CN102796879B - Method for preparing chromium-containing iron powder by direct reduction of calcium-free chromium slag - Google Patents
Method for preparing chromium-containing iron powder by direct reduction of calcium-free chromium slag Download PDFInfo
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Abstract
The invention discloses a method for preparing chromium-containing iron powder by direct reduction of calcium-free chromium slag, which belongs to the technical field of comprehensive utilization of chromium slag. The method comprises the following steps of: firstly, material preparation, wherein the calcium-free chromium slag is mixed with a reducing agent and fluxing agents comprising alumina, and the four-element alkalinity m(MgO+CaO)/m(SiO2+Al2O3) of the mixed material is equal to 0.9 to 1.3; secondly, agglomeration, wherein the mixed material is pressed or pelletized to obtain agglomerates; thirdly, reduction roasting, wherein the agglomerates are roasted in reducing atmosphere at a reduction temperature of 1,250 to 1,350 DEG C for 30 to 240 minutes; fourthly, crushing and fine grinding, wherein the roasted agglomerates are crushed and ground to be fine; and fifthly, magnetic separation, wherein the finely ground powder is subjected to magnetic separation at magnetic induction intensity of 100 to 200 mT, thereby separating the chromium-containing iron powder. According to the method, the calcium-free chromium slag is completely detoxified and fully recycled, the grade sum of calcium and iron in the prepared chromium-containing iron powder is over 80 percent, the chromium recovery rate and the iron recovery rate are respectively over 78 percent, and the method is low in energy consumption and free from secondary pollution.
Description
Technical field
The present invention relates to the technical field that chromium slag for comprehensive utilizes, more particularly, relate to a kind of method of ferrochrome powder that contains through direct-reduction preparation without calcium chromium slag.
Background technology
Chromic salts is one of main series product of China's inorganic chemical industry, be widely used in the industry such as metallurgy, process hides, pigment, dyestuff, spices, metal finishing, wood preservation, military project, be listed in one of the most competitive eight kinds of resource raw material product, the main products kind of chromic salts is sodium dichromate 99 and chromic trioxide.
Traditional chromium salt production method is for there being calcium sinter process, owing to using the calcareous fillers such as rhombspar, marble or unslaked lime, cause bed drain purge large (in approximately 1.5 ~ 2.5 tons of slags of Sodium chromate ton product), and contain a large amount of carcinogens yellow ultramarines, being difficult to removing toxic substances administers, causing the severe contamination to environment, is technique out of category in national industrial policies.For solving the problem of chromium salt production serious environment pollution, appropriate authority, enterprise have done a large amount of few calcium, calcium-free roasting technical study and have put into practice work both at home and abroad, although few calcium sinter process reduces bed drain purge to some extent, but the problem containing yellow ultramarine in slag does not solve, and belongs to restricted technique in national industrial policies.Without calcium chromium slag, be to utilize current state-of-the-art calcium-free roasting Technology to produce a kind of industrial residue discharging in chromic salts process, without calcium chromium slag, it is harmful waste residue, it is again available secondary resource, as a chromium salt production line of producing 50000 tons per year, annual expectation can be arranged without 40,000 tons of calcium chromium slags, if by containing Fe
2o
3, Cr
2o
3be respectively 36.5%, 9.5% and calculate, the pure Fe of annual loss, Cr resource are respectively 10220 tons, 2600 tons.The Cr of solubility in chromium slag
6+toxicity is violent, not only endangers ecotope, and affects animal and plant growth.In view of the serious harm of chromium slag, the exploitation of its harmless treatment and comprehensive utilization technique is extremely urgent.
Tradition is to storing up or landfill after sexavalent chrome removing toxic substances to the total trend for the treatment of of chromate slag, majority is thought not too large utility value or be difficult to process and do not emphasize that resource utilization rationally utilizes of chromium slag, also have a few studies towards comprehensive utilization future development, but its economic benefit is not obvious.The processing disposal technology of current domestic chromium slag is divided into removing toxic substances and processes and fully utilize two large classes, and wherein removing toxic substances is processed and is divided into again three kinds of methods, i.e. chemical method (dry method, wet method), microbial method and microwave method.Although have scholar to propose the technology of multiple improvement chromium slag, be difficult to realize industrialization.The technology of administering chromium slag also exists and may cause that secondary pollution, valuable element are not recycled utilizations, the many-sided problem such as not thorough of detoxifying.
