CN104086168B - What utilize production hydroquinones to produce contains manganese waste liquid and the clay method of getting soft magnetic manganese zinc iron compound material of zinc - Google Patents
What utilize production hydroquinones to produce contains manganese waste liquid and the clay method of getting soft magnetic manganese zinc iron compound material of zinc Download PDFInfo
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- CN104086168B CN104086168B CN201410263473.0A CN201410263473A CN104086168B CN 104086168 B CN104086168 B CN 104086168B CN 201410263473 A CN201410263473 A CN 201410263473A CN 104086168 B CN104086168 B CN 104086168B
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Abstract
The invention discloses a kind of utilize produce that hydroquinones produces containing manganese waste liquid and the clay method of getting soft magnetic manganese zinc iron compound material of zinc, comprise the steps: that zinc mud adds containing in manganese waste liquid, leaching, then filter, flocculant removing silicon, aluminium impurity is added in filtrate, in the scavenging solution containing manganese and zinc, add carbonic hydroammonium carry out co-precipitation, then washing obtains coprecipitated powder; Coprecipitated powder is obtained MnZn compound material with organic pickling after calcining and decomposing; In MnZn compound material, add the compound of at least one in di-iron trioxide or di-iron trioxide and mangano-manganic oxide, zinc oxide, then pre-burning obtains soft magnetic manganese zinc iron compound material.The present invention using produce that hydroquinones produces containing manganese waste liquid and zinc mud as raw material, solve problem of environmental pollution, the high value adequately achieving refuse utilizes, there will not be glass mark, not embrittlement, shear resistant good after making magnetic device, obtained magnetic device physical and chemical index, electromagnetic performance are completely qualified.
Description
Technical field
The invention belongs to the method producing soft magnetic manganese zinc iron compound material, be specifically related to a kind of utilize produce that hydroquinones produces containing manganese waste liquid and the clay method of getting soft magnetic manganese zinc iron compound material of zinc.
Background technology
Soft magnetic ferrite easy magnetization under comparatively low-intensity magnetic field also easily demagnetizes, and mainly does various inductance element, as the magnetic head etc. of the magnetic core of filter, transformer, antenna etc. and recording, video tape recorder.At present, producing soft magnetic manganese zinc iron powder, is mostly utilize traditional ceramics method technique.Must adopt the raw material of high-purity high-quality in the process of producing, very high to ingredient requirements such as iron oxide red, mangano-manganic oxide, zinc oxide, how many requirements of purity and impurity are relatively stricter, and when mechanical batch mixing bad environments, production cost is very high simultaneously.The material made also there will be glass mark and the defect such as frangible on final magnetic device, has a strong impact on product quality.
In order to overcome above-mentioned shortcoming, current people have the coprecipitated technique of employing to prepare magnetic ferrites, but never obtain large-scale industrial production, and its main cause has 2 points (1) to be adopt industrial chemicals and raw metal, and cost is high.(2) be the magnetic device be processed into, there is serious mass defect, particularly physical property cannot reach the quality requirement of regulation, such as: the brittleness problems etc. falling limit and arrisdefect when the surperficial piebald of magnetic device and inner glass mark, magnetic device cross cutting, many technical staff look for reason from the purity aspect of raw material and the aspect of firing of magnetic core always, never find solution.So coprecipitated technique is not quoted on a large scale in soft magnetic ferrite preparation field so far.
Hydroquinones is important organic intermediate, China also drops into suitability for industrialized production in 20 century 70 developments, and current domestic mainly taking uses aniline-manganese dioxide explained hereafter hydroquinones, and this technique is compared with external phenol-hydrogen peroxide process, there is product purity high, the advantages such as impurity is few.But its shortcoming is that the discharge capacity of waste liquid is large, under usual state, often producing one ton of hydroquinones about has 40 tons of Mn-bearing waste waters.The chemical constituent containing manganese waste liquid of hydroquinones is mainly the impurity such as manganese sulfate, ammonium sulfate, sulfuric acid and aluminium, calcium, magnesium silicon.At present, more domestic manufacturer utilizes and produces crystal manganese sulfate or the acid of common carbonic acid manganese and high-purity manganese carbonate etc. containing manganese waste liquid.Also do not prepare soft magnetism zinc-manganese iron compound material with it.
