CN103101957A - Method for preparing high-purity low-chlorine electroplating-grade cupric oxide - Google Patents
Method for preparing high-purity low-chlorine electroplating-grade cupric oxide Download PDFInfo
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Abstract
The invention discloses a method for preparing high-purity low-chlorine electroplating-grade cupric oxide. According to the method, copper, liquid ammonia and high-purity carbon dioxide are taken as raw materials, stronger ammonia water is prepared firstly, carbonated ammonia water is obtained through introducing the high-purity carbon dioxide into the stronger ammonia water and controlling carbonization degree, the carbonated ammonia water reacts with the copper under certain air pressure so as to prepare copper-ammonia complexation liquid, the copper-ammonia complexation liquid is then subjected to heating, ammonia distilling, separating, washing, drying and sieving so as to prepare high-purity heavy basic copper carbonate, and the heavy basic copper carbonate is then subjected to heating calcination and decomposition, thereby preparing the high-purity low-chlorine electroplating-grade cupric oxide. According to the method, the carbon dioxide is directly used as a raw material, so that the problems of the traditional method that impurities, such as heavy metal ions and chloride ions, are introduced by raw materials used in the production of basic copper carbonate are solved, the rate of reaction is increased, the production cycle is shortened, the production efficiency is greatly increased, and products are low in impurity content, high in purity, high in activity and wider in application; and meanwhile, the method is high in yield, low in energy consumption, and low in cost and hardly causes pollution.
Description
Technical field
The invention belongs to the cupric oxide production field, particularly a kind of method take carbonic acid gas high-purity low chlorine plating-grade copper oxide as raw material prepares.
Background technology
In the PCB manufacturing process, traditional electroplating technology is to adopt copper coin to do positive plate and supplementation with copper source, and is complex-shaped, porose because of electronic component, the shape such as male and fomale(M﹠F) arranged, in hole, because plating solution infiltration is not entered, thereby plate less than copper, convex part is large because of current density, coating is thicker, the sunk part current density is little, and coating is thinner, causes product defective.
PCB production general level electroplating technology in the market, this technique has overcome the shortcoming of traditional technology, but this technique must be added high-purity low COPPER OXYCHLORIDE 37,5 in electroplate liquid, to guarantee the electroplate liquid copper ion concentration, horizontal electroplating technology cupric oxide used is except high purity requires, to guarantee that also cupric oxide has enough fast dissolution rate in electroplate liquid, guarantee cupric oxide in electroplate liquid 30 seconds complete with interior dissolving.Production technique about cupric oxide, also have in present discloseder patents of invention and relate to, application number is 01127175.2 disclosed take copper sulfate and copper material as raw material, low-temperature oxidation through 80-85 ℃, obtain copper sulfate through crystallization, then with sodium hydroxide reaction, then the technique that makes active copper oxide through ball milling, press filtration, washing, oven dry, pulverizing the thickness state can occur at oxygenerating copper Process liquor, to through washing procedure repeatedly, therefore can produce a large amount of washess; Application number is the 200710076208.1 disclosed techniques of cupric oxide of producing through ammonia still process with alkaline etching waste liquid for producing, and because being makes with alkaline etching waste liquid for producing long-time ammonia still process under high temperature, highly basic state, so the cupric oxide activity is lower; Application number is that 200710071896.2 disclosed cupric nitrate and the sodium hydroxide used react through press filtration, drying, roasting oxygenerating process for copper, can produce nitrogen peroxide or nitrogen protoxide waste gas, and environment is caused certain pollution; Application number is 200810067243.1 take synthetic basic copper chloride as presoma, then through with the production technique of sodium hydroxide reaction manufacture order oblique system cupric oxide, but not yet experimental verification of its activity.At present level is electroplated with cupric oxide also take ventilation breather as raw material preparation, is obtained by traditional technology but ventilation breather is many, and the foreign matter contents such as iron, lead are high, and purity is low, and is active inadequate.
To sum up, develop a kind of production cost low, pollute little, quality better, the preparation method that active high level is electroplated with cupric oxide has become the manufacturing active demand of PCB.
