Method for recovering hydrochloric acid and germanium through direct two-stage distillation after germanium chlorination distillation

Abstract

The invention belongs to the technical field of resource regeneration, and particularly relates to a method for recycling hydrochloric acid and germanium through direct two-stage distillation after germanium chlorination distillation, which comprises germanium chlorination distillation, first-stage positive pressure acid steaming, second-stage negative pressure acid steaming and kettle stopping and slag liquid discharging. According to the invention, two-stage acid distillation is directly carried out in the original production equipment system after germanium chlorination distillation, so that the innovation of integrated continuous production of germanium chlorination distillation and acid distillation in the same equipment system is realized, the process is more energy-saving and economic, the operation is simpler and more convenient, the equipment utilization rate is higher, and the environment is more friendly; the recycling rate of hydrochloric acid is up to 60% or above; a one-stage positive-pressure acid steaming process is adopted, high-concentration hydrochloric acid with the HCl molar concentration larger than or equal to 9.5 mol / L is regenerated and can be directly returned to germanium chlorination distillation for use, and synchronous limit recovery of residual germanium in germanium chlorination distillation residues is achieved; therefore, full recycling of hydrochloric acid and germanium in germanium chlorination distillation waste acid and waste residues is realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of resource recycling, and particularly relates to a method for directly recovering hydrochloric acid and germanium by two-stage distillation after germanium chlorination distillation. Background Art

[0002] The germanium chlorination distillation residual acid residue is a mixed solution of waste acid and residue generated in the germanium distillation production process. The distillation residual acid residue has a complex composition, manifested in a relatively high acidity (generally, the molar concentration of HCl in the residual acid residue is 6.5 - 8.5 mol / L). Due to its containing various impurities such as silicon, iron, tin, antimony, bismuth, lead, zinc, magnesium, aluminum, and manganese, it cannot be directly recycled. The conventional process uses a direct neutralization method for waste acid treatment, which not only causes a large waste of hydrogen chloride, but also the trace germanium remaining in the residue cannot be recovered due to its too low content.

[0003] The existing recovery technologies for germanium distillation residual acid in industrial applications mainly include multi-effect evaporation method, ion exchange resin method, membrane separation method, and extraction method, each with its own advantages and disadvantages, which are described in detail as follows.

[0004] Multi-effect evaporation method: It is mainly used for the recovery treatment of solutions such as waste hydrochloric acid, waste hydrofluoric acid, and waste nitric acid. The working principle of the multi-effect evaporation method is based on the volatile characteristic of hydrochloric acid. By heating it to evaporate and generate acidic gas, and then condensing to recover the acid. Multi-effect evaporation means leaving a sufficient space in each effect separator for gas-liquid separation. The steam directly enters the next-effect evaporator from the top of the separator. Since the cross-sectional area of the outlet pipe of the separator is more than 2 times larger than that of the general steam pipe, there is no turning when introducing it into the next-stage evaporator, and the distance is short, which greatly reduces the steam resistance, increases the flow rate, and improves the heating efficiency; and because the gas-liquid separation is completed in the separator, the heat loss of the extracted steam is reduced. The heating steam condensate of the first-effect evaporator is passed into the hot water preheater through the steam trap, and the condensate is discharged from the hot water preheater, avoiding steam loss and also solving the noise and pollution of the steam trap. Using the heat of the condensate of each effect evaporator and the heat of the gas phase of the last effect, the waste hydrochloric acid solution is preheated multiple times. The main advantages of this method are multi-effect energy saving; the main disadvantages are the corrosion of equipment and the crystallization blockage problem after the waste acid solution is concentrated to a certain extent; and the molar concentration of the recovered acid HCl is less than 7 mol / L, lower than the concentration of the raw material waste acid, and cannot be reused in the germanium chlorination distillation process.

[0005] Ion exchange resin method: The separation of acid and salt is achieved by utilizing the function of certain ion exchange resins to absorb hydrochloric acid from the residual acid of germanium distillation and exclude metal salts. After the acid residue of the germanium distillation residue liquid is filtered by a filtering device, it flows through the resin bed from the bottom through a pipeline. The resin absorbs HCl, and the liquid containing other ions is discharged and enters the metal salt recovery system. Thus, the separation of acid and salt is realized. This method has the advantages of short process flow, easy operation, low energy consumption, treatment at room temperature, improving the service life of equipment and pipelines, and reducing the escape of chlorides. However, when treated at room temperature, the concentration of the recovered hydrochloric acid is relatively low, and concentrated hydrochloric acid needs to be added for use; moreover, there are many types and high concentrations of metal ions in the residual acid of germanium distillation, which easily causes resin poisoning.

[0006] Membrane separation method: The residual acid of germanium distillation can be separated and recycled through membrane separation technology, that is, the metal salt and acid are separated by using the ion selectivity of the membrane, and at the same time, hydrochloric acid and iron salt are recycled. Commonly used membrane separation methods include diffusion dialysis method, electrodialysis method, membrane distillation method, etc. The membrane separation method applied to the treatment of waste acid liquid is mainly the diffusion dialysis method. The diffusion dialysis method realizes the separation of acid and salt in the waste acid liquid by using the selective permeation of the anion exchange membrane. The diffusion dialysis process does not consume electricity and has low operating costs. Compared with the multi-effect evaporation method, the diffusion dialysis method can also obtain a regenerated acid with lower impurity content. However, the diffusion dialysis method has not been widely applied in engineering at present. The main reasons are as follows: its processing capacity is not large, resulting in a large-scale diffusion dialysis equipment; the concentration of the recovered acid is limited by the equilibrium concentration, that is, the concentration of the recovered acid cannot be higher than the concentration of the raw material waste acid; the residual liquid after recovering the acid still cannot be directly discharged; and a high content of metal impurities or particulate matter in the waste acid will greatly shorten the life of the membrane, etc.

[0007] Extraction method: There are mainly two methods. One is to use an extractant in the residual acid of germanium distillation to extract metal ions to achieve the purpose of purifying and regenerating hydrochloric acid; the other is to extract the free hydrochloric acid with an extractant for regeneration. The significant disadvantages of this method are the low concentration of the recovered hydrochloric acid, large loss of the organic phase, and high organic matter content in the regenerated acid, etc.