As China Patent No. ZL90103420.7, Granted publication day is on June 2nd, 1993, invention and created name is: Technology of processing chromium slag by vacuum reducing for obtaining variable kinds of products, this application case has overcome the problem that in prior art, the useful component in chromium slag is not fully used, take chromium slag, ferrosilicon and calcium oxide as main raw material, after batching, make agglomerate by a certain percentage, through high-temperature vacuum reduction, can directly produce sodium Metal 99.5, MAGNESIUM METAL and harmless slag; After magnetic separation, wet concentration, low ferrochrome can be separated, the useful slag after separated low ferrochrome, with ball mill match grinding cement or be used for making building block.This application case is processed be have in calcium sinter process production process, produce have a calcium chromium slag, to a certain degree to there being calcium chromium slag to fully utilize, but, its weak point is: (1) adopts vacuum reducing technique, its equipment is complicated, process parameter control difficulty is large, and industrial applications cost is high; (2) using ferrosilicon as reductive agent, its cost is high, has reduced the commercial value that chromium slag for comprehensive utilizes; (3) take calcium oxide as main solubility promoter, make compound basicity higher, departed from the best power source of reduction reaction and learned condition, make chromium slag be difficult for being reduced, or recovery time prolongation, recovery rate reduces.
In addition, Chinese Patent Application No.: 201010107049.9, invention and created name is: a kind of method fully utilizing without calcium chromium slag direct production croloy steel, this application case is got the raw materials ready according to metering, reducing and smelting, slag tap and tap a blast furnace, the steps such as refining cast are carried out, in without calcium chromium slag, allocate reductive agent into, in electric furnace, smelt, the chromium hot melt that smelting obtains directly enters refining furnace and carries out oxygen decarburization refining, obtain croloy steel, its main component is: C 0.2～6.0%, Cr 8.0.0～50.0%, Si 0.3～1.0%, S≤0.05%, P≤0.05%, V 0.1～0.5%, the various high-abrasive materials of production can directly be cast or forge and press to this kind of steel alloy, but its weak point is: (1) this application case by comprise impurity without the whole fusion smeltings of calcium chromium slag, and reduction temperature is 1500 ~ 1650 ℃, its quantity of slag is large, energy consumption is high, productivity is low, cause processing cost large, (2) it is serious to the erosion of furnace lining without the impurity element Na in calcium chromium slag, and maintenance of the equipment rate is high, (3) rate of recovery of the chromium element in this application case is low, without the chromium element in calcium chromium slag, is not fully recycled.
Adopt calcium-free roasting Technology to produce to discharge in chromic salts process without calcium chromium slag, compared calcium chromium slag, the content of its CaO greatly reduces, but the content of its MgO but reaches 20% left and right, quaternary basicity is about 1.5, in prior art in the comprehensive utilization technique without calcium chromium slag, the difficult point of most critical is exactly that the content of MgO is higher, be difficult to MgO separatedly with ferrochrome, make the rate of recovery of chromium, ferro element low, and the grade sum of the chromium after separation, iron is generally below 60%.Although the improvement without calcium chromium slag has obtained certain achievement at present, but realize without the removing toxic substances of calcium chromium slag and the recycling of high added value, just must break through the constraint of traditional improvement method, use multi-disciplinary knowledge, single innoxious governance pattern before changing, according to recycling industries and clean production concept, will as a kind of available resource, carry out suitability for industrialized production without calcium chromium slag.Only in this way could effectively solve without the utilization of calcium chromium slag for comprehensive not thoroughly, energy consumption is large, easily produces secondary pollution, the problem of high cost.
Summary of the invention
the technical problem that invention will solve
The object of the invention is to overcome in prior art and exist many-sided problems such as resource utilization degree is low, secondary pollution is serious, energy consumption is large without calcium chromic wastes disposal technology, a kind of method of ferrochrome powder that contains through direct-reduction preparation without calcium chromium slag is provided, it is main raw material that the present invention be take without calcium chromium slag, with addition of suitable reductive agent and fusing assistant, adopt direct-reduction roasting-efficient magnetic separation separating technology preparation reduction containing ferrochrome powder, preparation go back chromium in original product, iron grade sum reaches more than 80%, chromium, iron recovery reach more than 78% respectively.
