阅读说明：本技术 一种含锗盐酸溶液的回收方法 (Method for recovering germanium-containing hydrochloric acid solution ) 是由 何兴军 崔丁方 李恒方 陈知江 子光平 缪彦美 廖吉伟 朱家义 陈俊肖 于 2020-12-25 设计创作，主要内容包括：本发明公开了一种含锗盐酸溶液的回收方法,涉及化工生产回收技术领域。本发明包括以下步骤：S1：含锗稀盐酸溶液预处理,通过精馏塔余热蒸汽对含锗稀盐酸溶液进行预热；S2：精馏浓缩,将预处理后的含锗稀盐酸溶液输送至精馏塔内进行精馏；S3：氯化蒸馏；S4：精馏水解。本发明采用精馏浓缩,将原料中的水分离出来,得到20%的含锗浓盐酸溶液,再将该溶液进行氯化蒸馏得到粗四氯化锗,粗四氯化锗再水解得到二氧化锗,锗得到高效回收,同时氯离子返回生产进行再利用,且微波技术和超声波技术的引入,极大地改善化学反应环境,解决了现有的碱液中和回收锗的方法,锗的回收率低,形成大量的氯化钠高氯废水,容易污染环境的问题。(The invention discloses a method for recovering a germanium-containing hydrochloric acid solution, and relates to the technical field of chemical production recovery. The invention comprises the following steps: s1: pretreating the germanium-containing dilute hydrochloric acid solution, and preheating the germanium-containing dilute hydrochloric acid solution by using waste heat steam of a rectifying tower; s2: rectifying and concentrating, namely conveying the pretreated germanium-containing dilute hydrochloric acid solution into a rectifying tower for rectification; s3: chlorination distillation; s4: and (5) rectifying and hydrolyzing. The method adopts rectification concentration to separate water from raw materials to obtain a concentrated hydrochloric acid solution containing 20% of germanium, performs chlorination distillation on the solution to obtain crude germanium tetrachloride, hydrolyzes the crude germanium tetrachloride to obtain germanium dioxide, efficiently recovers the germanium, returns chloride ions to production for recycling, and introduces a microwave technology and an ultrasonic technology, thereby greatly improving the chemical reaction environment, solving the problems that the existing method for neutralizing and recovering the germanium by alkali liquor has low recovery rate of the germanium, forms a large amount of sodium chloride high-chlorine wastewater and is easy to pollute the environment.)

1. A method for recovering a germanium-containing hydrochloric acid solution is characterized by comprising the following steps: the method comprises the following steps:

s1: pretreating the germanium-containing dilute hydrochloric acid solution, preheating the germanium-containing dilute hydrochloric acid solution by using waste heat steam of a rectifying tower, starting an ultrasonic generator during preheating, placing the germanium-containing dilute hydrochloric acid solution in an ultrasonic field, and acting on the germanium-containing dilute hydrochloric acid solution through ultrasonic waves to thoroughly break up molecular aggregates;

s2: rectifying and concentrating, namely conveying the pretreated germanium-containing dilute hydrochloric acid solution into a rectifying tower, and rectifying, concentrating and separating to obtain a germanium-containing concentrated hydrochloric acid solution and water;

s3: chlorination distillation, namely conveying the germanium-containing concentrated hydrochloric acid solution into chlorination distillation equipment, starting a microwave generator, heating by microwave, continuously introducing preheated chlorine into the germanium-containing concentrated hydrochloric acid solution for reaction, starting the ultrasonic generator, acting on the germanium-containing concentrated hydrochloric acid solution by ultrasonic waves, performing auxiliary chlorination distillation, and obtaining crude germanium tetrachloride after chlorination distillation;

s4: and (3) rectification hydrolysis, namely conveying the crude germanium tetrachloride into a rectification tower for rectification purification, then carrying out ultrasonic hydrolysis after rectification purification, carrying out centrifugal filtration after hydrolysis, washing and drying to finally obtain the high-purity germanium dioxide.

2. The method according to claim 1, wherein the preheating temperature in S1 is set to 60-70 ℃.

3. The method as claimed in claim 1, wherein the step of S1 comprises subjecting the diluted hydrochloric acid solution containing germanium to ultrasonic treatment with 20-40 kHz ultrasonic wave.