Summary of the invention
The present invention has overcome the defective of existing technique, provide a kind of take liquefied ammonia, copper, carbonic acid gas as raw material, product purity is high, chlorinity is few, little, the low method that also can guarantee the high-purity low chlorine plating-grade copper oxide of preparation of Product Activity of cost is easily washed, polluted in production.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of method for preparing high-purity low chlorine plating-grade copper oxide comprises the following steps:
(1) liquefied ammonia is passed into make the strong aqua that concentration is 85 ~ 135g/L in water, then pass into high-purity carbon dioxide in the strong aqua and prepare carbonated aqueous ammonia, making degree of carbonisation is 80%～140%;
(2) carbonated aqueous ammonia of step (1) preparation is added in the copper material react, and blast air in reaction process, make the feed liquid of cupric ammoniate, the copper material with the reaction formula that carbonated aqueous ammonia reacts is:
2Cu+2(NH
4)
2?CO
3+O
2=2Cu(NH
3)
2CO
3?+2H
2O；
(3) feed liquid is filtered after adding hydrogen peroxide fully to react in the feed liquid of cupric ammoniate;
(4) make the high-purity ventilation breather of heavy after the filtrate thermal degradation after filtering and the mixed liquor that contains ventilation breather that will react gained separate, wash, dry, sieve, the reaction formula of decomposition reaction is:
3Cu(NH
3)
2CO
3?+H
2O=2CuCO
3?Cu(OH)
2+6NH
3↑+?CO
2↑；
(5) the high-purity ventilation breather heating and calcining of heavy that step (4) is made make cupric oxide powder and further cooling, sieving obtains high-purity low chlorine plating-grade copper oxide, calcining, the reaction formula that decomposes are:
CuCO
3·Cu(OH)
2=2CuO+CO
2+H
2O。
The pressure that passes into liquefied ammonia during the middle strong aqua processed of described step (1) is 0.05～0.2MPa; The described pressure that passes into carbonic acid gas in the strong aqua is 0.05～0.2MPa; Describedly pass into temperature less than the water quench of 15 ℃ to the spiral coil cooling tube that is arranged in strong aqua when passing into carbonic acid gas in the strong aqua.
The copper content of copper material 〉=99.5% in described step (2); The amount of substance of the copper of described copper material is greater than the amount of substance that adds the contained volatile salt of carbonated aqueous ammonia in the copper material; Described reaction is 1.01 * 10 in air pressure
5Pa～10 * 10
5Carry out under the air tight condition of Pa, the time that blasts air during reaction is 5～12 hours, and reaction end is that in the feed liquid of reacted cupric ammoniate, content of copper ion reaches 85～120g/L.
The volume ratio of the quality of the hydrogen peroxide that adds in the feed liquid of cupric ammoniate in described step (3) and the feed liquid of cupric ammoniate is 1～10 ㎏/cubic meter, and adding the reaction times after hydrogen peroxide is 2～6 hours; Described filter plant is accurate deep bed filter.
In described step (4), the temperature of filtrate heating is 70～98 ℃; Described decomposition is in normal pressure～0.8 * 10
5Carry out under the pressure of Pa; The terminal point of described decomposition for the reaction gained the mixed liquor that contains ventilation breather in content of copper ion less than 15g/L; Part water in ammonia, carbonic acid gas and former filtrate that described decomposition produces, liquefied ammonia prepare strong aqua again after condensation, recovery.
Separate in described step (4), washing isolates after original liquid with deionized water wash chlorion mass concentration≤60ppm to the washings for the mixed liquor that contains ventilation breather that will react gained again.
In described step (4), bake out temperature is 60～100 ℃; Described sieving is that 100 orders sieve.
In described step (5), the temperature of the high-purity ventilation breather heating and calcining of heavy is 500～800 ℃, and the time of heating and calcining is 0.5～5h; The cupric oxide powder that described calcining obtains further cooling temperature is 30 ~ 40 ℃.
