CN114797768A - Magnesium phosphate double salt-activated carbon composite material, preparation method thereof and application of composite material as potassium ion adsorption material - Google Patents

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

Info

Publication number
CN114797768A
CN114797768A CN202210280247.8A CN202210280247A CN114797768A CN 114797768 A CN114797768 A CN 114797768A CN 202210280247 A CN202210280247 A CN 202210280247A CN 114797768 A CN114797768 A CN 114797768A
Authority
CN
China
Prior art keywords
activated carbon
potassium
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.)
Granted
Application number
CN202210280247.8A
Other languages
Chinese (zh)
Other versions
CN114797768B (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

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid 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
    • B01J20/048—Solid 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24—Treatment 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working 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
    • C22B7/006—Wet processes
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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

Description

Magnesium phosphate double salt-activated carbon composite material, preparation method thereof and application of composite material 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 an 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 for supplementing or lacking crops in growth, has a very important position in agricultural production in China, and is also widely applied to industrial production of paint, pigment, glass, pharmacy, leather and the like. One of the more serious potassium-deficient areas in the world of China. Potassium is used as a non-renewable resource, the reserve is deficient, the occupied proportion is very low, the exploitation amount is limited, potassium used in the industry depends on import for a long time, and the development of the industry is greatly limited. The mineral substance of the natural silicate mineral is far from providing the potassium component, and compared with other material components, the mineral substance has rich potassium ion content in the ocean, and is an important way for effectively obtaining the potassium material.
To date, efficient separation and extraction of potassium from solution systems based on the introduction of impurities has been a major technical challenge. For example, the extraction of potassium from seawater with complex chemical resource components and variable environment is a key point of research and is also a difficult point. Evaporative crystallization is the most classical process technology route in extracting potassium from seawater. But the potassium salt prepared by the evaporation crystallization method has the defects of low purity, longer production period, high energy consumption, low efficiency and the like, so that the industrial requirement is difficult to meet. 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 make the potassium salt be insolublePrecipitating in a form, and purifying the precipitate to obtain the high-purity potassium salt. Sodium tetraphenylborate is, for example, a para-K + The precipitant has high selectivity and can completely precipitate with potassium; although the chemical precipitation method can obtain potassium salt with high purity, sodium tetraphenylborate is too expensive and economically unfeasible, so that the key point is to find a safe, cheap, environment-friendly and recyclable precipitator. The liquid membrane extraction method utilizes the difference of potassium distribution between an extractant phase and a water phase and a seawater phase to achieve the purpose of thickening or separating specific substances, and the commonly used extractants comprise isoamyl alcohol, a mixture of organic acid and phenol, polycyclic ether, n-butyl alcohol and the like.
Currently, the ion exchange adsorption method is a main measure for selectively separating target elements in a clean and efficient manner, and the principle thereof is that the ion exchange method is carried out by taking an ion exchanger as a carrier, and when the ion exchanger is contacted with liquid, ions available for exchange in the ion exchanger are exchanged with ions in the liquid, so that the ion enrichment is achieved. The key point of the method is to select a cheap, environment-friendly and efficient ion exchanger, and the common ion exchange method mainly comprises two aspects, on one hand, the inorganic ion exchanger is used as a potassium component removal exchange medium to realize the enrichment of solution potassium. The japanese scholars have developed many research results, and the synthesized zirconium tungstate and phosphate has the advantages of good selectivity and high stability for potassium components, but the zirconium compound is expensive, so the economic requirement cannot be over, and the industrialization cannot be realized until now. On the other hand, natural substances have high-efficiency selective enrichment adsorption on potassium components in the solution. For example, it is reported that the ionic sieve and natural zeolite have high selective adsorption performance for potassium ions in seawater, but the adsorption removal effect for a solution system with high potassium ion concentration still needs to be enhanced.
It can be said that how to extract the potassium component with high efficiency and selectivity has become the bottleneck problem of the solution potassium extraction technology development, develop a potassium extraction technology with low price and high efficiency and selectivity, is an important way of enriching potassium in the solution system, more importantly, not only in the field of extracting potassium from seawater, but also in the field of potassium purification in systems such as lithium ore leachate purification lithium and the like, and if the high efficiency separation of lithium and potassium components with similar properties to main groups in the field of lithium extraction is realized, the method has profound significance for the upgrade and innovation of the lithium extraction technology, and also lays an important foundation for the purification and smelting of rear-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 invention aims to provide the magnesium phosphate complex 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 purpose of the invention is to provide a preparation method of the magnesium phosphate double salt-activated carbon composite material, which has the advantages of simple process, convenient operation, low energy consumption and contribution to large-scale production.
