CN101671839A - Citric acid gold potassium for gilding and preparation method thereof - Google Patents
Citric acid gold potassium for gilding and preparation method thereof Download PDFInfo
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- CN101671839A CN101671839A CN200910066096A CN200910066096A CN101671839A CN 101671839 A CN101671839 A CN 101671839A CN 200910066096 A CN200910066096 A CN 200910066096A CN 200910066096 A CN200910066096 A CN 200910066096A CN 101671839 A CN101671839 A CN 101671839A
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Abstract
The invention relates to citric acid gold potassium for gilding and a preparation method thereof. The molecular formula of the citric acid gold potassium is KAu2N4C12H11O8. The citric acid gold potassium is prepared by dissolving auric chloride in water, concentrating and diluting for several times, and reacting the obtained liquid with sodium potassium, edetic acid and malononitrile in a reactor.The citric acid gold potassium has the advantages of low toxicity and no free cyanogens in the product. Compared with gold potassium cyanide, the total CN<-> content of the citric acid gold potassiumis 5-6 percent in case of the same gold content, and is above 50 percent lower than that in the gold potassium cyanide. The waste liquid after gilding only contains the micro-free CN<->, thereby thewaste water processing cost in electroplating enterprises is reduced.
Description
Technical field
The present invention relates to a kind of lemon acid gold salt for gold plating, particularly relate to a kind of citric acid gold potassium for gilding and preparation method thereof.
Background technology
In gold-plated industry, because potassium cyanide has very strong complexing power to gold ion, when electroplating, the most enterprises of China select inorganic electrogilding salt for use---and potassium cyanaurite is as gold-plated main salt, when electroplating, prepare acid gold-plated or alkaline gold plating solution again, to satisfy requirement to processing condition according to the characteristic of the solidity to corrosion of workpiece and coating, plating piece.
National Defense Industry Press's first version in June nineteen ninety in " practical electroplating technology " book of being write by Li Hongnian, Zhang Shaogong, ZhangBing Qian, Song Ziyu etc. of the second impression in November, 1993, has been introduced craft of gilding.Mainly contain that prussiate is gold-plated, sulphite is gold-plated, Citrate trianion is gold-plated etc., except that sulphite is gold-plated, and other gold-plated potassium auric cyanide KAu (CN) that all adopts
2As gold-plated main salt.When alkaline cyaniding was gold-plated, its subsidiary material were potassium cyanide, salt of wormwood, potassium primary phosphate, because potassium cyanide too high levels, toxicity are bigger in the electroplate liquid of this craft of gilding, most of enterprises seldom use.Citrate trianion is gold-plated, and to belong to slightly acidic gold-plated, more in gold-plated sector application, Citrate trianion is gold-plated also be with potassium auric cyanide as containing golden main salt, subsidiary material are citric acid, Tripotassium Citrate, potassium primary phosphate.
When producing gold-plated main salt potassium auric cyanide, 1 kilogram of potassium auric cyanide of every production will consume 1.2-1.8 kilogram highly toxic substance potassium cyanide (KCN).According to relevant, the annual gold that will consume more than hundred tons of industry is electroplated by China, and the usage quantity of potassium cyanide is about 300 tons.When electroplating, gold is reduced into metal ion and is plated on the object that is plated, and the potassium cyanide that plays complexing action is unbound state and remains in the waste plating solution and be discharged, and the annual like this prussiate that has approximately surplus in the of 300 ton is discharged in the physical environment.The toxicity of prussiate is extremely strong, its lethal quantity LD50=1mg/kg, and the prussiate that sucks 0.1g just can the causing death.How enterprise is because prussiate has unique complexing to gold as gold-plated main salt with prussiate.The making processes of potassium auric cyanide is to react the inorganic golden salt that generates with highly toxic substance potassium cyanide (KCN) and gold under certain temperature and condition, and its chemical name is a dicyan network potassium aurate, has another name called potassium auric cyanide, is commonly called as: golden salt, molecular formula are KAu (CN)
2, belong to inorganic salt compound.Potassium auric cyanide KAu (CN)
2Contain cyanogen (CN
-) 17-23%, wherein contain the free CN of 0.1-1%
-, its lethal quantity LD50=17mg/kg is a highly toxic substance, when electroplating, be mixed with electroplating solution after total CN
-Content is 2200mg/L, CN in the raffinate after the plating
-Content is 500-1089mg/L, even higher, and the discharging of this cyanide wastewater causes serious murder by poisoning and pollution to environment, makes fish, the shrimp disappearance of some rivers and lakes, and electroplating industry has become one of primary pollution source of our country.
