CN1308493C - Complex of ammonium thicoaurite and preparation process thereof - Google Patents
Complex of ammonium thicoaurite and preparation process thereof Download PDFInfo
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- CN1308493C CN1308493C CNB2004100093750A CN200410009375A CN1308493C CN 1308493 C CN1308493 C CN 1308493C CN B2004100093750 A CNB2004100093750 A CN B2004100093750A CN 200410009375 A CN200410009375 A CN 200410009375A CN 1308493 C CN1308493 C CN 1308493C
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Abstract
The present invention relates to a novel complex compound of ammonium thioaurite, and a preparing method thereof. The preparation of the complex compound is divided into two steps which are orderly carried out, step 1, ammonium gold sulfite solutions are prepared from ammonium bicarbonate, gold powder, sulfur dioxide and ammonium hydroxide; step 2, the novel compound of ammonium thioaurite is prepared by the reaction of the solutions and sulfur, and the physical features and the preparation method of the compound are disclosed in the specification. The present invention has the advantages of simple technological process, reasonable process, high yield, low cost and convenient use by users, and is favorable to industrialization production. Because the present invention adopts sulfur to prepare the crystal of ammonium thioaurite, the gilding materials (ammonium gold sulfite) which can be used for industry are obtained, and novel and reliable material sources are provided for the realization of non-cyanide gold plating technology, and the enhance of the environmental protection of electroplating industry. The product of the present invention is used for an electric gold plating technology, a chemical gold depositing technology, an electroforming technology, etc.
Description
Technical Field
The invention relates to a gold salt and a preparation method thereof, in particular to a gold ammonium thiosulfate complex and a preparation method thereof.
Background
The gold-containing material (gold salt) used in the existing electrogilding and chemical electrogilding processes is virulent potassium aurous cyanide, and 5 mg of gold-containing material can kill the gold. No matter the health of human body, the environmental protection is greatly damaged. National Committee 2002 (32) is a clear requirement for the national elimination of cyanidation electroplating.
Gold is a golden noble metal, has very stable chemical properties, is insoluble in various strong acids and is only soluble in aqua regia. The gold is used for electroplating various electronic components and printed circuit boards, and the performance of electronic products can be obviously improved. The protective agent is used for the surface layer of the electroplated jewelry and has excellent protective effect. Because of its excellent corrosion resistance, it is not easy to change its color after long-term wearing, and its golden color is luxurious and glaring, so that it is very beautiful when it is plated on the surface of jewelry.
Since the prior art can not obtain cyanide-free monovalent gold salt crystals, the cyanide-free gold plating technology appeared is limited to the use of a liquid gold ammonium sulfite solution as an additive of a gold source. Because of poor chemical stability, the gold can be reduced into monomer gold by carelessness, so that the electroplating solution is deteriorated, not only is the precious gold raw material wasted, but also the electroplating process cannot be carried out, and the limitation of liquid product storage, transportation and sale is large, so that the method cannot be popularized and applied in industrial production.
The cyanide-free gold plating and its alloy plating process have become the most interesting technology in the electroplating industry today. The development of cyanide-free gold salts has become an urgent task and an important subject in industrial production. Selecting proper additionThe agent is also important. France describes a gold-plated tin alloy solution containing a mixture of piperazine and an arsenic compound. Piperazine hexahydrate (C)4H10N2·6H2O) (Piperazine hexahydrate), a white or pale yellow crystalline substance, which dissolves in water and acid and functions as a brightener. It is described that this plating solution can obtain bright Au-Sn alloy plating layer containing 92% Au and 9% Sn.
Hydrazine sulfate (NH)4N2·H2SO4) It is a white rhombohedral crystal or powder, easily soluble in hot water and slightly soluble in cold water and alcohol. Its new use is introduced in japan. Namely, hydrazine sulfate additive, potassium pyrophosphate and potassium sulfite are added into the gold plating solution, so thatthe results of wide current density and stable cathode current efficiency can be obtained.When the concentration of metal impurities such as iron, nickel and the like in the solution is higher, the phenomenon of co-deposition of gold and the impurities can not occur. Therefore, the solution system of cyanide-free gold plating can be established, and the key is to prepare and produce a cyanide-free gold-containing salt.
