CN101191158B - Method for reclaiming metal cadmium from cadmium-containing waste material - Google Patents
Method for reclaiming metal cadmium from cadmium-containing waste material Download PDFInfo
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- CN101191158B CN101191158B CN2006101448237A CN200610144823A CN101191158B CN 101191158 B CN101191158 B CN 101191158B CN 2006101448237 A CN2006101448237 A CN 2006101448237A CN 200610144823 A CN200610144823 A CN 200610144823A CN 101191158 B CN101191158 B CN 101191158B
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Abstract
The invention relates to a method for reclaiming cadmium metals from cadmiferous waste materials, comprising the following steps: organic substances and water in the cadmiferous waste materials are removed; cadmium oxides in the cadmiferous waste materials after removal of the organic substances and the water are reduced to elementary cadmiums in reducing atmosphere; the elementary cadmiums are then evaporated into cadmium vapor; the cadmium vapor is condensed into cadmium metals, wherein, the reducing atmosphere is formed by reducing gas which comprises main air flow and auxiliary air flow; the main air flow and the auxiliary air flow conversely blows towards the cadmiferous waste materials after removal of the organic substances and the water; linear velocity of the auxiliary air flow is higher than that of the main air flow. The method for reclaiming the cadmium metals from the cadmiferous waste materials provided by the invention has the advantages of low energy consumption and simple procedures.
Description
Technical field
The invention relates to a kind of method that reclaims cadmium metal, more specifically about a kind of method that from cadmium-containing waste material, reclaims cadmium metal.
Background technology
Nickel-cadmium cell has that capacity is big, the life-span is long, make simple and low cost and other advantages, and cycle index can reach hundreds of even thousands of times.Along with development and national economy, nickel-cadmium cell has been widely used in the power supply system of aspects such as national defence, fire-fighting, space flight, household electrical appliance, office machine, communication equipment and power tool.
Nickel-cadmium cell generally comprises positive pole, negative pole and the barrier film between positive pole and negative pole, negative pole comprises the negative pole conducting base and is coated in the negative pole conducting base or is filled in negative material in the negative pole conducting base, negative material contains CdO and tackiness agent, and tackiness agent is generally organic polymer such as Xylo-Mucine.The nickel-cadmium cell charge and discharge cycles use repeatedly the back with regard to substantial loss use value, contain a large amount of cadmium metals and Cadmium oxide in these abandoned nickel and cadmium cells, if cadmium metal in the abandoned nickel and cadmium cell and Cadmium oxide are recycled, not only can avoid contaminate environment or be detrimental to health, but also can economize on resources.
CN 10555731C disclose a kind of in stove by thermal treatment from the Ni-Cd battery with include the method that reclaims cadmium metal and nickel the processing waste material of nickel, cadmium and other material, this method comprises: described waste material is placed in the stove; The carbon granule that adds q.s in described stove is as oxygen absorber, and to stop the formation of oxide compound, the amount of wherein said carbon granule is per 4.5 kilograms and places the waste material in the described stove to be added into nearly 85 gram carbon granules; One rare gas element is imported and remains in the atmosphere of described stove; Heat described stove through the effective time cycle, with the evaporation free water; Described furnace temperature is raise and remain to the effective time cycle of about 500-800 ℃ warp, with volatilization molecular water and nonmetallic substance; The described furnace temperature of raising arrive greater than about 900 ℃ through at least 2 hours, make the cadmium evaporation of described waste material and can not make the residue scrap melting; In the Room that cadmium imports with described stove is connected with described evaporation; Place described indoor described cadmium vapor condensation and curing by reducing described indoor described cadmium vapor temperature, making; From described chamber, reclaim described curing cadmium; In described stove, reclaim Ni-based recrement.
Because this method need be evaporated cadmium under greater than 900 ℃ high temperature, and the cadmium of evaporation need be derived from described stove, so the energy consumption of this method is big, complex steps.
Summary of the invention
The existing method energy consumption that reclaims cadmium metal from cadmium-containing waste material is big, the shortcoming of complex steps in order to overcome in the present invention, and the method that a kind of energy consumption is little, step simply reclaims cadmium metal from cadmium-containing waste material is provided.
The inventor finds, the reduction reaction that Cadmium oxide is reduced into the simple substance cadmium is the reaction between the atom on the Cadmium oxide interface, the simple substance cadmium that is reduced at first is to occur with the atom form, the cadmium of atom form mainly is gas phase (being cadmium steam), if reduction temperature is lower, then cadmium steam hinders further reduction reaction at the surface condensation of Cadmium oxide; And CN 10555731C disclosed method is at the surface coverage carbon granule of cadmium-containing waste material, the specific surface of carbon granule is bigger, has very strong adsorptivity, cadmium steam can be adsorbed on its surface, so this method need be increased to furnace temperature the cadmium evaporation that also keeps just making at least 2 hours in the waste material greater than about 900 ℃.