Summary of the invention
The objective of the invention is to propose a kind of free cyanogen that do not contain, the only residual gold-plated citric acid gold potassium that is used for that micro free cyanogen is arranged in the waste liquid after gold-plated.
For reaching above purpose, the present invention adopts following technical scheme:
A kind of citric acid gold potassium for gilding, its molecular formula is: KAu
2N
4C
12H
11O
8, structural formula is:
The present invention also proposes a kind of preparation method of above-mentioned citric acid gold potassium for gilding, comprises the steps:
In temperature is 80-85 ℃ water, add gold perchloride under a, normal pressure, the stirring, it is dissolved fully;
B, above-mentioned gold perchloride solution is concentrated under 80-85 ℃ of temperature, when waiting to be concentrated to original volume 1/5, make up water is to original volume in concentrated solution, and under similarity condition, reconcentration is to original volume 1/5, and restock water is to original volume;
C, above-mentioned gold perchloride solution temperature is remained on 80-85 ℃, potassium citrate solution is joined adjusting pH value in the reactor, when the pH value is transferred to 5-7, add edta solution, drip potassium citrate solution and propane dinitrile solution again, adjusting the pH value of solution value is 8-9, gets water white transparency shape solution;
D, the resulting water white transparency shape of c solution is moved in the water cooler cools off, make it be cooled to 0-5 ℃, and keep this temperature, left standstill 4-6 hour, occur white crystals body precipitation in the water cooler, sedimentary white crystals body is moved in the suction filter, suction filtration is removed moisture content;
E, the white crystals body that will remove moisture content are moved in the baking oven, and oven dry is finished product under 80-105 ℃ temperature.
As preferably, used potassium citrate solution concentration is 0.04-0.06g/ml among the step c.
As preferably, used edta solution concentration is 0.05-0.06g/ml among the step c.
As preferably, used propane dinitrile strength of solution is 0.15-0.25g/ml among the step c.
The advantage of citric acid gold potassium provided by the invention is: product does not contain free cyanogen, and the personnel that can not cause injure and environmental pollution; Product is through after electroplating, and the discharge of poisonous waste in the electroplating solution only is the thousandth point two of conditional electronic industrial chemicals, is lower than 8.02 times of state environmental emissioning standards; This product system cleaning electronics industrial chemicals can replace conditional electronic industrial chemicals potassium cyanaurite.
Description of drawings
Fig. 1 is the DSC-TGA curve of citric acid gold potassium;
Fig. 2 is the XRD figure of citric acid gold potassium;
Fig. 3 is a citric acid gold potassium crystalline infrared spectra spectrogram;
Fig. 4 composes entirely for citric acid gold potassium crystalline XPS;
Fig. 5 is the 4f spectrogram of Au in the citric acid gold potassium;
Fig. 6 is the 2p spectrogram of K in the citric acid gold potassium and the 1s spectrogram of C;
Fig. 7 is the 1s track spectrogram of N in the citric acid gold potassium;
Fig. 8 is the 1s spectrogram of O in the citric acid gold potassium;
Fig. 9 is the hydrogen spectrum of citric acid gold potassium nucleus magnetic resonance;
Figure 10 splits peak amplification effect figure for the hydrogen spectrum thunderclap of citric acid gold potassium nucleus magnetic resonance;
Figure 11 is the carbon spectrum of citric acid gold potassium nucleus magnetic resonance.