Currently, the cyanide-free gold salt gold ammonium thiosulfate { (NH) is prepared4)AuS2O3}·3H2The method of O has not been reported at home and abroad. For the preparation of compounds containing monovalent gold in addition to cyanogen, only aqueous solutions such as gold ammonium sulfite and gold sodium sulfite products have been reported. The products have the defects of low gold content and high preparation cost, and the preparation conditions are harsh, and the products can only be aqueous solutions, so that a lot of inconvenience is brought to use. Therefore, the development of a cyanide-free gold-plating material is urgently needed, so that the gold-plating industry gradually replaces the highly toxic potassium aurous cyanide, and the urgent need is urgent.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide cyanide-free gold-containing crystal aurum thiosulfate { NHH } which is simple and convenient to prepare and good in effect4)AuS2O3}·3H2O complex (common name is cyanide-free gold salt) and a preparation method thereof.
The object of the invention can be achieved by the following measures: the preparation of the ammonium gold thiosulfate comprises the following two steps in sequence:
the first step is as follows: the preparation of the gold ammonium sulfite solution comprises the steps of dissolving ammonium bicarbonate in water, wherein the weight ratio of the ammonium bicarbonate to the gold content in the gold powder is 1.8-3: 1, stirring at the temperature of 50 ℃ for 1 hour. Introducing sulfur dioxide gas into the solution at a gas pressure of 2.5Kpa-9.8Kpa and a flow rate of 2.5-8.5 liters/minute, adding gold powder, reacting for 45 minutes, adjusting the pH value by using a pH adjusting reagent, and complexing and dissolving gold oxide to prepare a gold ammonium thiosulfate solution;
the second step is that: preparing ammonium gold thiosulfate, namely heating the ammonium gold sulfite solution prepared in the first step to 80 ℃. Adding excessive sulfur according to the weight ratio of the sulfur to the gold content in the aurum sulfite solution of 1.8-2.5: 1. Neutralizing with ammonia water to pH 8.5-9.5, vacuum filtering to eliminate sulfur, decolorizing, evaporating at 80 deg.c, crystallizing at 1-30 deg.c and vacuum drying at 45-70 deg.c to vacuum degree of-0.03-0.6X 10-2Pa, drying for 2 hours to obtain { (NH)4)AuS2O3}·3H2O crystal products. Wherein, the reaction of the sulfur dioxide and the gold is carried out in the solution; gold used for preparing the ammonium gold thiosulfate comprises gold oxide, nano gold oxide and superfine gold powder; the pH adjusting agent used is ammonium hydroxide, potassium hydroxide or sodium hydroxide.
The reaction steps of the invention are as follows:
the product of the invention is white { (NH)4)AuS2O3}·3H2O, theoretical gold content is: 51.71 percent; the physical and chemical properties are as follows:
1. the chemical formula is as follows: { (NH)4)AuS2O3}·3H2O
2. Formula and weight: 381.32
3. Theoretical gold content: 51.71 percent
4. Color: white colour
5. The state is as follows: crystal body
6. Density: 6.51 g/cc
7. Melting point: decomposition at 265 deg.C by oxygen evolution
8. Boiling point: residual gold is decomposed at 370 DEG C
9. Solubility: is soluble in water
10. Saturation solubility: 23.50 g/100 ml aqueous solution
Compared with the prior art, the invention has the following advantages: the invention has the characteristics of simple process, reasonable flow, high yield, low cost, convenient use by users and contribution to environmental protection and industrial production. The invention adopts a group of sulfur-containing compounds to prepare the ammonium gold thiosulfate crystal. The gold-plating material, namely the gold ammonium sulfite, which can be used in industry is obtained, and a new and reliable material source is provided for realizing the cyanide-free gold-plating process.
Detailed Description
The present invention will be further illustrated by the following examples, but the present invention is not limited to these examples.
The main equipment used in the invention is as follows:
1. a constant-temperature water bath kettle: shanghai test Instrument factory production
2. And (3) vacuum drying oven: tianjin North China laboratory Instrument factory
3. Electric mixer: tianjin North China laboratory Instrument factory
4. A vacuum filter: is commercially available
5. Low-temperature stirring crystallizer: is commercially available
6. An electronic balance: constant-maturity weighing apparatus factory
7. Enamel reaction kettle: tianjin enamelware plant
Example 1:
the product of the invention is sequentially carried out in two steps:
1. preparation of gold ammonium thiosulfate solution
Weighing analytically pure carbonic acidHydrogen ammonium NH4HCO342.6 kg, dissolved in an enamel reactor containing 500 l of water, the temperature is maintained at 50 ℃ and stirring is carried out for 60 minutes. Introducing SO into the solution under stirring at a pressure of 2.5KPa and a flow rate of 2.5 liters per minute2And (3) slowly adding 21.3 kg of commercially available nano-scale gold oxide powder into the solution by using sulfur dioxide gas, keeping the reaction time for 45 minutes, then adding 35 liters of ammonia hydroxide solution, and complexing and dissolving gold oxide to obtain a gold ammonium sulfite solution.
