CN100567168C - A kind of preparation method of patina - Google Patents
A kind of preparation method of patina Download PDFInfo
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- CN100567168C CN100567168C CNB2008100358571A CN200810035857A CN100567168C CN 100567168 C CN100567168 C CN 100567168C CN B2008100358571 A CNB2008100358571 A CN B2008100358571A CN 200810035857 A CN200810035857 A CN 200810035857A CN 100567168 C CN100567168 C CN 100567168C
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Abstract
The invention belongs to technical field of inorganic chemical industry, be specifically related to a kind of important intermediate---the preparation method of patina who produces in a kind of various ferrite generative process.Concrete steps are as follows: building reaction unit, is 2.5 * 10 with volumetric molar concentration
-4～7.5 * 10
-4The aqueous ascorbic acid of mol/L is a solvent, FeSO
4As solute preparation ferrous iron solution, place the four-hole boiling flask under the nitrogen atmosphere; Basic solution is placed a pipe of constant voltage titration funnel, Fe
2(SO
4)
3Solution places another root pipe of constant voltage titration funnel; FeSO
4And Fe
2(SO
4)
3The volumetric molar concentration of solution equates; Adopt magnetic agitation, make the solution stirring in the four-hole boiling flask even, the pH value of solution in the four-hole boiling flask is adjusted to 6, dropping Fe
2(SO
4)
3Solution drips basic solution simultaneously, makes the pH value of solution remain on 6; Treat Fe
2(SO
4)
3After solution dripped off, the pH value of recording solution continued to drip basic solution in solution, and observe solution colour simultaneously and change, be 7 up to the pH of solution value, reaction finishes; Ageing promptly gets desired product.The patina purity height of the present invention's preparation, the reaction conditions gentleness.
Description
Technical field
The invention belongs to technical field of inorganic chemical industry, be specifically related to a kind of important intermediate---the preparation method of patina who produces in a kind of various ferrite generative process.
Background technology
At present, patina is as a kind of important intermediate product, not only can be to the research of its formation for preparation nano-level iron oxysome provide theoretical direction, and association areas such as metallic corrosion, environmental engineering are also had using value.It is that final product synthesizes that existing in recent years researchist begins with the patina, and the technology that adopts is that oxidation style and coprecipitation method are advanced usually.
Oxidation style is under oxygen free condition Fe (II) to be precipitated, and forms Fe (OH)
2Suspension, partial oxidation makes patina then.Though it is simple that oxidation style prepares the patina principle, difficult to the control ratio of ferrous ion degree of oxidation, required condition is very harsh, needs conditions such as strict controlled oxidation agent, pH value and each yin, yang ionic concentration.
Coprecipitation method is under the starvation condition, ferrous and ferrous solution mixed by a certain percentage, adding alkaline precipitating agent NaOH system.Coprecipitation method needs strict control oxygen in actually operating, accomplish oxygen free operation, and this brings difficulty to research, and running cost also can improve.Have spicule to exist in addition in the co-precipitation synthetic product, product yield awaits improving.
Summary of the invention
The preparation method who the purpose of this invention is to provide the patina that a kind of nucleation rate is fast, product yield is high.
The preparation method of the patina that the present invention proposes, concrete steps are as follows:
A, build reaction unit, first of four-hole boiling flask 10 mouthful connects 4, two mouthfuls of pipe connecting 4 tops of two mouthfuls of pipe connectings and connects respectively in 1, two constant voltage titration of constant voltage titration funnel funnel 1 and add Fe respectively
2(SO
4)
3 Solution 2 and basic solution 3, the soft rubber ball jam-pack of using suitable for reading of constant voltage titration funnel 1 is to prevent air admission; Second mouth in the four-hole boiling flask 10 connects mercurous chloride electrode 5 respectively and 7, the four mouths of 6, the three mouths connection pH electrode of nitrogen inlet pipe connect counter electrode 8 and working electrode 9 respectively, and four-hole boiling flask 10 places on the magnetic stirrer 11;
B, be 2.5 * 10 with volumetric molar concentration
-4～7.5 * 10
-4The xitix of mol/L (Vc) aqueous solution is solvent, FeSO
4As solute preparation 100ml concentration is the ferrous iron solution of 0.03～0.07M, places the four-hole boiling flask 10 under the nitrogen atmosphere;
C, the basic solution 3 of 0.1M is placed a pipe of constant voltage titration funnel 1,50ml concentration is the Fe of 0.03～0.07M
2(SO
4)
3 Solution 2 places another root pipe of constant voltage titration funnel 1; Wherein, FeSO
4And Fe
2(SO
4)
3The volumetric molar concentration of solution equates;
D, adopt magnetic agitation, make the solution stirring in the four-hole boiling flask 10 even, the pH value of solution in the four-hole boiling flask 10 is adjusted to 6, begin to drip Fe
2(SO
4)
3 Solution 2 drips basic solution 3 simultaneously, so that the pH value of solution remains on 6;
E, treat Fe
2(SO
4)
3After solution 2 dripped off, the pH value of recording solution continued to drip basic solution 3 in solution, and observe solution colour simultaneously and change, be 7 up to the pH of solution value, reaction finishes;
F, ageing promptly get desired product.
