CN104988313A - Method for separating fluorine, chlorine and nitrogen compounds in aluminum ash through vacuum metallurgy method - Google Patents
Method for separating fluorine, chlorine and nitrogen compounds in aluminum ash through vacuum metallurgy method Download PDFInfo
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- CN104988313A CN104988313A CN201510105995.2A CN201510105995A CN104988313A CN 104988313 A CN104988313 A CN 104988313A CN 201510105995 A CN201510105995 A CN 201510105995A CN 104988313 A CN104988313 A CN 104988313A
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- chlorine
- fluorine
- raw material
- aluminium ash
- purity
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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
- Y02P10/20—Recycling
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- Processing Of Solid Wastes (AREA)
Abstract
In the prior art, the aluminum ash is the slag produced from the smelting furnace during the alloy casting process and the dust collecting powder after the treatment, and the slagging flux and the refining agent are added during the production, such that the fluorine content and the chlorine content in the aluminum ash are high. The technology of the present invention is mainly used for separating the scattered chlorides and the scattered fluorides by using the vacuum metallurgy principle, wherein five separated products are obtained in one time at the temperature of more than 600 DEG C in the vacuum environment under the condition of thermal insulation for 5 min and respectively are Al2O3 with a purity of 95-98 wt%, AlN with a purity of 86-95 wt%, KMgAlF3 with a purity of 92-96 wt% and NaCl with a purity of 98-99 wt%. The method of the present invention has characteristics of no pollution and short process, and is the effective method for treating the aluminum ash waste containing the fluorine, chlorine and nitrogen compounds through the vacuum distillation method.
Description
Technical field
The present invention relates to the method be separated by the moieties in industry or life solid waste, belong to environment, chemical industry and metallurgical engineering technical field.
Background technology
Aluminium ash is that the slag that in alloy casting process, smelting furnace produces the present invention relates to the method be separated by the moieties in industry or life solid waste, belongs to environment, chemical industry and metallurgical engineering technical field.
And process after dust collection powder, due to produce in add slagging agent and refining agent, make the fluorine in aluminium ash and content of Cl element higher.The method that past aluminium industry is disposed is taken out as water purification agent raw material after being mostly the separation as far as possible many by the metallic aluminium in aluminium ash.Present aluminium ash by
countrybe classified as danger wastes, how dispose and become aluminium industry urgent problem.
The main chemical compositions of aluminium ash:
24～53wt% Al、1.3～16 wt% Cl、1.6～7 wt% Na、0.5～5 wt% F、0.7～6.7 wt% Si、2.2～2.7 wt% Mg、 0.2～0.4 wt% Fe。
the thing phase composite of aluminium ash:
40.82-56.35 wt% Al
2o
3; 4.2-5.98 wt% Al; 2.36-10.85wt% NaAl
7o
11; 2.51-10.78wt% NaCl; 2.37-2.45wt% KMgAlF
6; 2.2-4.95wt% Al
3.21si
0.47; 3.42-4.97wt% AlN; 0.56-0.74wt% Fe
2tiO
4; 12.5-21.99wt% MgAl
2o
4; 5wt% other.
Summary of the invention
This technology adopts the vacuum method not producing pollution to be separated fluorine-containing chlorine waste material and to reclaim fluorochemical and muriate.Theoretical according to vacuum metallurgy, the mixture for A-B two kinds of components can be separated can by calculate separation factor under the same terms (
) judge:
for the activity quotient of component A, B,
for the pure vapour pressure of component A, B, can be obtained by data and testing data
with
numerical value, according to
size substantially can judge that can the mixture of A, B be separated by vacuum distillation method.When
time, the mixture of A, B is not separated by vacuum distillation method, only has and works as
time, just can be isolated.
