CA1086958A - Hydrolysis of soluble copper in an aqueous ammoniacal liquor - Google Patents
Hydrolysis of soluble copper in an aqueous ammoniacal liquorInfo
- Publication number
- CA1086958A CA1086958A CA279,606A CA279606A CA1086958A CA 1086958 A CA1086958 A CA 1086958A CA 279606 A CA279606 A CA 279606A CA 1086958 A CA1086958 A CA 1086958A
- Authority
- CA
- Canada
- Prior art keywords
- copper
- ammonia
- calcium
- base
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0086—Treating solutions by physical methods
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process is provided for the recovery of copper oxide or copper hydroxide from an aqueous ammoniacal liquor containing copper in solution. The process comprises carrying out hydroly-sis of said soluble copper while controlling temperature, the concentration of free ammonia and the concentration of ammonium salt. The copper oxide or copper hydroxide precipitate formed by the hydrolysis is then recovered.
A process is provided for the recovery of copper oxide or copper hydroxide from an aqueous ammoniacal liquor containing copper in solution. The process comprises carrying out hydroly-sis of said soluble copper while controlling temperature, the concentration of free ammonia and the concentration of ammonium salt. The copper oxide or copper hydroxide precipitate formed by the hydrolysis is then recovered.
Description
This invention relates to a process for the recovery of copper oxide or copper hydroxide From an aqueous ammoniacal liquor conta;ning copper in solution.
Previously, when copper ores were leached by ammoniacal solutions, the soluble copper was separated and purified by a variety of physical or chemical me~lns, for example, by solvent - extraction or by precipitation as a sulphide. Some of the pre-vious processes for the recovery o~ soluble copper are expensive, or produce low yields, or produce a product containing a number of impurities.
- A process is provided for the recovery of copper oxide or copper hydroxide from an aqueous ammoniacal liquor containing copper in solution. The process comprises carrying out hydroly-sis of said soluble copper while controlling temperature, the ~`
.; ~
concentration of free ammonia and the concentration of ammonium salt, and recovering the copper oxide or copper hydroxide pre-` cipitate so formed. Preferably, the liquor is heated in the range from 60 to 250C, the ammonia to copper mole ratio is ` maintained at a value less than 10 and the ammonium salt con-centration is controlled to prevent inhibition of hydrolysis.
When copper bearing ores or concentrates are leached by ammoniacal solutions, the final solution commonly will con-tain soluble copper in the form of a complex cupramine ion~
Cu (NH3)~X where x depends on the ammonia strength of the solu-tion, and the pH.
. .~
The hydrolysis reaction is assumed to occur as follows ; for the cupric tetramine ion, as an example, ~13 Cu(NH3)4 +H20~ CuO + 2 NH3~ 2 NH+4 or,
Previously, when copper ores were leached by ammoniacal solutions, the soluble copper was separated and purified by a variety of physical or chemical me~lns, for example, by solvent - extraction or by precipitation as a sulphide. Some of the pre-vious processes for the recovery o~ soluble copper are expensive, or produce low yields, or produce a product containing a number of impurities.
- A process is provided for the recovery of copper oxide or copper hydroxide from an aqueous ammoniacal liquor containing copper in solution. The process comprises carrying out hydroly-sis of said soluble copper while controlling temperature, the ~`
.; ~
concentration of free ammonia and the concentration of ammonium salt, and recovering the copper oxide or copper hydroxide pre-` cipitate so formed. Preferably, the liquor is heated in the range from 60 to 250C, the ammonia to copper mole ratio is ` maintained at a value less than 10 and the ammonium salt con-centration is controlled to prevent inhibition of hydrolysis.
When copper bearing ores or concentrates are leached by ammoniacal solutions, the final solution commonly will con-tain soluble copper in the form of a complex cupramine ion~
Cu (NH3)~X where x depends on the ammonia strength of the solu-tion, and the pH.
