CN100389154C - Method for preparing pigment of zinc ferrite - Google Patents
Method for preparing pigment of zinc ferrite Download PDFInfo
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- CN100389154C CN100389154C CNB2006100107733A CN200610010773A CN100389154C CN 100389154 C CN100389154 C CN 100389154C CN B2006100107733 A CNB2006100107733 A CN B2006100107733A CN 200610010773 A CN200610010773 A CN 200610010773A CN 100389154 C CN100389154 C CN 100389154C
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- CN
- China
- Prior art keywords
- zinc ferrite
- zinc oxide
- liquid
- filter cake
- zinc
- Prior art date
- 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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- 229910001308 Zinc ferrite Inorganic materials 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 23
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000000049 pigment Substances 0.000 title claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011787 zinc oxide Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 12
- 235000010755 mineral Nutrition 0.000 claims abstract description 12
- 239000011707 mineral Substances 0.000 claims abstract description 12
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 7
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 20
- 239000012065 filter cake Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000011701 zinc Substances 0.000 abstract description 6
- 238000002386 leaching Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 3
- 239000000243 solution Substances 0.000 abstract 3
- 239000000463 material Substances 0.000 abstract 2
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 229910006540 α-FeOOH Inorganic materials 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- HVTHJRMZXBWFNE-UHFFFAOYSA-J sodium zincate Chemical group [OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Zn+2] HVTHJRMZXBWFNE-UHFFFAOYSA-J 0.000 description 10
- 230000008569 process Effects 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910002588 FeOOH Inorganic materials 0.000 description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011667 zinc carbonate Substances 0.000 description 2
- 235000004416 zinc carbonate Nutrition 0.000 description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000001058 brown pigment Substances 0.000 description 1
- -1 cheap Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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- Compounds Of Iron (AREA)
Abstract
The present invention relates to a method for preparing zinc ferrite pigment, which comprises the following steps: a mineral containing zinc oxide and ferrous sulfate are used as materials; zincate is obtained through leaching and purification in 6 to 40 wt% of hot alkaline solution; zincate solution is added in 8 to 25 wt% of ferrous sulfate solution, and the temperature of reaction solution is kept at 25 DEG C to 60 DEG C; zincate and ferrous sulfate coprecipitate alpha-FeOOH and Zn (OH) 2 under the condition of oxidization, and therefore, zinc ferrite pigment is obtained through filtration, washing, desiccation and calcination. The method has the advantages of wide material sources, low prices and low production cost.
Description
One, affiliated technical field: field of inorganic chemical engineering
Two, background technology:
Zinc ferrite is a kind of anticorrosion or painted yellowish brown pigment of soft magnetism, is widely used in coating, paint, plastics and stupalith etc., because of not containing heavy metal and poisonous element, belongs to safer environmentally friendly pigment.
The zinc ferrite industrial process is the purer zinc oxide of wet-mixed in the precipitation alpha-feooh, filters, dry, calcining and obtaining.
4FeSO
4+8NaOH+O
2→4FeOOH+4Na
2SO
4+2H
2O
2FeOOH+2ZnO→Zn
2Fe
2O
2+H
2O
In aforementioned production method, because of zinciferous raw material adopts than pure zinc oxide, price is higher, and production cost is higher.
The preparation method that Chinese patent 1554712 (publication number) discloses a kind of pigment of zinc ferrite powder is characterized in that with metal iron powder, zinc powder be raw material, directly the corrosion oxidation is synthetic in low temperature (＜100 ℃) water medium system, produces to be filemot zinc ferrite color powder.There are two big shortcomings in this method, and the one, adopting two kinds of metal powders is raw material, price is comparatively expensive; The 2nd, the speed of reaction of two kinds of corrosion of metal oxidizing reactions is extremely slow in the aqueous systems, and reacting finisheding degree is low, easily is mixed with the unreacted metal powder in the product, gives to commercially produce and brings big difficulty.
