CN103014216B - Reduction method of iron compound in iron-containing material - Google Patents

Reduction method of iron compound in iron-containing material Download PDF

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CN103014216B
CN103014216B CN201310005597.4A CN201310005597A CN103014216B CN 103014216 B CN103014216 B CN 103014216B CN 201310005597 A CN201310005597 A CN 201310005597A CN 103014216 B CN103014216 B CN 103014216B
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iron
solution
waste residue
reductive agent
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CN103014216A (en
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李小斌
刘楠
余顺文
彭志宏
刘桂华
周秋生
齐天贵
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Central South University
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Central South University
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Abstract

The invention discloses a reduction method of iron compound in an iron-containing material. Under the alkali hydrothermal condition, high-valence iron in the iron-containing material is reduced by using a reducing agent for facilitating the comprehensive utilization of iron in the iron-containing polymetallic ore or metallurgical waste residue. The reduction method has the advantages of extensive applicability, cheap and available reducing agent and the like, and is easily combined with the metallurgical process.

Description

The method of reducing of iron cpd in a kind of ferrous material
Technical field
The present invention relates to the method for reducing of ferric oxide in a kind of iron content polymetallic ore or iron containing metallurgical waste residue, belong to metallurgical technology field.
Background technology
In iron content polymetallic ore or metallurgical slag comprehensive utilization process, need the non-magnetic iron things such as rhombohedral iron ore wherein, pyrrhosiderite to be reduced to magnetite or metallic iron, so that the separation and concentration of wherein iron.Therefore, the reduction of iron mineral has important effect in the comprehensive utilization of ferrous material.
In metallurgical technology field iron mineral reduction main employing pyrogenic process process, and pyrogenic process process is for the comprehensive utilization of iron in ferrous material, there is the problem such as process more complicated, energy consumption height.Although wet reducing process easily combines with metallurgical process, flow process is simple, energy consumption is low, has no the research report of this aspect.
And for using for reference, in field of material preparation, the relevant report of reduced iron compound in hydrothermal system can be had.Chinese patent CN 101885512 A proposes a kind of in the hydrothermal system of 120 ~ 180 DEG C, adopts reduced iron powder by colloid Fe (OH) 3reduction is with the method preparing superfine Fe 3 O 4 particle; Chinese patent CN101323466A propose a kind of in Organic Alcohol solution by the mixture of iron trichloride and sodium hydroxide through hydrothermal treatment consists to prepare the method for nano ferriferrous oxide.Ni Xiaoming etc. (Journal ofCrystal Growth, 2005) propose a kind of under alkaline water heat condition, adopt hydrazine hydrate by Fe (OH) 3, Fe 2o 3be reduced to nanometer Fe or Fe 3o 4method; Glavee etc. propose a kind of borohydride reduction molysite compound that utilizes under hydrothermal conditions to prepare the method for nanometer metallic iron.But hydrazine hydrate in aforesaid method, hydroborate cost are high, and its handling object is pure iron cpd, need prepare specially.Therefore, in process iron content polymetallic ore or metallurgical slag comprehensive utilization iron process, aforesaid method is difficult to direct application.
Summary of the invention
The object of this invention is to provide the method for reducing of ferric oxide in a kind of iron content polymetallic ore or iron containing metallurgical waste residue, economy realizes the comprehensive utilization of iron in iron content polymetallic ore or metallurgical slag.
In order to achieve the above object, the inventive method comprises the steps:
1) join in alkaline solution by iron content polymetallic ore or iron containing metallurgical waste residue, reductive agent, be mixed with slurries, wherein alkaline solution is sodium hydroxide solution, sodium carbonate solution or sodium aluminate solution, and alkali concn is with Na 2o counts 10 ~ 300g/L, the amount of allocating into of iron content polymetallic ore or iron containing metallurgical waste residue counts 50 ~ 500g/L by the volume of alkaline solution, reductive agent is one or more the mixture in alcohols, carbohydrate, aldehydes, alkanes, activated carbon, graphite, coal, coal tar, wheat bran, and reductive agent consumption counts 0.2 ~ 200g/L by the volume of alkaline solution;
2) slurries prepared by are hydrothermal treatment consists 20 ~ 600min at 90 ~ 350 DEG C.
Preferably, in aforesaid method, reductive agent is one or more the mixture in methyl alcohol, glycerol, glucose, starch, formaldehyde, kerosene, coal, coal tar, wheat bran.
Tool of the present invention has the following advantages: 1) suitability is wide, not only can be used for the conversion of ferric oxide in iron content polymetallic ore or iron containing metallurgical waste residue, and can be used for the preparation of iron content functional materials; 2) reductive agent is cheap and easy to get; 3) easily combine with metallurgical process, simple.
