CN106637314B - A kind of preparation method of the gold sodium sulfide solution of cyanogen-less gold - Google Patents
A kind of preparation method of the gold sodium sulfide solution of cyanogen-less gold Download PDFInfo
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- CN106637314B CN106637314B CN201611159618.8A CN201611159618A CN106637314B CN 106637314 B CN106637314 B CN 106637314B CN 201611159618 A CN201611159618 A CN 201611159618A CN 106637314 B CN106637314 B CN 106637314B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/48—Electroplating: Baths therefor from solutions of gold
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G7/00—Compounds of gold
- C01G7/006—Compounds containing, besides gold, two or more other elements, with the exception of oxygen or hydrogen
Abstract
The present invention provides a kind of preparation methods of the gold sodium sulfide solution of cyanogen-less gold, this method is first to catch up with nitrate for chloric acid gold solution by aqua regia dissolution by elemental gold, sodium thiosulfate reaction is added in chlorauric acid solution again and generates the sub- golden sodium of thiosulfuric acid, then ethyl alcohol is added, the sub- golden sodium precipitation of thiosulfuric acid is precipitated, add sodium sulfite solution complexing, sulphur removal finally is filtered with activated carbon, obtains gold sodium sulfide solution.The preparation method of the present invention, it is concise in technology, easy to operate, and gold chloride and the sub- golden sodium recovery rate height of the thiosulfuric acid of sodium thiosulfate reaction generation, loss are less, and the sub- golden stable sodium of thiosulfuric acid is easily isolated, high conversion rate is complexed with sodium sulfite, thus not only purity is high for product obtained by the method for the present invention, but also the utilization rate of precious metals gold is also high, and gold sodium sulfide solution obtained is more stable.
Description
Technical field
The present invention relates to a kind of water-soluble preparation method of gold salt more particularly to a kind of water-soluble gold salts of cyanogen-less gold
Preparation method, specifically relate to a kind of preparation method of the gold sodium sulfide solution of cyanogen-less gold.
Background technology
Currently, common craft of gilding has cyanide craft of gilding and cyanogen-less gold technique two major classes both at home and abroad.Due to cyanogen
The stability of compound class solution is high, and applicable elements are wide, so cyanide craft of gilding is widely used by people for a long time, but by
The extremely toxic cyanide in plating solution, would seriously pollute the environment and caused huge harm to human body, and can be caused to resist
Harmful effect, thus be gradually eliminated.Although National Development and Reform Commission issued postponement in 2013 and eliminates cyanogen-containing gold-plated work
The notice of skill, but either government or industry, it will be not still to have strong requirement, gold-plated no cyaniding to cyanogen-less gold technique
Reversible trend.Current cyanogen-less gold technique, mainly there is that sulphite is gold-plated, halide is gold-plated, thiosulfate is gold-plated
Gold-plated etc. with thiomalic acid, more mature cyanogen-less gold technique is that sulphite is gold-plated.
Application No. is 200910227579.4 Chinese invention patent applications, disclose a kind of cyanogen-less gold sulfurous acid gold
The step of preparation method of sodium complex, this method is " to prepare gold chloride-alkali neutralization-addition sodium sulfite-filtering and concentrating
Obtain sediment-drying precipitate and crush to obtain product ", since this method is not separated by solid-liquid separation after alkali neutralization, band in product
There are a large amount of chlorides, cause product purity not high, in addition, alkali neutralization is by Au3+It is precipitated as the form of gold hydroxide, and hydroxide
Gold is unstable, and easy dehydration is converted into gold oxide, and then resolves into elemental gold, causes the utilization rate of gold low.
