CN103818970B - A kind of nanometer Zh 1 synthetic method - Google Patents
A kind of nanometer Zh 1 synthetic method Download PDFInfo
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- CN103818970B CN103818970B CN201410080026.1A CN201410080026A CN103818970B CN 103818970 B CN103818970 B CN 103818970B CN 201410080026 A CN201410080026 A CN 201410080026A CN 103818970 B CN103818970 B CN 103818970B
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Abstract
The invention discloses a kind of nanometer Zh 1 synthetic method.All adopt chemosynthesis nanometer Zh 1 for prior art, the invention provides a kind of biosynthetic means of nanometer Zh 1.Synthesis implementation method inoculates thiobacillus ferrooxidant in slurry reaction thing, and 30 DEG C of conditioned responses, pass into air; Work as 50%Fe
2+when having reacted, add oleic acid and continue reaction; Reaction terminates, washing, filtration, dry obtained nanometer Zh 1.Slurry reaction thing component is FeSO
47H
2o1.0kg/m
3~ 100kg/m
3, CO (NH
2)
20.2kg/m
3~ 20kg/m
3, dimethyl silicone oil 0.05g/m
3~ 2.3g/m
3, CaCl
20.25kg/m
3, NaH
2pO
40.2kg/m
3, Mg (NO
3)
20.18kg/m
3, glucose 0.05kg/m
3~ 0.3kg/m
3, pH2.5 ~ 5.5.The inventive method reactive material from start to finish exists with liquid slurry form, is conducive to automatic production, solves the problems such as prior art processes complicated difficult control, separation and purification is difficult, cost is high, particle accumulation is more serious.The present invention also provides the application method of thiobacillus ferrooxidant in the synthesis of nanometer Zh 1.
Description
Technical field
The present invention relates to a kind of nanometer Zh 1 synthetic method, particularly relate to a kind of biocatalytic synthesis of nanometer Zh 1, belong to synthesis chemical field.
Background technology
Nanometer Zh 1 is tradition and the one of important ferric oxide inorganic materials, except the general character advantage possessing ferric oxide inorganic materials, also possesses its exclusive feature, can be used as the surface lacquer of functional pigment for superior automobile, precision instrument, bike, motorcycle etc., and be used as the color additives etc. such as makeup, food, medicine.
At present, the main method preparing nanometer Zh 1 has oxygen (air) oxidation style, colloid chemistry methods, iron carbonyl oxidation style, sodium chlorate oxidation style etc. several.Wherein, oxygen (air) oxidation style is gas, solid, liquid phase reaction, and reaction mechanism and processing condition complexity, particle form is difficult to control, bad dispersibility.Use a large amount of organic solvent in colloid chemistry methods, abstraction and purification difficulty, and cost is higher.The preparation of the main raw material iron carbonyl in iron carbonyl oxidation style is more difficult, and cost is very high, and need could obtain nanometer iron oxide yellow through high-temperature calcination, and calcination process very easily causes particle coalescence or sintering, or particle crystal formation is changed.Although sodium chlorate oxidation style technique is simple, iron glue is larger to the impact of conversion process on particle form of iron oxide yellow.On the whole, these methods belong to chemical synthesis process, all there is different aspect and defect in various degree in chemical synthesis process.
Publication number is that the Chinese patent literature of CN1438318 and CN1896249 discloses the method utilizing microorganism catalysis to synthesize the yellow iron pigment of ihleite, specifically using ferrous sulfate and potassium sulfate, sodium sulfate, ammonium sulfate etc. as main reactant, free or immobilized microorganism are produced as catalyzer.But this biocatalysis synthetic technology does not relate to the synthesis of nanometer Zh 1.
Summary of the invention
Object of the present invention is exactly for the deficiencies in the prior art, a kind of nanometer Zh 1 synthetic method is provided, the particularly biosynthetic means of nanometer Zh 1, the method can utilize biosynthetic advantage to solve the technical problems such as existing synthetic method craft is complicated, separation and purification is difficult, cost is high, product quality is wayward.
