CN114797768B - Magnesium phosphate double salt-activated carbon composite material, preparation method thereof and application thereof as potassium ion adsorption material - Google Patents

Magnesium phosphate double salt-activated carbon composite material, preparation method thereof and application thereof as potassium ion adsorption material Download PDF

Info

Publication number
CN114797768B
CN114797768B CN202210280247.8A CN202210280247A CN114797768B CN 114797768 B CN114797768 B CN 114797768B CN 202210280247 A CN202210280247 A CN 202210280247A CN 114797768 B CN114797768 B CN 114797768B
Authority
CN
China
Prior art keywords
potassium
activated carbon
composite material
magnesium
double salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210280247.8A
Other languages
Chinese (zh)
Other versions
CN114797768A (en
Inventor
韩海生
王宇峰
孙伟
田佳
桑孟超
张荥斐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN202210280247.8A priority Critical patent/CN114797768B/en
Publication of CN114797768A publication Critical patent/CN114797768A/en
Application granted granted Critical
Publication of CN114797768B publication Critical patent/CN114797768B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D15/00Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/048Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10Obtaining alkali metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10Obtaining alkali metals
    • C22B26/12Obtaining lithium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006Wet processes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a magnesium phosphate double salt-activated carbon composite material, a preparation method thereof and application thereof as a potassium ion adsorption material. Adding phosphate, a magnesium source, active carbon and hydrogen peroxide into water, and stirring for reaction to obtain a reaction mixed solution; the composite material formed by loading magnesium phosphate double salt on active carbon is obtained by sequentially carrying out sedimentation, solid-liquid separation and drying on the reaction mixed solution after ultrasonic treatment, and the composite material has high selective adsorption and high adsorption capacity on potassium ions in a solution system, breaks through the defects of the existing potassium removal technologies such as an ion exchange method, a precipitation method and the like, and has great significance for the production and development of the industries of solution potassium extraction (such as the fields of seawater potassium extraction and the like) and solution potassium removal (the fields of lithium potassium separation and the like).

