CN103253697A - Method for preparing monovalent gold compound through selectively reducing trivalent gold - Google Patents
Method for preparing monovalent gold compound through selectively reducing trivalent gold Download PDFInfo
- Publication number
- CN103253697A CN103253697A CN2012100381254A CN201210038125A CN103253697A CN 103253697 A CN103253697 A CN 103253697A CN 2012100381254 A CN2012100381254 A CN 2012100381254A CN 201210038125 A CN201210038125 A CN 201210038125A CN 103253697 A CN103253697 A CN 103253697A
- Authority
- CN
- China
- Prior art keywords
- gold
- compound
- gold compound
- trivalent
- monovalence
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a method for preparing a monovalent gold compound. The method is characterized in that a trivalent gold compound, a ligand required by a target product and the like are used as raw materials, and undergo a selective reduction process having an electron transfer number to make trivalent gold become monovalent gold in order to obtain the monovalent gold compound product. The method has the characteristics of mild preparation process, good valence specificity of gold in the reaction product, high yield of the monovalent gold compound, and the like, can be used in the preparation of monovalent gold compounds, and can also be used for preparing other new gold compounds by using the monovalent gold compound as an intermediate.
Description
Technical field
The present invention relates to a kind of method of the trivalent gold compound being carried out selective reduction, it is raw material with the trivalent gold compound, be that 2 selective reduction process realizes the selective reduction of trivalent gold compound is obtained the monovalence gold compound by a kind of electron transfer number of controlling, and by the application in the made monovalence gold compound of this method.
Background technology
Because the trivalent gold compound exists following deficiency: 1) its toxicity is bigger than corresponding monovalence gold compound, its valence state existed uncertainty and can be changed into monovalence or zeroth order when 2) it was reduced, therefore in the procedure for processing of concrete industrial production and social life field such as printed-wiring board (PWB) (being PCB) and industries such as five metals electroplating industry, metal-powder, medicine, pottery (as CN91106360.9), nano material and catalyzer manufacturing, use mainly be the monovalence gold compound.
Common monovalence gold compound can be expressed with following general formula: [AuL
m]
± q, m and q are integer, and m represents ligancy, and q represents the charge number of complex ion, and L represents part, is positively charged ion or anionic compound when q is not equal to zero, they must have its combination under the ion of opposite sign, as the inferior golden potassium cyanide KAu(CN on the commodity market)
2, gold sodium sulfide Na
3[Au(SO
3)
2], thiosulfuric acid gold complex etc. (express for simplifying, they may with crystal water omit).Monovalence gold compound when q equals zero such as gold monochloride, gold monobromide, gold monoiodide AuI etc.
Up to now, the monovalence gold compound have comprise " gas-liquid-solid " phase reaction synthesis method, film electrolytic synthesis, to methods such as the trivalent gold compound reduce, as CN201010107673.9, CN201110059797.9, CN200910066096.0 etc. introduce, but deficiency such as they all exist, and technology is numerous and diverse, step is many, single batch of productive rate is low is exactly like this as phase reaction synthesis method, film electrolytic synthesis; And traditional make raw material by the method for reduction monovalence gold compound processed with the trivalent gold compound, because its reductive agent is confined to sulphite, thiosulphate etc., and these reductive agents itself possess the function of part (as inferior sulfate radical, thiosulfate anion) so sneak in the target product easily, make purity and the chemical stability of target product all descend significantly, and condition control directly was not reduced to metallic gold with the trivalent gold at that time easily; Atypical method of reducing is as adopting hydrazine hydrate, vat powder, zinc etc. as the method for reductive agent, then owing to they can't achieve effective control make the gold in the reduzate can't rest on the monovalence state reliably to auric reduction process, often become metallic gold, therefore the method for preparing aurous compound that neither be desirable can only be used for reclaiming golden process.The citric acid compounds also is the trivalent gold reductive agent of using always, and they are widely used in and hydrochloro-auric acid prepared in reaction nanometer gold, but they can't will be stabilized in the monovalence state thereby can't make relevant monovalence gold complex after the reduction of trivalent gold.