The invention provides a kind of method that reclaims cadmium metal from cadmium-containing waste material, this method comprises organic substance and the water of removing in the cadmium-containing waste material; The Cadmium oxide that to remove under reducing atmosphere in the cadmium-containing waste material of organic substance and water is reduced into the simple substance cadmium, and the cadmium evaporation is formed cadmium steam; The cadmium vapor condensation is formed cadmium metal, wherein, described reducing atmosphere is formed by reducing gas, described reducing gas comprises main air stream and substreams, main air stream and substreams be reverse to blow to the described cadmium-containing waste material of removing organic substance and water, and the linear velocity of substreams is greater than the linear velocity of main air stream.
In method provided by the invention, main air stream and substreams are reverse to blow to described cadmium-containing waste material, so main air stream and substreams formation gaseous exchange.Because the linear velocity of substreams is greater than the linear velocity of main air stream, gaseous exchange makes the cadmium atom disengaging Cadmium oxide surface that is reduced directly enter in the convection gas, helping reducing degree on the one hand deepens, on the other hand can be so that the simple substance cadmium can obtain the higher cadmium metal particle of purity in condensation under the steam ambient, that is to say that gaseous exchange constantly is brought into the cadmium steam on the Cadmium oxide interface in the convection gas, thereby promoted the evaporation and the condensation of cadmium.Therefore, method provided by the invention just can make the cadmium evaporation form cadmium steam under 300-500 ℃ lesser temps.The condensation in convection gas of cadmium steam forms liquid cadmium, because liquid cadmium has stronger spontaneous caking and aggregation tendency, can adsorb its cadmium steam on every side, form bigger liquid metal cadmium particle, the particle particle dia can slowly increase to the 0.1-1.5 millimeter, and cohesion forms solid particulate in the continuous convection process of gas.The particle dia of this solid particulate is easy to solid particulate is separated greater than the particle dia of other material in the cadmium-containing waste material.Therefore, the method energy consumption that reclaims cadmium metal from cadmium-containing waste material provided by the invention is low, and step is simple.
Embodiment
The method that reclaims cadmium metal in the cadmium-containing waste material provided by the invention comprises organic substance and the water of removing in the cadmium-containing waste material; The Cadmium oxide that to remove under reducing atmosphere in the cadmium-containing waste material of organic substance and water is reduced into the simple substance cadmium, and the cadmium evaporation is formed cadmium steam; The cadmium vapor condensation is formed cadmium metal, wherein, described reducing atmosphere is formed by reducing gas, described reducing gas comprises main air stream and substreams, main air stream and substreams be reverse to blow to the described cadmium-containing waste material of removing organic substance and water, and the linear velocity of substreams is greater than the linear velocity of main air stream.
Described reductive condition comprises that reduction temperature is 300-500 ℃, is preferably 320 ℃-450 ℃, and the recovery time is 20-100 minute, is preferably 30-80 minute, more preferably 40-60 minute.
Described reducing gas can be the existing various reducing gas that are used for redox reaction, and for example, reducing gas can be selected from one or more in ammonia, carbon monoxide and the hydrogen.
Described reducing gas comprises main air stream and substreams, the reverse described cadmium-containing waste material of removing organic substance and water, the formation gaseous exchange of blowing to of main air stream and substreams.Main air stream and substreams can be reverse on above-below direction, also can be reverse on left and right directions, under the preferable case, described main air stream blows to the described cadmium-containing waste material of removing organic substance and water from top to bottom, substreams blows to the described cadmium-containing waste material of removing organic substance and water from the bottom up, and main air stream and substreams form gaseous exchange.At this, blowing to the described cadmium-containing waste material of removing organic substance and water is construed as, the described cadmium-containing waste material of removing organic substance and water is deposited in together, and main air stream and substreams blow to respectively and pass through whole cadmium-containing waste material, rather than only blow over the surface of cadmium-containing waste material.
In order to make the cadmium atom that is reduced break away from the Cadmium oxide surface, the linear velocity of substreams is greater than the linear velocity of main air stream, can destroy the gas-liquid-solid three-phase balance of cadmium metal like this, impel the cadmium (being cadmium steam) of gas phase to move upward, enter into convection gas on the Cadmium oxide surface.The linear velocity of substreams be preferably main air stream linear velocity 1.1-5 doubly, more preferably 1.2-3 is doubly.The linear velocity of substreams can be the 25-60 meter per second, is preferably the 30-50 meter per second.