Description

Magnesium phosphate double salt-activated carbon composite material, preparation method thereof and application thereof as potassium ion adsorption material
Technical Field
The invention relates to a potassium ion adsorption material, in particular to a magnesium phosphate double salt-activated carbon composite material and a preparation method thereof, and also relates to application of the magnesium phosphate double salt-activated carbon composite material in potassium ion adsorption in a solution system, belonging to the technical field of potassium ion extraction and separation in the solution system.
Background
Potassium is used as a nutrient element necessary for crop growth, has very important position in agricultural production in China, and is widely applied to industrial production of paint pigment, glass, pharmacy, leather and the like. One of the serious potassium-deficient areas in the world of China. Potassium is taken as non-renewable resource, the reserves are deficient, the proportion is low, the yield is limited, the potassium used in the industry depends on import for a long time, and the development of the industry is greatly limited. The mineral substances of the natural silicate minerals are far insufficient for providing potassium components, and compared with other material components, the mineral substances of the natural silicate minerals have rich potassium ion content in the ocean and are important ways for effectively obtaining potassium substances.
So far, on the basis of introducing impurities, efficient separation and extraction of potassium from a solution system is a great challenge of the technology. For example, the extraction of potassium from seawater, which is a complex and environmentally variable chemical resource composition, is also a major point of research. Evaporative crystallization is the most classical process route in extracting potassium from seawater. However, the potassium salt of the evaporation crystallization method has the defects of low purity, long production period, high energy consumption, low efficiency and the like, so that the industrial requirement is difficult to reach. The chemical precipitation method is also an important method for enriching potassium in a solution system, and according to different characteristics of various potassium salts, a corresponding precipitant is added into the solution system to precipitate and separate out the potassium salts in an insoluble form, and then the precipitate is purified to obtain the potassium salts with higher purity. Sodium tetraphenylborate, for example, is a p-K + A precipitant which has high selectivity and forms more thorough precipitation with potassium; although the chemical precipitation method can obtain the potassium salt with higher purity, the price of the sodium tetraphenylborate is too high, and the method is not economically feasible, so that the search of a safe, low-cost, environment-friendly and recyclable precipitant is critical. The liquid film extraction method uses the difference of potassium distribution between the extractant substance phase and the water phase and the seawater phase to achieve the aim of thickening or separating specific substances, and the commonly used extractant is isoamyl alcohol, a mixture of organic acid and phenol, polycyclic ether, n-butanol and the like, and the method has high selectivity to potassium, but the extractant is expensive and is not suitableAnd (5) industrialized application.
When the ion exchanger contacts with liquid, the ion used for exchange in the exchanger can exchange with the ion in the liquid, so as to enrich the ion. The method is characterized in that the ion exchanger is selected to be low in cost, environment-friendly and efficient, and the common ion exchange method is mainly divided into two aspects, on one hand, the inorganic ion exchanger is used as a potassium component to remove the exchange medium, so that the enrichment of solution potassium is realized. The Japanese scholars develop more research results, and the synthesized zirconium tungstate phosphate has the advantages of good selectivity and high stability on potassium components, but the economic requirement cannot be met due to the expensive price of zirconium compounds, so far, industrialization cannot be realized. On the other hand, the natural substances have high-efficiency selective enrichment adsorption on potassium components in the solution. For example, research reports that ion sieves and natural zeolite have higher selective adsorption performance on potassium ions in seawater, but the adsorption removal effect of the ion sieves and the natural zeolite is still to be enhanced for a solution system with higher potassium ion concentration.
It can be said that how to extract potassium component with high efficiency and selectivity has become the bottleneck problem of solution potassium extraction technology development, develop a low-cost high-efficiency and selective potassium extraction technology, which is an important way to enrich potassium in solution system, more importantly, not only in the field of extracting potassium from sea water, but also in the field of purifying potassium in lithium mine leaching solution purification system, etc., and has wide application and development prospect, if realizing the high-efficiency separation of lithium and potassium components with similar main group properties in the field of extracting lithium, it will have profound significance to upgrade innovation of lithium extraction technology, and also lay an important foundation for purification smelting of back-end lithium products.
Disclosure of Invention
Aiming at the problems of low potassium removal efficiency, high cost and the like in the existing solution potassium extraction and liquid-phase potassium removal technologies, the first aim of the invention is to provide a magnesium phosphate double salt-activated carbon composite material which has high selective adsorption and high adsorption capacity on potassium ions in a solution system, and has great significance for the production and development of the industries of solution potassium extraction (such as the fields of seawater potassium extraction and the like) and solution potassium removal (such as the fields of lithium potassium separation and the like).
