CN1245458C - Method for preparing nano iron oxide yellow - Google Patents
Method for preparing nano iron oxide yellow Download PDFInfo
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- CN1245458C CN1245458C CN 02137552 CN02137552A CN1245458C CN 1245458 C CN1245458 C CN 1245458C CN 02137552 CN02137552 CN 02137552 CN 02137552 A CN02137552 A CN 02137552A CN 1245458 C CN1245458 C CN 1245458C
- Authority
- CN
- China
- Prior art keywords
- iron oxide
- oxide yellow
- nano iron
- solution
- reaction
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000013078 crystal Substances 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 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 abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 7
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims abstract description 6
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 5
- -1 polyoxyethylene Polymers 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 11
- 235000010215 titanium dioxide Nutrition 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000006227 byproduct Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000012423 maintenance Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 2
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 2
- 235000017550 sodium carbonate Nutrition 0.000 abstract 2
- 239000008187 granular material Substances 0.000 abstract 1
- 239000006228 supernatant Substances 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 230000004323 axial length Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940051164 ferric oxide yellow Drugs 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000001034 iron oxide pigment Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000005002 finish coating Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compounds Of Iron (AREA)
Abstract
The present invention discloses a method for preparing nanometer iron oxide yellow. Refined and purified green copperas (FeSO4) is used as raw materials. The present invention is characterized in that a certain quantity of mixing additives of sodium hexametaphosphate and polyoxyethylene alkylphenol ether (OP-10) are added in a solution of the refined green copperas FeSO4 at a certain temperature and the stirring speed; 10% of Na2CO3 solution is dripped until the pH value is from 3.5 to 6.5; a certain reaction temperature of 20 DEG C to 40 DEG C is kept; then, oxygen is led in at the speed of the oxygen flow of 0.12 m<3>/h to 0.18 m<3>/h to react to prepare the variety of nanometer iron oxide yellow; then, the temperature rises to 50 DEG C to 60 DEG C, and the oxygen is led in at the flow rate of 0.12 m<3>/h to 0.18 m<3>/h; 10% of Na2CO3 solution is dripped in the solution which comprises crystal seeds; the pH value of a system is kept within the range of 3.0 to 5.5; and a reaction is carried out for eight hours so that the crystal seeds grow. After the reaction is finished, supernatant liquid which comprises nanometer iron oxide yellow is filtered, dried and crushed so that granules of the nanometer iron oxide yellow are obtained. The method has the advantages of simple technological process, easy control, small granularity and uniform distribution of the prepared nanometer iron oxide yellow.
Description
Technical field
The invention discloses a kind of preparation method who prepares nano iron oxide yellow, belong to the compound technology field.
Background technology
The nanometer iron oxide yellow has transparent bright-coloured coloring effect and very strong fast light, weathering resistance, in fields such as the senior polychromatic finish coating of car, printing ink, plastics, food, medicine and makeup wide purposes is arranged, nano iron oxide yellow is again synthetic other nano-sized iron oxide pigment and the important presoma of iron magnetic material simultaneously.As functional very strong nano inorganic particulate material, its performance and morphological structure comprise that size and distribution, crystalline structure and form and aspect etc. are closely related.
There is the whole bag of tricks to be used for preparing iron oxide yellow.At Ullmanns Encyclopadie der technischen Chemie (5th Edition, Volume A20, a kind of method for preparing iron oxide yellow has been described p297), the starting material of its use are the ferrous sulfate that obtains among sour Xian of steel disc, or sulphate process is produced the ferrous sulfate that titanium dioxide obtains; As Chinese patent CN1056668, CN1125196, CN1143611, provide the method for utilizing spent pickle liquor, iron slag and production vitriolic fired slags etc. to prepare iron oxide yellow respectively; And for example German patent DE 31-19652953.0 provides iron protochloride in the preferred waste liquid to prepare the method for iron oxide yellow.All aforesaid methods all are used to prepare common ferric oxide yellow pigment, and do not relate to the control of nano iron oxide yellow morphological structure.In addition, German patent DE 19812260 provides the by product green vitriol that sulfate process titanium dioxide is produced to purify the method that the back prepares ferric oxide yellow pigment, but can not be used for the production of nano iron oxide yellow.Japanese Patent JP2001240500 relates to high-purity ferrous method of feedstock production nano iron oxide yellow that is of utilizing, and does not utilize the sulfate process titanium dioxide by product green vitriol that purifies with relating to.
