CN109355497B - In-situ leaching of serpentine with Mg by membrane electrochemistry2+Sequestration of CO2Apparatus and method of - Google Patents

In-situ leaching of serpentine with Mg by membrane electrochemistry2+Sequestration of CO2Apparatus and method of Download PDF

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CN109355497B
CN109355497B CN201811103668.3A CN201811103668A CN109355497B CN 109355497 B CN109355497 B CN 109355497B CN 201811103668 A CN201811103668 A CN 201811103668A CN 109355497 B CN109355497 B CN 109355497B
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朱萍
李祖良
钱光人
王杨君
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Abstract

The invention discloses a method for realizing electrolysis by using a membraneChemical in-situ leaching serpentine and simultaneously Mg2+Sequestration of CO2The method and the device utilize membrane electrochemistry to leach serpentine in situ and Mg simultaneously2+Sequestration of CO2The method adopts an electrochemical reaction tank separated by an anion exchange membrane, a gas diffusion electrode is adopted as an anode, stainless steel or graphite is adopted as a cathode, and the reaction comprises the following steps: in the anodic region, H2Formation of protons H at the gas diffusion electrode+The acid system of the anode area is used for leaching serpentine; in the polar region, H of cathodic electrode reaction2Transferring to anode region to form alkaline system OH in cathode region‑. The leaching rate of serpentine leaching in the anode region reaches 95%, and MgCO obtained in the cathode region3The purity of the product reaches more than 98.5 percent. Membrane electrochemical in-situ leaching of serpentine with Mg2+Sequestration of CO2The method realizes the synchronous comprehensive utilization of two natural resources and simultaneously carries out the treatment of greenhouse gas CO2The mineralization and the sealing are carried out, and the effect of killing two birds with one stone is realized.

Description

In-situ leaching of serpentine with Mg by membrane electrochemistry2+Sequestration of CO2Apparatus and method of
Technical Field
The invention relates to a treatment method and a process device for leaching serpentine, in particular to a method and a process device for leaching serpentine and extracting magnesium and CO2A method for mineralizing and sealing, and also relates to a method for utilizing serpentine, which is applied to the technical fields of mines, metallurgy, chemical industry and environment.
Background
China possesses serpentine with huge reserves, and the chemical general formula of the serpentine can be expressed as Mg6Si4O10(OH)8It is a 1:1 layered structure silicate mineral. The chemical composition is shown in Table 1, the main components are magnesium oxide and silicon dioxide, and the mass of the magnesium oxide and the silicon dioxide accounts for about 80% of that of serpentine ore. Mainly distributed in Jiangxi, Anhui, Qinghai provinces and the like. The serpentine unit structure layer (crystal layer) is formed by combining a silicon-oxygen tetrahedral sheet and a brucite octahedral sheet, and the octahedral voids are filled with magnesium. In the structural unit layer, the hydroxyl groups are distributed by internal hydroxyl and external hydroxyl, and the ratio of the internal hydroxyl to the external hydroxyl is 1: 3. As such, serpentine is alkaline in water, with a pH of about 10 to 11. The following reactions occur when encountering acids:
Mg3Si2O5(OH)4+6H+→3Mg2++2SiO2+2H2O (1)
TABLE 1 chemical composition of serpentine ores
Figure BDA0001807334370000011
As no good resource development technology exists, the comprehensive utilization of serpentine ore is an urgent problem to be solved. Meanwhile, as the serpentine has foliated or phosphorus flake crystals and large differentiation layers, China is open-pit mining, a large amount of crushed ores with the granularity of 2-3 cm are generated in the mining process, generally called serpentine powder ore or tailings, which account for 1/3-1/2 of the mining amount, are usually discarded as waste materials, thereby wasting mineral resources and occupying mining surfaces and farmlands. And most of the tailings are powdery substances, so that the tailings fly in the air, so that serious air pollution is caused, and the formation of haze is accelerated. For people and livestock living in a mine area within 20km, asbestos lung (the lung is a net) can be formed by inhaling the tailing dust for a long time, and the existence of people is greatly threatened.