Except the preparation method of above-mentioned monovalence gold compound, another kind method is to be raw material with the trivalent gold compound, by decomposition reaction to obtain the monovalence gold compound, prepare gold monochloride as carrying out the elevated temperature heat decomposition reaction with hydrochloro-auric acid or gold perchloride, carry out the elevated temperature heat decomposition reaction with hydrobromo-auric acid or gold tribromide and prepare gold monobromide, etc., but such preparation method obviously exists the condition harshness, the equipment requirements height, fatal deficiencies such as the purity of target product and productive rate are low, and the pyrolysis by product of this compounds is violents in toxicity such as chlorine, harm people and animals and environment.Develop the reduction depth controlled, make the trivalent gold can stably rest on the process for selective reduction of monovalence in reduction process, and this method is applied to the synthetic of monovalence gold compound, in case of necessity such monovalence gold compound further being synthesized other gold compound as intermediate, is purpose of the present invention.
Summary of the invention
The present invention provides the preparation method that price of gold attitude in a kind of, product simple as raw material, operational path with the trivalent gold compound is stablized the monovalence gold compound single, that preparation condition is gentle, reactions steps is few.Said monovalence gold compound can be that general formula is Au
mL
m.xH
2The material of O (m, n, x are integer) is as gold monobromide, aurous sulfide, aurous hydroxide etc.Said monovalence gold compound also can be inferior golden complex ion [AuL
m]
± q, it can have the counterion opposite with this Asia gold complex ion institute charging property when forming concrete product; For complex anion, its chemical formula general formula is M when being occurred with pure product by the formed compound of this gold complex ion
n[AuL
m]
p.xH
2O, wherein M representative and golden complex anion [AuL
m]
-qThe positively charged ion of balance, as inorganic cations such as sodium ion, potassium ion, ammonium ions, and the organic cation that is formed by organic amine (as primary amine, secondary amine, tertiary amine or quaternary ammonium etc.), x represents the number of crystal water, and m, n, p, x are integer; For golden complex cation, its chemical formula general formula is [AuL when being occurred with pure product by the formed compound of this gold complex ion
m]
pY
n.xH
2O, wherein Y representative and golden complex cation [AuL
m]
-qThe negatively charged ion of balance, as inorganic acid radical negatively charged ion, halide anion, organic carboxyl acid root negatively charged ion, azochlorosulfonate acid anion etc., x represents the number of crystal water, and m, n, p, x are integer.
By the present invention, the preparation method of preparation monovalence gold complex is: adopting the trivalent gold compound is raw material, is 2 process for selective reduction by electron transfer number, makes the trivalent gold compound be converted into the monovalence gold compound.Its process comprises: the reductive agent of this reduction depth controlled and trivalent gold compound generation electron-transfer reaction, and the trivalent gold obtains two electronics and becomes the monovalence gold, and the golden part be combined into that exists in it and the reaction system is monovalence gold compound target product.
By the present invention, the trivalent gold compound is carried out the employed reductive agent of selective reduction for containing sulfydryl (-SH or SH
-) soluble compound, as: two (2 mercapto ethanol) contracting isovaleric aldehyde, Mercaptobutanol, sulfydryl acetone, ethane thiol, mercapto glycerol, sulfydryl morpholine, thiohydracrylic acid, thioglycollic acid, mercaptoethylamine, mercaptopyridine, sulfhydryl piperidine, sulfydryl pyrazine, mercaptopyrimidine, mercaptopyrimidine formic acid, mercaptoethyl sulfonic acid, mercapto benzothiazole, mercaptobenzoimidazole, sulfydryl ethoxy ethanol, sulfohydrate are [as Sodium sulfhydrate Na
+(SH)
-] etc.
By the present invention, the consumption that the trivalent gold compound is carried out the employed reductive agent of selective reduction is: solubility sulfydryl (in molecule or mole number) contained in the reductive agent is in molecule or mole number) consumption be the twice of (in molecule or mole number) quantity of inferior golden product to be obtained or slightly many.
By the present invention, the usage quantity of trivalent gold selective reduction agent depends on that auric quantity to be restored is the quantity of the golden product in resulting Asia.In molecule or mole number, the usage quantity of trivalent gold selective reduction agent is the twice of auric quantity (quantity of inferior golden product namely to be obtained) to be restored or slightly many.
With existing reduction process and the reduction result ratio that as reductive agent the trivalent gold compound is carried out with sulphite, thiosulphate, hydrazine hydrate, vat powder, zinc, citric acid compounds etc., by this patent carry out to trivalent gold compound reduction process gentleness, reduction result is controlled and whole output monovalence gold, can not over reduction occur and make reduzate become golden situation, also avoid reductive agent to sneak in the target product, thereby the specificity of target product, purity and chemical stability are all guaranteed.
