CN107082429A - A kind of method that utilization Dust of Iron And Steel Works prepares cementite - Google Patents
A kind of method that utilization Dust of Iron And Steel Works prepares cementite Download PDFInfo
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- CN107082429A CN107082429A CN201710297219.6A CN201710297219A CN107082429A CN 107082429 A CN107082429 A CN 107082429A CN 201710297219 A CN201710297219 A CN 201710297219A CN 107082429 A CN107082429 A CN 107082429A
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The present invention discloses a kind of method that utilization Dust of Iron And Steel Works prepares cementite, including：Dust of Iron And Steel Works is well mixed with binding agent, and pelletizing material is made；The pelletizing material is made into green-ball and is calcined after drying, carburizing pelletizing is obtained；By the carburizing pelletizing in CO+CO2+H2Or reduced in bituminous coal gas, again in CO+CO after reduction2+H2Or CH4+H2Carry out cooling down in carburizing, inert atmosphere in gas, obtain pelletizing after carburizing；Pelletizing after the carburizing is carried out carrying out wet magnetic separation after wet ball-milling, ball milling, cementite is dried to obtain.The method that the present invention is provided prepares the electric furnace raw material that added value is high, not oxidizable, objectionable impurities content is low and grade is higher.
Description
Technical field
The present invention relates to a kind of field of metallurgy, more particularly to a kind of method that utilization Dust of Iron And Steel Works prepares cementite.
Background technology
China is as big steel country, and the crude steel yield of 2016 reaches 8.08 hundred million tons, and steel manufacture process can be produced greatly
The dust of amount, such as sintering dust separation ash, blast furnace dedusting ash, converter mud, electric furnace and converter dust-removing ash.General iron and steel enterprise dust
Yield be output of steel 8-15%, the Dust Capacity that Iron and Steel Enterprises in China is produced every year between ten thousand tons of 6400-12100, this
A little dust such as control it is bad will pollute environment, and dust contains substantial amounts of ferro element, and the very big of resource will be caused using bad
Waste.Therefore, if efficiently utilizing these dust, substantial amounts of iron resource can be provided for steel plant, moreover it is possible to reduce the environment of steel mill
Pollution, the sustainable development to China's steel industry is significant.
The method of processing Dust of Iron And Steel Works mainly includes following methods both at home and abroad at present：1. the processing side of steel mill of China typically
Method is that these dust are returned directly to sintering or pelletizing process participation dispensing, is prepared into by sintering process or pelletizing process
The sintering deposit or pellet of blast furnace；2. direct-reduction process and direct-reduction-magnetic method processing dust be using coal more than
The ferriferous oxide in dust is reduced into metallic iron at a temperature of 1000 DEG C, the non-ferrous metal such as lead, zinc is de- in reduction process volatilization
Remove, the too low reducting pellet of Iron grade can again by ball milling, magnetic separation process obtain more high-grade reduced iron powder be used for electric furnace or
Person's pneumatic steelmaking；3. wet-treating dust is the salt for the valuable element in dust being changed into chemical agent solubility, logical
Cross addition medicament and adjust pH value and separate valuable element in solution.
But sintering process conventional at present and pelletizing method processing dust, because the Iron grade of dust is low, obtained sintering deposit
Iron grade with pellet is relatively low, and sintering process and pelletizing method can not remove the non-ferrous metals such as the lead and zinc in dust, this
A little non-ferrous metals, which enter blast furnace, can cause furnace nodulation, corrosion furnace lining etc., and more low-grade sintering deposit or pellet can also make height
Stove smelts energy consumption increase.Direct-reduction process and direct-reduction-magnetic method processing dust, obtained reduced iron powder activity are high, easy
Oxidation, particularly wet ball grinding process is more oxidizable.Wet-treating dust, processing procedure leaching process treating capacity is big, in waste water
The environmental pollutions such as the acid, the alkali that contain are also more serious, and after wet-treating, ferro element therein is difficult to be utilized.
The content of the invention
In view of this, the present invention provides a kind of method that can prepare cementite for raw material using Dust of Iron And Steel Works, prepares
Go out the electric furnace raw material (cementite) that added value is high, not oxidizable, objectionable impurities content is low and grade is higher.
