CN107058720B - A method of cementite is prepared using low-grade complex iron ore - Google Patents

A method of cementite is prepared using low-grade complex iron ore Download PDF

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CN107058720B
CN107058720B CN201710294967.9A CN201710294967A CN107058720B CN 107058720 B CN107058720 B CN 107058720B CN 201710294967 A CN201710294967 A CN 201710294967A CN 107058720 B CN107058720 B CN 107058720B
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carburizing
pelletizing
ball
cementite
iron ore
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CN107058720A (en
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陈栋
国宏伟
李鹏
闫炳基
李洪玮
万康
唐建国
李俊
杨东润
陈布新
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Suzhou University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/02Roasting processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/14Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24Binding; Briquetting ; Granulating
    • C22B1/2406Binding; Briquetting ; Granulating pelletizing
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/14Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24Binding; Briquetting ; Granulating
    • C22B1/242Binding; Briquetting ; Granulating with binders
    • C22B1/243Binding; Briquetting ; Granulating with binders inorganic

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Geochemistry & Mineralogy (AREA)
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  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Materials Engineering (AREA)
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  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The present invention discloses a kind of method using low-grade complex iron ore preparation cementite, comprising: is uniformly mixed low-grade complex iron ore with binder, and pelletizing material is made;The pelletizing material is made into green-ball and is roasted after drying, carburizing pelletizing is obtained;By the carburizing pelletizing in CO+CO2+H2Or CH4+H2Carburizing, cooling in inert atmosphere is carried out in gas, obtains pelletizing after carburizing;Pelletizing after the carburizing is subjected to wet ball-milling, wet magnetic separation is carried out after ball milling, is dried to obtain cementite.Method provided by the invention prepares cementite efficient quick, low in cost, energy conservation and environmental protection.