4. The method for recovering the germanium-containing hydrochloric acid solution according to claim 1, wherein in S2, the temperature of the top of the rectification column is controlled to be 92-93 ℃, the temperature of the bottom of the rectification column is controlled to be 114-116 ℃, water is continuously produced at the top of the rectification column, a germanium-containing concentrated hydrochloric acid solution is continuously produced at the bottom of the rectification column, the produced germanium-containing concentrated hydrochloric acid solution contains about 5g/L of germanium and 20-25% of hydrochloric acid, the produced water has the conductivity of 450-500 μ S/cm and the pH value is neutral.

5. The method as claimed in claim 1, wherein the step of S3 comprises subjecting the concentrated hydrochloric acid solution containing germanium to ultrasonic treatment with ultrasonic wave having a frequency of 60-80 kHz.

6. The method as claimed in claim 1, wherein the temperature of the preheated chlorine gas in S3 is 60-65 ℃, the flow rate of the chlorine gas is 450-500L/h, and the temperature during the chlorination distillation is 84-85 ℃.

Technical Field

The invention belongs to the technical field of chemical production recovery, and particularly relates to a recovery method of a germanium-containing hydrochloric acid solution.

Background

High-purity germanium dioxide production usually adopts high-purity germanium tetrachloride to mix with high-purity water and hydrolysises, can produce a large amount of germanium-containing hydrogen chloride solutions after the hydrolysis finishes, this part waste liquid mainly exists with the mixture of the dilute hydrochloric acid that produces after germanium and the reaction, have very strong corrosivity and volatility, constitute very big influence to personnel's health and environment on every side, at present, adopt alkali lye to carry out neutralization recovery germanium mostly, the neutralization process is complicated, need adjust pH, control neutralizer addition speed etc., the rate of recovery of germanium is low, form a large amount of sodium chloride high chlorine waste water, the easy polluted environment, bring serious environmental protection problem.

Therefore, the existing methods for recovering the solution containing germanium hydrochloride cannot meet the requirements of practical use, so that there is a strong need in the market for improved techniques to solve the above problems.

Disclosure of Invention

The invention aims to provide a recovery method of a germanium-containing hydrochloric acid solution, which is characterized in that rectification concentration is adopted, water in raw materials is separated to obtain a germanium-containing concentrated hydrochloric acid solution with the concentration of 20-25%, then chlorination distillation is carried out on the solution to obtain crude germanium tetrachloride, the crude germanium tetrachloride is hydrolyzed again to obtain germanium dioxide, germanium is efficiently recovered, chloride ions return to production for reuse, and the introduction of a microwave technology and an ultrasonic technology greatly improves the chemical reaction environment, solves the problems that the existing method for neutralizing and recovering germanium by alkali liquor is low in recovery rate of germanium, forms a large amount of sodium chloride high-chlorine wastewater, and is easy to pollute the environment.

In order to solve the technical problems, the invention is realized by the following technical scheme:

the invention relates to a method for recovering a germanium-containing hydrochloric acid solution, which comprises the following steps:

s1: pretreating the germanium-containing dilute hydrochloric acid solution, preheating the germanium-containing dilute hydrochloric acid solution by using waste heat steam of a rectifying tower, starting an ultrasonic generator during preheating, placing the germanium-containing dilute hydrochloric acid solution in an ultrasonic field, and acting on the germanium-containing dilute hydrochloric acid solution through ultrasonic waves to thoroughly break up molecular aggregates;

s2: rectifying and concentrating, namely conveying the pretreated germanium-containing dilute hydrochloric acid solution into a rectifying tower, and rectifying, concentrating and separating to obtain a germanium-containing concentrated hydrochloric acid solution and water;

s3: chlorination distillation, namely conveying the germanium-containing concentrated hydrochloric acid solution into chlorination distillation equipment, starting a microwave generator, heating by microwave, continuously introducing preheated chlorine into the germanium-containing concentrated hydrochloric acid solution for reaction, starting the ultrasonic generator, acting on the germanium-containing concentrated hydrochloric acid solution by ultrasonic waves, performing auxiliary chlorination distillation, and obtaining crude germanium tetrachloride after chlorination distillation;

s4: and (3) rectification hydrolysis, namely conveying the crude germanium tetrachloride into a rectification tower for rectification purification, then carrying out ultrasonic hydrolysis after rectification purification, carrying out centrifugal filtration after hydrolysis, washing and drying to finally obtain the high-purity germanium dioxide.