[0008] The above-mentioned process technologies mainly have several common problems. One is that the concentration of the regenerated hydrochloric acid will be lower than the concentration of the residual acid of germanium chlorination distillation of the raw material, that is, the concentration of hydrochloric acid cannot be increased during the regeneration of hydrochloric acid, and the molar concentration of HCl in the produced hydrochloric acid cannot reach 9.5 mol / L and cannot be returned to the germanium chlorination distillation system for reuse; the other is that in the multi-effect evaporation method, after the residual acid and residue of distillation are cooled and separated from solid and liquid, the residual acid of germanium distillation is regenerated separately, and the cooling and separation process wastes the heat energy in the germanium distillation acid residue, resulting in energy waste, and at the same time, the germanium remaining in the germanium distillation residue is not further recovered. Summary of the Invention

[0009] To solve at least one of the problems of the prior art, the present invention provides a method for directly recovering hydrochloric acid and germanium by two-stage distillation after germanium chlorination distillation, which is a new technical solution for segmented recovery and hierarchical utilization of hydrochloric acid and germanium. The method of the present invention directly performs secondary acid distillation in the original production equipment system after germanium chlorination distillation, realizing the innovation of integrated continuous production of germanium chlorination distillation and acid distillation in the same equipment system, being more energy-saving and economical in process, more convenient in operation, having higher equipment utilization rate, being more environmentally friendly, and having a resource utilization rate of hydrochloric acid as high as over 60%; innovatively adopting a one-stage positive pressure acid distillation process to regenerate high-concentration hydrochloric acid with an HCl molar concentration of greater than or equal to 9.5 mol / L, which can be directly returned to germanium chlorination distillation for use, and realizing synchronous ultimate recovery of the germanium remaining in the germanium chlorination distillation residue; thus achieving full resource utilization of hydrochloric acid and germanium in the germanium chlorination distillation waste acid and waste residue.

[0010] The present invention first provides a germanium chlorination distillation system, including: a distillation reaction device; the distillation reaction device includes an enamel reaction kettle and an outer jacket; the enamel reaction kettle is used for heating and distilling to generate germanium tetrachloride gas; the outer jacket is arranged on the outer surface of the enamel reaction kettle; a steam device, communicated with the outer jacket, for introducing high-temperature steam into the outer jacket to heat the enamel reaction kettle; a cooling circulation device, communicated with the outer jacket, for introducing cooling water into the outer jacket to cool the materials in the enamel reaction kettle (i.e., cooling the enamel reaction kettle and the materials in the kettle); a refrigeration circulation device, communicated with the enamel reaction kettle, for condensing the germanium tetrachloride gas distilled out of the enamel reaction kettle or the hydrogen chloride gas distilled out of the enamel reaction kettle; a germanium tetrachloride collection tank, communicated with the refrigeration circulation device, for collecting the liquid germanium tetrachloride generated after the germanium tetrachloride gas distilled out of the enamel reaction kettle is condensed by the refrigeration circulation device; a high-concentration hydrochloric acid storage tank, communicated with the refrigeration circulation device, for collecting the high-concentration hydrochloric acid generated after the mixed gas of hydrogen chloride and water distilled out of the enamel reaction kettle is condensed by the refrigeration circulation device; a low-concentration hydrochloric acid storage tank, communicated with the refrigeration circulation device, for collecting the low-concentration hydrochloric acid generated after the mixed gas of hydrogen chloride and water distilled out of the enamel reaction kettle is condensed by the refrigeration circulation device; a negative pressure device, communicated with the low-concentration hydrochloric acid storage tank, for reducing the pressure in the enamel reaction kettle.

[0011] The germanium chlorination distillation system of the present invention is provided with a high-concentration hydrochloric acid storage tank, a low-concentration hydrochloric acid storage tank and a negative pressure system, which can realize the integrated continuous production of germanium chlorination distillation to produce germanium tetrachloride and hydrochloric acid regeneration production in the same system, being more energy-saving and economical in process, more convenient in operation, having higher equipment utilization rate, and being more environmentally friendly.

[0012] The present invention also provides a method for directly recovering hydrochloric acid and germanium by two-stage distillation after germanium chlorination distillation, using the above germanium chlorination distillation system; the method includes:

[0013] 1) Germanium chlorination distillation

[0014] Put the germanium-containing material, concentrated hydrochloric acid and oxidant into an enamel reaction kettle, and introduce steam into the outer jacket of the enamel reaction kettle for heating and distillation; the generated germanium tetrachloride gas is condensed and collected;

[0015] 2) First-stage positive-pressure acid distillation

[0016] After the germanium chlorination distillation in step 1) is completed, stop introducing high-temperature steam into the outer jacket of the enamel reaction kettle; introduce circulating cooling water into the outer jacket of the enamel reaction kettle to cool the mixture of distillation residue and distillation residual acid in the enamel reaction kettle in step 1) to 85 - 95 °C, and then stop introducing circulating cooling water into the outer jacket of the enamel reaction kettle;

[0017] Then open the acid receiving valve of the high-concentration hydrochloric acid storage tank, close the germanium tetrachloride receiving valve, and adjust the refrigerant outlet temperature of the refrigeration circulation equipment; then introduce high-temperature steam into the outer jacket of the enamel reaction kettle, control the temperature of the material in the enamel reaction kettle to be 105 - 120 °C, and the pressure to be 105000 - 120000 Pa; the distilled hydrogen chloride gas is condensed by the refrigeration circulation equipment and then enters the high-concentration hydrochloric acid storage tank; when the volume of the distilled hydrochloric acid accounts for 35% of the volume of the concentrated hydrochloric acid added in step 1) or when the molar concentration of HCl in the distilled hydrochloric acid is less than or equal to 9 mol / L, the first-stage positive-pressure acid distillation ends;

[0018] 3) Second-stage negative-pressure acid distillation

[0019] After the first-stage positive-pressure acid distillation in step 2) is completed, stop introducing high-temperature steam into the outer jacket of the enamel reaction kettle; close the acid receiving valve of the high-concentration hydrochloric acid storage tank, open the acid receiving valve of the low-concentration hydrochloric acid storage tank, start the negative-pressure equipment, and control the pressure in the enamel reaction kettle to be less than or equal to 90000 Pa; adjust the refrigerant outlet temperature of the refrigeration circulation equipment;

[0020] Then introduce high-temperature steam into the outer jacket of the enamel reaction kettle, control the temperature of the material in the enamel reaction kettle to be 95 - 110 °C, and the pressure to be less than or equal to 90000 Pa; the distilled hydrogen chloride gas is condensed by the refrigeration circulation equipment and then enters the low-concentration hydrochloric acid storage tank; when the volume of the hydrochloric acid to be distilled accounts for 25 - 35% of the volume of the concentrated hydrochloric acid added in step 1), the second-stage negative-pressure acid distillation ends;

[0021] 4) Stop the kettle and drain the residue liquid

[0022] After the second-stage negative-pressure acid distillation in step 3) is completed, the negative-pressure system is closed, and the high-temperature steam is stopped from being introduced into the outer jacket of the enamel reactor; water is added to the enamel reactor, and circulating cooling water is introduced into the outer jacket of the enamel reactor to cool down the waste materials in the enamel reactor; then the waste materials are discharged.

