阅读说明：本技术 一种含钾岩石中钾的提取方法 (Method for extracting potassium from potassium-containing rock ) 是由 薛希仕 俞大伟 徐凤 欧阳光前 陈太奇 孙宾宾 张文志 周友进 邹维维 于 2019-09-16 设计创作，主要内容包括：本发明属于含钾岩石处理技术领域,具体涉及一种含钾岩石中钾的提取方法,包括如下步骤：1)一次煅烧；2)冷却：将一次煅烧产物冷却至室温；3)超声波反应：将冷却产物与酸溶液混合,置于超声波反应釜中控制料温为80-100℃进行反应,反应后固液分离,得到固体；4)微波反应：将超声波反应产物与助剂混合,置于微波反应釜中控制料温为120-130℃进行反应；5)二次煅烧；利用本方法具有提高钾溶出率以及活性的特点,同时可处理多种含钾岩石,减少污水排放和热能消耗,缩短处理时间。(The invention belongs to the technical field of potassium-containing rock treatment, and particularly relates to a method for extracting potassium from potassium-containing rock, which comprises the following steps: 1) primary calcination; 2) and (3) cooling: cooling the primary calcined product to room temperature; 3) ultrasonic reaction: mixing the cooled product with an acid solution, placing the mixture in an ultrasonic reaction kettle, controlling the temperature of the material to be 80-100 ℃ for reaction, and carrying out solid-liquid separation after the reaction to obtain a solid; 4) microwave reaction: mixing the ultrasonic reaction product with an auxiliary agent, and placing the mixture in a microwave reaction kettle to react at the temperature of 120 ℃ and 130 ℃; 5) secondary calcination; the method has the characteristics of improving the dissolution rate and activity of potassium, can treat various potassium-containing rocks, reduces sewage discharge and heat energy consumption, and shortens treatment time.)

1. The method for extracting potassium from potassium-containing rocks is characterized by comprising the following steps of:

1) primary calcination: crushing the potassium-containing rock to 80-200 meshes according to the weight ratio of the potassium-containing rock: bone meal: carbon powder is 100: (1-3) adding bone meal and carbon powder in the proportion of (21-23), and calcining for 0.5-1h at the temperature of 600-;

2) and (3) cooling: cooling the primary calcined product to room temperature;

3) ultrasonic reaction: and (3) mixing the cooled product with an acid solution according to a solid-to-liquid ratio of 1: (1.2-1.5), placing the mixture in an ultrasonic reaction kettle, controlling the material temperature to be 80-100 ℃ to react for 30-50min, and carrying out solid-liquid separation after the reaction to obtain a solid;

4) microwave reaction: mixing the ultrasonic reaction product and an auxiliary agent according to a solid-liquid ratio of 1: (1.3-1.7), placing the mixture in a microwave reaction kettle, controlling the material temperature to be 120-130 ℃, and reacting for 30-50 min;

5) secondary calcination: the microwave reaction product is placed in a kiln and calcined for 60-120min at the temperature of 300-500 ℃.

2. The method as claimed in claim 1, wherein the carbon powder is activated at a ball mill rotation speed of 500-600r/min and a temperature of 60-80 ℃ for 2-3h and then taken out.

3. The method for extracting potassium from potassium-containing rocks as claimed in claim 1, wherein the potassium-containing rocks are composed of the following raw materials in parts by weight: 5-10 parts of illite, 3-8 parts of leucite, 11-16 parts of nepheline, 20-25 parts of muscovite, 4-9 parts of sericite, 30-40 parts of alunite and 50-60 parts of potassium feldspar.

4. The method for extracting potassium from potassium-containing rock as claimed in claim 1, wherein the power of the ultrasonic wave is 700-900w, and the frequency is 25-29 kHz.

5. The method for extracting potassium from potassium-containing rocks according to claim 1, wherein the acid solution is a hydrochloric acid solution having a concentration of 30 to 50%.

6. The method for extracting potassium from potassium-containing rocks as claimed in claim 1, wherein the auxiliary agent is composed of the following raw materials in parts by weight: 3-7 parts of calcium chloride, 1-5 parts of sodium carbonate, 6-10 parts of sodium chloride and 10-15 parts of tartaric acid.