The third purpose of the invention is to provide an application of the magnesium phosphate complex salt-activated carbon composite material, the magnesium phosphate complex salt-activated carbon composite material is used as an adsorption material to be applied to potassium ion adsorption in a solution system, high selectivity and high enrichment capacity are shown, the adsorption material can be recycled and reused, and the application method has strong application, high efficiency and low cost, and is particularly suitable for industrial production of potassium seawater extract or lithium and potassium separation and the like.
In order to achieve the technical purpose, the invention provides a preparation method of a magnesium phosphate complex 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 (3) carrying out ultrasonic treatment on the reaction mixed solution, and then sequentially carrying out sedimentation, solid-liquid separation and drying to obtain the catalyst.
The technical scheme of the invention utilizes the activated carbon as a carrier, and the phosphate and the magnesium salt generate the magnesium phosphate double salt under the promotion action of the 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 ingredients of the magnesium phosphate double salt, thereby greatly improving the adsorption capacity and the adsorption selectivity of the composite material. Meanwhile, the composite material takes the magnesium phosphate double salt as an adsorption active center of potassium ions, has specific activity affinity to potassium, can realize high-efficiency selective enrichment of potassium components in the solution, and effectively realizes the aim of extracting or removing potassium from the solution without increasing impurity elements of the solution.
As a preferable embodiment, the phosphate includes a sodium phosphate salt and/or an ammonium phosphate salt, and further preferably at least one of sodium pyrophosphate, trisodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, and ammonium phosphate. The phosphate has the main function of ionizing phosphate ions by hydrolysis in a solution system, theoretically, the water-soluble phosphate meets the requirements of the technical scheme of the invention, and the most preferable is ammonium phosphate from the comprehensive consideration of cost, water solubility and the like. According to the technical scheme, sodium phosphate salt/ammonium phosphate salt and magnesium-containing salt are fully combined to react, and a large amount of Na can be adsorbed in the crystal lattices of the magnesium phosphate complex salt + Or NH 4 + Can be mixed with K in solution + Effecting efficient ion exchange, Na + And NH 4 + With equal electron numbers, similar properties, but NH 4 + Charge ratio Na + More dispersed, and NH 4 + Has an ionic radius closer to K + Is 0.138nm, it is therefore more preferred to use ammonium phosphate salts for the synthesis of magnesium phosphate double salts, which is also characterized by the replacement of the adsorption material from the solution system by K + Provides important basic conditions, and more importantly, when K is + Enters the crystal lattice of the magnesium phosphate complex salt to gradually form a new phase, and the dissolved complex anion and K + The phases are communicated to form a 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 salts containing magnesium ions, theoretically, magnesium salts which are easily soluble in water are all suitable for the technical scheme of the invention, and magnesium chloride is preferably used in consideration of economic cost and disposal efficiency.
Preferably, the ratio of the activated carbon, the phosphate and the magnesium source is 0.5-1: 0.5-1.2: 1 in terms of the molar ratio of C, P to Mg. If too high a phosphate concentration is used, phosphate and other impurity metal ions, such as heavy metal ions of iron, copper and the like, are promoted to be combined and adhered to the surface of the adsorption material, which obviously reduces the adsorption of the adsorption material on potassium components in the solution, and the use of high-dosage activated carbon increases the preparation cost of the composite material, reduces the adsorption capacity of the adsorption material and increases the use cost. More preferably, the ratio of the activated carbon, the phosphate and the magnesium source is measured in a molar ratio of C, P to Mg of 0.8 to 1: 1. As a preferable scheme, the adding concentration of the activated carbon in water is 1-3 mol/L. The adding concentration of the activated carbon in the water is most preferably 1.5-2.5 mol/L.
Preferably, the hydrogen peroxide is added in the form of a solution with a concentration of 20-40 wt%. The volume concentration of the hydrogen peroxide added into the water is 0.2-5%. The addition of a low concentration of hydrogen peroxide helps to promote the reaction bonding of the active components in the solution system while increasing the rate of reaction.
As a preferred embodiment, 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. Better binding of reagents can be facilitated under preferred reaction conditions.
As a preferable scheme, the time of ultrasonic treatment is 40-60 min.
As a preferred embodiment, the drying conditions are: drying for 10-12 h at 160-200 ℃. The active carbon and magnesium phosphate double salt effective load can be realized at a higher temperature, and the stability characteristic of the composite material is enhanced.
The invention also provides a magnesium phosphate complex salt-activated carbon composite material, which is obtained by the preparation method.
The magnesium phosphate complex salt-active carbon composite material takes the active carbon as a carrier material, has the characteristics of high specific surface area, high porosity, good plasticity and the like, and the active component of the magnesium phosphate complex salt with special affinity to potassium ions is uniformly loaded on the active carbon carrier, so that the specific surface can be increased, more active adsorption sites are exposed, the adsorption capacity to the potassium ions is improved, and the adsorption selectivity, the stability and the service life of the composite material to the potassium ions are increased.
The invention also provides an application of the magnesium phosphate double salt-activated carbon composite material, which is used as an adsorption material for 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 an adsorption material in a solution system in a short time, and the removal and extraction of potassium components in the solution are realized.
