CN102965516B - A kind of method of manganese in recyclable slag - Google Patents
A kind of method of manganese in recyclable slag Download PDFInfo
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- CN102965516B CN102965516B CN201210499537.8A CN201210499537A CN102965516B CN 102965516 B CN102965516 B CN 102965516B CN 201210499537 A CN201210499537 A CN 201210499537A CN 102965516 B CN102965516 B CN 102965516B
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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
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Abstract
The invention provides the method for manganese in a kind of recyclable slag, by using tackiness agent that useless ink powder, slag are integrated together granulation, then carrying out destructive distillation, obtaining empyreumatic oil, provide pre-treatment for slag carries out precious metal regeneration.Produce empyreumatic oil in retort process to use as regenerated fuel, producing carbonization gas can act directly in gas retort as fuel, produces the raw material of destructive distillation slag as slag recover precious metals.Containing manganese waste material after the pre-treatment, drop in autoclave treater, with environmental friendliness, biodegradable N, N ˊ-ethylenediamine disuccinic acid for the agent that boils together, by the pH value modulation of extraction system, drop gets the manganese composition in waste.
Description
Technical field
The invention belongs to resource reclaim field of comprehensive utilization, be specifically related to a kind of method reclaiming manganese in slag.
Background technology
Manganese is the common metal that in the industrial and agricultural productions such as a kind of iron and steel, chemistry, special material, consumption is huge, but along with demand increase while, manganese can expected reserves continuous decrease.Meanwhile, containing the quantity of manganese thing also in continuous growth, therefore carry out reclaiming the pressure that can alleviate manganese metal reserves and decline to these things, also can reduce the huge Environmental costs that thing brings.It is a kind of common recovery method that chemistry drop is got, and the normal sequestrant used is ethylenediamine tetraacetic acid (EDTA) (EDTA) and sodium salt quasi-chelate compound thereof, and this sequestrant is strong to the sequestering power of metal ion, just has good drop to get efficiency.But this sequestrant is difficult to be degraded in physical environment, this quasi-chelate compound is used to bring Secondary Organic to pollute therefore for a long time, in a large number.
N, N'-ethylenediamine disuccinic acid be a kind of in physical environment degradable sequestrant, be applied to drop at present and fetched earth heavy metal ion in earth.
Summary of the invention
The present invention proposes a kind of method reclaiming discarded manganese metal, and useless ink powder, slag are integrated together granulation for using tackiness agent by technical scheme of the present invention, then carry out destructive distillation, obtain empyreumatic oil, provides pre-treatment for slag carries out precious metal regeneration.Produce empyreumatic oil in retort process to use as regenerated fuel, producing carbonization gas can act directly in gas retort as fuel, produces the raw material of destructive distillation slag as slag recover precious metals.Utilize eco-friendly N, N'-ethylenediamine disuccinic acid sequestrant, in autoclave treater, got containing the manganese composition in manganese metal in slag by chemical drop.
The present invention is realized by following technique means, and its concrete steps comprise:
1. take raw material: be (5 ~ 10) according to the mass ratio of slag, useless ink powder, tackiness agent and water: (0.1 ~ 3): (0.5 ~ 3): (0.5 ~ 1.5) takes raw material respectively;
2. granulation: after useless ink powder and slag are mixed in the ratio of step 1, slowly stir 10 ~ 30 minutes, then add tackiness agent and water, continue to puddle evenly, by raw material granulation, carry out destructive distillation subsequently;
3. destructive distillation product drops in autoclave treater, utilizes eco-friendly N, N'-ethylenediamine disuccinic acid sequestrant, by the pH value modulation of extraction system, is got containing the manganese composition in manganese metal in slag by chemical drop.
For in technical scheme mentioned above, need the adding of water appropriate, its method added water is that water repeatedly adds on a small quantity, until with hand hold hold raw material can be shaping, but to bond without raw material on hand.
For in technical scheme mentioned above, described destructive distillation condition is pyrolysis temperature 400 ~ 500 DEG C, and 2 ~ 3 hours time, more excellent destructive distillation condition is: 450 DEG C, time 2 h.
For 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 recovery slag provided by the present invention manganese metal method in use sequestrant to be: according to the mass ratio of 7 ~ 10:1, in autoclave treater, add environmental friendliness, biodegradable N, N'-ethylenediamine disuccinic acid.
In recovery slag provided by the present invention manganese metal method in, slag is low taste containing manganese mud, the manganese containing 1-5% massfraction.
In recovery slag provided by the present invention manganese metal method in, slag must through grinding pre-treatment step.
In recovery slag provided by the present invention manganese metal method in, operational condition feature is: with 25-80 DEG C, 200-600 rotating speed/minute condition under carry out the reclaimer operation of manganese.