In addition, recently, the fossil fuel has been used excessively as CO2The greenhouse effect caused by the dominant greenhouse gases is more and more remarkable. Elevated surface temperatures, rising sea levels, and frequent extreme weather have attracted widespread worldwide attention. 2013 Global CO2Has reached a surprising total emission of 334 million tons of atmospheric CO2Has increased from 280ppm prior to the industrial age to 440 ppm. CO22The emission reduction is not moderate. CO22Capture and sequestration technology (CCS) is an important approach to global warming and greenhouse effect. At present, three main sealing modes are available, namely geological sealing, ocean sealing and mineralization sealing. Compared with other sealing modes, the mineralized and sealed product is stable carbonate, the risk of leakage under the condition of long-term storage does not exist, and the existing environmental system cannot be damaged, so that the method has good potential. The calcium and magnesium element being CO2Mineralization of the basis of sequestration.
Thus, canThe method uses the characteristic of serpentine containing calcium and magnesium elements to extract magnesium elements by acid to absorb CO2And carrying out mineralization and sealing. However, as shown in reaction (2), Mg2+With CO2The reaction will produce acid, MgCO if the acid can not be transferred in time3Precipitation hardly occurs. Δ G can also be derived from the thermodynamic data as followsm θ(KJ/mol)＝74.1(KJ/mol)>0, indicating that the reaction does not spontaneously proceed in solution at ambient temperature. The acid must be removed to allow the reaction to proceed to the right to form MgCO3And (4) precipitating.
Figure BDA0001807334370000021
ΔGm θ(KJ/mol)→(-454.8) (-237.1) (-394.4) (-1012.2) (0)
ΔG(KJ/mol)＝(-1012.2)-(-454.8)-(-237.1)-(-394.4)＝74.1(KJ/mol)
However, at present, no relevant report about membrane electrochemical in-situ leaching of serpentine and simultaneous Mg2+ sequestration of CO2 exists, and how to realize low-cost serpentine becomes a technical problem to be solved urgently.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects of the prior art and provide a method for in-situ leaching serpentine by using membrane electrochemistry while simultaneously leaching Mg2+Sequestration of CO2To realize Mg to CO2The mineralization and the sealing, the leaching rate of the serpentine leaching is effectively improved, and the guarantee is provided for the serpentine treatment with low energy consumption, low cost and high yield.
In order to achieve the purpose, the invention adopts the following technical scheme:
in-situ leaching serpentine and Mg simultaneously by membrane electrochemistry2+Sequestration of CO2The reaction tank is divided into an anode region and a cathode region by an anion exchange membrane, and the anion exchange membrane allows anions to pass through while cations are blocked; the electrode in the anode region is made of gas diffusion electrode, and the electrode in the cathode region is made of any one or a composite material of stainless steel and graphite；
Putting the preactivated serpentine into an acid system solution in an anode region of membrane electrochemistry to form a serpentine-acid solution mixed system solution, wherein after the reaction starts, the following membrane electrochemical reaction can occur in the two electrode regions:
a) in the anodic region, H2Formation of protons H at the gas diffusion electrode+The acid system solution in the anode area is used for leaching serpentine;
b) in the cathode region, H reacted at the cathode electrode2Transferring the solution to an anode area through a gas conveying pipeline to form an alkaline system OH-solution in a cathode area;
CO is blown in the alkaline system OH-solution formed in the cathode zone through the gas adding pipeline2Filtering the alkaline system OH-solution containing the precipitated product in the cathode region by a cathode solution filtering device, and transferring the filtered solution to the cathode region through a liquid supply pipeline;
and (3) filtering the slurry after the reaction in the anode region by using an anode solution filtering device, crystallizing the filtered feed liquid in a crystallizing device to obtain a crystallized salt substance, and putting the obtained crystallized salt substance into the cathode region by using a feeding and conveying device to form a salt solution in the cathode region.