After adopting technique scheme, the beneficial effect that the present invention reaches is:
(1) directly to use high-purity carbon dioxide be the waste cupric oxide in the present invention, do not use agricultural or food grade bicarbonate of ammonia, avoided bringing into of heavy metal ion and chlorion, can guarantee the cupric oxide product purity, avoid take copper sulfate and sodium hydroxide as the chloride height of raw material and the defective that is difficult to wash;
(2) the present invention has increased the hydrogen peroxide deironing removal of impurity simultaneously, and in product, iron level reduces greatly, and product is purer, the active raising, and product application is more extensive;
(3) production process of the present invention realizes airtightly, and the ammonia assimilated efficiency can reach 98%, and the execute-in-place environment is greatly improved, and has reduced the waste of ammonia, has improved the utilization ratio of copper, has saved the energy, has also reduced production cost when more meeting environmental requirement;
(4) present method is more controlled than the produced in conventional processes process, quality product is more stable, production can realize serialization, also improved production efficiency in stable improving the quality of products, reduced production cost, simultaneously the by product in production process is reclaimed, utilizes, avoided the steam of cupric ammoniate directly to discharge, reduced the disqualification rate of product, the program of having avoided unacceptable product to remarket, improve the recovery rate of cupric oxide, obtained highly active plating cupric oxide, also reduced its production cost simultaneously.
To sum up, the method technical process that the present invention is more traditional is short, and the reaction times is short, and foreign matter content is low, and active high, loss is few, pollutes littlely, and cost is low.
Embodiment
Embodiment 1
(1) pressure of liquefied ammonia with 0.2MPa is passed in water, logical ammonia made the strong aqua that concentration is 135g/L in 6 hours, then the carbonic acid gas that passes into purity 〉=99.9% in the strong aqua prepares carbonated aqueous ammonia, open simultaneously water coolant, to being arranged in strong aqua but with in spiral coil cooling tube that strong aqua is connected do not pass into temperature less than the water quench of 15 ℃, the pressure that control passes into carbonic acid gas is 0.2MPa, and making degree of carbonisation is 140%, and the reaction formula that carbonic acid gas passes in strong aqua is as follows:
2NH
3+?CO
2+?H
2O=(NH
4)
2?CO
3；
(2) first pack 62.5 * 10 in encloses container
3Then the standard cathode copper of mol copper content 〉=99.95% inject 3m in container
3What step (1) was prepared contains 16.68 * 10
3The carbonated aqueous ammonia reaction of mol volatile salt blasts air simultaneously in container, making the air pressure in container is 10 * 10
5Pa, the time that blasts air is 12 hours, stops the drum air when in reacted feed liquid, copper ion concentration is 120g/L, reaction finishes, and obtains 3m
3The feed liquid that contains the cuprammonium compound, in copper material and carbonated aqueous ammonia, the reaction formula of volatile salt reaction is:
2Cu+2(NH
4)
2?CO
3+O
2=2Cu(NH
3)
2CO
3?+2H
2O；
(3) to 3m
3Add 15 ㎏ hydrogen peroxide to react in the feed liquid of cupric ammoniate, reaction times is 6 hours, the filtrate that the copper scale that then will be with the feed liquid of the reacted cupric ammoniate of hydrogen peroxide produces during by accurate filtering out of deep bed filter copper and iron containing compounds impurity must contain the cuprammonium compound;
(4) filtrate of containing the cuprammonium compound after filtering is heated to 98 ℃ under normal pressure, make cuprammonium compound generation decomposition reaction generate ventilation breather, when in the mixed liquor that contains ventilation breather after decomposition reaction being detected, copper ion concentration is less than 15g/L, decomposition reaction finishes, and obtains containing the mixed liquor of ventilation breather; Part water, liquefied ammonia in ammonia, carbonic acid gas and former filtrate that decomposition reaction simultaneously produces prepares strong aqua after passing into condenser condenses, recovery again, and the reaction formula of decomposition reaction is:
3Cu(NH
3)
2CO
3?+H
2O=2CuCO
3?Cu(OH)
2+6NH
3↑+?CO
2↑；
(5) mixed liquor that contains ventilation breather that decomposition reaction the is obtained whizzer of packing into, the mother liquor that first will contain in the mixed liquor of ventilation breather gets rid of to the greatest extent, then carry out five washings with deionized water, in washings after the 5th washing, the chlorion mass concentration is 30ppm, finish washing, from the whizzer discharging, obtain containing the ventilation breather of a small amount of moisture; And the washings that will contain the mother liquor that throws away in the mixed liquor of ventilation breather and first three time washing merges the raw material that in the container that adds dress copper material, conductization copper reacts, and the washings of last twice washing is for the preparation of carbonated aqueous ammonia;
(6) will dry at the temperature of 60 ℃ to the rear pulverizing of moisture≤2%, 100 orders from the ventilation breather that contains a small amount of moisture that whizzer goes out and sieve, analyze, weigh, pack, obtain the high-purity ventilation breather of heavy;
(7) the high-purity ventilation breather of heavy is packed into calcine in rotary kiln, calcining temperature is 500 ℃, and calcination time is 5 hours, obtains cupric oxide powder;
(8) after cupric oxide powder is collected with Stainless Steel Disc, cooling at the temperature of 30 ~ 40 ℃, again through the 100 orders cupric oxide finished product that sieves to get, product yield after testing is 99.51%, active 25S, and the impurity element mass concentration is Fe≤11 ppm, Pb≤2 ppm, Ni≤5 ppm, Zn≤5 ppm reach the requirement of technical standard order.
Embodiment 2
(1) pressure of liquefied ammonia with 0.1MPa is passed in water, logical ammonia made the strong aqua that concentration is 102g/L in 7 hours, then the carbonic acid gas that passes into purity 〉=99.9% in the strong aqua prepares carbonated aqueous ammonia, open simultaneously water coolant, to being arranged in strong aqua but with in spiral coil cooling tube that strong aqua is connected do not pass into temperature less than the water quench of 15 ℃, the pressure that control passes into carbonic acid gas is 0.1MPa, and making degree of carbonisation is 120%, and the reaction formula that carbonic acid gas passes in strong aqua is as follows:
2NH
3+?CO
2+?H
2O=(NH
4)
2?CO
3；
(2) first pack 62.5 * 10 in encloses container
3Then the standard cathode copper of mol copper content 〉=99.95% inject 3.5m in container
3What step (1) was prepared contains 12.6 * 10
3The carbonated aqueous ammonia reaction of mol volatile salt blasts air simultaneously in container, making the air pressure in container is 5 * 10
5Pa, the time that blasts air is 8 hours, stops the drum air when in reacted feed liquid, copper ion concentration is 95g/L, reaction finishes, and obtains 3.5m
3The feed liquid that contains the cuprammonium compound, in copper material and carbonated aqueous ammonia, the reaction formula of volatile salt reaction is:
2Cu+2(NH
4)
2?CO
3+O
2=2Cu(NH
3)
2CO
3?+2H
2O；
(3) to 3.5m
3Add 25 ㎏ hydrogen peroxide to react in the feed liquid of cupric ammoniate, reaction times is 4 hours, the filtrate that the copper scale that then will be with the feed liquid of the reacted cupric ammoniate of hydrogen peroxide produces during by accurate filtering out of deep bed filter copper and iron containing compounds impurity must contain the cuprammonium compound;
(4) filtrate of containing the cuprammonium compound after filtering is heated to 85 ℃ under normal pressure, make cuprammonium compound generation decomposition reaction generate ventilation breather, when in the mixed liquor that contains ventilation breather after decomposition reaction being detected, copper ion concentration is less than 15g/L, decomposition reaction finishes, and obtains containing the mixed liquor of ventilation breather; Part water, liquefied ammonia in ammonia, carbonic acid gas and former filtrate that decomposition reaction simultaneously produces prepares strong aqua after passing into condenser condenses, recovery again, and the reaction formula of decomposition reaction is:
3Cu(NH
3)
2CO