technical scheme
For achieving the above object, technical scheme provided by the invention is:
A kind of method of ferrochrome powder that contains through direct-reduction preparation without calcium chromium slag of the present invention, the steps include:
(1) batching: will mix with reductive agent, fusing assistant without calcium chromium slag, wherein fusing assistant comprises aluminum oxide, makes the quaternary basicity m(MgO+CaO of compound)/m(SiO
2+ Al
2o
3)=0.9 ~ 1.3, too high or the too low imbalance that all can cause quaternary slag system of quaternary basicity, reduction reaction temperature is moved to high-temperature zone, need higher energy consumption higher temperature and longer time could form slag phase, and suitable basicity can obtain good slag iron separating effect;
(2) agglomeration: the compound of step (1) is carried out to cake of press or pelletizing, obtain piece material;
(3) reducing roasting: the piece material of step (2) is carried out to roasting under reducing atmosphere, its reduction temperature is 1250 ~ 1350 ℃, the too low reduction reaction temperature that do not reach of temperature, excess Temperature can form burning makes iron form that liquid phase cohesion is difficult to fine grinding and energy consumption is high, recovery time is 30 ~ 240 min, it is incomplete that recovery time crosses short reaction, the long energy consumption that increases of recovery time, and cost is high;
(4) broken fine grinding: the piece material after step (3) roasting is broken, and fine grinding;
(5) magnetic separation: the powder after step (4) fine grinding is carried out to magnetic separation, and magnetic induction density during magnetic separation is 100 ~ 200 mT, isolates containing ferrochrome powder.When magnetic induction density is too high, the magnetism between magnetic pole is stronger, and impure more fine particle also can be adsorbed recovery, cause the magnetic separation rate of recovery higher, but grade can reduce; When magnetic induction density is too low, only have the small-particle that iron-holder is high just can be adsorbed recovery, product grade is higher, but the rate of recovery can be lower, so consider grade and the rate of recovery of product after magnetic separation, determine that magnetic induction density is to meet resource utilization most to recycle and require while being 100 ~ 200 mT.
Preferably, the fusing assistant described in step (1) also comprises Calcium Fluoride (Fluorspan) or boron oxide, and the add-on of described Calcium Fluoride (Fluorspan) or boron oxide is without 1% ~ 8% of calcium chromium slag weight.
Preferably, the reduction temperature in step (3) is 1300 ℃, and the time is 50 ~ 80 min.
Preferably, in step (4), after fine grinding, the granularity of powder is 50 ~ 200 orders.
Preferably, the ferrochrome powder that contains in step (5) after magnetic separation carries out secondary magnetic separation, and magnetic induction density during secondary magnetic separation is 40 ~ 100 mT.
beneficial effect
Adopt technical scheme provided by the invention, compare with existing known technology, there is following unusual effect:
(1) a kind of method of ferrochrome powder that contains through direct-reduction preparation without calcium chromium slag of the present invention, by adding aluminum oxide as fusing assistant, when the quaternary basicity of compound is 0.9 ~ 1.3, the reduction temperature of compound can complete efficiently reduction process when relatively low temperature, and slag phase and ferrochrome after reduction are easily separated, chromium after magnetic separation, iron grade sum reaches more than 80%, chromium, iron recovery reaches respectively more than 78%, the theoretical analysis, be likely that aluminum oxide has played good fluxing effect to magnesium oxide, make it in conjunction with forming new thing phase, through reduction reaction, cause ore phase reconstruction simultaneously, make the magnesium oxide can be by effective separation, greatly improved chromium after magnetic separation, the grade of iron, overcome in prior art that content of magnesia without calcium chromium slag is high causes reclaiming rear chromium, the difficult problem that iron grade is low, increased the resource utilization degree without calcium chromium slag, the rate of recovery is high, remarkable in economical benefits,
(2) a kind of method of ferrochrome powder that contains through direct-reduction preparation without calcium chromium slag of the present invention, according to metallurgical reaction engineering principle, the quaternary basicity of controlling compound of take is core, seek best kinetics of reduction condition, too high or the too low imbalance that all can cause quaternary slag system of quaternary basicity, reduction reaction temperature is moved to high-temperature zone, cause energy consumption to increase, cost is high, and the present invention determines that the quaternary basicity of compound is at 0.9 ~ 1.3 o'clock, reduction reaction temperature is 1250 ~ 1350 ℃, the reduction temperature of 1500 ~ 1650 ℃ compared to existing technology, energy consumption greatly reduces, processing cost is low,
(3) a kind of method of ferrochrome powder that contains through direct-reduction preparation without calcium chromium slag of the present invention, the impure minerals such as the siderochrome component without in the complicated mineral of calcium chromium slag and other gangue is effectively separated, by reduction reaction effect, chromium, iron major part are entered goes back in original product, form the ferrochrome of low chromium content, through ore grinding-magnetic separation, obtain the finished product, realize abundant recovery and utilization without calcium chromium slag solid waste, make to obtain comprehensive utilization of resources without calcium chromium slag, and non-secondary pollution.