Embodiment
Calculate by preparation 1000g citric acid gold potassium, its preparation method is as follows:
Embodiment 1: under normal temperature, normal pressure, in reactor, add 10000mL water, open agitator and heater switch, when making water temperature be raised to 85 ℃, under agitation condition, add gold perchloride 500g, it is dissolved fully; Above-mentioned gold perchloride lysate under agitation condition, is kept 85 ℃ of temperature, concentrate 4 hours, when volume to be concentrated to was 2000mL, to 10000mL, under similarity condition, reconcentration was during to 2000mL to the reactor make up water, and restock water is to 10000mL; Above-mentioned gold perchloride solution is kept 85 ℃ of temperature, get Tripotassium Citrate 800g, be dissolved in the 20000mL85 ℃ of hot water, remove by filter the trace impurity in the solution, the potassium citrate solution for preparing is joined in the reactor, and the limit edged is surveyed the pH value, stops to drip potassium citrate solution when the pH value is transferred to 5; Get ethylenediamine tetraacetic acid (EDTA) 50g, be dissolved in 1000mL85 ℃ of hot water, join in the reactor, promptly under the complexing condition, drip remaining potassium citrate solution and 300g propane dinitrile again and be dissolved in propane dinitrile solution in 2000mL40 ℃ the hot water, adjusting the pH value of solution value is 8, and solution is the water white transparency shape, synthetic finishing; Synthetic liquid in the reactor is moved in the water cooler, in the water cooler chuck, feed the frozen water cooling, make the synthetic liquid in the water cooler be cooled to 5 ℃, keep this temperature, left standstill 4 hours, white crystals body precipitation appears in water cooler, and sedimentary white crystals body is moved in the suction filter, and suction filtration is removed moisture content; The white crystals body of removing moisture content is moved in the baking oven, and oven dry is finished product under 80 ℃ temperature.
Embodiment 2: under normal temperature, normal pressure, in reactor, add 10000mL water, open agitator and heater switch, when making water temperature be raised to 80 ℃, under agitation condition, add gold perchloride 400g, it is dissolved fully; Above-mentioned gold perchloride lysate under agitation condition, is kept 80 ℃ of temperature, concentrate 10 hours, when volume to be concentrated to was 2000mL, to 10000mL, under similarity condition, reconcentration was during to 2000mL to the reactor make up water, and restock water is to 10000mL; Above-mentioned gold perchloride solution is kept 80 ℃ of temperature, get Tripotassium Citrate 1200g, be dissolved in the 20000mL80 ℃ of hot water, remove by filter the trace impurity in the solution, the potassium citrate solution for preparing is joined in the reactor, and the limit edged is surveyed the pH value, stops to drip potassium citrate solution when the pH value is transferred to 7; Get ethylenediamine tetraacetic acid (EDTA) 60g, be dissolved in 1000mL80 ℃ of hot water, join in the reactor, promptly under the complexing condition, drip remaining potassium citrate solution and 500g propane dinitrile again and be dissolved in propane dinitrile solution in 2000mL40 ℃ the hot water, adjusting the pH value of solution value is 9, and solution is the water white transparency shape, synthetic finishing; Synthetic liquid in the reactor is moved in the water cooler, in the water cooler chuck, feed the frozen water cooling, make the synthetic liquid in the water cooler be cooled to 0 ℃, keep this temperature, left standstill 6 hours, white crystals body precipitation appears in water cooler, and sedimentary white crystals body is moved in the suction filter, and suction filtration is removed moisture content; The white crystals body of removing moisture content is moved in the baking oven, and oven dry is finished product under 105 ℃ temperature.
The physico-chemical property of this citric acid gold potassium for gilding is: white or little yellow crystals or powder, and soluble in water, be slightly acidic, slight lemon tart flavour is arranged, fusing point is 149.5 ℃.
Adopt differential thermal analyzer and thermogravimetric analyzer, the DSC-TGA curve of measuring citric acid gold potassium as shown in Figure 1.
From accompanying drawing 1 as can be seen, before 176.2 ℃, as long as what deviate from is adsorbent, because experiment usefulness is crystal, adsorptive capacity is (0.21%) seldom, from 176.2 ℃～280.1 ℃, tangible three endotherm(ic)peaks appear, progressively the deviating from of the crystal water of this three peaks explanation, and 280.1 ℃ also in the minimizing that material takes place, this is mainly caused by the hydroxyl dehydration, and is different with deviating from of crystal water.Total material damage at dehydration peak is 2.31% from 176.2 ℃ to 280.1 ℃ three.
Adopt X-ray diffractometer that citric acid gold potassium is carried out the XRD test, the XRD figure that obtains citric acid gold potassium as shown in Figure 2.
Can see a lot of diffraction peaks from accompanying drawing 2, therefore its main peak height obviously illustrates this substance crystallization excellent property near 7000, illustrates that citric acid gold potassium is a crystalline state.This XRD figure spectrum is compared automatically with the XRD data that computer is deposited, and finding no the material diffraction peak position that is consistent can correspondingly coincide, and can this material of preliminary judgement be novel substance therefore.