7. The method for extracting potassium from potassium-containing rocks according to claim 1, wherein the microwave power is 5 to 15 kw.

Technical Field

The invention belongs to the technical field of potassium-containing rock treatment, and particularly relates to a method for extracting potassium from potassium-containing rock.

Background

The soluble potassium ore resources in China are deficient and are distributed extremely unevenly, but the reserves of the insoluble potassium-containing rock resources in China are large, so that the effective utilization of the insoluble potassium-containing rock resources is of research significance. According to the utilization process of the water-insoluble clock-containing rock, the utilization method can be divided into three parts:

firstly, the potassium-containing rock is directly applied to farmlands after being ground, but the method has large resource waste, and effective resources cannot be fully utilized;

secondly, a high-temperature roasting method: preparing slow-release potash fertilizer by a fire method: directly mixing potassium feldspar with auxiliary agents such as dolomite, limestone and the like, and sintering at high temperature to produce a citrate-soluble potassium-calcium fertilizer and a silicon compound fertilizer; for example, the phosphorus-potassium composite fertilizer is prepared by calcining serpentine or dolomite for phosphorus-potassium mine as an auxiliary agent at the temperature of 1400 ℃ and 1500 ℃, after the citrate-soluble potassium fertilizer is applied to soil, the citrate-soluble potassium fertilizer is slowly dissolved by organic acid secreted by the roots of plants, and is absorbed by the plants through ion exchange, so that nutrient elements are not easily leached and lost, and are not easily fixed by other compounds in the soil. Respectively grinding potassium feldspar and limestone into fine powder, mixing according to equal proportion, fully mixing, preparing into massive raw material, drying, sintering the dried raw material block in a high-temperature furnace at 1200 ℃ for 30min, wherein the potassium dissolution rate can reach more than 97.1 percent, and citric acid soluble potassium produced by the method can be slowly and completely dissolved out and absorbed by plants; ② sintering method. Korea Chilobrachys and the like utilize CaCl₂The potassium feldspar serving as an additive is sintered with the potassium feldspar, so that the reaction temperature is obviously reduced, the sintering temperature is 900 ℃ at most, and the potassium dissolution rate is over 90-95%; however, the high-temperature roasting method has low utilization rate of potassium because the product produced by the method is citrate soluble potassium, and because elements such as silicon, aluminum, iron and the like in potassium-containing rocks remain in fertilizers and cannot be absorbed by plants, the method is easy to cause desertification of soil, so that the method has the advantages of low yield, high yield and low costThe application of potash fertilizer produced by the method is greatly limited.

Thirdly, a wet chemical method: firstly, a pressure heating method: various leaching agents are used for decomposing potassium feldspar to prepare soluble potassium salt at the temperature of 150-500 ℃ and under the pressure of 0.3-6.1MPa, but the pressure is large, the investment cost is high, and the industrialization is difficult; ② a thermal decomposition water immersion method: the method comprises the steps of carrying out thermal decomposition reaction on potassium feldspar and an auxiliary agent at the temperature of 600-1200 ℃ to generate water-soluble potassium salt, and then adding water to extract and separate the potassium salt. Common auxiliary agents are fluoride, CaO and CaCO₃、CaSO₄Soda ash, caustic soda, etc.; qiulong et al uses potassium feldspar (7.5%) and apatite (10.25%) and mixes them, and uses wet extraction to remove water from the apatite, then adds CaCO₃And a small amount of additive, thermally decomposing for 2h at 900-950 ℃, and leaching potassium sulfate with water, wherein the potassium decomposition rate can reach 90-93%; through analysis, the composition of the residue is similar to that of cement clinker, and the residue can be directly used as cement; mahongwen, etc. mixes the insoluble potassium-bearing rock with soda ash or caustic soda according to a certain proportion, then sinters at the middle temperature of 750-850 ℃, then takes the caustic soda as the ingredient, and carries out hydrothermal extraction at the temperature of 98 ℃, thus preparing the potassium carbonate suitable for the production of the electronic industry; but the wet chemical method has serious raw material waste, long production period and difficult discharge of byproduct sewage.