[0023] Using the method of directly recovering hydrochloric acid and germanium by two-stage distillation after germanium chlorination distillation of the present invention, the resource utilization rate of hydrochloric acid is as high as over 60%. The method of the present invention innovatively adopts the process of first-stage positive-pressure acid distillation to regenerate high-concentration hydrochloric acid with a HCl molar concentration of greater than or equal to 9.5 mol / L, which can be directly returned to germanium chlorination distillation for use, and realizes the synchronous ultimate recovery of the residual germanium in the germanium chlorination distillation residue; thus, the full resource utilization of hydrochloric acid and germanium in the waste acid and waste residue of germanium chlorination distillation is realized.

[0024] Specifically, step 1) can be carried out according to the existing conventional germanium chlorination distillation production process.

[0025] Specifically, the germanium-containing material in step 1) is selected from germanium concentrate or regenerated germanium raw materials, which conform to the regulations in YS / T 300 "Germanium Concentrate" or GB / T 23522 "Regenerated Germanium Raw Materials".

[0026] Specifically, the concentration of concentrated hydrochloric acid in step 1) is greater than or equal to 9.5 mol / L, for example, 9.5 - 10.5 mol / L.

[0027] Specifically, the oxidant in step 1) is selected from ferric chloride, manganese dioxide or chlorine gas.

[0028] Specifically, after germanium chlorination distillation in step 1), the remaining materials in the enamel reactor are a mixture of distillation residue and distillation residual acid, among which the HCl molar concentration is 6.5 - 8.5 mol / L and cannot be directly reused or used for other purposes.

[0029] Specifically, after germanium chlorination distillation in step 1), the temperature of the remaining materials in the enamel reactor is 105 - 115 °C.

[0030] Specifically, stirring is carried out during the germanium chlorination distillation in step 1).

[0031] Specifically, in step 1), the refrigerant outlet temperature of the refrigeration cycle equipment is set to -10 to -5 °C for condensing the distilled germanium tetrachloride gas.

[0032] Specifically, in step 2), the temperature of the circulating cooling water introduced into the outer jacket of the enamel reactor is less than or equal to 40 °C for cooling the materials in the reactor through the outer jacket of the reactor.

[0033] Specifically, in step 2), the refrigerant outlet temperature of the refrigeration cycle equipment is set to -5 to 5 °C for condensing the mixed gas of distilled hydrogen chloride and water.

[0034] Specifically, stirring is carried out during the first-stage positive-pressure acid evaporation process in step 2).

[0035] Specifically, after the first-stage positive-pressure acid evaporation in step 2) ends, the high-temperature steam supply to the outer jacket of the enamel reactor is stopped, and the stirring is stopped.

[0036] Specifically, after the concentrated hydrochloric acid obtained from the first-stage positive-pressure acid evaporation in step 2) is mixed evenly, it contains 20-100 μg / ml of germanium and the molar concentration of HCl is greater than or equal to 9.5 mol / L. This concentrated hydrochloric acid can be directly returned to step 1) for use in the germanium chlorination and distillation process, recycling high-value germanium resources while regenerating hydrochloric acid.

[0037] Specifically, in step 3), the outlet temperature of the refrigerant of the refrigeration cycle equipment is adjusted and set to 5-10 °C.

[0038] Specifically, stirring is carried out during the second-stage negative-pressure acid evaporation process in step 3).

[0039] Specifically, after the second-stage negative-pressure acid evaporation in step 3) ends, the supply of high-temperature steam to the enamel reactor is stopped, and the stirring is stopped.

[0040] Specifically, after the concentrated hydrochloric acid obtained from the second-stage negative-pressure acid evaporation in step 3) is mixed evenly, the molar concentration of HCl is greater than or equal to 4.5 mol / L and it does not contain germanium, and it can be used for indium and gallium production, etc.

[0041] Specifically, in step 4), the volume of water (such as tap water) added is 50-70% of the volume of the concentrated hydrochloric acid input in step 1).

[0042] Specifically, in step 4), the temperature of the circulating cooling water supplied to the outer jacket of the enamel reactor is less than or equal to 40 °C, which is used to cool the materials inside the reactor through the outer jacket of the reactor.

[0043] Specifically, in step 4), when the temperature of the solution inside the enamel reactor cools to no more than 60 °C, the cooling cycle equipment is turned off.

[0044] Specifically, in step 4), when the temperature of the solution inside the enamel reactor cools to no more than 45 °C, the supply of circulating cooling water is stopped, and the waste materials are discharged. For example, the feeding port and the bottom valve of the enamel reactor are opened successively to discharge the residue liquid remaining after acid evaporation. The residue liquid remaining after acid evaporation is discharged to the environmental protection treatment system for compliance disposal.

[0045] In the present invention, by closing the steam in step 1) (while continuing stirring) and introducing circulating cooling water into the outer jacket of the enamel reactor to cool down the solution in the reactor, the pressure inside the reactor and the entire receiving system is reduced, so as to safely open the acid receiving valve of the high-concentration hydrochloric acid storage tank and close the germanium tetrachloride feeding valve in step 2), and complete the switching of the feeding system. The reason for controlling the temperature of the solution in the reactor at 85 - 95 °C at the end of the cooling is as follows: when the temperature is higher than 95 °C, the pressure in the system is relatively high, and the safety of valve switching and the system is insufficient; when the temperature is lower than 85 °C, it will cause waste of thermal energy.

[0046] In the present invention, by opening the acid receiving valve of the high-concentration hydrochloric acid storage tank and closing the germanium tetrachloride feeding valve in step 2), the purpose is that in step 2), the product to be distilled changes from germanium tetrachloride to high-concentration hydrochloric acid, and correspondingly, the germanium tetrachloride receiving container connected to the condensation system needs to be switched to a storage tank for high-concentration hydrochloric acid. The set value of the refrigerant outlet temperature of the refrigeration cycle equipment is adjusted, and the set value of -10 to -5 °C during the original germanium chlorination distillation is adjusted to -5 to 5 °C during the first-stage positive-pressure acid distillation, so as to reduce the energy consumption of the refrigeration system while fully meeting the condensation requirements for distilling high-concentration hydrochloric acid. The temperature of the solution in the enamel reactor is controlled at 105 - 120 °C, and the pressure inside the reactor is controlled at 105000 - 120000 Pa, with the aim of allowing HCl to evaporate faster than H2O in this stage in a high-temperature positive-pressure manner. That is to say, if all or as much as possible of the HCl distilled in this stage dissolves in the distilled H2O, a high-concentration hydrochloric acid solution can be obtained, and at the same time, the distilled HCl is fully condensed during the evaporation and condensation processes to ensure the high concentration of the acid distilled in this stage. If negative-pressure distillation is used in this stage, although a part of the evaporation energy can be further saved, part of the distilled HCl gas will not enter the condensed hydrochloric acid solution, or even if it condenses into the hydrochloric acid solution, part of it will escape again into the tail gas system, resulting in the loss of HCl and causing the molar acidity of the hydrochloric acid distilled in the first stage to be lower than the molar concentration of HCl in the residual acid of germanium chlorination distillation in step 1), and it cannot meet the standard for returning to germanium chlorination distillation for use. When the volume of the distilled hydrochloric acid accounts for 35% of the volume of the concentrated hydrochloric acid added in step 1) or when the molar concentration of HCl in the distilled hydrochloric acid sampled in real time is less than or equal to 9 mol / L, the first-stage positive-pressure acid distillation ends. The purpose is that under these conditions, it can be ensured that the molar concentration of HCl in the high-concentration hydrochloric acid distilled in the first stage is greater than or equal to 9.5 mol / L, or even greater than or equal to 10 mol / L after mixing, fully meeting the requirements for recycling in germanium chlorination distillation. At this time, the distilled and recovered germanium has reached the limit. If the acid distillation continues under these conditions, the amount of germanium distilled out is extremely small, and the concentration of the distilled hydrochloric acid also decreases rapidly, which may lead to the mixed acidity of the acid distilled in the first stage being lower than 9.5 mol / L, thus unable to be returned to germanium chlorination distillation for use.