The total amount of reducing gas is at least the Cadmium oxide Restore All that can make in the described cadmium-containing waste material of removing organic substance and water and becomes the required amount of simple substance cadmium, under the preferable case, every kilogram of described total amount of removing the employed reducing gas of cadmium-containing waste material of organic substance and water is the 0.15-0.45 cubic meter, more preferably the 0.2-0.35 cubic meter.The amount of substreams can be 0.05-0.5 times of main air stream, is preferably 0.1-0.3 doubly.The linear velocity of substreams, can realize less than the bore of main air stream nozzle by the bore that makes the substreams nozzle less than main air stream greater than the amount of main air stream, substreams.
Because the simple substance cadmium that Cadmium oxide is reduced into mainly is gas phase (being cadmium steam), effect at gaseous exchange, cadmium steam constantly enters into convection gas and is condensed into liquid phase (being liquid cadmium), because liquid cadmium has stronger spontaneous caking and aggregation tendency, can absorption the cadmium steam in the convection gas around it, the particle particle dia can slowly increase to the 0.1-1.5 millimeter, and cohesion forms solid particulate in the continuous convection process of gas, and solid particulate falls back under the action of gravity of self in the described cadmium-containing waste material of removing organic substance and water.Because the boiling point of cadmium metal is 765 ℃, therefore under 300-500 ℃ temperature, the cadmium metal of described solid particulate form no longer is evaporated, the particle dia of this solid particulate is greater than the particle dia of other material in the described cadmium-containing waste material of removing organic substance and water, after reduction reaction is finished, can be easy to solid particulate is separated.For example, can use 80-150 purpose screen cloth Separation and Recovery can not pass through the cadmium metal solid particulate of this screen cloth, the preferred 100-120 purpose screen cloth that uses, this screen cloth can for example can be nylon screen, acrylic screen cloth and metallic sieve for the conventional screen cloth that uses in this area.
Method of the present invention can be used the existing device that is used to reclaim cadmium, for example, existing industrial Reaktionsofen perhaps has stopping property and with the container of the recycle system, the described recycle system mainly is to be used to absorb the reduzate water vapor, makes that reducing gas can continue to use.From foregoing description as can be seen, method of the present invention is reduced into the simple substance cadmium with Cadmium oxide under 300-500 ℃ lesser temps, and reduction, condensation can be carried out in a container, and not needing derives cadmium steam, so step is simple, has saved equipment cost.
Wherein, can adopt existing the whole bag of tricks to remove organic substance and water in the cadmium-containing waste material, under the preferable case, the method of removing organic substance in the cadmium-containing waste material and water comprises cadmium-containing waste material is contacted with oxidizing gas, the temperature of contact is 250-500 ℃, is preferably 300-450 ℃, and the time of contact is 20-100 minute, be preferably 30-80 minute, the oxidizing gas consumption is enough to make the organic substance complete oxidation in the cadmium-containing waste material.Described oxidizing gas can be pure oxygen, also can be the mixed gas that contains oxygen, and in order to save cost, described oxidizing gas is preferably air.As long as the consumption of oxidizing gas can be with the carbon material oxidation in the solid matter fully, for example, every kilogram of employed oxidizing gas of cadmium-containing waste material can be the 0.02-0.6 cubic meter, is preferably the 0.05-0.3 cubic meter.In the present invention, if not otherwise specified, the amount of gas all is meant (comprising reducing gas and oxidizing gas) volume of the gas of depressing at 1 standard atmosphere.
Method of the present invention is applicable to from existing various cadmium-containing waste materials and reclaims cadmium metal that cadmium-containing waste material can negative material, the NI-G of usefulness not be processed clout, cadmium oxyhydroxide residue or their mixture for abandoned nickel and cadmium cell, nickel-cadmium cell.
When cadmium-containing waste material was abandoned nickel and cadmium cell, method of the present invention preferably before the organic substance in removing cadmium-containing waste material and/or the water was separated positive and negative electrode, with negative pole as this cadmium-containing waste material.Negative pole contacts with oxidizing gas, organic substance is oxidized to gaseous volatilization and falls, because the tackiness agent in the negative material of negative pole is an organic substance, after tackiness agent decomposes, the negative material that loads on the negative pole conducting base begins to come off, form powder, the broken screening of only need simply shaking can separate the negative pole conducting base with powder, promptly isolate the described cadmium-containing waste material of removing organic substance and water of powder form.Separate in the powder that obtains and contain Cadmium oxide, this powder is contacted with reducing gas as the described cadmium-containing waste material of removing organic substance and water.