Accompanying drawing explanation
Fig. 1 is a kind of process flow sheet of the method for ferrochrome powder that contains through direct-reduction preparation without calcium chromium slag of the present invention;
Fig. 2 is the reduction experiment device of embodiment 1.
Label declaration in schematic diagram: 1, nitrogengas cylinder; 2, spinner-type flowmeter; 3, tubular oven; 4, thermopair; 5, piece material samples; 6, plumbago crucible; 7, silica tube; 8, vent gas treatment bottle.
Embodiment
For further understanding content of the present invention, the present invention is described in detail in conjunction with the accompanying drawings and embodiments.
A kind of method of ferrochrome powder that contains through direct-reduction preparation without calcium chromium slag of the present embodiment, as shown in Figure 1, its concrete steps are as follows for its process flow sheet:
(1) batching: will be without calcium chromium slag and reductive agent, fusing assistant mixes, in the present embodiment, get 100 g without calcium chromium slag, reductive agent is got 30 g pulverized anthracites, adopt x-ray fluorescence spectrometry instrument and chemical analysis to analyze above-mentioned raw materials, without calcium chromium slag and hard coal physical and chemical index in Table 1 and table 2 shown in, without calcium chromium slag, through X-ray diffraction analysis, show that mineral mainly contain ferric chromate, magnetite, forsterite, magnesium-fayalite and silicate form, from the chemistry without calcium chromium slag and material phase analysis, find out, in chromium slag, mainly contain Fe, Mg, tri-kinds of elements of O, also has part Cr simultaneously, Si, Al, Na, Ca and other a small amount of element, mineral composition complex structure.Its quaternary basicity is 1.53 as calculated, i.e. m (MgO+CaO)/m (SiO
2+ Al
2o
3)=1.53, quaternary basicity m (MgO+CaO)/m (SiO in the present invention
2+ Al
2o
3) refer to degree sum and the SiO of MgO, CaO
2+ Al
2o
3the ratio of degree sum; Fusing assistant in the present embodiment is 6 g aluminum oxide and 3 g Calcium Fluoride (Fluorspan), adds after fusing assistant and reductive agent the quaternary basicity m(MgO+CaO of compound)/m(SiO
2+ Al
2o
3)=1.008.Because the effect of Calcium Fluoride (Fluorspan) and Sodium Fluoride is consistent, Calcium Fluoride (Fluorspan) in the present embodiment also can adopt Sodium Fluoride to replace, and its effect is consistent, and the Calcium Fluoride (Fluorspan) in the present embodiment can not add yet, be that fusing assistant only adopts aluminum oxide, now reduction temperature and recovery time need suitably to improve.In addition, the reductive agent in the present invention can be coal dust, also can adopt powdered carbon or other material replacements that can be used as reductive agent and heat can be provided.