Further, the preheating temperature in the S1 is set to be 60-70 ℃, the temperature of the germanium-containing dilute hydrochloric acid solution is raised, the feeding temperature is increased, the waste heat of the rectifying tower is used for preheating, the waste heat is utilized, the whole rectifying process is more energy-saving, the material separation in the rectifying tower is facilitated, and the kettle steam of the rectifying tower is saved.

Further, ultrasonic waves with the frequency of 20-40 kHz are adopted in S1 to carry out ultrasonic treatment on the germanium-containing dilute hydrochloric acid solution, the ultrasonic waves enable the germanium-containing dilute hydrochloric acid solution to be thoroughly dispersed, molecular agglomeration is avoided, and the subsequent rectification effect is improved.

Further, in the S2, the temperature of the top of the tower is controlled to be 92-93 ℃ in the rectifying process, the temperature of the bottom of the tower is controlled to be 114-116 ℃, water is continuously produced at the top of the rectifying process, a concentrated hydrochloric acid solution containing germanium is continuously produced at the bottom of the tower, the produced concentrated hydrochloric acid solution containing germanium is about 5g/L and 20-25% of hydrochloric acid, the conductivity of the produced water is 450-500 mu S/cm, and the pH value is neutral.

Further, adopt the ultrasonic wave of 60 ~ 80kHz frequency to carry out the supersound to containing germanium concentrated hydrochloric acid solution in S3, the ultrasonic wave makes containing germanium concentrated hydrochloric acid solution can fully contact with chlorine at chlorination in-process, improves the reaction progress, can make the chlorination more thoroughly.

Further, the temperature of the preheated chlorine in the S3 is set to be 60-65 ℃, the flow rate of the chlorine is controlled to be 450-500L/h, and the temperature in the chlorination distillation process is controlled to be 84-85 ℃.

The invention has the following beneficial effects:

the method comprises the steps of separating water from raw materials by rectification concentration to obtain a concentrated hydrochloric acid solution containing 20-25% of germanium, performing chlorination distillation on the solution to obtain crude germanium tetrachloride, hydrolyzing the crude germanium tetrachloride to obtain germanium dioxide, efficiently recovering germanium, returning chloride ions to production for recycling, and avoiding the environmental protection problem caused by high-chlorine wastewater.

According to the invention, the germanium-containing dilute hydrochloric acid solution is pretreated, and the germanium-containing dilute hydrochloric acid solution is preheated by the waste heat steam of the rectifying tower in advance, so that the feeding temperature is increased, the waste heat energy is utilized, the whole rectifying process is more energy-saving, the separation of materials in the rectifying tower is facilitated, and the steam in the kettle of the rectifying tower is saved.

According to the invention, in the pretreatment stage of the germanium-containing dilute hydrochloric acid solution, ultrasonic waves with the frequency of 20-40 kHz are adopted to carry out ultrasonic treatment on the germanium-containing dilute hydrochloric acid solution, so that the germanium-containing dilute hydrochloric acid solution is thoroughly dispersed, the molecular agglomeration is avoided, the subsequent rectification effect is improved, in the chlorination distillation stage, ultrasonic waves with the frequency of 60-80 kHz are adopted to carry out ultrasonic treatment on the germanium-containing concentrated hydrochloric acid solution, so that the germanium-containing concentrated hydrochloric acid solution can be fully contacted with chlorine gas in the chlorination process, in the reaction process, the heating is carried out through microwaves, the introduction of the microwave technology and the ultrasonic wave technology greatly improves the chemical reaction environment, the energy barrier required by the spanning diffusion control is reduced, the chlorination reaction is effectively strengthened, and the recovery rate of germanium in the germanium-containing waste liquid is improved.

Of course, it is not necessary for any one product that embodies the invention to achieve all of the above advantages simultaneously.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a process flow diagram of the present invention.

