CN102050480A - Method for preparing cuprous compound - Google Patents
Method for preparing cuprous compound Download PDFInfo
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- CN102050480A CN102050480A CN200910044725XA CN200910044725A CN102050480A CN 102050480 A CN102050480 A CN 102050480A CN 200910044725X A CN200910044725X A CN 200910044725XA CN 200910044725 A CN200910044725 A CN 200910044725A CN 102050480 A CN102050480 A CN 102050480A
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- cuprous
- ion
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- cupric
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Abstract
The invention relates to a method for preparing a cuprous compound, in particular to a method for preparing a cuprous compound from a cupric solution. The method comprises the following steps: in a solution containing cupric ions, in the existence of ligands which can form complex ions with cuprous ions, electrochemical reduction is performed on the cupric ions so that the cupric ions in the solution are only converted to cuprous complex ions, and the cuprous complex ions are used to prepare cuprous salt or cuprous oxide. The invention provides a simple and practical method for preparing cuprous ions from cupric ions; and the obtained solution containing cuprous ions can be used for conveniently preparing the cuprous compound. The obtained compound is easy to separate and purify.
Description
Technical field
The present invention relates to a kind of method for preparing the monovalence copper compound, particularly from the copper solutions that contains divalence, prepare the method for monovalence copper compound.
Background technology
About preparing the method that univalent copper ion is a cuprous ion solution, at present common have two kinds of methods:
1) by solution that contains bivalent cupric ion and metallic copper contrary disproportionation reaction takes place.Chinese patent CN1105341 (application number 94113822.4) has all introduced relevant preparation method with CN1583571 (application number 200410024943.4).
2) by compound solution that contains bivalent cupric ion and the reaction of relatively mild reductive agent, cupric compound is reduced to the monovalence copper compound.Common reductive agent has sulphite and sulfurous gas, Chinese patent CN1762821 (application number 94113822.4), Chinese patent CN1696062 (application number 94113822.4) have all introduced relevant method of reducing, and another part application number is that the Chinese patent of 200510029724.X also has similar introduction.
But, above-mentioned introduction from containing the method for cupric formulations prepared from solutions monovalence copper (cuprous) solion, in application, exist following obvious deficiency:
1) cost height must add metallic copper when producing cuprous compound by contrary disproportionation reaction, and its cost is very high.
2) reaction system complexity, target product separate the difficulty of purifying.When being reduced to monovalence copper with the production cuprous compound with cupric, reductive agent must add reductive agents such as S-WAT, sulfurous gas, sodium bisulfite, vat powder by adding, finally exist impurity such as sodium ion, inferior sulfate radical and sulfate radical in the reaction system, make the separation of target product (as cuprous chloride) and purification become difficult.
3) the bad control of speed of response is typical solid-liquid phase chemistry reaction when producing cuprous compound by contrary disproportionation reaction, and speed of response is slower; When being reduced to monovalence copper with the production cuprous compound with cupric, reductive agents such as sulphite and sulfurous gas comprising gas-liquid phase chemistry reaction process by adding, the bad control of speed of response, and easily generate multiple precipitation mixture in the production process, hinder carrying out smoothly of goal response, and parcel impurity has increased the difficulty of purification target product in interior.
Summary of the invention
An object of the present invention is, a kind of method for preparing the monovalence copper compound from the copper ion solution that contains divalence is provided.
Technical scheme of the present invention is, in containing the solution of bivalent cupric ion, containing and to form under the condition that the part of complex ion exists with univalent copper ion, by bivalent cupric ion is carried out electrochemical reduction, make the cupric in the solution only be converted into monovalence copper complex ion, then with suitable compound prepared in reaction monovalence copper compound or cuprous oxide compound.
What contain in this solution can be selected from haloid acid and halide-ions, class halide-ions such as thiocyanate ion (SCN with part (the being also referred to as complexing agent) material that univalent copper ion forms complex ion
-) and cyanogen root (CN
-), propane dinitrile (CNCH
2CN) and negatively charged ion (CNCHCN
-), amino acid (as: NH
2-R-CO
2H, R represent certain carbon skeleton, down together) and negatively charged ion (corresponding N H
2-R-CO
2 -), organic carboxyl acid (as: R-CO
2H) and negatively charged ion (corresponding R-CO
2 -), ammonia and organic amine compound (R-NH
2), pyridine and bipyridyliums compound thereof, porphyrins, pyrimidines, Schiff bases compound, trimeric cyanamide compounds, phenanthroline compounds, glyoxaline compound, quinolines, guanidine compound etc.In the practical application, the used ligand substance of cuprous ion can be a kind of, also can be made up of two or more cuprous ion part.