2. Preparation of gold ammonium thiosulfate
Heating the solution to 80 ℃, slowly adding 40 kg of excessive sulfur powder, stirring, dissolving for 1 hour, filtering when the solution is transparent and colorless, and slowly neutralizing with ammonia water until the pH value is equal to 8.5. Filtering to remove excessive sulfur, removing the color of the solution, evaporating the solution to 350L at 80 ℃, placing the solution into a low-temperature crystallizer, stirring at low temperature at 4-5 ℃, crystallizing for 2 hours, filtering crystals, transferring the crystals into a vacuum drying oven at 65 ℃ and a vacuum degree of-0.03 multiplied by 10-2Pa, dried for 2 hours, to obtain 38.1 kg of gold ammonium thiosulfate { (NH)4)AuS2O3}·3H2O white powder crystalline product with gold content: 49.9 percent.
Example 2:
the preparation is carried out as in example 1, with the exception of example 1: the commercially available gold oxide powder was used in place of the commercially available gold powder of the nanoscale in example 1 in an amount of 25 kg, and SO was added2Sulfur dioxide gas pressure 5.0KPa, flow 5L/min to obtain gold ammonium sulfite solution, slowly adding 55 kg of sulfur powder, slowly neutralizing with ammonia water to pH 9.5, evaporating the solution at 80 deg.C to 300L, placing into low temperature crystallizer, crystallizing at 10 deg.C, vacuum filtering to obtain crystals at 45 deg.C and vacuum degree of-0.6 × 10-2Drying under Pa for 2 hours, 35.6 kg of gold ammonium thiosulfate { (NH)4)AuS2O3}·3H2O white powder crystalline product with gold content: 24.5 percent.
Example 3:
the preparation is carried out as in example 1, with the exception of example 1: market forThe ultrafine gold powder was sold in an amount of 16 kg, SO, in place of the commercially available nanoscale gold powder in example 12The pressure of the sulfur dioxide gas is 9.2KPa,the flow rate is 8.0 l/min to obtain gold ammonium sulfite solution, slowly adding 30 kg of sulfur powder, slowly neutralizing with ammonia water to pH 9.0, evaporating the solution to 300 l at 80 deg.C, placing in a low-temperature crystallizer, crystallizing at 15 deg.C, suction filtering to obtain crystals at 50 deg.C and vacuum degree of-0.5 × 10-2Drying under Pa for 2 hours to obtain 37.8 kg of gold ammonium thiosulfate { (NH)4)AuS2O3}·3H2O white powder crystalline product with gold content: 40.0 percent.
The gold content of the product of the invention is 20-51.7%.
Product electrogilding application example:
weighing 1 g of ammonium gold thiosulfate crystal, adding 100 ml of hot water for dissolving, adding 35 g of sodium sulfite, 12 g of potassium citrate, 0.1 g of potassium sodium tartrate and 0.5 g of ethylenediamine tetraacetic acid, and preparing into an electroplating solution. The solution has good electroplating performance on copper, silver and nickel under the condition of 3.5-6.0V voltage. After 10-60 seconds of electroplating, the coating can reach 0.05-1.5 microns. Through detection:
1. the product can be used for gold electroplating or chemical gold plating in acidic, alkaline or neutral environment, and is an ideal material for replacing virulent potassium aurous cyanide in a cyanide electroplating process.
2. After the product is used for electroplating, the structure of gold is obviously thinner than that of a cyanogen-containing electroplating process, the coating is bright in color and luster, uniform and fine in thickness, the gold layer on the metal surface is good in adhesion effect, and the binding force is strong.
3. The coating adhesion is high and can reach 210-260 HV. Compared with a gold potassium cyanide electroplating layer, the gold phase structure is better when observed under a 2000-time electron microscope.
The product has high electroplating speed and current efficiency close to 95 percent.
