CN1168662C - Wet low-temperature oxidation and decomposition process of producing active copper oxide - Google Patents
Wet low-temperature oxidation and decomposition process of producing active copper oxide Download PDFInfo
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- CN1168662C CN1168662C CNB011271752A CN01127175A CN1168662C CN 1168662 C CN1168662 C CN 1168662C CN B011271752 A CNB011271752 A CN B011271752A CN 01127175 A CN01127175 A CN 01127175A CN 1168662 C CN1168662 C CN 1168662C
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Abstract
The present invention relates to a technological process of producing active cupric oxide, which is characterized in that the present invention comprises the steps as follows: firstly, adopting a low temperature oxidation method; secondly, adopting a wet method for decomposition. The low temperature oxidation method adopted in the present invention has the highest temperature of 80 to 90 DEG C and adopts oxygen in air as an oxidizing agent. The present invention has the advantages of low price and easy acquisition of raw material, easy operation and no environmental pollution. Because cupric oxide is prepared in solution at a low temperature, the cupric oxide products have a quick acid-soluble speed, which is only about 40 seconds as a normal speed and 30 seconds as the fastest speed. The present invention adopts a technological process of closed cycle with no pollution to the environment and is convenient for continuous and automatic production.
Description
The invention relates to a process production method of active copper oxide.
The active copper oxide powder is a copper oxide powder which is suitable for the development of electronic industry and aviation and aerospace industry and has unique performance, and has strict requirements on chemical components and acid dissolution speed reflecting the activity characteristic, namely 16ml of sulfuric acid with the concentration of 98% is prepared into 1000ml of solution, 10g of copper oxide powder is added, stirred and dissolved at normal temperature, and the dissolution is completed within 60 seconds.
According to new data, the copper oxide powder is mostly produced by a high-temperature method at present. For example, the reduced copper is produced by a chemical method, then the reduced copper is extruded into blocks, evaporated and dried at 150 ℃, sintered into copper oxide at 700-800 ℃, and ground into copper oxide powder. And for example, directly roasting the copper salt (copper sulfate) at 850-980 ℃ to generate the new copper oxide powder through thermal decomposition. Copper oxide powder is also produced by a copper ammonia solution microwave heating boiling reflux precipitation conversion method.
The production of the active copper oxide powder is still in the initial stage of China, and the technical standard of the product is not established yet. The research and development of the active copper oxide powder product is a new subject for filling the blank of China.
According to the data, the copper oxide powder prepared at low temperature has light specific gravity, is easy to be dissolved in dilute acid, is strongly burnt to prepare the copper oxide powder with high specific gravity, and is slowly dissolved in hot and concentrated acid.
Aimingat the defects in the prior art, the invention provides a process method for producing active copper oxide powder by low-temperature oxidation wet decomposition through exploring various process routes.
The specific process comprises the following steps:
1. the process method for producing the active copper oxide by low-temperature oxidation wet decomposition is characterized by comprising the following steps:
firstly, preparing a solution
(1) Adding 200-250 Kg of copper sulfate into 1000Kg of pure water, stirring and dissolving to prepare a copper sulfate solution with the specific gravity of 1.0-1.5,
(2) then adding 200Kg of sulfuric acid with the concentration of 98% into the solution to prepare a solution with the sulfuric acid content of 150-200 g/l;
second, low temperature oxidation
(1) Adding copper material into a stainless steel reactor, wherein the volume of the copper material accounts for about two thirds of the volume of the reactor,
(2) adding the prepared sulfuric acid-copper sulfate solution into the reactor, and covering the copper material with the solution,
(3) blowing compressed air into the reactorGas, and the pressure of the compressed air is maintained at 1-3 Kg/cm2，
(4) Then heating the reactor, maintaining the temperature at 80-85 ℃,
(5) the reaction time is controlled within 10-24 hours, when the specific gravity of the feed liquid rises to 1.38-1.40, the reaction end point is reached,
(6) stopping compressing air by the drum, keeping the temperature and settling for half an hour, then carrying out suction filtration on the supernatant into a crystallization kettle, introducing cooling water, stirring, cooling, crystallizing to room temperature, discharging, filtering, washing a filter cake with pure water, and centrifuging and spin-drying;
third, wet decomposition
(1) Preparing a solution
a. Preparation of copper sulfate solution
Adding 300-350 Kg of copper sulfate into 1000L of pure water, and stirring to completely dissolve the copper sulfate;
b. preparation of decomposition agent solution
Adding 200-250 Kg of decomposer into 1000L of pure water, and stirring for dissolving.