[0047] In the present invention, the acid receiving valve of the low-concentration hydrochloric acid storage tank in step 3) is opened, and the negative pressure device connected to the low-concentration storage tank is started to reduce the internal pressure of the low-concentration storage tank, pipeline and distillation kettle; subsequently, the acid receiving valve of the high-concentration hydrochloric acid storage tank in step 2) is closed; the purpose is that the product to be distilled out changes from high-concentration hydrochloric acid to low-concentration hydrochloric acid. Correspondingly, the first-stage high-concentration hydrochloric acid storage tank connected to the refrigeration cycle equipment needs to be switched to the storage tank for distilling out high-concentration hydrochloric acid in the second stage. And starting the negative pressure device will reduce the pressure of the distillation kettle and the system to less than or equal to 90000 Pa. In this way, the method of distilling acid under negative pressure can accelerate the acid discharging speed and reduce the energy consumption of acid distillation; adjust the set value of the refrigerant outlet temperature of the refrigeration cycle equipment, and adjust the set value of the first-stage positive pressure acid distillation from -5 to 5 °C to 5 to 10 °C. The purpose is to reduce the energy consumption of the refrigeration cycle equipment while fully meeting the condensation requirements for distilling out low-concentration hydrochloric acid. Open and control the steam valve to heat the mixture solution remaining from the first-stage positive pressure acid distillation in the enamel reaction kettle in step 2), and control the temperature of the solution in the kettle at 95 - 110 °C. The purpose is to distill acid at a lower temperature range to reduce energy consumption under the condition that the pressure in the kettle is less than or equal to 90000 Pa under negative pressure and on the premise of meeting the distillation efficiency of low-concentration hydrochloric acid. When the volume of the distilled low-concentration hydrochloric acid accounts for 25 - 35% of the volume of the concentrated hydrochloric acid added in step 1), the second-stage negative pressure acid distillation ends. The purpose is to maximize and most economically recover hydrochloric acid. If the volume of the low-concentration hydrochloric acid distilled in this stage accounts for less than 25% of the volume of the concentrated hydrochloric acid added in step 1), the hydrochloric acid recovery is insufficient. If it is greater than 35%, the salt content of the solution remaining in the enamel reaction kettle becomes higher, the distillation speed of hydrochloric acid becomes slower, the concentration of the distilled hydrochloric acid is low, and crystallization may occur in the kettle, which will cause adverse effects such as clogging valves and pipelines for subsequent slag discharge.

[0048] In the present invention, tap water is added into the enamel reaction kettle in step 4), and circulating cooling water is introduced into the outer jacket of the enamel reaction kettle to cool down the solution in the kettle. The purpose is that in addition to cooling, it can also dilute the mixed solution of residual acid and residue in the kettle, improve its fluidity, and prevent crystallization from occurring, so as to facilitate the discharge of the slag liquid.

[0049] In summary, the present invention adopts a new technical solution for directly segmenting and regenerating germanium after chlorination distillation and hierarchically utilizing hydrochloric acid and germanium. The advantages of adopting the above method are as follows: First, after germanium chlorination distillation, secondary acid evaporation is directly carried out in the original production equipment system, realizing the innovation of integrated continuous production of germanium chlorination distillation and acid evaporation in the same equipment system. It is more energy-saving and economical in terms of process, more convenient in operation, has higher equipment utilization rate, is more environmentally friendly, and the resource utilization rate of hydrochloric acid is as high as over 60%; Second, the innovative process of positive pressure acid evaporation in one stage is adopted to regenerate high-concentration hydrochloric acid with a HCl molar concentration greater than or equal to 9.5 mol / L, which can be directly returned to germanium chlorination distillation for use, and at the same time, the germanium remaining in the germanium chlorination distillation residue is recovered to the limit; thus, the full resource utilization of hydrochloric acid and germanium in the waste acid and waste residue of germanium chlorination distillation is realized. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 It is a schematic structural diagram of the germanium chlorination distillation system according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0051] In order to make the above objects, features, and advantages of the present invention more obvious and understandable, the following detailed description of the specific embodiments of the present invention is provided. Many specific details are set forth in the following description in order to fully understand the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below.

[0052] For the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.

[0053] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes the preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0054] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific embodiments of the description of the present invention, which will be obvious to those skilled in the art. Other embodiments obtained from the description of the present invention will be obvious to those skilled in the art. The description and examples of this application are merely exemplary.

[0055] Regarding the use of "comprising", "including", "having", "containing", etc. in this article, they are all open-ended terms, meaning including but not limited to.

[0056] The technical solutions described in the present invention, unless otherwise specified, are all conventional solutions in the art. The reagents or raw materials used, unless otherwise specified, are all purchased from commercial channels or are already publicly available.

[0057] Please refer to Figure 1 This embodiment provides a germanium chlorination distillation system, including: a distillation reaction device; the distillation reaction device includes an enamel reaction kettle 1 and an outer jacket 9; the enamel reaction kettle 1 is used for heating and distilling to generate germanium tetrachloride gas; the outer jacket 9 is arranged on the outer surface of the enamel reaction kettle 1; a steam device 2, communicated with the outer jacket 9, for introducing high-temperature steam into the outer jacket 9 to heat the enamel reaction kettle; a cooling circulation device 3, communicated with the outer jacket 9, for introducing cooling water into the outer jacket 9 to cool the materials in the enamel reaction kettle (i.e., cooling the enamel reaction kettle and the materials in the kettle); a refrigeration circulation device 4, communicated with the enamel reaction kettle 1, for condensing the germanium tetrachloride gas distilled out of the enamel reaction kettle 1 or the hydrogen chloride gas distilled out of the enamel reaction kettle 1; a germanium tetrachloride collection tank 5, communicated with the refrigeration circulation device 4, for collecting the liquid germanium tetrachloride generated after the germanium tetrachloride gas distilled out of the enamel reaction kettle 1 is condensed by the refrigeration circulation device 4; a high-concentration hydrochloric acid storage tank 7, communicated with the refrigeration circulation device 4, for collecting the high-concentration hydrochloric acid generated after the mixed gas of hydrogen chloride and water distilled out of the enamel reaction kettle 1 is condensed by the refrigeration circulation device 4; a low-concentration hydrochloric acid storage tank 8, communicated with the refrigeration circulation device 4, for collecting the low-concentration hydrochloric acid generated after the mixed gas of hydrogen chloride and water distilled out of the enamel reaction kettle 1 is condensed by the refrigeration circulation device 4; a negative pressure device 6, communicated with the low-concentration hydrochloric acid storage tank 8, for reducing the pressure in the enamel reaction kettle 1.

