A method for purifying metallic germanium by removing arsenic using waste acid

Abstract

The present invention relates to the field of chemical industry production technology, and discloses a method for purifying metallic germanium by removing arsenic using waste acid, comprising the following steps: S1: recovering a germanium enrichment from processing waste; S2: neutralizing the germanium-containing enrichment in S1; S3: distilling out high-purity germanium dioxide; S4: reducing to obtain a germanium ingot, wherein the processing waste in S1 comprises: cutting powder, fragments, filter paper, and etching liquid, and the mass fraction of germanium in the processing waste is: 60-70 parts of cutting powder, 80-90 parts of fragments, 20-30 parts of filter paper, and 2-10 parts of etching liquid. In S2, the method specifically comprises: S201: placing the processing waste in a reaction vessel, then adding lime milk to the reaction vessel, and continuously stirring until the pH value of the mixture is 10-11, then adding water, filtering, and obtaining a first filtrate with a chloride ion concentration of 120±10 g / L. Through this preparation method, the hydrochloric acid in the waste acid of germanium distillation can be utilized, and finally a germanium ingot with considerable economic benefits can be obtained.

Description

Technical Field

[0001] The invention relates to the technical field of chemical industrial production, in particular to a method for purifying metallic germanium by removing arsenic from waste acid. Background Art

[0002] Germanium distillation waste acid is the waste acid produced during the distillation of germanium in a hydrochloric acid system. Because germanium concentrate or germanium-enriched ash contains a large amount of heavy metals such as arsenic, lead, cadmium, etc., and contains dissolved silicon, the composition of germanium distillation waste acid is complex, but the acidity is relatively high, generally containing 6 to 9 mol / L of acid.

[0003] The traditional method for treating spent acid from germanium distillation is direct neutralization. Its biggest drawbacks are that it requires a large footprint and consumes a large amount of alkali, resulting in a waste of resources and increased wastewater treatment costs. Currently, the main methods for recycling spent acid from germanium distillation are evaporation and concentration, as well as extraction. However, the presence of impurities and soluble silicon in spent acid from germanium distillation presents certain challenges for the recycling of waste hydrochloric acid.

[0004] In view of the current status of the above-mentioned distillation waste acid treatment, providing a method for using waste acid to remove arsenic and purify metallic germanium, and utilizing the hydrochloric acid in the germanium distillation waste acid to ultimately obtain germanium ingots with considerable economic benefits is the research direction of technical personnel in this field. Summary of the Invention

[0005] (1) Technical problems solved

[0006] In view of the shortcomings of the prior art, the present invention provides a method for purifying metallic germanium by removing arsenic using waste acid.

[0007] (2) Technical solution

[0008] To achieve the above object, the present invention provides the following technical solution: a method for purifying metallic germanium by removing arsenic using waste acid, comprising the following steps:

[0009] S1: Recovery of germanium concentrate from processing waste;

[0010] S2: neutralize the germanium-containing enrichment in S1;

[0011] S3: distilling out high-purity germanium dioxide;

[0012] S4: reduction to obtain a germanium ingot.

[0013] Preferably, in said S1, the processing waste includes: cutting powder, fragments, filter paper, and corrosive liquid.

[0014] Preferably, the mass proportions of germanium in the processing waste are: 60-70 parts of cutting powder, 80-90 parts of fragments, 20-30 parts of filter paper, and 2-10 parts of etching solution.

[0015] Preferably, the S2 specifically includes:

[0016] S201: placing the processed waste into a reaction vessel, then adding lime milk to the reaction vessel and continuously stirring until the pH value of the mixture reaches 10-11, then adding water and filtering to obtain a first filtrate having a chloride ion concentration of 120±10 g / L;

[0017] S202: adding ferric chloride to the first filtrate and stirring and mixing, then adding phosphoric acid and nitric acid solutions, stirring and mixing until flocculation occurs and the Fe content of the mixed system is less than 5 mg / L, thereby obtaining a second filtrate;

[0018] S203: The pH value of the second filtrate is adjusted to neutral and then evaporated through a multi-effect evaporator to obtain a concentrated mother liquor with a Baume degree of 45 to 50 degrees, which is then heated to distill out germanium tetrachloride.