Accompanying drawing explanation
The XRD figure spectrum of ferric oxide used in Fig. 1 embodiment 12;
The XRD figure spectrum of hydrothermal treatment consists slag in Fig. 2 embodiment 12.
Embodiment
The following examples are to more clearly describe feature of the present invention, choose bauxite in aluminum oxide production process and red mud as exemplary ferrous material, but this do not form any restriction to applicable object of the present invention.
Embodiment 1
By diaspore type bauxite (main component: Al 2o 356.63%, SiO 29.85%, Fe 2o 318.56%, TiO 22.36%), lime, sodium aluminate solution (100mL) and formaldehyde are mixed with raw pulp.Wherein, sodium aluminate solution consists of: Na 2o k220.34g/L, Al 2o 3120.58g/L; By sodium aluminate solution volumeter, ore proportioning quantity is 255g/L, formaldehyde addition is 5g/L; Lime-crushed stone pile is 7% of dry ore weight.Prepared raw pulp stripping 60min at 260 DEG C, gained stripping slurries obtain dissolution fluid and stripping slag through solid-liquid separation.Stripping slag carries out magnetic separation under field intensity is 120kA/m, and full iron (TFe) mass percentage of gained iron ore concentrate and iron recovery are respectively 56.30% and 48.74%; And when not adding formaldehyde, other condition and being identical, full iron (TFe) mass percentage of magnetic concentrate and iron recovery are respectively 30.52% and 17.37%.
Embodiment 2
By high ferro trihydrate aluminium stone ore (Fe 2o 342%, Al 2o 330%), sodium aluminate solution (100mL) and methanol mixed are mixed with raw pulp.Wherein, sodium aluminate solution consists of: Na 2o k160.23g/L, Al 2o 382.72g/L; By sodium aluminate solution volumeter, ore proportioning quantity is 200g/L, methyl alcohol addition is 5g/L; Prepared raw pulp stripping 120min at 90 DEG C, gained stripping slurries obtain dissolution fluid and stripping slag through solid-liquid separation.Stripping slag carries out magnetic separation under field intensity is 120kA/m, and full iron (TFe) mass percentage of gained iron ore concentrate and iron recovery are respectively 55.12% and 35.32%; And when not adding methyl alcohol, other condition and being identical, full iron (TFe) mass percentage of magnetic concentrate and iron recovery are respectively 41.50% and 7.67%.
Embodiment 3
By red mud (Fe 2o 354%, Al 2o 314%), glycerol, sodium hydroxide solution (100mL) are hybridly prepared into slurries.Wherein concentration of sodium hydroxide solution is that 10g/L is (with Na 2o counts, lower same); By sodium hydroxide solution volumeter, red mud dosage is 50g/L, glycerol addition is 0.2g/L.The slurries prepared process 20min under the hydrothermal condition of 350 DEG C.Slag after above-mentioned hydrothermal treatment consists, is carry out magnetic separation in the magnetic separation tube of 120kA/m in field intensity, full iron (TFe) mass percentage of gained magnetic concentrate is 58.42%, the rate of recovery of iron is 55.31%.And do not add glycerol, other treatment condition identical time, full iron (TFe) mass percentage of magnetic concentrate and iron recovery are respectively 42.50% and 16.87%.
Embodiment 4
By red mud (Fe 2o 354%, Al 2o 314%), glucose, sodium carbonate solution (100mL) are hybridly prepared into slurries.Wherein sodium carbonate solution concentration is that 50g/L is (with Na 2o counts, lower same); By sodium carbonate solution volumeter, red mud dosage is 300g/L, glucose addition is 5g/L.The slurries prepared process 600min under the hydrothermal condition of 280 DEG C.Slag after above-mentioned hydrothermal treatment consists, is carry out magnetic separation in the magnetic separation tube of 120kA/m in field intensity, full iron (TFe) mass percentage of gained magnetic concentrate is 62.42%, the rate of recovery of iron is 75.68%.And do not add glucose, other treatment condition identical time, full iron (TFe) mass percentage of magnetic concentrate and iron recovery are respectively 41.35% and 18.87%.
Embodiment 5
By red mud (Fe 2o 354%, Al 2o 314%), starch, onium hydroxide solution (100mL) are hybridly prepared into slurries.Wherein concentration of sodium hydroxide solution is that 150g/L is (with Na 2o counts, lower same); By sodium hydroxide solution volumeter, red mud dosage is 500g/L, starch addition is 10g/L.The slurries prepared process 180min under the hydrothermal condition of 260 DEG C.Slag after above-mentioned hydrothermal treatment consists, is carry out magnetic separation in the magnetic separation tube of 120kA/m in field intensity, full iron (TFe) mass percentage of gained magnetic concentrate is 60.42%, the rate of recovery of iron is 70.24%.And do not add starch, other treatment condition identical time, full iron (TFe) mass percentage of magnetic concentrate and iron recovery are respectively 42.4% and 15.87%.
Embodiment 6
By red mud (Fe 2o 354%, Al 2o 314%), coal dust, onium hydroxide solution (100mL) are hybridly prepared into slurries.Wherein concentration of sodium hydroxide solution is that 300g/L is (with Na 2o counts, lower same); By sodium hydroxide solution volumeter, red mud dosage is 300g/L, coal dust addition is 200g/L.The slurries prepared process 180min under the hydrothermal condition of 350 DEG C.Slag after above-mentioned hydrothermal treatment consists, is carry out magnetic separation in the magnetic separation tube of 120kA/m in field intensity, full iron (TFe) mass percentage of gained magnetic concentrate is 57.32%, the rate of recovery of iron is 55.02%.And do not add coal dust, other treatment condition identical time, full iron (TFe) mass percentage of magnetic concentrate and iron recovery are respectively 43.65% and 20.87%.
