CN110586101A - Preparation process of nano iron oxide powder catalyst - Google Patents
Preparation process of nano iron oxide powder catalyst Download PDFInfo
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- CN110586101A CN110586101A CN201910953836.6A CN201910953836A CN110586101A CN 110586101 A CN110586101 A CN 110586101A CN 201910953836 A CN201910953836 A CN 201910953836A CN 110586101 A CN110586101 A CN 110586101A
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- preparation process
- iron oxide
- oxide powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- C01G49/06—Ferric oxide (Fe2O3)
Abstract
The invention discloses a preparation process of a nano iron oxide powder catalyst, which relates to the technical field of nano iron oxide preparation processes and comprises the following process steps: s1: preparing a ferric salt solution; s2: preparing a mixed solvent of absolute ethyl alcohol and distilled water, adding carbon black into the solvent, and uniformly stirring to obtain a first base solution; s3: preparing a first auxiliary agent, adding the first auxiliary agent into the first base liquid, and uniformly stirring to obtain a second base liquid; s4: dropwise adding the ferric salt solution into the second base solution adjusted to the hydrolysis condition for hydrolysis to obtain a solid-liquid mixed solution; s5: centrifuging, settling, washing and drying the solid-liquid mixed solution to obtain a solid material; s6: grinding the solid material, and then calcining at high temperature to obtain the nano iron oxide powder catalyst. The preparation method has the advantages of reducing the agglomeration and sintering of the intermediate and the product in the process of producing the nano ferric oxide.
Description
Technical Field
The invention relates to the technical field of nano iron oxide, in particular to a preparation process of a nano iron oxide powder catalyst.
Background
At present, researches on the catalytic degradation of organic matters by semiconductor photocatalysts mainly focus on a few cheap, stable and efficient wide-bandgap semiconductors, but the wide-bandgap semiconductors only respond to ultraviolet light, the light of the wide-bandgap semiconductors does not reach 5% of the solar spectrum on the ground, and the utilization rate of solar radiation is low. The nano iron oxide is a common multifunctional material with good optical property, magnetism and catalytic performance, and research results show that the nano iron oxide has good photocatalytic degradation performance on some organic pollutants. And the raw materials for preparing the nano iron oxide have the advantages of low price, environmental compatibility, no secondary pollution and the like, so the nano iron oxide has good application prospect in catalyzing and degrading organic pollutants.
The existing production process of nano iron oxide comprises a wet method and a dry method, wherein the wet method mainly comprises a hydrothermal method, a forced hydrolysis method, a gel-sol method, a colloid chemical method, a microemulsion method, a chemical precipitation method and the like. The dry method mainly comprises the following steps: flame pyrolysis, vapor deposition, low-temperature Plasma Chemical Vapor Deposition (PCVD), solid phase method, laser pyrolysis method, and the like. The industrial production of nano-iron oxide by gel-sol method usually comprises dissolving iron salt and auxiliary agent together to obtain precursor, and then evaporating, drying and calcining to obtain nano-iron oxide powder.
The above prior art solutions have the following drawbacks: most of the methods for preparing the nano-iron oxide have the defects that the particle size is difficult to control, and the particles are easy to agglomerate and sinter in the drying and calcining stages, and the defects can damage the catalytic activity of the nano-iron oxide and reduce the production quality of the nano-iron oxide.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation process of a nano iron oxide powder catalyst, which improves the control of particle size by utilizing iron hydroxide precipitate generated by carbon black adsorption so as to reduce the phenomena of agglomeration and sintering.
The above object of the present invention is achieved by the following technical solutions:
a preparation process of a nanometer iron oxide powder catalyst comprises the following process steps:
s1: preparing a ferric salt solution;
s2: preparing a mixed solvent of absolute ethyl alcohol and distilled water, adding carbon black into the solvent, and uniformly stirring to obtain a first base solution;
s3: preparing a first auxiliary agent, adding the first auxiliary agent into the first base liquid, and uniformly stirring to obtain a second base liquid;
s4: dropwise adding the ferric salt solution into a second base solution adjusted to be under hydrolysis conditions for hydrolysis to obtain a solid-liquid mixed solution;
s5: centrifuging, settling, washing and drying the solid-liquid mixed solution to obtain a solid material;
s6: grinding the solid material, and then calcining at high temperature to obtain the nano iron oxide powder catalyst.