The second aim of the invention is to provide a preparation method of the magnesium phosphate double salt-activated carbon composite material, which has simple process, convenient operation and low energy consumption and is beneficial to mass production.
The third purpose of the invention is to provide an application of the magnesium phosphate double salt-activated carbon composite material, wherein the magnesium phosphate double salt-activated carbon composite material is used as an adsorption material to be applied to potassium ion adsorption in a solution system, has high selectivity and high enrichment capacity, can realize the recycling and regeneration of the adsorption material, has strong application method applicability, high efficiency and low cost, and is particularly suitable for the industrial production of extracting potassium from seawater or separating lithium from potassium.
In order to achieve the technical aim, the invention provides a preparation method of a magnesium phosphate double salt-activated carbon composite material, which comprises the steps of adding phosphate, a magnesium source, activated carbon and hydrogen peroxide into water, and stirring for reaction to obtain a reaction mixed solution; and carrying out ultrasonic treatment on the reaction mixed solution, and sequentially carrying out sedimentation, solid-liquid separation and drying to obtain the catalyst.
According to the technical scheme, activated carbon is used as a carrier, phosphate and magnesium salt generate magnesium phosphate double salt under the promotion effect of hydrogen peroxide and are deposited on the surface of the activated carbon in situ to form the magnesium phosphate double salt-activated carbon composite material which has high specific surface area and porosity, fully exposed active sites and highly dispersed active components of the magnesium phosphate double salt, so that the adsorption capacity and the adsorption selectivity of the composite material can be greatly improved. Meanwhile, the composite material takes magnesium phosphate double salt as an adsorption active center of potassium ions, has specific active affinity to potassium, can realize efficient and selective enrichment of potassium components in solution, and effectively realizes the aim of extracting or removing potassium in solution while not increasing impurity elements in solution.
As a preferred embodiment, the phosphate comprises sodium phosphate and/or ammonium phosphate, more preferably sodium pyrophosphate, trisodium phosphate, hydrogen phosphateAt least one of disodium, sodium dihydrogen phosphate and ammonium phosphate. The main function of the phosphate is to hydrolyze and ionize in a solution system to obtain phosphate ions, and in theory, the water-soluble phosphate meets the requirements of the technical scheme of the invention, and the most preferable phosphate is ammonium from the comprehensive consideration of cost, water solubility and the like. According to the technical scheme, sodium phosphate/ammonium phosphate and magnesium salt are fully combined for reaction, and a large amount of Na is adsorbed in a magnesium phosphate double salt lattice + Or NH 4 + Can be combined with K in solution + Realize high-efficiency ion exchange, na + With NH 4 + Having equal electron numbers and similar properties, but NH 4 + Charge ratio Na + More dispersed, and NH 4 + Is closer to K + More preferably, the ammonium phosphate salt is used to synthesize the magnesium phosphate double salt, which is also characterized by that the adsorption material is substituted for K from solution system + Providing important basic conditions, more importantly, when K + Into the crystal lattice of magnesium phosphate complex salt, new phase is gradually formed, and the dissolved complex anions and K + The phases are mutually communicated to form new phase mineral sediment containing potassium.
As a preferred embodiment, the magnesium source includes at least one of magnesium sulfate, magnesium chloride, and magnesium oxide. The magnesium source is mainly a salt containing magnesium ions, and in theory, a magnesium salt which is easily soluble in water is suitable for the technical scheme of the present invention, and magnesium chloride is preferably used in view of economic cost and disposal efficiency.
As a preferred scheme, the ratio of the active carbon, the phosphate and the magnesium source is measured according to the mol ratio of C, P to Mg of 0.5-1:0.5-1.2:1. If too high a concentration of phosphate is used, phosphate and other impurity metal ions, such as heavy metal ions of iron, copper and the like, are promoted to be bonded on the surface of the adsorption material, which can obviously reduce the adsorption of the adsorption material to potassium components in the solution, and the use of high-dosage activated carbon can increase the preparation cost of the composite material, reduce the adsorption capacity of the adsorption material and increase the use cost. It is further preferred that the ratio of activated carbon, phosphate and magnesium source is measured in a molar ratio of C, P to Mg of 0.8 to 1:0.8 to 1:1. As a preferable scheme, the concentration of the activated carbon added in the water is 1-3 mol/L. The concentration of the activated carbon added to the water is most preferably 1.5 to 2.5mol/L.
As a preferred embodiment, the hydrogen peroxide is added in the form of a solution having a concentration of 20 to 40 wt%. The added volume concentration of the hydrogen peroxide in the water is 0.2% -5%. The addition of low concentrations of hydrogen peroxide helps to increase the rate of reaction while promoting reactive incorporation of the active components in the solution system.