(2) Wet decomposition of
a. Adding the prepared copper sulfate solution into the reaction kettle to one half of the volume of the kettle,
b. heating the kettle to raise the temperature, stirring at the same time,
c. when the temperature of the liquid material rises to 70 ℃, slowly adding the clear liquid of the decomposing agent till the pH value of the liquid material is 8-9
Stopping adding the solution of the decomposer, continuously heating to 80-90 ℃, stirring and reacting for 1-2 hours,
d. putting the reacted slurry into a wet ball mill for wet ball milling,
E. the ball milling slurry is pumped into a plate and frame filter press for filter pressing,
F. then separating the press-filtered copper oxide filter cake from the mother liquor,
G. the copper oxide filter cake is washed by washing liquor in a circulating way, and finally washed by pure water until no chloride ion reacts,
fourthly, drying, crushing and screening
(1) Putting the copper oxide filter cake into a dryer for drying at 105-110 ℃ for 3-4 hours,
(2) further crushing and grinding the dried copper oxide to improve the fineness of the product,
(3) and sieving the ground copper oxide to obtain the finished product of the active copper oxide powder.
The decomposing agent is either potassium hydroxide or sodium hydroxide.
When the decomposing agent is potassium hydroxide, the mother liquid is evaporated and crystallized to obtain potassium sulfate as side product.
When the decomposing agent used is sodium hydroxide,
(1) adding ammonium bicarbonate into the mother liquor obtained by pressure filtration to generate sodium bicarbonate, and precipitating, filtering and separating to obtain a byproduct sodium bicarbonate;
(2) then adding aluminum sulfate into the filtered filtrate, and evaporating and crystallizing to obtain a byproduct of aluminum ammonium alum.
The process method of the invention has the advantages of several aspects:
firstly, the high-temperature method for producing the copper oxide powder has poor operation environment and is easy to cause environmental pollution. The low-temperature oxidation method has the highest temperature of 80-90 ℃, takes oxygen in the air as an oxidant, is cheap and easy to obtain, is easy to operate, and does not produce environmental pollution.
And secondly, wet decomposition is adopted, the whole operation process is carried out in solution due to the selection of a proper decomposer, the decomposer reacts with copper ions to generate a new compound, and the new compound is further decomposed to generate copper oxide, and the copper oxide is generated in the solution at low temperature, so that the acid dissolution speed of the copper oxide is high, generally about 40 seconds, and the copper oxide can be dissolved in 30 seconds at the fastest speed.
And thirdly, a closed cycle process method is adopted, so that the environment is not polluted. The mother liquor after the copper sulfate is separated in the low-temperature oxidation process is returned to prepare sulfuric acid, namely a copper sulfate solution for recycling.
The washing liquid during the plate frame filter pressing washing is used for circular washing and also returns to the wet decomposition process for preparing solution, and the mother solution and the washing liquid are not discharged outwards in the whole operation process, so that closed cycle use is realized.
And fourthly, comprehensively utilizing the mother liquor and the washing liquor. The mother liquor and the washing liquor are used in a shunting way during plate-frame filter pressing, and the mother liquor is used for producing byproducts, thereby changing waste into valuable. Not only does not pollute the environment, but also improves the economic benefit and reduces the production cost.