By adopting the technical scheme, the iron salt solution is hydrolyzed when being added into the second base solution and is subjected to co-sedimentation together with the carbon black powder, then the residual auxiliary agent on the surface of the solid particles is removed through centrifugal sedimentation and washing, then drying and grinding are carried out, the particle size of the solid material is reduced, and then the solid material is decomposed through the calcining process to obtain the nano iron oxide powder. The method comprises the steps of adding carbon black powder into a solvent, wherein carbon black powder particles have a porous structure and a very large surface area, when iron salt is added into a second base liquid and is hydrolyzed and settled, generated iron hydroxide particles are captured and adsorbed by the carbon black powder particles during generation, and then the adsorbed particles are subjected to separation, drying and calcination processes integrally, wherein the carbon black powder particles prevent the aggregation of iron oxide particles and the growth of crystal grains, so that the nano iron oxide powder catalyst with less aggregation, small particle size and uniform dispersion can be prepared more efficiently, and the quality and catalytic performance of nano iron oxide are improved.
The invention is further configured to: the first auxiliary agent comprises the following components in percentage by weight:
by adopting the technical scheme, ferric ions begin to precipitate when the pH value is adjusted to about 2.7, the ferric ions can completely precipitate when the pH value is adjusted to about 3.7-4, the pH value of the first base solution is adjusted by the pH adjusting agent, the generation rate of ferric hydroxide precipitation can be controlled, the phenomenon that the generation rate is too slow and the production efficiency is reduced is avoided, and the phenomenon that the ferric hydroxide is easy to agglomerate and is not easy to be adsorbed by carbon black due to the too fast generation rate is also avoided. Sodium dodecyl benzene sulfonate and petroleum sodium sulfonate are anionic surfactants, can be adsorbed on the surface of carbon black particles in a solvent and exist as a dispersing agent, and stable dispersion of the carbon black particles is realized through electrostatic repulsion and steric hindrance. And simultaneously, the sodium dodecyl benzene sulfonate and the petroleum sodium sulfonate are compounded in a solvent, and are mutually attracted due to the hydrophobic effect between hydrocarbon chains of the sodium dodecyl benzene sulfonate and the petroleum sodium sulfonate to form various bulk phase association structures, so that the synergistic adsorption is generated on the surface of carbon black particles, and the dispersion effect is enhanced. And during the compounding, because of the existence of intermolecular force, the electrostatic repulsion between polar groups is reduced, so that the arrangement between the surfactant molecules is tighter, the adsorption uniformity of the surfactant molecules on the surfaces of carbon black particles is improved, the carbon black is dispersed more stably, and the adsorption effect on the generated ferric hydroxide precipitate is better.
After the added sodium bicarbonate is dissolved, a large amount of carbon dioxide bubbles can be generated by bicarbonate ions generated by dissociation of the added sodium bicarbonate under an acidic condition, the bubbles play a certain stirring effect on the solution in the process from generation to rising and breaking, and the agglomeration effect of carbon black particles or ferric hydroxide precipitates can be avoided to a certain extent.
The invention is further configured to: the pH regulator is selected from one or more of 2, 3-dihydroxysuccinic acid, citric acid, malic acid, lactic acid, adipic acid, acetic acid and phosphoric acid.
By adopting the technical scheme, the 2, 3-dihydroxy succinic acid, the citric acid, the malic acid, the lactic acid, the adipic acid, the acetic acid and the phosphoric acid are all organic weak acids, and have no harm to the environment basically, so that the treatment of waste liquid in the later period is more convenient, and the cost of waste liquid treatment can be reduced.