Among the present invention, described basic solution be in NaOH solution or the KOH solution etc. any, only require in the basic solution positively charged ion discord SO
4 2-Ion forms precipitation and gets final product.
Among the present invention, the ageing temperature is 65-75 ℃ described in the step (f), and digestion time is 1.5-3 hour; Perhaps ageing temperature is a normal temperature, and digestion time is 10-30 days.
Beneficial effect of the present invention:
The inventive method is used for synthetic intermediate, and to studies show that of patina structure, the patina crystal itself has neat regular lattice, if can directly be converted into Fe from the patina crystal
3O
4Deng ferrous oxide, have operability, and the particle size distribution situation that this method obtains may improve.
Among the present invention,, can reduce anion concentration because patina has extremely strong sorptive power, as: chromate, nitrate radical, therefore selenate radicals etc. can be used for environmental protection and handle the sewage that contains heavy metal.
Patina is as the intermediate product of steel corrosion, therefore at the aspect such as anticorrosion of iron and steel extremely important meaning arranged.It is the important research object of steel corrosion, thalassography etc.
The patina purity height of the present invention's preparation, the reaction conditions gentleness.
Description of drawings
Fig. 1 is preparation method's of the present invention reaction unit figure.
Fig. 2 is that embodiment 1 dripping method prepares electronic transmission Electronic Speculum (TEM) picture of patina placement after 15 days.
Fig. 3 is that embodiment 2 dripping methods prepare patina electronic transmission Electronic Speculum (TEM) picture on the same day.
Fig. 4 is that embodiment 2 dripping methods prepare electronic transmission Electronic Speculum (TEM) picture of 70 ℃ of ageings of patina after 2 hours.
Fig. 5 is that embodiment 2 dripping methods prepare electronic transmission Electronic Speculum (TEM) picture of patina normal temperature ageing after 15 days.
Fig. 6 adopts the prior art coprecipitation method to prepare electronic transmission Electronic Speculum (TEM) picture of 70 ℃ of ageings of patina after 2 hours, and its solvent is 5.0 * 10
-4The aqueous solution of mol/L xitix (Vc), FeSO
4And Fe
2(SO
4)
3Concentration is 0.05M, and is identical with the reaction conditions of embodiment 2.
Fig. 7 is that embodiment 3 dripping methods prepare electronic transmission Electronic Speculum (TEM) picture of 70 ℃ of ageings of patina after 2 hours.
Number in the figure: 1 is constant voltage titration funnel, and 2 is Fe
2(SO
4)
3Solution, 3 is basic solution, and 4 is two mouthfuls of pipe connectings, and 5 is mercurous chloride electrode, and 6 is the nitrogen inlet pipe, and 7 is pH electrode, and 8 is counter electrode, and 9 is working electrode, and 10 is four-hole boiling flask, and 11 is magnetic stirrer.
Embodiment
Advance to illustrate the present invention below by embodiment.
Embodiment 1: with 2.5 * 10
-4The aqueous solution of mol/L xitix (Vc) is made solvent, FeSO
4And Fe
2(SO
4)
3Concentration is 0.03M.
A, build reaction unit, first of four-hole boiling flask 10 mouthful connects 4, two mouthfuls of pipe connecting 4 tops of two mouthfuls of pipe connectings and connects respectively in 1, two constant voltage titration of constant voltage titration funnel funnel 1 and add Fe respectively
2(SO
4)
3 Solution 2 and NaOH solution 3, the soft rubber ball jam-pack of using suitable for reading of constant voltage titration funnel 1 is to prevent air admission; Second mouth in the four-hole boiling flask connects mercurous chloride electrode 5 respectively and 7, the four mouths of 6, the three mouths connection pH electrode of nitrogen inlet pipe connect counter electrode 8 and working electrode 9 respectively, and four-hole boiling flask 10 places on the magnetic stirrer 11;
B, employing contain xitix (Vc) 2.5 * 10
-4The aqueous solution of mol/L is made solvent, FeSO
4As solute preparation 100ml0.03M ferrous iron solution, place the four-hole boiling flask under the nitrogen atmosphere, prevent that oxygen dissolution enters solution in the air.