As a preferred scheme, the adsorption conditions are as follows: the temperature is 40-60 ℃, and the time is 30-60 min; the stirring speed is 150-200 r/min. Under the optimal adsorption condition, surface sites of the adsorption material can be ensured to be fully combined with potassium components, the efficient enrichment of the potassium components in the solution is realized, meanwhile, the adsorption reaction is influenced by the rates of external diffusion and internal diffusion, and the adsorption reaction can be promoted by keeping proper temperature and rotation 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 condition of the dosage can effectively realize the efficient enrichment of potassium components in the solution.
The magnesium phosphate complex salt-activated carbon composite material can be widely applied to separation and extraction of potassium components in a solution, can realize efficient 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 complex salt-activated carbon composite material provided by the invention comprises the following specific steps:
the method comprises the following steps: preparation of phosphate double salt-active carbon adsorption material
The magnesium salt, the activated carbon and a proper amount of hydrogen peroxide are sequentially added into a sodium phosphate salt or ammonium phosphate inorganic salt solution, the molar ratio of C, P to Mg in a solution system is controlled to be 0.5-1: 0.5-1.2: 1, the combination of impurity ions in the solution is promoted by the excessively high phosphorus concentration, the formation of an adsorbing material is influenced, the generated precipitate is adhered to the material, the adsorption performance of the rear-end material is influenced, the reaction can be promoted by the proper amount of hydrogen peroxide, 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 to be 10-13, 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 adsorbing material is about 85%, based on the solution chemical principle, the lower the solubility product is, the easier the adsorbing material is to generate, the theoretical basis is laid for simple and effective reaction preparation of the adsorbing material, meanwhile, the ultrasonic treatment control time is 40-60 min, so that the solution components are uniformly dispersed, and the drying is carried out in a drying oven for 10-12 h under the reaction condition of 160-200 ℃ to obtain the final product.
Step two: efficient extraction of potassium component in solution system
And (3) adding the composite adsorbing material obtained in the step one into a solution system containing a potassium component, and controlling the ratio of the using amount of the adsorbing material to the mass concentration of potassium ions in the solution to be 0.5-0.8: 1. The temperature in the adsorption process is controlled to be 40-60 ℃, the time is 30-60 min, a magnetic stirring device is used for uniformly rotating at the speed of 150-200 r/min, and the pH is controlled to be alkalescent. Through the full combination reaction of sodium phosphate salt/ammonium phosphate salt and magnesium-containing salt, a large amount of Na can be adsorbed in the crystal lattice of the magnesium phosphate complex salt + Or NH 4 + Can be mixed with K in solution + And high-efficiency ion exchange is realized. Na (Na) + And NH 4 + Has equal electron number and similar properties. But NH 4 + Charge ratio Na + More dispersed, and NH 4 + Has an ionic radius closer to K + Radius of 0.138 nm. This feature also replaces K with the adsorbent material from the solution system + Provides important basic conditions, and more importantly, when K is + Entering into crystal lattices of magnesium phosphate complex salt to gradually form a new phase, and the dissolved complex anion and K + The phases are communicated to form a new phase mineral sediment containing potassium. Meanwhile, due to the loading of the activated carbon, on one hand, the anion field in the lattice of the adsorbing material is weak, so that the water and the action among ions and the fully exposed complex anion active sites are opposite to K + The exchange behavior plays an important role, and on the other hand, the carrier function of the activated carbon can further promote the removal efficiency of the potassium component. And due to proper heating, the activity of the adsorption material sites can be increased, and the effective combination probability and range of the potassium component 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 is a great challenge in research, and the key point of the invention is to provide a phosphate double salt-activated carbon adsorption material capable of efficiently and selectively removing potassium in a solution, so that the enrichment of potassium components in the solution can be realized economically and efficiently at low cost under the condition of not introducing other impurities. The method firstly provides a magnesium phosphate double salt-activated carbon adsorption material to adsorb potassium components in the enriched solution, and 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 utilizing 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 the potassium removal process in industrial application, the adsorption material has the characteristics of large adsorption capacity, no secondary pollution and the like, is efficient and clean in the whole potassium removal process, is simple to operate, meets the potassium removal 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 renewable use, 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 large-scale production.
Drawings
Fig. 1 is an XRD pattern of the magnesium phosphate double salt-activated carbon composite prepared in example 2.
Detailed Description
The following specific examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
The method has the advantages that the experimental exploration for the efficient synthesis of the phosphate double salt-activated carbon adsorption material with economic cost has far influence on the synthesis rate and efficiency of substances under different conditions and dosage in a chemical reaction system. Adding corresponding reagents and 10ml of 30% hydrogen peroxide into 500ml of water according to the molar ratio of the activated carbon to the ammonium phosphate to the magnesium sulfate of 0.5:0.5:1, 0.8:0.8:1, 0.8:1.0:1 and 0.8:1.2:1 respectively, controlling the molar concentration of the activated carbon in the solution to be 2mol/L, controlling the conditions of initial reaction pH to be 3, 7, 11 and 13, 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 ultrasonic, carrying out solid-liquid separation by a Buchner funnel and a vacuum filter, and drying in a drying box for 12h at 160 ℃ to obtain the magnesium phosphate double salt-activated carbon adsorption material. And the mass of the product is weighed by a balance, and the synthesis rate of the adsorbing material is calculated. Table 1 below shows the synthesis rate of the adsorbent under different conditions. From the results of the experiment, it was found that under the condition of pH 11, PO was accompanied by 4 3- :Mg 2+ The synthesis rate of the adsorbing material gradually rises, the synthesis rate reaches an equilibrium state at 0.8:1, and the dosage of 0.8:0.8:1 is selected for subsequent experimental exploration in consideration of the cost and the characteristics of phosphate radicals. Compared with the alkaline environment, the synthesis rate under acidic and neutral adjustment is low, probably because the combination of ions is greatly hindered in the acidic environment, but the pH cannot be too high, and the magnesium ions are easily influenced by the adsorption of hydroxide radicals.