To solve above technical problem, the technical scheme is that utilizing Dust of Iron And Steel Works preparation cementite using a kind of
Method, including：
Dust of Iron And Steel Works is well mixed with binding agent, and pelletizing material is made；
The pelletizing material is made into green-ball and is calcined after drying, reduction pelletizing is obtained；
By the reduction pelletizing in CO+CO2+H2Or reduced in bituminous coal gas, again in CO+CO after reduction2+H2Or CH4+H2Gas
Carry out cooling down in carburizing, inert atmosphere in body, obtain pelletizing after carburizing；
Pelletizing after the carburizing is carried out carrying out wet magnetic separation after wet ball-milling, ball milling, cementite is dried to obtain.
It is preferred that, pelletizing material is made and specifically includes：
Added water when the Dust of Iron And Steel Works is mixed with binding agent, be well mixed, obtain pelletizing material.
It is preferred that, described Dust of Iron And Steel Works is that the relatively low described Dust of Iron And Steel Works of Iron grade is sintering dust separation ash, height
One or more in stove dedusting ash, blast furnace gas mud, converter mud, converter dust-removing ash, electric stove dust ash；
It is preferred that, described binding agent is bentonite or calcium hydroxide；
It is preferred that, the pelletizing material is made into green-ball and is calcined specially after drying：Dry bulb is in oxidisability, neutrality or goes back
In originality atmosphere, in being calcined 5-30min at 900-1100 DEG C.
It is preferred that, the temperature of the reduction is 900-1100 DEG C, the recovery time is 20-100min.
It is preferred that, the gas CO+CO of the reduction2+H2Middle CO：CO2：H2Volume ratio is (0~100)：(0~30)：(0~
100)；
Or the colliery of described reduction bituminous coal is than 0~3.0.
It is preferred that, the temperature of the carburizing is 550-850 DEG C, carburizing time is 60-300min.
The gas CO+CO that carburizing is used2+H2Middle CO：CO2：H2Volume ratio is (50~100)：(0~30)：(0~20)；
Or the CH4+H2Middle CH4：H2Volume ratio is (10~100)：(0~90).
It is preferred that, described to carry out wet ball-milling by pelletizing after the carburizing, wet magnetic separation is carried out after ball milling is specially：
Pelletizing after carburizing is crushed to granularity less than wet ball-milling is carried out after 1mm, and wet type magnetic is then carried out in magnetic separator
Choosing；
The magnetic field intensity of the magnetic separation process is 50~200mT.
The bright a kind of method that cementite is prepared there is provided utilization Dust of Iron And Steel Works of this law, wherein traditional sintering process and pelletizing
Method can only prepare the relatively low blast furnace burden of Iron grade, and non-ferrous metal can not also be removed.And carbonization prepared by the present invention
Iron can directly prepare electric furnace raw material, and non-ferrous metal also can be removed effectively, and whole technological process is short (reduces blast furnace
Ironmaking and the preparation process of blast furnace burden), the carbonization Iron grade prepared is high, is a kind of electric furnace steel making raw material of high-quality,
The carbon contained in cementite can also reduce the power consumption of EAF Steelmaking Process.Compared with direct-reduction and direct-reduction-magnetic method,
Product (cementite) normal temperature chemical property prepared by the present invention is more stable, not oxidizable, and cementite is that one kind compares reduced iron powder
The higher electric furnace steel making raw material of more high-quality, added value.Compared with wet-treating steel mill dust, the present invention do not produce containing alkali and
The waste water of the medicaments such as acid, therefore water pollution will not be produced.
Embodiment
In order that those skilled in the art more fully understands technical scheme, with reference to embodiment
The present invention is described in further detail.
It should be noted that the grade mentioned in the present invention is explained as follows：The weight percent of valuable constituent contains in product
Amount.
In order to obtain high-quality cementite, the invention provides the side that a kind of utilization Dust of Iron And Steel Works prepares cementite
Method, including：
Dust of Iron And Steel Works is well mixed with binding agent, and pelletizing material is made；
The pelletizing material is made into green-ball and is calcined after drying, carburizing pelletizing is obtained；
By the carburizing pelletizing in CO+CO2+H2Or reduced in bituminous coal gas, again in CO+CO after reduction2+H2Or CH4+H2Gas
Carry out cooling down in carburizing, inert atmosphere in body, obtain pelletizing after carburizing；
Pelletizing after the carburizing is carried out carrying out wet magnetic separation after wet ball-milling, ball milling, cementite is dried to obtain.
