CN-122010167-A - Method for preparing high-purity gallium tetrachloride based on continuous flow micro-reaction

Abstract

The invention discloses a method for preparing high-purity gallium tetrachloride based on continuous flow micro-reaction, which relates to the technical field of rare metal compound preparation, and the method takes gallium-containing solid recycle as a raw material to prepare the high-purity gallium tetrachloride through steps of crushing leaching, extraction purification, back extraction crystallization, continuous flow chlorination and the like in sequence; the method is characterized by comprising the steps of adopting a composite extractant prepared by esterification reaction of a main extractant and a synergistic complex component through a dehydration condensing agent, extracting leaching liquid with high selectivity to realize high-efficiency separation of impurities such as gallium, iron, aluminum and the like, and then placing the obtained high-purity gallium precursor in a continuous flow micro-reaction container to carry out chlorination reaction with chlorine. The method uses the waste material to replace high-purity gallium metal, greatly reduces the cost, ensures the high purity of the raw materials by the composite extractant, ensures the safety, the high efficiency and the controllability of the chlorination process by the continuous flow micro-reaction technology, and is suitable for the large-scale production of high-purity gallium tetrachloride.

Inventors

• TANG ZHIYONG
• CHENG BO
• LI WEN

Assignees

• 株洲火炬安泰新材料有限公司

Dates

Publication Date

20260512

Application Date

20260312

Claims (10)

1. 1. A method for preparing high-purity gallium tetrachloride based on continuous flow micro-reaction is characterized by comprising the following steps of; s1, taking a gallium-containing solid recycle, crushing and grinding; s2, leaching the crushed and ground gallium-containing solid recycle by adopting an acid solution to obtain a gallium-containing leaching solution; S3, extracting and purifying the leaching solution by adopting an organic solvent to obtain a load The organic phase containing a complex extractant; s4, back-extracting the load by using low-concentration acid liquor Is used for the preparation of a liquid crystal display, to obtain a high purity Is a stripping solution of (2); s5, evaporating and crystallizing the strip liquor obtained in the step S4 to obtain a high-purity gallium precursor; s6, introducing the high-purity gallium precursor into a continuous flow micro-reaction container for chlorination reduction reaction to generate the gallium tetrachloride; s7, separating and purifying the reaction product obtained in the step S6 to obtain the high-purity gallium tetrachloride.
2. 2. The method for preparing high-purity digallium tetrachloride based on continuous flow micro-reaction according to claim 1, wherein in step S1, the gallium-containing solid recycle is selected from one of gallium arsenide waste, gallium nitride waste, or copper indium gallium selenide photovoltaic waste.
3. 3. The method for preparing high purity digallium tetrachloride based on continuous flow micro-reaction according to claim 1, wherein in step S3, the complex extractant comprises a main extractant and a synergistic complex component.
4. 4. A method for preparing high purity digallium tetrachloride based on continuous flow micro-reaction according to claim 3, characterized in that: The main extractant is at least one selected from phosphoric acid extractant, phosphonic acid extractant and amine extractant; And/or the synergistic complex component is at least one selected from beta-diketone compounds, hydroxycarboxylic acid compounds, amino acid compounds and nitrogen-containing heterocyclic compounds.
5. 5. The method for preparing high-purity digallium tetrachloride based on continuous flow micro-reaction according to claim 3 or 4, wherein the preparation method of the composite extractant is as follows: mixing the main extractant and the synergistic complex component (14-19): 1-6 by volume ratio in an organic diluent, and adding a dehydration condensing agent for esterification reaction to obtain the product.
6. 6. The method for preparing high-purity gallium tetrachloride based on continuous flow micro-reaction according to claim 5, wherein the dehydration condensing agent is one selected from dicyclohexylcarbodiimide and diisopropylcarbodiimide.
7. 7. The method for preparing high purity digallium tetrachloride based on continuous flow micro-reaction according to claim 1, wherein in step S5, the high purity gallium precursor is anhydrous gallium chloride, gallium oxide, organic complex solid of gallium, or a combination thereof.
8. 8. The method for preparing high-purity digallium tetrachloride based on continuous flow micro-reaction according to claim 1, wherein in step S4, the low-concentration acid solution is a hydrochloric acid solution having a concentration in the range of 0.5 to 2.0 mol/L.
9. 9. The method for preparing high-purity digallium tetrachloride based on continuous flow micro-reaction according to claim 1, wherein in step S6, the continuous flow micro-reaction vessel is a micro-channel reactor or a tubular reactor.
10. 10. The method for preparing high-purity digallium tetrachloride based on continuous flow micro-reaction according to claim 9, wherein: The continuous flow micro-reaction container is made of hastelloy or quartz; and/or lining the continuous flow microreaction vessel with a fluoropolymer material.