As a preferable technical scheme of the invention, the porous inorganic membranes are respectively arranged at two sides of the anion exchange membrane, so that the anion exchange membrane is prevented from being damaged by scouring the anion exchange membrane by slurry, and the pore diameter of the porous inorganic membranes is in the range of 1 nanometer-1000 micrometers.
With the above gas diffusion electrode, platinum carbon is coated on the upper surface of the titanium mesh to form the gas diffusion electrode of the anode region.
The anion exchange membrane is preferably made of any one or more of cellulose esters, polysulfones, polyamides, chitosan, ethylene and phenyl ether.
As a preferred technical scheme of the invention, anions in the cathode region can migrate to the anode region, wherein the anions comprise any one anion or a mixture of any more anions of sulfate, phosphate, oxalate and citrate.
As a preferred technical scheme of the invention, in an anode tank, the temperature of the serpentine-acid solution mixed system solution is 10-100 ℃, the reaction time is controlled to be 15-500 min, and a stirring device is adopted to stir the serpentine-acid solution mixed system solution at the speed of 100-500 rpm; h through anodic diffusion electrode2The flow rate is controlled to be 1sccm to 1000sccm, the cell voltage is controlled to be 1-10V, and the current density is controlled to be 1A/cm2～1000A/cm2。
As the preferable technical scheme of the invention, in the cathode tank, the temperature of the salt solution in the cathode region is 10-100 ℃, and the reaction time in the cathode region is controlled to be 15-500 min.
As a preferred technical scheme of the invention, the feed liquid obtained after the serpentine leaching reaction in the anode region is filtered and crystallized to obtain magnesium sulfate, the magnesium sulfate is transferred to the cathode region to react to form Mg (OH)2(ii) a CO introduced into the cathode region2Dissolved in water with Mg (OH)2React to form MgCO3The product was precipitated.
The method utilizes membrane electrochemistry to leach serpentine in situ and simultaneously leach Mg2+Sequestration of CO2The device for leaching serpentine in situ and simultaneously leaching Mg2+Sequestration of CO2The method comprises the following steps:
putting the preactivated serpentine into an anode tank solution in an anode area of membrane electrochemistry to react, controlling the reaction temperature to be within the range of 10-100 ℃, controlling the reaction time to be 15-500 min, controlling the solid-liquid mass-volume ratio of the serpentine to the anode tank solution to be 0.1:10(g/mL) -1: 1(g/mL), forming the anode tank solution containing the serpentine, and stirring the anode tank solution at the speed of 100-500 rpm;
h through anodic diffusion electrode2The flow rate is controlled to be 1sccm to 1000sccm, the cell voltage is controlled to be 1-10V, and the current density is controlled to be 1A/cm2～1000A/cm2(ii) a Placing the porous inorganic membranes on two sides of the anion exchange membrane so as to prevent the slurry from scouring the anion exchange membrane to damage the anion exchange membrane;
in the cathode regionAdding metal salt to start reaction, and reacting electrons on the surface of the cathode to form H after the reaction is started2Then transferred to the anode region to form protons H on the surface of the diffusion electrode in the anode region+As an acid to provide leaching of serpentine, while anions in the cathode region migrate into the anode region, and Mg obtained from leaching of serpentine2+Combining to generate Mg salt; after the reaction is finished, filtering the slurry after the anode region reaction is finished, crystallizing the filtered feed liquid to obtain Mg salt, putting the Mg salt into the cathode region, and forming OH in the cathode region after the electrode reaction-Ions, and Mg of cathode region2+Binding to form Mg (OH)2(ii) a The cathode region is then reacted to form Mg (OH)2The suspension was transferred to a reaction tank and CO was bubbled2Form MgCO3Precipitating, filtering, transferring the filtered liquid to the cathode region, filtering, and collecting MgCO3；
Mixing the obtained Mg salt and the filtered solution to form a cathode tank solution according to the solid-liquid mass-volume ratio of 0.1:10(g/mL) to 1:1(g/mL) of the Mg salt and the filtered solution put in the cathode zone, wherein the reaction temperature of the cathode zone is 10-100 ℃, and the reaction time is 15-500 min;
in-situ leaching of serpentine in membrane electrochemistry while simultaneously leaching Mg2+Sequestration of CO2Formation of MgCO3And Mg is separated from the serpentine.
