CN101264481A - Cr6+ furnace cinder containing gas reduction curing method - Google Patents
Cr6+ furnace cinder containing gas reduction curing method Download PDFInfo
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- CN101264481A CN101264481A CNA2008101055701A CN200810105570A CN101264481A CN 101264481 A CN101264481 A CN 101264481A CN A2008101055701 A CNA2008101055701 A CN A2008101055701A CN 200810105570 A CN200810105570 A CN 200810105570A CN 101264481 A CN101264481 A CN 101264481A
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- slag
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- coal gas
- cao
- cro
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Abstract
The invention relates to a reducing and curing method for slag gas with Cr<6+>, belonging to the technical field of pollution-free treating for metallurgical slag. The method comprises the following steps: gas with a pressure is insufflated into a slag pot with Cr<6+> liquid metallurgical slag by a spray gun; a certain amount of flux is added at the same time of the gas insufflating process for lowering the viscosity of the slag; on the gas agitating, the slag with Cr<6+> is completely contacted with the active ingredients in the gas; under high temperature condition, the Cr<6+> of the slag is generated gradual reduction reaction with the CO in the gas from chromium with high valence to chromium with low valence; finally, a stable spinel is formed, enabling the Cr<6+> to be completely cured into the slag, and reaching the purpose of rendering the slag harmless. The reducing and curing method for slag gas with Cr<6+> has the advantages of low disposal cost and suitability for the application in iron and steel enterprises.
Description
Technical field
The invention belongs to the nuisanceless processing technology field of metallurgical slag, relate to and contain Cr
6+The method that the slag gas reduction curing is handled.
Background technology
Containing the chromium special steel is the special steel kind of most species, will add the ferrochrome that can satisfy its performance requirement during production, and the chromium element overwhelming majority enters in the liquid steel, enters in the slag but also have on a small quantity.The chromium element that enters in the slag often forms water-soluble substances, can not get under the situation about effectively handling, seriously the polluted underground water resource.And the processing of present special slag mainly lays particular emphasis on the recovery with metallic iron of clearing up of free CaO.China mainly is based on hot application technology to the processing of special slag, by watering free CaO is digested, and reclaims metallic iron by operations such as pulverizing, fine grinding, magnetic separation then, at last by adding stabilizing agent or carrying out making roadbed material after the stable processing of timeliness.The leaching of water soluble chromium ion and the pollution problem of environment also do not caused enough attention in the slag.
Along with the fast development of Chinese national economy, will further increase the demand that contains the chromium special steel, containing chromium special steel slag also can be more and more serious to the pollution problem of environment, and art methods is not to Cr
6+Carry out effective innoxious curing and handle, therefore, invented this and contained Cr
6+The method that the slag gas reduction curing is handled fundamentally solves water-solubility Cr
6+To the pollution problem of environment, eliminate restriction to the special steel industry development, promote the healthy sustainable development of special steel industry.
Summary of the invention
The object of the present invention is to provide a kind of Cr of containing
6+The slag gas reduction curing method utilizes the method for gas reduction to realize containing Cr
6+The harmless treatment of slag.Its method is to utilize CO in the coal gas to make Cr in the slag
6+The gradual deoxidizing reaction is changed to low price chromium by high valence chrome, forms stable spinelle at last, eliminates Cr
6+Harm.
The coal gas that will have certain pressure is blown into to be equipped with by spray gun and contains Cr
6+In the slag ladle of liquid metallurgical slag, in the winding-up course of gas, add a certain amount of flux simultaneously, contain Cr to reduce slag viscosity
6+Slag fully contacts with active ingredient CO in the coal gas under coal gas stirs, under hot conditions, and the Cr in the slag
6+With CO in the coal gas gradual deoxidizing reaction of high valence chrome to low price chromium taking place, form stable spinelle at last, makes Cr
6+Be solidificated in the slag fully.
Spray gun is blown into to be equipped with and contains Cr
6+The CO volume content is 16%～30% in the coal gas in the slag ladle of liquid metallurgical slag, and gas pressure is 0.2MPa～0.6MPa.
Cr
6+The temperature of liquid metallurgical slag is 1400～1700 ℃.
Flux of the present invention is fluorite, and addition is 0.5～10%.
Cr of the present invention
6+Slag composition comprises: CaO, SiO
2, MgO, Al
2O
3, Fe
2O
3Deng.