Application No. is 201510942820.7 Chinese invention patent applications, disclose a kind of cyanogen-less gold reagent sulfurous acid
The step of preparation method of golden sodium, this method is that " gold rolls-clean gold bullion-gold dissolving-flooding process-alkalization-solid-liquid point
From-cleaning-complex reaction-condensing crystallizing ", although the above method is separated by solid-liquid separation after alkalization, after alkali neutralization
Obtained gold hydroxide settling stability is poor, is not easy to washing separation, to obtain the low product of impurity content, cumbersome, and
And gold hydroxide is not high for the conversion ratio of gold sodium sulfide with sodium sulfite complexing, can cause the utilization rate of precious metal gold
It is low.
Invention content
To solve the problems, such as present on, the object of the present invention is to provide a kind of gold sodium sulfide solution of cyanogen-less gold
Preparation method, this method is simple for process, product purity is high and the utilization rate of precious metal gold is high.
In order to achieve the above object, the preparation method of the gold sodium sulfide solution of the cyanogen-less gold of the present invention, includes successively
Following steps：
（1）It puts into gold in a reservoir, chloroazotic acid is added, be completely dissolved gold at 40 ~ 70 DEG C of temperature；
（2）By step（1）Obtained solution is concentrated under reduced pressure at temperature≤90 DEG C, is concentrated into the mass concentration of GOLD FROM PLATING SOLUTION
It is 40~50%, stops heating, be cooled to room temperature, gold chloride crystallization is precipitated；
（3）Add pure water dissolving gold chloride to crystallize to that the mass concentration of GOLD FROM PLATING SOLUTION is 10~25%, quality is added under stiring
A concentration of 20~40% hypo solution reacts 3-4 hours, obtains the sub- golden sodium solution of thiosulfuric acid, sodium thiosulfate
Addition is 1.5-2.5 times of golden weight in chlorauric acid solution；
（4）The second of the sub- golden sodium solution volume of 2~5 times of thiosulfuric acids is added into the sub- golden sodium solution of thiosulfuric acid under stiring
Alcoholic solution, the sub- golden sodium of thiosulfuric acid is to be precipitated when being no longer precipitated with Precipitation, and precipitation is filtered out, the sub- gold of thiosulfuric acid is obtained
Sodium solid；
（5）The sodium sulfite solution that mass concentration is 20% is added in the sub- golden sodium solid of thiosulfuric acid, is heated to 30~50
DEG C, closed stirring 2~8 hours are kept the temperature, the addition of sodium sulfite is the sub- golden contained gold weight of sodium crystallization of thiosulfuric acid
0.5-0.8 times；
（6）Toward step（5）Activated carbon is added in obtained solution, filters, gold content is adjusted with pure water, obtains sulfurous acid gold
Sodium solution.
For the sub- golden sodium crystallization of thiosulfuric acid, the more preferable purity for improving product, in above-mentioned steps is further purified（4）Obtain sulphur
It is filtered after the pure water dissolving of 2~5 times of solid weights is added in the sub- golden sodium solid of thiosulfuric acid, then 2~5 times of filtrates is added into filtrate
The sub- golden sodium crystallization of thiosulfuric acid after purification is precipitated in the ethyl alcohol of volume.
In order to keep gold easy to dissolve, while avoiding the excess of chloroazotic acid, above-mentioned steps（1）The weight that feeds intake of middle gold and chloroazotic acid
Amount is than being 1:5~8.
In order to more preferably distill excessive chloroazotic acid, above-mentioned steps（2）Reduced pressure be vacuum degree be less than -0.08Mpa
Under the conditions of be concentrated under reduced pressure.
In order to be caught up with as possible except the nitric acid in chlorauric acid solution, above-mentioned steps（2）Be concentrated into distillate speed it is slower when, it is point more
Secondary addition appropriate hydrochloric acid to no rufous gas generates, and the hydrochloric acid total amount being repeatedly added is the 1-3 of gold weight contained by solution
Times.
The number that above-mentioned hydrochloric acid is added is 3-4 times preferred.
In order to make gold sodium sulfide solution storage more stablize, above-mentioned steps（6）Sulfite gold sodium solution pure water tune
It is whole to gold concentration be 80~100g/L.