[0058] The germanium chlorination distillation system of the embodiment of the present invention realizes the integrated continuous production of germanium chlorination distillation to produce germanium tetrachloride and hydrochloric acid regeneration production in the same system by adding a high-concentration hydrochloric acid storage tank, a low-concentration hydrochloric acid storage tank and a negative pressure system. The process is more energy-saving and economical, the operation is more convenient, the equipment utilization rate is higher, and it is more environmentally friendly.

[0059] Specifically, the distillation reaction equipment (including the enamel reactor and the outer jacket), the steam equipment, the cooling circulation system, the refrigeration circulation equipment, and the germanium tetrachloride collection tank can use the existing conventional process equipment for germanium material chlorination and distillation.

[0060] Specifically, the enamel reactor 1 is further provided with a feeding port and a discharging port (equipped with a bottom valve).

[0061] Specifically, the enamel reactor 1 further includes a stirrer 10 for stirring the materials therein.

[0062] Specifically, the steam equipment 2 is connected to the outer jacket 9 through a pipeline, and a steam valve 11 is provided on the pipeline for opening or closing the steam or controlling the steam flow rate.

[0063] Specifically, the cooling medium used in the cooling circulation equipment 3 is water.

[0064] Specifically, the cooling circulation equipment 3 is connected to the outer jacket 9 through a pipeline, and a circulating cooling water valve 12 is provided on the pipeline for opening or closing the cooling water or controlling the cooling water flow rate.

[0065] Specifically, the cooling medium used in the refrigeration circulation equipment 4 is a refrigerant (such as ethylene glycol solution or calcium chloride solution, etc.).

[0066] Specifically, a sampling port 14 is provided at the outlet of the refrigeration circulation equipment 4 for detecting the concentration of hydrochloric acid output from the refrigeration circulation equipment 4.

[0067] Specifically, the germanium tetrachloride collection tank 5 is connected to the refrigeration circulation equipment 4 through a pipeline, and a germanium tetrachloride receiving valve 13 is provided on the pipeline.

[0068] Specifically, the high-concentration hydrochloric acid storage tank 7 is connected to the refrigeration circulation equipment 4 through a pipeline, and a high-concentration hydrochloric acid storage tank acid-receiving valve 15 is provided on the pipeline.

[0069] Specifically, the low-concentration hydrochloric acid storage tank 8 is connected to the refrigeration circulation equipment 4 through a pipeline, and a low-concentration hydrochloric acid storage tank acid-receiving valve 16 is provided on the pipeline.

[0070] Specifically, the negative pressure equipment 6 is connected to the low-concentration hydrochloric acid storage tank 8 through a pipeline, and a negative pressure system connection valve 17 is provided on the pipeline.

[0071] Specifically, the negative pressure equipment 6 can be selected from a vacuum pump, a water jet vacuum unit, etc.

[0072] The following examples use the above germanium chlorination and distillation system.

[0073] Example 1

[0074] This embodiment provides a method for directly recovering hydrochloric acid and germanium by two-stage distillation after germanium chlorination distillation, including:

[0075] 1) Germanium chlorination distillation

[0076] According to the existing germanium material chlorination distillation process, after adding concentrated hydrochloric acid (concentration: 9.5 mol / L) and oxidant manganese dioxide to the germanium-containing material in an enamel reaction kettle, steam is introduced into the outer jacket of the enamel reaction kettle for heating and stirring to perform chlorination distillation, and crude germanium tetrachloride is produced.

[0077] 2) First-stage positive-pressure acid distillation

[0078] After the germanium chlorination distillation is completed, a mixture solution of distillation residue and distillation residual acid remains in the enamel reaction kettle; the steam is turned off, stirring is continued, and circulating cooling water at a temperature of 25 - 30 °C is introduced into the outer jacket of the enamel reaction kettle to cool the solution in the kettle to 93 °C. Stopping the introduction of circulating cooling water into the outer jacket of the enamel reaction kettle; opening the acid-receiving valve of the first-stage distillation recovery high-concentration hydrochloric acid storage tank, closing the germanium tetrachloride receiving valve, adjusting the set value of the refrigerant outlet temperature of the refrigeration circulation equipment to -5 °C; opening and controlling the steam valve, heating and maintaining stirring of the mixture solution of distillation residue and distillation residual acid remaining in the enamel reaction kettle in step 1), controlling the solution temperature in the enamel reaction kettle to be 110 - 118 °C, and the pressure in the enamel reaction kettle to be 110000 - 120000 Pa; the hydrochloric acid distilled out is condensed by the refrigeration circulation equipment and flows into the high-concentration hydrochloric acid storage tank; a sampling port is installed at the pipeline from the refrigeration circulation equipment to the storage tank for real-time sampling and detection of the distilled hydrochloric acid. When the volume of the distilled hydrochloric acid accounts for 35% of the volume of the concentrated hydrochloric acid added in step 1), heating is turned off and stirring is stopped. At this time, the molar concentration of HCl in the sampled distilled hydrochloric acid is 9.2 mol / L, and the first-stage positive-pressure acid distillation ends. The acidity of the high-concentration hydrochloric acid produced in this stage after mixing is 10.3 mol / L in terms of HCl molar concentration and 87.2 μg / ml in terms of germanium concentration, and it is reused for the germanium chlorination distillation process.

[0079] 3) Second-stage negative-pressure acid distillation

[0080] Open the acid inlet valve of the low-concentration hydrochloric acid storage tank for the second-stage negative-pressure distillation recovery, and start the negative-pressure system connected to the low-concentration storage tank to reduce the internal pressure of the low-concentration storage tank, pipeline, and distillation kettle, and control the internal pressure of the distillation kettle to be less than or equal to 90,000 Pa; then close the acid inlet valve of the high-concentration hydrochloric acid storage tank for the first-stage positive-pressure distillation recovery in step 2), adjust the set value of the refrigerant outlet temperature of the refrigeration cycle equipment to 5 °C, turn on the stirring, and open and control the steam valve to heat the mixture solution remaining after the first-stage positive-pressure acid distillation in the enamel reactor in step 2), and control the solution temperature in the kettle at 100-110 °C. When the volume of the distilled low-concentration hydrochloric acid accounts for 35% of the volume of the concentrated hydrochloric acid added in step 1), turn off the steam heating system, and the second-stage negative-pressure acid distillation ends. The low-concentration hydrochloric acid produced in this stage has a mixed HCl molar concentration of 4.6 mol / L and can be used for indium-gallium production, etc.

