquid.
In the above steps, the liquid temperature is controlled at 5 deg.C, and pH is controlled at 6-7.
Example 3
The utility model provides a purification concentrated system to magnesium lithium liquid that contains, includes stoste case 1, preprocessing unit, one-level filter unit, second grade filter unit, tertiary filter unit, level four filter unit and the online cleaning device who establishes ties in proper order.
The pretreatment unit comprises a delivery pump 2 and a self-cleaning filter 3 which are sequentially connected in series; the first-stage filtering unit comprises a plurality of first-stage ultrafiltration membranes 4 (made of PVDF and with the design pressure of 3.5Bar) connected in parallel; the secondary filtering unit comprises a secondary water production tank 5, a secondary delivery pump 6, a secondary security filter 7, a secondary high-pressure pump 8 and a secondary composite membrane filtering component 9 which are sequentially connected in series; the three-stage filtering unit comprises a three-stage water production tank 10, a three-stage delivery pump 11, a three-stage cartridge filter 12, a three-stage high-pressure pump 13 and a three-stage composite membrane filtering component 14 which are sequentially connected in series; the four-stage filtering unit comprises a four-stage water production tank 15, a four-stage delivery pump 16, a four-stage cartridge filter 17, a four-stage high-pressure pump 18 and a four-stage composite membrane filtering component 19 which are sequentially connected in series; and a concentrated lithium liquid collecting pipe 20 is arranged on the four-stage composite membrane filtering component.
The second-level composite membrane filtering assembly, the third-level composite membrane filtering assembly and the fourth-level composite membrane filtering assembly are composed of a plurality of composite membranes (PA materials), the inlets and the outlets of the composite membranes are sequentially connected, and the outlet of the first composite membrane is also connected with the outlet of the last composite membrane. Wherein the design pressure of a composite membrane of the secondary composite membrane filtration assembly is 19 Bar; the design pressure of a composite membrane of the three-stage composite membrane filtering assembly is 36 Bar; the design pressure of the composite membrane of the four-stage composite membrane filtering assembly is 66 Bar. The last composite membrane of the secondary composite membrane filtering component is connected with a concentrated magnesium liquid recovery pipe 21; and a weak liquid recovery pipe 22 is arranged on the last composite membrane of the three-stage composite membrane filtering component and the four-stage composite membrane filtering component.
The online cleaning device comprises a cleaning medicine box 23, a plurality of flushing pumps 24 and a security filter 25 which are connected in series in sequence; the cartridge filter is respectively connected with the ultrafiltration membrane, the second-stage composite membrane filtering component, the third-stage composite membrane filtering component and the fourth-stage composite membrane filtering component; and the ultrafiltration membrane, the second-level composite membrane filtering component, the third-level composite membrane filtering component and the fourth-level composite membrane filtering component are respectively provided with a cleaning water return pipe 26 connected with the cleaning medicine box.
Wherein, the concentrated liquid surface of the first-stage ultrafiltration membrane is also coated with a macroporous anti-blocking coating (the thickness is 5 microns, the porosity is 80 percent, and the average pore diameter is 0.5 micron), and the preparation method comprises the following steps: preparing 50 wt% of titanium dioxide colloidal solution according to a conventional method, adding cellulose, N-methyl perfluorohexane sulfonamide ethyl methacrylate and an adhesive into the silicon dioxide colloidal solution, and uniformly stirring to obtain a coating; and coating the coating on a concentrated liquid surface of the first-stage ultrafiltration membrane, aging at normal temperature for 8 hours, and completely drying to obtain the macroporous anti-blocking coating. The addition amount of the cellulose, N-methylperfluorohexanesulfonamido ethyl methacrylate and the binder was 3%, 1% and 0.5% by mass of the titanium dioxide colloid solution.
A purification and concentration method for magnesium-containing lithium liquid comprises the following steps:
(1) pre-filtering the magnesium-containing lithium liquid;
(2) filtering the pre-filtered magnesium-containing lithium liquid in an ultrafiltration membrane; the design pressure of the ultrafiltration membrane is 2.5-3.5 Bar;
(3) filtering the magnesium-containing lithium liquid by a cartridge filter, then concentrating and separating the magnesium-containing lithium liquid in a secondary composite membrane filtering assembly, and collecting separated concentrated magnesium liquid; the design pressure of the secondary composite membrane filtering component is 19 Bar;
(4) filtering the concentrated lithium liquid obtained in the step (3) by a cartridge filter, then, entering a three-stage composite membrane filtering assembly for concentration and separation, and collecting separated light liquid, wherein the design pressure of the three-stage composite membrane filtering assembly is 36 Bar;
(5) filtering the concentrated lithium liquid obtained in the step (4) by a cartridge filter, then concentrating and separating the concentrated lithium liquid in a four-stage composite membrane filtering assembly, and collecting separated light liquid, wherein the design pressure of the four-stage composite membrane filtering assembly is 66 Bar; and collecting concentrated lithium liquid.
