CN113321525A - Modified ceramsite capable of efficiently removing manganese and preparation method thereof - Google Patents
Modified ceramsite capable of efficiently removing manganese and preparation method thereof Download PDFInfo
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- CN113321525A CN113321525A CN202110668673.4A CN202110668673A CN113321525A CN 113321525 A CN113321525 A CN 113321525A CN 202110668673 A CN202110668673 A CN 202110668673A CN 113321525 A CN113321525 A CN 113321525A
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 18
- 239000011572 manganese Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000010881 fly ash Substances 0.000 claims abstract description 15
- 239000008188 pellet Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 12
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 12
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052661 anorthite Inorganic materials 0.000 claims description 6
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 claims description 6
- 229910001678 gehlenite Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
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- 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
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- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C02F3/00—Biological treatment of water, waste water, or sewage
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- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
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Abstract
The invention discloses a modified ceramsite capable of efficiently removing manganese, which is prepared from the following raw materials in parts by weight: 40-60 wt% of papermaking white mud, 40-60 wt% of fly ash and 0-10 wt% of kaolin. Also discloses a preparation method of the modified ceramsite for efficiently removing manganese, which comprises the following steps: (1) taking papermaking white mud and fly ash as main raw materials, taking kaolin as an additive, uniformly mixing according to a proportion, and then preparing green pellets by a centrifugal pelletizer, wherein the particle size of the green pellets is controllable within the range of 2-20 mm; (2) naturally curing the green pellets prepared in the step (1) for 20-24h, drying at 105 ℃, and finally calcining to obtain ceramsite; (3) and (3) mixing the ceramsite obtained in the step (2) with a NaOH solution for hydrothermal reaction, filtering, repeatedly washing the ceramsite by using deionized water until the pH value of the washing liquor is about 7, and finally drying to obtain the final modified ceramsite. The modified ceramsite prepared by the method disclosed by the invention is high in speed, large in adsorption capacity and remarkable in effect when being used for adsorbing and removing manganese.
Description
Technical Field
The invention belongs to the technical field of material preparation and environmental engineering water treatment, and particularly relates to a modified ceramsite capable of efficiently removing manganese and a preparation method thereof.
Background
With the social and economic development of China and the increase of urban population, the problem of water pollution becomes increasingly prominent. Although the traditional heavy metal sewage treatment methods have a plurality of methods, the harm caused by the defects of the traditional heavy metal sewage treatment methods is gradually remarkable. Therefore, it is urgent to find an economical and effective way to treat heavy metal ions in sewage.
The papermaking white mud is a byproduct generated in an alkali recovery process of a papermaking enterprise. The papermaking white mud produced by taking wood pulp as a raw material has high quality, and can basically realize the cyclic utilization in the process; and the papermaking white mud produced by taking straw pulp as a raw material has the problems of silicon interference and the like and cannot be recycled. Fly ash is an industrial waste of thermal power plants, and not only occupies land, but also pollutes the environment in the existing stacking and disposing mode. If the papermaking white mud and the fly ash are used as raw materials to fire the ceramsite and are used for sewage treatment, the influence of excessive solid waste accumulation on the environment can be reduced, and the condition of relatively short water resources in China at present can be improved, so that the effect of treating waste by waste is achieved.
As a water treatment material, ceramsite is widely concerned by people. The ceramsite is mostly used as a microbial carrier in the biological aerated filter, and has outstanding removal capacity on ammonia nitrogen, BOD and the like in the wastewater. However, the ceramsite has a large pore structure, a low specific surface area, a weak adsorption capacity, and a poor removal capacity for pollutants such as heavy metal ions in water, so that the wide application of the ceramsite is limited. Along with the stricter wastewater discharge standard and the increasing urgency of water resource recycling, the development of the cheap, high-performance and multifunctional ceramsite filter material has important significance.
Disclosure of Invention
The invention aims to solve the technical problem of providing modified ceramsite for efficiently removing manganese and a preparation method thereof.
In order to solve the technical problems, the embodiment of the invention provides a modified ceramsite capable of efficiently removing manganese, which mainly comprises papermaking white mud and fly ash as raw materials, and kaolin as an additive, wherein the papermaking white mud accounts for 40-60 wt%, the fly ash accounts for 40-60 wt%, and the kaolin accounts for 0-10 wt%.
The invention also provides a preparation method of the modified ceramsite for efficiently removing manganese as the claim 1, which comprises the following steps:
(1) mixing the raw materials uniformly according to a ratio, and making into green pellets by a centrifugal pelletizer, wherein the particle size of the green pellets is controllable within the range of 2-20 mm;
(2) naturally curing the green pellets prepared in the step (1) for 20-24h, drying at 105 ℃, and finally calcining to obtain ceramsite;
(3) and (3) mixing the ceramsite obtained in the step (2) with a NaOH solution for hydrothermal reaction, filtering, repeatedly washing the ceramsite by using deionized water until the pH value of the washing liquor is about 7, and finally drying to obtain the final modified ceramsite.
In the step (1), the main raw materials are papermaking white mud and fly ash, and the additive is kaolin, wherein the papermaking white mud accounts for 40-60 wt%, the fly ash accounts for 40-60 wt%, and the kaolin accounts for 0-10 wt%.
Wherein, in the step (2), the calcination temperature is 1000-1200 ℃, and the heat preservation time is 0-2 h.
Wherein, in the step (2), the obtained ceramsite takes anorthite and gehlenite as main mineral phases.
In the step (3), the concentration of the NaOH solution is 2-4mol/L, and the solid-to-liquid ratio is 1: 20-30 (solid unit g, liquid unit mL).
Wherein, in the step (3), when the ceramsite and the NaOH solution are subjected to hydrothermal reaction, the temperature of the oven is 100-160 ℃, and the heat preservation time is 8-12 h.