Table 1 is without calcium chromium slag detected result
| Chemical composition | TFe | Fe 2O 3 | MgO | Cr 2O 3 | SiO 2 | Al 2O 3 |
| Content/% | 31.49 | 45.03 | 20.83 | 8.56 | 8.13 | 7.26 |
| Chemical composition | Na 2O | CaO | MnO | CuO | SO 2 | Add up to |
| Content/% | 6.13 | 2.69 | 0.452 | 0.221 | 0.130 | ? |
The anthracitic technical analysis of table 2
| Composition | Fixed carbon | Ash content | Volatile matter | S | Moisture |
| Percentage composition % | 80.36 | 10.54 | 8.52 | 0.41 | 8.15 |
(2) agglomeration: the compound of step (1) is extruded on powder pressure-like machine
mm right cylinder sample, obtains piece material, what deserves to be explained is, the present invention, in pelletizing process, can adopt the conventional binding agents such as clay, to guarantee having enough balling properties, also can adopt the mode agglomeration of mechanical briquetting;
(3) reducing roasting: the piece material of step (2) is carried out to roasting under reducing atmosphere, its reduction temperature is 1300 ℃, time is 60 min, in the present embodiment without calcium chromium slag direct-reduction experimental installation as shown in Figure 2, piece material samples 5 is housed in plumbago crucible 6, silica tube 7 is positioned at the inside of tubular oven 3, 1400 ℃ of the maximum operating temperatures of tubular oven 3, built-in external diameter 70 mm of tube furnace in experimentation, the silica tube 7 of long 1600 mm is as reaction vessel, plumbago crucible 6 is put into silica tube 7 middle parts, the left side of this silica tube 7 is connected to nitrogengas cylinder 1 and spinner-type flowmeter 2, after finishing for reduction reaction, pass into nitrogen cooling as shielding gas, the middle part of tubular oven 3 is provided with thermopair 4, for actual thermometric, the right side of silica tube 7 is provided with vent gas treatment bottle 8, tail gas passes in water and discharges,
(4) broken fine grinding: the piece material after step (3) roasting is broken, and be finely ground to 100 orders;
(5) magnetic separation: the powder after step (4) fine grinding is carried out to magnetic separation, and magnetic induction density during magnetic separation is 120 mT, isolates containing ferrochrome powder, and its experiment parameter is as shown in table 3, wherein by the rate of recovery of (1) formula calculating Fe and Cr.
In formula: R
x-x element recovery rate;
W (x)-containing x element massfraction in ferrochrome powder;
M
chromium slagin-every assembly material without calcium chromium slag amount, 100 g;
M
coal dustquality of pc in-every assembly material;
M
fusing assistantfusing assistant quality in-every assembly material;
W(x
s)-without x element massfraction in calcium chromium slag;
M
1quality before-piece material samples reduction reaction;
M
2after-magnetic separation, contain the quality of ferrochrome powder.
Reduction-magnetic separation experimental result of table 3 embodiment 1
| Sequence number | Fusing assistant | Iron grade | Chromium grade | Mg content | Iron recovery | Chromium |
| Embodiment | ||||||
| 1 | Aluminum oxide 6 g: Calcium Fluoride (Fluorspan) 3 g | 72.54 | 13.56 | 6.73 | 80.34 | 80.70 |
embodiment 2
A kind of method of ferrochrome powder that contains through direct-reduction preparation without calcium chromium slag of the present embodiment, substantially with embodiment 1, the processing parameter of its concrete steps is:
(1) batching: 100 g are mixed with reductive agent, fusing assistant without calcium chromium slag, and wherein fusing assistant is aluminum oxide 9 g and Calcium Fluoride (Fluorspan) 3 g, and reductive agent is 30 g pulverized anthracites, the quaternary basicity m(MgO+CaO of compound)/m(SiO
2+ Al
2o
3)=0.9;
(2) agglomeration: the compound of step (1) is carried out to cake of press or pelletizing, obtain piece material;
(3) reducing roasting: the piece material of step (2) is carried out to roasting under reducing atmosphere, and its reduction temperature is 1300 ℃, and the time is 80 min;
(4) broken fine grinding: the piece material after step (3) roasting is broken, and fine grinding 80 orders;
(5) magnetic separation: the powder after step (4) fine grinding is carried out to magnetic separation, and magnetic induction density during magnetic separation is 130 mT, isolates containing ferrochrome powder, and its experiment parameter is as shown in table 4.