3?+H
2O=2CuCO
3?Cu(OH)
2+6NH
3↑+?CO
2↑；
(5) mixed liquor that contains ventilation breather that decomposition reaction the is obtained whizzer of packing into, the mother liquor that first will contain in the mixed liquor of ventilation breather gets rid of to the greatest extent, then carry out five washings with deionized water, laundry after the 5th washing washs that in liquid, the chlorion mass concentration is 50ppm, finish washing, from the whizzer discharging, obtain containing the ventilation breather of a small amount of moisture; And the washings that will contain the mother liquor that throws away in the mixed liquor of ventilation breather and first three time washing merges the raw material that in the container that adds dress copper material, conductization copper reacts, and the washings of last twice washing is for the preparation of carbonated aqueous ammonia;
(6) will dry at the temperature of 80 ℃ to the rear pulverizing of moisture≤2%, 100 orders from the ventilation breather that contains a small amount of moisture that whizzer goes out and sieve, analyze, weigh, pack, obtain the high-purity ventilation breather of heavy;
(7) the high-purity ventilation breather of heavy is packed into calcine in rotary kiln, calcining temperature is 600 ℃, and calcination time is 3 hours, obtains cupric oxide powder;
(8) after cupric oxide powder is collected with Stainless Steel Disc, cooling at the temperature of 30 ~ 40 ℃, again through the 100 orders cupric oxide finished product that sieves to get, product yield after testing is 99.55%, active 26S, and the impurity element mass concentration is Fe≤10 ppm, Pb≤2 ppm, Ni≤5 ppm, Zn≤5 ppm reach the requirement of technical standard order.
Embodiment 3
(1) pressure of liquefied ammonia with 0.05MPa is passed in water, logical ammonia made the strong aqua that concentration is 85g/L in 7 hours, then the carbonic acid gas that passes into purity 〉=99.9% in the strong aqua prepares carbonated aqueous ammonia, open simultaneously water coolant, to being arranged in strong aqua but with in spiral coil cooling tube that strong aqua is connected do not pass into temperature less than the water quench of 15 ℃, the pressure that control passes into carbonic acid gas is 0.05MPa, and making degree of carbonisation is 80%, and the reaction formula that carbonic acid gas passes in strong aqua is as follows:
2NH
3+?CO
2+?H
2O=(NH
4)
2?CO
3；
(2) first pack 62.5 * 10 in encloses container
3Then the standard cathode copper of mol copper content 〉=99.95% inject 3.2m in container
3What step (1) was prepared contains 6.4 * 10
3The carbonated aqueous ammonia reaction of mol volatile salt blasts air simultaneously in container, making the air pressure in container is 1.01 * 10
5Pa, the time that blasts air is 5 hours, stops the drum air when in reacted feed liquid, copper ion concentration is 85g/L, reaction finishes, and obtains 3.2m
3The feed liquid that contains the cuprammonium compound, in copper material and carbonated aqueous ammonia, the reaction formula of volatile salt reaction is:
2Cu+2(NH
4)
2?CO
3+O
2=2Cu(NH
3)
2CO
3?+2H
2O；
(3) to 3.2m
3Add 32 ㎏ hydrogen peroxide to react in the feed liquid of cupric ammoniate, reaction times is 2 hours, the filtrate that the copper scale that then will be with the feed liquid of the reacted cupric ammoniate of hydrogen peroxide produces during by accurate filtering out of deep bed filter copper and iron containing compounds impurity must contain the cuprammonium compound;
(4) filtrate of containing the cuprammonium compound after filtering is heated to 70 ℃ under normal pressure, make cuprammonium compound generation decomposition reaction generate ventilation breather, when in the mixed liquor that contains ventilation breather after decomposition reaction being detected, copper ion concentration is less than 15g/L, decomposition reaction finishes, and obtains containing the mixed liquor of ventilation breather; Part water, liquefied ammonia in ammonia, carbonic acid gas and former filtrate that decomposition reaction simultaneously produces prepares strong aqua after passing into condenser condenses, recovery again, and the reaction formula of decomposition reaction is:
3Cu(NH
3)
2CO
3?+H
2O=2CuCO
3?Cu(OH)
2+6NH
3↑+?CO
2↑；
