CN105152227A - Method for preparing high-coercivity ferroferric oxide magnetic powder from steel chlorohydric acid pickling waste solution - Google Patents

Method for preparing high-coercivity ferroferric oxide magnetic powder from steel chlorohydric acid pickling waste solution Download PDF

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Publication number
CN105152227A
CN105152227A CN201510679026.8A CN201510679026A CN105152227A CN 105152227 A CN105152227 A CN 105152227A CN 201510679026 A CN201510679026 A CN 201510679026A CN 105152227 A CN105152227 A CN 105152227A
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China
Prior art keywords
acid pickling
pickling waste
magnetic
hydrochloric acid
waste liquid
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Pending
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CN201510679026.8A
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Chinese (zh)
Inventor
王兴尧
吕飞飞
万光琴
杨亚强
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Tianjin University
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Tianjin University
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Publication of CN105152227A publication Critical patent/CN105152227A/en
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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
    • C01G49/02—Oxides; Hydroxides
    • C01G49/08—Ferroso-ferric oxide (Fe3O4)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/42—Magnetic properties

Abstract

The invention discloses a method for preparing high-coercivity Fe3O4 magnetic powder from a steel chlorohydric acid pickling waste solution. The method comprises the following steps: (1) heating the steel chlorohydric acid pickling waste solution, adjusting pH to be 3-6, stirring and filtering; (2) heating the filtrate, adjusting pH to be 7-12 while stirring to obtain a dark green viscous material, and stirring; (3) adding an oxidizing agent at a rotation speed, stirring, gradually changing dark green liquid into black liquid, and stopping when detecting the molar ratio of Fe<3+>/Fe<2+> in a range of 1.4-2.2; (4) adjusting the pH to be 8-11 while stirring, and ageing; and (5) filtering, washing filter cake with distilled water, drying and grinding the filter cake to obtain the high-coercivity Fe3O4 magnetic powder. Through the method, the acid pickling waste solution can be treated; the high-coercivity Fe3O4 magnetic powder applied to photocopy toner can be prepared; the waste is turned into wealth; the method is environmentally friendly and is short in reaction time, relatively simple to operate and low in energy consumption.