In recovery slag provided by the present invention manganese metal method in, in autoclave treater N, N'-ethylenediamine disuccinic acid sequestrant extraction manganese pH value condition be pH7-8.
In recovery slag provided by the present invention manganese metal method in, the pH condition that manganese-N, N'-ethylenediamine disuccinic acid chelating systems discharges mn ion is between pH3-5.
In recovery slag provided by the present invention manganese metal method in, in autoclave treater, the mass ratio of slag and N, N'-ethylenediamine disuccinic acid is between 7 ~ 10:1.
In recovery slag provided by the present invention manganese metal method in, discharge manganese-N under pH3-5 condition, in the process of N'-ethylenediamine disuccinic acid chelating systems mn ion, complete N, the recovery of N'-ethylenediamine disuccinic acid sequestrant and circulation simultaneously.
Embodiment
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1
1. take raw material: 150kg slag (containing manganese 3%), 19kg give up ink powder, 14kg clay and 15kg water.
2. granulation: after useless ink powder and slag being mixed in the ratio of step 1, slowly stir 20 minutes, then add clay and water, continue to puddle evenly, enter granulator granulation, the diameter of pellet is between 5 ~ 7cm.Staff enters in stove and is put well by the raw material made, and ensures furnace bottom all to cover, and to prevent local dry burning from causing body of heater to damage, destructive distillation is carried out in upper cover sealing subsequently; Start heat temperature raising, after rising to 450 DEG C from room temperature, be incubated 2.5 hours, stop heating, treat that temperature is down to room temperature from 450 DEG C and is come out of the stove, forbid directly to lower the temperature with water.
3. after test in laboratory destructive distillation, raw material oil length is 3.46%, raw material after obtained destructive distillation;
4. raw material after 50kg destructive distillation is added in 100L autoclave treater, drop into 5kgN under pH7 condition, N'-ethylenediamine disuccinic acid, stir with 300 revs/min of speed, and be warming up to 60 DEG C, process after 1.0 hours, filter, after filtrate cooling, adding dilute sulphuric acid makes pH value be adjusted to 4, after static 0.5 hour, will separate out N, N'-ethylenediamine disuccinic acid reclaims.
Embodiment 2
1. take raw material: 150kg slag (containing manganese 4.2%), 19kg give up ink powder, 14kg clay and 15kg water.
2. granulation: after useless ink powder and slag being mixed in the ratio of step 1, slowly stir 20 minutes, then add clay and water, continue to puddle evenly, enter granulator granulation, the diameter of pellet is between 5 ~ 7cm.Staff enters in stove and is put well by the raw material made, and ensures furnace bottom all to cover, and to prevent local dry burning from causing body of heater to damage, destructive distillation is carried out in upper cover sealing subsequently; Start heat temperature raising, after rising to 450 DEG C from room temperature, be incubated 2.5 hours, stop heating, treat that temperature is down to room temperature from 450 DEG C and is come out of the stove, forbid directly to lower the temperature with water.
3. after test in laboratory destructive distillation, raw material oil length is 3.46%, raw material after obtained destructive distillation;
4. raw material after 45kg destructive distillation is added in 100L autoclave treater, drop into 5kgN under pH7 condition, N'-ethylenediamine disuccinic acid, stir with 300 revs/min of speed, and be warming up to 70 DEG C, process after 1.0 hours, filter, after filtrate cooling, adding dilute sulphuric acid makes pH value be adjusted to 4, after static 0.5 hour, will separate out N, N'-ethylenediamine disuccinic acid reclaims.
Embodiment 3
1. take raw material: 150kg slag (containing manganese 4.5%), 19kg give up ink powder, 14kg clay and 15kg water.
2. granulation: after useless ink powder and slag being mixed in the ratio of step 1, slowly stir 20 minutes, then add clay and water, continue to puddle evenly, enter granulator granulation, the diameter of pellet is between 5 ~ 7cm.Staff enters in stove and is put well by the raw material made, and ensures furnace bottom all to cover, and to prevent local dry burning from causing body of heater to damage, destructive distillation is carried out in upper cover sealing subsequently; Start heat temperature raising, after rising to 450 DEG C from room temperature, be incubated 2.5 hours, stop heating, treat that temperature is down to room temperature from 450 DEG C and is come out of the stove, forbid directly to lower the temperature with water.
3. after test in laboratory destructive distillation, raw material oil length is 3.46%, raw material after obtained destructive distillation;
4. raw material after 45kg destructive distillation is added in 100L autoclave treater, drop into 5kgN under pH7 condition, N'-ethylenediamine disuccinic acid, stir with 300 revs/min of speed, and be warming up to 65 DEG C, process after 1.0 hours, filter, after filtrate cooling, adding dilute sulphuric acid makes pH value be adjusted to 4, after static 0.5 hour, will separate out N, N'-ethylenediamine disuccinic acid reclaims.