Adopt infrared spectrometric analyzer to record citric acid gold potassium crystalline infrared spectra spectrogram as shown in Figure 3.
From accompanying drawing 3 as can be seen, 3332.76cm
-1(vibration peak OH) illustrates the existence of hydroxyl, can be H to belong to hydroxyl
2Hydroxyl in O and the structure, 2978.32 belong to the peak of C-H; 2140.84cm
-1The peak belong to-the CN structure; 1589.23cm
-1The peak belong to carboxyl, 1413.72cm
-1The peak that belongs to H-C-H; 1388.65cm
-The peak that belongs to C-O, 1118.64cm
-1The peak belong to C-C.Find out that from infrared spectra the two keys and the triple-linked peak that do not have CC exist.
Adopt elemental analyser, by C, H, N constituent content in the combustion method detection citric acid gold potassium, twice test result is as follows:
| ??N％ | ??C％ | ??H％ | |
| For the first time | ??7.28 | ??18.63 | ??1.42 |
| For the second time | ??7.26 | ??18.64 | ??1.43 |
| Mean value | ??7.25 | ??18.64 | ??1.43 |
Adopt the x-ray photoelectron spectroscopy tester, record the full spectrum of citric acid gold potassium crystalline XPS as shown in Figure 4.As can be seen, each element of citric acid gold potassium crystalline all is presented on the spectrogram except that protium from accompanying drawing 4, and finds no the peak appearance of other impurity elements, illustrates that this crystal purity is higher.
Accompanying drawing 5 is the 4f spectrogram of Au in the citric acid gold potassium, and the matched curve among the figure shows the 4f track standard bimodal curve of gold element, respectively at 85.13eV and 88.81eV.We find from document, 0 ,+2, the gold of+3 valencys plays the peak position and is respectively 84.16eV, 86.34eV, 88.2eV, do not find+1 valency play the peak position.But from the 85.13eV of the peak position of this experimental result, between 0 valency and+divalent between, can conclude that this gold element is+1 valency.
Accompanying drawing 6 is the 2p spectrogram of K in the citric acid gold potassium and the 1s spectrogram of C, as can be seen, two peaks appear in the C peak from accompanying drawing 6, and the peak contrast document of 284.75eV position can be interpreted as C-C, C-H, the position of C in the C-O key, and the 287.33eV peak is the peak of C among the CN, this is because C and N are triple bonds, binding ability is strong, and C-C, C-H, C-O key all are singly-bounds.The K element presents the bimodal of 2p track standard: 292.62eV and 295.36eV, the 2p of corresponding potassium element respectively
3/2And 2p
1/2The position.
Accompanying drawing 7 is the 1s track spectrogram of N in the citric acid gold potassium, the position at its peak is 398.38eV, contrast according to document, three bond structures for the BN type of standard, the one-tenth key form that is N in the citric acid gold potassium is a triple bond, and this can be interpreted as N is that the cyano group form that forms with C is present in the citric acid gold potassium crystal.
Accompanying drawing 8 is the 1s spectrogram of O in the citric acid gold potassium, and tangible division has taken place at the match peak of the 1s track of middle oxygen among the figure, illustrates that two types O element form is present in the citric acid gold potassium crystal.The contrast document judges that first peak (530.96eV) illustrates the type of attachment of O and C, and second peak (532.38eV) illustrates that O is connected with H.
Adopt the high resolving power NMR spectrometer with superconducting magnet, the hydrogen that records the citric acid gold potassium nucleus magnetic resonance is composed as shown in Figure 9, as can be seen, has only the hydrogen atom structure of two classes to be present in the crystal from accompanying drawing 9.Wherein 4.84ppm is the H among the H-O; It is H among the C-H that thunderclap splits peak 2.6-2.8ppm.
Accompanying drawing 10 splits the enlarged view (accompanying drawing 10) at peak from 2.6～2.8ppm thunderclap for the hydrogen spectrum thunderclap of citric acid gold potassium nucleus magnetic resonance splits peak amplification effect figure, and two class C-H structures have been described, through regression Calculation, the structure of this two class C-H is CH
2Structure promptly can obtain R-CH
2And R '-CH
2The existence of structure.