[0019] Preferably, in S202, chlorine gas needs to be introduced, and the flow rate of the chlorine gas is 0.5-50 liters / minute.

[0020] Preferably, in S203, germanium tetrachloride is distilled out by steam heating.

[0021] Preferably, said S3 includes the following steps:

[0022] S301: adding hydrochloric acid flux to germanium tetrachloride for extraction to remove impurity arsenic, and purifying it through quartz tower distillation to obtain high-purity germanium tetrachloride;

[0023] S202: Germanium tetrachloride is hydrolyzed with high-purity water to obtain high-purity germanium dioxide (GeO2). Some impurities will enter the hydrolysis mother liquor, so the hydrolysis process is also a purification process. The germanium in the hydrolysis mother liquor can be returned for hydrochloric acid distillation.

[0024] Preferably, said S4 includes the following steps:

[0025] S401: drying and calcining pure germanium dioxide, and reducing it with hydrogen at 650-680° C. in a quartz tube of a reduction furnace to obtain metallic germanium;

[0026] S402: When the reduction is completed, the temperature can be gradually raised to 1000-1100°C to melt the germanium, and then slowly cooled to obtain a germanium ingot.

[0027] (3) Beneficial effects

[0028] Compared with the prior art, the present invention provides a method for purifying metallic germanium by removing arsenic using waste acid, which has the following beneficial effects:

[0029] 1. A method for purifying metallic germanium by removing arsenic from waste acid. Through this preparation method, the waste of raw materials can be reduced, the recycling effect of waste can be improved, and thus the waste of energy can be reduced.

[0030] 2. This method uses waste acid to remove arsenic and purify metallic germanium. Through this preparation method, the cost of treating chlorine-containing wastewater after neutralization is reduced, and the waste of resources is reduced.

[0031] 3. A method for purifying metallic germanium by removing arsenic from waste acid. Through this preparation method, the hydrochloric acid in the waste acid from germanium distillation can be utilized, and ultimately germanium ingots with considerable economic benefits can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention and do not constitute a limitation of the present invention. In the accompanying drawings:

[0033] Figure 1 It is a flow chart of the steps of the present invention. DETAILED DESCRIPTION

[0034] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0035] Examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, but are not to be construed as limiting the present invention.

[0036] In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", "circumferential" and the like to indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as limiting the present invention.

[0037] In the present invention, unless otherwise expressly specified or limited, the terms "mounted," "connected," "connect," "fixed," etc. should be understood broadly. For example, they may refer to fixed connection, detachable connection, or integration; mechanical connection or electrical connection; direct connection or indirect connection through an intermediate medium; internal communication between two components or interaction between two components. Those skilled in the art will understand the specific meanings of the above terms in the present invention based on specific circumstances.

[0038] Example 1

[0039] A method for purifying metallic germanium by removing arsenic using waste acid comprises the following steps:

[0040] S1: Recovering a germanium concentrate from processing waste; in S1, the mass fractions of germanium in the processing waste are: 60 parts of cutting powder, 80 parts of fragments, 20 parts of filter paper, and 2 parts of etching solution;

[0041] S2: neutralize the germanium-containing enrichment in S1;

[0042] S201: placing the processed waste into a reaction vessel, then adding lime milk to the reaction vessel and continuously stirring until the pH value of the mixture reaches 10-11, then adding water and filtering to obtain a first filtrate having a chloride ion concentration of 120±10 g / L;

[0043] S202: Adding ferric chloride to the first filtrate and stirring and mixing, then adding phosphoric acid and nitric acid solutions, stirring and mixing until flocculation occurs and the Fe content of the mixed system is less than 5 mg / L, thereby obtaining a second filtrate. Chlorine gas is also introduced at a flow rate of 0.5-50 L / min;

[0044] S203: adjusting the pH value of the second filtrate to neutral and evaporating the filtrate through a multi-effect evaporator to obtain a concentrated mother liquor with a Baume degree of 45 to 50 degrees, and then heating the mother liquor to distill out germanium tetrachloride by steam heating;

[0045] S3: distilling out high-purity germanium dioxide;

[0046] S301: adding hydrochloric acid flux to germanium tetrachloride for extraction to remove impurity arsenic, and purifying it through quartz tower distillation to obtain high-purity germanium tetrachloride;

[0047] S202: Germanium tetrachloride is hydrolyzed with high-purity water to obtain high-purity germanium dioxide (GeO2). Some impurities will enter the hydrolysis mother liquor, so the hydrolysis process is also a purification process. The germanium in the hydrolysis mother liquor can be returned for hydrochloric acid distillation.