. .~
The hydrolysis reaction is assumed to occur as follows ; for the cupric tetramine ion, as an example, ~13 Cu(NH3)4 +H20~ CuO + 2 NH3~ 2 NH+4 or,
(2) Cu(NH3)4 + 2 H20 - Cu(OH)2+ 2 NH3 + 2NH4+
Reaction (1) occurs at hi~h temperatures and reaction (2) at low temperatures. Both of the above reactions can be readily made to closely approach the thermodynamic equilibrium , ~
,. ~ . : ' , '~ ,, .
., ;., .
.:, . ~ . . . ,. . .. ~ , ... . : ' , . . .
position, and by a correct choice of reaction conditions, pref-; erably high temperatures and low free ammonia and amlnonium salt concentration, a high yield of cupric oxide can be obtained.
As can be deduced from the above reac~ions, higher yields will be obtained at low free ammonia ancl low ammonium concentrations in the original solutions.
The hydrolysis process of the present invention is carried out by heating the aqueous ammoniacal solution, prefer-ably in the range from 60 ~o 250C. The aqueous ammoniacal solution can be formed by leaching a copper ore or concentrate, for example, covellite, chalcopyrite, or scrap containing copper metal or copper compounds, with an ammoniacal oxidizing solution wh;ch may also contain ammonium salts.
In dilute solutions, high yields are possible in one step. To obtain maximum yields of copper oxide in more concen-trated solutions, however, more than one stage may be necessary ~ with removal of ammonia and ammonium ion between stages. For '!~ leach solutions of practical strength, for example, 20-60 grams per litre of copper9 it is not necessary to use more than two stages. However, any number of stages could be conveniently ~ 20 used. It is known to be advantageous in the ammoniacal leach-; ing of copper ores and concentrates to have a significant dis-solved copper content in the initial leaching solution. Therefore, the process of the present invention could be carried out effic-iently by the removal of a portion of the soluble copper from the solution and then returning the solution, after filtering off the copper oxide, to the leaching operation~ This will dilute the copper concentration of the liquor and should result in the efficient recovery of copper through one hydrolysis stage even in highly concentrated solutions.
As can be seen from the examples below, in dilute solutions, high yields are possible in one stage.
101~6951~
-- If ammonium ion accumulates in the solut~on either due to the hydrolysis reaction, or due to the chemistry of the leach;ng step and reaches such a concentration that effic-ient hydrolysis is hampered, the ammonium ion concentration is preferably reduced by a number of alternative methods. One of the most economical methods of reducing the ammonium ion con-centration is to add a stronger base than ammonia, preferably calcium oxide or calcium hydroxide. When calcium hydroxide ;s added, the reaction is as follows:
Reaction (1) occurs at hi~h temperatures and reaction (2) at low temperatures. Both of the above reactions can be readily made to closely approach the thermodynamic equilibrium , ~
,. ~ . : ' , '~ ,, .
., ;., .
.:, . ~ . . . ,. . .. ~ , ... . : ' , . . .
position, and by a correct choice of reaction conditions, pref-; erably high temperatures and low free ammonia and amlnonium salt concentration, a high yield of cupric oxide can be obtained.
As can be deduced from the above reac~ions, higher yields will be obtained at low free ammonia ancl low ammonium concentrations in the original solutions.
The hydrolysis process of the present invention is carried out by heating the aqueous ammoniacal solution, prefer-ably in the range from 60 ~o 250C. The aqueous ammoniacal solution can be formed by leaching a copper ore or concentrate, for example, covellite, chalcopyrite, or scrap containing copper metal or copper compounds, with an ammoniacal oxidizing solution wh;ch may also contain ammonium salts.