As a preferable embodiment, the stirring reaction conditions are as follows: the pH is controlled to be 10-13, the temperature is 30-50 ℃ and the time is 60-90 min. Better binding of reagents can be promoted under preferred reaction conditions.
As a preferable scheme, the ultrasonic treatment time is 40-60 min.
As a preferred embodiment, the drying conditions are: drying at 160-200 deg.c for 10-12 hr. The active carbon and magnesium phosphate double salt effective load can be realized at a higher temperature, and the stability characteristics of the composite material are enhanced.
The invention also provides a magnesium phosphate double salt-activated carbon composite material, which is obtained by the preparation method.
The magnesium phosphate double salt-activated carbon composite material takes activated carbon as a carrier material, has the characteristics of high specific surface area, high porosity, good plasticity and the like, and the magnesium phosphate double salt active component with special affinity to potassium ions is uniformly loaded on the activated carbon carrier, so that the specific surface area can be increased, more active adsorption sites are exposed, the adsorption capacity to potassium ions is improved, and the adsorption selectivity, stability and service life of the composite material to potassium ions are increased.
The invention also provides application of the magnesium phosphate double salt-activated carbon composite material as an adsorption material applied to potassium ion adsorption in a solution system.
The magnesium phosphate double salt-activated carbon composite material has strong affinity to potassium ions in a solution and strong adsorption capacity, so that the potassium ions can be efficiently enriched in the adsorption material in a short time in a solution system, and the removal and extraction of potassium components in the solution are realized.
As a preferred embodiment, the conditions of the adsorption are: the temperature is 40-60 ℃ and the time is 30-60 min; the stirring speed is 150-200 r/min. Under the preferential adsorption condition, the surface site of the adsorption material can be fully combined with the potassium component, so that the efficient enrichment of the potassium component in the solution is realized, the adsorption reaction is influenced by the external diffusion and the internal diffusion rate, and the adsorption reaction can be promoted by keeping proper temperature and rotating speed.
As a preferable scheme, the mass concentration ratio of the magnesium phosphate double salt-activated carbon composite material to potassium ions in a solution system is 0.5-0.8:1, and the dosage condition can effectively realize the efficient enrichment of potassium components in the solution.
The magnesium phosphate double salt-activated carbon composite material can be widely applied to separation and extraction of potassium components in solution, can realize high-efficiency enrichment of the potassium components not only for low-concentration potassium components in seawater but also for high-concentration potassium-containing solution, has the characteristics of large adsorption capacity, high activity and the like, is simple and easy to prepare, has economic cost, has wide industrial application value in the market, and provides an important technical means for extraction of the potassium components or removal of the potassium components.
The preparation method of the magnesium phosphate double salt-activated carbon composite material provided by the invention comprises the following specific steps:
step one: preparation of phosphoric acid double salt-activated carbon adsorption material
Magnesium salt, active carbon and a proper amount of hydrogen peroxide are sequentially added into a sodium phosphate or ammonium phosphate inorganic salt solution, and the molar ratio of C, P to Mg in a solution system is controlled to be 0.5-1:0.5-1.2:1, and the excessive content of phosphorus can promote the combination of impurity ions in the solution, so that on one hand, the formation of an adsorption material is influenced, on the other hand, the generated precipitate can be adhered to the material to influence the adsorption performance of a rear-end material, a proper amount of hydrogen peroxide can promote the reaction, the hydrogen peroxide is added in the form of a solution with the concentration of 20-40 wt%, and the addition volume concentration of the hydrogen peroxide in water is 0.2-5%. The pH value of the reaction is controlled between 10 and 13, the temperature is 30-50 ℃, the time is 60-90 min, a magnetic stirring device is used for uniformly rotating at a low speed, under the reaction condition, better combination reaction of two substances can be promoted, the synthesis rate of the adsorption material is about 85 percent, the lower the solubility product is, the easier the generation is based on the solution chemistry principle, the theoretical foundation is laid for simple and effective reaction preparation of the adsorption material, the ultrasonic treatment control time is 40-60 min, the solution components are uniformly dispersed, and the final product is obtained by drying in a drying box under the reaction condition of 160-200 ℃ for 10-12 h.
Step two: efficient extraction of potassium component in solution system