First have to mix dust binding agent preparing ball material processed, pelletizing material is made and specifically includes：In the Dust of Iron And Steel Works
Added water when being mixed with binding agent, be well mixed, obtain pelletizing material.Add water amount for the easy balling-up of pelletizing material balling process just
It is good, it is impossible to plus excessive water.It is preferred that, described Dust of Iron And Steel Works is that the relatively low described Dust of Iron And Steel Works of Iron grade is sintering
One or more in dedusting ash, blast furnace dedusting ash, blast furnace gas mud, converter mud, converter dust-removing ash, electric stove dust ash.Institute
The binding agent stated is bentonite or calcium hydroxide, and preferred described consumption of binder accounts for the 0-3% of dust gross weight, more elected as
1%~3%, most preferably 1.5%~3%；According to the present invention, the green-ball diameter of the preparation is preferably 8-16mm.
The dry bulb is calcined after pelletizing, is specially：Dry bulb in oxidisability, neutral or reducing atmosphere, in
5-30min is calcined at 900-1100 DEG C.After the completion of roasting, reduced, the temperature of the reduction is 900-1100 DEG C, reduction when
Between be 20-100min, progress carburizing after reduce, the temperature of the carburizing is 550-850 DEG C, carburizing time is 60-300min.
According to the present invention, in order to preferably be reduced, the gas CO+CO of the reduction2+H2Middle CO：CO2：H2Volume ratio
For (0~100)：(0~30)：(0~100)；It is furthermore preferred that the volume ratio of the reducing gas is
(20~90)：(10~25)：(20~80), be most preferably (40~60)：(10~20)：(20~30).
Or the colliery of described reduction bituminous coal is than 0~3.0, more preferably 1~3, most preferably 1.5~2.
In order to preferably carry out carburizing, the gas CO+CO that carburizing is used2+H2Middle CO：CO2：H2Volume ratio for (50~
100)：(0~30)：(0~20), more preferably, (50~90)：(10~25)：(20~80), be most preferably (50~65)：(10
~20)：(20~30)
Or the CH4+H2Middle CH4：H2Volume ratio is (10~100)：(0~90), more preferably (10~90)：(10~
80), it is most preferably (40~60)：(40~60).
In order to separate the iron standby purer cementite of carbonization, pelletizing after the carburizing is preferably subjected to wet ball-milling,
Wet magnetic separation is carried out after ball milling is specially：Pelletizing after carburizing is crushed to granularity less than wet ball-milling is carried out after 1mm, then in magnetic
Select and wet magnetic separation is carried out in machine；The magnetic field intensity of the magnetic separation process is 50~200mT.
It is the specific embodiment of the invention below：
Embodiment 1：The content of the Iron grade 37.29% of sintering electro-precipitating dust, lead and zinc is respectively 0.58% and 0.49%,
The content that its granularity is less than 0.075mm grades is 83.58%.2% bentonitic dedusting ash will be with the addition of in disc balling machine
A diameter of 8-16mm green-ball is prepared into, Balling time is 10min, and shatter strength of green pellet is 3.1 times/0.5m, after green-ball is dried
20min is calcined at 950 DEG C and in air, then at a temperature of 1000 DEG C and CO：CO2：H2For 60：20：In 20 mixed gas
40min is reduced, then carburizing 150min in this gas and at a temperature of 650 DEG C, hot-bulb is cooled down in nitrogen.Pelletizing is broken after cooling
It is broken to be less than 1mm to granularity.Under conditions of pulp density is 50%, ball milling 4min obtains ball milling fineness in conical ball mill
95% is less than 200 mesh, then ore pulp magnetic separation in magnetic field intensity is 150mT magnetic separator, can obtain carbonization Iron grade and be
84.6%, the cementite of the rate of recovery 79% of iron, the removal efficiency of lead and zinc is respectively 97.8% and 92.01%.
Embodiment 2：The Iron grade 36.86% of blast furnace cloth bag ash, the content of lead and zinc is respectively 4.85% and 0.61%, its
The content that granularity is less than 0.075mm grades is 78.15%.2.7% bentonitic compound will be with the addition of in disc balling machine
A diameter of 8-16mm green-ball is prepared into, Balling time is 10min, and shatter strength of green pellet is 3.0 times/0.5m, after green-ball is dried
At a temperature of at 1050 DEG C and colliery ratio is reduces 60min in 2.5 bituminous coal, gained goes back protocorm again in CH4：H2For 90:10
Mixed gas in and 750 DEG C at a temperature of carburizing 80min, hot-bulb cools down in nitrogen.To be crushed to granularity small for pelletizing after cooling
In 1mm.Under conditions of pulp density is 50%, ball milling 8min obtains ball milling fineness 98% less than 200 in conical ball mill
Mesh, then ore pulp magnetic separation in magnetic field intensity is 120mT magnetic separator, it is 87.2%, the recovery of iron that can obtain carbonization Iron grade
The removal efficiency of the cementite of rate 88%, lead and zinc is respectively 99.1% and 94.01%.