The invention is further configured to: the first base liquid in the step S2 is further added with a modifier, the mass ratio of the modifier to the solvent is (1-5) to (800-1000), and the modifier comprises the following components in percentage by weight:
by adopting the technical scheme, the hydrogen peroxide has strong oxidizing property, and when the hydrogen peroxide is added into the first base liquid, the hydrogen peroxide has a certain oxidizing effect on the carbon black. The surface oxygen content of the carbon black is generally low, and the oxygen content is reduced along with the increase of the particle size, so that the hydrophilicity of the carbon black is not strong, and the dispersion stability of the carbon black in an aqueous solution is poor, while hydrogen peroxide can change the nonpolar surface of the carbon black into a local polar surface, so that the oxygen-containing polar groups on the surface of the carbon black are increased, the adsorption force among carbon black particles is reduced, the binding force between the carbon black particles and the particles needing to be adsorbed is increased, the dispersibility of the carbon black is improved, and the agglomeration of the carbon black is reduced. Some metal ions possibly exist in the cheap carbon black, the carbon black can promote the decomposition of hydrogen peroxide after being mixed into the solution, and the added sodium silicate can play an adsorption effect on the metal ions and play a protection effect on the hydrogen peroxide.
The invention is further configured to: the modifier in the step S2 is prepared into a solution, then the solution is added into the first base liquid for 5-10 times, and the modifier is added for the next time after the low-speed stirring for 1-5 min after each addition.
By adopting the technical scheme, the modified liquid is added into the first base liquid for multiple times, so that the oxidation efficiency of hydrogen peroxide can be improved, and the reduction of the oxidation efficiency caused by the decomposition of hydrogen peroxide can be avoided. The low stirring speed can also reduce the consumption of hydrogen peroxide.
The invention is further configured to: the hydrolysis condition parameters of the second base liquid in the step S4 are adjusted as follows:
the pH value range of the second base liquid is as follows: 3.7-4;
the temperature of the second base liquid is controlled as follows: 78-85 ℃.
By adopting the technical scheme, when the pH value of the second base liquid is controlled to be 3.7-4, the ferric ions in the ferric salt can be hydrolyzed completely, and then the hydrolyzed product can be gradually adsorbed by the carbon black, so that an intermediate product is obtained. When the temperature of the second base liquid is controlled to be 78-85 ℃, the hydrolysis reaction efficiency is highest, and the movement of the molecular and ion microscopic particles is violent, so that the production efficiency of the whole process is high.
The invention is further configured to: and in the step S4, the dropping speed of the iron salt solution is controlled to be 28 ml/min-40 ml/min.
By adopting the technical scheme, if the dripping speed of the ferric salt is higher than 40ml/min, the local concentration of the ferric salt in the second base solution is easily too high, so that the generation amount of ferric hydroxide precipitate is fast and much, and the ferric hydroxide precipitate is easy to agglomerate and is not adsorbed by carbon black, thereby influencing the particle size of the finally obtained nano ferric oxide. If the dripping speed of the ferric salt is lower than 28ml/min, the efficiency of generating the ferric hydroxide is too low, so that the production efficiency of the process is reduced.
The invention is further configured to: the drying process in the step S5 specifically includes the following steps: the method comprises the steps of firstly, rapidly freezing a washed solid to-45 to-50 ℃ by using liquid nitrogen, then, delivering the solid into a freeze dryer for freeze drying, controlling the drying temperature to-50 to-52 ℃ and controlling the pressure to be 12 to 15 Pa.
By adopting the technical scheme, the freeze drying enables the water in the solid to be directly converted from solid to gas for removal, no liquid water is generated in the water removal process, the collapse of a carbon black adsorption structure in the solid is effectively prevented, so that the iron hydroxide particles are re-agglomerated, and finally the nano particles with good dispersibility are obtained.
Compared with the prior art, the invention has the beneficial effects that:
1. by adding the carbon black particles into the prepared solvent in advance, iron hydroxide precipitates generated in hydrolysis can be adsorbed by the carbon black particles when the iron hydroxide precipitates are generated at the beginning, so that the iron hydroxide is dispersed more uniformly, and agglomeration and sintering in the later drying and calcining processes are reduced;
2. the carbon black is modified by adding the modifier and the surfactant in the first auxiliary agent, so that the carbon black particles are not easy to agglomerate to influence the adsorption effect of the carbon black particles on the ferric hydroxide.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples.