In the above steps, the liquid temperature is controlled at 35 deg.C, and pH is controlled at 8-9.
Comparative example 1
A purification and concentration method for magnesium-containing lithium liquid comprises the following steps:
(1) pre-filtering the magnesium-containing lithium liquid;
(2) filtering the pre-filtered magnesium-containing lithium liquid in an ultrafiltration membrane; the design pressure of the ultrafiltration membrane is 2 Bar;
(3) filtering the magnesium-containing lithium liquid by a cartridge filter, then concentrating and separating the magnesium-containing lithium liquid in a secondary composite membrane filtering assembly, and collecting separated concentrated magnesium liquid; the design pressure of the secondary composite membrane filtering component is 15 Bar;
(4) filtering the concentrated lithium liquid obtained in the step (3) by a cartridge filter, then, entering a three-stage composite membrane filtering assembly for concentration and separation, and collecting separated light liquid, wherein the design pressure of the three-stage composite membrane filtering assembly is 30 Bar;
(5) filtering the concentrated lithium liquid obtained in the step (4) by a cartridge filter, then concentrating and separating the concentrated lithium liquid in a four-stage composite membrane filtering assembly, and collecting separated light liquid, wherein the design pressure of the four-stage composite membrane filtering assembly is 60 Bar; and collecting concentrated lithium liquid.
In each step, the temperature of the liquid is controlled to be 20 ℃, and the pH value is controlled to be 7-8.
Comparative example 2
A purification and concentration method for magnesium-containing lithium liquid comprises the following steps:
(1) pre-filtering the magnesium-containing lithium liquid;
(2) filtering the pre-filtered magnesium-containing lithium liquid in an ultrafiltration membrane; the design pressure of the ultrafiltration membrane is 4 Bar;
(3) filtering the magnesium-containing lithium liquid by a cartridge filter, then concentrating and separating the magnesium-containing lithium liquid in a secondary composite membrane filtering assembly, and collecting separated concentrated magnesium liquid; the design pressure of the secondary composite membrane filtering component is 20 Bar;
(4) filtering the concentrated lithium liquid obtained in the step (3) by a cartridge filter, then, entering a three-stage composite membrane filtering assembly for concentration and separation, and collecting separated light liquid, wherein the design pressure of the three-stage composite membrane filtering assembly is 40 Bar;
(5) filtering the concentrated lithium liquid obtained in the step (4) by a cartridge filter, then concentrating and separating the concentrated lithium liquid in a four-stage composite membrane filtering assembly, and collecting separated light liquid, wherein the design pressure of the four-stage composite membrane filtering assembly is 70 Bar; and collecting concentrated lithium liquid.
In each step, the temperature of the liquid is controlled to be 20 ℃, and the pH value is controlled to be 7-8.