Implementation process and the control condition of this patent comprise:
I) reaction density control is respectively 1ppm (1mg/L), itself and saturation solubility as the upper and lower limit scope of working concentration of the reductive agent of reactant 1; As the upper and lower limit scope of working concentration of the trivalent gold compound of reactant 2 be respectively 5ppm (5mg/L), with and saturation solubility; Except reductive agent and two kinds of main reactants of trivalent gold compound, produced by the trivalent gold and also can add designed golden part such as phenanthroline (Phen), imidazoles etc. in the inferior golden product of target in the reaction process of monovalence gold compound, and other auxiliary material is as pH regulator agent, all kinds of SOLVENTS etc.
II) temperature of reduction reaction process control, the temperature of reduction reaction process is controlled upper and lower limit scope and is respectively: the freezing point of reaction mixture, with and boiling point.
III) any in below Xiang Guan reducing process can be selected: 1) reductive agent that will have an above-mentioned feature evenly mixes with the trivalent gold compound, 2) also can be that the trivalent gold compound is joined in the reductive agent of above-mentioned feature, 3) can also be that the reductive agent that will have above-mentioned feature is added in the system that contains the trivalent gold compound 4) certain combinations of above-mentioned three kinds of technologies.
IV) in concrete implementation process, the reductive agent that uses both can be with a kind of, also can be to use the combination of the multiple reductive agent of above-mentioned reductive agent molecular characterization of meeting of two or more, the reductive agent usage quantity is as the criterion with the demand that trivalent gold compound to be restored is reduced to fully the monovalence gold compound.
V) last handling process of target product also can comprise after reduction reaction was finished: concentrate, extracting and separating, washing purifying, solid-liquid separation etc. obtain the necessary operation of pure target product, and the measure that target product is protected of other necessity such as nitrogen filled protection, negative-pressure operation, vacuum operating etc.
Application Areas
This method that the trivalent gold compound is carried out selective reduction that the present invention relates to, it can be applicable to the preparation field of monovalence gold compound, also the above-mentioned monovalence gold compound that obtains further can be synthesized other gold compound as intermediate.
Embodiment
Embodiment 1:
Getting Gold Content is the gold tribromide of 10.1 grams, it is dissolved in the DI(deionizations of 150 grams) in the water, to wherein dripping 15 gram mercapto glycerols, drip process control temp below 65 ℃, drip off the back and said mixture was carried out reduced-pressure backflow 10 hours being lower than under 85 ℃ the temperature, cooling, solid-liquid separation, throw out drying after twice DI water washing obtains yellow-gray powder-product 13.9 grams, be gold monobromide after measured, inferior gold content in the product is 70.8%, and product purity is nearly 99.5%, in the inferior gold rate of recovery nearly 97.5%; Explanation can be prepared relevant aurous compound by this patent.The gold monobromide product that the gold tribromide of same weight raw material makes by the elevated temperature heat decomposition reaction, its output are 14.1 grams, and Gold Content is 67.5% after measured, and purity only 94.7% is in the inferior gold rate of recovery nearly 94.2%.
Embodiment 2:
Getting Gold Content is gold tribromide, AR level Potassium Bromide 20 grams and Hydrogen bromide 10 grams of 9 grams, they are mixed with 500 gram solution with water, to the gram of Dropwise 5 wherein thioglycollic acid, drip process control temp below 70 ℃, fill nitrogen after dropwising said mixture is carried out negative pressure backflow 3 hours, be cooled to room temperature, solid-liquid separation, throw out through DI water, ethanol, acetone, butyl glycol ether washing final vacuum drying, obtains yellow-gray powder 10.2 grams respectively, is gold monobromide after measured.Explanation can be prepared relevant aurous compound by this patent.
Get wet product 5.8 grams of the not dry gold monobromide that makes by last method (being 4 grams when converting to dry product), under guaranteeing its prerequisite of all dissolving, it is fed in 220 ml solns that contain 4.3 gram potassium cyanide in batches, when being lower than 9, regulates by adding potassium hydroxide pH value of solution, the clear solution of gained is carried out heating evaporation to be concentrated, stop heating when in solution, crystallisate occurring soon, be cooled to room temperature, find to have in the reactor a large amount of white crystals things to occur; Solid-liquid separation is also carried out repeatedly DI water washing to throw out, and the crystallisate of gained carries out vacuum-drying under 85 ℃, and products obtained therefrom is weighed as 4.3 grams.This product is after measured: Gold Content is 84.2%, is the potassium cyanaurite product; The aurous compound first time (gold monobromide) that explanation makes by this patent also can be converted into the aurous compound of other type easily.