Fifthly, the process has strong adaptability. Is suitable for various copper materials, such as electrolytic copper, waste red copper, copper mud and crude copper oxide, and can also directly adopt copper sulfate, copper nitrate and the like. The decomposer for wet decomposition can be potassium hydroxide or sodium hydroxide.
And sixthly, the invention is easy to realize continuous and automatic production. The main processes are all carried out in solution, so that the pipeline reaction, continuous production, computer control and automatic operation can be carried out, the operation environment is greatly improved, the labor intensity is reduced, and the labor productivity is improved.
FIG. 1 is a process flow diagram of potassium hydroxide as a decomposing agent,
FIG. 2 is a process flow diagram of the decomposition of sodium hydroxide.
The invention is further described below by way of example.
Example 1:
the process flow taking metal copper as a raw material and potassium hydroxide as a decomposer is as follows:
firstly, preparing a solution
(1) Adding 200Kg of copper sulfate into 1000Kg of pure water, stirring and dissolving to prepare a copper sulfate solution with the specific gravity of 1.2,
(2) 200Kg of sulfuric acid with a concentration of 98% was added to the solution.
Referring to fig. 1, when the mother liquor I is recycled, copper sulfate does not need to be added, and the acid content in the mother liquor I is analyzed and detected, and the balance is made up according to the sulfuric acid content of 150 g/l.
Second, low temperature oxidation
(1) Adding copper material into a stainless steel reactor, wherein the volume of the copper material accounts for about two thirds of the volume of the reactor,
(2) adding the prepared sulfuric acid-copper sulfate solution into a reactor, and allowing the solution to completely cover the copper material,
(3) blowing compressed air into the reactor, and maintaining the pressure of the compressed air at 2Kg/cm2，
(4) Then the reactor is heated, the temperature is maintained at 80 ℃,
(5) and reaction time: the reaction time is 20-24 hours when the solution is prepared by pure water for the first time. And after the mother liquor I is adopted for liquid preparation in a closed cycle, the reaction time is controlled to be 10-12 hours. The reaction end point is the end point when the specific gravity of the feed liquid rises to 1.38,
(6) stopping blowing compressed air when the reaction end point is reached, keeping the temperature and settling for half an hour, then carrying out suction filtration on the supernatant into a crystallization kettle, introducing cooling water, stirring, cooling, crystallizing to room temperature, discharging and filtering, and washing a filter cake with pure water and then carrying out centrifugal drying; the mother liquor I and the washing liquor are combined and returned to the solution preparation.
The basic principle of the low-temperature oxidation reaction is as follows:
due to Cu2SO4The oxidation reaction with oxygen in compressed air is easy to carry out;
this repeated reaction causes the copper metal to dissolve into solution.
Third, wet decomposition
(1) Preparing a solution
a. Preparation of copper sulfate solution
Adding 300Kg of powdery copper sulfate into 1000L of pure water, and stirring to completely dissolve the powdery copper sulfate;
b. preparation of decomposition agent solution
200Kg of potassium hydroxide decomposer was added to 1000L of purified water and dissolved by stirring.
(2) Wet decomposition of
a. Adding the prepared copper sulfate solution into the reaction kettle to one half of the volume of the kettle,
b. introducing steam into the kettle jacket to heat and raise the temperature, stirring simultaneously,
c. when the temperature of the liquid material rises to 70 ℃, slowly adding the clear solution of the potassium hydroxide decomposer till the pH value of the liquid material is 8, stopping adding the solution of the potassium hydroxide decomposer, continuously raising the temperature to 80 ℃, stirring and reacting for 1 hour,
d. the reacted slurry is put into a wet ball mill for wet ball milling, the wet ball mill adopts corundum plate linings, corundum balls with different sizes are ground for about 1 hour,
E. the ball milling slurry is pumped into a plate and frame filter press for filter pressing,
F. evaporating and crystallizing the pressure-filtered mother liquor II to produce a byproduct potassium sulfate,
G. and (3) circularly washing the copper oxide filter cake with washing liquid, finally washing with pure water until no chloride ion reaction exists, returning the washing liquid to the working procedure to prepare a copper sulfate solution, and drying the qualified filter cake.