Description

A method of cementite is prepared using low-grade complex iron ore
Technical field
The present invention relates to a kind of field of metallurgy more particularly to a kind of sides using low-grade complex iron ore preparation cementite Method.
Background technique
China's iron ore deposit is abundant, and reserves are about 15,000,000,000 t.Although China's iron ore deposit is abundant, with other iron content Ore resources country abundant compares, China's iron ore deposit: 1. the more rich ores of lean ore are few, wherein 97.5% iron ore is poor iron ore, greatly The Iron grade of part iron ore is between 25-35%;2. ore type and complicated component, wherein 18.0% hematite is accounted for, The siderite for accounting for 3.4% accounts for 2.3% limonite ore, account for 1.1% spiegel ore and account for 5.3% mixed ore etc. five Seed type ore, poor due to sorting performance, lean ore majority is not yet utilized.China is as big steel country, 70% or more iron Ore relies on import, this seriously constrains the sustainable development of China's steel industry.Therefore, as can Efficient Development is poor using these Iron ore can be relieved the pressure of China's iron ore deposit shortage, be of great significance to the sustainable development of China's steel industry.
Cementite is a kind of raw material of electric furnace steel making, it has, and not spontaneous combustion, secondary oxidation be insensitive, iron oxide content The advantages that low energy consumption for low, preparation process, energy consumption of electric furnace can be greatly reduced in carbon content height.Therefore, cementite is a kind of good electricity Furnace furnace charge.It is significantly greatly increased, is carbonized at present iron since the gangue content height of charging stock for electric furnace will lead to its steelmaking process power consumption It is standby to utilize high-grade iron ore.But the abundant ore source in China is few, only accounts for the 2.5% of Iron Ore Reserve.Therefore, as can it is sharp High-grade cementite is prepared with low-grade iron ore, this is not only expected to the Efficient Development for substantially promoting China's low-grade iron ore resource It utilizes, and good steelmaking feed can be provided for China's steel industry.
The preparation method of cementite mainly includes following methods both at home and abroad at present:
Traditional cementite preparation method is using high-grade iron ore as raw material, with CO, CO2And H2Mixed gas or CH4And H2Mixed gas be carburizing gas, between 550-850 DEG C and fluidized bed in carry out carburizing obtain iron carbide powder.
High grade iron miberal powder is prepared into agglomerate, agglomerate is in 900 ° or so roastings a period of times, then with CO, CO2And H2It is mixed Close gas or CH4And H2Mixed gas be carburizing gas, between 550-850 DEG C carry out carburizing be prepared containing cementite Agglomerate.
Existing carburizing tech is by high-grade Iron Ore Powder or iron ore agglomerate, in CO, CO2And H2Mixed gas or CH4 And H2Mixed gas in and 550-850 DEG C of temperature range in carry out carburizing, iron mineral therein is converted into cementite, and gangue Object phase composition it is constant, the gangue contained in ore, which is eventually present in be added in electric furnace together in cementite, is made steel. And gangue content increase can greatly increase the power consumption of EAF Steelmaking Process, therefore the method for tradition preparation cementite can only be with Gao Pin Position iron ore is raw material, can not be using iron ore of low ore grade as raw material.
Summary of the invention
In view of this, the present invention provides a kind of method that can prepare cementite using low-grade complex iron ore for raw material, Efficient quick, low in cost, energy conservation and environmental protection.
In order to solve the above technical problems, the technical scheme is that preparing carbon using low-grade complex iron ore using a kind of Change the method for iron, comprising:
Low-grade complex iron ore is uniformly mixed with binder, and pelletizing material is made;
The pelletizing material is made into green-ball and is roasted after drying, carburizing pelletizing is obtained;
By the carburizing pelletizing in CO+CO2+H2Or CH4+H2Carburizing, cooling in inert atmosphere is carried out in gas, is obtained Pelletizing after carburizing;
Pelletizing after the carburizing is subjected to wet ball-milling, wet magnetic separation is carried out after ball milling, is dried to obtain cementite.
Preferably, pelletizing material is made to specifically include:
Add water when the low-grade complex iron ore is mixed with binder, is uniformly mixed, obtains pelletizing material.
Preferably, the low-grade complex iron ore is the lower siderite of Iron grade, limonite, bloodstone, high ferro-aluminum One of mine, magnetic iron ore and speculum iron are a variety of;
Preferably, the binder is bentonite or calcium hydroxide;
Preferably, the consumption of binder range is 0-3%;
Preferably, the green-ball diameter is 8-16mm.
Preferably, the pelletizing material is made into green-ball and is roasted after drying specifically: dry bulb is in oxidisability, neutrality or goes back In originality atmosphere, 5-30min is roasted at 900-1100 DEG C.
Preferably, the temperature of the carburizing be 550-850 DEG C, carburizing time 30-300min.
Preferably, the gas CO+CO that the carburizing uses2+H2Middle CO: CO2∶H2Volume ratio is (50~100): (0~30) : (0~20);
Or the CH4+H2Middle CH4∶H2Volume ratio is (10~100): (0~90).
Preferably, described that pelletizing after the carburizing is subjected to wet ball-milling, wet magnetic separation is carried out after ball milling specifically:
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 strength of the magnetic separation process is 50~200mT.
The present invention provides a kind of method using low-grade complex iron ore preparation cementite, wherein iron ore pellets carburizings Afterwards, the dissociation of cementite and gangue can be realized by wet ball-milling, then cementite and arteries and veins can be efficiently separated by wet magnetic separation Stone obtains high-grade cementite, and the Iron grade limitation of raw material needed for preparation cementite can be significantly reduced in this greatly expands The source of carbonization iron material.In addition, the present invention using low-grade complex iron ore as raw material, passes through high-temperature concretion, carburizing, wet ball-milling With cementite can be purified after magnetic separation, obtain the higher steel-making raw material (cementite) of good added value, added value is above The added value of iron ore concentrate or reduced iron powder prepared by conventional method low-grade complex iron ore, this can be greatly facilitated low-grade complex The efficient utilization of iron ore iron.In addition to this, the present invention can effectively improve the grade of cementite, reduce using cementite as raw material EAF Steelmaking Process power consumption.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, With reference to embodiment The present invention is described in further detail.
The technical scheme is that using a kind of method using low-grade complex iron ore preparation cementite, comprising:
Low-grade complex iron ore is uniformly mixed with binder, and pelletizing material is made;
The pelletizing material is made into green-ball and is roasted after drying, carburizing pelletizing is obtained;
By the carburizing pelletizing in CO+CO2+H2Or CH4+H2Carburizing, cooling in inert atmosphere is carried out in gas, is obtained Pelletizing after carburizing;
Pelletizing after the carburizing is subjected to wet ball-milling, wet magnetic separation is carried out after ball milling, is dried to obtain cementite.
In order to which low-grade Complex Iron Ore is preferably prepared cementite, raw material and binder are mixed first, made It is specifically included at pelletizing material, adds water when the low-grade complex iron ore is mixed with binder, be uniformly mixed, obtain pelletizing material. Add the amount of water by pelletizing material on the basis of balling process is easy balling-up.
According to the present invention, the low-grade complex iron ore is the lower siderite of Iron grade, limonite, bloodstone, height One of ferro-aluminum mine, magnetic iron ore and speculum iron are a variety of.The binder is bentonite or calcium hydroxide.
Preferably, the consumption of binder range be 0-3%, more preferably 1.5~3%, most preferably 1.8%~ 3%.The green-ball diameter is 8-16mm.
After preparing pelletizing, pelletizing is roasted, the pelletizing material is made into green-ball and is roasted after drying specifically: is dry Ball roasts 5-30min at 900-1100 DEG C in oxidisability, neutrality or reducing atmosphere.The temperature of the carburizing is 550- 850 DEG C, carburizing time 30-300min.
Preferably, the gas CO+CO that the carburizing uses2+H2Middle CO: CO2∶H2Volume ratio is (50~100): (0~30) : (0~20), more preferably (55~80): (10~25): (5~20), most preferably (60~65): (15~20): (10~ 20)。
Or the CH4+H2Middle CH4∶H2Volume ratio is (10~100): (0~90), more preferably (20~70): (10~ 60), most preferably (40~60): (40~60).
After carburizing, iron and carbon in pelletizing form cementite, then are separated by wet ball-milling and wet magnetic separation, described Pelletizing after the carburizing is subjected to wet ball-milling, carries out wet magnetic separation after ball milling specifically:
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 strength of told magnetic separation process is 50~200mT.
The following are specific embodiments of the present invention:
Embodiment 1: the Iron grade 33.20% of siderite, the content that siderite is less than 0.075mm grade is 78.58%, small In 0.045mm content be 66.06%.It is 8- that 2% bentonitic siderite, which will be added to, and be prepared into diameter in disc balling machine The green-ball of 16mm, Balling time 10min, shatter strength of green pellet are 3.2 times/0.5m, after green-ball is dry at 900 DEG C and nitrogen It is middle roasting 15min after again 700 DEG C at a temperature of and CO: CO2∶H2For carburizing 180min in 60: 20: 20 mixed gas, hot-bulb It is cooling in nitrogen.Pelletizing is crushed to less than 1mm after cooling.Under conditions of pulp density is 50%, in conical ball mill Ball milling 4min obtains ball milling fineness 90% less than 200 mesh, and then ore pulp magnetic separation in the magnetic separator that magnetic field strength is 150mT can Obtaining carbonization Iron grade is 84.2%, the cementite of the rate of recovery 78% of iron.
Embodiment 2: the Iron grade 40.82% of siderite, the content that siderite is less than 0.075mm grade is 81.58%.It will It is added to 2.1% bentonitic siderite and is prepared into the green-ball that diameter is 8-16mm in disc balling machine, Balling time is 10min, shatter strength of green pellet are 3.5 times/0.5m, are roasted at 900 DEG C and in nitrogen after 15min after green-ball is dry again 800 At a temperature of DEG C and CH4∶H2For carburizing 70min in 60: 40 mixed gas, hot-bulb cooling in nitrogen.Pelletizing is broken after cooling To less than 1mm.Under conditions of pulp density is 50%, ball milling 5min obtains ball milling fineness 95% and is less than in conical ball mill 200 mesh, then ore pulp magnetic separation in the magnetic separator that magnetic field strength is 150mT, can obtain carbonization Iron grade is 87.2%, and iron returns The cementite of yield 80%.
Embodiment 3: the Iron grade of limonite is 41.23%, and the content that limonite is less than 0.075mm grade is 83.53%. 1.8% bentonitic limonite will be added to and be prepared into the green-ball that diameter is 8-16mm in disc balling machine, Balling time is 10min, shatter strength of green pellet are 3.6 times/0.5m, at 900 DEG C and roast 20min in air after green-ball is dry, then exist again At a temperature of 650 DEG C and CO: CO2∶H2For carburizing 200min in 60: 20: 20 mixed gas, hot-bulb cooling in nitrogen.It is cooling Pelletizing is crushed to less than 1mm afterwards.Under conditions of pulp density is 50%, it is thin to obtain ball milling by ball milling 4min in conical ball mill Degree 95% is less than 200 mesh, and then ore pulp magnetic separation in the magnetic separator that magnetic field strength is 160mT, can obtain carbonization Iron grade is 85.2%, the cementite of the rate of recovery 76% of iron.
Embodiment 4: the Iron grade of high alumina iron ore is 46.63%, and the content that limonite is less than 0.075mm grade is 81.43%.2.5% bentonitic limonite will be added to and be prepared into the green-ball that diameter is 8-16mm in disc balling machine, made The ball time is 10min, and shatter strength of green pellet is 3.0 times/0.5m, at 950 DEG C and roasts 20min in air after green-ball is dry, Then again 700 DEG C at a temperature of and CO: CO2∶H2For carburizing 200min in 65: 15: 20 mixed gas, hot-bulb is in nitrogen It is cooling.Pelletizing is crushed to less than 1mm after cooling.Under conditions of pulp density is 50%, the ball milling 4min in conical ball mill Ball milling fineness 96% is obtained less than 200 mesh, then ore pulp magnetic separation in the magnetic separator that magnetic field strength is 150mT, can be carbonized Iron grade is 86.3%, the cementite of the rate of recovery 80% of iron.
Embodiment 5: the Iron grade of bloodstone is 38.65%, and the content for being less than 0.075mm grade is 83.55%.It will add 3.0% bentonitic limonite has been added to be prepared into the green-ball that diameter is 8-16mm in disc balling machine, Balling time is 10min, shatter strength of green pellet are 3.0 times/0.5m, at 1000 DEG C and roast 20min in air after green-ball is dry, then exist again At a temperature of 750 DEG C and CH4∶H2For carburizing 80min in 50: 50 mixed gas, hot-bulb cooling in nitrogen.Pelletizing after cooling It is crushed to and is less than 1mm.Under conditions of pulp density is 50%, ball milling 3min obtains ball milling fineness 92% in conical ball mill Less than 200 mesh, then ore pulp magnetic separation in the magnetic separator that magnetic field strength is 120mT, can obtain carbonization Iron grade is 86.89%, The cementite of the rate of recovery 82% of iron.
The above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair Limitation of the invention, protection scope of the present invention should be defined by the scope defined by the claims..For the art For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change It also should be regarded as protection scope of the present invention into retouching.

