CN101979679A - Method for treating chromite by sulfuric acid leaching - Google Patents

Method for treating chromite by sulfuric acid leaching Download PDF

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CN101979679A
CN101979679A CN2010105112467A CN201010511246A CN101979679A CN 101979679 A CN101979679 A CN 101979679A CN 2010105112467 A CN2010105112467 A CN 2010105112467A CN 201010511246 A CN201010511246 A CN 201010511246A CN 101979679 A CN101979679 A CN 101979679A
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sulfuric acid
chromite
filter residue
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breeze
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刘承军
史培阳
姜茂发
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Northeastern University China
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Abstract

The invention discloses a method for treating chromite by sulfuric acid leaching, which comprises the following steps of: grinding the chromite into mineral powder, adding sulfuric acid into the mineral powder, stirring the mixture, and adding an oxidant into the mixture, wherein the oxidant is chromic anhydride, potassium chlorate or ammonium persulphate, and the adding amount of the oxidant is 0.2 to 7 percent of the mass of the mineral powder; heating the mixture at the temperature of between 120 and 190 DEG C for 30 to 90 minutes under the pressure of between 0.2 and 1.2MPa, filtering the reaction products after the reaction is finished, and performing solid-liquid separation, wherein the filter residue is directly used as a raw material for melting silicon iron; and removing iron from the filtrate to obtain chromium sulfate solution, and further preparing chromium sulfate by a direct crystallization method. Compared with the prior art, the method has the most remarkable characteristics of short process flow and no 'three-waste' emission. The filter residue does not contain hexavalent chromium, and the weight of the filter residue is light and only about 10 percent of the weight of the chromite, so the filter residue can be used as the raw material for melting the silicon iron.

Description

A kind of sulfuric acid leaches the method for handling chromite
Technical field
The invention belongs to technical field of mineral processing, relate to the processing technology of chromite, be specifically related to sulfuric acid and leach the method for handling chromite.
Background technology
Chromic salts preparation technology is many at present is raw material with the chromite, adopts calcification baking technique, and not only technical process is long, and generation contains Cr in a large number in process of production 6+Waste residue, and this waste residue has been classified as the most important thing that solid waste is administered by countries in the world.The main production of chromic salts has following several:
(1) chromite has calcium roasting-soda ash leaching-removal of impurities-concentrated-acidifying-denitration-crystallization-sodium dichromate 99-reduction-chromium sulfate solution (not only to produce 1 ton of sodium dichromate 99 generation and contain Cr 6+About 2.5 tons of waste residue, also produce a large amount of sexavalent chrome solution, chromium recovery ratio low 75% ~ 82%);
(2) chromite calcium-free roasting-soda ash leaching-removal of impurities-concentrate-acidifying-denitration-crystallization-sodium dichromate 99-reduction-chromium sulfate solution (is not only produced 1 ton of sodium dichromate 99 generation and is contained Cr 6+Waste residue be about 1 ton, also produce a large amount of sexavalent chrome solution, chromium recovery ratio low 70% ~ 82%);
(3) chromite molten-salt growth method leaching-removal of impurities-concentrate-acidifying-crystallization-sodium dichromate 99-reduction-chromium sulfate solution (not suitability for industrialized production).
(4) chromite sulfuric acid leaches under the normal pressure, and the tailings main component is a silicon-dioxide, and oxygenant and sulfuric acid consumption big (not suitability for industrialized production).
China is as producing country the biggest in the world and country of consumption, its chromic salts output accounts for 1/3rd of the world, improve present alkaline process (the calcium roasting is arranged) and sulfuric acid extract technology, not only can avoid the generation of contamination phenomenon from beginning of production, and have important practical significance for the Sustainable development of chromic salts industry.
Summary of the invention
Prepare the weak point of chromic salts technology existence at present chromite, the invention provides a kind of sulfuric acid and leach the method for handling chromite, reach the purpose that improves chromium yield, minimizing " three wastes " discharging, minimizing environmental pollution and reduce production costs.
The technological process of the inventive method is as follows.
Chromite is ground to form granularity 38～180
Figure DEST_PATH_IMAGE001
Breeze, the adding mass concentration is 50%～85% sulfuric acid in breeze, and the sulfuric acid add-on is 0.5～1.5 times of powdered ore quality, stirs, mixing speed is 45～500 rev/mins, add oxygenant, oxygenant is chromic trioxide, Potcrate or ammonium persulphate, and its add-on is 0.2%～7% of a powdered ore quality, heating, Heating temperature is 120～190 ℃, and the control reaction pressure is 0.2 ~ 1.2MPa, and the reaction times is 30～90min.
Above-mentioned technological process main chemical reactions is as follows:
Figure DEST_PATH_IMAGE002
(1)
Figure DEST_PATH_IMAGE003
(2)
Figure DEST_PATH_IMAGE004
(3)
Figure 2010105112467100002DEST_PATH_IMAGE005
(4)
Chromic anhydride dissolving Fe (CrO 2) 2Main equation as follows:
Figure DEST_PATH_IMAGE006
(5)
Potcrate dissolving Fe (CrO 2) 2Main equation as follows:
Figure 2010105112467100002DEST_PATH_IMAGE007
(6)
Ammonium persulphate dissolving Fe (CrO 2) 2Main equation as follows:
Figure DEST_PATH_IMAGE008
(7)
After-filtration is finished in reaction, carries out solid-liquid separation, and the filter residue composition is mainly the silicon-dioxide of ferric metasilicate and trace, and the mass content of chromium is lower than 0.3% in the filter residue.Filtrate is that chromium sulphate and ferric sulfate are the mixing solutions of main component.Filter residue is directly as the raw material of smelting duriron.Obtain chromium sulfate solution by filtrate being carried out the deironing processing, further the method by direct crystallization prepares chromium sulphate.Prepared chromium sulphate product index is as shown in table 1, adopts chemical analysis method.
The present invention compared with the prior art, outstanding feature is that technical process is short the most, does not have " three wastes " discharging.Filter residue does not contain sexavalent chrome, and filter residue weight is few, only is about 10% of chromite weight, can be used as the raw material of smelting duriron.
 
The chromium sulphate index of table 1 direct crystallization preparation
Figure DEST_PATH_IMAGE009
Description of drawings
Fig. 1 is a process flow diagram of the present invention;
Fig. 2 is X-ray diffraction (XRD) curve of embodiment 1 filter residue.
Embodiment
The main chemical compositions of the chromite of embodiment processing is as shown in table 2.
The chromite main chemical compositions of table 2 embodiment processing
Figure DEST_PATH_IMAGE010
Embodiment 1
It is as follows that sulfuric acid leaches the method technological process of handling chromite.
Chromite is ground to form granularity 100
Figure 489971DEST_PATH_IMAGE001
Breeze, the adding mass concentration is 68% sulfuric acid in breeze, and the sulfuric acid add-on is 1.0 times of powdered ore quality, stirs, mixing speed is 250 rev/mins, add oxygenant, oxygenant is a chromic trioxide, and its add-on is 3.2% of a powdered ore quality, heating, Heating temperature is 155 ℃, and the control reaction pressure is 0.7MPa, and the reaction times is 60min.
Above-mentioned technological process main chemical reactions is as follows:
Figure 407112DEST_PATH_IMAGE002
(1)
Figure 249166DEST_PATH_IMAGE003
(2)
Figure 644375DEST_PATH_IMAGE004
(3)
Figure 521064DEST_PATH_IMAGE005
(4)
Chromic anhydride dissolving Fe (CrO 2) 2Main equation as follows:
Figure 405844DEST_PATH_IMAGE006
(5)
After-filtration is finished in reaction, and filter plant adopts plate-and-frame filter press, and pressure 1.6MPa carries out solid-liquid separation, and the filter residue composition is the silicon-dioxide of ferric metasilicate and trace, and the mass content of chromium is lower than 0.3% in the filter residue.Filtrate is that chromium sulphate and ferric sulfate are the mixing solutions of main component.Filter residue is directly as the main raw material of smelting duriron.Obtain chromium sulfate solution by filtrate being carried out the deironing processing, further the method by direct crystallization prepares chromium sulphate.Prepared chromium sulphate product index is as shown in table 1, adopts chemical analysis method.
Embodiment 2
It is as follows that sulfuric acid leaches the method technological process of handling chromite.
Chromite is ground to form granularity 180
Figure 672877DEST_PATH_IMAGE001
Breeze, the adding mass concentration is 85% sulfuric acid in breeze, and the sulfuric acid add-on is 0.5 times of powdered ore quality, stirs, mixing speed is 500 rev/mins, add oxygenant, oxygenant is a Potcrate, and its add-on is 7% of a powdered ore quality, heating, Heating temperature is 190 ℃, and the control reaction pressure is 1.2MPa, and the reaction times is 30min.
Above-mentioned technological process main chemical reactions is as follows:
Figure 931164DEST_PATH_IMAGE002
(1)
Figure 600043DEST_PATH_IMAGE003
(2)
Figure 655724DEST_PATH_IMAGE004
(3)
Figure 472370DEST_PATH_IMAGE005
(4)
Potcrate dissolving Fe (CrO 2) 2Main equation as follows:
Figure 209382DEST_PATH_IMAGE007
(6)
After-filtration is finished in reaction, and filter plant adopts plate-and-frame filter press, and pressure 1.6MPa carries out solid-liquid separation, and the filter residue composition is the silicon-dioxide of ferric metasilicate and trace, and the mass content of chromium is lower than 0.3% in the filter residue.Filtrate is that chromium sulphate and ferric sulfate are the mixing solutions of main component.Filter residue is directly as the main raw material of smelting duriron.Obtain chromium sulfate solution by filtrate being carried out the deironing processing, further the method by direct crystallization prepares chromium sulphate.Prepared chromium sulphate product index is as shown in table 1, adopts chemical analysis method.
Embodiment 3
It is as follows that sulfuric acid leaches the method technological process of handling chromite.
Chromite is ground to form granularity 38
Figure 795084DEST_PATH_IMAGE001
Breeze, the adding mass concentration is 50% sulfuric acid in breeze, and the sulfuric acid add-on is 1.5 times of powdered ore quality, stirs, mixing speed is 45 rev/mins, add oxygenant, oxygenant is an ammonium persulphate, and its add-on is 0.2% of a powdered ore quality, heating, Heating temperature is 120 ℃, and the control reaction pressure is 0.2MPa, and the reaction times is 90min.
Above-mentioned technological process main chemical reactions is as follows:
Figure 224928DEST_PATH_IMAGE002
(1)
Figure 528871DEST_PATH_IMAGE003
(2)
Figure 803994DEST_PATH_IMAGE004
(3)
Figure 509782DEST_PATH_IMAGE005
(4)
Ammonium persulphate dissolving Fe (CrO 2) 2Main equation as follows:
?(7)
After-filtration is finished in reaction, and filter plant adopts plate-and-frame filter press, and pressure 1.6MPa carries out solid-liquid separation, and the filter residue composition is the silicon-dioxide of ferric metasilicate and trace, and the mass content of chromium is lower than 0.3% in the filter residue.Filtrate is that chromium sulphate and ferric sulfate are the mixing solutions of main component.Filter residue is directly as the main raw material of smelting duriron.Obtain chromium sulfate solution by filtrate being carried out the deironing processing, further the method by direct crystallization prepares chromium sulphate.Prepared chromium sulphate product index is as shown in table 1, adopts chemical analysis method.
Embodiment 4
It is as follows that sulfuric acid leaches the method technological process of handling chromite.
Chromite is ground to form granularity 60
Figure 907265DEST_PATH_IMAGE001
Breeze, the adding mass concentration is 60% sulfuric acid in breeze, and the sulfuric acid add-on is 1.2 times of powdered ore quality, stirs, mixing speed is 180 rev/mins, add oxygenant, oxygenant is a chromic trioxide, and its add-on is 1.5% of a powdered ore quality, heating, Heating temperature is 150 ℃, and the control reaction pressure is 0.8MPa, and the reaction times is 45min.
Above-mentioned technological process main chemical reactions is as follows:
Figure 698504DEST_PATH_IMAGE002
(1)
Figure 777318DEST_PATH_IMAGE003
(2)
Figure 340542DEST_PATH_IMAGE004
(3)
Figure 174506DEST_PATH_IMAGE005
(4)
Chromic anhydride dissolving Fe (CrO 2) 2Main equation as follows:
Figure 125145DEST_PATH_IMAGE006
(5)
After-filtration is finished in reaction, and filter plant adopts plate-and-frame filter press, and pressure 1.6MPa carries out solid-liquid separation, and the filter residue composition is the silicon-dioxide of ferric metasilicate and trace, and the mass content of chromium is lower than 0.3% in the filter residue.Filtrate is that chromium sulphate and ferric sulfate are the mixing solutions of main component.Filter residue is directly as the main raw material of smelting duriron.Obtain chromium sulfate solution by filtrate being carried out the deironing processing, further the method by direct crystallization prepares chromium sulphate.Prepared chromium sulphate product index is as shown in table 1, adopts chemical analysis method.

Claims (4)

1. a sulfuric acid leaches the method for handling chromite, it is characterized in that: chromite is ground to form breeze, in breeze, add sulfuric acid, stir, add oxygenant, oxygenant is a chromic trioxide, Potcrate or ammonium persulphate, its add-on are 0.2%～7% of powdered ore quality, heating, Heating temperature is 120～190 ℃, the control reaction pressure is 0.2～1.2MPa, and the reaction times is 30～90min, and after-filtration is finished in reaction, carry out solid-liquid separation, filter residue directly as the raw material of smelting duriron, obtains chromium sulfate solution by filtrate being carried out the deironing processing, and further the method by direct crystallization prepares chromium sulphate.
2. leach the method for handling chromite according to the described sulfuric acid of claim 1, it is characterized in that chromite is ground to form the breeze that granularity is 38～180 m.
3. leach the method for handling chromite according to the described sulfuric acid of claim 1, it is characterized in that adding mass concentration and be 50%～85% sulfuric acid in breeze, the sulfuric acid add-on is 0.5～1.5 times of powdered ore quality.
4. leach the method for handling chromite according to the described sulfuric acid of claim 1, it is characterized in that mixing speed is 45～500 rev/mins.
CN2010105112467A 2010-10-19 2010-10-19 Method for treating chromite by sulfuric acid leaching Pending CN101979679A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102268545A (en) * 2011-07-20 2011-12-07 广西冶金研究院 Intensified leaching method and device
CN104843790A (en) * 2015-05-22 2015-08-19 四川省银河化学股份有限公司 Method for preparing sodium chromate from chromite by acid dissolution oxygenation
CN105347399A (en) * 2014-08-21 2016-02-24 中国科学院过程工程研究所 Chromium leaching method by ammonium sulfate roasting decomposition of chromite
CN105695760A (en) * 2016-03-02 2016-06-22 东北大学 Method for carrying out two-stage countercurrent leaching on chromium-containing vanadium slag and extracting vanadium and chromium in separating manner
CN106186067A (en) * 2016-07-06 2016-12-07 于佳湲 A kind of method producing chromic oxide for raw material cleaning with chromite
CN108910950A (en) * 2018-10-12 2018-11-30 成都铬科高化工技术有限责任公司 A method of by preparing sodium chromate from chromite
CN111620370A (en) * 2020-05-15 2020-09-04 重庆理工大学 Electric field enhanced efficient chromite leaching method
CN113998741A (en) * 2021-11-12 2022-02-01 单淼 Method for preparing iron-based electrode material by taking waste iron sheet as raw material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《中国稀土学报》 20020930 史培阳等 铬铁矿硫酸浸出试验研究 第472-474页 1-4 第20卷, 2 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102268545A (en) * 2011-07-20 2011-12-07 广西冶金研究院 Intensified leaching method and device
CN102268545B (en) * 2011-07-20 2012-12-12 广西冶金研究院 Intensified leaching method and device
CN105347399A (en) * 2014-08-21 2016-02-24 中国科学院过程工程研究所 Chromium leaching method by ammonium sulfate roasting decomposition of chromite
CN105347399B (en) * 2014-08-21 2017-11-14 中国科学院过程工程研究所 A kind of method that ammonium sulfate Roasting Decomposition chromite leaches chromium
CN104843790A (en) * 2015-05-22 2015-08-19 四川省银河化学股份有限公司 Method for preparing sodium chromate from chromite by acid dissolution oxygenation
CN105695760A (en) * 2016-03-02 2016-06-22 东北大学 Method for carrying out two-stage countercurrent leaching on chromium-containing vanadium slag and extracting vanadium and chromium in separating manner
CN105695760B (en) * 2016-03-02 2018-05-29 东北大学 A kind of method of two sections of counterflow leachings of vanadium slag containing chromium type and separation and Extraction vanadium chromium
CN106186067A (en) * 2016-07-06 2016-12-07 于佳湲 A kind of method producing chromic oxide for raw material cleaning with chromite
CN106186067B (en) * 2016-07-06 2017-11-17 于佳湲 A kind of method using chromite as raw material clean manufacturing chrome green
CN108910950A (en) * 2018-10-12 2018-11-30 成都铬科高化工技术有限责任公司 A method of by preparing sodium chromate from chromite
CN111620370A (en) * 2020-05-15 2020-09-04 重庆理工大学 Electric field enhanced efficient chromite leaching method
CN113998741A (en) * 2021-11-12 2022-02-01 单淼 Method for preparing iron-based electrode material by taking waste iron sheet as raw material

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Application publication date: 20110223