The basic principle of wet decomposition is as follows:
fourthly, drying, crushing and screening
(1) Putting the copper oxide filter cake into a dryer for drying at 105 ℃ for 3-4 hours,
(2) further crushing and grinding the dried copper oxide to improve the fineness of the product,
(3) and sieving the ground copper oxide to obtain the finished product of the active copper oxide powder.
Example 2:
the process flow taking metal copper as a raw material and sodium hydroxide as a decomposer is as follows:
the first procedure is to prepare a solution; the second step, low temperature oxidation, was the same as in example 1.
Third step, wet decomposition
(1) Preparing a solution
a. Preparation of copper sulfate solution
Adding 300Kg of powdery copper sulfate into 1000L of pure water or the washing liquid in the process, and stirring to completely dissolve the powdery copper sulfate;
b. preparation of decomposition agent solution
200Kg of sodium hydroxide decomposer was added to 1000L of purified water, and dissolved by stirring.
(2) Wet decomposition of
a. The prepared copper sulfate solution is injected into an enamel reaction kettle, the volume of the prepared copper sulfate solution is not more than one half of the volume of the reaction kettle,
b. introducing steam into the jacket of the reaction kettle, heating, stirring,
c. when the temperature of the feed liquid is raised to 70 ℃, the sodium hydroxide clear liquid is slowly added, the sodium hydroxide solution is stopped adding when the pH value of the feed liquid reaches 8, the temperature iscontinuously raised to 80 ℃, the stirring reaction is carried out for 1 hour,
d. putting the reacted slurry into a wet ball mill for wet ball milling for 1 hour,
e. pumping the slurry subjected to wet ball milling into a plate-and-frame filter press for filter pressing,
f. the mother liquor II filtered out by pressure is evaporated and crystallized to obtain a by-product sodium sulfate, and because the economic benefit of the sodium sulfate is poor, the process adopts the steps of adding ammonium bicarbonate into the mother liquor II to generate sodium bicarbonate (sodium bicarbonate), precipitating, filtering and separating to obtain the by-product sodium bicarbonate, adding aluminum sulfate into the separated mother liquor III, evaporating and crystallizing to obtain the by-product aluminum ammonium alum,
g. the filter cake in the plate-and-frame filter press is washed by washing liquor and oyster circularly and finally by pure water until no chloride ion reaction occurs,
h. the washing liquid returns to the working procedure to prepare the copper sulfate solution,
I. the qualified filter cake is sent to be dried,
j. the basic principle of wet decomposition is as follows:
the subsequent drying, crushing and screening processes are the same as in example 1.
Claims (5)
1. The process method for producing the active copper oxide by low-temperature oxidation wet decomposition is characterized by comprising the following steps:
firstly, preparing a solution
(1) Adding 200-250 Kg of copper sulfate into 1000Kg of pure water, stirring and dissolving to prepare a copper sulfate solution with the specific gravity of 1.0-1.5,
(2) then adding 200Kg of sulfuric acid with the concentration of 98% into the solution to prepare a solution with the sulfuric acid content of 150-200 g/l;
second, low temperature oxidation
(1) Adding copper material into a stainless steel reactor, wherein the volume of the copper material accounts for about two thirds of the volume of the reactor,
(2) adding the prepared sulfuric acid-copper sulfate solution into a reactor, and covering copper materials with the solution,
(3) blowing compressed air into the reactor, and maintaining the pressure of the compressed air at 1-3 Kg/cm2，
(4) Then heating the reactor, maintaining the temperature at 80-85 ℃,
(5) the reaction time is controlled within 10-24 hours, when the specific gravity of the feed liquid rises to 1.38-1.40, the reaction end point is reached,
(6) stopping compressing air by the drum, keeping the temperature and settling for half an hour, then carrying out suction filtration on the supernatant into a crystallization kettle, introducing cooling water, stirring, cooling, crystallizing to room temperature, discharging, filtering, washing a filter cake with pure water, and centrifuging and spin-drying;
third, wet decomposition
(1) Preparing a solution
a. Preparation of copper sulfate solution
Adding 300-350 Kg of copper sulfate into 1000L of pure water, and stirring to completely dissolve the copper sulfate;
b. preparation of decomposition agent solution
Adding 200-250 Kg of decomposer into 1000L of pure water, and stirring for dissolving.