As the preferred technical scheme of the invention, the serpentine is leached in situ and Mg is simultaneously leached2+Sequestration of CO2In an anode tank, the temperature of a serpentine-acid solution mixed system solution is 10-100 ℃, the reaction time is controlled to be 15-500 min, and a stirring device is adopted to stir the serpentine-acid solution mixed system solution at the speed of 100-500 rpm; h through anodic diffusion electrode2The flow rate is controlled to be 1sccm to 1000sccm, the cell voltage is controlled to be 1-10V, and the current density is controlled to be 1A/cm2～1000A/cm2(ii) a In the cathode tank, the temperature of the salt solution in the cathode region is 10-100 ℃, and the reaction time in the cathode region is controlled to be 15-500 min.
The principle of the invention is as follows:
the invention adopts membrane electrochemistry to solve H+Migration problem, realization of treatment of serpentine and mineralization of CO (carbon monoxide) for sequestration of greenhouse gas2The purpose of (1). The method is that the reaction tank is divided into an anode region and a cathode region by an anion exchange membrane, the anion exchange membrane allows anions to pass through, and cations are blocked. The electrode of the anode area adopts a gas diffusion electrode; the electrodes of the cathode region are made of stainless steel or graphite. After the reaction starts, the following membrane electrochemical reactions occur in the bipolar area:
an anode region: h2→2H++2e
2H++SO4 2-→H2SO4
3H2SO4+Mg3Si2O5(OH)4→3MgSO4+2SiO2+5H2O
A cathode region: 2H2O+Mg2++2e→Mg(OH)2+H2
2Mg(OH)2+4CO2→2Mg(HCO3)2
Figure BDA0001807334370000041
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the method utilizes the characteristics of the membrane electrochemical reaction tank, and by virtue of the specificity of anion exchange, the leaching rate of the membrane electrochemical reaction tank in leaching serpentine in an anode region can reach 95%, and MgCO obtained in a cathode region3The purity of the serpentine can reach more than 98.5 percent, and the recycling treatment capacity of the serpentine is obviously improved;
2. the method of the invention leaches serpentine in situ and Mg simultaneously by membrane electrochemistry2+Sequestration of CO2The method realizes the synchronous comprehensive utilization of two natural resources and simultaneously carries out the treatment of greenhouse gas CO2The mineralization and the sealing are carried out, so that the effect of killing two birds with one stone is realized;
3. the device has the advantages of simple structure, easy control and use, small occupied area and high efficiency of treating serpentine.
Drawings
FIG. 1 shows in-situ leaching of serpentine in anode and Mg in cathode of a membrane electrochemical anode according to an embodiment of the present invention2+Mineralizing and sequestering CO2The process equipment structure schematic diagram.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
example one
In this example, referring to FIG. 1, an in situ leaching of serpentine with Mg using membrane electrochemistry2+Sequestration of CO2The device of (2), characterized in that: dividing the reaction tank into an anode region and a cathode region by an anion exchange membrane, wherein the anion exchange membrane allows anions to pass through and prevents cations from being blocked; the electrode of the anode region is a gas diffusion electrode, and the electrode of the cathode region is made of any one material or a composite material of stainless steel and graphite;
according to the solid-liquid mass-to-volume ratio of 0.1:10(g/mL) to 1:1(g/mL), preactivated serpentine with the particle size of 60-200 meshes is put into an acid system solution in an anode region of membrane electrochemistry to form a serpentine-acid solution mixed system solution, and after the reaction starts, the following membrane electrochemical reaction can occur in an bipolar region:
a) in the anodic region, H2Formation of protons H at the gas diffusion electrode+The acid system solution in the anode area is used for leaching serpentine;
b) in the cathode region, H reacted at the cathode electrode2Transferring the alkaline solution to the anode region through a gas conveying pipeline to form an alkaline system OH in the cathode region-A solution;
basic system OH formed in the cathode region-Bubbling CO into the solution through an air charging pipeline2To form a precipitated product, an alkaline system OH containing the precipitated product in the cathode region-Filtering the solution by a cathode solution filtering device, and transferring the filtered solution to a cathode region through a liquid supply pipeline;
and (2) filtering the slurry after the reaction in the anode region by using an anode solution filtering device, crystallizing the filtered feed liquid in a crystallizing device to obtain a crystallized salt substance, and feeding the obtained crystallized salt substance into the cathode region by using a feeding and conveying device according to the solid-liquid mass-to-volume ratio of 0.1:10(g/mL) to 1:1(g/mL) of the salt substance to the filtered solution to form the salt solution in the cathode region.
