CN110302753B - Preparation method of magnesium oxide-carbon composite microspheres - Google Patents

Preparation method of magnesium oxide-carbon composite microspheres Download PDF

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CN110302753B
CN110302753B CN201910550145.1A CN201910550145A CN110302753B CN 110302753 B CN110302753 B CN 110302753B CN 201910550145 A CN201910550145 A CN 201910550145A CN 110302753 B CN110302753 B CN 110302753B
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magnesium oxide
carbon composite
magnesium
carbon
composite microspheres
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CN110302753A (en
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叶俊伟
宁桂玲
柴政泽
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Dalian University of Technology
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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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

Abstract

The invention belongs to the technical field of new materials, and provides a preparation method of magnesium oxide-carbon composite microspheres. The method has the characteristics of simple and convenient operation, no use of surfactant and continuous preparation. The prepared composite microsphere material has high specific surface area, can adsorb heavy metal ions, antibiotics and organic dyes in sewage, and can kill bacteria in water.

Description

Preparation method of magnesium oxide-carbon composite microspheres
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a preparation method and application of magnesium oxide-carbon composite microspheres.
Background
As an important adsorbent, catalyst and antibacterial material, the nano magnesium oxide (MgO) has wide application in the fields of water treatment, industrial catalysis, antibacterial products and the like. The preparation of nano-magnesia in different shapes of sheet, flower, fiber and the like by thermal decomposition of different magnesium-containing precursors has been reported in a large quantity. In order to improve the dispersibility and stability of nano-magnesia, magnesia-based composites with different compositions and application properties are reported in succession, for example, Li-MgO compositesThe composite structure can be used for oxidative coupling of methane and oxidative dehydrogenation of ethane, and MgO-TiO2The composite film can be used for gas sensing, the ZnO-MgO composite material has good adsorption property on linezolid antibiotics, and the MgO coats Ag/TiO2The composite material can be used for photocatalytic degradation of phenol in water under sunlight.
The carbon material has rich pore structure and large specific surface area, so the magnesium oxide-carbon composite material has wide application prospect in the fields of adsorbents and catalysis. There are reports of preparing a hollow spherical MgO-C composite material by an arc spraying method using magnesium graphite, and also reports of preparing a massive or spongy magnesium oxide-carbon composite material by a direct calcination method using Mg-MOF-74, mesoporous carbon containing magnesium salts, or biomass containing magnesium salts as a precursor. Many methods also have the problems of high cost, irregular particle morphology, difficult continuous preparation and the like, and currently, a method for simply preparing the magnesium oxide-carbon composite microspheres is lacked.
Disclosure of Invention
The invention aims to provide a preparation method of magnesium oxide-carbon composite microspheres, and the prepared magnesium oxide-carbon composite material can be used in the field of water treatment, in particular to the adsorption of metal ions and organic dyes in water.
The technical scheme of the invention is as follows:
a preparation method of magnesium oxide-carbon composite microspheres comprises the following steps:
step 1, mixing a magnesium salt solution and a carbon-containing raw material solution, and preparing into a precursor solution under the stirring condition;
and 2, under the stirring condition of 200-500 r/min at the temperature of 10-90 ℃, enabling the precursor solution to pass through an aerosol generator by carrier gas, then enabling the precursor solution to enter a tubular furnace for calcination reaction, then separating a gas phase and a solid phase by the carrier gas through a solid-gas separator, and collecting solid powder to obtain the magnesium oxide-carbon composite microspheres.
Washing the magnesium oxide-carbon composite microsphere primary product with water, drying in a 60 ℃ oven, and then putting the product in an N oven2Calcining for 2h in the atmosphere to obtain the magnesium oxide-carbon composite microspheres.
The molar ratio of the magnesium salt to the carbon-containing raw material is 1: 0.2-1: 2.
The calcination temperature is 400-1000 ℃.
The magnesium salt is magnesium chloride hexahydrate, magnesium nitrate hexahydrate or magnesium sulfate heptahydrate, and the concentration of the magnesium salt solution is 0.01-4 mol/L; the carbon-containing raw materials are glucose, maltose and a mixture of the raw materials with a molar ratio of 1: 0.2-4 of formaldehyde and resorcinol, and the molar ratio is 1: 0.4-4 of phenol and formaldehyde or beta-cyclodextrin, wherein the concentration of the carbon-containing raw material solution is 0.01-4 mol/L.
The carrier gas is air, nitrogen or helium.