Embodiment 7
By red mud (Fe 2o 354%, Al 2o 314%), wheat bran, onium hydroxide solution (100mL) are hybridly prepared into slurries.Wherein concentration of sodium hydroxide solution is that 50g/L is (with Na 2o counts, lower same); By sodium hydroxide solution volumeter, red mud dosage is 300g/L, wheat bran addition is 50g/L.The slurries prepared process 180min under the hydrothermal condition of 200 DEG C.Slag after above-mentioned hydrothermal treatment consists, is carry out magnetic separation in the magnetic separation tube of 120kA/m in field intensity, full iron (TFe) mass percentage of gained magnetic concentrate is 56.32%, the rate of recovery of iron is 53.12%.And do not add wheat bran, other treatment condition identical time, full iron (TFe) mass percentage of magnetic concentrate and iron recovery are respectively 40.25% and 15.62%.
Embodiment 8
By high ferro trihydrate aluminium stone ore (Fe 2o 342%, Al 2o 330%), sodium aluminate solution (100mL) and kerosene are hybridly prepared into raw pulp.Wherein, sodium aluminate solution consists of: Na 2o k160.23g/L, Al 2o 382.72g/L; By sodium aluminate solution volumeter, ore proportioning quantity is 280g/L, kerosene addition is 5g/L; Prepared raw pulp stripping 90min at 145 DEG C.Above-mentioned stripping slag carries out magnetic separation under field intensity is 120kA/m condition, and full iron (TFe) mass percentage of gained iron ore concentrate and iron recovery are respectively 57.42% and 45.32%; And when not adding kerosene, other condition and being identical, full iron (TFe) mass percentage of magnetic concentrate and iron recovery are respectively 41.92% and 10.82%.
Embodiment 9
By diaspore type bauxite (main component: Al 2o 356.63%, SiO 29.85%, Fe 2o 318.56%, TiO 22.36%), lime, sodium aluminate solution (100mL) and coal tar are mixed with raw pulp.Sodium aluminate solution consists of: Na 2o k220.34g/L, Al 2o 3120.58g/L; By sodium aluminate solution volumeter, ore proportioning quantity is 255g/L, coal tar addition is 30g/L; Lime-crushed stone pile is 7% of dry ore weight.Prepared raw pulp stripping 120min at 260 DEG C.Above-mentioned stripping slag carries out magnetic separation under field intensity is 120kA/m, and full iron (TFe) mass percentage of gained iron ore concentrate and iron recovery are respectively 58.35% and 54.39%; And when not adding coal tar, other condition and being identical, full iron (TFe) mass percentage of magnetic concentrate and iron recovery are respectively 31.02% and 17.57%.
Embodiment 10
By diaspore type bauxite (main component: Al 2o 356.63%, SiO 29.85%, Fe 2o 318.56%, TiO 22.36%), lime, sodium aluminate solution (100mL), methyl alcohol, starch are mixed with raw pulp.Wherein, sodium aluminate solution consists of: Na 2o k220.34g/L, Al 2o 3120.58g/L; By sodium aluminate solution volumeter, ore proportioning quantity is 255g/L, methyl alcohol addition is 0.5g/L, starch addition is 2g/L; Lime-crushed stone pile is 7% of dry ore weight.Prepared raw pulp stripping 120min at 260 DEG C.Above-mentioned stripping slag carries out magnetic separation under field intensity is 120kA/m, and full iron (TFe) mass percentage of gained iron ore concentrate and iron recovery are respectively 55.75% and 50.87%; And the contrast and experiment of not adding methyl alcohol and starch reductive agent is with embodiment 9.
Embodiment 11
By red mud (Fe 2o 354%, Al 2o 314%), formaldehyde, starch, coal tar, onium hydroxide solution (100mL) are hybridly prepared into slurries.Wherein, concentration of sodium hydroxide solution is that 100g/L is (with Na 2o counts, lower same); By sodium hydroxide solution volumeter, red mud dosage is 300g/L, formaldehyde addition is 0.2g/L, starch addition is 2g/L, coal tar addition is 2g/L.The slurries prepared process 300min under the hydrothermal condition of 240 DEG C.Slag after above-mentioned hydrothermal treatment consists, is carry out magnetic separation in the magnetic separation tube of 120kA/m in field intensity, full iron (TFe) mass percentage of gained magnetic concentrate is 57.42%, the rate of recovery of iron is 62.25%.And do not add formaldehyde, coal tar and starch reductive agent, other treatment condition identical time, full iron (TFe) mass percentage of magnetic concentrate and iron recovery are respectively 41.25% and 16.32%.
Embodiment 12
By analytical pure Fe 2o 3, sodium hydroxide solution, formaldehyde and glucose is hybridly prepared into slurries.Wherein, concentration of sodium hydroxide solution is that 150g/L is (with Na 2o counts); By sodium hydroxide solution volumeter, analytical pure Fe 2o 3dosage is 200g/L, formaldehyde addition is 0.5g/L, glucose dosage is 5g/L.The slurries prepared process 180min under the hydrothermal condition of 280 DEG C.Before and after hydrothermal treatment consists, the X-ray diffracting spectrum (XRD) of material respectively as depicted in figs. 1 and 2.Fe in diffraction peak and Jade5.0 in Fig. 1 2o 3standard diagram (PDF24-0072#) conform to, diffraction peak and Fe in Fig. 2 3o 4standard diagram (PDF 07-0322#) conform to, illustrate that, in the hydrothermal treatment process of above-mentioned interpolation reductive agent, reduzate is Z 250.