In hydroquinones reduction, workshop section also can produce zinc mud, and main component is that zinc hydroxide, zinc oxide and zinc are simultaneously also containing a large amount of aluminium.
Zinc mud is also from the discarded object of pharmaceutical factory, smeltery etc., and main component is that zinc hydroxide, zinc oxide and zinc are simultaneously also containing a large amount of aluminium.Also be current urgent problem to its recycling.
Summary of the invention
Because the above-mentioned defect of prior art, technical problem to be solved by this invention be to provide a kind of utilize produce that hydroquinones produces containing manganese waste liquid and the clay method of getting soft magnetic manganese zinc iron compound material of zinc.
For achieving the above object, the invention provides a kind of utilize produce that hydroquinones produces containing manganese waste liquid and the clay method of getting soft magnetism zinc-manganese iron compound material of zinc, it is characterized in that: comprise the steps:
(1), by zinc mud add produce that hydroquinones produces containing in manganese waste liquid, leaching, then filters, and adds flocculant removing silicon, aluminium impurity, obtain the scavenging solution containing manganese and zinc in filtrate;
(2), above-mentioned containing the scavenging solution of manganese and zinc in add carbonic hydroammonium and carry out co-precipitation, then washing obtains coprecipitated powder;
(3), above-mentioned coprecipitated powder is obtained MnZn compound material with organic acid washing after air suspension calcining and decomposing;
(4), in this MnZn compound material, add the compound of at least one in di-iron trioxide or di-iron trioxide and mangano-manganic oxide, zinc oxide, mix, then pre-burning obtains soft magnetic manganese zinc iron compound material.
What the present invention utilized production hydroquinones to produce contains manganese waste liquid, utilize manganese wherein and Waste Sulfuric Acid, do not adopt bright sulfur acid, simultaneously, the zinc mud discarded object zinc mud of hydroquinones reduction section or other pharmaceutical factory, smeltery etc. produced is as the raw material of reaction, solve a large amount of problem containing manganese waste liquor contamination environment, and the high value achieving these discarded objects utilizes.By fully leaching zinc mud containing manganese waste liquid.Under the effect of flocculant, by the sial removing in waste material.And then obtain coprecipitated powder through the precipitation of carbonic hydroammonium, while precipitation, magnesium is removed.Again through air suspension calcining, by powder dispersion suspension, after Decomposition of Calcium Carbonate can be avoided like this to become calcium oxide, there is secondary response again, generate ferrite structure, bad removal.That is, what calcium carbonate of the present invention obtained after firing is calcium oxide, is convenient to remove.Finally, the material after calcining cleans through organic acid by we, is removed by calcium oxide.Obtain MnZn compound material.Obtain compound material finally by pre-burning after adding di-iron trioxide, obtain product through sand milling granulation.The present invention utilizes waste material, and through the material that coprecipitation method is obtained, there will not be glass mark, not embrittlement, shear resistant good after making magnetic device, obtained magnetic device physical and chemical index, electromagnetic performance are completely qualified.
As preferably: in step (1), described flocculant is organic flocculant or inorganic flocculating agent.Described inorganic flocculating agent is bodied ferric sulfate.Sial is conducive to remove completely like this.
In technique scheme: in step (3), the temperature of calcining and decomposing is 650-800 DEG C.
In technique scheme: in step (3), described organic acid is citric acid, glycolic, sulfamic acid, one or more in EDTA.The mass concentration of described citric acid is 0.2%-1%.Calcium citrate is slightly soluble in water, and a small amount of calcium oxide impurity, as cleaning fluid, when cleaning, only washes by the calcium citrate of low concentration.
As preferably: in step (4), carry out pre-burning in rotary furnace, the temperature of pre-burning is 800-900 DEG C.
In technique scheme: Mn in soft magnetic manganese zinc iron compound material
3o
4: Fe
2o
3; The ratio of quality and the number of copies of ZnO is 1-90:1-90:1-90.