C, with the NaOH solution of 0.1M and the Fe of 50ml 0.03M
2(SO
4)
3Solution places constant voltage titration funnel respectively.
D, employing magnetic agitation fully stir, and guarantee that solution stirring is even, and pH value of solution value in the four-hole boiling flask is adjusted to 6, drip Fe
2(SO
4)
3Solution drips NaOH solution simultaneously to keep the pH value constant.
E, treat Fe in the constant voltage titration funnel
2(SO
4)
3Solution drips off, and continue to drip NaOH in solution, and it is constant to keep rate of addition 4d/s (every drop volume is approximately 0.55ml).
F, record Fe
2(SO
4)
3PH value change situation after solution drips off is observed solution colour simultaneously and is changed, and up to pH=7, reaction finishes.
Ageing can obtain the patina crystal about 2 hours under g, the 70 ℃ of conditions.
As can be seen from Figure 2, because the low excessively speed that causes patina to form of reactant concn is slow excessively, the reaction times increases, but patina still can normally generate.Analyze theoretically, reactant concn did not have saying of minimum concentration during patina generated and tests, but because the requirement of detection means restriction and reaction times length, reactant concn can not be too low.
Embodiment 2: with 5.0 * 10
-4The aqueous solution of mol/L xitix (Vc) is made solvent, FeSO
4And Fe
2(SO
4)
3Concentration be 0.05M.
A, build reaction unit, first of four-hole boiling flask 10 mouthful connects 4, two mouthfuls of pipe connecting 4 tops of two mouthfuls of pipe connectings and connects respectively in 1, two constant voltage titration of constant voltage titration funnel funnel 1 and add Fe respectively
2(SO
4)
3 Solution 2 and NaOH solution 3, the soft rubber ball jam-pack of using suitable for reading of constant voltage titration funnel 1 is to prevent air admission; Second mouth in the four-hole boiling flask connects mercurous chloride electrode 5 respectively and 7, the four mouths of 6, the three mouths connection pH electrode of nitrogen inlet pipe connect counter electrode 8 and working electrode 9 respectively, and four-hole boiling flask 10 places on the magnetic stirrer 11;
B, employing contain xitix (Vc) 5.0 * 10
-4The aqueous solution of mol/L is made solvent, FeSO
4As solute preparation 100ml0.05M ferrous iron solution, place the four-hole boiling flask under the nitrogen atmosphere, prevent that oxygen dissolution enters solution in the air.
C, with the NaOH solution of 0.1M and the Fe of 50ml 0.05M
2(SO
4)
3Solution places constant voltage titration funnel respectively.
D, employing magnetic agitation fully stir, and guarantee that solution stirring is even, and pH value of solution value in the four-hole boiling flask is adjusted to 6, drip Fe
2(SO
4)
3Solution drips NaOH simultaneously to keep the pH value constant.
E, treat Fe in the constant voltage titration funnel
2(SO
4)
3Solution drips off, and continue to drip NaOH in solution, and it is constant to keep rate of addition 4d/s (every drop volume is approximately 0.55ml).
F, record Fe
2(SO
4)
3PH value change situation after solution drips off is observed solution colour simultaneously and is changed, and up to pH=7, reaction finishes.
Ageing is about 2 hours or normal temperature ageing more than 10 days under g, the 70 ℃ of conditions, can obtain having the patina crystal of neat regular lattice.
As can be seen from Figure 3, patina does not have the patina crystal and generates when reaction process, and the patina crystalline forms needs certain digestion time, and ageing is the crystal formation requisite committed step of patina.
As can be seen from Figure 4, dripping method prepares patina, and 70 ℃ of ageings can obtain having the patina crystal of neatly regular lattice after 2 hours.
As can be seen from Figure 5, dripping method prepares patina, still contains the acicular iron oxide hydroxide crystal in the product of normal temperature ageing after 15 days.
By Fig. 4 and Fig. 5 more as can be known, add thermal aging with normal temperature ageing compare, add thermal aging and accelerate crystallisation process.
As can be seen from Figure 6, coprecipitation method prepares patina, contains the acicular iron oxide hydroxide crystal in the product of 70 ℃ of ageings after 2 hours, and product purity is not high, and patina crystalline lattice and irregular regular, and crystalline form is relatively poor.
More as can be known, dripping method prepares patina and prepares patina with coprecipitation method and compare by Fig. 4 and Fig. 6, and there is not tangible acicular iron oxide hydroxide crystal in the product that dripping method prepares the patina gained, and only visible hexagonal patina crystal, selectivity of product is obviously improved.