In dilute solutions, high yields are possible in one step. To obtain maximum yields of copper oxide in more concen-trated solutions, however, more than one stage may be necessary ~ with removal of ammonia and ammonium ion between stages. For '!~ leach solutions of practical strength, for example, 20-60 grams per litre of copper9 it is not necessary to use more than two stages. However, any number of stages could be conveniently ~ 20 used. It is known to be advantageous in the ammoniacal leach-; ing of copper ores and concentrates to have a significant dis-solved copper content in the initial leaching solution. Therefore, the process of the present invention could be carried out effic-iently by the removal of a portion of the soluble copper from the solution and then returning the solution, after filtering off the copper oxide, to the leaching operation~ This will dilute the copper concentration of the liquor and should result in the efficient recovery of copper through one hydrolysis stage even in highly concentrated solutions.
As can be seen from the examples below, in dilute solutions, high yields are possible in one stage.
101~6951~
-- If ammonium ion accumulates in the solut~on either due to the hydrolysis reaction, or due to the chemistry of the leach;ng step and reaches such a concentration that effic-ient hydrolysis is hampered, the ammonium ion concentration is preferably reduced by a number of alternative methods. One of the most economical methods of reducing the ammonium ion con-centration is to add a stronger base than ammonia, preferably calcium oxide or calcium hydroxide. When calcium hydroxide ;s added, the reaction is as follows:
(3) (NH4)2 S04 + Ca(OH)2~ 2 NH3 + CaS04 + 2 H20 The calcium sulfate can then be filtered off, and the ammonia liberated by the reaction, as well as any "free" ammonia and a ' portion of the complexed ammonia, already in the solution, can - be recovered from the solution by conventional methods, for ex-~ ample, distillation and absorption in an aqueous solution.
..~
In carrying out the process of the present invention with more concentrated solutions, it may be preferable to reduce the dissolved ammonia concentration (even if the ammonium , ~ .
ion is not removed) prior to the hydrolysis step in order to obtain a higher yield. This may be done by heating the solution `~ to drive off the ammonia which is then recovered by conventional ,, .j ...
~' means. It has been found that ammonia may-be reduced in this way to a value of x less than 4 in the formula Cu(NH3)2x with ~ resulting good yields on hydrolysis. If the calcium hydroxide ; or calcium oxide is added to reduce the ammonium ion concentra-tion, then both the ammonia liberated by the addition of the base and the ammonia dissolved in solution and a portion of the complexed ammonia can be removed by heating. This also can be carried out until the value of x is less than 4, with resulting good yields. It is preferable to adjust the ammonia content so that the molar ration of total ammonia to dissolved copper is between 2 and 8, and more preferably between 3.5 and 6.
The solution may contain amounts of other metals cap-able of forming soluble metal amines in ammoniacal solution, for example, nickel, zinc and silver.
;
~` . ........................ .
,,; . . . .
`` ~VI~ 5~
The following examples further illustrate the pre-ferred embodiment of the invention.
Example 1 A solution containing 29.2 grams per litre of copper and 10 moles of total ammonia per mole of copper was heated successively in steps from 25 to 200C. A significant decrease in copper content occurred as shown below as temperature increased, even though these are not the most favourable conditions for high cupric oxide yield.
Tem C 25 75 100 125 150 175 200 P- . . _ _ .
%Cu recovered 0 0 02.1 12.7 26.0 37.3 , ' ' '''.
Example 2 A solution containing 28.7 grams per litre of copper and 5 moles of total ammonia per mole of copper was heated successively in steps from 25 to 200C. The lower ammonia content than in Example 1 allowed a higher yield of solid cupric oxide to be obtained, as shown below.
Temp. C 25 75 100 125_ 150 _175 200 .
%Cu recovered 0 0 5.2 31.048.1 61.0 67.6 Example 3 A solution containing 3.84 grams per litre of copper and 5.7 moles of total ammonia per mole of copper was heated successively in steps from 25 to 150C. The results given below show that in more dilute solutions, high yields of copper oxide are pos-sible. In this example9 the yield was over 99%.
Tem C 25 75 87 100 125 150 P~
%Cu recovered 1 51.8 72.1 85.4 96.4 99.2 Example 4 A solution containing 29.98 grams per litre of copper, 3.75 moles/litre of ammonia and 1.0 mole/litre of ammonium sulfate lO~g5~
was treated at 25C with sufficient lime to react with the am-monium sulfate in the solution. The calcium sulfate Formed was filtered off, washed and the wash liquor and filtrate combined.