Description

A kind of steel hydrochloric acid pickling waste liquid prepares the method for high-coercive force ferroferric oxide magnetic powder
Technical field
The invention belongs to the environmental technology field of Pollution abatement, relate to one steel hydrochloric acid pickling waste liquid and prepare high-coercive force Z 250 (Fe 3o 4) method of magnetic.
Background technology
Steel hydrochloric acid pickling waste liquid is one of Hazardous wastes that output in domestic is larger, carries out processing treatment, can strengthen its corrosion resistance, extend its work-ing life to the surface of steel beam column.Because steel rolling component exposes the oxidized quality affecting product in atmosphere, need to carry out pre-treatment to component surface.Hydrochloric acid is generally adopted to carry out pickling to steel rolling surface preparation, to remove iron rust and the impurity on surface.And Fe is had in the process of pickling 2+continuous generation, the concentration of acid simultaneously also can constantly reduce, and when the effect of acid is not so good, then needs to discharge spent acid, changes new acid.If directly discharged by spent acid, can cause huge pollution to environment, be also self-evident to the injury of human health.The existence of steel hydrochloric acid pickling waste liquid, seriously governs the Sustainable development of economic society.This pickle solution directly enters river without any process, causes pollution of estuary, ecological damage, therefore carries out improvement to it imperative.
Photographic developer is ink powder again, and be a kind of Office Consumables in duplicating machine developing process, consumption costs is many, and its demand increases year by year.Wherein main raw material is exactly the high-coercive force ferroferric oxide magnetic powder of black.Produce the pattern of high-grade ink powder to magnetic, size-grade distribution, magnetic property has higher requirement.
Summary of the invention
The object of the invention is to solve current domestic steel hydrochloric acid pickling waste liquid and need a difficult problem to be processed, there is provided a kind of and can not only solve the pollution problem of steel hydrochloric acid pickling waste liquid to environment, and can obtain high value-added product prepare high-coercive force Fe with steel hydrochloric acid pickling waste liquid 3o 4the method of magnetic.
Technical scheme of the present invention is summarized as follows:
One steel hydrochloric acid pickling waste liquid prepares high-coercive force Fe 3o 4the method of magnetic, comprises the following steps:
(1) steel hydrochloric acid pickling waste liquid being heated to 60-70 DEG C, adding alkali and make pH=3-6, is stir 20-40min under the condition of 100-300r/min at rotating speed, filters;
(2) filtrate is warming up to 70-95 DEG C, is add alkali under the condition of 300-600r/min to make pH=7-12 at rotating speed, obtains blackish green thick substances, stir 15-45min;
(3) at rotating speed be 300-600r/min condition under, add oxygenant, stir, blackish green liquid gradually becomes black liquor, measure Fe 3+/ Fe 2+mol ratio stop within the scope of 1.4-2.2, preferred 1.7-1.9;
(4) 20-95 DEG C, under rotating speed is the condition of 200-300r/min, adds alkali and make pH=8-11, ageing 0.5-2h;
(5) mixed solution after ageing filtered, use distilled water wash filter cake, filter cake is dried, grind, obtain high-coercive force Fe 3o 4magnetic.
Preferably, step (2) described temperature is 80 DEG C.
Step (4) described pH=8.5.
Alkali is preferred: NaOH, KOH or NH 3h 2o.
Oxygenant is preferred: NaNO 3, KNO 3or NaClO 3.
Advantage of the present invention:
Method of the present invention both can process steel hydrochloric acid pickling waste liquid, can obtain again the Fe of the high-coercive force of black 3o 4magnetic, reaches the object turned waste into wealth, environmental protection.Present method reaction times is short, and operate fairly simple, energy consumption is low, obtains the Fe being applicable to high-coercive force in photocopy toner 3o 4magnetic.
Accompanying drawing explanation
Fig. 1 is the Fe that embodiment 1 obtains 3o 4the TEM picture of magnetic.
Fig. 2 is the Fe that embodiment 1 obtains 3o 4the XRD figure spectrum of magnetic.
Fig. 3 is the Fe that embodiment 1 obtains 3o 4the particle diameter collection of illustrative plates of magnetic.
Fig. 4 is the Fe that embodiment 1 obtains 3o 4the VSM collection of illustrative plates of magnetic.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, and the following examples understand the present invention better to enable those skilled in the art to, but do not impose any restrictions the present invention.
Embodiment 1
One steel hydrochloric acid pickling waste liquid prepares high-coercive force Fe 3o 4the method of magnetic, comprises the steps:
(1) 100ml steel hydrochloric acid pickling waste liquid being heated to 70 DEG C, adding NaOH and make pH=4, is stir 20min under the condition of 300r/min at rotating speed, filters;
(2) 50ml filtrate is warming up to 80 DEG C, is add NaOH under the condition of 300r/min to make pH=7 at rotating speed, obtains blackish green thick substances, stir 45min;
(3) at rotating speed be 300r/min condition under, add the NaNO of 30wt% 3aqueous solution 9ml, stir, blackish green liquid gradually becomes black liquor, measures Fe 3+/ Fe 2+mol ratio stop when being 1.9;
(4) 20 DEG C, under rotating speed is the condition of 300r/min, adds NaOH and make pH=8, ageing 0.5h;
(5) mixed solution after ageing filtered, use distilled water wash filter cake, filter cake is dried, grind, obtain the Fe of high-coercive force 3o 4magnetic.
Fe 3o 4the TEM picture of magnetic, XRD figure spectrum, particle diameter collection of illustrative plates and VSM collection of illustrative plates are shown in Fig. 1, Fig. 2, Fig. 3 and Fig. 4.
Embodiment 2
One steel hydrochloric acid pickling waste liquid prepares high-coercive force Fe 3o 4the method of magnetic, comprises the steps:
(1) 100ml steel hydrochloric acid pickling waste liquid is heated to 60 DEG C, adds NH 3h 2o makes pH=3, is to stir 30min under the condition of 200r/min at rotating speed, filters;
(2) 50ml filtrate being warming up to 70 DEG C, is add NH under the condition of 500r/min at rotating speed 3h 2o makes pH=7.5, obtains blackish green thick substances, stirs 30min;
(3) at rotating speed be 500r/min condition under, add the KNO of 30wt% 3aqueous solution 12ml, stir, blackish green liquid gradually becomes black liquor, measures Fe 3+/ Fe 2+mol ratio stop when being 1.8;
(4) 50 DEG C, under rotating speed is the condition of 250r/min, add NH 3h 2after O makes pH=8.5, ageing 1h;
(5) mixed solution after ageing filtered, use distilled water wash filter cake, filter cake is dried, grind, obtain the Fe of high-coercive force 3o 4magnetic.
Embodiment 3
One steel hydrochloric acid pickling waste liquid prepares high-coercive force Fe 3o 4the method of magnetic, comprises the steps:
(1) 100ml steel hydrochloric acid pickling waste liquid being heated to 60 DEG C, adding KOH and make pH=6, is stir 40min under the condition of 100r/min at rotating speed, filters;
(2) 50ml filtrate is warming up to 95 DEG C, is add KOH under the condition of 600r/min to make pH=12 at rotating speed, obtains blackish green thick substances, stir 15min;
(3) at rotating speed be 600r/min condition under, add NaClO 32g, stir, blackish green liquid gradually becomes black liquor, measures Fe 3+/ Fe 2+mol ratio stop when being 1.7;
(4) 95 DEG C, under rotating speed is the condition of 200r/min, adds KOH and make pH=11, ageing 2h;
(5) black liquor after ageing filtered, use distilled water wash filter cake, filter cake is dried, grind, obtain the Fe of high-coercive force 3o 4magnetic.
The particle diameter of table 1 embodiment 1-3 magnetic and magnetic
Embodiment Median size/nm Specific saturation magnetization (emu/g) Remanent magnetism (emu/g) Coercive force (Hc/Oe)
1 580 103 5.1 72
2 500 97 5.5 75
3 600 95 5.8 80
Bayer Bitterfeld GmbH 550 95 2 29