In-situ leaching serpentine and Mg simultaneously by membrane electrochemistry2+Sequestration of CO2The device for leaching serpentine in situ and simultaneously leaching Mg2+Sequestration of CO2The method comprises the following steps:
according to the ratio of solid-liquid mass to volume of 0.1:10(g/mL), putting preactivated serpentine with the particle size of 200 meshes into an anode tank solution in an anode area of membrane electrochemistry for reaction, controlling the reaction temperature to be 100 ℃ and the reaction time to be 15min to form the anode tank solution containing the serpentine, and stirring the anode tank solution at the speed of 500 rpm;
h through anodic diffusion electrode2The flow rate is controlled to be 1sccm to 1000sccm, the cell voltage is controlled to be 10V, and the current density is controlled to be 1000A/cm2(ii) a Placing the porous inorganic membranes on two sides of the anion exchange membrane so as to prevent the slurry from scouring the anion exchange membrane to damage the anion exchange membrane;
MgSO is added in the cathode zone4·7H2O starts reaction, and after the reaction starts, electrons react on the surface of the cathode to form H2Then transferred to the anode region to form protons H on the surface of the diffusion electrode in the anode region+As the acid for leaching serpentine and, at the same time, SO in the cathode region4 2Anions migrate into the anodic compartment with Mg obtained by leaching serpentine2+Combine to form MgSO4(ii) a After the reaction is finished, filtering the slurry after the anode region reaction is finished, and crystallizing the filtered feed liquid to obtain MgSO4·7H2O, then MgSO4·7H2O is put into the cathode region, and OH-ions are formed in the cathode region after electrode reaction with Mg in the cathode region2+Binding to form Mg (OH)2(ii) a The cathode region is then reacted to form Mg (OH)2The suspension was transferred to a reaction tank and CO was bubbled2Form MgCO3Precipitating, filtering, transferring the filtered liquid to the cathode region, filtering, and collecting MgCO3；
Mixing the obtained Mg salt with the filtered solution according to the solid-liquid mass-to-volume ratio of 0.1:10(g/mL) of the Mg salt added in the cathode region and the filtered solution to form a cathode tank solution, wherein the reaction temperature in the cathode region is 10 ℃ and the reaction time is 500 min;
in-situ leaching of serpentine in membrane electrochemistry while simultaneously leaching Mg2+Sequestration of CO2Formation of MgCO3And Mg is separated from the serpentine. The specific process flow diagram of this example is shown with reference to fig. 1. In conclusion, the leaching rate of serpentine in the anode zone reaches 95%, and MgCO obtained in the cathode zone3The purity of the product reaches more than 98.5 percent.
