CN1255323C - Production technology of ferrous sulfate vitriol from hematite - Google Patents
Production technology of ferrous sulfate vitriol from hematite Download PDFInfo
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- CN1255323C CN1255323C CN 200410012472 CN200410012472A CN1255323C CN 1255323 C CN1255323 C CN 1255323C CN 200410012472 CN200410012472 CN 200410012472 CN 200410012472 A CN200410012472 A CN 200410012472A CN 1255323 C CN1255323 C CN 1255323C
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Abstract
The present invention discloses a technique for preparing ferrous sulfate heptahydrate from hematite. In the technique, hematite ores are crushed and are ground and processed into powder of 80 to 100 meshes; after the powder is concentrated into mineral powder with T<Fe> more than 65%, two techniques of acid dissolving and reduction are carried out, namely that the ferrous sulfate heptahydrate with the content of 96% is prepared through the processes of soaking the mineral powder in sulfuric acid to generate sulfuric acid ferric solution, reducing digestion liquid, crystallizing reduction liquid at low temperature and drying the ferrous sulfate heptahydrate in vacuum. In the present invention, the ferrous sulfate heptahydrate is prepared from hematite; the present invention has the advantages of abundant cheap raw material easily obtained and no environmental pollution in production processes and is suitable for large-scale industrial production. The ferrous sulfate heptahydrate is widely used in industries of medicine, agricultural chemicals, feed, sewage treatment, etc. The product of the present invention reaches the first grade of the industrial water treating agent with Chinese standard GB10531-89 and provides a new way for the application of the hematite in the field of chemical industry.
Description
Technical field
The invention belongs to the inorganic salt field, relate to a kind of technology of producing iron vitriol, particularly with rhombohedral iron ore be raw material adopt acid molten-technology that the reduction two-step approach is produced iron vitriol.
Background technology
The production technique of present industrial iron vitriol has two kinds, and first kind is iron filings-Production By Sulfuric Acid Process iron vitriol, and its production process is sulfuric acid and iron filings reaction, promptly gets ferrous sulfate through precipitation, crystallization, dehydration.Its chemical reaction is as follows:
Second kind is that the titanium white by product method is produced iron vitriol, and its production process is to decompose ilmenite with sulfuric acid, generates FeSO
4And Fe
2(SO
4)
3, wherein ferric iron reduces with iron wire, through freezing and crystallizing, can obtain byproduct FeSO
4.7H
2O, its chemical reaction is:
The problem that above-mentioned two kinds of producing and manufacturing technique exist is: the raw materials cost of iron filings-sulfuric acid process is higher, and the price of iron filings is subject to the fluctuation of iron and steel price, and its source is limited, is not suitable for large-scale industrial production; The titanium white by product method will consume a large amount of sulfuric acid, the spent acid that discharges in the production process, waste water, waste residue and waste gas, and serious environment pollution, and the foreign matter content height of product iron vitriol, the grade of product is lower.
Natural rhombohedral iron ore mainly is to be used for the raw material of smelting iron and steel industry as the blast furnace refining pig iron.Iron vitriol is commonly called as green vitriol, is widely used in industries such as medicine, agricultural chemicals, feed and sewage disposal.
Summary of the invention
The present invention is primarily aimed in the production technique of existing iron vitriol, raw material iron filings price higher and originate limited, be not suitable for large-scale industrial production, and product foreign matter content height, grade is low and produce in the problem of the waste water,waste gas and industrial residue serious environment pollution of discharging, the technology of producing iron vitriol from rhombohedral iron ore that a kind of raw material is cheap and easy to get, be suitable for large-scale industrial production, non-environmental-pollution is provided.
The present invention realize technical scheme that above-mentioned purpose adopts be with rhombohedral iron ore stone through Mechanical Crushing, and ore grinding is processed as 80～100 orders, selected breeze to TFe＞65%; Next is the Fe that adds in breeze in industrial sulphuric acid and the breeze
2O
3Carry out sour molten reaction and generate the ferric sulphate dissolution fluid, filter and dilute with water; With iron filings the ferric sulphate in the dissolution fluid of dilution is reduced to ferrous sulfate at last, filtration also makes reduced liquid separate out the iron vitriol crystallization at low temperatures, and fractional crystallization also carries out vacuum-drying, promptly gets iron vitriol.
Wherein, the proportioning raw materials of the molten reaction of described acid is the Fe in industrial sulphuric acid and the breeze
2O
3Mol ratio be 1: 4.3; The optimum process condition of the molten reaction of described acid is: sulfuric acid concentration is 45%, temperature of reaction is that 110 ℃, reaction times are 2.0hr, and the solubility rate of rhombohedral iron ore is more than 92%; The ferric sulphate dissolution fluid that the molten reaction of described acid generates filters and is diluted with water to 23～24 ° of Be ', carries out reduction reaction again; Described reduction reaction operational condition is: temperature of reaction is that 45 ℃～75 ℃, reaction times are 2.0hr, and ferric sulphate is reduced to ferrous sulfate can reach 100%; The temperature of described vacuum-drying iron vitriol for≤65 ℃, vacuum tightness be 13.33KPa, time of drying 2.0hr.
The innovation part of the invention process technique scheme is: replace iron filings with ground hematite and produce iron vitriol, the raw material reserves are abundant, cheap, be suitable for large-scale industrial production, explored reserves had 50120Mt in 90 years, wherein industrial reserves accounts for 67.9% of total reserves, and is at the forefront in the world; And the iron filings output that derives from part machinery processing is limited, is not suitable for the mass-producing serialization and produces.Raw materials cost of the present invention is cheap, calculates at comparable price, and raw materials cost can descend 40%.The present invention proposes a kind of acid molten-reduction two step process, overcome the severe contamination that a large amount of waste water,waste gas and industrial residue of existing in the titanium white by product method technology causes environment; And the iron vitriol product purity height by this explained hereafter, foreign matter content is low, meets the industrial water conditioning agent acceptable end product of GB GB10531-89.The technology quality index of this product such as following table 1, table 2:
The technology quality index of table 1. product
| Element or compound title | Content (%) | ||||||
| Measured value | GB GB10531-89 | ||||||
| Drinking water treatment is used | Process water is handled and is used | ||||||
| Premium grads | Acceptable end product | Salable product | Premium grads | Acceptable end product | Salable product | ||
| Ferrous sulfate (FeSO 4·7H 2O) content, % 〉= | 95.68 | 97.0 | 94.0 | 90.0 | 97.0 | 94.0 | 90.0 |
| Titanium dioxide (TiO 2) content ,≤ | 0.0143 | 0.5 | 0.5 | 0.75 | 0.5 | 0.5 | 0.75 |
| Water insoluble matter content, %≤ | 0.0000 | 0.2 | 0.5 | 0.75 | 0.2 | 0.5 | 0.75 |
| Free acid is (with H 2SO 4Meter)≤ | 0.3170 | 0.35 | 1.0 | 2.0 | - | - | - |
| Arsenic (As), %≤ | 0.000013 | 0.0005 | 0.0005 | 0.0005 | - | - | - |
| Heavy metal (in Pb) %≤ | 0.00055 | 0.002 | 0.002 | 0.002 | - | - | - |
Table 2. product micronutrient levels unit: ug/g=10
-6(ppm)=10
-4%
| Element | Pb | Zn | Cu | As | Mn | Si | Ca | Mg |
| Content | 5.5 | 9.8 | 18.7 | 0.13 | 35.1 | 7.5 | 9.8 | 0.9 |
Embodiment
Embodiment
The present invention is described in more detail below in conjunction with embodiment:
Get and originate in Australian rhombohedral iron ore as the raw material of producing iron vitriol, be processed as 100 orders through pulverizing, ore grinding, and selected with methods such as magnetic separation or flotation be 65% breeze, use sulfuric acid-phosphoric acid mixing acid decomposition method again, potassium bichromate titrimetric method measures full iron respectively and ferrous content sees Table 1:
The iron level of the Australian ground hematite of table 1
| Mineral name | Total iron TFe % | FeO ％ | Fe 2O 3 ％ |
| Australia's ground hematite | 64.85 | 8.56 | 83.20 |
Ground hematite and industrial sulphuric acid are that raw material carries out following steps successively:
(1) acid is molten
Press the Fe in the ground hematite
2O
3With the mol ratio of industrial sulphuric acid be 1: 4.3, in ground hematite, add concentration and be 45% sulfuric acid, be 110 ℃ of reaction 2.0hr down in temperature of reaction, the oxide compound of the iron of various valence states in the rhombohedral iron ore can be free in the solution, solubility rate is more than 92%.The chemical reaction of the molten process of acid is:
(2) reduction
The ferric sulphate solution that will filter and be diluted to 23～24 ° of B é (proportion is 1.1896～1.1995) is heated to 45 ℃～75 ℃, and drops into excessive reductive agent iron filings, carries out following reduction reaction:
The about 2.0hr of reduction reaction, high ferro Fe
3+Be reduced to ferrous Fe
2+Can reach for 100% (not showing red) with the ammonium thiocyanate indication.Reduction process is carried out following reaction simultaneously:
(3) crystallization
The ferrous sulfate reduced liquid about 0 ℃ in solution crystallization separate out iron vitriol crystal, i.e. green vitriol:
Ferrous sulfate is dense in the reduced liquid, when concentration reaches 2.3～2.6mol/l (35%～40%), is the crystallizable absinthe-green ferrous sulfate crystal that goes out at normal temperatures.In order to improve the yield of ferrous sulfate, with reference to the dissolubility data of ferrous sulfate in water, reduced liquid adopts the method that is refrigerated to 0 ℃ favourable to yield, but not only rapid crystallization goes out iron vitriol, and the mother liquor amount is few, and the residual quantity of product is also few in the mother liquor.Like this, crystalline mother solution can directly be delivered to the usefulness that complex acid workshop section makes the dilution vitriol oil.If adopt spontaneous nucleation, the one, the time is long, and it is big to occupy the crystallizing pond area; The 2nd, summer the temperature height, the crystal of separating out is few, the residual quantity of product is higher in the mother liquor, should not make the thinner of pickling liquor, must be with mother liquor secondary concentration, crystallization.
(4) vacuum-drying
The iron vitriol crystal of separating out contains residual mother liquor after liquid-solid separation.Because of iron vitriol easy-weathering in dry air, in damp atmosphere, easily be oxidized to brown xanchromatic ferric subsulfate, change four water things into by seven water things when being heated to 56.6 ℃, 64.4 ℃ transform a water thing again " know; common dry 100 ℃ will obtain a water thing, adopt to be lower than≤65 ℃, the vacuum-drying 2.0hr of vacuum tightness 13.332KPa for this reason.
Claims (6)
1. produce iron vitriol technology from rhombohedral iron ore, it is characterized in that rhombohedral iron ore stone, and ore grinding is processed as 80～100 orders through Mechanical Crushing, selected to T
Fe＞65% breeze; Next is the Fe that adds in breeze in industrial sulphuric acid and the breeze
2O
3Carry out sour molten reaction and generate the ferric sulphate dissolution fluid, filter and dilute with water; With iron filings the ferric sulphate in the dissolution fluid of dilution is reduced to ferrous sulfate at last, filtration also makes reduced liquid separate out the iron vitriol crystallization at low temperatures, and fractional crystallization also carries out vacuum-drying, promptly gets iron vitriol.
2. according to claim 1 from rhombohedral iron ore production iron vitriol technology, the proportioning raw materials that it is characterized in that sour molten reaction is the Fe in industrial sulphuric acid and the breeze
2O
3Mol ratio be 1: 4.3.
3. according to claim 1ly produce iron vitriol technology from rhombohedral iron ore, it is characterized in that the optimum process condition of sour molten reaction is: sulfuric acid concentration is 45%, temperature of reaction is that 110 ℃, reaction times are 2.0hr, and the solubility rate of rhombohedral iron ore is more than 92%.
4. according to claim 1 from rhombohedral iron ore production iron vitriol technology, it is characterized in that sour molten reaction generates the ferric sulphate dissolution fluid, must be diluted with water to 23～24 ° of Be ', carry out reduction reaction again.
5. according to claim 1ly produce iron vitriol technology from rhombohedral iron ore, it is characterized in that the operational condition of reduction reaction is: temperature of reaction is that 45 ℃～75 ℃, reaction times are 2.0hr, and ferric sulphate is reduced to ferrous sulfate can reach 100%.
6. according to claim 1ly produce iron vitriol technology from rhombohedral iron ore, the temperature that it is characterized in that the vacuum-drying iron vitriol for≤65 ℃, vacuum tightness be 13.33KPa, time of drying 2.0hr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410012472 CN1255323C (en) | 2004-08-06 | 2004-08-06 | Production technology of ferrous sulfate vitriol from hematite |
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|---|---|---|---|
| CN 200410012472 CN1255323C (en) | 2004-08-06 | 2004-08-06 | Production technology of ferrous sulfate vitriol from hematite |
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| CN1255323C true CN1255323C (en) | 2006-05-10 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023138778A1 (en) * | 2022-01-21 | 2023-07-27 | Amateq Holding Gmbh | Method of producing iron(ii) sulfate heptahydrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010125205A1 (en) * | 2009-04-27 | 2010-11-04 | Tioxide Europe, S.L. | Method for producing ferrous sulphate from pyrite ash |
| CN101817563B (en) * | 2010-04-10 | 2011-08-03 | 湖南新恒光科技有限公司 | Process for preparing high-purity ferrous sulfate by adopting pyrite smelting slag |
| CN103194598A (en) * | 2013-04-19 | 2013-07-10 | 贵州东华工程股份有限公司 | Method for improving recovery rate of gold ore difficult to treat by adopting sulfuric acid leaching reduction process |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023138778A1 (en) * | 2022-01-21 | 2023-07-27 | Amateq Holding Gmbh | Method of producing iron(ii) sulfate heptahydrate |
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