The invention discloses a preparation process of a nano iron oxide powder catalyst, which comprises the following process steps:
s1: preparing ferric salt solution, mixing ferric nitrate and distilled water, stirring and dissolving to obtain the ferric nitrate solution with the concentration of 230g/L for later use.
S2: preparing a mixed solvent of absolute ethyl alcohol and distilled water mixed according to the mass ratio of 1: 1, preparing a modifier solution, adding carbon black powder into the solvent according to the mass ratio of 130 g: 1L to the mixed solvent, adding the modifier according to the mass ratio of 1: 1000 to the mixed solvent for 5 times, stirring at a low speed for 1-5 min after each addition, adding the next modifier, and finally stirring uniformly to obtain the first base liquid.
S3: preparing a first auxiliary agent, uniformly mixing 60% of pH regulator, 20% of sodium dodecyl benzene sulfonate, 10% of petroleum sodium sulfonate and 10% of sodium bicarbonate according to the weight percentage, adding the mixture into the first base solution, and then uniformly stirring to obtain a second base solution.
S4: and controlling the pH value of the second base liquid to be 3.7 and the temperature to be 78 ℃, and then dripping the ferric nitrate solution into the second base liquid at the dripping speed of 28ml/min to obtain a solid-liquid mixed solution.
S5, centrifuging and settling the solid-liquid mixed solution, washing the solid-liquid mixed solution for 5 times by using absolute ethyl alcohol and distilled water, quickly cooling the solid-liquid mixed solution to-45 ℃ by using liquid nitrogen, and then sending the cooled solid-liquid mixed solution into a freeze dryer for freeze drying to obtain a solid material. The drying temperature is controlled at-50 deg.C, and the pressure is controlled at 13.3 Pa.
S6: grinding the solid material, and then calcining at 700 ℃ to obtain the nano iron oxide powder catalyst.
In the above step, the pH regulator is selected from 2, 3-dihydroxysuccinic acid.
The improver comprises the following components in percentage by weight: 60% of hydrogen peroxide, 3% of chromium salt, 17% of sodium silicate and 20% of trisodium phosphate.
Examples 2 to 7 differ from example 1 in that the components of the first auxiliary agent are in the following table in weight percent.
Examples 8 to 18 are different from example 1 in that the ratio of each component in the pH adjustor is shown in the following table.
Examples 2 to 1 are different in that the addition amount of the modifier and the ratio of the mixed solvent and the percentage content of each component in the modifier are as follows.
Examples 24 to 28 are different from example 1 in that the number of times of addition of the modifier and the stirring time after each addition are shown in the following table.
Examples 29 to 32 are different from example 1 in that the parameters in step S4 are controlled as shown in the following table.
Examples 32 to 35 differ from example 1 in that the freeze-drying parameters were controlled as shown in the following table.
| Examples | Rapid freezing temperature (. degree. C.) | Drying temperature (. degree.C.) | Drying pressure (Pa) |
| Example 32 | -46 | -50 | 12.75 |
| Example 33 | -47 | -51 | 13.5 |
| Example 34 | -48 | -51.5 | 14.25 |
| Example 35 | -50 | -52 | 15 |
Comparative example
Comparative example 1 differs from example 1 in that no carbon black was added in step S2;
the difference between the comparative example 2 and the example 1 is that the sodium dodecyl benzene sulfonate and the sodium petroleum sulfonate are not added into the first auxiliary agent;
comparative example 3 differs from example 1 in that no modifier is added to the first base liquid;
comparative example 4 differs from example 1 in that the drying process uses oven drying.
Detection method
Particle size test
Measured by GB/T5211.18-2015 Water method for measuring Sieve residue (Manual operation), the results are shown in the following table.