[0048] S4: reduction to obtain a germanium ingot.

[0049] S401: drying and calcining pure germanium dioxide, and reducing it with hydrogen at 650-680° C. in a quartz tube of a reduction furnace to obtain metallic germanium;

[0050] S402: When the reduction is completed, the temperature can be gradually raised to 1000-1100°C to melt the germanium, and then slowly cooled to obtain a germanium ingot.

[0051] Example 2

[0052] A method for purifying metallic germanium by removing arsenic using waste acid comprises the following steps:

[0053] S1: Recovering a germanium concentrate from processing waste; in S1, the mass fractions of germanium in the processing waste are: 63 parts of cutting powder, 83 parts of debris, 23 parts of filter paper, and 5 parts of etching solution;

[0054] S2: neutralize the germanium-containing enrichment in S1;

[0055] S201: placing the processed waste into a reaction vessel, then adding lime milk to the reaction vessel and continuously stirring until the pH value of the mixture reaches 10-11, then adding water and filtering to obtain a first filtrate having a chloride ion concentration of 120±10 g / L;

[0056] S202: Adding ferric chloride to the first filtrate and stirring and mixing, then adding phosphoric acid and nitric acid solutions, stirring and mixing until flocculation occurs and the Fe content of the mixed system is less than 5 mg / L, thereby obtaining a second filtrate. Chlorine gas is also introduced at a flow rate of 0.5-50 L / min;

[0057] S203: adjusting the pH value of the second filtrate to neutral and evaporating the filtrate through a multi-effect evaporator to obtain a concentrated mother liquor with a Baume degree of 45 to 50 degrees, and then heating the mother liquor to distill out germanium tetrachloride by steam heating;

[0058] S3: distilling out high-purity germanium dioxide;

[0059] S301: adding hydrochloric acid flux to germanium tetrachloride for extraction to remove impurity arsenic, and purifying it through quartz tower distillation to obtain high-purity germanium tetrachloride;

[0060] S202: Germanium tetrachloride is hydrolyzed with high-purity water to obtain high-purity germanium dioxide (GeO2). Some impurities will enter the hydrolysis mother liquor, so the hydrolysis process is also a purification process. The germanium in the hydrolysis mother liquor can be returned for hydrochloric acid distillation.

[0061] S4: reduction to obtain a germanium ingot.

[0062] S401: drying and calcining pure germanium dioxide, and reducing it with hydrogen at 650-680° C. in a quartz tube of a reduction furnace to obtain metallic germanium;

[0063] S402: When the reduction is completed, the temperature can be gradually raised to 1000-1100°C to melt the germanium, and then slowly cooled to obtain a germanium ingot.

[0064] Example 3

[0065] A method for purifying metallic germanium by removing arsenic using waste acid comprises the following steps:

[0066] S1: Recovering a germanium concentrate from processing waste; in S1, the mass fractions of germanium in the processing waste are: 65 parts of cutting powder, 85 parts of debris, 25 parts of filter paper, and 7 parts of etching solution;

[0067] S2: neutralize the germanium-containing enrichment in S1;

[0068] S201: placing the processed waste into a reaction vessel, then adding lime milk to the reaction vessel and continuously stirring until the pH value of the mixture reaches 10-11, then adding water and filtering to obtain a first filtrate having a chloride ion concentration of 120±10 g / L;

[0069] S202: Adding ferric chloride to the first filtrate and stirring and mixing, then adding phosphoric acid and nitric acid solutions, stirring and mixing until flocculation occurs and the Fe content of the mixed system is less than 5 mg / L, thereby obtaining a second filtrate. Chlorine gas is also introduced at a flow rate of 0.5-50 L / min;

[0070] S203: adjusting the pH value of the second filtrate to neutral and evaporating the filtrate through a multi-effect evaporator to obtain a concentrated mother liquor with a Baume degree of 45 to 50 degrees, and then heating the mother liquor to distill out germanium tetrachloride by steam heating;