Under atmospheric pressure environment, Al
2o
3, KMgAlF
3, separation factor between NaCl all close to 1, namely
, these components form mixture can not by volatile matter from, even if under electrolysis temperature, KMgAlF
3also can only volatilize on a small quantity with NaCl, this characteristic ensure that ice crystal stone-type ionogen can keep volatile quantity very little at electrolysis temperature, this physical property hardly by the impact of type of heating, even if adopt microwave, plasma, high-energy radiation also cannot less than at ambient pressure with 1000 DEG C complete and be separated.
Investigate KMgAlF
3certain explanation can be obtained, KMgAlF with the fusing point of NaCl and boiling point
3all ionic compound with NaCl, fusing point relatively, after temperature is more than 800 DEG C, KMgAlF
3formation molten salt system will be melted with NaCl, therefore produce " azeotropic " phenomenon, i.e. KMgAlF
3volatilize with while NaCl; And volatile quantity is less, do not reach and Al
2o
3the object be separated.And in the normal pressure thermal analyses process of aluminium ash, we find the KMgAlF taking the lead in melting
3with NaCl fused salt and Al
2o
3surface tension comparatively large, can Al be wrapped in
2o
3surface, further increases separating difficulty.
Under vacuum, Al
2o
3with KMgAlF
3, Al
2o
3with the separation factor of NaCl all up to 10
5above, KMgAlF
3very strong distillation phenomenon is shown with NaCl, from 420 DEG C, first KMgAlF
3distillation can form gaseous state rapidly, be separated after collection of sublimating and obtain KMgAlF
3powder, the rate of recovery is more than 98%; Then NaCl also can complete-the process of separated and collected that distils-sublimate, and the rate of recovery is more than 99%.Whole distillation-process of sublimating is very fast, can complete in 10 minutes, and the rate of recovery is also high especially, does not produce environment and pollutes.The required thermal source of heating can multiple choices as required, can adopt gas, resistance, electric arc, microwave, even sun power.
1. technical process is short: only just can complete whole sepn process by a vacuum oven in actually operating, raw material does not need pre-treatment substantially, and product does not also need secondary processing.
2. pollution-free: vacuum metallurgy is owned by France in physical sepn purification techniques, does not need other chemical feedstockss, produces without any waste.
3. product purity is high: most of product reaches industrial raw material rank, can recycle.
4. drop into low: early investment major part is for buying vacuum oven, and equipment inexpensively, floor space is little, operator are few, working strength is little and the work period is long.Enhance production capacities and only need to increase vacuum oven more, do not need to transform existing equipment.
embodiment:
Technical process: most of technical process is all integrated in vacuum oven, site technique is extremely simple.
Reference
fig. 1. the technical process of aluminium ash vacuum metallurgy method recycle utilization
embodiment 1:
The 4# aluminium ash that raw material adopts cloud aluminium to provide, each treatment capacity is 300kg, often kind of material adopts different process data to complete 4 experiments, processing parameter: top temperature 700 DEG C, top temperature soaking time: 3 minutes, to heat speed: 100 DEG C/min, vacuum tightness: 500Pa, pumpdown time before heating: 1 minute.Experimental data is as follows:
Material composition:
54.82wt% Al
2O
3; 5.98wt% Al; 7.60wt% NaAl
7O
11; 8.50wt% NaCl; 2.37wt% KMgAlF
6; 2.20wt% Al
3.21Si
0.47; 4.90wt% AlN; 0.56wt% Fe
2TiO
4; 18.9wt% MgAl
2O
4。
Separating material 1:95wt% Al
2o
3, 4wt%AlN, 1wt% other, output capacity 77%;
Separating material 2:5wt% Al
2o
3, 94wt%AlN, 1wt% other, output capacity 4%;
Separating material 3:4wt% NaCl, 96wt% KMgAlF
3, output capacity 3%;
Separating material 4:98wt% NaCl, 2wt% KMgAlF
3, output capacity 8%;
Separating material 5:97 wt% Al, 3wt% other, output capacity 7%.
Note: material content is that producer's data 2. separating material all adopts wt%, 3. output capacity=separating material quality/total raw material quality.