And (3) adding the composite adsorption material obtained in the step (I) into a solution system containing a potassium component, and controlling the mass concentration ratio of the dosage of the adsorption material to potassium ions in the solution to be 0.5-0.8:1. The adsorption process should be controlled at 40-60 ℃ for 30-60 min, and the magnetic stirring device is used to uniformly rotate at 150-200 r/min, and the pH is controlled to be alkalescent. Through the full combination reaction of sodium phosphate/ammonium phosphate and magnesium salt, a large amount of Na is adsorbed in the magnesium phosphate double salt lattice + Or NH 4 + Can be combined with K in solution + Realizing high-efficiency ion exchange. Na (Na) + With NH 4 + Has equal electron number and similar properties. But NH 4 + Charge ratio Na + More dispersed, and NH 4 + Is closer to K + Radius 0.138nm. This feature is also the substitution of the adsorbent material for K from the solution system + Providing important basic conditions, more importantly, when K + Into the crystal lattice of magnesium phosphate complex salt, new phase is gradually formed, and the dissolved complex anions and K + The phases are mutually communicated to form new phase mineral sediment containing potassium. Meanwhile, because the active carbon is loaded, on one hand, the anion field in the grid of the adsorption material is weaker, so that the water and the action among ions and the fully exposed complex anion active sites are specific to K + Plays a critical role in the exchange behavior of the activated carbon, and on the other hand, the carrier function of the activated carbon can furtherPromoting the removal efficiency of the potassium component. And the activity of the adsorption material sites can be increased due to proper heating, so that the effective combination probability and range of the adsorption material sites and potassium components in the solution are increased.
Compared with the prior industrial potassium removal technology, the technical scheme of the invention has the beneficial technical effects that:
at present, the efficient separation and extraction of potassium from a solution system are a great challenge in research, and the key of the invention is to provide a phosphate double salt-activated carbon adsorption material capable of efficiently and selectively removing potassium in the solution, so that the enrichment of potassium components in the solution can be realized economically and cost-effectively under the condition of no other impurities introduced. The method provides magnesium phosphate double salt-activated carbon adsorption material for adsorbing and enriching potassium components in the solution for the first time, and the surface sites of the composite material have high-efficiency affinity adsorption effect on the potassium components in the solution. Compared with the existing method for removing potassium from a solution system by using a chemical precipitation method, an extraction method, an ion exchange adsorption method and the like, the invention of the adsorption material can realize the upgrading of a potassium removing process in industrial application, and the adsorption material has the characteristics of large adsorption capacity, no secondary pollution and the like, is efficient and clean in the whole potassium removing process, is simple to operate, meets the potassium removing process and production under industrial conditions, and has great significance for removing and purifying potassium in the solution. More importantly, the adsorption material has the characteristic of being renewable and can realize the recycling of industrial potassium removal materials.
The preparation method of the magnesium phosphate double salt-activated carbon composite material has the advantages of simple process, convenient operation and low energy consumption, and is beneficial to mass production.
Drawings
Fig. 1 is an XRD pattern of the magnesium phosphate double salt-activated carbon composite material prepared in example 2.
Detailed Description
The following specific examples are intended to further illustrate the present invention, but not to limit the scope of the claims.
Example 1
For the experimental exploration of the economic cost-effective synthesis of the phosphoric acid double salt-activated carbon adsorption material, substances are adsorbed under different conditions and dosages in a chemical reaction systemThe synthesis rate and efficiency are far affected. Adding corresponding reagent and 10ml30% hydrogen peroxide into 500ml water according to the mol ratio of 0.5:0.5:1, 0.8:0.5:1, 0.8:0.8:1, 0.8:1.0:1 and 0.8:1.2:1 of active carbon, controlling the conditions of initial reaction pH to 3, 7, 11 and 13, controlling the reaction temperature to be 50 ℃ for 60min, rotating at a constant speed under the condition of magnetic stirring for 200r/min, uniformly dispersing for 60min through ultrasound, performing solid-liquid separation through a Buchner funnel and a vacuum filter, and drying in a drying oven at 160 ℃ for 12h to obtain the magnesium phosphate double salt-active carbon adsorption material. And weighing the mass of the product by a balance, and calculating the synthesis rate of the adsorption material. Table 1 below shows the synthesis rates of the adsorbent materials under different conditions. From the experimental results, it can be seen that under the condition of ph=11, the reaction with PO 4 3- :Mg 2+ The synthesis rate of the adsorption material gradually rises, and reaches an equilibrium state at 0.8:1, and the use amount of 0.8:0.8:1 is selected for subsequent experimental exploration in consideration of the cost and the phosphate characteristic. The synthesis rate is low under acidic and neutral conditions relative to alkaline conditions, probably because the binding of the ions is greatly hindered in acidic conditions, but the pH cannot be too high and magnesium ions are susceptible to adsorption by hydroxyl groups.
TABLE 1 Synthesis of adsorbent materials under different conditions
C:PO 4 3- :Mg 2+ Initial pH of solution reaction Adsorption material synthesis rate (%)
0.5:0.5:1 10.97 53.25%
0.8:0.5:1 10.96 67.43
0.8:0.8:1 10.93 93.07
0.8:1.0:1 11.06 94.57
0.8:1.2:1 11.02 95.36
0.8:0.8:1 2.97 23.03
0.8:0.8:1 5.97 37.21
0.8:0.8:1 13.10 88.34
Example 2