U.S. Pat-A 3832455 describes a kind of production method of pigment of zinc ferrite, in the copperas solution that contains zinc oxide or zinc carbonate, precipitate a-FeOOH, reaction conditions is 49 ℃～52 ℃ of temperature, and it is between 5～6 that precipitation is finished the pH value, generates precipitated liquid and filters, washs, calcines; European patent EP-B 154919 discloses the pure method for preparing pigment of zinc ferrite of a kind of color, in containing the copperas solution of zinc oxide, by control precipitin reaction condition, makes zinc oxide surface be settled out the a-FeOOH particulate of strip.After generating the precipitated liquid filtration, filter cake washs, calcines, cools off, pulverizes.For color and luster and the photo and thermal stability that improves pigment of zinc ferrite, in containing the ferrous sulfate precipitation process of zinc oxide, add multiple additives, these technological processs are described in respectively as U.S. Pat-A 4222790, German patent DE-A 3136279, Japanese Patent JP-B 57011829 is in a series of patents of U.S. Pat-A 5254162 or the like.In above-mentioned two pigment of zinc ferrite preparation process, adopting zinc oxide or zinc carbonate is pigment, and price is comparatively expensive.
Three, content of the present invention
1, the object of the present invention is to provide a kind of method for preparing pigment of zinc ferrite, from containing the zinc oxide mineral, obtain zincate through alkali lye lixiviate, purification, the co-precipitation under oxidizing condition of zincate and ferrous sulfate goes out alpha-feooh and Zn (OH)
2, after filtration, washing, dry, calcining and obtain the method for pigment of zinc ferrite.The raw materials used source of this method is wide, and is cheap, and production cost is low.
2, the present invention finishes according to the following steps
Raw material is for containing the zinc oxide mineral, and ferrous sulfate contains the zinc oxide dust that contains of sulphide ores after the zinc oxide mineral comprise roasting, metallurgical industry;
(1), contains the zinc oxide mineral with the alkali lixiviate
To contain in the alkali lye of 6～40wt% that the zinc oxide mineral add 50 ℃～80 ℃, 20～40 minutes after-filtration of lixiviate under stirring condition, filter residue is with 50～80 ℃ of hot washes, washing lotion both can be used for leaching process alkali lye dosing next time and had used, also can merge, depend on that raw material contains zinc oxide what and lixiviate concentration of lye with filtrate.Filtrate is the required zincate solution of precipitin reaction;
Lixiviate reaction: ZnO+2NaOH → Na
2ZnO
2+ H
2O
(2), precipitin reaction
The first step precipitin reaction: in 8～25wt% of pneumatic blending copperas solution, add zincate solution, between 25 ℃～60 ℃ of the maintenance reaction liquid temperature, when reaching 5.5～6.5, liquid phase PH valve stops to add zincate solution, along with the further oxidation of air, liquid phase PH valve progressively descends, and when liquid phase PH valve reduced to 4～3, nucleogenesis was finished, obtain precipitated liquid
The second step precipitin reaction: the precipitated liquid that the first step is obtained is warming up to 70 ℃～90 ℃ under pneumatic blending, and continue adding zincate solution is to stop in 4～5 o'clock until reacting liquid pH value, and precipitin reaction is finished;
Precipitin reaction: 4Na
2ZnO
2+ 4FeSO
4+ 6H
2O+O
2→ 4FeOOH+4Zn (OH)
2+ 4Na
2SO
4
(3), throw out filtration, washing, drying
Precipitated liquid is filtered, and filter cake is with 50 ℃～80 ℃ hot washes 2～3 times, and is following dry 5 minutes～15 minutes in 150 ℃～300 ℃ again.Obtain dried throw out;
(4), throw out calcining, cooling, pulverizing
Dried throw out was calcined 10 minutes～15 minutes down in 800 ℃～900 ℃, and cooling obtains yellowish brown zinc ferrite product after the pulverizing.