Getting the potassium cyanaurite product for preparing by last method, to be mixed with Gold Content be that the chemical gold plating liquid of 2.0 grams per liters has carried out following application experiment, condition is as follows: employing PCB(printed circuit board (PCB)) line layer of nickel plating (being to be capped one deck chemical Ni-plating layer above the copper on the printed circuit board circuitry) of industry is substrate, chemical gold plating liquid pH value is 4.5 ~ 6.5,50 ~ 65 ℃ of the temperature of chemical gilding process, 2.5 ~ 8 minutes chemical gilding time; Found that: adopt this patent to prepare the aurous compound of gained, its chemical gilding application performance such as gold-plated speed, thickness and bonding force have all reached the craft of gilding requirement of relevant industries.
Embodiment 3:
Getting Gold Content is 10
.The potassium chloraurate of 3 grams is made into the 300 gram aqueous solution, being added drop-wise at leisure in the above-mentioned solution until the pH value with potassium hydroxide solution is 3.5 ~ 6.5, down will contain thiomethyl alcohol and mercaptopyridine (their blending ratio is mol ratio 1:2) mixture solution joins above-mentioned containing in the auric Glass Containers in batches at subzero 5 ℃, adition process is kept stirring, no longer separates out till the throw out in solution; Finish the back underpressure distillation and concentrate volume to 35% of mother liquor amount, leave standstill, solid-liquid separation and throw out repeatedly washed then, the throw out drying obtains 13.5 products.This product is analyzed, found that its price of gold attitude is monovalence, Gold Content is 63.5%, and product is the inferior gold of mercaptopyridine, illustrates by this patent and can prepare relevant aurous compound.
As Jin Yuan, prepared ceramic Jinsui River of following component with above-mentioned aurous compound by the conventional formulation in ceramic Jinsui River: the inferior gold of mercaptopyridine (in gold 10%), in bismuth compound (in bismuth 0.3%), chromium cpd (in chromium 0.05%), rhodium compound (with rhodium 0.06%), contain pimelinketone and tetrahydrofuran (THF) and other conventional weighting agent in addition.Household china has been carried out the application experiment of ceramic gilding in 750～850 ℃ of temperature ranges with above-mentioned ceramic Jinsui River, the result shows that indexs such as its color and luster, bonding force, wear resistance, anti-impact gold have all reached the requirement of relevant industries; The aurous compound that explanation is prepared by this patent can be used for ceramic field.With traditional ceramic Jinsui River aurous compound ratio, the aurous compound synthetic route of this patent is shorter, and it is lower with the aurous compound of this patent pottery to be carried out the required temperature of gilding process.
Claims (4)
1. one kind prepares the method for monovalence gold compound from the trivalent gold compound, and it is characterized in that: the trivalent gold compound optionally is reduced to the monovalence gold compound.
2. according to the method for claim 1, it is characterized in that: employed trivalent gold selective reduction agent is the soluble compound that contains sulfydryl.
3. more than the twice of consumption (in molecule or the mole number of solubility sulfydryl contained in the reductive agent) for (in molecule or mole number) quantity of inferior golden product to be obtained of trivalent gold selective reduction agent.