The molar ratio in 500ml of water is 0.8:0.8:1 activated carbon, ammonium phosphate and magnesium chloride and 10ml of 30% hydrogen peroxide were added, the solubility of the activated carbon being 2mol/L. Controlling the initial pH of the solution reaction to be 11, controlling the reaction temperature to be 50 ℃ and the reaction time to be 60min, rotating at a constant speed under the condition of magnetic stirring of 200r/min, uniformly dispersing for 60min by using ultrasonic waves, performing solid-liquid separation by using a Buchner funnel and a vacuum filter, and drying in a drying oven at 160 ℃ for 12h to obtain the phosphoric acid double salt-activated carbon adsorption material. The solution system with different potassium concentrations is prepared by a laboratory as a study object (0.5 g/L,1g/L,5g/L and 20 g/L), so that the removal effect of the phosphoric acid double salt-activated carbon adsorption material on the different initial potassium concentrations is explored, the pH value of the solution is regulated to 3, 7, 9, 11 and 13 according to the dosage of the adsorption material and the dosage of the agent with the potassium ion mass concentration of 0.8:1 in the solution system with different initial potassium solubility, the adsorption temperature is controlled to 50 ℃, the adsorption time is controlled to 30min, and the solution is uniformly rotated at the speed of 200r/min by a magnetic stirring device. After aging for half an hour, the supernatant in the solution was taken and the measurement of the potassium component in the solution was performed by ICP. Table 2 below shows the effect of removing the potassium component from each solution system. The experimental result shows that the adsorption material has good removal effect on solution systems with different initial concentrations in alkaline environment, and the potassium removal rate is 98.43% for a single low-solubility potassium solution system with 0.5 g/L; for a 20g/L high potassium component solution system, the potassium removal rate was 96.26%. This indicates that the adsorbent material has excellent potassium removal properties. In addition, during the test, the adsorption of the adsorption material for removing potassium is also influenced by the reaction pH condition, and experimental data show that the adsorption material has poor potassium removing effect under acidic and neutral conditions, which is probably because the acidic condition inhibits the affinity of the surface site of the adsorption material with potassium components, so that the potassium removing rate is reduced. In alkaline condition, the surface site activity of the adsorption material is increased, so that more effective adsorption removal possibility is provided for potassium removal.
TABLE 2 variation of Potassium removal Rate and lithium loss Rate in solution System
Concentration of potassium pH of solution Potassium removal Rate (%)
0.5g/L 10.96 98.43
1.0g/L 11.02 97.07
5g/L 10.98 96.57
20g/L 10.97 96.26
1.0g/L 2.93 27.03
1.0g/L 6.97 76.21
1.0g/L 9.00 97.15
1.0g/L 13.10 86.34
Example 3
The solution is prepared by taking lithium mother solution rich in high-concentration potassium component in Sichuan industry and potassium-containing solution in seawater as research treatment objectsThe system has higher potassium concentration and simultaneously has high content of lithium component, and because the lithium and the potassium are in the same main group, the chemical properties are very similar, and if the traditional precipitation method or the evaporative crystallization method is adopted, the effective removal of the potassium component in the solution can not be certainly realized. The molar ratio in 500ml of water is 0.8:0.8:1 activated carbon, ammonium phosphate and magnesium chloride and 10ml of 30% hydrogen peroxide were added, the solubility of the activated carbon being 2mol/L. Controlling the initial pH of the solution reaction to be 11, the reaction temperature to be 50 ℃ and the time to be 60min, rotating at a constant speed under the condition of magnetic stirring at 200r/min, and carrying out solid-liquid separation by a Buchner funnel and a vacuum filter to obtain the phosphoric acid double salt-activated carbon adsorption material. Adding an adsorption material into the lithium mother solution according to the dosage of the adsorption material and the dosage of the medicament with the mass concentration of potassium ions of 0.5:1, 0.8:1 and 1:1, controlling the adsorption temperature to be 50 ℃ and the adsorption time to be 30min, and uniformly rotating at the speed of 200r/min by a magnetic stirring device. After aging for half an hour, the supernatant in the solution was taken and the measurement of the potassium component in the solution was performed by ICP. Table 3 below shows the effect of adsorbing materials to remove potassium components from different solutions at different amounts. Meanwhile, in order to investigate whether the adsorption material has the adsorption effect on other ions with similar properties, the loss of the lithium component under different solution conditions is also measured. As shown in the table below, in the seawater solution system, the adsorption material can effectively realize enrichment of potassium components in seawater, the overall potassium removal rate is 98.75%, and the potassium removal rate in the solution gradually rises along with the increase of the use amount of the adsorption material. At 0.8:1, the overall removal rate reached an equilibrium maximum. More importantly, in the process of removing the potassium component, almost no obvious loss of lithium exists in the adsorption material and K + When the dosage ratio is 1:1, the loss rate of lithium reaches 5.67 percent. This is due to the increased amount of adsorbent material, which increases the probability of free phosphate being combined with the lithium component to some extent, and increases the loss rate of the lithium component. However, in general, the composite adsorption material has unique selective adsorption on the potassium component, is not interfered by ions with similar properties, and simultaneously provides reference significance for removing the potassium component in an actual solution system.
TABLE 3 removal Rate of Potassium component and lithium loss Rate variation in solution System