Claims (6)

1. a kind of method using low-grade complex iron ore preparation cementite characterized by comprising
Add water when low-grade complex iron ore is mixed with binder, is uniformly mixed, obtains pelletizing material;The low-grade complex iron Mine is one of the lower siderite of Iron grade, limonite, bloodstone, high alumina iron ore, magnetic iron ore and speculum iron or a variety of;Institute The binder stated is bentonite or calcium hydroxide;
After the pelletizing material is made green-ball and dried by dry bulb in oxidisability, neutrality or reducing atmosphere, in 900-1100 DEG C Lower roasting 5-30min, obtains carburizing pelletizing;
By the carburizing pelletizing in CO+CO2+H2Or CH4+H2Carburizing, cooling in inert atmosphere is carried out in gas, after obtaining carburizing Pelletizing;
Pelletizing after the carburizing is subjected to wet ball-milling, wet magnetic separation is carried out after ball milling, is dried to obtain cementite.
2. the method according to claim 1, wherein the consumption of binder range is 0-3%.
3. the method according to claim 1, wherein the green-ball diameter is 8-16mm.
4. the method according to claim 1, wherein the temperature of the carburizing is 550-850 DEG C, carburizing time is 30-300min。
5. the method according to claim 1, wherein the gas CO+CO that the carburizing uses2+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).
6. the method according to claim 1, wherein described carry out wet ball-milling, ball for pelletizing after the carburizing Wet magnetic separation is carried out after mill specifically:
Pelletizing after carburizing is crushed to granularity less than wet ball-milling ball milling is carried out after 1mm, and wet type magnetic is then carried out in magnetic separator Choosing;
The magnetic field strength of the magnetic separation process is 50~200mT.
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