Wherein the volumetric molar concentration of part is preferably the twice of cupric ion volumetric molar concentration or more than the twice.
For being reduced to cupprous current potential from cupric, can be according to standard electrode potential in conjunction with concrete reduction system, the voltage that applies by adjustment is that the current potential of negative electrode remains on the suitable reduction potential.Can observe does not have copper simple substance to separate out on the negative electrode, have univalent copper ion to produce simultaneously again.
By aforesaid method the concentration of cathodic area monovalence copper complex ion is reached more than 10 grams per liters.Prolong the activity duration, the cuprous concentration in the solution can continue to rise.Get the solution that contains monovalence copper complex ion and further can prepare the monovalence copper compound.
According to the embodiment of the invention, after the taking-up of cathodic area solution, to the dense potassium hydroxide solution that wherein adds q.s, low-temperature reduced-pressure distills part ammonia, raffinate cooling back solid-liquid separation, and the gained filter cake obtains the thick product of Red copper oxide through washing, oven dry.
According to embodiments of the invention, after the cathodic area solution of gained chloride ion-containing takes out, carry out the low-temperature reduced-pressure evaporation concentration, cooling back gained concentrated solution is poured in the cold water fast and is hydrolyzed, obtain white depositions after the solid-liquid separation, this throw out obtains the cuprous chloride product through 1% dilute hydrochloric acid and industrial spirit washing, drying.
According to embodiments of the invention, gained cathodic area solution to wherein adding hydrazine hydrate, obtains containing the mixture of red precipitate after taking out, and collects this throw out and obtain copper powder after washing, drying.
According to embodiments of the invention, after gained cathodic area solution therefrom took out, to wherein adding sodium cyanide, the gained mixture was poured in a large amount of cold water and is obtained white depositions, collects this throw out and obtain the cuprous cyanide product after washing, drying.
The invention provides and a kind ofly simple prepare the method for univalent copper ion, and use the univalent copper ion solution that obtains through this method can prepare the monovalence copper compound easily by bivalent cupric ion.Resulting compound separation is purified simple.
Embodiment
Embodiment 1:
It is a kind of that (main composition is CuCl by 200 gram cupric chlorides
22H
2O cupric about 37%), the blue alkaline copper ammonia solution that forms of 800 milliliters of DI (deionization) water, 50 gram thanomins, 25 gram Sodium L-alaninates, 200 milliliters of industrial ammonias and 230 gram industrial ammonium chlorides, its pH is 8.5-9, containing cupric is the 60-80 grams per liter.Get 1 liter of this liquid, (the negative and positive polar region is separated by a semi-permeable membranes to be placed on the cathodic area of an electrochemical reduction device, film is the cavity block that Beijing global Li Da company is produced), positive column solution is ammonia-ammonium chloride (100 grams per liter) buffered soln (adding ammoniacal liquor when positive column pH value is lower than 8) of alkalescence, negative electrode adopts copper coin, anode adopts graphite cake, the output DC equipment is a C25 type DZ47-63 high frequency switch power, keeps electric current 1-2A reaction 4 hours under temperature is 20-30 ℃, the condition of control cathode reduction potential; The cuprous concentration that records cathodic area solution reaches 10.5 grams per liters, illustrates by present method the cupric in the alkaline copper ammonia complex solution to be converted into monovalence copper.