Calcination process: 2FeOOH+2Zn (OH)
2→ Zn2Fe
2O
5+ 5H
2O
3, the advantage that compared with prior art had of present technique
(1). adopt to contain the zinc oxide mineral as raw material, cheap, raw material sources wide, low, the economical rationality of the more traditional method of production cost.
(2). adopt the highly basic lixiviate to contain the zinc oxide mineral, because impurity is throw out, it is comparatively simple and convenient to remove impurity, and impurity seldom reacts with highly basic, in can utilizing, the low-grade zinc raw material that contains.
Four, description of drawings:
Fig. 1 is a process flow sheet of the present invention
Five, embodiment
Embodiment one: the zinc sulfide ore that 1kg contains after the roasting of zinc 25wt% joins in the potassium hydroxide solution of 1.6kg 18wt%, under whipped state, keep 30 minutes after-filtration of 60 ℃ of lixiviates of temperature, filter residue is with 60 ℃ of hot washes, washing lotion is used for lixiviate alkali lye preparation next time, and filtrate is sodium zincate solution;
With the 4.1kg concentration expressed in percentage by weight is 20%FeSO
47H
2O adds above-mentioned sodium zincate solution under bubbling air stirs, the adding of sodium zincate solution stops when reacting liquid pH value rises to 6, keeps 35 ℃ of temperature to continue bubbling air and stirs, and when reacting liquid pH value reduces to 3.6, precipitates into nuclear process and finishes; Reacting liquid temperature is increased to 78 ℃, adds sodium zincate solution for the second time under pneumatic blending, and the adding of sodium zincate solution stops when the pH value rises to 4.2, and coprecipitation reaction is finished; Precipitated liquid is filtered, and filter cake is with 60 ℃ of hot washes 3 times, and is following dry 6 minutes in 200 ℃ again; Dried filter cake is 10 minutes postcooling of calcining under 860 ℃, pulverize and obtain yellowish brown zinc ferrite product 0.558kg.
Embodiment two: 1.7kg contains containing in the sodium hydroxide solution that zinc oxide dust joins 3.5kg 30wt% of zinc 15wt%, under agitation keep 35 minutes after-filtration of 62 ℃ of lixiviates of temperature, filter residue is with 80 ℃ of hot washes, washing lotion is used for lixiviate alkali lye preparation next time, and filtrate is purer sodium zincate solution;
4.5kg concentration expressed in percentage by weight is 20% FeSO
47H
2O under bubbling air stirs, adds above-mentioned sodium zincate solution, and the adding of sodium zincate solution stops when reacting liquid pH value rises to 5.9, keeps 40 ℃ of temperature to continue bubbling air and stirs, and when reacting liquid pH value reduces to 3.7, precipitates into nuclear process and finishes; Reacting liquid temperature is increased to 75-85 ℃, adds sodium zincate solution for the second time under pneumatic blending, and the adding of sodium zincate solution stops when the pH value rises to 4.4, and coprecipitation reaction is finished; Precipitated liquid is filtered, and filter cake is with 70 ℃ of hot washes 2 times, and in 150 ℃ of dryings 15 minutes down; Dried filter cake is 10 minutes postcooling of calcining under 900 ℃, pulverize and obtain yellowish brown zinc ferrite product 0.562kg.
Claims (5)
1. method for preparing pigment of zinc ferrite, it is characterized in that: the present invention finishes according to the following steps, and raw material is for containing zinc oxide mineral and ferrous sulfate,
To contain in the heat alkali liquid of zinc oxide mineral adding 6～40wt%, 20～40 minutes after-filtration of lixiviate under stirring condition, the filter residue hot wash, filtrate is the required zincate solution of precipitin reaction;
The first step precipitin reaction: in 8～25wt% of pneumatic blending copperas solution, add zincate solution, between 25 ℃～60 ℃ of the maintenance reaction liquid temperature, when reaching 5.5～6.5, liquid phase PH valve stops to add zincate solution, along with the further oxidation of air, liquid phase PH valve descends, when liquid phase PH valve reduces to 4～3, nucleogenesis is finished, obtain precipitated liquid, the second step precipitin reaction: the precipitated liquid that the first step is obtained is warming up to 70～90 ℃ under pneumatic blending, continue adding zincate solution is to stop in 4～5 o'clock until reacting liquid pH value, and precipitin reaction is finished;
Precipitated liquid after filtration, filter cake with hot wash after drying must do filter cake;
Dried filter cake obtains yellowish brown zinc ferrite product after calcining, cooling, pulverizing.