Claims (5)

1. prepare high-coercive force Fe with steel hydrochloric acid pickling waste liquid for one kind 3o 4the method of magnetic, is characterized in that comprising the following steps:
(1) steel hydrochloric acid pickling waste liquid being heated to 60-70 DEG C, adding alkali and make pH=3-6, is stir 20-40min under the condition of 100-300r/min at rotating speed, filters;
(2) filtrate is warming up to 70-95 DEG C, is add alkali under the condition of 300-600r/min to make pH=7-12 at rotating speed, obtains blackish green thick substances, stir 15-45min;
(3) at rotating speed be 300-600r/min condition under, add oxygenant, stir, blackish green liquid gradually becomes black liquor, measure Fe 3+/ Fe 2+mol ratio stop within the scope of 1.4-2.2;
(4) 20-95 DEG C, under rotating speed is the condition of 200-300r/min, adds alkali and make pH=8-11, ageing 0.5-2h;
(5) mixed solution after ageing filtered, use distilled water wash filter cake, filter cake is dried, grind, obtain high-coercive force Fe 3o 4magnetic.
2. one steel hydrochloric acid pickling waste liquid according to claim 1 prepares high-coercive force Fe 3o 4the method of magnetic, is characterized in that step (2) described temperature is 80 DEG C.
3. one steel hydrochloric acid pickling waste liquid according to claim 1 prepares high-coercive force Fe 3o 4the method of magnetic, is characterized in that step (4) described pH=8.5.
4. the one steel hydrochloric acid pickling waste liquid according to claim 1,2 or 3 prepares high-coercive force Fe 3o 4the method of magnetic, is characterized in that described alkali is NaOH, KOH or NH 3h 2o.
5. the one steel hydrochloric acid pickling waste liquid according to claim 1,2 or 3 prepares high-coercive force Fe 3o 4the method of magnetic, is characterized in that described oxygenant can be NaNO 3, KNO 3or NaClO 3.
CN201510679026.8A 2015-10-19 2015-10-19 Method for preparing high-coercivity ferroferric oxide magnetic powder from steel chlorohydric acid pickling waste solution Pending CN105152227A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105753068A (en) * 2016-02-04 2016-07-13 河北爱德斯蒂尔环保科技有限公司 Method for preparing iron oxide red through steel acid pickling waste liquor
CN105800696A (en) * 2016-03-02 2016-07-27 天津大学 Method for preparing high-magnetism ferroferric oxide powder from steel pickling waste liquid
CN109133450A (en) * 2018-08-10 2019-01-04 天津城建大学 A method of iron oxide black pigment is prepared using steel pickling waste liquor
CN109589914A (en) * 2018-11-09 2019-04-09 广州润方环保科技有限公司 A kind of method and its application preparing magnetic bio charcoal using the synchronous pyrolysis of Chinese medicine dreg and magnetization
CN109589915A (en) * 2018-11-09 2019-04-09 广州润方环保科技有限公司 A kind of method and its application using iron and steel pickling waste liquid and the magnetic bio charcoal of agriculture and forestry organic waste material preparation removal Cr VI

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105753068A (en) * 2016-02-04 2016-07-13 河北爱德斯蒂尔环保科技有限公司 Method for preparing iron oxide red through steel acid pickling waste liquor
CN105800696A (en) * 2016-03-02 2016-07-27 天津大学 Method for preparing high-magnetism ferroferric oxide powder from steel pickling waste liquid
CN109133450A (en) * 2018-08-10 2019-01-04 天津城建大学 A method of iron oxide black pigment is prepared using steel pickling waste liquor
CN109589914A (en) * 2018-11-09 2019-04-09 广州润方环保科技有限公司 A kind of method and its application preparing magnetic bio charcoal using the synchronous pyrolysis of Chinese medicine dreg and magnetization
CN109589915A (en) * 2018-11-09 2019-04-09 广州润方环保科技有限公司 A kind of method and its application using iron and steel pickling waste liquid and the magnetic bio charcoal of agriculture and forestry organic waste material preparation removal Cr VI

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Application publication date: 20151216