Compared with the prior art, the invention has the following effects and benefits: the magnesium salt and the carbon-containing raw material are mixed with water solution or sol, the precursor is formed after atomization by an aerosol generator, and then the precursor is continuously calcined by carrier gas, so that the magnesium oxide-carbon composite microsphere can be simply and conveniently obtained, and the preparation method has the characteristics of simple and convenient operation, no surfactant and continuous preparation. The prepared composite microsphere material has high specific surface area, can adsorb heavy metal ions, antibiotics and organic dyes in sewage, and can kill bacteria in water.
Drawings
Fig. 1 is a scanning electron microscope image of the prepared magnesium oxide-carbon composite microspheres.
Fig. 2 is a transmission electron microscope image of the prepared magnesium oxide-carbon composite microsphere.
Fig. 3 is an isotherm of prepared magnesium oxide-carbon composite microspheres adsorbing congo red.
Fig. 4 is an isotherm of adsorption of pb (ii) of the prepared magnesium oxide-carbon composite microsphere.
Detailed Description
The following describes specific embodiments of the present invention with reference to the technical solutions, but the scope of the present invention is not limited thereto.
Example 1
2mol/L of 100mL MgCl2Mixing with 0.5 mol/L100 mL glucose solution, stirring, passing through an aerosol generator and a tubular pyrolysis furnace with air flow rate of 1.0L/min, wherein the temperature of the tubular furnace is 600 ℃, and separating gas phase and solid phase by a solid-gas separator to obtain a primary product. After the primary product is washed by water for three times,drying in an oven at 60 ℃ followed by N2Placing the mixture in a tubular furnace in the atmosphere, and calcining the mixture for 2 hours at the temperature of 600 ℃ to obtain the magnesium oxide-carbon composite microspheres. The structure is shown in fig. 1 and 2.
The magnesium oxide-carbon composite microspheres have excellent adsorption performance on organic dyes represented by Congo red and heavy metal ions represented by Pb (II). Respectively using Congo red of 100ppm, 500ppm and 1000ppm as test solution, selecting 5min, 10min, 15min, 20min and 25min as test time points, wherein the adsorption experiment result shows that the absorption balance is basically achieved within 5min, the adsorption rate is high, the removal rates are respectively 99.85%, 99.2% and 96.8%, and the pseudo-second-stage kinetic adsorption model is met; as shown in the figure 3, the Congo red adsorption isotherm shows that the adsorption conforms to the Langmuir model, and the theoretical adsorption amount is as high as 4024 mg/g.
Studies have shown that the adsorption of Pb (II) by the magnesium oxide-carbon composite microspheres conforms to the Langmuir model with theoretical adsorption amounts of 5166mg/g, using 1000ppm, 2000ppm, 3000ppm, 4000ppm and 5000ppm aqueous solutions of Pb (II) as test solutions, respectively, as shown in FIG. 4.
Experimental results of experiments on tetracycline adsorption of the magnesium oxide-carbon composite microspheres show that under 50ppm, adsorption balance is basically achieved within 5min, the adsorption rate is high, and the removal rate is 95.5%; at 100ppm, the adsorption balance is basically achieved within 15min, and the removal rate is 82.1 percent respectively.
In addition, antibacterial experiments show that the antibacterial rate of the prepared composite microspheres to escherichia coli and staphylococcus aureus is more than 98%.
Example 2
2mol/L of 100mLMgCl2Mixing with 0.5 mol/L100 mL resorcinol and formaldehyde solution (molar ratio is 1: 2), stirring uniformly, passing through an aerosol generator and a tubular pyrolysis furnace of a reaction device by nitrogen with flow rate of 1.5L/min, wherein the temperature of the tubular pyrolysis furnace is 600 ℃, separating gas phase and solid phase by a solid-gas separator, and collecting solid powder to obtain a primary product; washing the collected crude product with water for three times, centrifuging, drying the collected solid powder in an oven at 60 deg.C, and then N2Calcining for 2h at 500 ℃ in the atmosphere to obtain the magnesium oxide-carbon composite microspheres.The magnesium oxide-carbon composite microspheres have excellent adsorption performance on organic dyes represented by Congo red and heavy metal ions represented by Pb (II); antibacterial experiments show that the antibacterial rate of the composite microspheres to escherichia coli and staphylococcus aureus reaches 99%.
Example 3
1mol/L of 100mL MgCl2Mixing with 100mL beta-cyclodextrin solution dissolved in hot water at a concentration of 0.1mol/L, stirring under heating, passing through an aerosol generator and a tubular pyrolysis furnace of a reaction device at a flow rate of 1.5L/min under a temperature of 600 deg.C, separating gas phase and solid phase by a solid-gas separator, collecting solid powder to obtain an initial product, washing with water for three times, centrifuging, drying in an oven at 80 deg.C, and drying in N2Calcining for 2h at 500 ℃ in the atmosphere to obtain the magnesium oxide-carbon composite microspheres. The prepared magnesium oxide-carbon composite microspheres have excellent adsorption performance on Congo red and Pb (II), and the antibacterial rate on escherichia coli and staphylococcus aureus reaches 99%.