Detailed Description

The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.

Example one

Referring to fig. 1, the present invention is a method for recovering a hydrochloric acid solution containing germanium, comprising the following steps:

s1: pretreating the germanium-containing dilute hydrochloric acid solution, preheating the germanium-containing dilute hydrochloric acid solution by using waste heat steam of a rectifying tower, setting the preheating temperature to be 60 ℃, starting an ultrasonic generator when preheating, placing the germanium-containing dilute hydrochloric acid solution in an ultrasonic field, acting on the germanium-containing dilute hydrochloric acid solution through ultrasonic waves, thoroughly scattering molecular aggregates, and performing ultrasonic treatment on the germanium-containing dilute hydrochloric acid solution by using ultrasonic waves with the frequency of 20 kHz;

s2: rectifying and concentrating, namely conveying the pretreated germanium-containing dilute hydrochloric acid solution into a rectifying tower, rectifying, concentrating and separating to obtain a germanium-containing concentrated hydrochloric acid solution and water, wherein the temperature of the top of the tower is controlled to be 92-93 ℃ in the rectifying process, the temperature of the bottom of the tower is controlled to be 114-116 ℃, water is continuously produced at the top of the rectifying tower in the rectifying process, the germanium-containing concentrated hydrochloric acid solution is continuously produced at the bottom of the tower, the germanium-containing concentrated hydrochloric acid solution is about 5g/L and 20-25% of hydrochloric acid, the conductivity of the produced water is 450-500 mu s/cm, and the pH value is neutral;

s3: performing chlorination distillation, namely conveying the germanium-containing concentrated hydrochloric acid solution into chlorination distillation equipment, starting a microwave generator, heating by microwaves, continuously introducing preheated chlorine into the germanium-containing concentrated hydrochloric acid solution for reaction, setting the preheated temperature of the chlorine to be 60 ℃, controlling the flow rate of the chlorine to be 450L/h, controlling the temperature to be 84-85 ℃ in the chlorination distillation process, starting an ultrasonic generator, acting on the germanium-containing concentrated hydrochloric acid solution by ultrasonic waves, performing auxiliary chlorination distillation, obtaining crude germanium tetrachloride after chlorination distillation, and performing ultrasonic treatment on the germanium-containing concentrated hydrochloric acid solution by adopting the ultrasonic waves with the frequency of 60 kHz;

s4: and (3) rectification hydrolysis, namely conveying the crude germanium tetrachloride into a rectification tower for rectification purification, then carrying out ultrasonic hydrolysis after rectification purification, carrying out centrifugal filtration after hydrolysis, washing and drying to finally obtain the high-purity germanium dioxide.

Example two

Referring to fig. 1, the present invention is a method for recovering a hydrochloric acid solution containing germanium, comprising the following steps:

s1: pretreating the germanium-containing dilute hydrochloric acid solution, preheating the germanium-containing dilute hydrochloric acid solution by using waste heat steam of a rectifying tower, setting the preheating temperature to be 70 ℃, starting an ultrasonic generator when preheating, placing the germanium-containing dilute hydrochloric acid solution in an ultrasonic field, acting on the germanium-containing dilute hydrochloric acid solution through ultrasonic waves, thoroughly scattering molecular aggregates, and performing ultrasonic treatment on the germanium-containing dilute hydrochloric acid solution by using ultrasonic waves with the frequency of 40 kHz;

s2: rectifying and concentrating, namely conveying the pretreated germanium-containing dilute hydrochloric acid solution into a rectifying tower, rectifying, concentrating and separating to obtain a germanium-containing concentrated hydrochloric acid solution and water, wherein the temperature of the top of the tower is controlled to be 92-93 ℃ in the rectifying process, the temperature of the bottom of the tower is controlled to be 114-116 ℃, water is continuously produced at the top of the rectifying tower in the rectifying process, the germanium-containing concentrated hydrochloric acid solution is continuously produced at the bottom of the tower, the germanium-containing concentrated hydrochloric acid solution is about 5g/L and 20-25% of hydrochloric acid, the conductivity of the produced water is 450-500 mu s/cm, and the pH value is neutral;