Embodiment 3：The Iron grade of electric stove dust ash is 47.63%, and the content of zinc is 2.35%, and its granularity is less than
The content of 0.075mm grades is 92.53%.1.5% bentonitic dedusting ash will be with the addition of to be prepared into disc balling machine directly
Footpath is 8-16mm green-ball, and Balling time is 10min, and shatter strength of green pellet is 3.3 times/0.5m, after green-ball drying at 900 DEG C
With 20min is calcined in air, then again at a temperature of 1000 DEG C and CO：H2For 60：50min is reduced in 40 mixed gas,
Again in CO：CO2：H2For 60：20：Carburizing 150min in 20 mixed gas and at a temperature of 600 DEG C, hot-bulb cools down in nitrogen.It is cold
But pelletizing is crushed to granularity less than 1mm after.Under conditions of pulp density is 50%, ball milling 6min is obtained in conical ball mill
Ball milling fineness 92% is less than 200 mesh, and then ore pulp magnetic separation in magnetic field intensity is 160mT magnetic separator, can obtain cementite product
Position is 86.2%, the cementite of the rate of recovery 86% of iron, and the removal efficiency of zinc is 91.2%.
Embodiment 4：The Iron grade of converter dust-removing ash is 56.38%, and the content of zinc is 0.56%, and its granularity is less than
The content of 0.075mm grades is 85.78%.3.0% bentonitic compound will be with the addition of to be prepared into disc balling machine directly
Footpath is 8-16mm green-ball, and Balling time is 10min, and shatter strength of green pellet is 3.1 times/0.5m, after green-ball drying at 950 DEG C
Be calcined 15min in air, roasting ball is 2.5 in colliery ratio and reduction temperature is to reduce 60min under conditions of 1075 DEG C, then
Again at a temperature of 650 DEG C and CO：CO2：H2For 65：15：Carburizing 150min in 20 mixed gas, hot-bulb is cooled down in nitrogen.
Pelletizing is crushed to granularity less than 1mm after cooling.Under conditions of pulp density is 50%, ball milling 4min is obtained in conical ball mill
It is less than 200 mesh to ball milling fineness 90%, then ore pulp magnetic separation in magnetic field intensity is 150mT magnetic separator, can obtain cementite
Grade is 86.8%, the cementite of the rate of recovery 83.2% of iron, and the removal efficiency of zinc is 95.2%.
The bright a kind of method that cementite is prepared there is provided utilization Dust of Iron And Steel Works of this law, wherein traditional sintering process and pelletizing
Method can only prepare the relatively low blast furnace burden of Iron grade, and non-ferrous metal can not also be removed.And carbonization prepared by the present invention
Iron can directly prepare electric furnace raw material, and non-ferrous metal also can be removed effectively, and whole technological process is short (reduces blast furnace
Ironmaking and the preparation process of blast furnace burden), the carbonization Iron grade prepared is high, is a kind of electric furnace steel making raw material of high-quality,
The carbon contained in cementite can also reduce the power consumption of EAF Steelmaking Process.Compared with direct-reduction and direct-reduction-magnetic method,
Product (cementite) normal temperature chemical property prepared by the present invention is more stable, not oxidizable, and cementite is that one kind compares reduced iron powder
The higher electric furnace steel making raw material of more high-quality, added value.Compared with wet-treating steel mill dust, the present invention do not produce containing alkali and
The waste water of the medicaments such as acid, therefore water pollution will not be produced.
It the above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
The limitation of the present invention, protection scope of the present invention should be defined by claim limited range.For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, some improvements and modifications can also be made, these change
Enter and retouch and also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of method that utilization Dust of Iron And Steel Works prepares cementite, it is characterised in that including：
Dust of Iron And Steel Works is well mixed with binding agent, and pelletizing material is made；
The pelletizing material is made into green-ball and is calcined after drying, carburizing pelletizing is obtained；
By the carburizing pelletizing in CO+CO2+H2Or reduced in bituminous coal gas, again in CO+CO after reduction2+H2Or CH4+H2In gas
Cooled down in carburizing, inert atmosphere, obtain pelletizing after carburizing；
Pelletizing after the carburizing is carried out carrying out wet magnetic separation after wet ball-milling, ball milling, cementite is dried to obtain.