Accompanying drawing 11 is the carbon spectrum of citric acid gold potassium nucleus magnetic resonance, and four types carbon is as can be seen from the figure arranged in the crystal, and the displacement that influence took place of the group that links to each other in conjunction with the position at different carbon peak and with carbon can be judged the carbon structure type at these four peaks.
Through document contrast and analysis, this carbon of four types is respectively:
45ppm is :-CH
2-;
74ppm is:
152ppm is :-CNM (M is a metal)
178ppm is :-COO
-
The main raw material of preparation citric acid gold potassium is a gold perchloride, Tripotassium Citrate, propane dinitrile, EDTA.From raw material, the main body composition is a former three, and the amount of EDTA is fewer, and its possible effect is a complexing trivalent gold ion.From chemical reaction, the amount of substance of Tripotassium Citrate and propane dinitrile (mole number) is much larger than the amount of substance of gold perchloride, and Tripotassium Citrate and propane dinitrile mainly are organic substances, has certain weak reducing property, and the trivalent gold utensil has stronger oxidation susceptibility, therefore the trivalent gold will be reduced to the univalent gold ion in preparation process, EDTA to the complexing action of monovalence gold ion a little less than.The cyano group of propane dinitrile has very strong electron-withdrawing power, and the monovalence gold ion can provide electron pair, therefore is easy to form complexing ion.Owing on the propane dinitrile two cyano group are arranged, two cyano group are equal to, and the monovalence gold ion is easy to form sequestering action with two cyano group, and the stability of this chelating is greater than the complexing ion of single cyano group and the formation of monovalence gold ion, therefore, guaranteeing to form inner complex under the excessive situation of propane dinitrile.Because propane dinitrile is a neutral molecule, the inner complex of Xing Chenging is a cationic structural like this.Its structure is:
The structure of Tripotassium Citrate is:
Tripotassium Citrate is a strong electrolyte, and the locations of structures unanimity of two carboxyls is obviously arranged, and these two carboxyls easily combine with the chelating positively charged ion that forms previously in crystallisation process, and the intermediary carboxyl can only be followed less positively charged ion combination owing to the steric hindrance reason, i.e. potassium ion.
By above analysis, in conjunction with the analysis of different experiments process to each group, each component concentration, the molecular formula that can draw this citric acid gold potassium is KAu
2N
4C
12H
11O
8, structural formula is:
Calculate by molecular formula, in the citric acid gold potassium shown in the mass content following table of each element:
| Element | ??Au | ??K | ??N | ??C | ??H | ??O |
| Content % | ??51.04 | ??5.05 | ??7.23 | ??18.65 | ??1.43 | ??16.58 |
Citric acid gold potassium for gilding provided by the invention is a low toxicity material.Through the rat acute percutaneous toxicity test, animal does not occur poisoning manifestations and death in contamination in back 14 days, and the dead animal rate is zero, acute through skin LD to rat
50Greater than 2500mg/kg bw, see Occupational Health and Poisoning Control Inst., China Disease Prevention and Co's report.Through small white mouse test acute oral toxicity lethal quantity is LD50=681mg/kg, sees disease prevention and control center, Henan Province examining report.The true yellow gold content can reach 51.05%, sees the analytical test report of Henan Prov. Analytical Test Center.Do not contain free cyanogen, product when identical gold content, total CN
-Content is 5-6%, than CN in the potassium auric cyanide
-Content is low more than 50%, and free CN-content only has 0.124mg/L in the waste liquid after gold-plated, under the same case, and the free CN in the gold-plated waste liquid of potassium auric cyanide
-Content is 1069mg/L, has reduced the cost for wastewater treatment of electroplating enterprise.Can reduce the prussiate environmental pollution caused by discharge from the source, meet the national energy-saving and emission-reduction and the strategy of sustainable development, see the research report of department of chemistry of Fudan University about low cyanogen citric acid gold salt.
