CN102965516A - Method capable of recovering manganese out of slag - Google Patents
Method capable of recovering manganese out of slag Download PDFInfo
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- CN102965516A CN102965516A CN2012104995378A CN201210499537A CN102965516A CN 102965516 A CN102965516 A CN 102965516A CN 2012104995378 A CN2012104995378 A CN 2012104995378A CN 201210499537 A CN201210499537 A CN 201210499537A CN 102965516 A CN102965516 A CN 102965516A
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- slag
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- 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
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Abstract
The invention provides a method capable of recovering manganese out of slag. The method comprises the steps of integrating spent powdered ink and slag by using an adhesive, granulating and then carrying out dry distillation on the materials to obtain dry distillate oil to provide pretreatment for the slag for noble metal regeneration. In the dry distillation process, the generated dry distillate oil can be used as a regenerated fuel, the generated dry distillation gas can be used as fuel to directly act in a dry distillation furnace and the generated dry distillation residues serve as raw materials for regenerating noble metals by using the slag; and after being pretreated, the wastes containing manganese are thrown into a kettle-type processor; and with environment-friendly and biodegradable N,N'-ethylenediamine disuccinic acid as a chelating agent, the component manganese can be leached out of the wastes by regulating pH value of an extraction system.
Description
Technical field
The invention belongs to resource and reclaim the comprehensive utilization field, be specifically related to a kind of method that reclaims manganese in the slag.
Background technology
Manganese is the huge common metal of consumption in the industrial and agricultural productions such as a kind of iron and steel, chemistry, special material, when still increasing along with demand, but the expected reserves continuous decrease of manganese.Meanwhile, contain the quantity of manganese thing also in continuous growth, therefore these things are reclaimed the pressure that can alleviate the decline of manganese metal reserves, also can reduce the huge Environmental costs that thing brings.It is a kind of common recovery method that the chemistry drop is got, and the sequestrant that often uses is ethylenediamine tetraacetic acid (EDTA) (EDTA) and sodium salt class sequestrant thereof, and this sequestrant is strong to the sequestering power of metal ion, just has good drop to get efficient.But this sequestrant is difficult to be degraded in physical environment, therefore uses for a long time, in a large number this type of sequestrant to bring Secondary Organic to pollute.
N, the N'-ethylenediamine disuccinic acid be a kind of in physical environment degradable sequestrant, be applied at present the drop heavy metal ion in the earth that fetches earth.
Summary of the invention
The present invention proposes a kind of method that reclaims discarded manganese metal, and then technical scheme of the present invention carries out destructive distillation for using will give up ink powder, slag of tackiness agent to be incorporated into together granulation, obtains empyreumatic oil, provides pre-treatment for slag carries out precious metal regeneration.Produce empyreumatic oil in the retort process and can be used as the regenerated fuel use, the generation carbonization gas can be used as fuel and acts directly in the gas retort, produces the destructive distillation slag as the raw material of slag recover precious metals.Utilize eco-friendly N, N'-ethylenediamine disuccinic acid sequestrant in the autoclave treater, is got by chemical drop and to be contained the manganese composition in the manganese metal in the slag.
The present invention realizes that by following technique means its concrete steps comprise:
1. take by weighing raw material: the mass ratio according to slag, useless ink powder, tackiness agent and water is (5 ~ 10): (0.1 ~ 3): (0.5 ~ 3): (0.5 ~ 1.5) takes by weighing respectively raw material;
2. granulation: will give up ink powder and slag slowly stirred 10 ~ 30 minutes after mixing in the ratio of step 1, then added tackiness agent and water, continue to puddle evenly after, with the raw material granulation, carry out subsequently destructive distillation;
3. the destructive distillation product drops in the autoclave treater, utilizes eco-friendly N, and N'-ethylenediamine disuccinic acid sequestrant by the pH value modulation of extraction system, is got by chemical drop and to be contained the manganese composition in the manganese metal in the slag.
In technical scheme mentioned above, the adding of water needs an amount of, and its method that adds water is, water repeatedly adds on a small quantity, until with hand hold hold raw material can moulding, but get final product without the raw material bonding on hand.
In technical scheme mentioned above, described destructive distillation condition is 400 ~ 500 ℃ of pyrolysis temperatures, and 2 ~ 3 hours time, more excellent destructive distillation condition is: 450 ℃, and time 2 h.
