CN105399144A - Manganese removal method for high manganese steel pickling waste liquor - Google Patents
Manganese removal method for high manganese steel pickling waste liquor Download PDFInfo
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- CN105399144A CN105399144A CN201510941352.1A CN201510941352A CN105399144A CN 105399144 A CN105399144 A CN 105399144A CN 201510941352 A CN201510941352 A CN 201510941352A CN 105399144 A CN105399144 A CN 105399144A
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- CN
- China
- Prior art keywords
- demanganization
- pickle liquor
- high mangaenese
- mangaenese steel
- acid solution
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
Abstract
The invention discloses a manganese removal method for high manganese steel pickling waste liquor. The method comprises the steps: with the high manganese steel pickling waste liquor as a raw material, adding NaClO, carrying out an oxidation reaction, reducing while adding iron, and carrying out ammonia-aeration oxidation treatment, precipitation and clarification overflow to obtain a manganese-removed ferrous chloride solution with higher purity. Iron oxide red can be obtained from the ferrous chloride solution through later acid regeneration spray roasting technology. The method has simple reaction process and can be generalized to other acid regeneration units.
Description
Technical field
The invention belongs to materialogy field, particularly relate to a kind of method of high mangaenese steel spent pickle liquor demanganization, be exactly by a kind of high mangaenese steel spent pickle liquor by demanganization process specifically, finally obtain high purity Fe
2+solution.
Background technology
High mangaenese steel is born in the very long years of more than 120 year so far, the abrasive wear under opposing thump, large pressure effect, with " more pressure is harder " performance of its uniqueness, in the high-abrasive material field in century more than one, is in the dominant role of taking as own duty.After entering 21 century, information is super greatly with great strength and vigour, not only high mangaenese steel not replace by other steel grades, tempo is faster, become the first-selected high-abrasive material of the Advanced Equipments such as magnetic suspension train, New Main Battle Tank, Mining machinery people, Gu Naimocailiaojie calls it by the fine-sounding name of " immortal high-abrasive material ".
In order to comply with the needs of market to high mangaenese steel kind, Baosteel unit is devoted to the rolling of high mangaenese steel kind, pickling and acid regeneration process.The iron protochloride that pickling produces at high temperature reacts with water and oxygen, and generate ferric oxide and hydrogenchloride, hydrogenchloride gets back to pickling system recycle, and ferric oxide is byproduct.The brown iron oxide that acid regeneration is produced is mainly used in making magneticsubstance, therefore the chemical purity of brown iron oxide, physicals and consistence thereof and the quality of production of stability to soft magnetic ferrite most important.
At present, about to overlap in hydrochloric acid regenerating device 85% in the world 200 is LURGI and the development of Lu Tena company and design more, and Lu Tena hydrochloric acid regenerating device accounts for the overwhelming majority in this regenerating unit of 85%.Acid regeneration unit adopts the spray roasting technology of Ruthner mostly both at home and abroad at present.Adopt the brown iron oxide of the method production because of thermolysis under atomize, therefore the ferric oxide granularity generated is tiny, active better, purity is high, is produce the important raw and processed materials needed for soft magnetic ferrite.
When current high mangaenese steel pickle solution carries out acid regeneration, mainly there is MnO severe overweight phenomenon in its brown iron oxide produced, cannot reach the judgement requirement of first grade in new national standard GB/T24244-2009.This is mainly mainly derived from pickling high mangaenese steel kind due to the unit spent acid of 1800 unit process, introduces a large amount of manganese sources, and in existing acid regeneration process operating process, cannot realize the effect of demanganization in acid cleaning process.For this reason on existing silica removal device, study the feasibility of demanganization process and study demanganization, silica removal integration, the quality of brown iron oxide is further improved, meet the requirement of GB/T24244-2009, to the economic benefit promoting Baosteel corporate image and raising product, there is important effect.
Summary of the invention
The object of the invention is to the deficiency overcoming the existence of above-mentioned prior art, a kind of method of high mangaenese steel spent pickle liquor demanganization is provided.The present invention with high mangaenese steel spent pickle liquor for raw material, mainly through simple preoxidation in early stage, the ammonia-oxidation style in full reductive agent later stage in mid-term by the Mn in high mangaenese steel spent acid solution
2+get rid of, the technical process related to is simple, and scale is easy to control, the cost-saving and energy.