Claims (2)

1. the method for reducing of ferric oxide in iron content polymetallic ore or iron containing metallurgical waste residue, is characterized in that, comprise the following steps:
1) join in alkaline solution by iron content polymetallic ore or iron containing metallurgical waste residue, reductive agent, be mixed with slurries, wherein alkaline solution is sodium hydroxide solution, sodium carbonate solution or sodium aluminate solution, and alkali concn is with Na 2o counts 10 ~ 300g/L, the amount of allocating into of iron content polymetallic ore or iron containing metallurgical waste residue counts 50 ~ 500g/L by the volume of alkaline solution, reductive agent is one or more the mixture in alcohols, carbohydrate, aldehydes, alkanes, activated carbon, graphite, coal, coal tar, wheat bran, and reductive agent consumption counts 0.2 ~ 200g/L by the volume of alkaline solution;
2) slurries prepared by are hydrothermal treatment consists 20 ~ 600min at 90 ~ 350 DEG C.
2. the method for reducing of ferric oxide in a kind of iron content polymetallic ore according to claim 1 or iron containing metallurgical waste residue, it is characterized in that, described reductive agent is one or more the mixture in methyl alcohol, glycerol, glucose, starch, formaldehyde, kerosene, coal, coal tar, wheat bran.
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CN103521205A (en) * 2013-10-10 2014-01-22 上海大学 Method of preparing core-shell structure TiO2 material with high photocatalytic activity
CN103755005B (en) * 2014-01-02 2016-12-07 上海大学 Ferric ion reduction method
CN104327885B (en) * 2014-10-10 2016-10-12 昆明理工大学 A kind of waste oil miscella fuel reducing agent being applied to during metallurgical pyrometallurgical smelting
CN105238924A (en) * 2015-10-23 2016-01-13 辽宁科技大学 Method for extracting aluminum and iron from high-iron diasporic bauxite
CN105801077A (en) * 2016-02-17 2016-07-27 中国科学院地球化学研究所 Preparation method of red mud/carbon-based magnetic composite material
CN105710383A (en) * 2016-04-30 2016-06-29 安徽农业大学 Method for preparing Cu powder by reducing CuO by adopting glycerinum
CN106319226A (en) * 2016-08-22 2017-01-11 中国铝业股份有限公司 Method for comprehensively recycling aluminium oxide, sodium oxide and ferric oxide from red mud

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CN101914650A (en) * 2010-06-29 2010-12-15 同济大学 Method for reducing oxidation state iron into simple substance iron by using glycerol

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