In technical scheme mentioned above, described useless ink powder is waste duplicator, and the granularity of useless ink powder is 5 ~ 10 microns, useless ink powder organic content 30 ~ 60%.
In the recovery slag provided by the present invention in the method for manganese metal the sequestrant that uses be: according to the mass ratio of 7 ~ 10:1, in the autoclave treater, add environmental friendliness, biodegradable N, the N'-ethylenediamine disuccinic acid.
In the method for manganese metal, slag contains the manganese of 1-5% massfraction for low taste contains manganese mud in the recovery slag provided by the present invention.
In the method for manganese metal, slag must be through grinding pre-treatment step in the recovery slag provided by the present invention.
In the method for manganese metal, the operational condition characteristics are in the recovery slag provided by the present invention: with 25-80 ℃, the 200-600 rotating speed/minute condition under carry out the reclaimer operation of manganese.
In the recovery slag provided by the present invention in the method for manganese metal, N in the autoclave treater, the pH value condition of N'-ethylenediamine disuccinic acid sequestrant extraction manganese is pH 7-8.
In the recovery slag provided by the present invention in the method for manganese metal, manganese-N, the pH condition that N'-ethylenediamine disuccinic acid chelating system discharges mn ion is between the pH 3-5.
In the recovery slag provided by the present invention in the method for manganese metal, slag and N in the autoclave treater, the mass ratio of N'-ethylenediamine disuccinic acid is between 7 ~ 10:1.
In the method for manganese metal, discharge manganese-N under the pH 3-5 condition in the recovery slag provided by the present invention, in the process of N'-ethylenediamine disuccinic acid chelating system mn ion, finish simultaneously N, recovery and the circulation of N'-ethylenediamine disuccinic acid sequestrant.
Embodiment
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1
1. take by weighing raw material: 150kg slag (containing manganese 3%), 19kg useless ink powder, 14kg clay and 15kg water.
2. granulation: will give up ink powder and slag slowly stirred 20 minutes after mixing in the ratio of step 1, then added clay and water, continue to puddle evenly after, advance granulator granulation, the diameter of pellet is between 5 ~ 7cm.The staff enters the raw material that will make in the stove and puts well, guarantees furnace bottom is all covered, and causes body of heater to damage to prevent local dry burning, and destructive distillation is carried out in subsequently loam cake sealing; The beginning heat temperature raising, rise to 450 ℃ from room temperature after insulation 2.5 hours, stopped heating treats that temperature is down to room temperature from 450 ℃ and comes out of the stove, and forbids water directly to be lowered the temperature.
3. detect through the laboratory that the raw material oil length is 3.46% after the destructive distillation, make raw material after the destructive distillation;
4. raw material after the 50kg destructive distillation is added in the 100L autoclave treater, drop into 5kgN under pH 7 conditions, the N'-ethylenediamine disuccinic acid stirs with 300 rev/mins of speed, and be warming up to 60 ℃, process after 1.0 hours, filter, after the filtrate cooling, adding dilute sulphuric acid makes the pH value be adjusted to 4, after static 0.5 hour, will separate out N, the N'-ethylenediamine disuccinic acid reclaims.
Embodiment 2
1. take by weighing raw material: 150kg slag (containing manganese 4.2%), 19kg useless ink powder, 14kg clay and 15kg water.
2. granulation: will give up ink powder and slag slowly stirred 20 minutes after mixing in the ratio of step 1, then added clay and water, continue to puddle evenly after, advance granulator granulation, the diameter of pellet is between 5 ~ 7cm.The staff enters the raw material that will make in the stove and puts well, guarantees furnace bottom is all covered, and causes body of heater to damage to prevent local dry burning, and destructive distillation is carried out in subsequently loam cake sealing; The beginning heat temperature raising, rise to 450 ℃ from room temperature after insulation 2.5 hours, stopped heating treats that temperature is down to room temperature from 450 ℃ and comes out of the stove, and forbids water directly to be lowered the temperature.