Description

Method for preparing high-purity gallium tetrachloride based on continuous flow micro-reaction Technical Field The invention relates to the technical field of rare metal compound preparation, in particular to a method for preparing high-purity gallium tetrachloride based on continuous flow micro-reaction. Background High-purity gallium chloride is a key precursor for preparing third-generation semiconductor materials such as gallium arsenide, gallium nitride and the like. At present, the industrial production of high-purity gallium tetrachloride mainly adopts a direct chlorination method, namely, high-purity (usually more than or equal to 99.99%) gallium metal is taken as a raw material and reacts with chlorine at high temperature. The method has the obvious defects that: firstly, the high-purity gallium metal is extremely expensive, so that the production cost is high; Secondly, the chlorination reaction of gallium metal releases heat severely, and the traditional kettle-type reactor has the problems of low heat and mass transfer efficiency, easiness in local overheating, multiple side reactions, large potential safety hazard and the like, and the quality and consistency of products are difficult to control. To reduce reliance on virgin metallic gallium, industry has begun to focus on the recovery of gallium from gallium-containing solid waste. However, the recycled materials have complex components and are often accompanied by a large amount of impurity ions such as iron (Fe), aluminum (Al), copper (Cu), and the like, and the chemical properties and the likeSimilarly, separation and purification are extremely difficult. The traditional separation methods such as precipitation, extraction and the like have limited selectivity, and the gallium intermediate meeting the requirement of semiconductor grade purity is difficult to obtain. If the crude product with low purity is directly chloridized, the subsequent purification process is long, the yield is low, and the purity of the final product is difficult to guarantee. Therefore, the development of the method for directly preparing the ultra-high purity gallium tetrachloride can efficiently and selectively extract the gallium from the complex waste material, is coupled with a safe and efficient conversion process, and has important significance for reducing the cost of the semiconductor raw material and realizing the recycling of resources. Disclosure of Invention The invention aims to provide a method for preparing high-purity gallium tetrachloride based on continuous flow micro-reaction, which solves the problems mentioned in the background art. The invention is realized in such a way that a method for preparing high-purity gallium tetrachloride based on continuous flow micro-reaction comprises the following steps of; s1, taking a gallium-containing solid recycle, crushing and grinding; s2, leaching the crushed and ground gallium-containing solid recycle by adopting an acid solution to obtain a gallium-containing leaching solution; S3, extracting and purifying the leaching solution by adopting an organic solvent to obtain a load The organic phase containing a complex extractant; s4, back-extracting the load by using low-concentration acid liquor Is used for the preparation of a liquid crystal display, to obtain a high purityIs a stripping solution of (2); s5, evaporating and crystallizing the strip liquor obtained in the step S4 to obtain a high-purity gallium precursor; s6, introducing the high-purity gallium precursor into a continuous flow micro-reaction container for chlorination reduction reaction to generate the gallium tetrachloride; s7, separating and purifying the reaction product obtained in the step S6 to obtain the high-purity gallium tetrachloride. In the further technical scheme, in the step S1, the gallium-containing solid recycle is selected from one of gallium arsenide waste, gallium nitride waste or copper indium gallium selenium photovoltaic waste. In a further technical scheme of the invention, in the step S3, the composite extractant comprises a main extractant and a synergistic complex component. The main extractant is at least one selected from phosphoric acid extractant, phosphonic acid extractant and amine extractant; And/or the synergistic complex component is at least one selected from beta-diketone compounds, hydroxycarboxylic acid compounds, amino acid compounds and nitrogen-containing heterocyclic compounds. The preparation method of the composite extractant comprises the following steps: mixing the main extractant and the synergistic complex component (14-19): 1-6 by volume ratio in an organic diluent, and adding a dehydration condensing agent for esterification reaction to obtain the product. The further technical scheme is that the dehydration condensing agent is selected from dicyclohexylcarbodiimide and diisopropylcarbodiimide. In the step S5, the high-purity gallium precursor is anhydrous gallium chloride, gallium oxide,