To can use the conventional screen cloth of this area to sieve in negative pole conducting base and the powder separating process, the mesh diameter of screen cloth can be 0.1-5 centimetre, is preferably 0.2-1 centimetre.
Below by embodiment the present invention is explained in more detail.
Embodiment 1-10
Embodiment 1-10 is used for illustrating the method that reclaims cadmium metal from cadmium-containing waste material of the present invention.
The positive and negative electrode of abandoned nickel and cadmium cell is separated, 20 kilograms of negative poles are placed have stopping property and (interface is all arranged at the bottom of this container and top with the container of the recycle system, the bore of bottom interface is less than the bore of top interface) in, under condition as shown in table 1, contact with air.Negative pole integral body is shaken brokenly then, crosses the nylon mesh of 1 centimetre of mesh, obtains containing the powder mixture of Cadmium oxide.16 kilograms of these powder mixtures are placed have stopping property and with the container of the recycle system, under condition as shown in table 2, main air stream blows to described powder from top to bottom, substreams blows to described powder from the bottom up, reduce, condensation, with 110 purpose screen cloth Separation and Recovery can not be by this screen cloth the cadmium metal solid particulate.And with the purity of cadmium in the chemical titration cadmium metal solid particulate, the result is as shown in table 2.
In addition, use chemical titration to measure the amount M1 of Cadmium oxide in the described powder mixture that contains Cadmium oxide respectively, and reduction and isolate the cadmium metal solid particulate after residue in the amount M2 of Cadmium oxide, and utilize following formula to calculate reduction ratio:
Reduction ratio (%)=(M1-M2)/M1 * 100%
Table 1
| The embodiment numbering | The consumption of air (cubic meter) | Duration of contact (minute) | The contact temperature (℃) |
| 1 | 2.0 | 45 | 320 |
| 2 | 1.6 | 50 | 260 |
| 3 | 1.2 | 50 | 250 |
| 4 | 2.5 | 55 | 310 |
| 5 | 3.0 | 40 | 350 |
| 6 | 1.5 | 60 | 460 |
| 7 | 2.2 | 60 | 400 |
| 8 | 0.6 | 70 | 450 |
| 9 | 2.0 | 35 | 300 |
| 10 | 1.6 | 75 | 400 |
Table 2
| The embodiment numbering | The type of reducing gas | The total amount of reducing gas (cubic meter) | The ratio of the amount of substreams and the amount of main air stream | The linear velocity of substreams (meter per second) | The ratio of the linear velocity of substreams and the linear velocity of main air stream | Recovery time (minute) | Reduction temperature (℃) | The purity of cadmium (%) | Reduction ratio (%) |
| 1 | NH 3 | 5.2 | 0.1 | 50 | 3 | 60 | 500 | 95.4 | 93.6 |
| The embodiment numbering | The type of reducing gas | The total amount of reducing gas (cubic meter) | The ratio of the amount of substreams and the amount of main air stream | The linear velocity of substreams (meter per second) | The ratio of the linear velocity of substreams and the linear velocity of main air stream | Recovery time (minute) | Reduction temperature (℃) | The purity of cadmium (%) | Reduction ratio (%) |
| 2 | NH 3 | 3.2 | 0.3 | 50 | 3 | 60 | 300 | 96.2 | 93.4 |
| 3 | NH 3 | 5.2 | 0.1 | 35 | 1.5 | 45 | 450 | 96.2 | 92.7 |
| 4 | NH 3 | 3.2 | 0.3 | 35 | 1.2 | 60 | 350 | 97.6 | 93.3 |
| 5 | NH 3 | 3.2 | 0.1 | 35 | 3 | 75 | 300 | 97.5 | 94.2 |
| 6 | NH 3 | 4.0 | 0.15 | 35 | 2.5 | 45 | 380 | 97.7 | 95.7 |
| 7 | NH 3 | 4.5 | 0.15 | 40 | 2.7 | 50 | 450 | 98.8 | 96.3 |
| 8 | NH 3 | 4.0 | 0.15 | 40 | 1.6 | 55 | 420 | 99.2 | 99.8 |
| 9 | NH 3 | 4.5 | 0.2 | 50 | 2 | 58 | 420 | 99.3 | 98.8 |
| 10 | NH 3 | 5.2 | 0.2 | 50 | 2.1 | 42 | 360 | 99.3 | 99.4 |
From embodiment 1-10 and last table 2 as can be seen, method of the present invention just can reclaim cadmium metal from cadmium-containing waste material under 300-450 ℃ temperature, compare with the pyritous method of existing needs more than 900 ℃, energy consumption is less, and method steps of the present invention is fairly simple, reduction ratio can reach more than 92%, and the purity that reclaims the cadmium that obtains can reach more than 95%.