The preparation method of the gold sodium sulfide solution of the cyanogen-less gold of the present invention, first prepares chlorauric acid solution, then in chlorine
Sodium thiosulfate is added in auric acid solution, forms the sub- golden sodium of thiosulfuric acid, ethyl alcohol is added, precipitation is precipitated, precipitation and separation adds
Sodium sulfite is complexed, and then filtering adjustment gold content obtains finished product, due to the thio sulphur of gold chloride and sodium thiosulfate reaction generation
Sour sub- golden sodium recovery rate is high, loss is few, and the sub- golden stable sodium of thiosulfuric acid is easily isolated, and high conversion rate is complexed with sodium sulfite,
Thus not only purity is high for product obtained by the method for the present invention, but also the utilization rate of precious metals gold is also high.The preparation of the present invention
Method, simple for process, using the sub- golden sodium of thiosulfuric acid under the complexing environment of sodium sulfite, itself occurs disproportionated reaction and is made
Gold sodium sulfide solution it is more stable, be conducive to push cyanogen-less gold process of industrialization.
Specific implementation mode
With reference to specific embodiment, technical scheme of the present invention will be further described, but these embodiments are not used
To limit the scope of the invention, under the premise of not departing from theory of the present invention, such as chloric acid gold preparation process or technique are joined
Several changes, is within the scope of protection of the invention.
Embodiment 1
（1）Cut 8.2g gold（Containing gold 99.99%）, slowly it is put into the flask with sour device for absorbing tail gas, is added new
The chloroazotic acid 50g of preparation is slowly heated to 60 DEG C under stiring, and heat preservation to gold is completely dissolved；
（2）Decompressor is connected, control vacuum degree is less than -0.08Mpa, opens heating water bath, and the control of above-mentioned solution is existed
Be concentrated under reduced pressure within 90 DEG C, be concentrated into distillate speed it is slower when, hydrochloric acid 16g is added three times, until the not rufous of nitrogen oxides
Gas generates, and continues to concentrate, until detecting that the gold concentration in solution is 48%, stops heating, is cooled to room temperature, chlorine gold is precipitated
Acid crystal；
（3）The dissolving of 24g pure water is added into gold chloride crystallization, adjustment gold concentration is 20%, is added under agitation
Reaction 3 hours is stirred at room temperature in the hypo solution of 54.7g a concentration of 30%, generates the sub- golden sodium of thiosulfuric acid；
（4）Be added 95% ethyl alcohol 250ml into above-mentioned solution under agitation, the sub- golden sodium of thiosulfuric acid with Precipitation,
Precipitation is filtered out, is filtered in the precipitation filtered out plus after the dissolving of 50g pure water, 95% ethyl alcohol is added into filtrate under stiring
200ml is precipitated the sub- golden sodium crystallization of refined thiosulfuric acid, filters out spare；
（5）By the sub- golden sodium crystallization input flask of refined thiosulfuric acid, adds pure water 50g to dissolve, add 20% sodium sulfite
Solution 24g is heated to 45 DEG C, and sealed thermal insulating stirs 6 hours, is converted to gold sodium sulfide solution and a small amount of sulphur is precipitated；
（6）0.5g activated carbons are added into solution, sulphur removal is filtered after stirring half an hour, adjusts content with pure water, obtains nothing
Color clear gold sodium sulfide solution 100ml, the 80.3g/L containing gold.