(5) mixed liquor that contains ventilation breather that decomposition reaction the is obtained whizzer of packing into, the mother liquor that first will contain in the mixed liquor of ventilation breather gets rid of to the greatest extent, then carry out five washings with deionized water, laundry after the 5th washing washs that in liquid, the chlorion mass concentration is 40ppm, finish washing, from the whizzer discharging, obtain containing the ventilation breather of a small amount of moisture; And the washings that will contain the mother liquor that throws away in the mixed liquor of ventilation breather and first three time washing merges the raw material that in the container that adds dress copper material, conductization copper reacts, and the washings of last twice washing is for the preparation of carbonated aqueous ammonia;
(6) will dry at the temperature of 100 ℃ to the rear pulverizing of moisture≤2%, 100 orders from the ventilation breather that contains a small amount of moisture that whizzer goes out and sieve, analyze, weigh, pack, obtain the high-purity ventilation breather of heavy;
(7) the high-purity ventilation breather of heavy is packed into calcine in rotary kiln, calcining temperature is 680 ℃, and calcination time is 1.5 hours, obtains cupric oxide powder;
(8) after cupric oxide powder is collected with Stainless Steel Disc, cooling at the temperature of 30 ~ 40 ℃, again through the 100 orders cupric oxide finished product that sieves to get, product yield after testing is 99.5%, active 26S, and the impurity element mass concentration is Fe≤15 ppm, Pb≤2 ppm, Ni≤8ppm, Zn≤33 ppm reach the requirement of technical standard order.
Embodiment 4
(1) pressure of liquefied ammonia with 0.1MPa is passed in water, logical ammonia made the strong aqua that concentration is 120g/L in 5 hours, then the carbonic acid gas that passes into purity 〉=99.9% in the strong aqua prepares carbonated aqueous ammonia, open simultaneously water coolant, to being arranged in strong aqua but with in spiral coil cooling tube that strong aqua is connected do not pass into temperature less than the water quench of 15 ℃, the pressure that control passes into carbonic acid gas is 0.15MPa, and making degree of carbonisation is 100%, and the reaction formula that carbonic acid gas passes in strong aqua is as follows:
2NH
3+?CO
2+?H
2O=(NH
4)
2?CO
3；
(2) first pack 62.5 * 10 in encloses container
3Then the standard cathode copper of mol copper content 〉=99.95% inject 3m in container
3What step (1) was prepared contains 10.59 * 10
3The carbonated aqueous ammonia reaction of mol volatile salt blasts air simultaneously in container, making the air pressure in container is 1.01 * 10
5Pa, the time that blasts air is 9 hours, stops the drum air when in reacted feed liquid, copper ion concentration is 100g/L, reaction finishes, and obtains 3m
3The feed liquid that contains the cuprammonium compound, in copper material and carbonated aqueous ammonia, the reaction formula of volatile salt reaction is:
2Cu+2(NH
4)
2?CO
3+O
2=2Cu(NH
3)
2CO
3?+2H
2O；
(3) to 3m
3Add 3 ㎏ hydrogen peroxide to react in the feed liquid of cupric ammoniate, reaction times is 6 hours, the filtrate that the copper scale that then will be with the feed liquid of the reacted cupric ammoniate of hydrogen peroxide produces during by accurate filtering out of deep bed filter copper and iron containing compounds impurity must contain the cuprammonium compound;
(4) filtrate of containing the cuprammonium compound after filtering is heated to 95 ℃ under normal pressure, make cuprammonium compound generation decomposition reaction generate ventilation breather, when in the mixed liquor that contains ventilation breather after decomposition reaction being detected, copper ion concentration is less than 15g/L, decomposition reaction finishes, and obtains containing the mixed liquor of ventilation breather; Part water, liquefied ammonia in ammonia, carbonic acid gas and former filtrate that decomposition reaction simultaneously produces prepares strong aqua after passing into condenser condenses, recovery again, and the reaction formula of decomposition reaction is:
3Cu(NH
3)
2CO
3?+H
2O=2CuCO
3?Cu(OH)
2+6NH
3↑+?CO
2↑；