The product of the invention is used for the processes of gold electroplating, chemical gold immersion, electroforming and the like.
Claims (5)
1. The gold ammonium thiosulfate complex is characterized by comprising the following physicochemical properties:
(1) color: white colour
(2) Molecular weight: 381.32
(3) Theoretical gold content: 51.71 percent
(4) The chemical formula is as follows: { (NH)4)AuS2O3}·3H2O
(5) The state is as follows: crystal body
(6) Density: 6.51 g/cc
(7) Melting point: decomposition at 265 deg.C by oxygen evolution
(8) Boiling point: residual gold is decomposed at 370 DEG C
(9) Solubility: is soluble in water
(10) Saturation solubility: 23.50 g/100 ml water solution/25 ℃.
2. A process for the preparation of gold ammonium thiosulfate as claimed in claim 1, characterized in that it is carried out in two steps in the following order:
the first step is as follows: the preparation of the gold ammonium sulfite solution comprises the steps of dissolving ammonium bicarbonate in water, wherein the weight ratio of the ammonium bicarbonate to the gold content in the gold powder is 1.8-3: 1, stirring at the temperature of 50 ℃ for 1 hour. Introducing sulfur dioxide gas into the solution at a gas pressure of 2.5Kpa-9.8Kpa and a flow rate of 2.5-8.5 liters/minute, adding gold powder, reacting for 45 minutes, adjusting the pH value by using a pH adjusting reagent, and complexing and dissolving gold oxide to preparea gold ammonium sulfite solution;
the second step is that: preparing ammonium gold thiosulfate, heating the ammonium gold sulfite solution prepared in the first step to 80 ℃, and adding excessive sulfur according to the weight ratio of the sulfur to the gold in the ammonium gold sulfite solution of 1.8-2.5: 1. Neutralizing with ammonia water to pH 8.5-9.5, vacuum filtering to eliminate sulfur, decolorizing, evaporating, crystallizing at 1-30 deg.c and vacuum drying at 45-70 deg.c to vacuum degree of-0.03-0.6X 10-2Pa, drying for 2 hours to obtain the gold ammonium thiosulfate { (NH)4)AuS2O3}·3H2O crystal products.
3. The method for preparing the ammonium gold thiosulfate according to claim 2, characterized in that the gold powder used for preparing the ammonium gold thiosulfate comprises gold oxide, nano-gold oxide and ultrafine gold powder.
4. The method of claim 2, wherein the reaction between sulfur dioxide and gold is in solution.
5. The method for preparing gold ammonium thiosulfate in claim 2, characterized in that the pH adjusting agent used is ammonium hydroxide, potassium hydroxide, sodium hydroxide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100093750A CN1308493C (en) | 2004-07-27 | 2004-07-27 | Complex of ammonium thicoaurite and preparation process thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100093750A CN1308493C (en) | 2004-07-27 | 2004-07-27 | Complex of ammonium thicoaurite and preparation process thereof |
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| CN1598071A CN1598071A (en) | 2005-03-23 |
| CN1308493C true CN1308493C (en) | 2007-04-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103741180A (en) * | 2014-01-10 | 2014-04-23 | 哈尔滨工业大学 | Cyanide-free bright electrogilding additive and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5302278A (en) * | 1993-02-19 | 1994-04-12 | Learonal, Inc. | Cyanide-free plating solutions for monovalent metals |
| CN1494606A (en) * | 2001-02-28 | 2004-05-05 | ƽ | Bath for galvanic deposition of gold and gold alloys, and use thereof |
-
2004
- 2004-07-27 CN CNB2004100093750A patent/CN1308493C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5302278A (en) * | 1993-02-19 | 1994-04-12 | Learonal, Inc. | Cyanide-free plating solutions for monovalent metals |
| CN1494606A (en) * | 2001-02-28 | 2004-05-05 | ƽ | Bath for galvanic deposition of gold and gold alloys, and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| 无氰浸镀液 王丽丽编译，电镀与精饰，第18卷第6期 1996 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103741180A (en) * | 2014-01-10 | 2014-04-23 | 哈尔滨工业大学 | Cyanide-free bright electrogilding additive and application thereof |
| CN103741180B (en) * | 2014-01-10 | 2015-11-25 | 哈尔滨工业大学 | Non-cyanide bright electrogilding additive and application thereof |
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| Publication number | Publication date |
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| CN1598071A (en) | 2005-03-23 |
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