The invention has the beneficial effects as follows: the present invention using produce that hydroquinones produces containing manganese waste liquid and zinc mud as raw material, solve problem of environmental pollution, the high value adequately achieving refuse utilizes, through the material that coprecipitation method of the present invention is obtained, there will not be glass mark, not embrittlement, shear resistant good after making magnetic device, obtained magnetic device physical and chemical index, electromagnetic performance are completely qualified.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1
1. (this water is containing manganese 47g/l to measure the sour manganese water 3.0L that contains producing hydroquinones generation, sulfur acid 40g/l), pour in 5L beaker, stir the zinc mud 91g (containing zinc 55%) adding hydroquinones reduction section and produce, after leaching, filter, obtain filtrate.Add bodied ferric sulfate 0.075g in filtrate, stir, then filter and obtain filtrate, filtrate adds flocculant again, and filter obtained scavenging solution 3L, this liquid is containing manganese 47g/l, containing zinc 16.7g/l.
2. coprecipitated: to measure the scavenging solution 3L containing manganese and zinc, pour in 5L beaker, add appropriate carbonic hydroammonium, make whole MnZns all coprecipitated reaction Formed hydrochlorate, the coprecipitated powder that coprecipitated powder is obtained qualified after water washing.
3. by obtained coprecipitated powder at 800 DEG C, in dynamic suspension calciner, calcine through air suspension and carry out predecomposition 2 seconds and obtain MnZn compound material, this MnZn compound material is the citric acid washing of 2/1000ths through mass concentration, obtains qualified MnZn compound material.
4. prepare burden: needed for proportioning, add Fe
2o
3860g, mixes.
5. by the material that mixes after feed supplement in Muffle furnace 850 DEG C again, pre-burning 2h.
6. Preburning material sand milling granulation again, obtains the completely qualified magnetic device of physical and chemical index, electromagnetic performance through iron coating.
Embodiment 2
1. measure containing sour manganese water 80M
3(containing manganese 47g/l, sulfur acid 40g/l), pumps into 100M
3in reactor, stir the zinc mud 2.43T adding hydroquinones reduction section and produce, filter, add flocculant PAM2g in filtrate after leaching, stir, obtain filtrate, filtrate repeats to add flocculant 2 times again, filters obtained scavenging solution 80M
3, this liquid is containing manganese 47g/l, iron content 16.7g/l.
2. coprecipitated: to measure the scavenging solution 65M containing manganese and zinc
3, pump into 100M
3in reactor, add appropriate carbonic hydroammonium, make whole MnZns all coprecipitated reaction Formed hydrochlorate, the coprecipitated powder that coprecipitated powder is obtained qualified after water washing.
3. obtained coprecipitated powder to be sent in shower furnace at 650 DEG C with conveying worm after band filter again washing and filtering, calcine through air suspension and carry out predecomposition 2 seconds and obtain MnZn compound material, this MnZn compound material is the sulfamic acid washing of 5/1000ths through mass concentration, obtains qualified MnZn compound material.
4. prepare burden: needed for proportioning, add Fe
2o
318.628 ton, mix.
5. by the material that mixes after feed supplement in rotary kiln 900 DEG C again, pre-burning 40min.
6. Preburning material is completely qualified through the obtained all magnetic device physical and chemical indexs of iron coating, electromagnetic performance again.
Embodiment 3
1. (this water is containing manganese 47g/l to measure the sour manganese water 3.0L that contains producing hydroquinones generation, sulfur acid 40g/l), pour in 5L beaker, stir the zinc mud 91g (containing zinc 55%) adding hydroquinones reduction section and produce, after leaching, filter, obtain filtrate.Add bodied ferric sulfate 0.08g in filtrate, stir, then filter and obtain filtrate, filtrate again adds flocculant and filters obtained scavenging solution 3L, and this liquid is containing manganese 47g/l, containing zinc 16.7g/l.
2. coprecipitated: to measure the scavenging solution 3L containing manganese and zinc, pour in 5L beaker, add appropriate carbonic hydroammonium, make whole MnZns all coprecipitated reaction Formed hydrochlorate, the coprecipitated powder that coprecipitated powder is obtained qualified after water washing.
3. by obtained coprecipitated powder at 800 DEG C, in dynamic suspension calciner, calcine through air suspension and carry out predecomposition 2 seconds and obtain MnZn compound material, this MnZn compound material is the washing of centesimal glycolic through mass concentration, obtains qualified MnZn compound material.
4. prepare burden: needed for proportioning, add Fe
2o
3560g, mixes.
5. by the material that mixes after feed supplement in Muffle furnace 800 DEG C again, pre-burning 2h.