Embodiment 4
1. take raw material: 150kg slag (containing manganese 3.5%), 19kg give up ink powder, 14kg clay and 15kg water.
2. granulation: after useless ink powder and slag being mixed in the ratio of step 1, slowly stir 20 minutes, then add clay and water, continue to puddle evenly, enter granulator granulation, the diameter of pellet is between 5 ~ 7cm.Staff enters in stove and is put well by the raw material made, and ensures furnace bottom all to cover, and to prevent local dry burning from causing body of heater to damage, destructive distillation is carried out in upper cover sealing subsequently; Start heat temperature raising, after rising to 450 DEG C from room temperature, be incubated 2.5 hours, stop heating, treat that temperature is down to room temperature from 450 DEG C and is come out of the stove, forbid directly to lower the temperature with water.
3. after test in laboratory destructive distillation, raw material oil length is 3.46%, raw material after obtained destructive distillation;
4. raw material after 35kg destructive distillation is added in 100L autoclave treater, drop into 5kgN under pH7 condition, N'-ethylenediamine disuccinic acid, stir with 500 revs/min of speed, and be warming up to 80 DEG C, process after 1.0 hours, filter, after filtrate cooling, adding dilute sulphuric acid makes pH value be adjusted to 4, after static 0.5 hour, will separate out N, N'-ethylenediamine disuccinic acid reclaims.
Embodiment 5
The slag used is: slag (containing manganese 2.5%);
Method described in step 1 ~ 2 of embodiment 1 is utilized to prepare raw material after destructive distillation;
Raw material after 50kg destructive distillation is added in 100L autoclave treater, drop into 5kgN under pH7 condition, N'-ethylenediamine disuccinic acid, stir with 500 revs/min of speed, and be warming up to 80 DEG C, process after 1.0 hours, filter, after filtrate cooling, adding dilute sulphuric acid makes pH value be adjusted to 4, after static 0.5 hour, will separate out N, N'-ethylenediamine disuccinic acid reclaims.
Embodiment 6
The slag used is: slag (containing manganese 3.5%);
Method described in step 1 ~ 2 of embodiment 1 is utilized to prepare raw material after destructive distillation;
Raw material after 50kg destructive distillation is added in 100L autoclave treater, drop into 5kgN under pH7 condition, N'-ethylenediamine disuccinic acid, stir with 300 revs/min of speed, and be warming up to 60 DEG C, process after 1.0 hours, filter, after filtrate cooling, adding dilute sulphuric acid makes pH value be adjusted to 4, after static 0.5 hour, will separate out N, N'-ethylenediamine disuccinic acid reclaims.
Embodiment 7
In above embodiment manganese-N, N'-ethylenediamine disuccinic acid chelating systems after acidifying discharge mn ion concentration analyzed by icp ms.
In the low taste slag of table 1, the drop of manganese gets efficiency
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Fe content (mass percent) in 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 overall extraction efficiency of manganese | 70 | 74 | 82 | 90 | 95 | 66 |
Claims (4)
1. reclaim a method for manganese metal in slag, it is characterized in that: comprise following operation steps:
1. raw material is taken: be (5 ~ 10) according to the mass ratio of slag, useless ink powder, tackiness agent and water: (0.1 ~ 3): (0.5 ~ 3): (0.5 ~ 1.5) takes raw material respectively;
2. granulation: after useless ink powder and slag are mixed in the ratio of step 1, slowly stir 10 ~ 30 minutes, then add tackiness agent and water, continue to puddle evenly, by raw material granulation, carry out destructive distillation subsequently; Destructive distillation condition is 400 ~ 500 DEG C, 2 ~ 3 hours;
3. N is added to destructive distillation product according to the mass ratio of 7 ~ 10:1, N'-ethylenediamine disuccinic acid; By the pH value modulation of extraction system, with 25-80 DEG C, 200-600 rotating speed/minute condition under carry out the recovery of manganese; The pH value condition of extraction is pH7-8.
2. a kind of method reclaiming manganese metal in 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. a kind of method reclaiming manganese metal in slag according to claim 1, is characterized in that: slag contains the carbon deposit composition of 10-20% massfraction, the manganese of 20-30% massfraction, 50-55% quality oxide aluminium, 5-10% massfraction magnesium oxide or ferric oxide.
4. a kind of method reclaiming manganese metal in slag according to claim 1, is characterized in that: destructive distillation condition is 450 DEG C, time 2 h.
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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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| CN201210499537.8A CN102965516B (en) | 2012-11-28 | 2012-11-28 | A kind of method of manganese in recyclable slag |
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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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- 2012-11-28 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 |
|---|
| 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;罗璐瑕等;《农业环境科学学报》;20081231;第27卷(第3期);932-936 * |
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