Embodiment 2
（1）Cut 8.3g gold（Containing gold 99.99%）, slowly it is put into the flask with sour device for absorbing tail gas, is added new
The chloroazotic acid 50g of preparation is slowly heated to 55 DEG C under stiring, and heat preservation to gold is completely dissolved；
（2）Decompressor is connected, control vacuum degree is less than -0.08Mpa, opens heating water bath, and the control of above-mentioned solution is existed
Be concentrated under reduced pressure within 90 DEG C, be concentrated into distillate speed it is slower when, points of 4 times addition hydrochloric acid 20g, until the not rufous of nitrogen oxides
Gas generates, and continues to concentrate, until detecting a concentration of the 45% of GOLD FROM PLATING SOLUTION, stops heating, is cooled to room temperature, and chlorine gold is precipitated
Acid crystal；
（3）The dissolving of 25g pure water is added into gold chloride crystallization, adjustment gold concentration is 20%, and 55g is added under agitation
A concentration of 30% hypo solution is stirred to react 4 hours at room temperature, generates the sub- golden sodium of thiosulfuric acid；
（4）Be added 95% ethyl alcohol 300ml into above-mentioned solution under agitation, the sub- golden sodium of thiosulfuric acid with Precipitation,
Precipitation is filtered out, is filtered after the dissolving of 50g pure water is added in the precipitation filtered out, 95% ethyl alcohol is added into filtrate under stiring
250ml is precipitated the sub- golden sodium crystallization of refined thiosulfuric acid, filters out spare；
（5）By the sub- golden sodium crystallization input flask of refined thiosulfuric acid, adds pure water 50g to dissolve, add 20% sodium sulfite
Solution 25g is heated to 50 DEG C, and sealed thermal insulating stirs 7 hours, is converted to gold sodium sulfide solution and a small amount of sulphur is precipitated；
（6）0.5g activated carbons are added into solution, filters sulphur removal after stirring half an hour, adjusts content, obtain achromaticity and clarification
Gold sodium sulfide solution 100ml, the 80.4g/L containing gold.
By product made from above-described embodiment 1-2, its content and purity are detected, testing result such as following table：
As can be seen from the above table, the product obtained by preparation method of the present invention, purity are high, gold utilization rate reach 96% with
On, and indices reach the same technical target of the product of international esbablished corporation.
Claims (7)
1. a kind of preparation method of the gold sodium sulfide solution of cyanogen-less gold, in turn includes the following steps：
（1）It puts into gold in a reservoir, chloroazotic acid is added, be completely dissolved gold at 40 ~ 70 DEG C of temperature；
（2）By step（1）Obtained solution is concentrated under reduced pressure at temperature≤90 DEG C, and the mass concentration for being concentrated into GOLD FROM PLATING SOLUTION is 40
~50%, stop heating, be cooled to room temperature, gold chloride crystallization is precipitated；
（3）Add pure water dissolving gold chloride to crystallize to that the mass concentration of GOLD FROM PLATING SOLUTION is 10~25%, mass concentration is added under stiring
It for 20~40% hypo solution, reacts 3-4 hours, obtains the sub- golden sodium solution of thiosulfuric acid, the addition of sodium thiosulfate
Amount is 1.5-2.5 times of golden weight in chlorauric acid solution；
（4）The ethyl alcohol that the sub- golden sodium solution volume of 2~5 times of thiosulfuric acids is added into the sub- golden sodium solution of thiosulfuric acid under stiring is molten
Liquid, the sub- golden sodium of thiosulfuric acid is to be precipitated when being no longer precipitated with Precipitation, and precipitation is filtered out, it is solid to obtain the sub- golden sodium of thiosulfuric acid
Body；
（5）The sodium sulfite solution that mass concentration is 20% is added in the sub- golden sodium solid of thiosulfuric acid, is heated to 30~50 DEG C,
Closed stirring 2~8 hours are kept the temperature, the addition of sodium sulfite is the 0.5- of the sub- golden contained gold weight of sodium crystallization of thiosulfuric acid
0.8 times；
（6）Toward step（5）Activated carbon is added in obtained solution, filters, adjusts gold content with pure water, it is molten to obtain gold sodium sulfide
Liquid.
2. the preparation method of the gold sodium sulfide solution of cyanogen-less gold according to claim 1, it is characterised in that：Institute
State step（4）It obtains filtering after the pure water dissolving of 2~5 times of solid weights is added in the sub- golden sodium solid of thiosulfuric acid, then to filtrate
The sub- golden sodium crystallization of thiosulfuric acid after purification is precipitated in the middle ethyl alcohol that 2~5 times of filtrate volumes are added.
