CN1598071A - Complex of ammonium thicoaurite and preparation process thereof - Google Patents
Complex of ammonium thicoaurite and preparation process thereof Download PDFInfo
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- CN1598071A CN1598071A CN 200410009375 CN200410009375A CN1598071A CN 1598071 A CN1598071 A CN 1598071A CN 200410009375 CN200410009375 CN 200410009375 CN 200410009375 A CN200410009375 A CN 200410009375A CN 1598071 A CN1598071 A CN 1598071A
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Abstract
The invention relates to the complex of new sulfur aurous ammonium and its preparation method. The method is divided into two steps one use the ammonium bicarbonate, gold powder, sulfur dioxide and ammonium hydroxide to form the solution of gold ammonium sulfurous acid; second, use the solution to react with the sulphur to get the new sulfur aurous ammonium. The physical feature of the complex and its manufacturing method refers to the specification. The invention is featured by simple technique, reasonable precess, high yield, low cost and easy application and is benefit to inductrial production. The invention can be applied to plating the gold, aggradating the gold in chemical method and electroform.
Description
Technical Field
The invention relates to a gold salt and a preparation method thereof, in particular to a novel ammonium thiuram 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. It is also important to select the appropriate additives. 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 that the 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. It follows that a cyanide-free gold plating solution system can be established, criticalAlso prepares and produces a cyanide-free gold-containing salt.
Currently, the cyanide-free gold salt gold ammonium thioate { (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 conditionsare 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 a cyanide-free gold-containing crystal thioaurin ammonium { (NH) which is simple and convenient to prepare and has good 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 novel preparation of aurous thionium 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 prepare a gold ammonium sulfite solution;
the second step is that: preparing ammonium thicoaurite by heating the solution of ammonium thicoaurite prepared in the first step to 80 deg.C. 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 filteringto remove sulfur, decolorizing, evaporating at 80 deg.C, crystallizing at 1-30 deg.C, vacuum drying at 45-70 deg.C, and vacuum degree of-0.03E ∞-0.6×10-2Pa, 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 aurous sulfide 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: 265 decomposition 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 thiuram crystals. 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 sulfite solution
Weighing analytically pure ammonium bicarbonate NH4HCO342.6 kg, dissolved in an enamel reactor containing 500 l of water, thetemperature 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 minute2Sulfur dioxide gas, slowly adding commercially available nanometer gold oxide powder 21.3 kg into the solution, maintaining the reaction time at 45 min, and adding 35L ammonium hydroxide solutionAnd (4) complexing and dissolving gold oxide to obtain a gold ammonium sulfite solution.
2. Preparation of ammonium thidaaurous
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 aurous ammonium thioate { (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 temperaturecrystallizer, crystallizing at 10 deg.C, vacuum filtering to obtain crystals at 45 deg.C and vacuum degree of-0.6 × 10-2pa for 2 hours, to obtain 35.6 kg of aurous ammonium thioate { (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: the commercially available nano-grade gold powder of example 1 was replaced with commercially available ultrafine gold powder in an amount of 16 kg, SO2Sulfur dioxide gas pressure of 9.2KPa, flow rate of 8.0L/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 at 80 deg.C to 300L, placing into low-temperature crystallizer, crystallizing at 15 deg.C, suction filtering to obtain crystal, 50 deg.C, and vacuum degree of-0.5 × 10-2Drying under Pa for 2 hours to obtain 37.8 kg of aurous ammonium thioate { (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 thidawsite 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. Novel aurous thioammonium complexes characterized by 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: 265 decomposition 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 preparing the aurous thioammonium of 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 prepare a gold ammonium sulfite solution;
the second step is that: preparing ammonium thicoaurite, heating the ammonium thicoaurite solution to 80 deg.C, adding excessive sulfur according to the weight ratio of sulfur to gold in the ammonium thicoaurite 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 { (NH) of the invention4)AuS2O3}·3H2O crystal products.
3. The method for preparing aurous ammonium thiosulfate as claimed in claim 2, characterized in that the gold powder used for preparing the aurous ammonium thiosulfate comprises gold oxide, nano-gold oxide and ultra-fine gold powder.
4. The method of claim 2, wherein the reaction between sulfurdioxide and gold is in solution.
5. The process for preparing aurous thioammonium according to claim 2, characterized in that the pH adjusting agent used is ammonium hydroxide, potassium hydroxide, sodium hydroxide.
Priority Applications (1)
| 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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|---|---|---|---|
| CNB2004100093750A CN1308493C (en) | 2004-07-27 | 2004-07-27 | Complex of ammonium thicoaurite and preparation process thereof |
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| CN1598071A true CN1598071A (en) | 2005-03-23 |
| CN1308493C CN1308493C (en) | 2007-04-04 |
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| 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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| US5302278A (en) * | 1993-02-19 | 1994-04-12 | Learonal, Inc. | Cyanide-free plating solutions for monovalent metals |
| JP4183240B2 (en) * | 2001-02-28 | 2008-11-19 | ヴィーラント デンタル ウント テクニーク ゲーエムベーハー ウント コー カーゲー | Gold and gold alloy electrodeposition bath and its usage |
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Owner name: BEIJING JINFEITENG SCIENCE AND TECHNOLOGY CO.,LTD Free format text: FORMER OWNER: TENG XIANDI; TENG FEI Effective date: 20071214 |
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Effective date of registration: 20071214 Address after: Room 5002, Ding Jun building, building 75, No. 4, Beijing, Haidian District, Suzhou Street: 100080 Patentee after: Beijing Gold Technology Co., Ltd. Address before: No. 5, Beiyuan court, Anding house, Beijing, Chaoyang District: 100012 Co-patentee before: Teng Fei Patentee before: Tengxian |
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Owner name: SHANGHAI HENGYUAN PRECIOUS METALS CO., LTD. Free format text: FORMER OWNER: BEIJING JINFEITENG TECHNOLOGY CO., LTD. Effective date: 20110117 |
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Free format text: CORRECT: ADDRESS; FROM: 100080 ROOM 5002, DINGJUN BUILDING, BUILDING 4, NO.75, SUZHOU STREET, HAIDIAN DISTRICT, BEIJING TO: 201505 NO.18, LANE 5011, NANTING HIGHWAY, TINGLIN TOWN, JINSHAN DISTRICT, SHANGHAI |
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Effective date of registration: 20110117 Address after: 201505 No. 5011, Lane 18, South Ting Road, ting Lin Town, Shanghai, Jinshan District Patentee after: Shanghai Heng Yuangui Pioneer Metals Corporation Address before: 100080, Beijing, Suzhou Street, Haidian District No. 4, building 75, Ting Jun building, room 5002 Patentee before: Beijing Gold Technology Co., Ltd. |
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Granted publication date: 20070404 Termination date: 20110727 |