And (4) conclusion: tests show that the mass percent of the residue on the sieve in example 1 is the minimum when the test sieve with the sieve pore of 45 mu m in diameter is used for sieving, and the comparative examples 1-4 are all larger than that in example 1, which shows that the carbon black, sodium dodecyl benzene sulfonate, petroleum sodium sulfonate, modifier and freeze drying step have certain influence on the agglomeration of the finished product nano iron oxide, and the data show that the influence of the carbon black and cooling step on the agglomeration of the nano iron oxide is the maximum, and the influence of the modifier is small due to the addition of the sodium dodecyl benzene sulfonate and the petroleum sodium sulfonate in the first auxiliary agent.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (8)
1. A preparation process of a nanometer iron oxide powder catalyst is characterized by comprising the following process steps:
s1: preparing a ferric salt solution;
s2: preparing a mixed solvent of absolute ethyl alcohol and distilled water, adding carbon black into the solvent, and uniformly stirring to obtain a first base solution;
s3: preparing a first auxiliary agent, adding the first auxiliary agent into the first base liquid, and uniformly stirring to obtain a second base liquid;
s4: dropwise adding the ferric salt solution into the second base solution adjusted to the hydrolysis condition for hydrolysis to obtain a solid-liquid mixed solution;
s5: centrifuging, settling, washing and drying the solid-liquid mixed solution to obtain a solid material;
s6: grinding the solid material, and then calcining at high temperature to obtain the nano iron oxide powder catalyst.
2. The preparation process of the nano iron oxide powder catalyst according to claim 1, wherein the preparation process comprises the following steps: the first auxiliary agent comprises the following components in percentage by weight:
3. the preparation process of the nano iron oxide powder catalyst according to claim 2, wherein the preparation process comprises the following steps: the pH regulator is selected from one or more of 2, 3-dihydroxysuccinic acid, citric acid, malic acid, lactic acid, adipic acid, acetic acid and phosphoric acid.
4. The preparation process of the nano iron oxide powder catalyst according to claim 3, wherein the preparation process comprises the following steps: the first base liquid in the step S2 is further added with a modifier, the mass ratio of the modifier to the solvent is (1-5) to (800-1000), and the modifier comprises the following components in percentage by weight:
5. the preparation process of the nano iron oxide powder catalyst according to claim 4, wherein the preparation process comprises the following steps: the modifier in the step S2 is prepared into a solution, then the solution is added into the first base liquid for 5-10 times, and the modifier is added for the next time after the low-speed stirring for 1-5 min after each addition.
6. The preparation process of the nano iron oxide powder catalyst according to claim 1, wherein the preparation process comprises the following steps: the hydrolysis condition parameters of the second base liquid in the step S4 are adjusted as follows:
the pH value range of the second base liquid is as follows: 3.7-4;
the temperature of the second base liquid is controlled as follows: 78-85 ℃.
7. The preparation process of the nano iron oxide powder catalyst according to claim 1, wherein the preparation process comprises the following steps: and in the step S4, the dropping speed of the iron salt solution is controlled to be 28 ml/min-40 ml/min.
8. The preparation process of the nano iron oxide powder catalyst according to claim 1, wherein the preparation process comprises the following steps: the drying process in the step S5 specifically includes the following steps: the method comprises the steps of firstly, rapidly freezing a washed solid to-45 to-50 ℃ by using liquid nitrogen, then, delivering the solid into a freeze dryer for freeze drying, controlling the drying temperature to-50 to-52 ℃ and controlling the pressure to be 12 to 15 Pa.
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Citations (2)
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|---|---|---|---|---|
| CN102432065A (en) * | 2011-09-07 | 2012-05-02 | 内蒙古科技大学 | Method for synthesizing nanometer titanium dioxide through using carbon to adsorb titanium tetrachloride hydrolysis system |
| CN103723705A (en) * | 2012-10-15 | 2014-04-16 | 海洋王照明科技股份有限公司 | Graphene/nano-aluminum compound and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432065A (en) * | 2011-09-07 | 2012-05-02 | 内蒙古科技大学 | Method for synthesizing nanometer titanium dioxide through using carbon to adsorb titanium tetrachloride hydrolysis system |
| CN103723705A (en) * | 2012-10-15 | 2014-04-16 | 海洋王照明科技股份有限公司 | Graphene/nano-aluminum compound and preparation method thereof |
Non-Patent Citations (3)
| Title |
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| 李金星等: "炭吸附纳米氧化铁的制备及其可见光催化性能", 《人工晶体学报》 * |
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| 魏玉涵等: "改性炭黑的表面性质与微观结构", 《胶体与聚合物》 * |
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