Embodiment 2:
A kind of green acid copper solution that is formed by 200 gram cupric chlorides (cupric about 37%), 1000 milliliters of DI water, 50 gram glycine, 25 gram butyric acid, 150 milliliters of technical hydrochloric acids and 50 gram sodium-chlor, containing cupric is the 50-70 grams per liter.Get 1 liter of this liquid, be placed on the cathodic area of an electrochemical reduction device, the negative and positive polar region is separated by an ion-exchange membrane (anode membrane of sky, Shandong dimension membrane technique company limited), the positive column is the dilution heat of sulfuric acid of 5% (W/V), the output DC equipment is a C25 type DZ47-63 high frequency switch power, negative electrode adopts the titanium plate, and anode adopts titanium base ruthenium iridium activated coating plate (company's product is reached in Shaanxi), keeps electric current 1-2A reaction 4 hours under temperature is 20-30 ℃, the condition of control cathode reduction potential; The cuprous concentration that records cathodic area solution reaches 11.2 grams per liters, illustrates by present method the cupric in the acid chlorization copper solutions to be converted into monovalence copper.
Embodiment 3:
It is a kind of that (main composition is CuCl by 100 gram cupric chlorides
22H
2O cupric about 37%), the blue alkaline copper ammonia solution that forms of 650 milliliters of DI (deionization) water, 30 gram propane dinitrile, 20 gram pyridines, 280 milliliters of industrial ammonias and 230 gram industrial ammonium chlorides, its pH is 8.5-9, containing cupric is the 30-40 grams per liter.Get 2 liters of this liquid, (the negative and positive polar region is separated by a semi-permeable membranes to be placed on the cathodic area of an electrochemical reduction device, film is the cavity block of sky, Shandong dimension membrane technique company limited), the output DC equipment is a C25 type DZ47-63 high frequency switch power, negative electrode adopts stainless steel plate; Positive column solution is sulfur acid ammonium (100 grams per liter) and the alkaline aqueous solution that contains sodium hydroxide (add ammoniacal liquor and be not less than 8 to keep its pH value when positive column pH value is lower than 8), anode adopts the active laminate of titanium base ruthenium iridium (Shaanxi is reached company and produced product), keeps electric current 1-2A reaction 6 hours under temperature is 30-40 ℃, the condition of control cathode reduction potential; Cathodic area solution is taken out then to the 4N potassium hydroxide solution that wherein adds q.s, low-temperature reduced-pressure distills part ammonia, raffinate cooling back solid-liquid separation, the gained filter cake is through washing, oven dry, obtain thick product 16.5 grams of Red copper oxide, the content of Red copper oxide reaches 90% in this thick product by analysis, illustrates by present method to prepare the monovalence copper products from alkaline cupric solution.
Embodiment 4:
A kind of green acid cupric solution that forms by 200 gram cupric chlorides (cupric about 37%), 1000 milliliters of DI water, 25 gram oxysuccinic acid, 100 milliliters of technical hydrochloric acids and 100 gram ammonium chlorides.Get 1 liter of this liquid, be placed on the cathodic area of an electrochemical reduction device, the negative and positive polar region is separated (film is the anode membrane that Beijing global Li Da company is produced) by a semi-permeable membranes, the positive column is the dilution heat of sulfuric acid of 3% (W/V), the output DC equipment is a C25 type DZ47-63 high frequency switch power, negative electrode adopts the titanium plate, and anode adopts the active laminate of titanium base iridium tantalum (the auspicious prosperous titanium industry in Shaanxi company product), is that holding current is 1-2A reaction 5 hours under 35-45 ℃, the condition of control cathode reduction potential in temperature; Gained cathodic area solution carries out the low-temperature reduced-pressure evaporation concentration after taking out, cooling back gained concentrated solution is poured into fast in 15 liters of cold water and is hydrolyzed, obtain white depositions after the solid-liquid separation, this throw out obtains cuprous chloride product 16.3 grams through 1% dilute hydrochloric acid and industrial spirit washing, drying, its cuprous chloride effective content reaches 95% by analysis, illustrates by present method the cupric in the acidic solution to be converted into the monovalence copper products.