From the content analysis result of separating material 3, separating material 4 can find out fluorine contained by separating material and chlorine compound very micro-, oxide compound is also separated substantially with nitride, and separating obtained AlN may be used for the raw materials for production of refractory part/structural part.
Embodiment 2:
The 5# aluminium ash that raw material adopts cloud aluminium to provide, each treatment capacity is 400kg, often kind of material adopts different process data to complete 3 experiments, processing parameter: top temperature 570 DEG C, top temperature soaking time: 3 minutes, to heat speed: 100 DEG C/min, vacuum tightness: 700Pa, pumpdown time before heating: 50 seconds.Experimental data is as follows:
Material composition: 50.13wt% Al
2o
3, 5.90wt% Al, 8..60wt% NaAl
7o
11, 8.43wt% NaCl, 2.15wt% KMgAlF
6, 1.80wt% Al
3.21si
0.47, 4.01wt% AlN, 0.62wt% Fe
2tiO
4, 18.26wt% MgAl
2o
4.
Separating material 1:93wt% Al
2o
3, 7wt%AlN, 1wt% other, output capacity 82%;
Separating material 2:4wt% Al
2o
3, 96wt%AlN, output capacity 2%;
Separating material 3:5wt% NaCl, 95wt% KMgAlF
3, output capacity 5%;
Separating material 4:97wt% NaCl, 3wt% KMgAlF
3, output capacity 8%;
Separating material 5:97 wt% Al, 3wt% other, output capacity 3%.
Relative to example 1, under lesser temps and vacuum tightness, from analytical results can find out the fluorine of separating material 3,4 gained and chlorine compound very pure, from the output capacity analytical results of separating material 3,4, fluorine and chlorine compound are collected very complete, do not spill into the pollutent in air, but oxide compound and nitride separation not very thorough.
Industrialization cost of disposal is estimated:
According to common vacuum oven treatment capacity: within 10T/ days, calculate.Enhance production capacities and only need take advantage of in corresponding multiple.
Day output 10T, She Beitouzi $150 ten thousand, energy consumption 1500kWh, plant area 70m
2x8m(is high), workman's number 12 work day; Day output 100T, She Beitouzi $1500 ten thousand, energy consumption 1.5 ten thousand kWh, plant area 700m
2x8m(is high), workman's number 120 work day; Day output 10NT, She Beitouzi $150N ten thousand, energy consumption 1500N kWh, plant area 70N m
2x8m(is high), workman's number 12N work day.
Separated product purposes and price:
95-98wt% Al
2o
3can be used as electrolytic aluminum raw material, refractory materials, industrial ceramics raw material, Jia Ge $5/kg; 98-99 wt% NaCl can be used as industrial chemicals, Jia Ge $0.4 unit/kg; 86-95wt% AlN can be used as refractory part, structural part, price 70 yuan/kg; 92-96 wt% KMgAlF
3as slagging agent/industrial raw material, 5 yuan/kg, above price is very large by impurities affect.
accompanying drawing explanation:
fig. 1it is the technical process of aluminium ash vacuum metallurgy method recycle utilization
figure.
Claims (9)
1. adopt fluorine, chlorine and the nitrogen compound in the method separation aluminium ash of heating under vacuum distillation-condensation, completed by following steps:
A) aluminium ash is placed in encloses container, extracts the portion gas (step-down) in container out, in container, manufacture certain vacuum tightness;
B) aluminium ash is heated to certain temperature (intensification), causes the distillation/of fluorine, chlorine or nitrogen compound or volatilize in a large number;
C) raw material to be heated volatilization through several times, and wherein pollution substance content is up to standard;
D) sublimation gases or volatilization gas difference or mixed collection after condensation.
2. the method for claim 1, separate raw materials can be the aluminium ash produced in aluminum alloy melt casting process, also can be that other are fluorine-containing, the solid waste of chlorine, sulphur, arsenic, nitrogen and compound thereof.
3. the method for claim 1, the fluorochemical in raw material, muriate, sulfide, arsenide or nitride can volatilize in a large number in normal pressure or subnormal ambient.