Reduction-magnetic separation experimental result of table 4 embodiment 2
| Sequence number | Fusing assistant | Iron grade | Chromium grade | Mg content | Iron recovery | Chromium recovery ratio |
| Embodiment 2 | Aluminum oxide 9 g: Calcium Fluoride (Fluorspan) 3 g | 68.73 | 12.86 | 8.13 | 81.12 | 80.45 |
A kind of method of ferrochrome powder that contains through direct-reduction preparation without calcium chromium slag of the present embodiment, substantially with embodiment 1, the processing parameter of its concrete steps is:
(1) batching: 100 g are mixed with reductive agent, fusing assistant without calcium chromium slag, and wherein fusing assistant is aluminum oxide 1 g and Calcium Fluoride (Fluorspan) 3 g, and reductive agent is 30 g pulverized anthracites, the quaternary basicity m(MgO+CaO of compound)/m(SiO
2+ Al
2o
3)=1.3;
(2) agglomeration: the compound of step (1) is carried out to cake of press or pelletizing, obtain piece material;
(3) reducing roasting: the piece material of step (2) is carried out to roasting under reducing atmosphere, and its reduction temperature is 1300 ℃, and the time is 50 min;
(4) broken fine grinding: the piece material after step (3) roasting is broken, and fine grinding 120 orders;
(5) magnetic separation: the powder after step (4) fine grinding is carried out to magnetic separation, and magnetic induction density during magnetic separation is 110 mT, isolates containing ferrochrome powder, and its experiment parameter is as shown in table 5.
Reduction-magnetic separation experimental result of table 5 embodiment 3
| Sequence number | Fusing assistant | Iron grade | Chromium grade | Mg content | Iron recovery | Chromium |
| Embodiment | ||||||
| 3 | Aluminum oxide 1 g: Calcium Fluoride (Fluorspan) 3 g | 69.23 | 10.83 | 8.35 | 79.45 | 78.56 |
embodiment 4
A kind of method of ferrochrome powder that contains through direct-reduction preparation without calcium chromium slag of the present embodiment, substantially with embodiment 1, the processing parameter of its concrete steps is:
(1) batching: 100 g are mixed with reductive agent, fusing assistant without calcium chromium slag, and wherein fusing assistant is aluminum oxide 6 g and Calcium Fluoride (Fluorspan) 8 g, and reductive agent is 30 g pulverized anthracites, the quaternary basicity m(MgO+CaO of compound)/m(SiO
2+ Al
2o
3)=1.008;
(2) agglomeration: the compound of step (1) is carried out to cake of press or pelletizing, obtain piece material;
(3) reducing roasting: the piece material of step (2) is carried out to roasting under reducing atmosphere, and its reduction temperature is 1250 ℃, and the time is 240 min;
(4) broken fine grinding: the piece material after step (3) roasting is broken, and fine grinding 50 orders;
(5) magnetic separation: the powder after step (4) fine grinding is carried out to magnetic separation, and magnetic induction density during magnetic separation is 100 mT, isolates containing ferrochrome powder, and its experiment parameter is as shown in table 6.
Reduction-magnetic separation experimental result of table 6 embodiment 4
| Sequence number | Fusing assistant | Iron grade | Chromium grade | Mg content | Iron recovery | Chromium recovery ratio |
| Embodiment 4 | Aluminum oxide 6 g: Calcium Fluoride (Fluorspan) 8 g | 67.71 | 12.38 | 8.08 | 79.43 | 78.61 |
embodiment 5
A kind of method of ferrochrome powder that contains through direct-reduction preparation without calcium chromium slag of the present embodiment, substantially with embodiment 1, the processing parameter of its concrete steps is:
(1) batching: 100 g are mixed with reductive agent, fusing assistant without calcium chromium slag, and wherein fusing assistant is aluminum oxide 6 g and Calcium Fluoride (Fluorspan) 1 g, and reductive agent is 30 g pulverized anthracites, the quaternary basicity m(MgO+CaO of compound)/m(SiO
2+ Al
2o
3)=1.008;
(2) agglomeration: the compound of step (1) is carried out to cake of press or pelletizing, obtain piece material;
(3) reducing roasting: the piece material of step (2) is carried out to roasting under reducing atmosphere, and its reduction temperature is 1350 ℃, and the time is 30 min;
(4) broken fine grinding: the piece material after step (3) roasting is broken, and fine grinding 150 orders;
(5) magnetic separation: the powder after step (4) fine grinding is carried out to magnetic separation, and magnetic induction density during magnetic separation is 200 mT, isolates containing ferrochrome powder;
(6) secondary magnetic separation: the ferrochrome powder that contains after magnetic separation in step (5) is carried out to secondary magnetic separation, and magnetic induction density during secondary magnetic separation is 70 mT.Its experiment parameter is as shown in table 7.