Under the high-temperature condition, high valence chrome is reverted to chromium at a low price, the reduction potential of requirement is very low, CO/CO in the blast furnace gas
2Can satisfy the thermodynamics requirement fully.Make the Cr in the slag
6+With CO in the coal gas gradual deoxidizing reaction of high valence chrome to low price chromium taking place, form stable spinelle at last, the leaching phenomenon of chromium ion no longer takes place, thereby solved the problem of contaminant water.In the slag ladle in the liquid slag contingent chemical reaction as follows:
Na
2OCrO
3Or CaOCrO
3+ CO → CaOCr
2O
3+ CO
2
CaO·CrO
3+CO+MgO→MgO·Cr
2O
3+CaO+CO
2
CaO·CrO
3+CO+FeO→FeO·Cr
2O
3+CaO+CO
2
3CaO·CrO
3+CO→CaO+CrO·Cr
2O
3+CO
2
MgOCr
2O
3, FeOCr
2O
3, CrOC
r2O
3Deng the mineral form all be spinelle, highly stable at occurring in nature, chromite ore exists with this form, can not take place that chromium ion leaches or 3 valency chromium are oxidized to the phenomenon of 6 valency chromium.Such slag is to stack or as construction material contaminant water resource more not.
Coal powder injection gas process is carried out under a relative airtight condition, and reaction gas enters in the deduster, is used for other purposes after dedusting.Because chromated oxide content is lower in the slag, the tolerance of consumption is very little, and coal gas chemistry heat drop is low seldom.And owing to carry out fully heat exchange with liquid slag, physics heat increases considerably, can be used as preheating heating furnace fuel, it is partially recycled that heat of slags has been obtained.Slag after gas reduction is handled can adopt present existing conventional treatment method to be for further processing, and is broken, mill, reclaim metal etc., makes roadbed material then.
The CO content requirement is not high in the reducing gas required for the present invention, and too high CO content is crossed reduction with chromium ion on the contrary easily, and according to our research, the coal gas CO content that the present invention sprays into is that 16%-30% is more suitable.
The present invention needs coal gas is sprayed in people's reactor, and therefore to the requirement to some extent of coal gas jetting pressure, gas pressure is low excessively, and it is not enough that coal gas stirs kinetic energy, and the chromium ion reduction is inhomogeneous, and jetting pressure is excessive, and kinetic energy consumption is big.According to research, the selected pressure of the present invention is 0.2MPa-0.6MPa.
The present invention is to the also requirement to some extent of fusing point of slag, and temperature is low excessively, and slag viscosity is excessive, and temperature is too high, and the furnace lining etch is serious, and therefore, slag temperature of the present invention is 1400-1700 ℃.
According to above-mentioned purpose and method principle, concrete technical scheme of the present invention is:
After the present invention's processing, basically with Cr in the slag
6+Transfer stable spinelle phase to, thereby solved the safe handling problem of containing chromium slag, the present invention handles simply, the coal gas source is wide, and processing cost is low.
Description of drawings
Fig. 1 is experiment process figure of the present invention.Wherein, valve 1, add press 2,, on the valve 3, gas holder 4, valve 5, coal gas spray gun 6, steel slag tank 7 valves 8, deduster 9.
The specific embodiment
Implementation process as shown in Figure 1, the coal gas that contains CO enters through valve 1 and adds press 2 and pressurize, coal gas after the pressurization enters high pressure gas storage tank 4 through valve 3, coal gas with certain pressure is connected on the coal gas spray gun 6 through valve 5, liquid special steel slag ladle 7 will be housed then move on the coal gas winding-up station, and the coal gas spray gun is inserted in the liquid slag, jet and stir, in coal powder injection gas process, add a certain amount of flux,, make reaction more abundant to reduce slag viscosity.Cr in coal gas and the slag liquid
6+After the reaction, chemical energy has reduction slightly, but physics heat enlarges markedly, and enters deduster 9 through valve 8, and the clean gas after the dedusting can use or return gaspipe network for heating furnace, and dedusting ash is regularly discharged from deduster.
Main device is to add press, gas tank and slag ladle.Use the composition of containing chromium slag to see Table 1, with containing chromium slag heat release slag ladle, be warming up to temperature required, the CO coal gas that contains with certain pressure is blown into slag ladle by spray gun and reduces again, behind the reduction 30min, slag is cooled off, and carry out leaching test, operating condition of being taked in the test and Cr according to national standard HJ/T301-2007
6+Leaching the results are shown in Table 2.
As seen from Table 2, under the condition that the present invention gave, the containing chromium slag after the reduction can reach the prevention and cure of pollution standard of roadbed material.
As seen from Table 2, slag temperature is high more, and required coal gas ejection pressure can reduce, but slag temperature should not be low excessively, otherwise slag viscosity is excessive; And slag temperature is too high, and the furnace lining etch is serious, and therefore, slag temperature of the present invention is 1400-1700 ℃.
By adding fluorite, can reduce slag viscosity, therefore can reduce the slag temperature when smelting.Show that by test the addition of fluorite is good with 0.5%～10%.
The present invention is less demanding to CO content, and the CO content of 16%-30% just can satisfy chromic reduction.For iron and steel enterprise, blast furnace gas just can be used as source of the gas.Therefore visible running cost of the present invention is lower.