This example addresses H using membrane electrochemistry+Migration problem, realization of treatment of serpentine and mineralization of CO (carbon monoxide) for sequestration of greenhouse gas2The purpose of (1). The method is that the reaction tank is divided into an anode area and a cathode area by an anion exchange membrane, and the anion exchange membrane allows SO4 2The anions pass through, while the cations are blocked. The anion exchange membrane can adopt cellulose ester high molecular materials. The electrode of the anode area adopts a gas diffusion electrode, and platinum carbon is coated on the titanium mesh; the electrode of the cathode region adopts a stainless steel electrode. After the reaction starts, the following membrane electrochemical reactions occur in the bipolar area:
an anode region: h2→2H++2e
2H++SO4 2-→H2SO4
3H2SO4+Mg3Si2O5(OH)4→3MgSO4+2SiO2+5H2O
A cathode region: 2H2O+Mg2++2e→Mg(OH)2+H2
2Mg(OH)2+4CO2→2Mg(HCO3)2
Figure BDA0001807334370000061
In this embodiment, the porous inorganic membranes are disposed on both sides of the anion exchange membrane, so as to prevent the slurry from scouring the anion exchange membrane and damaging the anion exchange membrane, and the pore diameter of the porous inorganic membrane is 1 nm. And a gas diffusion electrode is adopted, and platinum carbon is coated on the titanium mesh to form the gas diffusion electrode in the anode area. The anion exchange membrane is made of cellulose ester high molecular materials. Anions in the cathode region can migrate to the anode region, where the anions are sulfate anions. In this example, the liquid obtained after the reaction of leaching serpentine in the anode region was filtered and crystallized to obtain magnesium sulfate, which was transferred to the cathode region to react to form Mg (OH)2(ii) a CO introduced into the cathode region2Dissolved in water with Mg (OH)2React to form MgCO3The product was precipitated. This example utilizes the characteristics of a membrane electrochemical reaction cell to allow anionic SO by virtue of the specificity of anion exchange4 2-The positive ions are prevented from passing through the anion exchange membrane after transferring from the cathode to the anode, so that the leaching rate of the positive ions in the anode region for leaching serpentine reaches 95 percent, and MgCO obtained in the cathode region3The purity of the product reaches more than 98.5 percent. This example shows the in situ leaching of serpentine with Mg by membrane electrochemistry2+Sequestration of CO2The method realizes the synchronous comprehensive utilization of two natural resources and simultaneously carries out the treatment of greenhouse gas CO2The mineralization and the sealing are carried out, and the effect of killing two birds with one stone is realized.
Example two
This embodiment is substantially the same as the first embodiment, and is characterized in that:
in this example, an in situ leaching of serpentine with Mg using membrane electrochemistry2+Sequestration of CO2The method comprises the following steps:
according to the ratio of solid-liquid mass to volume of 1:1(g/mL), putting preactivated serpentine with the particle size of 60 meshes into an anode tank solution in an anode area of membrane electrochemistry for reaction, controlling the reaction temperature to be 10 ℃ and the reaction time to be 500min, forming the anode tank solution containing the serpentine, and stirring the anode tank solution at the speed of 100 rpm;
h through anodic diffusion electrode2The flow rate is controlled to be 1sccm to 1000sccm, the cell voltage is controlled to be 1V, and the current density is controlled to be 1A/cm2(ii) a Placing the porous inorganic membranes on two sides of the anion exchange membrane so as to prevent the slurry from scouring the anion exchange membrane to damage the anion exchange membrane;
MgSO is added in the cathode zone4·7H2O starts reaction, and after the reaction starts, electrons react on the surface of the cathode to form H2Then transferred to the anode region to form protons H on the surface of the diffusion electrode in the anode region+As the acid for leaching serpentine and, at the same time, SO in the cathode region4 2-Anions migrate to the anode region and react with Mg obtained by leaching serpentine2+Combine to form MgSO4(ii) a After the reaction is finished, filtering the slurry after the anode region reaction is finished, and crystallizing the filtered feed liquid to obtain MgSO4·7H2O, then MgSO4·7H2O is put into the cathode region, and OH is formed in the cathode region after electrode reaction-Ions, and Mg of cathode region2+Binding to form Mg (OH)2(ii) a The cathode region is then reacted to form Mg (OH)2The suspension was transferred to a reaction tank and CO was bubbled2Form MgCO3Precipitating, filtering, transferring the filtered liquid to the cathode region, filtering, and collecting MgCO3；