The concentrated lithium solution purified and concentrated in example 1 and comparative examples 1 and 2 and the separated diluted solution were subjected to water quality testing, and the results were as follows:
the raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the systems used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (4)
1. The utility model provides a purification concentrated system to magnesium-containing lithium liquid which characterized in that: the device comprises a stock solution tank (1), a pretreatment unit, a primary filtering unit, a secondary filtering unit, a tertiary filtering unit and a quaternary filtering unit which are sequentially connected in series; the pretreatment unit comprises a delivery pump (2) and a self-cleaning filter (3) which are sequentially connected in series; the first-stage filtering unit comprises a plurality of first-stage ultrafiltration membranes (4) connected in parallel; the secondary filtering unit comprises a secondary water production tank (5), a secondary delivery pump (6), a secondary security filter (7), a secondary high-pressure pump (8) and a secondary composite membrane filtering component (9) which are sequentially connected in series; the three-stage filtering unit comprises a three-stage water production tank (10), a three-stage delivery pump (11), a three-stage cartridge filter (12), a three-stage high-pressure pump (13) and a three-stage composite membrane filtering assembly (14) which are sequentially connected in series; the four-stage filtering unit comprises a four-stage water production tank (15), a four-stage delivery pump (16), a four-stage cartridge filter (17), a four-stage high-pressure pump (18) and a four-stage composite membrane filtering component (19) which are sequentially connected in series; a concentrated lithium liquid collecting pipe (20) is arranged on the four-level composite membrane filtering component; the first-stage ultrafiltration membrane is made of PVDF (polyvinylidene fluoride); the composite film is made of PA material;
the water inlet surface of the first-stage ultrafiltration membrane is coated with a macroporous anti-blocking coating, and the preparation method comprises the following steps: preparing 50-60wt% of titanium dioxide colloidal solution according to a conventional method, adding cellulose, N-methyl perfluorohexane sulfonamide ethyl methacrylate and an adhesive into the silicon dioxide colloidal solution, and uniformly stirring to obtain a coating; coating the coating on a concentrated liquid surface of a first-stage ultrafiltration membrane, aging at normal temperature for 8-12h, and thoroughly drying to obtain a macroporous anti-blocking coating; the addition amounts of the cellulose, the methacrylic acid [ N-methyl perfluorohexane sulfonamide ] ethyl ester and the adhesive are respectively 3-5%, 1-3% and 0.5-1.5% of the mass of the titanium dioxide colloid solution;
the design pressure of the first-stage ultrafiltration membrane is 2.5-3.5 Bar; the design pressure of a composite membrane of the secondary composite membrane filtering assembly is 17-19 Bar; the design pressure of a composite membrane of the three-stage composite membrane filtering assembly is 34-36 Bar; the design pressure of a composite membrane of the four-stage composite membrane filtering assembly is 64-66 Bar;
the last composite membrane of the secondary composite membrane filtering component is connected with a concentrated magnesium liquid recovery pipe (21); a weak liquid recovery pipe (22) is arranged on the last composite membrane of the three-stage composite membrane filtering component and the four-stage composite membrane filtering component;
the purifying and concentrating system for the magnesium-containing lithium liquid further comprises an online cleaning device, wherein the online cleaning device comprises a cleaning medicine box (23), a plurality of flushing pumps (24) and a cartridge filter (25), which are connected in series in sequence; the cartridge filter is respectively connected with the first-stage ultrafiltration membrane, the second-stage composite membrane filtering component, the third-stage composite membrane filtering component and the fourth-stage composite membrane filtering component; and the first-stage ultrafiltration membrane, the second-stage composite membrane filtering component, the third-stage composite membrane filtering component and the fourth-stage composite membrane filtering component are respectively provided with a cleaning water return pipe (26) connected with the cleaning medicine box.
2. The purification and concentration system for magnesium-containing lithium liquid according to claim 1, wherein the second-stage composite membrane filtration module, the third-stage composite membrane filtration module and the fourth-stage composite membrane filtration module are composed of a plurality of composite membranes, the inlets and the outlets of the composite membranes are sequentially connected, and the outlet of the first composite membrane is further connected with the outlet of the last composite membrane.
3. A method for purifying and concentrating magnesium-containing lithium liquid by using the system of claim 1 or 2, which is characterized by comprising the following steps:
(1) pre-filtering the magnesium-containing lithium liquid;
(2) filtering the pre-filtered magnesium-containing lithium liquid in a first-stage ultrafiltration membrane; the design pressure of the first-stage ultrafiltration membrane is 2.5-3.5 Bar;
(3) filtering the magnesium-containing lithium liquid by a secondary cartridge filter, then concentrating and separating the magnesium-containing lithium liquid in a secondary composite membrane filtering assembly, and collecting separated concentrated magnesium liquid; the design pressure of a composite membrane of the secondary composite membrane filtering assembly is 17-19 Bar;
(4) filtering the concentrated lithium liquid obtained in the step (3) by a three-stage cartridge filter, then, entering a three-stage composite membrane filtering assembly for concentration and separation, and collecting separated light liquid, wherein the design pressure of a composite membrane of the three-stage composite membrane filtering assembly is 34-36 Bar;
(5) filtering the concentrated lithium liquid obtained in the step (4) by a four-stage cartridge filter, then concentrating and separating the concentrated lithium liquid in a four-stage composite membrane filtering assembly, and collecting separated light liquid, wherein the design pressure of a composite membrane of the four-stage composite membrane filtering assembly is 64-66 Bar; and collecting concentrated lithium liquid.
4. The method for purifying and concentrating magnesium-containing lithium liquid according to claim 3, wherein the temperature of the liquid is controlled to be 5 to 35 ℃ and the pH value is controlled to be 6 to 9 in the steps (1) to (5).
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