Claims (8)

1. A preparation method of a magnesium phosphate double salt-activated carbon composite material is characterized by comprising the following steps: adding phosphate, a magnesium source, active carbon and hydrogen peroxide into water, and stirring for reaction to obtain a reaction mixed solution; carrying out ultrasonic treatment on the reaction mixed solution, and sequentially carrying out sedimentation, solid-liquid separation and drying to obtain the catalyst;
the proportion of the active carbon, the phosphate and the magnesium source is measured according to the mol ratio of C, P to Mg of 0.5-1:0.5-1.2:1, and the adding concentration of the active carbon in water is 1-3 mol/L;
the conditions of the stirring reaction are as follows: the pH is controlled to be 10-13, the temperature is 30-50 ℃ and the time is 60-90 min.
2. The method for preparing the magnesium phosphate double salt-activated carbon composite material according to claim 1, which is characterized in that:
the phosphate comprises sodium phosphate salt and/or ammonium phosphate salt;
the magnesium source comprises at least one of magnesium sulfate, magnesium chloride and magnesium oxide.
3. The method for preparing the magnesium phosphate double salt-activated carbon composite material according to claim 1, which is characterized in that: the added volume concentration of the hydrogen peroxide in the water is 0.2% -5%; the hydrogen peroxide is added in the form of a solution with the mass percent concentration of 20-40%.
4. The method for preparing the magnesium phosphate double salt-activated carbon composite material according to claim 1, which is characterized in that: the ultrasonic treatment time is 40-60 min.
5. The method for preparing the magnesium phosphate double salt-activated carbon composite material according to claim 1, which is characterized in that: the drying conditions are as follows: drying at 160-200 deg.c for 10-12 hr.
6. A magnesium phosphate double salt-activated carbon composite material is characterized in that: obtained by the production process according to any one of claims 1 to 5.
7. The use of a magnesium phosphate double salt-activated carbon composite material as claimed in claim 6, characterized in that: the potassium ion adsorbent is applied to potassium ion adsorption in a solution system as an adsorption material.
8. The use of a magnesium phosphate double salt-activated carbon composite material according to claim 7, wherein:
the solution system contains lithium ions and/or sodium ions, and the pH is alkaline;
the conditions of the adsorption are as follows: the temperature is 40-60 ℃, the time is 30-60 min, and the stirring speed is 150-200 r/min.
CN202210280247.8A 2022-03-22 2022-03-22 Magnesium phosphate double salt-activated carbon composite material, preparation method thereof and application thereof as potassium ion adsorption material Active CN114797768B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210280247.8A CN114797768B (en) 2022-03-22 2022-03-22 Magnesium phosphate double salt-activated carbon composite material, preparation method thereof and application thereof as potassium ion adsorption material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210280247.8A CN114797768B (en) 2022-03-22 2022-03-22 Magnesium phosphate double salt-activated carbon composite material, preparation method thereof and application thereof as potassium ion adsorption material