Mixing the obtained Mg salt and the filtered solution to form a cathode tank solution according to the solid-liquid mass to volume ratio of 1:1(g/mL) of the Mg salt and the filtered solution put in the cathode zone, wherein the reaction temperature in the cathode zone is 100 ℃, and the reaction time is 15 min;
this example utilizes membrane electrochemical in situ leaching of serpentine with Mg2+Sequestration of CO2The method of (1), an anion exchange membrane-isolated electrochemical reaction cell, the anode using a gas diffusion electrode and the cathode using stainless steel or graphite, comprises the following reaction steps: a) anode region, H2Formation of protons H at the gas diffusion electrode+Of the anodic regionThe acid system is used for leaching serpentine; b) cathode region, cathode electrode reacted H2Transferring to anode region to form alkaline system OH in cathode region-. The leaching rate of serpentine leaching in the anode region reaches 95%, and MgCO obtained in the cathode region3The purity of the product reaches more than 98.5 percent. Membrane electrochemical in-situ leaching of serpentine with Mg2+Sequestration of CO2The method realizes the synchronous comprehensive utilization of two natural resources and simultaneously carries out the treatment of greenhouse gas CO2The mineralization and the sealing are carried out, and the effect of killing two birds with one stone is realized.
While the embodiments of the present invention have been described with reference to the accompanying drawings, the present invention is not limited to the above embodiments, but various changes can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions as long as the purpose of the present invention is met, as long as the present invention does not deviate from the membrane electrochemical in-situ leaching of serpentine and Mg by the membrane electrochemical method2+Sequestration of CO2The technical principle and the inventive concept of the device and the method are all within the protection scope of the invention.

Claims (7)

1. In-situ leaching serpentine and Mg simultaneously by membrane electrochemistry2+Sequestration of CO2The reaction tank is divided into an anode region and a cathode region by an anion exchange membrane, and the anion exchange membrane allows anions to pass through while allowing cations to be blocked; the electrode of the anode region is a gas diffusion electrode, and the electrode of the cathode region is made of any one material or a composite material of stainless steel and graphite; the membrane electrochemical reaction takes place in the bipolar region, where in the anodic region H2Formation of protons H at the gas diffusion electrode+(ii) a Forming an acid system solution in the anode region; in the cathode region, H reacted at the cathode electrode2Transferring the alkaline solution to the anode region through a gas conveying pipeline to form an alkaline system OH in the cathode region-A solution; the method is characterized in that:
a) putting the preactivated serpentine into an acid system solution in an anode area of membrane electrochemistry to form a serpentine-acid solution mixed system solution;
b) filtering the slurry after the reaction in the anode region by using an anode solution filtering device, crystallizing the filtered feed liquid in a crystallizing device to obtain a crystallized salt substance, and putting the obtained crystallized salt substance into the cathode region by using a feeding and conveying device to form a cathode region salt solution;
c) basic system OH formed in the cathode region-Bubbling CO into the solution through an air charging pipeline2To form a precipitated product, an alkaline system OH containing the precipitated product in the cathode region-Filtering the solution by a cathode solution filtering device, and transferring the filtered solution to a cathode region through a liquid supply pipeline;
d) the porous inorganic membranes are respectively arranged on two sides of the anion exchange membrane, so that the anion exchange membrane is prevented from being damaged by slurry scouring the anion exchange membrane, and the pore diameter of the porous inorganic membranes is in the range of 1 nanometer-1000 micrometers.
2. The use of membrane electrochemistry of in situ leaching of serpentine with Mg as claimed in claim 12+Sequestration of CO2The device of (2), characterized in that: and a gas diffusion electrode is adopted, and platinum carbon is coated on the titanium mesh to form the gas diffusion electrode in the anode area.
3. The use of membrane electrochemistry of in situ leaching of serpentine with Mg as claimed in claim 12+Sequestration of CO2The device of (2), characterized in that: the anion exchange membrane is made of any one or more of cellulose ester, polysulfone, polyamide, chitosan, ethylene and phenylate.