[0081] 4) Stop the kettle and drain the residue liquid

[0082] Close the negative-pressure system, continue stirring, add tap water (with a volume of 70% of the volume of the concentrated hydrochloric acid input in step 1)) to the enamel reactor, and introduce circulating cooling water at 25-30 °C into the outer jacket of the enamel reactor to cool the solution in the kettle; when the solution temperature in the enamel reactor cools to 60 °C, turn off the refrigeration cycle equipment; when the solution temperature in the enamel reactor cools to 45 °C, stop introducing the circulating cooling water, open the charging port and bottom valve of the enamel reactor, and discharge the residue liquid remaining after acid distillation to the environmental protection treatment system for compliance disposal.

[0083] Using the method of this embodiment, the volume of the high-concentration hydrochloric acid produced by the first-stage positive-pressure acid distillation accounts for 35% of the volume of the concentrated hydrochloric acid input for germanium chlorination distillation, the acidity is a HCl molar concentration of 10.3 mol / L, and the germanium concentration is 87.2 μg / ml; the volume of the high-concentration hydrochloric acid produced by the second-stage positive-pressure acid distillation accounts for 35% of the volume of the concentrated hydrochloric acid input for germanium chlorination distillation, and the acidity is a HCl molar concentration of 4.6 mol / L; the cumulative volume of the regenerated hydrochloric acid accounts for 70% of the volume of the concentrated hydrochloric acid input for germanium chlorination distillation.

[0084] Example 2

[0085] This embodiment provides a method for directly recovering hydrochloric acid and germanium by two-stage distillation after germanium chlorination distillation, including:

[0086] 1) Germanium chlorination distillation

[0087] According to the existing germanium material chlorination distillation process, germanium-containing materials are added with concentrated hydrochloric acid (concentration of 10.6 mol / L) and oxidant ferric chloride in an enamel reactor, and then steam is introduced into the outer jacket of the enamel reactor for heating and stirring for chlorination distillation to produce crude germanium tetrachloride.

[0088] 2) First-stage positive-pressure acid distillation

[0089] After the germanium chlorination distillation is completed, a mixture solution of distillation residue and distillation residual acid remains in the enamel reactor; turn off the steam, continue stirring, and pass circulating cooling water with a temperature of 25 - 40°C into the outer jacket of the enamel reactor to cool the solution in the reactor to 90°C. Stop passing circulating cooling water into the outer jacket of the enamel reactor; open the acid receiving valve of the high-concentration hydrochloric acid storage tank for one-stage distillation recovery, close the germanium tetrachloride feeding valve, and adjust the set value of the refrigerant outlet temperature of the refrigeration circulation equipment to 0°C; open and control the steam valve, heat the mixture solution of distillation residue and distillation residual acid remaining in the enamel reactor in step 1) and keep stirring, control the solution temperature in the enamel reactor to be 110 - 115°C, and the pressure in the enamel reactor to be 110000 - 117000 pa. The distilled hydrochloric acid flows into the high-concentration hydrochloric acid storage tank after being condensed by the refrigeration circulation equipment. A sampling port is installed at the pipeline from the refrigeration circulation equipment to the storage tank for real-time sampling and detection of the distilled hydrochloric acid. When the volume of the distilled hydrochloric acid accounts for 33% of the volume of the concentrated hydrochloric acid added in step 1), turn off the heating and stop stirring. At this time, the molar concentration of HCl in the sampled distilled hydrochloric acid is 9.0 mol / L, and the first-stage positive-pressure acid distillation ends. The acidity of the high-concentration hydrochloric acid produced in this stage is 9.8 mol / L in terms of HCl molar concentration and 79.4 μg / ml in terms of germanium concentration after mixing, and it is recycled for the germanium chlorination distillation process.

[0090] 3) Second-stage negative-pressure acid distillation

[0091] Open the acid receiving valve of the low-concentration hydrochloric acid storage tank for second-stage negative-pressure distillation recovery, and start the negative-pressure system connected to the low-concentration storage tank to reduce the internal pressure of the low-concentration storage tank, pipeline, and distillation kettle, and control the internal pressure of the distillation kettle to be less than or equal to 85000 pa; then close the acid receiving valve of the high-concentration hydrochloric acid storage tank for first-stage positive-pressure distillation recovery in step 2), adjust the set value of the refrigerant outlet temperature of the refrigeration circulation equipment to 7°C, start stirring, and open and control the steam valve to heat the mixture solution remaining after the first-stage positive-pressure acid distillation in the enamel reactor in step 2), and control the solution temperature in the kettle to be 100 - 110°C. When the volume of the distilled low-concentration hydrochloric acid accounts for 30% of the volume of the concentrated hydrochloric acid added in step 1), turn off the steam heating system, and the second-stage negative-pressure acid distillation ends. The low-concentration hydrochloric acid produced in this stage has a molar concentration of 7.2 mol / L in terms of HCl after mixing and can be used for indium-gallium production, etc.

[0092] 4) Stop the kettle and drain the slag liquid

[0093] Turn off the negative pressure system and continue stirring. Add tap water (with a volume of 60% of the volume of concentrated hydrochloric acid added in Step 1) into the enamel reactor, and introduce circulating cooling water at 25 - 40 °C into the outer jacket of the enamel reactor to cool the solution in the reactor. When the temperature of the solution in the enamel reactor cools to 50 °C, turn off the refrigeration cycle equipment. When the temperature of the solution in the enamel reactor cools to 45 °C, stop introducing circulating cooling water, open the charging port and bottom valve of the enamel reactor, and discharge the residue liquid remaining from the acid evaporation to the environmental protection treatment system for compliant disposal.

[0094] Using the method of this embodiment, the volume of high - concentration hydrochloric acid produced by the first - stage positive - pressure acid evaporation accounts for 33% of the volume of concentrated hydrochloric acid input for germanium chlorination distillation. The acidity is 9.8 mol / L in terms of HCl molar concentration and 79.4 μg / ml in terms of germanium concentration; the volume of high - concentration hydrochloric acid produced by the second - stage positive - pressure acid evaporation accounts for 30% of the volume of concentrated hydrochloric acid input for germanium chlorination distillation, and the acidity is 7.2 mol / L in terms of HCl molar concentration; the cumulative volume of regenerated hydrochloric acid accounts for 63% of the volume of concentrated hydrochloric acid input for germanium chlorination distillation.