Claims (8)

1. The preparation method of the magnesium oxide-carbon composite microsphere is characterized by comprising the following steps:
step 1, mixing a magnesium salt solution and a carbon-containing raw material solution, and preparing a precursor solution under the stirring condition;
step 2, under the stirring condition of 200-500 r/min at the temperature of 10-90 ℃, enabling the precursor solution to pass through an aerosol generator by carrier gas, then enabling the precursor solution to enter a tubular furnace for calcination reaction, then separating a gas phase and a solid phase by the carrier gas through a solid-gas separator, and collecting solid powder to obtain the magnesium oxide-carbon composite microspheres;
the magnesium salt is magnesium chloride hexahydrate, magnesium nitrate hexahydrate or magnesium sulfate heptahydrate, and the concentration of the magnesium salt solution is 0.01-4 mol/L; the carbon-containing raw materials are glucose, maltose and a mixture of the raw materials with a molar ratio of 1: 0.2-4 of formaldehyde and resorcinol, and the molar ratio is 1: 0.4-4 of phenol and formaldehyde or beta-cyclodextrin, wherein the concentration of the carbon-containing raw material solution is 0.01-4 mol/L.
2. The method according to claim 1, wherein the magnesium oxide-carbon composite microspheres are washed with water, dried in an oven at 60 ℃, and then N-dried2Calcining for 2h in the atmosphere to obtain the magnesium oxide-carbon composite microspheres.
3. The method according to claim 1 or 2, wherein the molar ratio of the magnesium salt to the carbonaceous starting material is 1:0.2 to 1: 2.
4. The method according to claim 1 or 2, wherein the calcination temperature is 400 to 1000 ℃.
5. The preparation method according to claim 3, wherein the calcination temperature is 400 to 1000 ℃.
6. The method according to claim 1, 2 or 5, wherein the carrier gas is air, nitrogen or helium.
7. The method according to claim 3, wherein the carrier gas is air, nitrogen or helium.
8. The method according to claim 4, wherein the carrier gas is air, nitrogen or helium.
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CN112167706B (en) * 2020-09-28 2022-09-02 江苏中烟工业有限责任公司 Additive for cigarette filter stick for reducing ammonia in cigarette smoke and preparation method and application thereof
CN114735671B (en) * 2021-01-07 2023-10-31 中国石油天然气股份有限公司 Nitrogen-doped carbon microsphere as well as preparation method and application thereof
CN113244888B (en) * 2021-05-17 2023-10-20 内蒙古工业大学 Modified brown coal-based adsorption material and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5561934A (en) * 1978-10-31 1980-05-10 Yousuke Kojiyouba Deodorant
CN1675384A (en) * 2002-08-21 2005-09-28 新日本制铁株式会社 Method of granulating sintering material for iron manufacturing
CN101514025A (en) * 2009-02-16 2009-08-26 大连理工大学 Method for preparing ultra pure magnesium oxide powder
CN103626623A (en) * 2012-08-23 2014-03-12 中国石油天然气股份有限公司 Ethylbenzene dehydrogenation-hydrogen selective oxidation method used for producing styrene
CN107433180A (en) * 2017-08-23 2017-12-05 内江师范学院 A kind of sandwich structure nano adsorber of carbon coating magnesia and preparation method thereof
CN108975360A (en) * 2018-07-20 2018-12-11 大连理工大学 A kind of preparation method, device and the application of spherical shape magnesia
CN109908967A (en) * 2017-12-13 2019-06-21 中国石油化工股份有限公司 A kind of composite carrier and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104226351B (en) * 2013-06-17 2016-09-07 中国石油化工股份有限公司 Butadiene catalyst made by butylene oxidation dehydrogen preparation method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5561934A (en) * 1978-10-31 1980-05-10 Yousuke Kojiyouba Deodorant
CN1675384A (en) * 2002-08-21 2005-09-28 新日本制铁株式会社 Method of granulating sintering material for iron manufacturing
CN101514025A (en) * 2009-02-16 2009-08-26 大连理工大学 Method for preparing ultra pure magnesium oxide powder
CN103626623A (en) * 2012-08-23 2014-03-12 中国石油天然气股份有限公司 Ethylbenzene dehydrogenation-hydrogen selective oxidation method used for producing styrene
CN107433180A (en) * 2017-08-23 2017-12-05 内江师范学院 A kind of sandwich structure nano adsorber of carbon coating magnesia and preparation method thereof
CN109908967A (en) * 2017-12-13 2019-06-21 中国石油化工股份有限公司 A kind of composite carrier and preparation method thereof
CN108975360A (en) * 2018-07-20 2018-12-11 大连理工大学 A kind of preparation method, device and the application of spherical shape magnesia

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"MgO modified nanoporous carbon composites for methanol separation";Ma Xiaoyu et al;《RSC ADVANCES》;20130415;第3卷(第26期);第10397页左栏第2段，第10397页第2节，第10401页第4节 *

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