Titanium dioxide is a kind of and national economy important industrial chemicals in close relations, mainly adopt the Production By Sulfuric Acid Process titanium white in China, produce a large amount of useless by products in process of production, according to statistics, adopt one ton of titanium white of Production By Sulfuric Acid Process, discharge 3～4 tons of ferrous sulfate (green vitriol) solids, directly discharging will make environment be subjected to severe contamination as not handling; And the present traditional purposes of titanium white by product green vitriol, as being used as water purification agent, fertilizer, soil improvement agent and common iron oxide pigment etc., then added value of product is very low, and economic benefit is not high yet, should manage to make full use of this resource.
Summary of the invention
Purpose of the present invention is exactly to utilize the by product green vitriol of sulfate process titanium dioxide production to prepare the nano iron oxide yellow of high added value.Another object of the present invention provides a kind of method that adopts the processing parameter of controlling crystal seed formation and process of growth to prepare nano iron oxide yellow.
For achieving the above object, the present invention by the following technical solutions:
A kind of method for preparing nano iron oxide yellow of the present invention, it is with refining FeSO
4Be raw material, it is characterized in that under certain temperature and stirring velocity, a certain amount of mixed additive Sodium hexametaphosphate 99 and alkylphenol polyoxyethylene are joined refining FeSO
4In the solution, drip 10% Na
2CO
3Solution makes the pH value in the 3.5-6.5 scope, and keeps 20-40 ℃ of certain reaction temperature; Then with 0.12-0.18m
3The logical oxygen flow aerating oxygen of/h reacts, preparation nano iron oxide yellow crystal seed; And then be warming up to 50-60 ℃, again with 0.12-0.18m
3The flow aerating oxygen of/h, the Na of dropping 10% in the solution that contains crystal seed
2CO
3Solution, maintenance system pH value reacted 8 hours in the 3.0-5.5 scope, made seeded growth; Reaction will contain suspension filtered, drying, the pulverizing of nano iron oxide yellow after finishing, and obtain the nano iron oxide yellow particle.
In the process of preparation nano iron oxide yellow crystal seed, stirring velocity is 150-250rpm; Described mixed additive concentration content is the alkylphenol polyoxyethylene of Sodium hexametaphosphate 99 and the 0.020g/l of 0.013g/l.
The pH value of above-mentioned preparation nano iron oxide yellow crystal seed is 5.5-6.5, and temperature of reaction is 25-35 ℃, and logical oxygen flow is 0.16m
3/ h.
PH value in the above-mentioned nano iron oxide yellow seeded growth process is 5.5, and logical oxygen flow is 0.16m
3/ h, the temperature of reaction of nano iron oxide yellow seeded growth is 55 ℃.
Above-mentioned refining FeSO
4The source be the by product green vitriol of sulfuric acid legal system titanium white, and purify and get, wherein Mn through technology
2+Content less than 0.065%, Ti
4+Content is less than 0.01%.
The inventive method mainly is that nanometer iron oxide yellow crystal seed forms and the processing parameter of process of growth by regulating, and controls particle form and aspect, crystal formation and size as pH value, temperature, conditions such as logical oxygen flow, stir speed (S.S.) and additive.
The advantage and the effect of the inventive method are:
1) because the by product green vitriol of employing Production By Sulfuric Acid Process titanium white is a raw material, can eliminate environmental pollution, have obvious social and economic benefits.
2) to prepare the technological process of nano iron oxide yellow simple for the inventive method, and control easily belongs to the liquid phase reaction under the normal temperature and pressure, and easily expands the suitability for industrialized production scale to.
3) product steady quality, the nano iron oxide yellow particle diameter degree of preparation is little, is evenly distributed good dispersity.
The inventive method main chemical reactions formula is:
1) crystal seed preparation
2) seeded growth
The nano iron oxide yellow lovely luster of the inventive method preparation, by the x-ray diffractometer analysis and observation, its crystal formation is the alpha-feooh structure, utilizes electronic lens to observe pattern and is fusiform or needle-like, radical length is 100～120nm, axial length 20～40nm.
Embodiment
After specific embodiments of the invention are described in.
Embodiment 1
Get the FeSO that 400ml concentration is the purification of 15% (g/g)
4Solution (Mn wherein
2+Content less than 0.065%, Ti
4+Content is less than 0.01%), low whipping speed is that 150-250rpm, temperature are 25-35 ℃ of adding 0.013g/L Sodium hexametaphosphate 99 and 0.020g/LOP-10 mixed additive down, adds 10% Na again
2CO
3Solution to pH value is 5.5～6.5, with 0.16m
3/ h flow aerating oxygen reacts under 25-35 ℃, preparation nano iron oxide yellow crystal seed; And then be warming up to 55 ℃, again with 0.16m
3The flow aerating oxygen of/h, the Na of dropping 10% in the solution that contains crystal seed
2CO
3Solution, keeping the pH value is 5.5, reacts 8 hours, makes seeded growth, after reaction finishes, to contain nano iron oxide yellow suspension filtered, drying, pulverize, and obtain the nano iron oxide yellow particle and be bright-coloured yellow, crystal formation is the alpha-feooh structure, particles dispersed is good, and the particle radical length is 100-120nm, and axial length is 20-40nm.