6. Preburning material sand milling granulation again, obtains the completely qualified magnetic device of physical and chemical index, electromagnetic performance through iron coating.
Embodiment 4
1. measure produce that hydroquinones produces containing sour manganese water 3.0L (this water containing manganese 47g/l, sulfur acid 40g/l), pour in 5L beaker, stir and add zinc mud 91g (containing zinc 50%), after leaching, filter, obtain filtrate.Add flocculant PAC0.085g in filtrate, stir, then filter obtained scavenging solution 3L, this liquid is containing manganese 47g/l, containing zinc 16.7g/l.
2. coprecipitated: to measure the scavenging solution 3L containing manganese and zinc, pour in 5L beaker, add appropriate carbonic hydroammonium, make whole MnZns all coprecipitated reaction Formed hydrochlorate, the coprecipitated powder that coprecipitated powder is obtained qualified after water washing.
3. by obtained coprecipitated powder at 800 DEG C, in dynamic suspension calciner, calcine through air suspension and carry out predecomposition 2 seconds and obtain MnZn compound material, this MnZn compound material is the EDTA washing of 5/1000ths through mass concentration, obtains qualified MnZn compound material.
4. prepare burden: needed for proportioning, add Fe
2o
3860g, zinc oxide 25g mix.
5. by the material that mixes after feed supplement in Muffle furnace 800 DEG C again, pre-burning 2h.
6. Preburning material sand milling granulation again, obtains the completely qualified magnetic device of physical and chemical index, electromagnetic performance through iron coating.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that those of ordinary skill in the art just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technical staff in the art, all should by the determined protection range of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (6)
1. what utilize production hydroquinones to produce contains manganese waste liquid and the clay method of getting soft magnetism zinc-manganese iron compound material of zinc, it is characterized in that: comprise the steps:
(1), by zinc mud add produce that hydroquinones produces containing in manganese waste liquid, leaching, then filters, and adds flocculant removing silicon, aluminium impurity, obtain the scavenging solution containing manganese and zinc in filtrate;
(2), above-mentioned containing the scavenging solution of manganese and zinc in add carbonic hydroammonium and carry out co-precipitation, then washing obtains coprecipitated powder;
(3), by above-mentioned coprecipitated powder through air suspension calcining and decomposing, then obtain zinc-manganese compound material with organic pickling, the temperature of calcining and decomposing is 650-800 DEG C;
(4), in this zinc-manganese compound material, add at least one into di-iron trioxide, mangano-manganic oxide and zinc oxide, mix, then pre-burning obtains soft magnetism zinc-manganese iron compound material, and the temperature of pre-burning is 800-900 DEG C.
2. what utilize production hydroquinones to produce according to claim 1 contains manganese waste liquid and the clay method of getting soft magnetism zinc-manganese iron compound material of zinc, and it is characterized in that: in step (1), described flocculant is organic flocculant or inorganic flocculating agent.
3. what utilize production hydroquinones to produce according to claim 2 contains manganese waste liquid and the clay method of getting soft magnetism zinc-manganese iron compound material of zinc, it is characterized in that: described in step (1), inorganic flocculating agent is bodied ferric sulfate.
4. what according to any one of claim 1-3, utilize production hydroquinones to produce contains manganese waste liquid and the clay method of getting soft magnetism zinc-manganese iron compound material of zinc, it is characterized in that: in step (3), described organic acid is citric acid, glycolic, sulfamic acid, one or more in EDTA.
5. what utilize production hydroquinones to produce according to claim 4 contains manganese waste liquid and the clay method of getting soft magnetism zinc-manganese iron compound material of zinc, it is characterized in that: the mass concentration of described citric acid is 0.2%-1%.
6. what utilize production hydroquinones to produce according to claim 1 contains manganese waste liquid and the clay method of getting soft magnetism zinc-manganese iron compound material of zinc, it is characterized in that: Mn in soft magnetism zinc-manganese iron compound material
3o
4: Fe
2o
3; The ratio of quality and the number of copies of ZnO is 1-90:1-90:1-90.
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| CN115572159B (en) * | 2022-08-25 | 2023-06-02 | 安徽格派锂电循环科技有限公司 | Method for preparing manganese-zinc ferrite material from copper-manganese waste liquid |
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