Claims (10)
1. method that from cadmium-containing waste material, reclaims cadmium metal, this method comprises organic substance and the water of removing in the cadmium-containing waste material; The Cadmium oxide that to remove under reducing atmosphere in the cadmium-containing waste material of organic substance and water is reduced into the simple substance cadmium, and the cadmium evaporation is formed cadmium steam; The cadmium vapor condensation is formed cadmium metal, it is characterized in that, described reducing atmosphere is formed by reducing gas, described reducing gas comprises main air stream and substreams, main air stream and substreams be reverse to blow to the described cadmium-containing waste material of removing organic substance and water, the linear velocity of substreams is greater than the linear velocity of main air stream, and described reductive condition comprises that reduction temperature is 300-500 ℃, and the recovery time is 20-100 minute.
2. method according to claim 1, wherein, described main air stream blows to the described cadmium-containing waste material of removing organic substance and water from top to bottom, and substreams blows to the described cadmium-containing waste material of removing organic substance and water from the bottom up.
3. method according to claim 1, wherein, described reducing gas is selected from one or more in ammonia, carbon monoxide and the hydrogen.
4. method according to claim 1, wherein, the linear velocity of described substreams be main air stream linear velocity 1.1-5 doubly.
5. according to claim 1 or 4 described methods, wherein, the linear velocity of described substreams is the 25-60 meter per second.
6. method according to claim 1, wherein, every kilogram of described total amount of removing the employed reducing gas of cadmium-containing waste material of organic substance and water is the 0.15-0.45 cubic meter.
7. method according to claim 1, wherein, the consumption of substreams be main air stream consumption 0.05-0.5 doubly.
8. method according to claim 1, wherein, the method of removing organic substance in the cadmium-containing waste material and water comprises cadmium-containing waste material is contacted with oxidizing gas, the temperature of contact is 250-500 ℃, the time of contact is 20-100 minute, and the oxidizing gas consumption is enough to make the organic substance complete oxidation in the cadmium-containing waste material.
9. method according to claim 8, wherein, described cadmium-containing waste material is the negative pole of nickel-cadmium cell, this negative pole is with after oxidizing gas contacts, and also comprises the negative pole broken screening of shaking, and isolates the described cadmium-containing waste material of removing organic substance and water of powder form.
10. method according to claim 1 wherein, after cadmium vapor condensation formation cadmium metal, also comprises and uses screen cloth separating metal cadmium.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2006101448237A CN101191158B (en) | 2006-11-21 | 2006-11-21 | Method for reclaiming metal cadmium from cadmium-containing waste material |
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| CN2006101448237A CN101191158B (en) | 2006-11-21 | 2006-11-21 | Method for reclaiming metal cadmium from cadmium-containing waste material |
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| CN101191158B true CN101191158B (en) | 2010-06-23 |
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Families Citing this family (3)
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| CN101942564B (en) * | 2010-08-21 | 2013-09-25 | 赵志强 | Process for producing pure cadmium by continuous reduction and distillation of zinc cadmium slag and sponge cadmium |
| CN109266868B (en) * | 2018-11-22 | 2020-12-01 | 深圳技术大学 | A kind of method of recovering cadmium in cadmium sulfide |
| CN113564361A (en) * | 2021-05-19 | 2021-10-29 | 兰州有色冶金设计研究院有限公司 | Pyrogenic treatment and recovery process of cadmium telluride thin-film solar cell |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063314A (en) * | 1991-01-09 | 1992-08-05 | 冶金工业部长沙矿冶研究院 | Method and device for recovering cadmium by reduction distillation |
| CN1095112A (en) * | 1993-01-19 | 1994-11-16 | 日用电池有限公司 | Be used for the apparatus and method that nickel and cadmium reclaim |
| JP2003253352A (en) * | 2002-03-04 | 2003-09-10 | Sumitomo Metal Mining Co Ltd | Cadmium purification method |
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2006
- 2006-11-21 CN CN2006101448237A patent/CN101191158B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063314A (en) * | 1991-01-09 | 1992-08-05 | 冶金工业部长沙矿冶研究院 | Method and device for recovering cadmium by reduction distillation |
| CN1095112A (en) * | 1993-01-19 | 1994-11-16 | 日用电池有限公司 | Be used for the apparatus and method that nickel and cadmium reclaim |
| JP2003253352A (en) * | 2002-03-04 | 2003-09-10 | Sumitomo Metal Mining Co Ltd | Cadmium purification method |
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