For achieving the above object, technical scheme of the present invention is as follows:
A kind of nanometer Zh 1 synthetic method, it is characterized in that: be biocatalytic synthesis, implementation method is: prepare slurry reaction thing, described slurry reaction thing component is FeSO
47H
2o 1.0Kg/m
3~ 100Kg/m
3, CO (NH
2)
20.2Kg/m
3~ 20Kg/m
3, dimethyl silicone oil 0.05g/m
3~ 2.3g/m
3, CaCl
20.25Kg/m
3, NaH
2pO
40.2Kg/m
3, Mg (NO
3)
20.18Kg/m
3, glucose 0.05Kg/m
3~ 0.3Kg/m
3, pH 2.5 ~ 5.5; In slurry reaction thing, inoculate thiobacillus ferrooxidant, react under 30 DEG C of temperature condition, in reaction process, pass into air; As 50%Fe in slurry reaction thing
2+when having reacted, add oleic acid and continue reaction, oleic acid add-on 0.05mol/m
3~ 0.1mol/m
3; Reaction terminates, washing, filtration, dry obtained nanometer Zh 1.
In above-mentioned synthetic method, thiobacillus ferrooxidant (Acidithiobacillus ferrooxidans) is conventional bacterial classification in biocatalysis synthesis, can obtain (as China typical culture collection center CCTCCM88063, American Type Culture Collection center ATCC23270) from how each channel or method.Generally by the usual working method of industry when bacterial classification uses, the enrichment of 9K liquid nutrient medium and dilution is adopted to be coated with plate isolation purifying.
The know-why of above-mentioned synthetic method is: the ferrous sulfate in slurry is under the effect of microorganism, and oxydrolysis, at microorganism and dimethyl silicone oil, CO (NH
2)
2, NaH
2pO
4under the catalysis of composite assistant, transform and form ferric oxide, and in microbial cell surface deposition, thus form nanometer Zh 1 rapidly.CaCl
2, Mg (NO
3)
2, glucose etc. is conducive to maintaining microbial activity and cell surface is active, the oxidative synthesis of accelerating oxidation iron.
Under optimum condition, aforesaid method can do following optimization:
Above-mentioned synthetic method, CO (NH in slurry reaction thing
2)
2with FeSO
47H
2o mass values controls at 1:5.
Above-mentioned synthetic method, dimethyl silicone oil and Fe in slurry reaction thing
2+volumetric molar concentration ratio≤3.8:100.
Above-mentioned synthetic method, the initial pH 2.5 of slurry reaction thing.
Above-mentioned synthetic method, thiobacillus ferrooxidant inoculum size 5 × 10
6individual/mL ~ 8 × 10
6individual/mL.
Above-mentioned synthetic method, stirs passing under air condition in reaction process, air flow quantity 50L/min ~ 100L/min, and is more excellent with 50L/min.
Above-mentioned synthetic method, oleic acid add-on 0.05mol/m
3.
Above-mentioned synthetic method, works as 95%Fe
2+be judged as when having reacted that reaction terminates.
The present invention provides the application of thiobacillus ferrooxidant in the synthesis of nanometer Zh 1 simultaneously.
Compared with prior art, the invention has the beneficial effects as follows: (1) provides the biosynthetic means of nanometer Zh 1, the method is using the solution of particular combination proportions as reactant, the nanometer oxide yellow iron product with premium properties can be obtained at normal temperatures through Biocatalytic Conversion, Technology is simple, workable, reactive material from start to finish exists with liquid slurry form, be conducive to automatic production, solve the control of prior art processes complicated difficult, separation and purification difficulty, cost is high, the problems such as particle accumulation is more serious, there is important technical show-how meaning and social value.(2) application method of thiobacillus ferrooxidant in the synthesis of nanometer Zh 1 is provided.
Embodiment
Below in conjunction with preferred embodiment, technical solution of the present invention will be further described.
Embodiment one
Adopt the inventive method synthesis of nano Zh 1.
(1) slurry reaction thing preparation:
Slurry reaction thing component: FeSO
47H
2o 40Kg/m
3, CO (NH
2)
28Kg/m
3, dimethyl silicone oil 0.5g/m
3, CaCl
20.25Kg/m
3, NaH
2pO
40.2Kg/m
3, Mg (NO
3)
20.18Kg/m
3, glucose 0.1Kg/m
3;
The initial pH to 2.5 of slurry is regulated with 4mol/L sulfuric acid or 4mol/L sodium hydroxide.