TABLE 1 Synthesis of adsorbent under different conditions
C:PO 4 3- :Mg 2+ Initial pH of solution reaction Adsorbent 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
In 500ml of water, the molar ratio is 0.8:0.8:1 adding activated carbon, ammonium phosphate and magnesium chloride and 10ml of 30% hydrogen peroxide, wherein the solubility of the activated carbon is 2 mol/L. Controlling the initial pH value of the solution to be 11, controlling the reaction temperature to be 50 ℃ and the time to be 60min, uniformly rotating 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 box at 160 ℃ for 12h to obtain the phosphate double salt-activated carbon adsorption material. The method is characterized in that a laboratory self-made solution system with different potassium concentrations is taken as a research object (0.5g/L, 1g/L, 5g/L and 20g/L) to explore the removal effect of the phosphate double salt-activated carbon adsorption material on different initial potassium concentrations, the pH value of the solution is adjusted to be 3, 7, 9, 11 and 13 according to the dosage of the adsorption material and the dosage of a medicament with the potassium ion mass concentration of 0.8:1, the adsorption temperature is controlled to be 50 ℃, the adsorption time is 30min, and the solution is uniformly rotated at the speed of 200r/min through a magnetic stirring device in the solution systems with different initial potassium solubilities. After aging for half an hour, the supernatant in the solution was taken and the potassium component in the solution was measured by ICP. Table 2 below shows the effect of removing the potassium component in each solution system. According to experimental results, the adsorbing material has a good removing effect on solution systems with different initial concentrations in an alkaline environment, and the potassium removing rate is 98.43% for a single low-solubility potassium solution system of 0.5 g/L; for the 20g/L high potassium component solution system, the potassium removal rate is 96.26%. This indicates that the adsorbent material has excellent potassium removal performance. In addition, in the test process, the adsorption and potassium removal of the adsorption material are also influenced by the reaction pH condition, and the experimental data show that the potassium removal effect of the adsorption material is poor under the acidic and neutral conditions, which probably results in the reduction of the potassium removal rate because the affinity of the surface site of the adsorption material and the potassium component is inhibited by the acidic condition. In alkaline conditions, the activity of the surface sites of the adsorbing material is increased, and more effective adsorption and removal possibility is provided for removing potassium.
TABLE 2 variation of potassium removal and lithium loss in the solution system
Concentration of potassium pH of the 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 lithium mother liquor rich in high-concentration potassium components in a certain industry in Sichuan and a potassium-containing solution in seawater are taken as research processing objects, the solution system has high potassium concentration and high-content lithium components, the lithium and potassium are in the same main group, the chemical properties are very similar, and if a traditional precipitation method or an evaporative crystallization method is adopted, the research on effectively removing the potassium components in the solution cannot be realized undoubtedly. In 500ml of water, the molar ratio is 0.8:0.8:1 adding activated carbon, ammonium phosphate and magnesium chloride and 10ml of 30% hydrogen peroxide, wherein the solubility of the activated carbon is 2 mol/L. Controlling the initial pH value of the solution to be 11, the reaction temperature to be 50 ℃, the time to be 60min, carrying out magnetic stirring at a constant speed under the condition of 200r/min, and carrying out solid-liquid separation through a Buchner funnel and a vacuum filter to obtain the phosphate double salt-activated carbon adsorption material. Adding the adsorbing material into the lithium mother liquor according to the dosage of the adsorbing material and the dosage of the potassium ions with the mass concentration of 0.5:1, 0.8:1 and 1:1, controlling the adsorption temperature at 50 ℃, and the adsorption time at 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 potassium component in the solution was measured by ICP. Table 3 below shows the removal of the potassium component from different solutions with different amounts of adsorbent material. Meanwhile, in order to investigate whether the adsorbing material has the same adsorption effect on other ions with similar properties, the loss of the lithium component under different solution conditions is also measured. As can be seen from the following table, in a seawater solution system, the adsorption material can effectively realize the enrichment of potassium components in seawater, the removal rate of the whole potassium is 98.75 percent, and the adsorption material is used along withThe potassium removal rate in the solution gradually increases with the increase of the dosage. At 0.8:1, the overall removal rate reaches the equilibrium maximum. More importantly, during the process of removing the potassium component, lithium is hardly obviously lost, and the lithium is absorbed by the absorbing material and K + When the dosage ratio is 1:1, the loss rate of lithium reaches 5.67%. This is because the increase in the amount of the adsorbent increases the probability of binding of the free phosphate to the lithium component to some extent, increasing the loss rate of the lithium component. However, in general, the composite adsorption material has unique selective adsorption on potassium components and is not interfered by ions with similar properties, and meanwhile, the composite adsorption material also provides reference significance for removing the potassium components in an actual solution system.
TABLE 3 Change in the removal rate of the Potassium component and the lithium loss rate in the solution System
Figure BDA0003557569610000091