3. the preparation method of the gold sodium sulfide solution of cyanogen-less gold according to claim 1 or 2, it is characterised in that：
The step（1）The charged material weight of middle gold and chloroazotic acid ratio is 1:5~8.
4. the preparation method of the gold sodium sulfide solution of cyanogen-less gold according to claim 3, it is characterised in that：It is described
Step（2）Reduced pressure be vacuum degree be less than -0.08Mpa under conditions of be concentrated under reduced pressure.
5. the preparation method of the gold sodium sulfide solution of cyanogen-less gold according to claim 4, it is characterised in that：It is described
Step（2）Be concentrated into distillate speed it is slower when, several times be added appropriate hydrochloric acid to no rufous gas generates, repeatedly addition
Hydrochloric acid total amount be 1-3 times of gold weight contained by solution.
6. the preparation method of the gold sodium sulfide solution of cyanogen-less gold according to claim 5, it is characterised in that：It is described
The number that hydrochloric acid is added is 3-4 times.
7. the preparation method of the gold sodium sulfide solution of cyanogen-less gold according to claim 6, it is characterised in that：It is described
Step（6）It is 80~100g/L that sulfite gold sodium solution, which is adjusted with pure water to gold concentration,.
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| CN107986319A (en) * | 2017-12-01 | 2018-05-04 | 深圳市前海绿智源科技有限公司 | Method without cyanogen gold salt is prepared using the molten method of iodine |
| CN112301388A (en) * | 2019-07-25 | 2021-02-02 | 山东亿福金业珠宝首饰有限公司 | Cyanide-free electroplating process |
| JP6841969B1 (en) * | 2020-10-30 | 2021-03-10 | 松田産業株式会社 | Potassium gold cyanide crystals and potassium gold cyanide solution |
| CN113046800A (en) * | 2021-02-04 | 2021-06-29 | 深圳市金正龙科技有限公司 | Gold sodium sulfite electroplating solution and preparation method thereof |
| JP6953068B1 (en) * | 2021-02-25 | 2021-10-27 | 松田産業株式会社 | Gold plating solution containing gold sulfite and replenisher for gold plating solution containing gold sulfite |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3438748A (en) * | 1965-12-29 | 1969-04-15 | Agfa Gevaert Nv | Method for the preparation of thiogold (1) compounds |
| US3966880A (en) * | 1975-06-17 | 1976-06-29 | American Chemical & Refining Company Inc. | Method for producing alkali metal gold sulfite |
| CN101734708A (en) * | 2009-12-22 | 2010-06-16 | 三门峡朝阳科技有限公司 | Preparation method of cyanide-free gold sodium sulfite complex for gold plating |
| CN105568269A (en) * | 2015-12-16 | 2016-05-11 | 励福(江门)环保科技股份有限公司 | Preparation method of cyanide-free gold plating reagent sodium gold sulfite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5416330B2 (en) * | 2005-03-10 | 2014-02-12 | 日本高純度化学株式会社 | Method for producing gold sulfite aqueous solution for gold plating solution |
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- 2016-12-15 CN CN201611159618.8A patent/CN106637314B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3438748A (en) * | 1965-12-29 | 1969-04-15 | Agfa Gevaert Nv | Method for the preparation of thiogold (1) compounds |
| US3966880A (en) * | 1975-06-17 | 1976-06-29 | American Chemical & Refining Company Inc. | Method for producing alkali metal gold sulfite |
| CN101734708A (en) * | 2009-12-22 | 2010-06-16 | 三门峡朝阳科技有限公司 | Preparation method of cyanide-free gold sodium sulfite complex for gold plating |
| CN105568269A (en) * | 2015-12-16 | 2016-05-11 | 励福(江门)环保科技股份有限公司 | Preparation method of cyanide-free gold plating reagent sodium gold sulfite |
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