Claims (5)
1. method for preparing nano iron oxide yellow, it is with refining FeSO
4Be raw material, it is characterized in that under certain temperature and stirring velocity, a certain amount of mixed additive Sodium hexametaphosphate 99 and alkylphenol polyoxyethylene are joined refining FeSO
4In the solution, drip 10% Na
2CO
3Solution makes the pH value in the 3.5-6.5 scope, and keeps 20-40 ℃ of certain reaction temperature; Then with 0.12-0.18m
3The logical oxygen flow aerating oxygen of/h reacts, preparation nano iron oxide yellow crystal seed; And then be warming up to 50-60 ℃, again with 0.12-0.18m
3The flow aerating oxygen of/h, the Na of dropping 10% in the solution that contains crystal seed
2CO
3Solution, maintenance system pH value reacted 8 hours in the 3.0-5.5 scope, made seeded growth; Reaction will contain suspension filtered, drying, the pulverizing of nano iron oxide yellow after finishing, and obtain the nano iron oxide yellow particle.
2. a kind of method for preparing nano iron oxide yellow as claimed in claim 1 is characterized in that stirring velocity is 150-250rpm in the process of preparation nano iron oxide yellow crystal seed; Described mixed additive concentration content is the alkylphenol polyoxyethylene of Sodium hexametaphosphate 99 and the 0.020g/l of 0.013g/l.
3. a kind of method for preparing nano iron oxide yellow as claimed in claim 1 is characterized in that the pH value of described preparation nano iron oxide yellow crystal seed is 5.5-6.5, and temperature of reaction is 25-35 ℃, and logical oxygen flow is 0.16m
3/ h.
4. a kind of method for preparing nano iron oxide yellow as claimed in claim 1 is characterized in that the pH value in the described nano iron oxide yellow seeded growth process is 5.5, and logical oxygen flow is 0.16m
3/ h, the temperature of reaction of nano iron oxide yellow seeded growth is 55 ℃.
5. a kind of method for preparing nano iron oxide yellow as claimed in claim 1 is characterized in that refining FeSO
4The source be the by product green vitriol of sulfuric acid legal system titanium white, and purify and get, wherein Mn through technology
2+Content less than 0.065%, Ti
4+Content is less than 0.01%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02137552 CN1245458C (en) | 2002-10-21 | 2002-10-21 | Method for preparing nano iron oxide yellow |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02137552 CN1245458C (en) | 2002-10-21 | 2002-10-21 | Method for preparing nano iron oxide yellow |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1415664A CN1415664A (en) | 2003-05-07 |
| CN1245458C true CN1245458C (en) | 2006-03-15 |
Family
ID=4749031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02137552 Expired - Fee Related CN1245458C (en) | 2002-10-21 | 2002-10-21 | Method for preparing nano iron oxide yellow |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1245458C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432156C (en) * | 2005-04-30 | 2008-11-12 | 河南黄河旋风股份有限公司 | Process for preparing nano iron oxide yellow pigment |
| CN105670345B (en) * | 2016-01-05 | 2017-12-22 | 萧县金鹭纺织品有限公司 | A kind of fire-retardant Method for preparing medium-temperature-rirontant irontant oxide yellow pigment |
| CN106000230A (en) * | 2016-07-27 | 2016-10-12 | 升华集团德清华源颜料有限公司 | High-pressure reaction vessel special for preparation of low-length/diameter-ratio iron oxide yellow |
| CN107640790B (en) * | 2017-11-15 | 2019-10-18 | 成都先进金属材料产业技术研究院有限公司 | The method that titanium white by product object prepares high-purity ferrous sulfate crystal |
| CN113104901B (en) * | 2021-04-13 | 2024-02-09 | 江西理工大学 | Method for preparing iron oxide yellow from rare earth waste acid leaching slag |
| CN113292103A (en) * | 2021-05-25 | 2021-08-24 | 永兴朗丰色料实业有限公司 | Method for producing nano iron oxide red by utilizing solid waste |
| CN117326597B (en) * | 2023-08-30 | 2024-05-24 | 宁波爱诗化妆品有限公司 | Method for regulating and controlling size of nano iron oxide yellow, nano iron oxide yellow and application thereof |
-
2002
- 2002-10-21 CN CN 02137552 patent/CN1245458C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1415664A (en) | 2003-05-07 |
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