3. detect through the laboratory that the raw material oil length is 3.46% after the destructive distillation, make raw material after the destructive distillation;
4. raw material after the 45kg destructive distillation is added in the 100L autoclave treater, drop into 5kgN under pH 7 conditions, the N'-ethylenediamine disuccinic acid stirs with 300 rev/mins of speed, and be warming up to 70 ℃, process after 1.0 hours, filter, after the filtrate cooling, adding dilute sulphuric acid makes the pH value be adjusted to 4, after static 0.5 hour, will separate out N, the N'-ethylenediamine disuccinic acid reclaims.
Embodiment 3
1. take by weighing raw material: 150kg slag (containing manganese 4.5%), 19kg useless ink powder, 14kg clay and 15kg water.
2. granulation: will give up ink powder and slag slowly stirred 20 minutes after mixing in the ratio of step 1, then added clay and water, continue to puddle evenly after, advance granulator granulation, the diameter of pellet is between 5 ~ 7cm.The staff enters the raw material that will make in the stove and puts well, guarantees furnace bottom is all covered, and causes body of heater to damage to prevent local dry burning, and destructive distillation is carried out in subsequently loam cake sealing; The beginning heat temperature raising, rise to 450 ℃ from room temperature after insulation 2.5 hours, stopped heating treats that temperature is down to room temperature from 450 ℃ and comes out of the stove, and forbids water directly to be lowered the temperature.
3. detect through the laboratory that the raw material oil length is 3.46% after the destructive distillation, make raw material after the destructive distillation;
4. raw material after the 45kg destructive distillation is added in the 100L autoclave treater, drop into 5kgN under pH 7 conditions, the N'-ethylenediamine disuccinic acid stirs with 300 rev/mins of speed, and be warming up to 65 ℃, process after 1.0 hours, filter, after the filtrate cooling, adding dilute sulphuric acid makes the pH value be adjusted to 4, after static 0.5 hour, will separate out N, the N'-ethylenediamine disuccinic acid reclaims.
Embodiment 4
1. take by weighing raw material: 150kg slag (containing manganese 3.5%), 19kg useless ink powder, 14kg clay and 15kg water.
2. granulation: will give up ink powder and slag slowly stirred 20 minutes after mixing in the ratio of step 1, then added clay and water, continue to puddle evenly after, advance granulator granulation, the diameter of pellet is between 5 ~ 7cm.The staff enters the raw material that will make in the stove and puts well, guarantees furnace bottom is all covered, and causes body of heater to damage to prevent local dry burning, and destructive distillation is carried out in subsequently loam cake sealing; The beginning heat temperature raising, rise to 450 ℃ from room temperature after insulation 2.5 hours, stopped heating treats that temperature is down to room temperature from 450 ℃ and comes out of the stove, and forbids water directly to be lowered the temperature.
3. detect through the laboratory that the raw material oil length is 3.46% after the destructive distillation, make raw material after the destructive distillation;
4. raw material after the 35kg destructive distillation is added in the 100L autoclave treater, drop into 5kgN under pH 7 conditions, the N'-ethylenediamine disuccinic acid stirs with 500 rev/mins of speed, and be warming up to 80 ℃, process after 1.0 hours, filter, after the filtrate cooling, adding dilute sulphuric acid makes the pH value be adjusted to 4, after static 0.5 hour, will separate out N, the N'-ethylenediamine disuccinic acid reclaims.
Embodiment 5
The slag that uses is: slag (containing manganese 2.5%);
Utilize the step 1 of embodiment 1 ~ 2 described methods to prepare raw material after the destructive distillation;
Raw material after the 50kg destructive distillation is added in the 100L autoclave treater, drop into 5kgN under pH 7 conditions, the N'-ethylenediamine disuccinic acid stirs with 500 rev/mins of speed, and be warming up to 80 ℃, process after 1.0 hours, filter, after the filtrate cooling, adding dilute sulphuric acid makes the pH value be adjusted to 4, after static 0.5 hour, will separate out N, the N'-ethylenediamine disuccinic acid reclaims.
Embodiment 6
The slag that uses is: slag (containing manganese 3.5%);
Utilize the step 1 of embodiment 1 ~ 2 described methods to prepare raw material after the destructive distillation;
Raw material after the 50kg destructive distillation is added in the 100L autoclave treater, drop into 5kgN under pH 7 conditions, the N'-ethylenediamine disuccinic acid stirs with 300 rev/mins of speed, and be warming up to 60 ℃, process after 1.0 hours, filter, after the filtrate cooling, adding dilute sulphuric acid makes the pH value be adjusted to 4, after static 0.5 hour, will separate out N, the N'-ethylenediamine disuccinic acid reclaims.