Publications (2)

Publication Number Publication Date
CN114797768A CN114797768A (en) 2022-07-29
CN114797768B true CN114797768B (en) 2023-08-11

Family

ID=82531562

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210280247.8A Active CN114797768B (en) 2022-03-22 2022-03-22 Magnesium phosphate double salt-activated carbon composite material, preparation method thereof and application thereof as potassium ion adsorption material

Country Status (1)

Country Link
CN (1) CN114797768B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005028342A (en) * 2003-07-11 2005-02-03 Taihei Chemical Industrial Co Ltd Adsorbent for purifying water
CN102424914A (en) * 2011-11-29 2012-04-25 中南大学 Method for comprehensively recovering aluminum and potassium from vanadium extraction from stone coal
CN102838111A (en) * 2012-09-25 2012-12-26 滑县大潮林物产有限责任公司 Method for removing potassium from activated carbon of super capacitor
WO2019160982A1 (en) * 2018-02-17 2019-08-22 Lilac Solutions, Inc. Integrated system for lithium extraction and conversion
CN111137909A (en) * 2020-01-14 2020-05-12 中南大学 Method for stepwise recovering lithium and magnesium in salt lake brine

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5587500B2 (en) * 2010-07-09 2014-09-10 リサーチ インスティチュート オブ インダストリアル サイエンス アンド テクノロジー Method for extracting lithium from a lithium-containing solution
US20190062172A1 (en) * 2017-08-30 2019-02-28 Boost Environmental systems Inc. Process for removal or recovery of ammonium nitrogen from wastewater streams

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005028342A (en) * 2003-07-11 2005-02-03 Taihei Chemical Industrial Co Ltd Adsorbent for purifying water
CN102424914A (en) * 2011-11-29 2012-04-25 中南大学 Method for comprehensively recovering aluminum and potassium from vanadium extraction from stone coal
CN102838111A (en) * 2012-09-25 2012-12-26 滑县大潮林物产有限责任公司 Method for removing potassium from activated carbon of super capacitor
WO2019160982A1 (en) * 2018-02-17 2019-08-22 Lilac Solutions, Inc. Integrated system for lithium extraction and conversion
CN111137909A (en) * 2020-01-14 2020-05-12 中南大学 Method for stepwise recovering lithium and magnesium in salt lake brine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Phosphate recovery from aqueous solution through adsorption by magnesium modified multi-walled carbon nanotubes;Shoupei Jiang;《Science of the Total Environment》;第148907(1-10)页 *

Also Published As

Publication number Publication date
CN114797768A (en) 2022-07-29

Similar Documents

Publication Publication Date Title
CN107188330B (en) Method for adsorbing and purifying acidic wastewater
Zhang et al. Phosphorus recovery from wastewater and sewage sludge as vivianite
CN112237897B (en) Layered double-metal-based nano lanthanum material and preparation method and application thereof
CN102220488A (en) Method for separating rare earth from phosphate ore
CN102229506B (en) Method for recovering phosphorus and potassium from urine effluent and producing slow-release composite fertilizer of phosphorus and potassium
CN103599745A (en) Modified calcium silicate and its application in sewage dephosphorization
CN113426402B (en) Preparation method and application of lanthanum-aluminum multi-element composite mineral phosphorus removal material
CN107759036B (en) Treatment method and device for preparing compound fertilizer from sludge
CN113926419B (en) Preparation method of Keggin chain structure aluminum series lithium adsorbent
CN101691250A (en) Adsorbing agent for adsorbing phosphate groups and adsorption method
CN101503217A (en) Preparation and use method of dephosphorization carboxyl functionalized nano Fe2O3 adsorbing agent for wastewater
Zhang et al. Enhanced removal of phosphate from aqueous solution using Mg/Fe modified biochar derived from excess activated sludge: removal mechanism and environmental risk
CN112359232A (en) Ion adsorption type rare earth extraction method using calcium chloride as leaching agent
CN114917873A (en) Preparation method and application of europium-based metal organic framework adsorption material Eu-MOF
CN102390879B (en) Method for simultaneously and selectively removing nitrate and phosphate from secondary biochemical effluent
CN114797781A (en) Preparation method of lanthanum-loaded nitrogen-doped porous carbon-phosphorus adsorption material
CN114768752A (en) Fly ash loaded hydrotalcite-like compound composite adsorbent, preparation method and application
CN110721654A (en) Magnetic crystal/amorphous lanthanum zirconium iron oxide phosphorus removal adsorbent and synthesis method thereof
CN114797768B (en) Magnesium phosphate double salt-activated carbon composite material, preparation method thereof and application thereof as potassium ion adsorption material
CN110681344B (en) Zirconium series nano hybrid material and application method thereof
CN110386633B (en) Denitrification and/or phosphorus removal medicament, preparation thereof and application thereof in wastewater adsorption and combined production of slow release fertilizer
CN109499551B (en) Phosphate-based chelate resin and preparation and uranium-containing wastewater treatment methods thereof
Huang et al. A perspective on molecular recognition technology for recovering critical metals from minerals and processing wastes
US20200087169A1 (en) Methods of removing and recovering phosphorus from aqueous solutions
CN111253943A (en) Passivation repairing agent for cadmium-polluted soil and preparation method and repairing method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant