CN104109756A - High-purity iron oxide red wet-pyrogenic integrated device and preparation method of high-purity iron oxide red - Google Patents
High-purity iron oxide red wet-pyrogenic integrated device and preparation method of high-purity iron oxide red Download PDFInfo
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Abstract
The invention relates to the technical field of high-purity iron oxide red and in particular relates to a high-purity iron oxide red wet-pyrogenic integrated device and a preparation method of high-purity iron oxide red. The high-purity iron oxide red wet-pyrogenic integrated device comprises a wet ball mill, an acid leaching tank, a primary filter, a calcium and magnesium removal tank, a secondary filter, a preconcentrator, a slurry absorption tower, a hydrolysis calcining furnace and a rotary calcining kiln, wherein the discharge end of the wet ball mill is fixedly connected together with the feed end of the acid leaching tank via a first pipeline. The device and the preparation method have the beneficial effects that the high-purity iron oxide red is produced by utilizing the pyrometallurgy equipment, namely the rotary calcining kiln, and the generated chlorine-containing high-temperature flue gases provide heat for the hydrolysis calcining furnace, achieve wet dust collection and remove HCl and dust in the flue gases; removal of impurities in siderite is completed by utilizing the acid leaching technology of wet metallurgy; hydrochloric acid in the invention can be recycled and other media are not introduced, so that no byproducts are generated and secondary pollution is avoided, thus reducing the production cost and achieving comprehensive utilization of low-grade siderite.
Description
Technical field
The present invention relates to high-purity iron oxide red technical field, is a kind of high-purity iron oxide red wet fiery one subtraction unit and high-purity iron oxide red preparation method.
Background technology
Hydrometallurgy is exactly the process that metalliferous mineral raw material carries out chemical treatment or organic solvent extraction, separating impurity, extraction metal and compound thereof in the aqueous solution of acidic medium or alkaline medium.The advantage of hydrometallurgy be in raw material valuable metal comprehensively to reclaim degree high, and production process more easily realizes serialization and automatization.For pyrometallurgy, fuel, electric energy or other energy produce high temperature, at high temperature, and extraction and finishing metal or its compound from ore.Pyrometallurgy generally divides the steps such as ore preparation, smelting, refining and flue gas processing.The main chemical reactions of pyrometallurgy is reduction-oxidation reaction.Pyrometallurgy has technical maturity, and easily large-scale production, has dominant position at metallurgy industry.But pyrogenic process also exist to ore grade require high, energy consumption is high, high-temperature flue gas is difficult to the problem of thoroughly processing, thereby has increased production cost.
And wet method to low grade ore have suitability, to the difficult separating mineral of similar metalliferous mineral there is suitability and valuable metal comprehensive utilization yield high, process the feature thoroughly of polluting, be strong supplementing to pyrometallurgy.But in hydrometallurgy, acidic medium, alkaline medium or other media used cannot cyclic regeneration, and will form by product cannot process, and mostly forms solid, liquid debris is discharged, and can work the mischief to environment.
China's spathic iron ore resource is very abundant, but average iron content 30% to 35%, and ore is adopted, choosing, smelting are all more difficult, so utilization ratio is not high.Industry technology personnel research emphasis is technique of preparing at present, mainly comprises: the combined process flows such as the single flow process such as flotation, high intensity magnetic separation and roasting-magnetic separation.But show through practice for many years, it is high that prior art all exists running cost, produce secondary pollution problems, cause most spathic iron ores all in idle state.
Summary of the invention
The invention provides a kind of high-purity iron oxide red wet fiery one subtraction unit and high-purity iron oxide red preparation method, overcome the deficiency of above-mentioned prior art, it can effectively solve prior art and all exist running cost high, produces secondary pollution, causes all problems in idle state of spathic iron ore.
One of technical scheme of the present invention realizes by following measures: a kind of high-purity iron oxide red wet fiery one subtraction unit, comprises ball mill by wet process, acidleach tank, single filter machine, calcium-magnesium removing tank, cascade filtration machine, preconcentrator, slurry absorption tower, hydrolysis calcining furnace and rotary calciner, the feed end of the discharge end of ball mill by wet process and acidleach tank is fixed together by the first pipeline, the liquid feeding end of the discharge end of acidleach tank and single filter machine is fixed together by the second pipeline, the feed end of the outlet end of single filter machine and calcium-magnesium removing tank is fixed together by the 3rd pipeline, be installed with cleaner pipe on the top of calcium-magnesium removing tank, the liquid feeding end of the discharge end of calcium-magnesium removing tank and cascade filtration machine is fixed together by the 4th pipeline, the outlet end of cascade filtration machine and the feed end of preconcentrator are fixed together by the 5th pipeline, the feed end of the discharge end of preconcentrator and hydrolysis calcining furnace is fixed together by the 6th pipeline, below hydrolysis calcining furnace, be installed with worm conveyor by support, the hydrolysis discharge end of calcining furnace and the feed end of worm conveyor are corresponding, the discharge end of worm conveyor and the feed end of rotary calciner are fixed together by the 7th pipeline, between the liquid feeding end on slurry absorption tower and the second pipeline, be fixedly connected with the 8th pipeline, between the outlet end on slurry absorption tower and the top of acidleach tank, be fixedly connected with the 9th pipeline, the inlet end on the outlet side of preconcentrator and slurry absorption tower is fixed together by the tenth pipeline, on the second pipeline, the 4th pipeline and the 6th pipeline, is installed with respectively pump.
The further optimization and/or improvements to one of foregoing invention technical scheme below:
There are respectively hydrochloric acid absorption tower and tail gas washing tower in the above-mentioned outside at preconcentrator; The outlet side on slurry absorption tower and the inlet end of hydrochloric acid absorption tower are fixed together by the 11 pipeline, the outlet side of hydrochloric acid absorption tower and the inlet end of tail gas washing tower are fixed together by the 12 pipeline, on the 12 pipeline, are installed with blower fan; Between the top of acidleach tank and the 11 pipeline, be fixedly connected with the 13 pipeline; On the outlet side of tail gas washing tower, be fixedly connected with escape pipe, on the liquid feeding end of tail gas washing tower, be fixedly connected with water inlet pipe, the outlet end of tail gas washing tower and the liquid feeding end of hydrochloric acid absorption tower are fixed together by the 14 pipeline, between the outlet end of hydrochloric acid absorption tower and the 9th pipeline, be fixedly connected with the 15 pipeline, on the 14 pipeline and the 15 pipeline, be installed with respectively pump, on the second pipeline and the 8th pipeline, be installed with respectively valve.
There are respectively producer gas generator and cyclonic separator in the above-mentioned outside at hydrolysis calcining furnace; The inlet end of producer gas generator outlet side and hydrolysis calcining furnace is fixed together by the 16 pipeline, the hydrolysis outlet side of calcining furnace and the feed end of cyclonic separator are fixed together by the 17 pipeline, the outlet side of cyclonic separator and the inlet end of preconcentrator are fixed together by the 18 pipeline, on the discharge end of cyclonic separator, be fixedly connected with tremie pipe, the discharge end of tremie pipe is positioned at the top of worm conveyor corresponding; Between the inlet end of rotary calciner and the 16 pipeline, be fixedly connected with the 19 pipeline, between the outlet side of rotary calciner and the bottom of hydrolysis calcining furnace, be fixedly connected with the 20 pipeline; On the 16 pipeline and the 19 pipeline, be installed with respectively valve.
Above-mentionedly on the discharge end of rotary calciner, be fixedly connected with discharge nozzle, on discharge nozzle, be installed with valve.
Above-mentionedly on acidleach tank, be installed with agitator; On calcium-magnesium removing tank, be installed with agitator.
Two of technical scheme of the present invention realizes by following measures: a kind of high-purity iron oxide red preparation method, carry out in the steps below: the first step, spathic iron ore is added and in ball mill by wet process, carries out ball milling, after ball milling, enter and in the pickling liquor in acidleach tank, carry out acidleach by the first pipeline, pickling liquor is aqueous hydrochloric acid, the temperature of pickling liquor is 85 DEG C to 95 DEG C, and the pH value of pickling liquor is 4 to 5, obtains slurry after acidleach one time, second step, one time slurry enters in single filter machine and slurry absorption tower by the second pipeline and the 8th pipeline respectively, after slurry in slurry absorption tower and smoke reaction, get back in acidleach tank by the 9th pipeline, after entering a slurries filtration in single filter machine, obtain one-level filtrate, one-level filtrate is reacted and is obtained secondary slurry with the ammonium fluoride aqueous solution in cleaner pipe by the 3rd pipeline in calcium-magnesium removing tank, the temperature of reaction of one-level filtrate and ammonium fluoride aqueous solution is 78 DEG C to 82 DEG C, in ammonium fluoride aqueous solution, the amount of substance of Neutral ammonium fluoride is 1.2 times to 1.3 times of the total amount of substance of calcium ions and magnesium ions in one-level filtrate, the 3rd step, secondary slurry is entered in cascade filtration machine and is filtered by the 4th pipeline, after filtration, obtain secondary filtrate, secondary filtrate is entered in preconcentrator and is concentrated and obtain concentrated solution by the 5th pipeline, and the volume of concentrated solution is 70% to 85% of secondary filtrate volume, the 4th step, concentrated solution enters the hydrolysis reaction that is hydrolyzed in calcining furnace by the 6th pipeline, solid phase after hydrolysis reaction is entered in rotary calciner and is calcined by worm conveyor and the 7th pipeline, after calcining, obtain quality percentage composition and be 99.4% to 99.9% high-purity iron oxide red.
Two the further optimization and/or improvements to foregoing invention technical scheme below:
The coal gas that above-mentioned producer gas generator produces is entered in hydrolysis calcining furnace and rotary calciner and is burnt by the 16 pipeline and the 19 pipeline respectively, flue gas in rotary calciner enters in hydrolysis calcining furnace by the 20 pipeline, flue gas in hydrolysis calcining furnace is entered in cyclonic separator and is separated by the 17 pipeline, solid phase after separation enters in worm conveyor by tremie pipe, flue gas after separation is entered in preconcentrator and is reacted with secondary filtrate by the 18 pipeline, in preconcentrator, reacted flue gas is entered in slurry absorption tower and is reacted with a slurry by the tenth pipeline, in slurry absorption tower, reacted flue gas is entered in hydrochloric acid absorption tower and is reacted with the liquid phase in hydrochloric acid absorption tower by the 11 pipeline, in hydrochloric acid absorption tower, reacted flue gas is entered after reacting with the water in water inlet pipe in tail gas washing tower and is discharged from escape pipe by the 12 pipeline, in the reacted flue gas of tail gas washing tower, HCl concentration is less than 5PPm, in tail gas washing tower, reacted liquid phase enters in hydrochloric acid absorption tower by the 14 pipeline, in hydrochloric acid absorption tower, reacted liquid phase enters in acidleach tank by the 15 pipeline, gas in acidleach tank enters in hydrochloric acid absorption tower by the 13 pipeline.
The mass percent concentration of above-mentioned ammonium fluoride aqueous solution is 20% to 40%; Or/and in the first step, the particle diameter after spathic iron ore ball milling is 60 order to 100 orders.
800 DEG C to 900 DEG C of the calcining temperatures of above-mentioned rotary calciner; Or/and, 600 DEG C to 700 DEG C of the bottom temps of hydrolysis calcining furnace, the top of hydrolysis calcining furnace is 350 DEG C to 450 DEG C, the quality percentage composition that goes out to be hydrolyzed ferric oxide in the solid phase of calcining furnace is 94.5% to 96.5%.
In above-mentioned spathic iron ore, the quality percentage composition of iron is 30% to 45%, and magnesian quality percentage composition is less than 1%, and the quality percentage composition of calcium oxide is less than 2%, and the quality percentage composition of aluminum oxide is less than 1%.
It is high-purity iron oxide red that the present invention utilizes pyrometallurgy equipment rotary calciner to produce, and the chloride high-temperature flue gas of generation both provided heat for hydrolysis calcining kiln, had realized again wet dedusting, had removed HCl and the dust in flue gas; Utilize the acidleach technology of hydrometallurgy, completed removing of impurity in spathic iron ore, the hydrochloric acid in the present invention can recycle, do not introduce other media, produce without byproduct, there is no secondary pollution, thereby reduce production cost, realized the comprehensive utilization of low-grade spathic iron ore.
Brief description of the drawings
Accompanying drawing 1 is process flow diagram of the present invention.
Coding in accompanying drawing is respectively: 1 is ball mill by wet process, 2 is acidleach tank, 3 is single filter machine, 4 is calcium-magnesium removing tank, 5 is cascade filtration machine, 6 is preconcentrator, 7 is slurry absorption tower, 8 is hydrolysis calcining furnace, 9 is rotary calciner, 10 is the first pipeline, 11 is the second pipeline, 12 is the 3rd pipeline, 13 is cleaner pipe, 14 is the 4th pipeline, 15 is the 5th pipeline, 16 is the 6th pipeline, 17 is worm conveyor, 18 is the 7th pipeline, 19 is the 8th pipeline, 20 is the 9th pipeline, 21 is the tenth pipeline, 22 is pump, 23 is hydrochloric acid absorption tower, 24 is tail gas washing tower, 25 is the 11 pipeline, 26 is the 12 pipeline, 27 is blower fan, 28 is the 13 pipeline, 29 is escape pipe, 30 is water inlet pipe, 31 is the 14 pipeline, 32 is the 15 pipeline, 33 is producer gas generator, 34 is cyclonic separator, 35 is the 16 pipeline, 36 is the 17 pipeline, 37 is the 18 pipeline, 38 is tremie pipe, 39 is the 19 pipeline, 40 is the 20 pipeline, 41 is discharge nozzle, 42 is agitator.
Embodiment
The present invention is not subject to the restriction of following embodiment, can determine concrete embodiment according to technical scheme of the present invention and practical situation.
In the present invention, for convenience of description, the description of the relative position relation of each parts is to be all described according to the Butut mode of Figure of description 1, as: the position relationship of forward and backward, upper and lower, left and right etc. is to determine according to the Butut direction of Figure of description 1.
Below in conjunction with embodiment and accompanying drawing, the invention will be further described:
Embodiment 1, as shown in Figure 1, this high-purity iron oxide red wet fiery one subtraction unit comprises ball mill by wet process 1, acidleach tank 2, single filter machine 3, calcium-magnesium removing tank 4, cascade filtration machine 5, preconcentrator 6, slurry absorption tower 7, hydrolysis calcining furnace 8 and rotary calciner 9; the feed end of the discharge end of ball mill by wet process 1 and acidleach tank 2 is fixed together by the first pipeline 10, the liquid feeding end of the discharge end of acidleach tank 2 and single filter machine 3 is fixed together by the second pipeline 11, the feed end of the outlet end of single filter machine 3 and calcium-magnesium removing tank 4 is fixed together by the 3rd pipeline 12, be installed with cleaner pipe 13 on the top of calcium-magnesium removing tank 4, the liquid feeding end of the discharge end of calcium-magnesium removing tank 4 and cascade filtration machine 5 is fixed together by the 4th pipeline 14, the feed end of the outlet end of cascade filtration machine 5 and preconcentrator 6 is fixed together by the 5th pipeline 15, the feed end of the discharge end of preconcentrator 6 and hydrolysis calcining furnace 8 is fixed together by the 6th pipeline 16, below hydrolysis calcining furnace 8, be installed with worm conveyor 17 by support, the discharge end of hydrolysis calcining furnace 8 is corresponding with the feed end of worm conveyor 17, the feed end of the discharge end of worm conveyor 17 and rotary calciner 9 is fixed together by the 7th pipeline 18, between the liquid feeding end on slurry absorption tower 7 and the second pipeline 11, be fixedly connected with the 8th pipeline 19, between the outlet end on slurry absorption tower 7 and the top of acidleach tank 2, be fixedly connected with the 9th pipeline 20, the inlet end on the outlet side of preconcentrator 6 and slurry absorption tower 7 is fixed together by the tenth pipeline 21, on the second pipeline 11, the 4th pipeline 14 and the 6th pipeline 16, is installed with respectively pump 22.Ball mill by wet process 1, acidleach tank 2, single filter machine 3, calcium-magnesium removing tank 4, cascade filtration machine 5, preconcentrator 6, slurry absorption tower 7, hydrolysis calcining furnace 8 and rotary calciner 9 are existing public equipment.
Can according to actual needs, above-described embodiment 1 be made further optimization and/or improvements:
As shown in Figure 1, there are respectively hydrochloric acid absorption tower 23 and tail gas washing tower 24 in the outside of preconcentrator 6; The inlet end of the outlet side on slurry absorption tower 7 and hydrochloric acid absorption tower 23 is fixed together by the 11 pipeline 25, the inlet end of the outlet side of hydrochloric acid absorption tower 23 and tail gas washing tower 24 is fixed together by the 12 pipeline 26, on the 12 pipeline 26, is installed with blower fan 27; Between the top of acidleach tank 2 and the 11 pipeline 25, be fixedly connected with the 13 pipeline 28; On the outlet side of tail gas washing tower 24, be fixedly connected with escape pipe 29, on the liquid feeding end of tail gas washing tower 24, be fixedly connected with water inlet pipe 30, the liquid feeding end of the outlet end of tail gas washing tower 24 and hydrochloric acid absorption tower 23 is fixed together by the 14 pipeline 31, between the outlet end of hydrochloric acid absorption tower 23 and the 9th pipeline 20, be fixedly connected with the 15 pipeline 32, on the 14 pipeline the 31 and the 15 pipeline 32, be installed with respectively pump 22, on the second pipeline 11 and the 8th pipeline 19, be installed with respectively valve.Blower fan 27 has ensured that the high-purity iron oxide red wet fiery one subtraction unit of the present invention is in micro-vacuum state.
As shown in Figure 1, there are respectively producer gas generator 33 and cyclonic separator 34 in the outside of hydrolysis calcining furnace 8; The inlet end of producer gas generator 33 outlet sides and hydrolysis calcining furnace 8 is fixed together by the 16 pipeline 35, the hydrolysis outlet side of calcining furnace 8 and the feed end of cyclonic separator 34 are fixed together by the 17 pipeline 36, the inlet end of the outlet side of cyclonic separator 34 and preconcentrator 6 is fixed together by the 18 pipeline 37, on the discharge end of cyclonic separator 34, be fixedly connected with tremie pipe 38, the discharge end of tremie pipe 38 is positioned at the top of worm conveyor 17 corresponding; Between the inlet end of rotary calciner 9 and the 16 pipeline 35, be fixedly connected with the 19 pipeline 39, between the outlet side of rotary calciner 9 and the bottom of hydrolysis calcining furnace 8, be fixedly connected with the 20 pipeline 40; On the 16 pipeline the 35 and the 19 pipeline 39, be installed with respectively valve.
As shown in Figure 1, on the discharge end of rotary calciner 9, be fixedly connected with discharge nozzle 41, on discharge nozzle 41, be installed with valve.
As shown in Figure 1, on acidleach tank 2, be installed with agitator 42; On calcium-magnesium removing tank 4, be installed with agitator 42.
Embodiment 2, as shown in Figure 1, the preparation method that this is high-purity iron oxide red, carry out in the steps below: the first step, spathic iron ore is added and in ball mill by wet process 1, carries out ball milling, after ball milling, enter and in the pickling liquor in acidleach tank 2, carry out acidleach by the first pipeline 10, pickling liquor is aqueous hydrochloric acid, the temperature of pickling liquor is 85 DEG C to 95 DEG C, and the pH value of pickling liquor is 4 to 5, obtains slurry after acidleach one time, second step, one time slurry enters in single filter machine 3 and slurry absorption tower 7 by the second pipeline 11 and the 8th pipeline 19 respectively, after slurry in slurry absorption tower 7 and smoke reaction, get back in acidleach tank 2 by the 9th pipeline 20, after entering a slurries filtration in single filter machine 3, obtain one-level filtrate, one-level filtrate is reacted and is obtained secondary slurry with the ammonium fluoride aqueous solution in cleaner pipe 13 by the 3rd pipeline 12 in calcium-magnesium removing tank 4, the temperature of reaction of one-level filtrate and ammonium fluoride aqueous solution is 78 DEG C to 82 DEG C, in ammonium fluoride aqueous solution, the amount of substance of Neutral ammonium fluoride is 1.2 times to 1.3 times of the total amount of substance of calcium ions and magnesium ions in one-level filtrate, the 3rd step, secondary slurry is entered in cascade filtration machine 5 and is filtered by the 4th pipeline 14, after filtration, obtain secondary filtrate, secondary filtrate is entered in preconcentrator 6 and is concentrated and obtain concentrated solution by the 5th pipeline 15, and the volume of concentrated solution is 70% to 85% of secondary filtrate volume, the 4th step, concentrated solution enters the hydrolysis reaction that is hydrolyzed in calcining furnace 8 by the 6th pipeline 16, solid phase after hydrolysis reaction is entered in rotary calciner 9 and is calcined by worm conveyor 17 and the 7th pipeline 18, after calcining, obtain quality percentage composition and be 99.4% to 99.9% high-purity iron oxide red.Control the pH value of acidleach, ensure that the Al of a slurry is qualified.In secondary slurry, the average content of Ca ion is 5PPm, and the average content of magnesium ion is 9PPM.In acidleach tank 2, the amount of substance of hydrochloric acid is 75% to 85% of iron in spathic iron ore, magnesium, calcium and the total amount of substance of aluminium, and in acidleach tank 2, the reaction times is 1.0h to 2.0h.
Can according to actual needs, above-described embodiment 2 be made further optimization and/or improvements:
As shown in Figure 1, the coal gas that producer gas generator 33 produces is entered in hydrolysis calcining furnace 8 and rotary calciner 9 and is burnt by the 16 pipeline the 35 and the 19 pipeline 39 respectively, flue gas in rotary calciner 9 enters in hydrolysis calcining furnace 8 by the 20 pipeline 40, flue gas in hydrolysis calcining furnace 8 is entered in cyclonic separator 34 and is separated by the 17 pipeline 36, solid phase after separation enters in worm conveyor 17 by tremie pipe 38, flue gas after separation is entered in preconcentrator 6 and is reacted with secondary filtrate by the 18 pipeline 37, in preconcentrator 6, reacted flue gas is entered in slurry absorption tower 7 and is reacted with a slurry by the tenth pipeline 21, in slurry absorption tower 7, reacted flue gas is entered in hydrochloric acid absorption tower 23 and is reacted with the liquid phase in hydrochloric acid absorption tower 23 by the 11 pipeline 25, in hydrochloric acid absorption tower 23, reacted flue gas is entered after reacting with the water in water inlet pipe 30 in tail gas washing tower 24 and is discharged from escape pipe 29 by the 12 pipeline 26, in the reacted flue gas of tail gas washing tower 24, HCl concentration is less than 5PPm, in tail gas washing tower 24, reacted liquid phase enters in hydrochloric acid absorption tower 23 by the 14 pipeline 31, in hydrochloric acid absorption tower 23, reacted liquid phase enters in acidleach tank 2 by the 15 pipeline 32, gas in acidleach tank 2 enters in hydrochloric acid absorption tower 23 by the 13 pipeline 28.The medial temperature that hydrolysis calcining furnace 8 is discharged flue gas is 400 DEG C, and its flue gas content (volume fraction %) is, HCl:8.15%, H
2o:42.18%, N
2: 39.52%, CO
2: 7.49%; After secondary filtrate contacts with the flue gas of discharging in cyclonic separator 34, the volume of concentrated solution is 70% to 85% of secondary filtrate volume, the average flue gas concentration that goes out preconcentrator 6 is 1.28 times of flue gas concentration of discharging in cyclonic separator 34, the flue gas average content (massfraction %) that goes out preconcentrator 6 is, HCl:5.77%, H
2o:53.26%, N
2: 32%; Producer gas generator 33 is existing known two sections of producer gas generators, by coal gas desulfurization, and the clean gas that average generation is 30 DEG C.The flooding quantity of water inlet pipe 30 is 50% to 80% of hydrochloric acid absorption tower 23 liquid outlet quantity quality, and the average salt acid concentration of entering the liquid phase of hydrochloric acid absorption tower 23 by the 14 pipeline 31 is 0.1% to 0.5%, and the average salt acid concentration that goes out the liquid phase of hydrochloric acid absorption tower 23 is 5% to 6%.
As required, the mass percent concentration of ammonium fluoride aqueous solution is 20% to 40%; Or/and in the first step, the particle diameter after spathic iron ore ball milling is 60 order to 100 orders.
As required, 800 DEG C to 900 DEG C of the calcining temperatures of rotary calciner 9; Or/and, 600 DEG C to 700 DEG C of the bottom temps of hydrolysis calcining furnace 8, the top of hydrolysis calcining furnace 8 is 350 DEG C to 450 DEG C, the quality percentage composition that goes out to be hydrolyzed ferric oxide in the solid phase of calcining furnace 8 is 94.5% to 96.5%.
As required, in spathic iron ore, the quality percentage composition of iron is 30% to 45%, and magnesian quality percentage composition is less than 1%, and the quality percentage composition of calcium oxide is less than 2%, and the quality percentage composition of aluminum oxide is less than 1%.The loss on ignition average out to 30% of spathic iron ore.
In the present invention, the average leaching yield of a slurry is as shown in table 1; Average solid phase composition after hydrolysis reaction is as shown in table 2; The average high-purity iron oxide red composition obtaining after calcining is as shown in table 3; Baosteel one-level Ferric Oxide Used for Soft Ferrite index is as shown in table 4; The present invention obtains as can be seen from Table 3 high-purity iron oxide redly can reach soft magnetic bodies iron oxide product index.
Acidleach and hydrolysis reaction that the present invention carries out in acidleach tank 2 and hydrolysis calcining furnace 8 are as follows:
The present invention utilizes the inherent advantage of the low-grade mineral of hydrometallurgical process, can obtain the high-quality starting material of high-grade intermediate product as pyrometallurgy, by the technique of pyrometallurgy maturation, finally can obtain the product of high-quality; And the unserviceable high-temperature flue gas that pyrogenic process produces, when can be used as wet method thermal source, rely on wet method to carry out the processing of sour reprocessing cycle and dedusting etc., form a series of efficient utilizations to low-grade mineral, form environmental friendliness, the novel process that energy efficient utilizes.The present invention is by the chemical mineral processing of low-grade mineral, the reprocessing cycle of acid medium and the cascade utilization of heat; By wet fiery one method, utilize hydrochloric acid to carry out acidleach to spathic iron ore, then remove silicon, aluminium, calcium, magnesium in spathic iron ore, obtain pure iron protochloride and ferric chloride Solution, then carry out pyrohydrolysis, when obtaining chloride ferric oxide, utilize spathic iron ore slurry to absorb the HCl in flue gas, realized the cyclic regeneration of high temperature acidleach and hydrochloric acid; And chloride ferric oxide enters and carries out high-temperature calcination in rotary calciner 9, when obtaining high purity ferric oxide product, chloride high-temperature dust-containing flue gas enters pyrohydrolysis system, as the thermal source of pyrohydrolysis.And high-temperature flue gas chloride, dust-laden in rotary calciner 9 carries out dedusting by cyclonic separator 34, slurry absorption tower 7, hydrochloric acid absorption tower 23 and tail gas washing tower 24, realizes the qualified discharge of dust and HCl; Hydrochloric acid in the present invention can recycle, does not introduce other media, produces without byproduct, there is no secondary pollution, thereby has reduced production cost, has realized the comprehensive utilization of low-grade spathic iron ore.
The high-purity iron oxide red wet fiery one subtraction unit of the present invention is also applicable to low-grade magnesite and red soil nickel ore etc.
Above technical characterictic has formed embodiments of the invention, and it has stronger adaptability and implementation result, can increase and decrease according to actual needs non-essential technical characterictic, meets the demand of different situations.
Table 1
| Element | Fe | Al | Ca | Mg | Si |
| Leaching yield/% | 75 to 85 | 3 to 5 | 20 to 25 | 25 to 35 | 0 to 0.05 |
Table 2
| Material | Fe 2O 3 | Al 2O 3 | CaO | MgO | Cl |
| Content (%) | 94.5 to 96.5 | 0 to 0.007 | 0 to 0.015 | 0 to 0.009 | 1.0 to 5.0 |
Table 3
| Material | Fe 2O 3 | Al 2O 3 | CaO | MgO | Cl |
| Content (%) | 99.4 to 99.9 | 0 to 0.009 | 0 to 0.018 | 0 to 0.009 | 0 to 0.13 |
Table 4
| Material | Fe 2O 3 | Al 2O 3 | CaO | MgO | SiO 2 | Cl |
| Content (%) | >99.30 | <0.01 | <0.02 | <0.01 | <0.012 | <0.15 |
Claims (10)
1. a high-purity iron oxide red wet fiery one subtraction unit, is characterized in that comprising ball mill by wet process, acidleach tank, single filter machine, calcium-magnesium removing tank, cascade filtration machine, preconcentrator, slurry absorption tower, hydrolysis calcining furnace and rotary calciner, the feed end of the discharge end of ball mill by wet process and acidleach tank is fixed together by the first pipeline, the liquid feeding end of the discharge end of acidleach tank and single filter machine is fixed together by the second pipeline, the feed end of the outlet end of single filter machine and calcium-magnesium removing tank is fixed together by the 3rd pipeline, be installed with cleaner pipe on the top of calcium-magnesium removing tank, the liquid feeding end of the discharge end of calcium-magnesium removing tank and cascade filtration machine is fixed together by the 4th pipeline, the outlet end of cascade filtration machine and the feed end of preconcentrator are fixed together by the 5th pipeline, the feed end of the discharge end of preconcentrator and hydrolysis calcining furnace is fixed together by the 6th pipeline, below hydrolysis calcining furnace, be installed with worm conveyor by support, the hydrolysis discharge end of calcining furnace and the feed end of worm conveyor are corresponding, the discharge end of worm conveyor and the feed end of rotary calciner are fixed together by the 7th pipeline, between the liquid feeding end on slurry absorption tower and the second pipeline, be fixedly connected with the 8th pipeline, between the outlet end on slurry absorption tower and the top of acidleach tank, be fixedly connected with the 9th pipeline, the inlet end on the outlet side of preconcentrator and slurry absorption tower is fixed together by the tenth pipeline, on the second pipeline, the 4th pipeline and the 6th pipeline, is installed with respectively pump.
2. high-purity iron oxide red wet fiery one subtraction unit according to claim 1, is characterized in that there are respectively hydrochloric acid absorption tower and tail gas washing tower in the outside of preconcentrator; The outlet side on slurry absorption tower and the inlet end of hydrochloric acid absorption tower are fixed together by the 11 pipeline, the outlet side of hydrochloric acid absorption tower and the inlet end of tail gas washing tower are fixed together by the 12 pipeline, on the 12 pipeline, are installed with blower fan; Between the top of acidleach tank and the 11 pipeline, be fixedly connected with the 13 pipeline; On the outlet side of tail gas washing tower, be fixedly connected with escape pipe, on the liquid feeding end of tail gas washing tower, be fixedly connected with water inlet pipe, the outlet end of tail gas washing tower and the liquid feeding end of hydrochloric acid absorption tower are fixed together by the 14 pipeline, between the outlet end of hydrochloric acid absorption tower and the 9th pipeline, be fixedly connected with the 15 pipeline, on the 14 pipeline and the 15 pipeline, be installed with respectively pump, on the second pipeline and the 8th pipeline, be installed with respectively valve.
3. high-purity iron oxide red wet fiery one subtraction unit according to claim 1 and 2, is characterized in that there are respectively producer gas generator and cyclonic separator in the outside that is hydrolyzed calcining furnace; The inlet end of producer gas generator outlet side and hydrolysis calcining furnace is fixed together by the 16 pipeline, the hydrolysis outlet side of calcining furnace and the feed end of cyclonic separator are fixed together by the 17 pipeline, the outlet side of cyclonic separator and the inlet end of preconcentrator are fixed together by the 18 pipeline, on the discharge end of cyclonic separator, be fixedly connected with tremie pipe, the discharge end of tremie pipe is positioned at the top of worm conveyor corresponding; Between the inlet end of rotary calciner and the 16 pipeline, be fixedly connected with the 19 pipeline, between the outlet side of rotary calciner and the bottom of hydrolysis calcining furnace, be fixedly connected with the 20 pipeline; On the 16 pipeline and the 19 pipeline, be installed with respectively valve.
4. according to the high-purity iron oxide red wet fiery one subtraction unit described in claim 1 or 2 or 3, it is characterized in that being fixedly connected with discharge nozzle on the discharge end of rotary calciner, on discharge nozzle, be installed with valve.
5. according to the high-purity iron oxide red wet fiery one subtraction unit described in claim 1 or 2 or 3 or 4, it is characterized in that being installed with agitator on acidleach tank; On calcium-magnesium removing tank, be installed with agitator.
6. the high-purity iron oxide red preparation method of the high-purity iron oxide red wet fiery one subtraction unit described in a right to use requirement 3, it is characterized in that carrying out in the steps below: the first step, spathic iron ore is added and in ball mill by wet process, carries out ball milling, after ball milling, enter and in the pickling liquor in acidleach tank, carry out acidleach by the first pipeline, pickling liquor is aqueous hydrochloric acid, the temperature of pickling liquor is 85 DEG C to 95 DEG C, and the pH value of pickling liquor is 4 to 5, obtains slurry after acidleach one time, second step, one time slurry enters in single filter machine and slurry absorption tower by the second pipeline and the 8th pipeline respectively, after slurry in slurry absorption tower and smoke reaction, get back in acidleach tank by the 9th pipeline, after entering a slurries filtration in single filter machine, obtain one-level filtrate, one-level filtrate is reacted and is obtained secondary slurry with the ammonium fluoride aqueous solution in cleaner pipe by the 3rd pipeline in calcium-magnesium removing tank, the temperature of reaction of one-level filtrate and ammonium fluoride aqueous solution is 78 DEG C to 82 DEG C, in ammonium fluoride aqueous solution, the amount of substance of Neutral ammonium fluoride is 1.2 times to 1.3 times of the total amount of substance of calcium ions and magnesium ions in one-level filtrate, the 3rd step, secondary slurry is entered in cascade filtration machine and is filtered by the 4th pipeline, after filtration, obtain secondary filtrate, secondary filtrate is entered in preconcentrator and is concentrated and obtain concentrated solution by the 5th pipeline, and the volume of concentrated solution is 70% to 85% of secondary filtrate volume, the 4th step, concentrated solution enters the hydrolysis reaction that is hydrolyzed in calcining furnace by the 6th pipeline, solid phase after hydrolysis reaction is entered in rotary calciner and is calcined by worm conveyor and the 7th pipeline, after calcining, obtain quality percentage composition and be 99.4% to 99.9% high-purity iron oxide red.
7. high-purity iron oxide red preparation method according to claim 6, it is characterized in that the coal gas that producer gas generator produces is entered in hydrolysis calcining furnace and rotary calciner and burnt by the 16 pipeline and the 19 pipeline respectively, flue gas in rotary calciner enters in hydrolysis calcining furnace by the 20 pipeline, flue gas in hydrolysis calcining furnace is entered in cyclonic separator and is separated by the 17 pipeline, solid phase after separation enters in worm conveyor by tremie pipe, flue gas after separation is entered in preconcentrator and is reacted with secondary filtrate by the 18 pipeline, in preconcentrator, reacted flue gas is entered in slurry absorption tower and is reacted with a slurry by the tenth pipeline, in slurry absorption tower, reacted flue gas is entered in hydrochloric acid absorption tower and is reacted with the liquid phase in hydrochloric acid absorption tower by the 11 pipeline, in hydrochloric acid absorption tower, reacted flue gas is entered after reacting with the water in water inlet pipe in tail gas washing tower and is discharged from escape pipe by the 12 pipeline, in the reacted flue gas of tail gas washing tower, HCl concentration is less than 5PPm, in tail gas washing tower, reacted liquid phase enters in hydrochloric acid absorption tower by the 14 pipeline, in hydrochloric acid absorption tower, reacted liquid phase enters in acidleach tank by the 15 pipeline, gas in acidleach tank enters in hydrochloric acid absorption tower by the 13 pipeline.
8. according to the high-purity iron oxide red preparation method described in claim 6 or 7, the mass percent concentration that it is characterized in that ammonium fluoride aqueous solution is 20% to 40%; Or/and in the first step, the particle diameter after spathic iron ore ball milling is 60 order to 100 orders.
9. according to the high-purity iron oxide red preparation method described in claim 6 or 7 or 8, it is characterized in that 800 DEG C to 900 DEG C of the calcining temperatures of rotary calciner; Or/and, 600 DEG C to 700 DEG C of the bottom temps of hydrolysis calcining furnace, the top of hydrolysis calcining furnace is 350 DEG C to 450 DEG C, the quality percentage composition that goes out to be hydrolyzed ferric oxide in the solid phase of calcining furnace is 94.5% to 96.5%.
10. according to the high-purity iron oxide red preparation method described in claim 6 or 7 or 8 or 9, the quality percentage composition that it is characterized in that iron in spathic iron ore is 30% to 45%, magnesian quality percentage composition is less than 1%, the quality percentage composition of calcium oxide is less than 2%, and the quality percentage composition of aluminum oxide is less than 1%.
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Effective date of registration: 20181224 Address after: 835000 No. 16 Workshop of Block A4, First Opening Area, Border Cooperation Center of Holguos Port, Yili Kazakh Autonomous Prefecture, Xinjiang Uygur Autonomous Region Patentee after: Xinjiang Zhaofeng Biotechnology Co., Ltd. Address before: Room 303, Venture Building, 682 Tianjin South Road High-tech Venture Service Center, Urumqi High-tech Industrial Development Zone, Xinjiang Uygur Autonomous Region, 830011 Patentee before: XINJIANG DAZHENG ENVIRONMENTAL PROTECTION TECHNOLOGY CO., LTD. |