Reduction-magnetic separation experimental result of table 7 embodiment 5
| Sequence number | Fusing assistant | Iron grade | Chromium grade | Mg content | Iron recovery | Chromium recovery ratio |
| Embodiment 5 | Aluminum oxide 6 g: Calcium Fluoride (Fluorspan) 1 g | 68.72 | 12.42 | 7.08 | 81.57 | 80.08 |
A kind of method of ferrochrome powder that contains through direct-reduction preparation without calcium chromium slag of the present embodiment, substantially with embodiment 1, the processing parameter of its concrete steps is:
(1) batching: 100 g are mixed with reductive agent, fusing assistant without calcium chromium slag, and wherein fusing assistant is aluminum oxide 6 g and boron oxide 5 g, and reductive agent is 30 g pulverized anthracites, the quaternary basicity m(MgO+CaO of compound)/m(SiO
2+ Al
2o
3)=1.008;
(2) agglomeration: the compound of step (1) is carried out to cake of press or pelletizing, obtain piece material;
(3) reducing roasting: the piece material of step (2) is carried out to roasting under reducing atmosphere, and its reduction temperature is 1310 ℃, and the time is 65 min;
(4) broken fine grinding: the piece material after step (3) roasting is broken, and fine grinding 200 orders;
(5) magnetic separation: the powder after step (4) fine grinding is carried out to magnetic separation, and magnetic induction density during magnetic separation is 150 mT, isolates containing ferrochrome powder;
(6) secondary magnetic separation: the ferrochrome powder that contains after magnetic separation in step (5) is carried out to secondary magnetic separation, and magnetic induction density during secondary magnetic separation is 100 mT.Its experiment parameter is as shown in table 8.
Reduction-magnetic separation experimental result of table 8 embodiment 6
| Sequence number | Fusing assistant | Iron grade | Chromium grade | Mg content | Iron recovery | Chromium |
| Embodiment | ||||||
| 6 | Aluminum oxide 6 g: boron oxide 5 g | 68.65 | 12.47 | 7.78 | 81.15 | 80.36 |
embodiment 7
A kind of method of ferrochrome powder that contains through direct-reduction preparation without calcium chromium slag of the present embodiment, substantially with embodiment 1, the processing parameter of its concrete steps is:
(1) batching: 100 g are mixed with reductive agent, fusing assistant without calcium chromium slag, and wherein fusing assistant is aluminum oxide 6 g and Calcium Fluoride (Fluorspan) 3 g, and reductive agent is 30 g pulverized anthracites, the quaternary basicity m(MgO+CaO of compound)/m(SiO
2+ Al
2o
3)=1.008;
(2) agglomeration: the compound of step (1) is carried out to cake of press or pelletizing, obtain piece material;
(3) reducing roasting: the piece material of step (2) is carried out to roasting under reducing atmosphere, and its reduction temperature is 1280 ℃, and the time is 55 min;
(4) broken fine grinding: the piece material after step (3) roasting is broken, and fine grinding 150 orders;
(5) magnetic separation: the powder after step (4) fine grinding is carried out to magnetic separation, and magnetic induction density during magnetic separation is 120 mT, isolates containing ferrochrome powder;
(6) secondary magnetic separation: the ferrochrome powder that contains after magnetic separation in step (5) is carried out to secondary magnetic separation, and magnetic induction density during secondary magnetic separation is 40 mT.Its experiment parameter is as shown in table 9.
Reduction-magnetic separation experimental result of table 9 embodiment 7
| Sequence number | Fusing assistant | Iron grade | Chromium grade | Mg content | Iron recovery | Chromium recovery ratio |
| Embodiment 7 | Aluminum oxide 6 g: Calcium Fluoride (Fluorspan) 3 g | 68.12 | 12.57 | 7.18 | 79.37 | 80.69 |
In embodiment 1 ~ 7, by processing of the present invention, that after magnetic separation, reclaims contains in ferrochrome powder, the weight content of its MgO is 6% ~ 8%, and the weight content without MgO in calcium chromium slag is 20% left and right before processing, illustrate that MgO is entered in tailings by good slag making, thereby greatly improved the grade of chromium, iron after magnetic separation.
Below schematically the present invention and embodiment thereof are described, this description does not have restricted.So, if those of ordinary skill in the art is enlightened by it, in the situation that not departing from the invention aim, without the creationary technical scheme similar to this technical scheme and the embodiment of designing, all should belong to protection scope of the present invention.