Use the chemical composition of containing chromium slag in table 1 test
| Composition | SiO 2 | Al 2O 3 | CaO | MgO | Fe 2O 3 | Cr 2O 3 | Cr VI |
| Mass content/% | 23.6 | 9.7 | 42.5 | 10.4 | 8.2 | 4.5 | 1.1 |
Table 2 experimental condition and result
Claims (4)
1, a kind of Cr that contains
6+The method of the gas reduction harmless treatment of metallurgical slag is characterized in that, technology is: the coal gas that will have certain pressure is blown into to be equipped with by spray gun and contains Cr
6+In the slag ladle of liquid metallurgical slag, in the winding-up course of gas, add a certain amount of flux simultaneously, contain Cr to reduce slag viscosity
6+Slag fully contacts with active ingredient CO in the coal gas under coal gas stirs, under hot conditions, and the Cr in the slag
6+With CO in the coal gas gradual deoxidizing reaction of high valence chrome to low price chromium taking place, form stable spinelle at last, makes Cr
6+Be solidificated in the slag fully; The gradual deoxidizing reaction equation is as follows:
Na
2OCrO
3Or CaOCrO
3+ CO → CaOCr
2O
3+ CO
2,
CaO·CrO
3+CO+MgO→MgO·Cr
2O
3+CaO+CO
2，
CaO·CrO
3+CO+FeO→FeO·Cr
2O
3+CaO+CO
2，
3CaO·CrO
3+CO→CaO+CrO·Cr
2O
3+CO
2。
According to the described processing method of claim 1, it is characterized in that 2, spray gun is blown into to be equipped with and contains Cr
6+The CO volume content is 16%～30% in the coal gas in the slag ladle of liquid metallurgical slag, and gas pressure is 0.2MPa～0.6MPa.
3, according to the described processing method of claim 1, it is characterized in that Cr
6+The temperature of liquid metallurgical slag is 1400～1700 ℃.
According to the described processing method of claim 1, it is characterized in that 4, described flux is fluorite, addition is 0.5%～10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101055701A CN101264481A (en) | 2008-04-30 | 2008-04-30 | Cr6+ furnace cinder containing gas reduction curing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101055701A CN101264481A (en) | 2008-04-30 | 2008-04-30 | Cr6+ furnace cinder containing gas reduction curing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101264481A true CN101264481A (en) | 2008-09-17 |
Family
ID=39987302
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|---|---|---|---|
| CNA2008101055701A Pending CN101264481A (en) | 2008-04-30 | 2008-04-30 | Cr6+ furnace cinder containing gas reduction curing method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105039616A (en) * | 2015-09-08 | 2015-11-11 | 华北理工大学 | Coprocessing method for AOD stainless steel residues stored in piles and LF refining residues |
| CN105039615A (en) * | 2015-09-08 | 2015-11-11 | 华北理工大学 | Processing method for stockpiled AOD stainless steel slag |
| CN105200172A (en) * | 2015-09-08 | 2015-12-30 | 华北理工大学 | Synergistic processing method of stacked EAF stainless steel slag and LF refining slag |
| CN107243500A (en) * | 2017-06-28 | 2017-10-13 | 河南科技大学 | A kind of high-temp. vortex melting formula chromium residue detoxifying device and its detoxification |
| CN109811094A (en) * | 2019-03-05 | 2019-05-28 | 许晖 | A kind of device and method using blowing process pretreatment steel slag |
-
2008
- 2008-04-30 CN CNA2008101055701A patent/CN101264481A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105039616A (en) * | 2015-09-08 | 2015-11-11 | 华北理工大学 | Coprocessing method for AOD stainless steel residues stored in piles and LF refining residues |
| CN105039615A (en) * | 2015-09-08 | 2015-11-11 | 华北理工大学 | Processing method for stockpiled AOD stainless steel slag |
| CN105200172A (en) * | 2015-09-08 | 2015-12-30 | 华北理工大学 | Synergistic processing method of stacked EAF stainless steel slag and LF refining slag |
| CN105039615B (en) * | 2015-09-08 | 2017-09-01 | 华北理工大学 | Store up the processing method of AOD stainless steel slags |
| CN107243500A (en) * | 2017-06-28 | 2017-10-13 | 河南科技大学 | A kind of high-temp. vortex melting formula chromium residue detoxifying device and its detoxification |
| CN107243500B (en) * | 2017-06-28 | 2019-05-21 | 河南科技大学 | A kind of high-temp. vortex melting formula chromium residue detoxifying device and its detoxification |
| CN109811094A (en) * | 2019-03-05 | 2019-05-28 | 许晖 | A kind of device and method using blowing process pretreatment steel slag |
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Open date: 20080917 |