The object of the invention is to be achieved through the following technical solutions:
The present invention relates to a kind of method of high mangaenese steel spent pickle liquor demanganization, described method comprises the steps:
S1, with high mangaenese steel spent pickle liquor for raw material, often raise in manganese steel spent pickle liquor and add NaClO44.7 ~ 89.4g, react in reactive tank; After overflow, obtain containing MnO
2the spent acid solution of particulate matter;
S2, described in often liter containing MnO
2add iron 56 ~ 112g in the spent acid solution of particulate matter, react in dissolving tank, obtain Fe
3+be reduced to Fe
2+spent acid solution;
S3, the volume ratio of spent acid solution obtained according to ammoniacal liquor and step S2 are 0.0072: 1, drip ammoniacal liquor, blast air, react in reactive tank; Overflow to settling bath, after precipitation leaves standstill, overflow obtains the higher solution of ferrous chloride of demanganization purity.
Wherein, when the volume ratio of the spent acid solution that ammoniacal liquor and step S2 obtain is less than 0.0072: 1, abundant Fe (OH) 3 colloidal sol can not be produced, also just MnO2, the SiO2 etc. in spent acid solution can not be suspended thing and flocculate, good impurity-eliminating effect can not be played; When being greater than 0.0072: 1, now reaction produces a large amount of Fe (OH) 3 colloidal sol, although can better adsorb MnO2, SiO2 etc. to be suspended thing, iron loss amount increases, and makes the production declining of later stage red iron oxide, and cost raises.
High mangaenese steel spent pickle liquor, for be high mangaenese steel spent acid solution in 1800 units, containing iron ion 100g/L, mn ion 0.8g/L, H
+concentration is 8%, and temperature is 75 ~ 85 DEG C.If do not carry out demanganization process in spent acid, there is MnO severe overweight phenomenon in the brown iron oxide that the later stage, it produced after roasting, cannot reach the judgement requirement of first grade in new national standard GB/T24244-2009.
Preferably, in step S1, the described reaction times is 0.5h ~ 1h.Be 1L according to spent acid solution volume and NaClO mass ratio: after (44.7-89.4) g adds NaClO, in reactive tank 1, react 0.5h ~ 1h, be easy to realize demanganization.If the reaction times is too short, oxidizing reaction is thorough not, causes sample waste; If the reaction times is too of a specified duration, increase running cost.NaClO mass ratio is 1L: (44.7-89.4) g, and mass ratio is too large, and oxygenant quantity not sufficient, can not by Mn
2+be deposited to rational scope, ratio is too little, and oxygenant is too much excessive, causes medicine to waste, and cost increases.
Preferably, in step S2, the described reaction times is 40 ~ 50min.Be more preferably 45min.If the reaction times is too short, reaction cannot thoroughly be carried out; Reaction times is too of a specified duration, reduces spent acid treatment capacity, increases operation cost.
Preferably, in step S3, the described reaction times is 0.3h ~ 0.7h.Be more preferably 0.5h.Equally, if the reaction times is too short, reaction cannot thoroughly be carried out; Reaction times is too of a specified duration, reduces spent acid treatment capacity, increases operation cost.
Preferably, in step S3, during described reaction, control temperature is 55 ~ 65 DEG C, and pH value is 4.0.If temperature is lower, need long reaction time, increase the load of unit; If temperature is too high, speed of response is fast, the Fe (OH) of formation
3the Quality Down of colloidal sol, its porous character is destroyed, and absorption property declines, and can not will be suspended the thorough sedimentation of thing; PH value is too large, and the ammonia vol of needs is more, Fe (OH)
3growing amount increase, iron loss amount rise, be unfavorable for cost control; PH value is too little, Fe (OH)
3growing amount increase, adsorptive power is inadequate, can not will be suspended MnO
2, SiO
2flocculating settling.
Preferably, in step S3, the time that described precipitation leaves standstill is 1 ~ 1.5h.