(5) mixed liquor that contains ventilation breather that decomposition reaction the is obtained whizzer of packing into, the mother liquor that first will contain in the mixed liquor of ventilation breather gets rid of to the greatest extent, then carry out five washings with deionized water, laundry after the 5th washing washs that in liquid, chlorine ion concentration is 60ppm, finish washing, from the whizzer discharging, obtain containing the ventilation breather of a small amount of moisture; And the washings that will contain the mother liquor that throws away in the mixed liquor of ventilation breather and first three time washing merges the raw material that in the container that adds dress copper material, conductization copper reacts, and the washings of last twice washing is for the preparation of carbonated aqueous ammonia;
(6) will dry at the temperature of 80 ℃ to the rear pulverizing of moisture≤2%, 100 orders from the ventilation breather that contains a small amount of moisture that whizzer goes out and sieve, analyze, weigh, pack, obtain the high-purity ventilation breather of heavy;
(7) the high-purity ventilation breather of heavy is packed into calcine in rotary kiln, calcining temperature is 800 ℃, and calcination time is 0.5 hour, obtains cupric oxide powder;
(8) after cupric oxide powder is collected with Stainless Steel Disc, cooling at the temperature of 30 ~ 40 ℃, again through the 100 orders cupric oxide finished product that sieves to get, product yield after testing is 99.53%, active 26S, and the impurity element mass concentration is Fe≤10 ppm, Pb≤6 ppm, Ni≤6 ppm, Zn≤7 ppm reach the requirement of technical standard order.
Above embodiment is all preferred embodiments of the present invention, for a person skilled in the art, makes the protection domain that simple replacement all belongs to claim of the present invention on the basis of above-described embodiment.
Claims (8)
1. method for preparing high-purity low chlorine plating-grade copper oxide is characterized in that: comprise the following steps:
(1) liquefied ammonia is passed into make the strong aqua that concentration is 85 ~ 135g/L in water, then pass into high-purity carbon dioxide in the strong aqua and prepare carbonated aqueous ammonia, making degree of carbonisation is 80%～140%;
(2) carbonated aqueous ammonia of step (1) preparation is added in the copper material react, and blast air in reaction process, make the feed liquid of cupric ammoniate, the copper material with the reaction formula that carbonated aqueous ammonia reacts is:
2Cu+2(NH
4)
2?CO
3+O
2=2Cu(NH
3)
2CO
3?+2H
2O；
(3) feed liquid is filtered after adding hydrogen peroxide fully to react in the feed liquid of cupric ammoniate;
(4) make the high-purity ventilation breather of heavy after the filtrate thermal degradation after filtering and the mixed liquor that contains ventilation breather that will react gained separate, wash, dry, sieve, the reaction formula of decomposition reaction is:
3Cu(NH
3)
2CO
3?+H
2O=2CuCO
3?Cu(OH)
2+6NH
3↑+?CO
2↑；
(5) the high-purity ventilation breather heating and calcining of heavy that step (4) is made make cupric oxide powder and further cooling, sieving obtains high-purity low chlorine plating-grade copper oxide, calcining, the reaction formula that decomposes are:
CuCO
3·Cu(OH)
2=2CuO+CO
2+H
2O。
2. a kind of method for preparing high-purity low chlorine plating-grade copper oxide according to claim 1 is characterized in that: the pressure that passes into liquefied ammonia in described step (1) during strong aqua processed is 0.05～0.2MPa; The described pressure that passes into carbonic acid gas in the strong aqua is 0.05～0.2MPa; Describedly pass into temperature less than the water quench of 15 ℃ to the spiral coil cooling tube that is arranged in strong aqua when passing into carbonic acid gas in the strong aqua.
3. a kind of method for preparing high-purity low chlorine plating-grade copper oxide according to claim 1, is characterized in that: the copper content of copper material 〉=99.5% in described step (2); The amount of substance of the copper of described copper material is greater than the amount of substance that adds the contained volatile salt of carbonated aqueous ammonia in the copper material; Described reaction is 1.01 * 10 in air pressure
5Pa～10 * 10
5Carry out under the air tight condition of Pa, the time that blasts air during reaction is 5～12 hours, and reaction end is that in the feed liquid of reacted cupric ammoniate, content of copper ion reaches 85～120g/L.