This liquor was boiled to drive off liberated ammonia until the final solution (when boiling was stopped) contained 24.o gram/
litre of copper and 1.32 moles/litre of ammonia (ammonia to copper molar ratio of 3.5). This solution was then hydrolyzed at a tem-perature of 175C with the final solution containing 3.67 grams/
litre of dissolved copper (85% recovery as copper oxide~.
Example 5 -A solution containing 30.0 grams/litre of copper with an ammonia/
copper molar ratio of 5.45 was hydrolyzed in steps at temperatures from 100 to 200C. Copper recovery as the oxide was 67.7%.
..~
In carrying out the process of the present invention with more concentrated solutions, it may be preferable to reduce the dissolved ammonia concentration (even if the ammonium , ~ .
ion is not removed) prior to the hydrolysis step in order to obtain a higher yield. This may be done by heating the solution `~ to drive off the ammonia which is then recovered by conventional ,, .j ...
~' means. It has been found that ammonia may-be reduced in this way to a value of x less than 4 in the formula Cu(NH3)2x with ~ resulting good yields on hydrolysis. If the calcium hydroxide ; or calcium oxide is added to reduce the ammonium ion concentra-tion, then both the ammonia liberated by the addition of the base and the ammonia dissolved in solution and a portion of the complexed ammonia can be removed by heating. This also can be carried out until the value of x is less than 4, with resulting good yields. It is preferable to adjust the ammonia content so that the molar ration of total ammonia to dissolved copper is between 2 and 8, and more preferably between 3.5 and 6.
The solution may contain amounts of other metals cap-able of forming soluble metal amines in ammoniacal solution, for example, nickel, zinc and silver.
;
~` . ........................ .
,,; . . . .
`` ~VI~ 5~
The following examples further illustrate the pre-ferred embodiment of the invention.
Example 1 A solution containing 29.2 grams per litre of copper and 10 moles of total ammonia per mole of copper was heated successively in steps from 25 to 200C. A significant decrease in copper content occurred as shown below as temperature increased, even though these are not the most favourable conditions for high cupric oxide yield.
Tem C 25 75 100 125 150 175 200 P- . . _ _ .
%Cu recovered 0 0 02.1 12.7 26.0 37.3 , ' ' '''.
Example 2 A solution containing 28.7 grams per litre of copper and 5 moles of total ammonia per mole of copper was heated successively in steps from 25 to 200C. The lower ammonia content than in Example 1 allowed a higher yield of solid cupric oxide to be obtained, as shown below.
Temp. C 25 75 100 125_ 150 _175 200 .
%Cu recovered 0 0 5.2 31.048.1 61.0 67.6 Example 3 A solution containing 3.84 grams per litre of copper and 5.7 moles of total ammonia per mole of copper was heated successively in steps from 25 to 150C. The results given below show that in more dilute solutions, high yields of copper oxide are pos-sible. In this example9 the yield was over 99%.
Tem C 25 75 87 100 125 150 P~
%Cu recovered 1 51.8 72.1 85.4 96.4 99.2 Example 4 A solution containing 29.98 grams per litre of copper, 3.75 moles/litre of ammonia and 1.0 mole/litre of ammonium sulfate lO~g5~
was treated at 25C with sufficient lime to react with the am-monium sulfate in the solution. The calcium sulfate Formed was filtered off, washed and the wash liquor and filtrate combined.
This liquor was boiled to drive off liberated ammonia until the final solution (when boiling was stopped) contained 24.o gram/
litre of copper and 1.32 moles/litre of ammonia (ammonia to copper molar ratio of 3.5). This solution was then hydrolyzed at a tem-perature of 175C with the final solution containing 3.67 grams/
litre of dissolved copper (85% recovery as copper oxide~.