Compared with prior art, the beneficial effect that the present invention has is: novelty of the present invention proposes to adopt before dissolving tank, adds NaClO method, has taken into full account ClO
-with Mn
2+, Fe
2+an adaptive of electrode electromotive force and the impact of now 8%HCL, under this highly acidity, increase the oxidisability of oxygenant, although now iron ion is also oxidized, can be passed through the pickle solution in later stage and the reaction on iron limit, the iron ion after being oxidized is reduced to Fe
2+; Meanwhile, in the later stage of the present invention, by control ph, adopt ammonia-oxidation style by Fe
2+partial oxidation is Fe (OH)
3colloidal sol, the charge adsorption performance utilizing it larger, will be oxidized gained MnO
2carry out coagulation, thus obtain high-purity Fe
2+solution, is beneficial to and prepares the high Fe of purity
2o
3iron oxide red.The present invention adopts oxidation style to transfer Mn2+ to MnO2 by rational electrode electromotive force coupling early stage; In conjunction with the existing silicon removing process in later stage, utilize and generate Fe (OH)
3colloidal sol, the method for flocculation sediment, removes manganese, silicon, the final red iron oxide obtained containing below 0.3%MnO.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make certain adjustments and improvements.These all belong to protection scope of the present invention.
embodiment 1
The present embodiment relates to a kind of method of high mangaenese steel spent pickle liquor demanganization; Described method steps comprises:
(1) with high mangaenese steel spent pickle liquor for raw material, (containing iron ion 100g/L in pickle solution, mn ion 0.8g/L, H
+concentration is 8%, and temperature is about 80 DEG C),
(2) according to spent acid solution volume and NaClO mass ratio be 1L: 55g add NaClO after, in reactive tank 1 react 0.5h, after overflow, obtain containing MnO
2the spent acid solution of particulate matter.
(3) be 1L: 112g add iron limit (in cold-rolled process, steel band trimming, the part dropped is called scrap iron limit) according to spent acid solution volume and iron limit mass ratio, in dissolving tank, react 45min, obtain Fe
3+be reduced to Fe
2+spent acid solution.
(4) be 0.0072: 1 according to ammoniacal liquor and spent acid solution volume ratio, drip ammoniacal liquor, blast air, temperature of reaction is 60 DEG C, and control pH, to 4.0, reacts 0.5h in reactive tank, overflow to settling bath, after precipitation leaves standstill 1h, overflow obtains the higher solution of ferrous chloride of demanganization purity.
embodiment 2
The present embodiment relates to a kind of method of high mangaenese steel spent pickle liquor demanganization; Described method steps comprises:
(1) with high mangaenese steel spent pickle liquor for raw material, (containing iron ion 100g/L in pickle solution, mn ion 0.8g/L, H
+concentration is 8%, and temperature is about 80 DEG C);
(2) according to spent acid solution volume and NaClO mass ratio be 1L: 89.4g add NaClO after, in reactive tank 1 react 1h, after overflow, obtain containing MnO
2the spent acid solution of particulate matter;
(3) be 1L: 56g add iron limit according to spent acid solution volume and iron limit mass ratio, in dissolving tank, react 45min, obtain Fe
3+be reduced to Fe
2+spent acid solution;
(4) be 0.0072: 1 according to ammoniacal liquor and spent acid solution volume ratio, drip ammoniacal liquor, blast air, temperature of reaction is 60 DEG C, and control pH, to 4.0, reacts 0.5h in reactive tank, overflow to settling bath, after precipitation leaves standstill 1h, overflow obtains the higher solution of ferrous chloride of demanganization purity.
embodiment 3
The present embodiment relates to a kind of method of high mangaenese steel spent pickle liquor demanganization; Described method steps comprises:
(1) with high mangaenese steel spent pickle liquor for raw material, (containing iron ion 100g/L in pickle solution, mn ion 0.8g/L, H
+concentration is 8%, and temperature is about 80 DEG C);
(2) according to spent acid solution volume and NaClO mass ratio be 1L: 66g add NaClO after, in reactive tank 1 react 0.8h, after overflow, obtain containing MnO
2the spent acid solution of particulate matter;
(3) be 1L: 100g add iron limit according to spent acid solution volume and iron limit mass ratio, in dissolving tank, react 45min, obtain Fe
3+be reduced to Fe
2+spent acid solution;
(4) be 0.0072: 1 according to ammoniacal liquor and spent acid solution volume ratio, drip ammoniacal liquor, blast air, temperature of reaction is 60 DEG C, and control pH, to 4.0, reacts 0.5h in reactive tank, overflow to settling bath, after precipitation leaves standstill 1h, overflow obtains the higher solution of ferrous chloride of demanganization purity.
embodiment 4
The present embodiment relates to a kind of method of high mangaenese steel spent pickle liquor demanganization; Described method steps comprises:
(1) with high mangaenese steel spent pickle liquor for raw material, (containing iron ion 100g/L in pickle solution, mn ion 0.8g/L, H
+concentration is 8%, and temperature is about 80 DEG C),
(2) according to spent acid solution volume and NaClO mass ratio be 1L: 44.7g add NaClO after, in reactive tank 1 react 0.6h, after overflow, obtain containing MnO
2the spent acid solution of particulate matter.