(2) microbe inoculation
Get above-mentioned slurry reaction thing 100L, inoculation thiobacillus ferrooxidant microorganism cells, inoculating cell total concn controls 5 × 10
6individual/mL.
(3) react
After inoculation, reactant reacts, reaction conditions is temperature about 30 DEG C, pass into air condition under stir air flow quantity 50L/min; As 50%Fe in slurry
2+when having reacted, add oleic acid, add-on is 0.05mol/m
3, continue the Fe of reaction to more than 95%
2+react.
(4) blowing
Reaction terminates, and by the slurry sediment of acquisition, washing, filtration, 90 DEG C of dry 2h, obtain product.
The above product that obtains is detected.Product samples particle is long fusiform, path length 50nm ~ 80nm, wide be 10nm ~ 30nm, X-ray diffraction analysis d value is 4.197 (110), 2.453 (111), 2.755 (130), consistent with JCPDS standard, iron content 62.1%, conform to standard theoretical value, be defined as nanometer Zh 1.
Embodiment two
Adopt the inventive method synthesis of nano Zh 1.
(1) slurry reaction thing preparation:
Slurry reaction thing component: FeSO
47H
2o 100Kg/m
3, CO (NH
2)
220Kg/m
3, dimethyl silicone oil 2.3g/m
3, CaCl
20.25Kg/m
3, NaH
2pO
40.2Kg/m
3, Mg (NO
3)
20.18Kg/m
3, glucose 0.3Kg/m
3;
The initial pH to 5.5 of slurry is regulated with 8mol/L sulfuric acid or 4mol/L sodium hydroxide.
(2) microbe inoculation
Get above-mentioned slurry reaction thing 100L, inoculation thiobacillus ferrooxidant microorganism cells, inoculating cell total concn controls 8 × 10
6individual/mL.
(3) react
After inoculation, reactant reacts, reaction conditions is temperature about 30 DEG C, pass into air condition under stir air flow quantity 100L/min; As 50%Fe in slurry
2+when having reacted, add oleic acid, add-on is 0.1mol/m
3, continue the Fe of reaction to more than 95%
2+react.
(4) blowing
Reaction terminates, and by the slurry sediment of acquisition, washing, filtration, 100 DEG C of dry 3h, obtain product.
The above product that obtains is detected.Product samples particle is long fusiform, path length 50nm ~ 80nm, wide be 10nm ~ 30nm, X-ray diffraction analysis d value is 4.193 (110), 2.451 (111), 2.745 (130), consistent with JCPDS standard, iron content 62.3%, conform to standard theoretical value, be defined as nanometer Zh 1.
Embodiment three
Adopt the inventive method synthesis of nano Zh 1.
(1) slurry reaction thing preparation:
Slurry reaction thing component: FeSO
47H
2o 1Kg/m
3, CO (NH
2)
20.2Kg/m
3, dimethyl silicone oil 0.05g/m
3, CaCl
20.25Kg/m
3, NaH
2pO
40.2Kg/m
3, Mg (NO
3)
20.18Kg/m
3, glucose 0.05Kg/m
3;
The initial pH to 3.5 of slurry is regulated with 8mol/L sulfuric acid or 4mol/L sodium hydroxide.
(2) microbe inoculation
Get above-mentioned slurry reaction thing 100L, inoculation thiobacillus ferrooxidant microorganism cells, inoculating cell total concn controls 7 × 10
6individual/mL.
(3) react
After inoculation, reactant reacts, reaction conditions is temperature about 30 DEG C, pass into air condition under stir air flow quantity 100L/min; As 50%Fe in slurry
2+when having reacted, add oleic acid, add-on is 0.1mol/m
3, continue the Fe of reaction to more than 95%
2+react.
(4) blowing
Reaction terminates, and by the slurry sediment of acquisition, washing, filtration, 105 DEG C of dry 3h, obtain product.
The above product that obtains is detected.Product samples particle is long fusiform, path length 50nm ~ 80nm, wide be 10nm ~ 35nm, X-ray diffraction analysis d value is 4.189 (110), 2.453 (111), 2.741 (130), consistent with JCPDS standard, iron content 62.4%, conform to standard theoretical value, be defined as nanometer Zh 1.