(2) Wet decomposition of
a. Adding the prepared copper sulfate solution into the reaction kettle to one half of the volume of the kettle,
b. heating the kettle to raise the temperature, stirring at the same time,
c. when the temperature of the liquid material is raised to 70 ℃, slowly adding the clear liquid of the decomposing agent till the pH value of the liquid material is 8-9, stopping adding the solution of the decomposing agent, continuously raising the temperature to 80-90 ℃, stirring and reacting for 1-2 hours,
d. putting the reacted slurry into a wet ball mill for wet ball milling,
E. the material paddle is thrown into a plate-and-frame filter press for filter pressing,
F. then separating the press-filtered copper oxide filter cake from the mother liquor,
G. the copper oxide filter cake is washed by washing liquor in a circulating way, and finally washed by pure water until no chloride ion reacts,
fourthly, drying, crushing and screening
(1) Putting the copper oxide filter cake into a dryer for drying at 105-110 ℃ for 3-4 hours,
(2) further crushing and grinding the dried copper oxide to improve the fineness of the product,
(3) and sieving the ground copper oxide to obtain the finished product of the active copper oxide powder.
2. The process for producing active copper oxide by low-temperature oxidation wet decomposition according to claim 1, wherein: the decomposing agent is either potassium hydroxide or sodium hydroxide.
3. The process for producing active copper oxide by low-temperature oxidation wet decomposition according to claim 1, wherein: when the decomposing agent is potassium hydroxide, the mother liquid is evaporated and crystallized to obtain potassium sulfate as side product.
4. The process for producing active copper oxide by low-temperature oxidation wet decomposition according to claim 1, wherein: when the decomposing agent used is sodium hydroxide,
(1) adding ammonium bicarbonate into the mother liquor obtained by pressure filtration to generate sodium bicarbonate, and precipitating, filtering and separating to obtain a byproduct sodium bicarbonate;
(2) then adding aluminum sulfate into the filtered filtrate, and evaporating and crystallizing to obtain a byproduct of aluminum ammonium alum.
5. The process for producing active copper oxide by low-temperature oxidation wet decomposition according to claim 1, wherein: the copper material of the raw material is electrolytic copper, waste red copper, copper mud, crude copper oxide, copper sulfate or copper nitrate.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB011271752A CN1168662C (en) | 2001-09-03 | 2001-09-03 | Wet low-temperature oxidation and decomposition process of producing active copper oxide |
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| CNB011271752A CN1168662C (en) | 2001-09-03 | 2001-09-03 | Wet low-temperature oxidation and decomposition process of producing active copper oxide |
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| CN1168662C true CN1168662C (en) | 2004-09-29 |
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| CN102091781B (en) * | 2011-03-14 | 2012-02-29 | 南京东南铜业有限公司 | Method for producing active copper granules |
| CN102616827B (en) * | 2012-04-25 | 2013-12-25 | 廖勇志 | Method for industrially preparing high-purity active copper oxide |
| CN103074499B (en) * | 2013-01-31 | 2014-07-30 | 云南驰宏锌锗股份有限公司 | Method for producing high-quality copper sulfate through low-pressure oxygen leaching of copper slag |
| CN106414781B (en) * | 2014-04-15 | 2019-08-30 | 水ｉｎｇ株式会社 | The processing method of cupric acid waste liquid |
| CN109911928B (en) * | 2019-03-20 | 2021-06-29 | 金川集团股份有限公司 | Method for quickly dissolving copper |
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