Embodiment 3: with 7.5 * 10
-4The aqueous solution of mol/L xitix (Vc) is made solvent, FeSO
4And Fe
2(SO
4)
3Concentration is that 0.07M is an example:
A, build reaction unit, first of four-hole boiling flask 10 mouthful connects 4, two mouthfuls of pipe connecting 4 tops of two mouthfuls of pipe connectings and connects respectively in 1, two constant voltage titration of constant voltage titration funnel funnel 1 and add Fe respectively
2(SO
4)
3 Solution 2 and NaOH solution 3, the soft rubber ball jam-pack of using suitable for reading of constant voltage titration funnel 1 is to prevent air admission; Second mouth in the four-hole boiling flask connects mercurous chloride electrode 5 respectively and 7, the four mouths of 6, the three mouths connection pH electrode of nitrogen inlet pipe connect counter electrode 8 and working electrode 9 respectively, and four-hole boiling flask 10 places on the magnetic stirrer 11;
B, employing contain xitix (Vc) 7.5 * 10
-4The aqueous solution of mol/L is made solvent, FeSO
4As solute preparation 100ml0.07M ferrous iron solution, place the four-hole boiling flask under the nitrogen atmosphere, prevent that oxygen dissolution enters solution in the air.
C, with the NaOH solution of 0.1M and the Fe of 50ml 0.07M
2(SO
4)
3Solution places constant voltage titration funnel respectively.
D, employing magnetic agitation are adjusted to 6 with pH value of solution value in the four-hole boiling flask, drip Fe
2(SO
4)
3Solution drips NaOH simultaneously to keep the pH value constant.
E, treat Fe in the constant voltage titration funnel
2(SO
4)
3Solution drips off, and continue to drip NaOH in solution, and it is constant to keep rate of addition 4d/s (every drop volume is approximately 0.55ml).
F, record Fe
2(SO
4)
3PH value change situation after solution drips off is observed solution colour simultaneously and is changed, and up to pH=7, reaction finishes.
Ageing can obtain the patina crystal, but have a large amount of acicular iron oxide hydroxide crystal about 2 hours under g, the 70 ℃ of conditions.
As can be seen from Figure 7, dripping method prepares patina, and 70 ℃ of ageings are after 2 hours, because reactant concn is too high, oxidation rate is accelerated, a large amount of acicular iron oxide hydroxide crystal that makes generation, and the patina crystal yield that obtains is not high.
Embodiment 4: coprecipitation method prepares patina.Solvent is 5.0 * 10
-4The aqueous solution of mol/L xitix (Vc), FeSO
4And Fe
2(SO
4)
3Concentration is 0.05M, and the remaining reaction condition is identical with embodiment 2.
A, build reaction unit, first of four-hole boiling flask 10 mouthful connects 4, two mouthfuls of pipe connecting 4 tops of two mouthfuls of pipe connectings and connects respectively in 1, two constant voltage titration of constant voltage titration funnel funnel 1 and add Fe respectively
2(SO
4)
3 Solution 2 and KOH solution 3, the soft rubber ball jam-pack of using suitable for reading of constant voltage titration funnel 1 is to prevent air admission; Second mouth in the four-hole boiling flask connects mercurous chloride electrode 5 respectively and 7, the four mouths of 6, the three mouths connection pH electrode of nitrogen inlet pipe connect counter electrode 8 and working electrode 9 respectively, and four-hole boiling flask 10 places on the magnetic stirrer 11;
B, under high-speed stirring with Fe
2(SO
4)
3Add fast in the four-hole boiling flask, mix with wherein ferrous iron solution;
C, drip KOH then, regulate the constant pressure funnel valve of KOH, and it is constant to keep the rate of addition 4d/s (every drop volume is approximately 0.55ml) of KOH;
D, record pH value change up to pH=7, and reaction finishes;
Ageing contained the acicular iron oxide hydroxide crystal about 2 hours under e, the 70 ℃ of conditions in the product, and product purity is not high, and patina crystalline lattice and irregular regular, and crystalline form is relatively poor.