Embodiment 5:
A kind of acid copper etching waste liquor (also claiming mashed plate liquid) from the Hunan China strain state PCB of Time Incorporation (printed circuit board) division department, with hydrogen peroxide with its color by the not too transparent blackish green transparent bright green that is converted into, its acidity is 2.8 after measured, and cupric is 105 grams per liters (wherein cuprous content is lower than 0.3 grams per liter).Get 2 liters of this liquid, be placed on the cathodic area of an electrochemical reduction device, the negative and positive polar region is separated (film is the anode membrane of sky, Shandong dimension membrane technique company limited) by a semi-permeable membranes, the positive column is the dilution heat of sulfuric acid of 3% (W/V), the output DC equipment is a C25 type DZ47-63 high frequency switch power, and negative electrode adopts the titanium plate, and anode adopts the active laminate of titanium base iridium tantalum (the auspicious prosperous titanium in Shaanxi is company's product already), under the condition of control cathode reduction potential, keep 35-45 ℃ of temperature, electric current 1-2A, reacted 8 hours; Gained cathodic area solution carries out the low-temperature reduced-pressure evaporation concentration after taking out, cooling back gained concentrated solution is poured into fast in 25 liters of cold water and is hydrolyzed, obtain white depositions after the solid-liquid separation, this throw out obtains cuprous chloride product 25.1 grams through 1% dilute hydrochloric acid and industrial spirit washing, drying, its effective content reaches 96% by analysis, illustrates by present method will to be converted into the monovalence copper products from the cupric in the PCB industry acidic waste etching liquid.
Embodiment 6:
A kind of alkaline etching waste liquid for producing from Hunan China strain state PCB division department of Time Incorporation, blueness, band ammonia flavor, its pH is 8.2, cupric is 115 grams per liters, chlorion 185 grams per liters.Get 500 milliliters of this liquid, with pH is ammonia-chloride buffer solution dilution to 1 of 8.5 liter, (the negative and positive polar region is separated by a semi-permeable membranes to be placed on the cathodic area of an electrochemical reduction device, film is the cavity block of sky, Shandong dimension membrane technique company limited), anolyte for by ammonium sulfate (150 grams per liter) and sodium hydroxide form alkaline aqueous solution (when positive column pH value is lower than 8, adding ammoniacal liquor), negative electrode adopts stainless steel plate, anode adopts graphite cake, the output DC equipment is a C25 type DZ47-63 high frequency switch power, is 25-35 ℃ in temperature, keep electric current 1.2-2A reaction 6 hours under the condition of control cathode reduction potential; The cuprous concentration that records cathodic area solution reaches 15.5 grams per liters, illustrates by present method the cupric in the PCB alkaline etching waste liquid for producing to be converted into monovalence copper.
Embodiment 7:
A kind of green acid copper solution that is formed by 200 gram cupric chlorides (cupric about 37%), 1000 milliliters of DI water, 150 milliliters of technical hydrochloric acids and 50 gram ammonium chlorides, containing cupric is the 50-70 grams per liter.Get 1.2 liters of this liquid, be placed on the cathodic area of an electrochemical reduction device, the negative and positive polar region is separated (film is the anode membrane that Beijing global Li Da company is produced) by a semi-permeable membranes, the positive column is the dilution heat of sulfuric acid of 3% (W/V), the output DC equipment is a C25 type DZ47-63 high frequency switch power, negative electrode adopts the titanium plate, and anode adopts graphite cake, is that holding current is 0.8-1.2A reaction 5 hours under 35-45 ℃, the condition of control cathode reduction potential in temperature; Gained cathodic area solution therefrom takes out 500 milliliters, to wherein adding sodium cyanide 5 grams, the gained mixture is poured in a large amount of cold water and is obtained white depositions, collect this throw out and after washing, drying, obtain cuprous cyanide product 7.5 grams, its cuprous cyanide effective content reaches 94.8% by analysis, illustrates by present method to go out monovalence copper compound product from acid cupric formulations prepared from solutions.
Embodiment 8:
A kind of solution that cupric is 60 grams per liters that contains that restrains citric acids, 100 milliliters of technical hydrochloric acids, 50 gram sodium-chlor and some milliliters of DI water by 200 gram cupric chlorides (cupric about 37%), 15 gram acetic acid, 10.Get 1 liter of this liquid, be placed on the cathodic area of an electrochemical reduction device, the negative and positive polar region is separated (film is the anode membrane that Beijing global Li Da company is produced) by a semi-permeable membranes, the positive column is the dilution heat of sulfuric acid of 3% (W/V), the output DC equipment is a C25 type DZ47-63 high frequency switch power, negative electrode adopts titanium copper composition board (in the face of that face of anodic is a copper), anode adopts graphite cake, in temperature is that holding current is 1.5-2A reaction 20 hours under 30-35 ℃, the condition of control cathode reduction potential, records its cuprous concentration and reaches 55 grams per liters; Therefrom take out 500 milliliters, to wherein adding hydrazine hydrate 15 grams, obtain containing the mixture of red precipitate, collect this throw out and after washing, drying, obtain copper powder 27.2 grams, its effective metal content reaches 98.3% by analysis, illustrates that the tart bivalent cupric ion can be converted into cuprous ion, also further prepare elemental copper thus by present method is main copper powder product.