Patent No. CN201610907570.8 discloses a method for preparing a low-silicon X-type molecular sieve by melting and activating potassium-containing rock with NaCO-NaOH mixed alkali, but the method has strict requirements on the contents of potassium oxide, silicon oxide, aluminum oxide, sodium oxide and ferrous oxide in the potassium-containing rock, so that the components of a treated object need to be detected during treatment, and the control difficulty is high.

Disclosure of Invention

The invention provides a method for extracting potassium from potassium-containing rocks to solve the technical problems.

The method is realized by the following technical scheme:

a method for extracting potassium from potassium-containing rocks comprises the following steps:

1) primary calcination: crushing the potassium-containing rock to 80-200 meshes according to the weight ratio of the potassium-containing rock: bone meal: carbon powder is 100: (1-3) adding bone meal and carbon powder in the proportion of (21-23), and calcining for 0.5-1h at the temperature of 600-;

2) and (3) cooling: cooling the primary calcined product to room temperature;

3) ultrasonic reaction: and (3) mixing the cooled product with an acid solution according to a solid-to-liquid ratio of 1: (1.2-1.5), placing the mixture in an ultrasonic reaction kettle, controlling the material temperature to be 80-100 ℃ to react for 30-50min, and carrying out solid-liquid separation after the reaction to obtain a solid;

4) microwave reaction: mixing the ultrasonic reaction product and an auxiliary agent according to a solid-liquid ratio of 1: (1.3-1.7), placing the mixture in a microwave reaction kettle, controlling the material temperature to be 120-130 ℃, and reacting for 30-50 min;

5) secondary calcination: the microwave reaction product is placed in a kiln and calcined for 60-120min at the temperature of 300-500 ℃.

The carbon powder is activated for 2-3h at the ball mill rotation speed of 500-600r/min and the temperature of 60-80 ℃ and then taken out.

The potassium-containing rock is composed of the following raw materials in parts by weight: 5-10 parts of illite, 3-8 parts of leucite, 11-16 parts of nepheline, 20-25 parts of muscovite, 4-9 parts of sericite, 30-40 parts of alunite and 50-60 parts of potassium feldspar.

The power of the ultrasonic wave is 700-900w, and the frequency is 25-29 kHz.

The acid solution is a hydrochloric acid solution with the concentration of 30-50%.

The auxiliary agent comprises the following raw materials in parts by weight: 3-7 parts of calcium chloride, 1-5 parts of sodium carbonate, 6-10 parts of sodium chloride and 10-15 parts of tartaric acid.

The microwave power is 5-15 kw.

Has the advantages that:

from the mineralogical perspective, common water-insoluble potassium-containing rocks mainly comprise potash feldspar, biotite, leucite, illite, glauconite, alunite and the like, and the molecular formulas and the potassium oxide contents of various water-insoluble potassium-containing rocks are shown in table 1:

TABLE 1

By utilizing various minerals with different structures, the minerals can be mutually activated by utilizing the characteristics of different structures and different component contents, so that the migration of metal ions is improved; the application utilizes the bone meal and the carbon powder to improve the melting characteristic of the minerals, so that the soluble potassium is quickly dissolved out.

The invention utilizes the ultrasonic effect to change the mineral structure, combines tartaric acid as a crystal modifier, and coordinates the exchange effect of calcium chloride, sodium carbonate and sodium chloride to fully dissolve soluble potassium to change partial insoluble potassium, utilizes the microwave treatment and the acid action to activate components such as potassium, silicon, aluminum and the like in the mineral, and finally combines the calcination treatment to further dissolve the potassium, and utilizes the liquid gasification effect to improve the activity of the dissolved potassium, thereby improving the utilization rate of the potassium.

In conclusion, the method has the characteristics of improving the dissolution rate and activity of potassium, can treat various potassium-containing rocks, reduce sewage discharge and heat energy consumption, shorten the total treatment time, is simple and easy to control, and reduces the calcination temperature and time.

Detailed Description

The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.