(3) be 1L: 112g add iron limit according to spent acid solution volume and iron limit mass ratio, in dissolving tank, react 45min, obtain Fe
3+be reduced to Fe
2+spent acid solution.
(4) be 0.0072: 1 according to ammoniacal liquor and spent acid solution volume ratio, drip ammoniacal liquor, blast air, temperature of reaction is 60 DEG C, and control pH, to 4.0, reacts 0.5h in reactive tank, overflow to settling bath, after precipitation leaves standstill 1h, overflow obtains the higher solution of ferrous chloride of demanganization purity.
In sum, the method for high mangaenese steel spent pickle liquor demanganization provided by the invention, mainly by the Mn in spent acid solution
2+in highly acidity situation, be oxidized to MnO
2throw out, the later stage passes through Fe
2+be oxidized to Fe (OH)
3carry out flocculation adsorption, by MnO
2be deposited in settling bath, overflow obtains high-purity Fe
2+solution, obtains the high red iron oxide of purity by follow-up high-temperature roasting technique.This is simple to operate, does not impact existing operation, easy handling, is applicable to industrialized production.
Claims (7)
1. a method for high mangaenese steel spent pickle liquor demanganization, is characterized in that, described method comprises the steps:
S1, with high mangaenese steel spent pickle liquor for raw material, often raise in manganese steel spent pickle liquor and add NaClO44.7 ~ 89.4g, react in retort; After overflow, obtain containing MnO
2the spent acid solution of particulate matter;
S2, described in often liter containing MnO
2add iron 56 ~ 112g in the spent acid solution of particulate matter, react in dissolving tank, obtain Fe
3+be reduced to Fe
2+spent acid solution, this spent acid solution flows into late phase reaction groove;
S3, the volume ratio of spent acid solution obtained according to ammoniacal liquor and step S2 are 0.0072: 1, drip ammoniacal liquor, blast air, react in reactive tank; Overflow to settling bath, after precipitation leaves standstill, overflow obtains the higher solution of ferrous chloride of demanganization purity.
2. the method for high mangaenese steel spent pickle liquor demanganization according to claim 1, is characterized in that, containing iron ion 100g/L in described high mangaenese steel spent pickle liquor, mn ion 0.8g/L, HCl mass percent concentration is 8%, and temperature is 75 ~ 85 DEG C.
3. the method for high mangaenese steel spent pickle liquor demanganization according to claim 1, is characterized in that, in step S1, the described reaction times is 0.5h ~ 1h.
4. the method for high mangaenese steel spent pickle liquor demanganization according to claim 1, is characterized in that, in step S2, the described reaction times is 40 ~ 50min.
5. the method for high mangaenese steel spent pickle liquor demanganization according to claim 1, is characterized in that, in step S3, the described reaction times is 0.3h ~ 0.7h.
6. the method for high mangaenese steel spent pickle liquor demanganization according to claim 1, is characterized in that, in step mule S3, during described reaction, control temperature is 55 ~ 65 DEG C, and pH value is 4.0.
7. the method for high mangaenese steel spent pickle liquor demanganization according to claim 1, is characterized in that, in step S3, the time that described precipitation leaves standstill is 1 ~ 1.5h.
Priority Applications (1)
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| CN201510941352.1A CN105399144A (en) | 2015-12-15 | 2015-12-15 | Manganese removal method for high manganese steel pickling waste liquor |
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| CN201510941352.1A CN105399144A (en) | 2015-12-15 | 2015-12-15 | Manganese removal method for high manganese steel pickling waste liquor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111573739A (en) * | 2020-06-09 | 2020-08-25 | 首钢集团有限公司 | Method for producing iron oxide red from high manganese steel waste acid liquid |
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2015
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| CN111573739A (en) * | 2020-06-09 | 2020-08-25 | 首钢集团有限公司 | Method for producing iron oxide red from high manganese steel waste acid liquid |
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Application publication date: 20160316 |