2. according to the method described in claim 1, it is characterised in that pelletizing material is made and specifically includes：
Added water when the Dust of Iron And Steel Works is mixed with binding agent, be well mixed, obtain pelletizing material.
3. method according to claim 1 or 2, it is characterised in that described Dust of Iron And Steel Works is sintering dust separation ash, blast furnace
One or more in dedusting ash, blast furnace gas mud, converter mud, converter dust-removing ash, electric stove dust ash.
4. method according to claim 1 or 2, it is characterised in that described binding agent is bentonite or calcium hydroxide.
5. according to the method described in claim 1, it is characterised in that the pelletizing material is made into green-ball and roasting tool is carried out after drying
Body is：Dry bulb is in oxidisability, neutral or reducing atmosphere, in being calcined 5-30min at 900-1100 DEG C.
6. according to the method described in claim 1, it is characterised in that the temperature of the reduction is 900-1100 DEG C, recovery time
For 20-100min.
7. method according to claim 8, it is characterised in that the gas CO+CO of the reduction2+H2Middle CO：CO2：H2Volume
Than for (0~100)：(0~30)：(0~100)；
Or the colliery of the reduction bituminous coal is than 0~3.0.
8. according to the method described in claim 1, it is characterised in that the temperature of the carburizing is 550-850 DEG C, carburizing time is
60-300min。
9. method according to claim 8, it is characterised in that the gas CO+CO that the carburizing is used2+H2Middle CO：CO2：H2
Volume ratio is (50~100)：(0~30)：(0~20)；
Or the CH4+H2Middle CH4：H2Volume ratio is (10~100)：(0~90).
10. according to the method described in claim 1, it is characterised in that described that pelletizing after the carburizing is subjected to wet ball-milling, ball
Wet magnetic separation is carried out after mill is specially：
Pelletizing after carburizing is crushed to granularity less than wet ball-milling is carried out after 1mm, and wet magnetic separation is then carried out in magnetic separator；
The magnetic field intensity of the magnetic separation process is 50~200mT.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108217654A (en) * | 2018-01-31 | 2018-06-29 | 杨汉玉 | A kind of preparation method of catalyst for preparing hydrogen and catalyzing manufacturing of hydrogen method |
| CN108677022A (en) * | 2018-06-19 | 2018-10-19 | 苏州大学 | A kind of method that sintering dust separation ash prepares removing harmful element during cementite |
| CN109052402A (en) * | 2018-08-16 | 2018-12-21 | 陕西科技大学 | A kind of method of the continuous preparation pure phase carbonization iron nano-particle of green |
| CN109652604A (en) * | 2019-01-30 | 2019-04-19 | 上海大学 | A method of cementite is prepared using ferriferous oxide two-step method |
| CN110396591A (en) * | 2019-08-27 | 2019-11-01 | 苏州大学 | Iron ore method for carburizing |
| CN111826528A (en) * | 2020-07-31 | 2020-10-27 | 苏州大学 | Method for recycling coke in process of preparing iron carbide by using blast furnace dust |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108217654A (en) * | 2018-01-31 | 2018-06-29 | 杨汉玉 | A kind of preparation method of catalyst for preparing hydrogen and catalyzing manufacturing of hydrogen method |
| CN108677022A (en) * | 2018-06-19 | 2018-10-19 | 苏州大学 | A kind of method that sintering dust separation ash prepares removing harmful element during cementite |
| CN109052402A (en) * | 2018-08-16 | 2018-12-21 | 陕西科技大学 | A kind of method of the continuous preparation pure phase carbonization iron nano-particle of green |
| CN109652604A (en) * | 2019-01-30 | 2019-04-19 | 上海大学 | A method of cementite is prepared using ferriferous oxide two-step method |
| CN110396591A (en) * | 2019-08-27 | 2019-11-01 | 苏州大学 | Iron ore method for carburizing |
| CN111826528A (en) * | 2020-07-31 | 2020-10-27 | 苏州大学 | Method for recycling coke in process of preparing iron carbide by using blast furnace dust |
| CN111826528B (en) * | 2020-07-31 | 2022-04-22 | 苏州大学 | Method for recycling coke in process of preparing iron carbide by using blast furnace dust |
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Application publication date: 20170822 |