Embodiment 7
Manganese-N among the above embodiment, N'-ethylenediamine disuccinic acid chelating system discharges the concentration of mn ion and analyzes by icp ms after acidifying.
The drop of manganese is got efficient in the low taste of table 1 slag
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Manganese content (mass percent) in the manganese | 5 | 3 | 3.5 | 4.5 | 2.5 | 3.7 |
| Temperature of processor (° C) | 60 | 70 | 65 | 80 | 80 | 60 |
| Stir (rotating speed/minute) | 300 | 300 | 400 | 500 | 500 | 300 |
| The whole extraction efficiency of manganese | 70 | 74 | 82 | 90 | 95 | 66 |
Claims (5)
1. the method for manganese in the recyclable slag is characterized in that: comprise following operation steps:
1. take by weighing raw material: the mass ratio according to slag, useless ink powder, tackiness agent and water is (5 ~ 10): (0.1 ~ 3): (0.5 ~ 3): (0.5 ~ 1.5) takes by weighing respectively raw material;
2. granulation: will give up ink powder and slag slowly stirred 10 ~ 30 minutes after mixing in the ratio of step 1, then added tackiness agent and water, continue to puddle evenly after, with the raw material granulation, carry out subsequently destructive distillation; The destructive distillation condition is 400 ~ 500 ℃, 2 ~ 3 hours;
3. to the mass ratio adding N of destructive distillation product according to 7 ~ 10:1, N'-ethylenediamine disuccinic acid; By the pH value modulation of extraction system, with 25-80 ℃, the 200-600 rotating speed/minute condition under carry out the recovery of manganese; The pH value condition of extraction is pH 7-8.
2. the method for manganese in a kind of recyclable slag according to claim 1 is characterized in that: the granularity of useless ink powder is 5 ~ 10 microns, useless ink powder organic content 30 ~ 60%.
3. the method for manganese in a kind of recyclable slag according to claim 1, it is characterized in that: slag contains the carbon deposit composition of 10-20% massfraction, the manganese of 20-30% massfraction, 50-55% quality aluminum oxide, 5-10% massfraction magnesium oxide or ferric oxide.
4. the method for manganese in a kind of recyclable slag according to claim 1, it is characterized in that: the pH condition of extraction is between the pH 3-5.
5. the method for manganese in a kind of recyclable slag according to claim 1, it is characterized in that: the destructive distillation condition is 450 ℃, time 2 h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210499537.8A CN102965516B (en) | 2012-11-28 | 2012-11-28 | A kind of method of manganese in recyclable slag |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210499537.8A CN102965516B (en) | 2012-11-28 | 2012-11-28 | A kind of method of manganese in recyclable slag |
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| CN102965516A true CN102965516A (en) | 2013-03-13 |
| CN102965516B CN102965516B (en) | 2016-01-27 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1144717A (en) * | 1995-07-10 | 1997-03-12 | 吴杰 | Method for comprehensive utilization of waste catalyst in fluidized bed furancarbinol production |
| CN1332044A (en) * | 2001-07-20 | 2002-01-23 | 大连东泰产业废弃物处理有限公司 | Waste duplicator ink powder treating process |
| CN1557977A (en) * | 2004-01-20 | 2004-12-29 | 大连东泰产业废弃物处理有限公司 | Method of handling spent catalyst |
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2012
- 2012-11-28 CN CN201210499537.8A patent/CN102965516B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1144717A (en) * | 1995-07-10 | 1997-03-12 | 吴杰 | Method for comprehensive utilization of waste catalyst in fluidized bed furancarbinol production |
| CN1332044A (en) * | 2001-07-20 | 2002-01-23 | 大连东泰产业废弃物处理有限公司 | Waste duplicator ink powder treating process |
| CN1557977A (en) * | 2004-01-20 | 2004-12-29 | 大连东泰产业废弃物处理有限公司 | Method of handling spent catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 罗璐瑕等: "利用生物可降解螯合剂[S,S]－乙二胺二琥珀酸浸提沉积物中重金属的影响因素研究", 《农业环境科学学报》 * |
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