4. a kind of method for preparing high-purity low chlorine plating-grade copper oxide according to claim 1, it is characterized in that: the volume ratio of the quality of the hydrogen peroxide that adds in the feed liquid of cupric ammoniate in described step (3) and the feed liquid of cupric ammoniate is 1～10 ㎏/cubic meter, and adding the reaction times after hydrogen peroxide is 2～6 hours; Described filter plant is accurate deep bed filter.
5. a kind of method for preparing high-purity low chlorine plating-grade copper oxide according to claim 1 is characterized in that: in described step (4), the temperature of filtrate heating is 70～98 ℃; Described decomposition is in normal pressure～0.8 * 10
5Carry out under the pressure of Pa; The terminal point of described decomposition for the reaction gained the mixed liquor that contains ventilation breather in content of copper ion less than 15g/L; Part water in ammonia, carbonic acid gas and former filtrate that described decomposition produces, liquefied ammonia prepare strong aqua again after condensation, recovery.
6. a kind of method for preparing high-purity low chlorine plating-grade copper oxide according to claim 1 is characterized in that: separate in described step (4), washing isolates after original liquid with deionized water wash chlorion mass concentration≤60ppm to the washings for the mixed liquor that contains ventilation breather that will react gained again.
7. a kind of method for preparing high-purity low chlorine plating-grade copper oxide according to claim 1 is characterized in that: in described step (4), bake out temperature is 60～100 ℃; Described sieving is that 100 orders sieve.
8. a kind of method for preparing high-purity low chlorine plating-grade copper oxide according to claim 1 is characterized in that: in described step (5), the temperature of the high-purity ventilation breather heating and calcining of heavy is 500～800 ℃, and the time of heating and calcining is 0.5～5h; The cupric oxide powder that described calcining obtains further cooling temperature is 30 ~ 40 ℃.
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| CN111239203A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Preparation method of copper oxide film |
| CN115124066A (en) * | 2022-07-22 | 2022-09-30 | 李晓清 | Continuous production process of basic copper carbonate based on ammonia circulation system |
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| CN104925846A (en) * | 2014-03-17 | 2015-09-23 | 北京化工大学 | Preparation method of nano copper oxide and application of nano copper oxide in lithium ion battery |
| CN104445360A (en) * | 2014-12-03 | 2015-03-25 | 金川集团股份有限公司 | Production method of high-purity active copper oxide powder |
| CN106517294A (en) * | 2015-09-09 | 2017-03-22 | 有研稀土新材料股份有限公司 | Method for preparing metal oxide |
| CN106517294B (en) * | 2015-09-09 | 2021-02-26 | 有研稀土新材料股份有限公司 | Process for producing metal oxide |
| CN107955956A (en) * | 2016-10-14 | 2018-04-24 | 株式会社荏原制作所 | Cupric oxide powder, the method for electroplating substrate, the method for management electroplate liquid |
| CN106745179A (en) * | 2016-12-23 | 2017-05-31 | 广东光华科技股份有限公司 | A kind of process for cleanly preparing of electronic grade high-purity copper oxide |
| WO2018113177A1 (en) * | 2016-12-23 | 2018-06-28 | 广东光华科技股份有限公司 | Process for clean production of electronic grade high-purity copper oxide |
| US10479694B2 (en) | 2016-12-23 | 2019-11-19 | Guangdong Guanghua Sci-Tech Co., Ltd. | Process of clean production of electronic grade high-purity copper oxide |
| CN111239203A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Preparation method of copper oxide film |
| CN110980792A (en) * | 2019-10-26 | 2020-04-10 | 韩亚半导体材料(贵溪)有限公司 | Processing technology of high-purity copper oxide powder applied to integrated circuit |
| CN115124066A (en) * | 2022-07-22 | 2022-09-30 | 李晓清 | Continuous production process of basic copper carbonate based on ammonia circulation system |
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