4. according to the method for claim 1 and 2, it is characterized in that: it can be applicable to the preparation of monovalence gold compound, also the monovalence gold compound that obtains like this can be applied to prepare other new gold compound as intermediate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100381254A CN103253697A (en) | 2012-02-20 | 2012-02-20 | Method for preparing monovalent gold compound through selectively reducing trivalent gold |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100381254A CN103253697A (en) | 2012-02-20 | 2012-02-20 | Method for preparing monovalent gold compound through selectively reducing trivalent gold |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103253697A true CN103253697A (en) | 2013-08-21 |
Family
ID=48957979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100381254A Pending CN103253697A (en) | 2012-02-20 | 2012-02-20 | Method for preparing monovalent gold compound through selectively reducing trivalent gold |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103253697A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103969199A (en) * | 2013-10-21 | 2014-08-06 | 国家纳米科学中心 | Measuring method for GNP (gold nano-particle) concentration |
| CN111440101A (en) * | 2020-03-06 | 2020-07-24 | 厦门大学 | Preparation method of cysteine aurous acid solid |
| CN111364074B (en) * | 2020-02-21 | 2021-06-25 | 厦门大学 | Preparation method of composite coordination low-concentration monovalent gold cyanide-free gold-plating electroplating solution |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671839A (en) * | 2009-08-31 | 2010-03-17 | 三门峡恒生科技研发有限公司 | Citric acid gold potassium for gilding and preparation method thereof |
-
2012
- 2012-02-20 CN CN2012100381254A patent/CN103253697A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671839A (en) * | 2009-08-31 | 2010-03-17 | 三门峡恒生科技研发有限公司 | Citric acid gold potassium for gilding and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王锦化等: "Au(Ⅲ)、Ag(I)与巯基乙酸苯胺的配合物及其在贵金属回收中的应用"", 《应用化学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103969199A (en) * | 2013-10-21 | 2014-08-06 | 国家纳米科学中心 | Measuring method for GNP (gold nano-particle) concentration |
| CN111364074B (en) * | 2020-02-21 | 2021-06-25 | 厦门大学 | Preparation method of composite coordination low-concentration monovalent gold cyanide-free gold-plating electroplating solution |
| CN111440101A (en) * | 2020-03-06 | 2020-07-24 | 厦门大学 | Preparation method of cysteine aurous acid solid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bernardo et al. | Comparison of the influence of saturated nitrogen and sulfur donor atoms on the properties of copper (II/I)-macrocyclic polyamino polythiaether ligand complexes: redox potentials and protonation and stability constants of CuIL species and new structural data | |
| TWI600794B (en) | Non-cyanogen gold plating bath and method of manufacturing non-cyanogen gold plating bath | |
| SG192150A1 (en) | Stabilized metal nanoparticles and methods for production thereof | |
| CN102731536A (en) | Anionic type gold complex and application thereof | |
| CN103253697A (en) | Method for preparing monovalent gold compound through selectively reducing trivalent gold | |
| CN110029374A (en) | A kind of cyanide-free alkaline copper plating electroplate liquid and electroplating technology | |
| TWI418668B (en) | Method of replenishing indium ions in indium electroplating compositions | |
| Pillay et al. | Aqueous route to stable luminescent tetranuclear copper (I) dithiophosphonate clusters | |
| JP5523445B2 (en) | Method for producing palladium (hydrogen) carbonate complex having amine ligand | |
| CN106748924B (en) | The production method of high yield thioacetic acid | |
| CN107955133A (en) | Imidazole Type Latent Curing Agent containing triazine ring structure and preparation method thereof | |
| CN105836814B (en) | The method of one kind synthesis ammino palladium (II) of sulfuric acid four | |
| CN106946753B (en) | The synthesis technology of sodium polydithio-dipropyl sulfonate | |
| Fairley et al. | Synthesis and characterization of homo-and heteronuclear molecular Al 3+ and Th 4+ species chelated by the ethylenediaminetetraacetate (edta) ligand | |
| Guo | Synthesis and characterization of Ag 2 C 2· 2AgClO 4· 2H 2 O: a novel layer-type structure with the acetylide dianion functioning in a µ 6-η 1, η 1: η 2, η 2: η 2, η 2 bonding mode inside an octahedral silver cage | |
| CN115231608B (en) | Chemical method for preparing multi-sulfide nanocrystalline at normal temperature | |
| JP5859628B1 (en) | New production method for gold compounds | |
| Schubert et al. | Acid-catalyzed synthesis of zinc imidazolates and related bimetallic metal-organic framework compounds | |
| Ray et al. | Trivalent nickel: sulfur coordination (NiN2O2S2) vs. oxygen coordination (NiN2O4) | |
| CN104591256B (en) | A kind of method that cuprous oxide is prepared under copper chloride system | |
| JP2013224496A (en) | Gold sulfite salt aqueous solution for gold plating solution | |
| CN108276455A (en) | A kind of synthetic method of L- xyloses | |
| US6353081B1 (en) | Curing agents for epoxy compounds, processes for their production and their use | |
| CN103288121A (en) | Reverse disproportionation reaction for synthesis of monovalent gold complex | |
| CN108754554B (en) | A kind of gold plating liquid and a kind of gold plating method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C05 | Deemed withdrawal (patent law before 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130821 |