Claims (6)
1. method for preparing cuprous compound, it is characterized in that in containing the solution of bivalent cupric ion, contain and to form under the condition that the part of complex ion exists with univalent copper ion, by bivalent cupric ion is carried out electrochemical reduction, make the cupric in the solution only be converted into monovalence copper complex ion, prepare cuprous salt or cuprous oxide compound by monovalence copper complex ion again.
2. the method for the cuprous complex ion of preparation according to claim 1 is characterized in that said part is to select in the following compounds one or more: from haloid acid and halide-ions thereof, thiocyanate ion, cyanogen root, propane dinitrile (CNCH
2CN) and negatively charged ion, amino acid and negatively charged ion thereof, organic carboxyl acid and negatively charged ion thereof, ammonia and organic amine compound, pyridine and bipyridyliums compound thereof, porphyrins, pyrimidines, Schiff bases compound, trimeric cyanamide compounds, phenanthroline compounds, glyoxaline compound, quinolines, guanidine compound.
3. the method for the cuprous complex ion of preparation according to claim 2 is characterized in that said part is to be selected from: acetic acid, citric acid, hydrochloric acid, ammonium chloride, oxysuccinic acid, propane dinitrile, pyridine, industrial ammonia, glycine, butyric acid, sodium-chlor, thanomin, Sodium L-alaninate.
4. according to the method for claim 2 or the cuprous complex ion of 3 described preparations, the volumetric molar concentration that it is characterized in that part is the twice of cupric ion volumetric molar concentration or more than the twice.
5. the method for the cuprous complex ion of preparation according to claim 1 is characterized in that and will add the dense potassium hydroxide solution of q.s in the solution of cathodic area, back solid-liquid separation, and the gained filter cake obtains Red copper oxide through washing, oven dry.
6. the method for the cuprous complex ion of preparation according to claim 1, it is characterized in that the cathodic area solution of gained chloride ion-containing or cryanide ion is carried out the low-temperature reduced-pressure evaporation concentration, cooling back gained concentrated solution is poured in the cold water fast and is hydrolyzed, obtain white depositions after the solid-liquid separation, this throw out obtains cuprous chloride or cuprous cyanide through washing, drying.
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|---|---|---|---|
| CN200910044725A CN102050480B (en) | 2009-11-06 | 2009-11-06 | Method for preparing cuprous compound |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022528A (en) * | 2012-12-04 | 2013-04-03 | 中国科学院金属研究所 | Method for cleanly removing copper ions in copper-bearing vanadium solution |
| CN105624721A (en) * | 2015-12-31 | 2016-06-01 | 上海大不同木业科技有限公司 | Preparation method for copper-amine (ammonia) complex compound |
| CN111392747A (en) * | 2020-03-24 | 2020-07-10 | 宁波神化特种化学品集成有限公司 | Preparation method of cuprous cyanide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101252154A (en) * | 2008-04-01 | 2008-08-27 | 天津大学 | Method for preparing cuprous thiocyanate thin film using triethanolamine complexing water-based galvanic deposit liquid |
-
2009
- 2009-11-06 CN CN200910044725A patent/CN102050480B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022528A (en) * | 2012-12-04 | 2013-04-03 | 中国科学院金属研究所 | Method for cleanly removing copper ions in copper-bearing vanadium solution |
| CN103022528B (en) * | 2012-12-04 | 2015-06-03 | 中国科学院金属研究所 | Method for cleanly removing copper ions in copper-bearing vanadium solution |
| CN105624721A (en) * | 2015-12-31 | 2016-06-01 | 上海大不同木业科技有限公司 | Preparation method for copper-amine (ammonia) complex compound |
| CN111392747A (en) * | 2020-03-24 | 2020-07-10 | 宁波神化特种化学品集成有限公司 | Preparation method of cuprous cyanide |
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