Cyanide content contrast before and after citric acid gold potassium and potassium auric cyanide are electroplated
Be mixed with every liter of electroplating solution that contains gold 6 grams
| Project | Potassium auric cyanide | Citric acid gold potassium | Tank liquor cyanogen slippage |
| The preparation tank liquor is with golden salt amount | 8.79 gram | 11.77 gram | |
| Contain the cyanogen amount in the tank liquor | 2200 mg/litre | 176 mg/litre | 2024 milligrams |
| Electroplate the raffinate cyanide content | 1069 mg/litre | 0.124 mg/litre | 1068.8 milligram |
Can see that from last table in plating tank, when Gold Content all was 6 grams per liters, total cyanide was 2200 mg/litre, prussiate residual quantity 1069 mg/litre in the raffinate after the plating.Cyanide content is 176 mg/litre in organic golden salt bath solution, and cyanide content only has 0.124 mg/litre in the plating raffinate, than low 8621 times of prussiate in the potassium auric cyanide raffinate.
Above result is tested by Fudan University in Shanghai.
The gold-plated system coating performance of citric acid gold potassium test report according to University of Electronic Science and Technology's microelectronics and solid electronic institute, the gold-plated cobalt of citric acid gold potassium all has remarkable advantages aspect coating compactness, coating surface morphology, the coating crystallinity, and the gold-plated nickel of citric acid gold potassium is similar to each performance of the gold-plated cobalt coating of potassium cyanaurite, and the coating performance of the gold-plated nickel system of potassium cyanaurite is the poorest.Therefore, it is gold-plated that citric acid gold potassium substitutes potassium cyanaurite, and with regard to coating, the performance of citric acid gold potassium is more excellent than potassium cyanaurite performance.
Substitute the application report of potassium cyanaurite according to another citric acid gold potassium in the electrogilding system of University of Electronic Science and Technology's microelectronics and solid electronic institute and Huafeng Enteriprises Co., Ltd., Sichuan, from the electrochemistry experiment test result, no matter be 23K system or CM system, citric acid gold potassium substitutes the electrogilding plating bath cyclic voltammetry scan good reproducibility of potassium cyanaurite, show bath stability, though the gold deposition potential than the low 0.1V of potassium cyanaurite system about, but still be dominance craft of gilding scope, there is not change to current technology; According to the evidence of electroplating technique to electric, mechanical, the electrochemical properties of product, anti-multiple environment, in gold-plated (nickel, cobalt) alloy system of thinking U.S. prosperous and ROHM AND HAAS, citric acid gold potassium is can replace potassium cyanaurite fully, and the performance of its coating does not have yet and can observedly reduce.
Claims (5)
1. citric acid gold potassium for gilding, it is characterized in that: the molecular formula of this citric acid gold potassium for gilding is: KAu
2N
4C
12H
11O
8, structural formula is:
2. a method for preparing citric acid gold potassium for gilding as claimed in claim 1 is characterized in that, comprises the steps:
In temperature is 80-85 ℃ water, add gold perchloride under a, normal pressure, the stirring, it is dissolved fully;
B, above-mentioned gold perchloride solution is concentrated under 80-85 ℃ of temperature, when waiting to be concentrated to original volume 1/5, make up water is to original volume in concentrated solution, and under similarity condition, reconcentration is to original volume 1/5, and restock water is to original volume;
C, above-mentioned gold perchloride solution temperature is remained on 80-85 ℃, potassium citrate solution is joined adjusting pH value in the reactor, when the pH value is transferred to 5-7, add edta solution, drip potassium citrate solution and propane dinitrile solution again, adjusting the pH value of solution value is 8-9, gets water white transparency shape solution;
D, the resulting water white transparency shape of step c solution is moved in the water cooler cools off, make it be cooled to 0-5 ℃, and keep this temperature, left standstill 4-6 hour, occur white crystals body precipitation in the water cooler, sedimentary white crystals body is moved in the suction filter, suction filtration is removed moisture content;
E, the white crystals body that will remove moisture content are moved in the baking oven, and oven dry is finished product under 80-105 ℃ temperature.
3. the method for preparation according to claim 2 citric acid gold potassium for gilding as claimed in claim 1 is characterized in that, used potassium citrate solution concentration is 0.04-0.06g/ml among the step c.
4. the method for preparation according to claim 2 citric acid gold potassium for gilding as claimed in claim 1 is characterized in that, used edta solution concentration is 0.04-0.06g/ml among the step c.
5. the method for preparation according to claim 2 citric acid gold potassium for gilding as claimed in claim 1 is characterized in that, used propane dinitrile strength of solution is 0.15-0.25g/ml among the step c.
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