s3: chlorination distillation, namely conveying the germanium-containing concentrated hydrochloric acid solution into chlorination distillation equipment, starting a microwave generator, heating by microwaves, continuously introducing preheated chlorine into the germanium-containing concentrated hydrochloric acid solution for reaction, setting the preheated temperature of the chlorine to be 65 ℃, controlling the flow rate of the chlorine to be 450-500L/h, controlling the temperature to be 84-85 ℃ in the chlorination distillation process, starting an ultrasonic generator, acting on the germanium-containing concentrated hydrochloric acid solution by ultrasonic waves, performing auxiliary chlorination distillation, obtaining crude germanium tetrachloride after chlorination distillation, and performing ultrasonic treatment on the germanium-containing concentrated hydrochloric acid solution by the ultrasonic waves with the frequency of 80 kHz;

s4: and (3) rectification hydrolysis, namely conveying the crude germanium tetrachloride into a rectification tower for rectification purification, then carrying out ultrasonic hydrolysis after rectification purification, carrying out centrifugal filtration after hydrolysis, washing and drying to finally obtain the high-purity germanium dioxide.

EXAMPLE III

Referring to fig. 1, the present invention is a method for recovering a hydrochloric acid solution containing germanium, comprising the following steps:

s1: pretreating the germanium-containing dilute hydrochloric acid solution, preheating the germanium-containing dilute hydrochloric acid solution by using waste heat steam of a rectifying tower, setting the preheating temperature to 65 ℃, starting an ultrasonic generator when preheating, placing the germanium-containing dilute hydrochloric acid solution in an ultrasonic field, acting on the germanium-containing dilute hydrochloric acid solution through ultrasonic waves, thoroughly scattering molecular aggregates, and performing ultrasonic treatment on the germanium-containing dilute hydrochloric acid solution by using ultrasonic waves with the frequency of 30 kHz;

s2: rectifying and concentrating, namely conveying the pretreated germanium-containing dilute hydrochloric acid solution into a rectifying tower, rectifying, concentrating and separating to obtain a germanium-containing concentrated hydrochloric acid solution and water, wherein the temperature of the top of the tower is controlled to be 92-93 ℃ in the rectifying process, the temperature of the bottom of the tower is controlled to be 114-116 ℃, water is continuously produced at the top of the rectifying tower in the rectifying process, the germanium-containing concentrated hydrochloric acid solution is continuously produced at the bottom of the tower, the germanium-containing concentrated hydrochloric acid solution is about 5g/L and 20-25% of hydrochloric acid, the conductivity of the produced water is 450-500 mu s/cm, and the pH value is neutral;

s3: chlorination distillation, namely conveying the germanium-containing concentrated hydrochloric acid solution into chlorination distillation equipment, starting a microwave generator, heating by microwaves, continuously introducing preheated chlorine into the germanium-containing concentrated hydrochloric acid solution for reaction, setting the preheated temperature of the chlorine to be 62.5 ℃, controlling the flow rate of the chlorine to be 450-500L/h, controlling the temperature to be 84-85 ℃ in the chlorination distillation process, starting the ultrasonic generator, acting on the germanium-containing concentrated hydrochloric acid solution by ultrasonic waves, performing auxiliary chlorination distillation, obtaining crude germanium tetrachloride after chlorination distillation, and performing ultrasonic treatment on the germanium-containing concentrated hydrochloric acid solution by adopting the ultrasonic waves with the frequency of 70 kHz;

s4: and (3) rectification hydrolysis, namely conveying the crude germanium tetrachloride into a rectification tower for rectification purification, then carrying out ultrasonic hydrolysis after rectification purification, carrying out centrifugal filtration after hydrolysis, washing and drying to finally obtain the high-purity germanium dioxide.

The method adopts rectification concentration to separate water from raw materials to obtain a concentrated hydrochloric acid solution containing 20-25% of germanium, performs chlorination distillation on the solution to obtain crude germanium tetrachloride, hydrolyzes the crude germanium tetrachloride to obtain germanium dioxide, efficiently recovers the germanium, and returns chloride ions to production for reuse.

The above are only preferred embodiments of the present invention, and the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made to the technical solutions described in the above embodiments, and to some of the technical features thereof, are included in the scope of the present invention.