Claims (10)

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, activated carbon and hydrogen peroxide into water, and stirring for reaction to obtain a reaction mixed solution; and (3) carrying out ultrasonic treatment on the reaction mixed solution, and then sequentially carrying out sedimentation, solid-liquid separation and drying to obtain the catalyst.
2. The preparation method of the magnesium phosphate double salt-activated carbon composite material according to claim 1, characterized in that:
the phosphate comprises a sodium phosphate salt and/or an 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 or 2, wherein: the proportion of the activated carbon, the phosphate and the magnesium source is measured according to the molar ratio of C, P to Mg of 0.5-1: 0.5-1.2: 1, and the adding concentration of the activated carbon in water is 1-3 mol/L.
4. The preparation method of the magnesium phosphate double salt-activated carbon composite material according to claim 1, characterized in that: the volume concentration of the hydrogen peroxide added into 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%.
5. The preparation method of the magnesium phosphate double salt-activated carbon composite material according to claim 1, characterized in that: 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.
6. The preparation method of the magnesium phosphate double salt-activated carbon composite material according to claim 1, characterized in that: the ultrasonic treatment time is 40-60 min.
7. The preparation method of the magnesium phosphate double salt-activated carbon composite material according to claim 1, characterized in that: the drying conditions are as follows: drying for 10-12 h at 160-200 ℃.
8. The magnesium phosphate double salt-activated carbon composite material is characterized in that: the preparation method of any one of claims 1 to 7.
9. The use of the magnesium phosphate double salt-activated carbon composite material according to claim 8, wherein: the potassium ion adsorbent is used as an adsorbing material for potassium ion adsorption in a solution system.
10. The use of the magnesium phosphate double salt-activated carbon composite material according to claim 9, wherein:
the solution system comprises lithium ions and/or sodium ions, and the pH is alkaline;
the adsorption conditions 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 true CN114797768A (en) 2022-07-29
CN114797768B 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 (7)