Claims (9)
1. a nanometer Zh 1 synthetic method, is characterized in that: be biocatalytic synthesis, implementation method is:
Prepare slurry reaction thing, described slurry reaction thing component is FeSO
47H
2o 1.0Kg/m
3~ 100Kg/m
3, CO (NH
2)
20.2Kg/m
3~ 20Kg/m
3, dimethyl silicone oil 0.05g/m
3~ 2.3g/m
3, CaCl
20.25Kg/m
3, NaH
2pO
40.2Kg/m
3, Mg (NO
3)
20.18Kg/m
3, glucose 0.05Kg/m
3~ 0.3Kg/m
3, pH 2.5 ~ 5.5;
Thiobacillus ferrooxidant is inoculated in slurry reaction thing;
React under 30 DEG C of temperature condition, in reaction process, pass into air;
As 50%Fe in slurry reaction thing
2+when having reacted, add oleic acid and continue reaction, oleic acid add-on 0.05mol/m
3~ 0.1mol/m
3;
Reaction terminates, washing, filtration, dry obtained nanometer Zh 1.
2. method according to claim 1, is characterized in that: described slurry reaction thing, CO (NH
2)
2with FeSO
47H
2o mass ratio 1:5.
3. method according to claim 1, is characterized in that: described slurry reaction thing, dimethyl silicone oil and Fe
2+volumetric molar concentration ratio≤3.8:100.
4. method according to claim 1, is characterized in that: described slurry reaction thing component is: FeSO
47H
2o 40Kg/m
3, CO (NH
2)
28Kg/m
3, dimethyl silicone oil 0.5g/m
3, CaCl
20.25Kg/m
3, NaH
2pO
40.2Kg/m
3, Mg (NO
3)
20.18Kg/m
3, glucose 0.1Kg/m
3.
5., according to the arbitrary described method of Claims 1 to 4, it is characterized in that: described slurry reaction thing, initial pH2.5.
6. according to the arbitrary described method of Claims 1 to 4, it is characterized in that: described slurry reaction thing, regulate initial pH value with sulfuric acid or sodium hydroxide.
7., according to the arbitrary described method of Claims 1 to 4, it is characterized in that: described thiobacillus ferrooxidant inoculum size 5 × 10
6individual/mL ~ 8 × 10
6individual/mL.
8. according to the arbitrary described method of Claims 1 to 4, it is characterized in that: stir passing under air condition in reaction process, air flow quantity 50L/min ~ 100L/min.
9., according to the arbitrary described method of Claims 1 to 4, it is characterized in that: described oleic acid add-on 0.05mol/m
3.
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|---|---|---|---|
| CN201410080026.1A CN103818970B (en) | 2014-03-06 | 2014-03-06 | A kind of nanometer Zh 1 synthetic method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410080026.1A CN103818970B (en) | 2014-03-06 | 2014-03-06 | A kind of nanometer Zh 1 synthetic method |
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| CN103818970B true CN103818970B (en) | 2015-09-09 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438318A (en) * | 2003-03-11 | 2003-08-27 | 南京农业大学 | Microbial-catalytic synthesizing method of pyrite ammonia alum |
| CN1896249A (en) * | 2006-06-23 | 2007-01-17 | 兰州大学 | Continuous catalytic synthesis of vitriol pyrite by solid microbion |
| CN103305553A (en) * | 2013-06-18 | 2013-09-18 | 中国科学院成都生物研究所 | Biological resourceful treatment method for ferrous sulfate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL132506A (en) * | 1999-10-21 | 2006-06-11 | Biopigment Ltd | Method for production of iron oxide pigments |
-
2014
- 2014-03-06 CN CN201410080026.1A patent/CN103818970B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438318A (en) * | 2003-03-11 | 2003-08-27 | 南京农业大学 | Microbial-catalytic synthesizing method of pyrite ammonia alum |
| CN1896249A (en) * | 2006-06-23 | 2007-01-17 | 兰州大学 | Continuous catalytic synthesis of vitriol pyrite by solid microbion |
| CN103305553A (en) * | 2013-06-18 | 2013-09-18 | 中国科学院成都生物研究所 | Biological resourceful treatment method for ferrous sulfate |
Non-Patent Citations (1)
| Title |
|---|
| 用硫酸亚铁制纳米氧化铁黄;何云清等;《四川文理学院学报(自然科学)》;20070930;第17卷(第5期);第40－42页 * |
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