Claims (2)
1, a kind of preparation method of patina is characterized in that concrete steps are as follows:
A, build reaction unit, first of four-hole boiling flask (10) mouthful connects two mouthfuls of pipe connectings (4), and two mouthfuls of pipe connectings (4) top connects constant voltage titration funnel (1) respectively, adds Fe respectively in two constant voltage titration funnels (1)
2(SO
4)
3Solution (2) and basic solution (3), the soft rubber ball jam-pack of using suitable for reading of constant voltage titration funnel (1) is to prevent air admission; Second mouth in the four-hole boiling flask connects mercurous chloride electrode (5) and nitrogen inlet pipe (6) respectively, and the 3rd mouth connects pH electrode (7), and the 4th mouth connects counter electrode (8) and working electrode (9) respectively, and four-hole boiling flask (10) places on the magnetic stirrer (11);
B, be 2.5 * 10 with volumetric molar concentration
-4～7.5 * 10
-4The aqueous ascorbic acid of mol/L is a solvent, FeSO
4As solute preparation 100ml concentration is the ferrous iron solution of 0.03～0.07M, places the four-hole boiling flask under the nitrogen atmosphere;
C, the basic solution of 0.1M is placed a pipe of constant voltage titration funnel (1), 50ml concentration is the Fe of 0.03～0.07M
2(SO
4)
3Solution places another root pipe of constant voltage titration funnel (1); Wherein, FeSO
4And Fe
2(SO
4)
3The volumetric molar concentration of solution equates;
D, adopt magnetic agitation, make the solution stirring in the four-hole boiling flask even, the pH value of solution in the four-hole boiling flask (10) is adjusted to 6, begin to drip Fe
2(SO
4)
3Solution (2) drips basic solution (3) simultaneously, makes the pH value of solution remain on 6;
E, treat Fe
2(SO
4)
3After solution (2) dripped off, the pH value of recording solution continued to drip basic solution (3) in solution, and observe solution colour simultaneously and change, be 7 up to the pH of solution value, reaction finishes;
F, ageing promptly get desired product;
Wherein, described basic solution is NaOH solution or KOH solution.
2, the preparation method of patina according to claim 1 is characterized in that the ageing temperature is 65-75 ℃ described in the step (f), and digestion time is 1.5-3 hour; Perhaps ageing temperature is a normal temperature, and digestion time is 10-30 days.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108946820A (en) * | 2018-08-06 | 2018-12-07 | 武汉轻工大学 | A kind of carbonate patina and preparation method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104909444A (en) * | 2015-06-29 | 2015-09-16 | 上海大学 | Organic anion intercalated patina material and preparation method and application thereof |
| CN105776493B (en) * | 2016-03-19 | 2019-08-06 | 上海大学 | A kind of preparation method of the laminated metal compound for Organic Pollutants in Wastewater processing |
| CN110078184A (en) * | 2019-05-11 | 2019-08-02 | 中铁二十一局集团第六工程有限公司 | Patina/active carbon compound coagulant preparation method and be used for tunnel sewage treatment |
| CN111135798B (en) * | 2020-01-09 | 2022-04-08 | 常熟理工学院 | Rust material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5480571A (en) * | 1991-05-31 | 1996-01-02 | Toda Kogyo Corp. | Process for producing acicular goethite particles and acicular magnetic iron oxide particles |
| CN1926071A (en) * | 2004-04-26 | 2007-03-07 | 三菱麻铁里亚尔株式会社 | Reducing water purification material, method for producing reducing water purification material, method for treating wastewater, and wastewater treatment apparatus |
-
2008
- 2008-04-10 CN CNB2008100358571A patent/CN100567168C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5480571A (en) * | 1991-05-31 | 1996-01-02 | Toda Kogyo Corp. | Process for producing acicular goethite particles and acicular magnetic iron oxide particles |
| CN1926071A (en) * | 2004-04-26 | 2007-03-07 | 三菱麻铁里亚尔株式会社 | Reducing water purification material, method for producing reducing water purification material, method for treating wastewater, and wastewater treatment apparatus |
Non-Patent Citations (4)
| Title |
|---|
| Analysis of Iron Oxyhydroxides and Oxides Converted fromGreen Rust in Aqueous Solution. Katsuya INOUE et al.ISIJ International,Vol.47 No.3. 2007 * |
| Coprecipitation of Fe(II) and Fe(III) cations in sulphatedaqueous medium and formation of hydroxysulphate green rust. Christian Ruby et al.Solid State Sciences,Vol.5 . 2003 * |
| 制备Fe(OH)2过程中出现的绿色物质. 孟哲.化学世界，第7期. 2006 * |
| 绿锈的研究进展. 宋芳等.上海化工，第32卷第12期. 2007 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108946820A (en) * | 2018-08-06 | 2018-12-07 | 武汉轻工大学 | A kind of carbonate patina and preparation method thereof |
| CN108946820B (en) * | 2018-08-06 | 2021-06-08 | 武汉轻工大学 | Carbonate patina and preparation method thereof |
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