4. The use of membrane electrochemistry of in situ leaching of serpentine with Mg as claimed in claim 12+Sequestration of CO2The device of (2), characterized in that: anions in the cathode region can migrate to the anode region, wherein the anions include any one or a mixture of any of sulfate, phosphate, oxalate, citrate.
5. The use of membrane electrochemistry of in situ leaching of serpentine with Mg as claimed in claim 12+Sequestration of CO2The device of (2), characterized in that: filtering and crystallizing the material liquid obtained after the reaction of leaching serpentine in the anode region to obtain magnesium sulfate, transferring the magnesium sulfate to the cathode region, and reacting to form Mg (OH)2(ii) a CO introduced into the cathode region2Dissolved in water with Mg (OH)2React to form MgCO3The product was precipitated.
6. In-situ leaching serpentine and simultaneously leaching Mg2+Sequestration of CO2The method of in situ leaching of serpentine with Mg using membrane electrochemistry as claimed in claim 12+Sequestration of CO2The device of (2), characterized in that:
according to the solid-liquid mass-to-volume ratio of 0.1:10(g/mL) to 1:1(g/mL), preactivated serpentine with the particle size of 60-200 meshes is put into an anode tank solution in an anode area of membrane electrochemistry to react, the reaction temperature is controlled within the range of 10-100 ℃, the reaction time is 15-500 min, the anode tank solution containing the serpentine is formed, and the stirring speed of the anode tank solution is 100-500 rpm;
h through anodic diffusion electrode2The flow rate is controlled to be 1sccm to 1000sccm, the cell voltage is controlled to be 1-10V, and the current density is controlled to be 1A/cm2～1000A/cm2(ii) a Placing porous inorganic membranes on both sides of the anion exchange membrane, thereby preventing the slurry from scouring the anion exchange membrane and damaging the anion exchange membrane;
adding metal salt in the cathode region to start reaction, and reacting electrons on the surface of the cathode to form H after the reaction is started2Then transferred to the anode region to form protons H on the surface of the diffusion electrode in the anode region+As an acid to provide leaching of serpentine, while anions in the cathode region migrate into the anode region, and Mg obtained from leaching of serpentine2+Combining to generate Mg salt; after the reaction is finished, filtering the slurry after the anode region reaction is finished, crystallizing the filtered feed liquid to obtain Mg salt, putting the Mg salt into the cathode region, and forming OH in the cathode region after the electrode reaction-Ions, and Mg of cathode region2+Binding to form Mg (OH)2(ii) a The cathode region is then reacted to form Mg (OH)2The suspension was transferred to a reaction tank and CO was bubbled2Form MgCO3Precipitating, filtering, transferring the filtered liquid to the cathode region, filtering, and collecting MgCO3；
Mixing the obtained Mg salt and the filtered solution to form a cathode tank solution according to the solid-liquid mass-volume ratio of 0.1:10(g/mL) to 1:1(g/mL) of the Mg salt and the filtered solution put in the cathode zone, wherein the reaction temperature of the cathode zone is 10-100 ℃, and the reaction time is 15-500 min;
in-situ leaching of serpentine in membrane electrochemistry while Mg2+Sequestration of CO2Formation of MgCO3And Mg is separated from the serpentine.
7. The in situ leaching of serpentine with Mg of claim 62+Sequestration of CO2The method of (2), characterized by: in an anode tank, controlling the temperature of the serpentine-acid solution mixed system solution at 10-100 ℃, controlling the reaction time at 15-500 min, and stirring the serpentine-acid solution mixed system solution at 100-500 rpm by adopting a stirring device; h through anodic diffusion electrode2The flow rate is controlled to be 1sccm to 1000sccm, the cell voltage is controlled to be 1-10V, and the current density is controlled to be 1A/cm2～1000A/cm2(ii) a In the cathode tank, the temperature of the salt solution in the cathode region is 10-100 ℃, and the reaction time in the cathode region is controlled to be 15-500 min.
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