[0095] Example 3

[0096] This embodiment provides a method for directly recovering hydrochloric acid and germanium by two - stage distillation after germanium chlorination distillation, including:

[0097] 1) Germanium chlorination distillation

[0098] According to the existing germanium material chlorination distillation process, germanium - containing materials are added with concentrated hydrochloric acid (concentration of 10.1 mol / L) and oxidant manganese dioxide in an enamel reactor, and then steam is introduced into the outer jacket of the enamel reactor for heating and stirring for chlorination distillation to produce crude germanium tetrachloride.

[0099] 2) First - stage positive - pressure acid evaporation

[0100] After the germanium chlorination distillation is completed, a mixture solution of distillation residue and distillation residual acid remains in the enamel reactor; turn off the steam, continue stirring, and pass circulating cooling water with a temperature of 25 - 35°C into the outer jacket of the enamel reactor to cool the solution in the reactor to 87°C. Stop passing circulating cooling water into the outer jacket of the enamel reactor; open the acid receiving valve of the high-concentration hydrochloric acid storage tank for the first-stage distillation recovery, close the germanium tetrachloride feeding valve, and adjust the set value of the refrigerant outlet temperature of the refrigeration circulation equipment to 5°C; open and control the steam valve, heat the mixture solution of the distillation residue and distillation residual acid remaining in the enamel reactor in step 1) and keep stirring, control the solution temperature in the enamel reactor to be 105 - 113°C, and the pressure in the enamel reactor to be 105000 - 115000 pa. The distilled hydrochloric acid flows into the high-concentration hydrochloric acid storage tank after being condensed by the condensation system. A sampling port is installed at the pipeline from the refrigeration circulation equipment to the storage tank for real-time sampling and detection of the distilled hydrochloric acid; when the volume of the distilled hydrochloric acid accounts for 35% of the volume of the concentrated hydrochloric acid added in step 1), turn off the heating and stop stirring. At this time, the molar concentration of HCl in the sampled distilled hydrochloric acid is 9.6 mol / L, and the first-stage positive-pressure acid distillation ends; the acidity of the high-concentration hydrochloric acid produced in this stage after mixing is 10.7 mol / L in terms of HCl molar concentration and 82.5 μg / ml in terms of germanium concentration, and it is used for recycling in the germanium chlorination distillation process.

[0101] 3) Second-stage negative-pressure acid distillation: Open the acid receiving valve of the low-concentration hydrochloric acid storage tank for the second-stage negative-pressure distillation recovery, and start the negative-pressure system connected to the low-concentration storage tank to reduce the internal pressure of the low-concentration storage tank, pipeline, and distillation kettle, and control the internal pressure of the distillation kettle to be less than or equal to 80000 pa; then close the acid receiving valve of the high-concentration hydrochloric acid storage tank for the first-stage positive-pressure distillation recovery in step 2), adjust the set value of the refrigerant outlet temperature of the refrigeration circulation equipment to 5°C, start stirring, and open and control the steam valve to heat the mixture solution remaining after the first-stage positive-pressure acid distillation in the enamel reactor in step 2), and control the solution temperature in the kettle to be 100 - 108°C.; when the volume of the distilled low-concentration hydrochloric acid accounts for 30% of the volume of the concentrated hydrochloric acid added in step 1), turn off the steam heating system, and the second-stage negative-pressure acid distillation ends; the low-concentration hydrochloric acid produced in this stage has a molar concentration of 7.1 mol / L in terms of HCl after being mixed and can be used for indium-gallium production, etc.

[0102] 4) Stop the kettle and drain the slag liquid

[0103] Turn off the negative pressure system and continue stirring. Add tap water (the volume of tap water is 60% of the volume of the highly concentrated hydrochloric acid added in step 1) into the enamel reactor, and introduce circulating cooling water at 25 - 35°C into the outer jacket of the enamel reactor to cool the solution in the reactor. When the temperature of the solution in the enamel reactor cools to 55°C, turn off the refrigeration circulation equipment. When the temperature of the solution in the enamel reactor cools to 42°C, stop introducing the circulating cooling water, open the charging port and bottom valve of the enamel reactor, and discharge the residue liquid remaining from the acid evaporation to the environmental protection treatment system for compliant disposal.

[0104] Using the regeneration method of this embodiment, the volume of the highly concentrated hydrochloric acid produced by the first-stage positive-pressure acid evaporation accounts for 35% of the volume of the concentrated hydrochloric acid input in the germanium chlorination distillation. The acidity is that the molar concentration of HCl is 10.7 mol / L and the germanium concentration is 82.5 μg / ml. The volume of the highly concentrated hydrochloric acid produced by the second-stage positive-pressure acid evaporation accounts for 30% of the volume of the concentrated hydrochloric acid input in the germanium chlorination distillation, and the acidity is that the molar concentration of HCl is 7.1 mol / L. The cumulative volume of the regenerated hydrochloric acid accounts for 65% of the volume of the concentrated hydrochloric acid input in the germanium chlorination distillation.

[0105] Although the present invention has been described in detail above with general descriptions, specific embodiments and experiments, based on the present invention, some modifications or improvements can be made, which are obvious to those skilled in the art. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection required by the present invention.

Claims

1. A germanium chlorination distillation system, characterized in that, Comprising: A distillation reaction device; the distillation reaction device includes an enamel reactor and an outer jacket; the enamel reactor is used for heating and distilling to generate germanium tetrachloride gas; the outer jacket is arranged on the outer surface of the enamel reactor; A steam device, communicated with the outer jacket, and used for introducing high-temperature steam into the outer jacket to heat the enamel reactor; A cooling circulation device, communicated with the outer jacket, and used for introducing cooling water into the outer jacket to cool the materials in the enamel reactor; A refrigeration circulation device, communicated with the enamel reactor, and used for condensing the germanium tetrachloride gas distilled out from the enamel reactor or the hydrogen chloride gas distilled out from the enamel reactor; A germanium tetrachloride collection tank, communicated with the refrigeration circulation device, and used for collecting the liquid germanium tetrachloride generated after the germanium tetrachloride gas distilled out from the enamel reactor is condensed by the refrigeration circulation device; A high-concentration hydrochloric acid storage tank, communicated with the refrigeration circulation device, and used for collecting the high-concentration hydrochloric acid generated after the mixed gas of hydrogen chloride and water distilled out from the enamel reactor is condensed by the refrigeration circulation device; A low-concentration hydrochloric acid storage tank, communicated with the refrigeration circulation device, and used for collecting the low-concentration hydrochloric acid generated after the mixed gas of hydrogen chloride and water distilled out from the enamel reactor is condensed by the refrigeration circulation device; A negative pressure device, communicated with the low-concentration hydrochloric acid storage tank, and used for reducing the pressure in the enamel reactor.