Example 5 -A solution containing 30.0 grams/litre of copper with an ammonia/
copper molar ratio of 5.45 was hydrolyzed in steps at temperatures from 100 to 200C. Copper recovery as the oxide was 67.7%.
Claims (9)
EXCLUSIVE PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS
FOLLOWS:
1. A process for the recovery of copper oxide or copper hydroxide from an aqueous ammoniacal liquor, containing copper in solution, saidprocess comprising carrying out hyrdolysis of said soluble copper while the liquor is heated in the range from 60° to 250°C, the ammonia to copper mole ratio is maintained at a value less than 10, and the ammonium salt concentration is controlled to prevent inhibition of the hydrolysis and recovering the copper oxide or copper hydroxide precipitate so formed.
2. A process as claimed in claim 1 wherein the ammonia to copper mole ratio is maintained at a value in the range from 3.5 to 6.
3. A process for the recovery of copper oxide from an aqueous ammoniacal liquor containing copper in solution, said process comprising carrying out hydrolysis of said soluble copper by heating the solution in the range from 60° to 250°C, removing the copper oxide precipitate so formed, adding to the liquid an approximately stoichiometric amount of a stronger base than ammonia relative to ammonia present as ammonium salt, and driving off the liberated and free ammonia in the liquor by heating said liquor.
4. A method as claimed in claim 3 wherein the base is added before the hydrolysis step.
5. A method as claimed in claim 3 wherein the base is added both before and after the hydrolysis step.
6. A process as claimed in claim 3 wherein the base is calcium oxide or calcium hydroxide.
7. A process as claimed in claim 4 wherein the base is calcium oxide or calcium hydroxide.
8. A process as claimed in claim 5 wherein the base is calcium oxide or calcium hydroxide
9. A process as claimed in claim 6, 7 or 8 wherein calcium sulfate is formed by the addition of the base, filter-ing off the calcium sulfate and reducing the remaining soluble calcium in the resulting liquors to a low level by the addition of stoichiometric amounts of carbonate or oxalate ion, and then removing the calcium salt precipitated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA279,606A CA1086958A (en) | 1977-06-01 | 1977-06-01 | Hydrolysis of soluble copper in an aqueous ammoniacal liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA279,606A CA1086958A (en) | 1977-06-01 | 1977-06-01 | Hydrolysis of soluble copper in an aqueous ammoniacal liquor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1086958A true CA1086958A (en) | 1980-10-07 |
Family
ID=4108784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA279,606A Expired CA1086958A (en) | 1977-06-01 | 1977-06-01 | Hydrolysis of soluble copper in an aqueous ammoniacal liquor |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1086958A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113526771A (en) * | 2021-08-27 | 2021-10-22 | 湖北石河医药科技有限公司 | Treatment method of wastewater in allylamine production process and application of wastewater in allylamine production process |
| CN113735157A (en) * | 2021-09-18 | 2021-12-03 | 武汉大学 | Preparation method of petal-shaped copper oxide nanosheet and application of petal-shaped copper oxide nanosheet |
-
1977
- 1977-06-01 CA CA279,606A patent/CA1086958A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113526771A (en) * | 2021-08-27 | 2021-10-22 | 湖北石河医药科技有限公司 | Treatment method of wastewater in allylamine production process and application of wastewater in allylamine production process |
| CN113526771B (en) * | 2021-08-27 | 2024-06-18 | 湖北石河医药科技有限公司 | Treatment method of wastewater in allylamine production process and application of wastewater in allylamine production process |
| CN113735157A (en) * | 2021-09-18 | 2021-12-03 | 武汉大学 | Preparation method of petal-shaped copper oxide nanosheet and application of petal-shaped copper oxide nanosheet |
| CN113735157B (en) * | 2021-09-18 | 2022-06-03 | 武汉大学 | Preparation method of petal-shaped copper oxide nanosheet and application of petal-shaped copper oxide nanosheet |
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| Date | Code | Title | Description |
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| MKEX | Expiry |