2. method for preparing pigment of zinc ferrite according to claim 1 is characterized in that: alkali liquid temperature, residue washing water temp and filter cake washing water temp that dissolving contains the zinc oxide mineral are 50～80 ℃.
3. method for preparing pigment of zinc ferrite according to claim 1 is characterized in that: filter cake with hot wash after again in 150 ℃～300 ℃ dry 5～15 minutes down.
4. method for preparing pigment of zinc ferrite according to claim 1 is characterized in that: dried filter cake was calcined 10～15 minutes down in 800～900 ℃.
5. according to each described method for preparing pigment of zinc ferrite among the claim 1-4, it is characterized in that: describedly contain the zinc oxide dust that contains that the zinc oxide mineral are sulphide ores after the roasting or metallurgical industry.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100107733A CN100389154C (en) | 2006-03-24 | 2006-03-24 | Method for preparing pigment of zinc ferrite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100107733A CN100389154C (en) | 2006-03-24 | 2006-03-24 | Method for preparing pigment of zinc ferrite |
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| Publication Number | Publication Date |
|---|---|
| CN1843940A CN1843940A (en) | 2006-10-11 |
| CN100389154C true CN100389154C (en) | 2008-05-21 |
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| CNB2006100107733A Expired - Fee Related CN100389154C (en) | 2006-03-24 | 2006-03-24 | Method for preparing pigment of zinc ferrite |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430323B (en) * | 2016-09-20 | 2018-01-12 | 四川大学 | A kind of method for preparing ferrite |
| CN106241883B (en) * | 2016-09-20 | 2018-01-12 | 四川大学 | The preparation method of ferrite |
| CN107352585A (en) * | 2017-08-02 | 2017-11-17 | 浙江神光材料科技有限公司 | The preparation method of transparent zinc-iron yellow pigment |
| CN108358604B (en) * | 2018-03-29 | 2021-04-20 | 广西钦州市品艺堂坭兴陶有限公司 | Manufacturing method of colored nixing pottery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3832455A (en) * | 1972-10-25 | 1974-08-27 | Smith G Labor | Preparation of zinc ferrite yellow pigments |
| US4681637A (en) * | 1984-03-16 | 1987-07-21 | Bayer Aktiengesellschaft | Process for the production of yellow-brown zinc ferrite pigments |
| CN1554712A (en) * | 2003-12-23 | 2004-12-15 | 长沙矿冶研究院 | Preparation method of zinc ferrite pigment powder |
| CN1624048A (en) * | 2003-10-24 | 2005-06-08 | 拜尔化学公司 | Thermally stable zinc ferrite colouring pigments, process for manufacturing them and their use |
-
2006
- 2006-03-24 CN CNB2006100107733A patent/CN100389154C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3832455A (en) * | 1972-10-25 | 1974-08-27 | Smith G Labor | Preparation of zinc ferrite yellow pigments |
| US4681637A (en) * | 1984-03-16 | 1987-07-21 | Bayer Aktiengesellschaft | Process for the production of yellow-brown zinc ferrite pigments |
| CN1624048A (en) * | 2003-10-24 | 2005-06-08 | 拜尔化学公司 | Thermally stable zinc ferrite colouring pigments, process for manufacturing them and their use |
| CN1554712A (en) * | 2003-12-23 | 2004-12-15 | 长沙矿冶研究院 | Preparation method of zinc ferrite pigment powder |
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| Publication number | Publication date |
|---|---|
| CN1843940A (en) | 2006-10-11 |
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