2. The germanium chlorination distillation system according to claim 1, wherein, The enamel reactor is further provided with a feeding port and a discharging port; and / or, The enamel reactor further includes a stirrer for stirring the materials therein.

3. The germanium chlorination distillation system according to claim 1 or 2, characterized in that, The steam device is communicated with the outer jacket through a pipeline, and a steam valve is arranged on the pipeline for opening or closing the steam or controlling the steam flow rate; and / or, The cooling circulation device is communicated with the outer jacket through a pipeline, and a circulating cooling water valve is arranged on the pipeline for opening or closing the cooling water or controlling the cooling water flow rate.

4. The germanium chlorination distillation system according to any one of claims 1-3, characterized in that, A sampling port is arranged at the outlet of the refrigeration circulation device for detecting the concentration of the hydrochloric acid output from the refrigeration circulation device.

5. The germanium chlorination distillation system according to any one of claims 1-4, characterized in that, The germanium tetrachloride collection tank is communicated with the refrigeration circulation device through a pipeline, and a germanium tetrachloride receiving valve is arranged on the pipeline; and / or, The high-concentration hydrochloric acid storage tank is communicated with the refrigeration circulation device through a pipeline, and a high-concentration hydrochloric acid storage tank acid receiving valve is arranged on the pipeline; and / or, The low-concentration hydrochloric acid storage tank is communicated with the refrigeration circulation device through a pipeline, and a low-concentration hydrochloric acid storage tank acid receiving valve is arranged on the pipeline.

6. The germanium chlorination distillation system according to any one of claims 1-5, characterized in that, The negative pressure device is communicated with the low-concentration hydrochloric acid storage tank through a pipeline, and a negative pressure system connection valve is arranged on the pipeline; and / or, The negative pressure device is selected from a vacuum pump or a water jet vacuum unit.

7. A method for directly recovering hydrochloric acid and germanium by two-stage distillation after germanium chlorination distillation, which is characterized in that, Using the germanium chlorination distillation system according to any one of claims 1-6; the method includes: 1), Germanium chlorination distillation Put the germanium-containing material, concentrated hydrochloric acid and an oxidant into the enamel reactor, and introduce steam into the outer jacket of the enamel reactor for heating and distillation; the generated germanium tetrachloride gas is condensed and then collected; 2), First-stage positive-pressure acid distillation After the germanium chlorination distillation in step 1) ends, stop passing high-temperature steam into the outer jacket of the enamel reactor; pass circulating cooling water into the outer jacket of the enamel reactor to cool the mixture of distillation residue and distillation residual acid in the enamel reactor in step 1) to 85 - 95 °C, and then stop passing circulating cooling water into the outer jacket of the enamel reactor; Then open the acid receiving valve of the high-concentration hydrochloric acid storage tank, close the germanium tetrachloride receiving valve, and adjust the refrigerant outlet temperature of the refrigeration circulation equipment; then pass high-temperature steam into the outer jacket of the enamel reactor, control the temperature of the material in the enamel reactor to be 105 - 120 °C, and the pressure to be 105000 - 120000 pa; the distilled hydrogen chloride gas is condensed by the refrigeration circulation equipment and then enters the high-concentration hydrochloric acid storage tank; when the volume of the distilled hydrochloric acid accounts for 35% of the volume of the concentrated hydrochloric acid added in step 1) or when the molar concentration of HCl in the distilled hydrochloric acid is less than or equal to 9 mol / L, the first-stage positive-pressure acid distillation ends; 3) Second-stage negative-pressure acid distillation After the first-stage positive-pressure acid distillation in step 2) ends, stop passing high-temperature steam into the outer jacket of the enamel reactor; close the acid receiving valve of the high-concentration hydrochloric acid storage tank, open the acid receiving valve of the low-concentration hydrochloric acid storage tank, start the negative-pressure equipment, and control the pressure in the enamel reactor to be less than or equal to 90000 pa; adjust the refrigerant outlet temperature of the refrigeration circulation equipment; Then pass high-temperature steam into the outer jacket of the enamel reactor, control the temperature of the material in the enamel reactor to be 95 - 110 °C, and the pressure to be less than or equal to 90000 pa; the distilled hydrogen chloride gas is condensed by the refrigeration circulation equipment and then enters the low-concentration hydrochloric acid storage tank; when the volume of the hydrochloric acid to be distilled accounts for 25 - 35% of the volume of the concentrated hydrochloric acid added in step 1), the second-stage negative-pressure acid distillation ends; 4) Stop the reactor and discharge the residue liquid After the second-stage negative-pressure acid distillation in step 3) ends, close the negative-pressure system and stop passing high-temperature steam into the outer jacket of the enamel reactor; add water into the enamel reactor and pass circulating cooling water into the outer jacket of the enamel reactor to cool the waste material in the enamel reactor; then discharge the waste material.

8. The method for directly recovering hydrochloric acid and germanium by two-stage distillation after germanium chlorination distillation according to claim 7, characterized in that, In step 1), the concentration of the concentrated hydrochloric acid is greater than or equal to 9.5 mol / L; and / or, In step 1), the oxidant is selected from ferric chloride, manganese dioxide or chlorine; and / or, After the germanium chlorination distillation in step 1), the temperature of the remaining material in the enamel reactor is 105 - 115 °C; and / or, During the germanium chlorination distillation in step 1), stirring is carried out; and / or, In step 1), the refrigerant outlet temperature of the refrigeration circulation equipment is set to -10 to -5 °C.

9. The method for directly recovering hydrochloric acid and germanium by two-stage distillation after germanium chlorination distillation according to claim 7 or 8, characterized in that, In step 2), the temperature of the circulating cooling water passed into the outer jacket of the enamel reactor is less than or equal to 40 °C; and / or, In step 2), the refrigerant outlet temperature of the refrigeration circulation equipment is set to -5 to 5 °C; and / or, During the first-stage positive-pressure acid distillation in step 2), stirring is carried out; and / or, After the concentrated hydrochloric acid obtained from the first-stage positive-pressure acid distillation in step 2) is mixed evenly, it contains 20 - 100 μg / ml of germanium and the molar concentration of HCl is greater than or equal to 9.5 mol / L.

10. The method for directly recovering hydrochloric acid and germanium by two-stage distillation after germanium chlorination distillation according to any one of claims 7-9, characterized in that, In step 3), the refrigerant outlet temperature of the refrigeration circulation equipment is adjusted and set to 5 - 10 °C; and / or, Step 3) Stirring is carried out during the two-stage negative-pressure acid evaporation; and / or, After the concentrated hydrochloric acid obtained by the two-stage negative-pressure acid evaporation is mixed evenly, the molar concentration of HCl is greater than or equal to 4.5 mol / L and it does not contain germanium.

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