[0071] S3: distilling out high-purity germanium dioxide;

[0072] S301: adding hydrochloric acid flux to germanium tetrachloride for extraction to remove impurity arsenic, and purifying it through quartz tower distillation to obtain high-purity germanium tetrachloride;

[0073] S202: Germanium tetrachloride is hydrolyzed with high-purity water to obtain high-purity germanium dioxide (GeO2). Some impurities will enter the hydrolysis mother liquor, so the hydrolysis process is also a purification process. The germanium in the hydrolysis mother liquor can be returned for hydrochloric acid distillation.

[0074] S4: reduction to obtain a germanium ingot.

[0075] S401: drying and calcining pure germanium dioxide, and reducing it with hydrogen at 650-680° C. in a quartz tube of a reduction furnace to obtain metallic germanium;

[0076] S402: When the reduction is completed, the temperature can be gradually raised to 1000-1100°C to melt the germanium, and then slowly cooled to obtain a germanium ingot.

[0077] Example 4

[0078] A method for purifying metallic germanium by removing arsenic using waste acid comprises the following steps:

[0079] S1: Recovering a germanium concentrate from processing waste; in S1, the mass fractions of germanium in the processing waste are: 68 parts of cutting powder, 88 parts of debris, 28 parts of filter paper, and 9 parts of etching solution;

[0080] S2: neutralize the germanium-containing enrichment in S1;

[0081] S201: placing the processed waste into a reaction vessel, then adding lime milk to the reaction vessel and continuously stirring until the pH value of the mixture reaches 10-11, then adding water and filtering to obtain a first filtrate having a chloride ion concentration of 120±10 g / L;

[0082] S202: Adding ferric chloride to the first filtrate and stirring and mixing, then adding phosphoric acid and nitric acid solutions, stirring and mixing until flocculation occurs and the Fe content of the mixed system is less than 5 mg / L, thereby obtaining a second filtrate. Chlorine gas is also introduced at a flow rate of 0.5-50 L / min;

[0083] S203: adjusting the pH value of the second filtrate to neutral and evaporating the filtrate through a multi-effect evaporator to obtain a concentrated mother liquor with a Baume degree of 45 to 50 degrees, and then heating the mother liquor to distill out germanium tetrachloride by steam heating;

[0084] S3: distilling out high-purity germanium dioxide;

[0085] S301: adding hydrochloric acid flux to germanium tetrachloride for extraction to remove impurity arsenic, and purifying it through quartz tower distillation to obtain high-purity germanium tetrachloride;

[0086] S202: Germanium tetrachloride is hydrolyzed with high-purity water to obtain high-purity germanium dioxide (GeO2). Some impurities will enter the hydrolysis mother liquor, so the hydrolysis process is also a purification process. The germanium in the hydrolysis mother liquor can be returned for hydrochloric acid distillation.

[0087] S4: reduction to obtain a germanium ingot.

[0088] S401: drying and calcining pure germanium dioxide, and reducing it with hydrogen at 650-680° C. in a quartz tube of a reduction furnace to obtain metallic germanium;

[0089] S402: When the reduction is completed, the temperature can be gradually raised to 1000-1100°C to melt the germanium, and then slowly cooled to obtain a germanium ingot.

[0090] Example 5

[0091] A method for purifying metallic germanium by removing arsenic using waste acid comprises the following steps:

[0092] S1: Recovering a germanium concentrate from processing waste; in S1, the mass fractions of germanium in the processing waste are: 70 parts of cutting powder, 90 parts of debris, 30 parts of filter paper, and 10 parts of etching solution;

[0093] S2: neutralize the germanium-containing enrichment in S1;

[0094] S201: placing the processed waste into a reaction vessel, then adding lime milk to the reaction vessel and continuously stirring until the pH value of the mixture reaches 10-11, then adding water and filtering to obtain a first filtrate having a chloride ion concentration of 120±10 g / L;

[0095] S202: Adding ferric chloride to the first filtrate and stirring and mixing, then adding phosphoric acid and nitric acid solutions, stirring and mixing until flocculation occurs and the Fe content of the mixed system is less than 5 mg / L, thereby obtaining a second filtrate. Chlorine gas is also introduced at a flow rate of 0.5-50 L / min;