Claims (5)
1. without calcium chromium slag, through direct-reduction preparation, contain a method for ferrochrome powder, the steps include:
(1) batching: will mix with reductive agent, fusing assistant without calcium chromium slag, wherein fusing assistant is aluminum oxide, makes the quaternary basicity m(MgO+CaO of compound)/m(SiO
2+ Al
2o
3)=0.9 ~ 1.3;
(2) agglomeration: the compound of step (1) is carried out to cake of press or pelletizing, obtain piece material;
(3) reducing roasting: the piece material of step (2) is carried out to roasting under reducing atmosphere, and its reduction temperature is 1250 ~ 1350 ℃, and the time is 30 ~ 240 min;
(4) broken fine grinding: the piece material after step (3) roasting is broken, and fine grinding;
(5) magnetic separation: the powder after step (4) fine grinding is carried out to magnetic separation, and magnetic induction density during magnetic separation is 100 ~ 200 mT, isolates containing ferrochrome powder.
According to claim 1 a kind of without calcium chromium slag through direct-reduction preparation the method containing ferrochrome powder, it is characterized in that: the fusing assistant described in step (1) also comprises Calcium Fluoride (Fluorspan) or boron oxide, the add-on of described Calcium Fluoride (Fluorspan) or boron oxide is without 1% ~ 8% of calcium chromium slag weight.
3. a kind of method of ferrochrome powder that contains through direct-reduction preparation without calcium chromium slag according to claim 1 and 2, is characterized in that: the reduction temperature in step (3) is 1300 ℃, and the time is 50 ~ 80 min.
4. a kind of method of ferrochrome powder that contains through direct-reduction preparation without calcium chromium slag according to claim 3, is characterized in that: in step (4), after fine grinding, the granularity of powder is 50 ~ 200 orders.
5. a kind of method of ferrochrome powder that contains through direct-reduction preparation without calcium chromium slag according to claim 4, is characterized in that: the ferrochrome powder that contains in step (5) after magnetic separation carries out secondary magnetic separation, and magnetic induction density during secondary magnetic separation is 40 ~ 100 mT.
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| CN103103346A (en) * | 2013-01-08 | 2013-05-15 | 内蒙古包钢钢联股份有限公司 | Recycling method for calcium-free chromium slag sintered building block |
| CN103643040B (en) * | 2013-08-23 | 2015-09-16 | 甘肃锦世化工有限责任公司 | A kind for the treatment of process without calcium chromium slag |
| CN104017927B (en) * | 2014-06-03 | 2015-11-25 | 中信锦州金属股份有限公司 | A kind of chromium slag melting that utilizes is containing the method for chromium pig iron |
| CN104313362B (en) * | 2014-10-10 | 2016-05-25 | 昆明理工大学 | A kind of method of microwave aluminothermic reduction crome metal |
| CN105039615B (en) * | 2015-09-08 | 2017-09-01 | 华北理工大学 | Store up the processing method of AOD stainless steel slags |
| EP3601625B1 (en) * | 2017-03-21 | 2021-05-19 | Brother Group (Hong Kong) Limited | Process for preparing iron- and chrome-containing particles |
| CN107226703B (en) * | 2017-06-07 | 2020-07-31 | 西南科技大学 | Preparation method of calcium-free roasting chromium slag compact refractory material |
| CN107858476B (en) * | 2017-12-26 | 2020-03-10 | 攀枝花市仁通钒业有限公司 | Composite slag modifier for converter steelmaking |
| CN109368956B (en) * | 2018-11-30 | 2019-09-13 | 广东省资源综合利用研究所 | A kind of phosphorous heavy metal sewage sludge harmless resource processing method |
| CN113564363B (en) * | 2021-07-26 | 2022-08-16 | 中钢集团马鞍山矿山研究总院股份有限公司 | Method for enriching and recovering chromium resource by synergistic utilization of chromium-containing sludge and chromium-containing waste residue |
| CN114164346B (en) * | 2021-12-10 | 2023-04-07 | 中南大学 | Method for synergistically recovering valuable metals in chromium-containing waste residues and carbon-containing waste materials |
| CN114990330B (en) * | 2022-05-27 | 2024-09-20 | 中国恩菲工程技术有限公司 | Chromium slag harmless recycling treatment method, active micro powder material composition and active micro powder material |
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