* 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
US20130129586A1 (en) * 2010-07-09 2013-05-23 Research Institute Of Industrial Science & Technology Method for economical extraction of lithium from solution including lithium
US20190062172A1 (en) * 2017-08-30 2019-02-28 Boost Environmental systems Inc. Process for removal or recovery of ammonium nitrogen from wastewater streams
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

Patent Citations (7)

* 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
US20130129586A1 (en) * 2010-07-09 2013-05-23 Research Institute Of Industrial Science & Technology Method for economical extraction of lithium from solution including lithium
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
US20190062172A1 (en) * 2017-08-30 2019-02-28 Boost Environmental systems Inc. Process for removal or recovery of ammonium nitrogen from wastewater streams
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 (3)

* Cited by examiner, † Cited by third party
Title
JIA TIAN 等: "Alkali circulating leaching of arsenic from copper smelter dust based on arsenic-alkali efficient separation", 《JOURNAL OF ENVIRONMENTAL MANAGEMENT 》, pages 1 - 10 *
SHOUPEI JIANG: "Phosphate recovery from aqueous solution through adsorption by magnesium modified multi-walled carbon nanotubes", 《SCIENCE OF THE TOTAL ENVIRONMENT》, pages 1 - 10 *
相建海主编: "《中国海情》", 31 December 2002, 北京：开明出版社, pages: 163 *

Also Published As

Publication number Publication date
CN114797768B (en) 2023-08-11

Similar Documents

Publication Publication Date Title
Wang et al. Phosphorus recovery from the liquid phase of anaerobic digestate using biochar derived from iron− rich sludge: a potential phosphorus fertilizer
CN107188330B (en) Method for adsorbing and purifying acidic wastewater
Carrillo et al. Characterization and recovery of phosphorus from wastewater by combined technologies
CN101503217B (en) Preparation and use method of dephosphorization carboxyl functionalized nano Fe2O3 adsorbing agent for wastewater
CN101780421B (en) Ammonia nitrogen adsorbent and preparation method and application method thereof
Zhang et al. Phosphorus recovery from wastewater and sewage sludge as vivianite
RU2547496C2 (en) Magnetic composite sorbent
CN112237897B (en) Layered double-metal-based nano lanthanum material and preparation method and application thereof
CN103861568A (en) Preparation method and application of magnetic chitosan nanometer material
CN102115234A (en) Preparation method of flocculant capable of removing phosphate from red mud
CN113426402B (en) Preparation method and application of lanthanum-aluminum multi-element composite mineral phosphorus removal material
CN103599745A (en) Modified calcium silicate and its application in sewage dephosphorization
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
CN110560012A (en) Method for removing phosphorus in water by using resin-loaded hydrated iron oxide
CN111892229B (en) Method for deeply purifying and efficiently recovering trace phosphorus in biochemical tail water
Kajjumba et al. A review of the application of cerium and lanthanum in phosphorus removal during wastewater treatment: Characteristics, mechanism, and recovery
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
Jia et al. Tri-functional lanthanum-based biochar for efficient phosphorus recovery, bacterial inhibition, and soil fertility enhancement
CN114797768B (en) Magnesium phosphate double salt-activated carbon composite material, preparation method thereof and application thereof as potassium ion adsorption material
CN110106356B (en) Method for separating lithium from salt lake brine by using powder type titanium ion exchanger
CN109851084B (en) Resourceful treatment method for reducing content of ammonia nitrogen, calcium and magnesium ions in manganese-containing wastewater
CN109126684B (en) Preparation method of base iron-loaded mixed ash adsorbent

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