4. the method for claim 3, raw material needs to control in certain temperature, and scope is from-100 DEG C to 3000 DEG C.
5. the method for claim 3, raw material needs to control under a certain pressure, and scope is from 0 to 10
6pa.
6. the method for claim 4, heating method can adopt resistance, electric arc, plasma, solid fuel, geseous fuel, geseous fuel, microwave, sun power, heat pump or several array mode.
7. the method for claim 1, condensation process comprises sublimates or liquefies, and condensing temperature scope is from 150 DEG C to 3000 DEG C.
8. the method for claim 1, condensation collection process comprises multiple temperature section, collects fluorine, chlorine, sulphur, arsenic, nitrogen and compound thereof respectively.
9. claim 1 a) step-down and b) temperature-rise period be not fixed routine, the step-down again that can first heat up, first step-down heat up again, limit intensification limit step-down, only heat up, only step-down or hocket.
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|---|---|---|---|
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| CN201510105995.2A CN104988313A (en) | 2015-03-12 | 2015-03-12 | Method for separating fluorine, chlorine and nitrogen compounds in aluminum ash through vacuum metallurgy method |
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Cited By (6)
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| CN107352567A (en) * | 2016-05-09 | 2017-11-17 | 青海大学 | Method for preparing high-purity aluminum oxide by vacuum reduction, distillation and purification |
| CN110144457A (en) * | 2019-05-15 | 2019-08-20 | 东北大学 | The method that AL-Si-Fe alloy is produced in the pretreatment carbon thermal reduction of aluminium ash |
| CN110482503A (en) * | 2019-09-11 | 2019-11-22 | 中国铝业股份有限公司 | A kind of method of Quadratic aluminum dust comprehensive utilization of resources |
| CN113233482A (en) * | 2021-07-01 | 2021-08-10 | 东北大学 | Secondary aluminum ash resource utilization method |
| CN115679116A (en) * | 2022-10-28 | 2023-02-03 | 甘肃东兴铝业有限公司 | Method for preparing intermediate alloy by extracting simple substance aluminum in aluminum ash through vacuum furnace |
| CN116177910A (en) * | 2022-09-27 | 2023-05-30 | 洛阳理工学院 | Novel suspension preheating calcination method for industrial secondary aluminum ash |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107352567A (en) * | 2016-05-09 | 2017-11-17 | 青海大学 | Method for preparing high-purity aluminum oxide by vacuum reduction, distillation and purification |
| CN107352567B (en) * | 2016-05-09 | 2019-10-18 | 青海大学 | Method for preparing high-purity aluminum oxide by vacuum reduction, distillation and purification |
| CN110144457A (en) * | 2019-05-15 | 2019-08-20 | 东北大学 | The method that AL-Si-Fe alloy is produced in the pretreatment carbon thermal reduction of aluminium ash |
| CN110482503A (en) * | 2019-09-11 | 2019-11-22 | 中国铝业股份有限公司 | A kind of method of Quadratic aluminum dust comprehensive utilization of resources |
| CN113233482A (en) * | 2021-07-01 | 2021-08-10 | 东北大学 | Secondary aluminum ash resource utilization method |
| CN116177910A (en) * | 2022-09-27 | 2023-05-30 | 洛阳理工学院 | Novel suspension preheating calcination method for industrial secondary aluminum ash |
| CN116177910B (en) * | 2022-09-27 | 2024-05-14 | 洛阳理工学院 | Industrial secondary aluminum ash suspension preheating calcination method |
| CN115679116A (en) * | 2022-10-28 | 2023-02-03 | 甘肃东兴铝业有限公司 | Method for preparing intermediate alloy by extracting simple substance aluminum in aluminum ash through vacuum furnace |
| CN115679116B (en) * | 2022-10-28 | 2024-02-20 | 甘肃东兴铝业有限公司 | Method for preparing intermediate alloy by extracting elemental aluminum from aluminum ash by utilizing vacuum furnace |
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