[0096] S203: adjusting the pH value of the second filtrate to neutral and evaporating the filtrate through a multi-effect evaporator to obtain a concentrated mother liquor with a Baume degree of 45 to 50 degrees, and then heating the mother liquor to distill out germanium tetrachloride by steam heating;

[0097] S3: distilling out high-purity germanium dioxide;

[0098] S301: adding hydrochloric acid flux to germanium tetrachloride for extraction to remove impurity arsenic, and purifying it through quartz tower distillation to obtain high-purity germanium tetrachloride;

[0099] S202: Germanium tetrachloride is hydrolyzed with high-purity water to obtain high-purity germanium dioxide (GeO2). Some impurities will enter the hydrolysis mother liquor, so the hydrolysis process is also a purification process. The germanium in the hydrolysis mother liquor can be returned for hydrochloric acid distillation.

[0100] S4: reduction to obtain a germanium ingot.

[0101] S401: drying and calcining pure germanium dioxide, and reducing it with hydrogen at 650-680° C. in a quartz tube of a reduction furnace to obtain metallic germanium;

[0102] S402: When the reduction is completed, the temperature can be gradually raised to 1000-1100°C to melt the germanium, and then slowly cooled to obtain a germanium ingot.

[0103] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variants thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or device comprising a series of elements includes not only those elements, but also other elements not explicitly listed, or elements inherent to such process, method, article, or device. In the absence of further limitations, an element defined by the statement "comprising a reference structure" does not exclude the presence of additional identical elements in the process, method, article, or device comprising the element.

Claims

1. A method for purifying metallic germanium by removing arsenic from waste acid, characterized in that: The following steps are involved: S1: Recovery of germanium concentrate from processing waste; S2: neutralize the germanium-containing enrichment in S1; S3: distilling out high-purity germanium dioxide; S4: reduction to obtain germanium ingot; Said S2 specifically includes: S201: Placing the processed waste into a reaction vessel, then adding lime milk to the reaction vessel and continuously stirring until the pH value of the mixture reaches 10-11, then adding water and filtering to obtain a first filtrate having a chloride ion concentration of 120±10 g / L; S202: adding ferric chloride to the first filtrate and stirring and mixing, then adding phosphoric acid and nitric acid solutions, stirring and mixing until flocculation occurs and the Fe content of the mixed system is less than 5 mg / L, thereby obtaining a second filtrate; S203: adjusting the pH value of the second filtrate to neutral and evaporating the filtrate through a multi-effect evaporator to obtain a concentrated mother liquor with a Baume degree of 45 to 50 degrees, which is then heated to distill out germanium tetrachloride; The S3 includes the following steps: S301: adding hydrochloric acid flux to germanium tetrachloride for extraction to remove impurity arsenic, and purifying it through quartz tower distillation to obtain high-purity germanium tetrachloride; S302: hydrolyzing germanium tetrachloride with high-purity water to obtain high-purity germanium dioxide; The S4 comprises the following steps: S401: drying and calcining high-purity germanium dioxide, and reducing it with hydrogen at 650-680° C. in a quartz tube of a reduction furnace to obtain metallic germanium; S402: When the reduction is completed, the temperature can be gradually raised to 1000-1100°C to melt the germanium, and then slowly cooled to obtain a germanium ingot.

2. The method for purifying metallic germanium by removing arsenic from waste acid according to claim 1, wherein: In S1, the processing waste includes: cutting powder, fragments, filter paper, and corrosive liquid.

3. The method for purifying metallic germanium by removing arsenic from waste acid according to claim 2, wherein: The mass proportions of germanium in the processing waste are: 60-70 parts of cutting powder, 80-90 parts of fragments, 20-30 parts of filter paper, and 2-10 parts of etching solution.

4. The method for purifying metallic germanium by removing arsenic from waste acid according to claim 1, wherein: In the step S202, chlorine gas needs to be introduced at a flow rate of 0.5-50 liters / minute.

5. The method for purifying metallic germanium by removing arsenic from waste acid according to claim 1, wherein: In S203, germanium tetrachloride is distilled out by steam heating.

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