The technical scheme of the invention has the following beneficial effects:
(1) the modified ceramsite prepared by the invention adopts solid waste as raw materials, realizes pollution control and resource utilization of the solid waste, and has the advantages of low cost, economy and environmental protection. The preparation process of the ceramsite is simple and easy to operate.
(2) According to the invention, on the basis of carrying out ceramsite research by using papermaking white mud and fly ash as main raw materials, the ceramsite is modified by a hydrothermal method, and alkali liquor can permeate into the inside of the ceramsite through pores and can carry out chemical reaction with the ceramsite. The phases of anorthite and anorthite of the ceramsite are kept unchanged, but part of new-phase calcium hydroxide is generated. It shows that in the hydrothermal reaction process, part of calcium ions in the ceramsite are activated and react with sodium hydroxide, so that the surface alkalinity of the ceramsite is enhanced, and the adsorbability of heavy metal ions is enhanced. The modified ceramsite and the preparation method thereof can realize pollution control and resource utilization of solid wastes, and the modified ceramsite is used for adsorbing heavy metals in sewage, so that sustainable development is realized.
(3) The modified ceramsite prepared by the method disclosed by the invention is high in speed, large in adsorption capacity and remarkable in effect when being used for adsorbing and removing manganese.
Drawings
FIG. 1 shows XRD patterns of ceramsite before and after modification in the example of the present invention.
FIG. 2 is a graph showing the comparison of the manganese removal effect before and after modification of ceramsite in the example of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
The embodiment of the invention provides a modified ceramsite capable of efficiently removing manganese, which is prepared from the main raw materials of papermaking white mud and fly ash, and an additive of kaolin, wherein the papermaking white mud accounts for 40-60 wt%, the fly ash accounts for 40-60 wt%, and the kaolin accounts for 0-10 wt%.
The preparation method of the modified ceramsite capable of efficiently removing manganese comprises the following steps:
(1) mixing the raw materials uniformly according to a ratio, and making into green pellets by a centrifugal pelletizer, wherein the particle size of the green pellets is controllable within the range of 2-20 mm;
(2) naturally curing the green pellets prepared in the step (1) for 20-24h, drying at 105 ℃, and finally calcining to obtain ceramsite;
(3) and (3) mixing the ceramsite obtained in the step (2) with a NaOH solution for hydrothermal reaction, filtering, repeatedly washing the ceramsite by using deionized water until the pH value of the washing liquor is about 7, and finally drying to obtain the final modified ceramsite.
The technical scheme of the invention is further illustrated by the following specific examples.
Example 1
Selecting the following raw materials in percentage by mass: fly ash: kaolin 50: 40: 10, uniformly mixing the materials by a cement mortar stirrer, controlling the water-solid ratio to be 0.05, and putting the mixture into a centrifugal ball forming mill to prepare green balls. The green pellets are naturally maintained for 24 hours, then are placed into a drying box to be dried for 12 hours at the temperature of 105 ℃, finally are moved into a high-temperature calcining furnace to be calcined, the heating rate is 10 ℃/min to 800 ℃, the temperature is kept for 1 hour at the temperature of 800 ℃, then the temperature is increased to 1100 ℃ at the speed of 5 ℃/min, the temperature is kept for 2 hours, and finally the green pellets are cooled along with the furnace to prepare the ceramsite taking the gehlenite as the main mineral phase, wherein the XRD (X-ray diffraction) spectrum of the ceramsite is shown as 'before modification' in figure 1.
Example 2
Mixing the ceramsite prepared in the example 1 with 3mol/L NaOH solution for hydrothermal reaction, wherein the solid-liquid ratio is 1: 24 (solid unit g, liquid unit mL), the oven temperature is 160 ℃, and the holding time is 12 h. Performing solid-liquid separation by filtering, repeatedly washing the ceramsite by using deionized water until the pH value of the washing liquid is about 7, and finally drying to obtain the final modified ceramsite, wherein the XRD (X-ray diffraction) spectrum of the modified ceramsite is shown in figure 1. As can be seen from the comparison of the results of example 1 and example 2, the modified ceramsite still uses gehlenite as the main phase, but the alkaline solution can permeate into the inside of the ceramsite and carry out a chemical reaction, so that part of calcium hydroxide is generated.
Example 3
The adsorption effect of the ceramsite before and after modification in the example 1 and the example 2 on manganese ions is detected by adopting a static adsorption method. Preparing a simulated manganese-containing waste liquid by utilizing analytically pure manganese chloride, wherein the concentration of manganese ions is 200mg/L, the adding amount is 20g/L, the water bath temperature is 25 ℃, the oscillation speed is 120r/min, sampling is carried out at different time intervals (5, 10, 15, 20, 30, 40, 60 and 120min), a water sample is filtered and extracted through a filter membrane of 0.45 mu m, the concentration of residual manganese is measured, and the removal rate is calculated, and the result is shown in figure 2. It can be seen that the removal rate of the modified ceramsite is obviously improved compared with the removal rate of the ceramsite before modification. The modified ceramsite can reach adsorption balance in about 40min, and the removal rate is 100%.
The principle of the invention is as follows:
(1) the main component of the papermaking white mud is calcium carbonate which is decomposed in the calcining process and escapes from the ceramsite in the form of water molecules and carbon dioxide molecules, so that the prepared ceramsite has a porous structure and a rough surface, and is beneficial to adsorption.
(2) In the modification process, the ceramsite and alkali are subjected to hydrothermal reaction, and the alkali liquor can permeate into the inside of the ceramsite through pores and can be subjected to chemical reaction. The phases of anorthite and anorthite of the ceramsite are kept unchanged, but part of new-phase calcium hydroxide is generated. It shows that in the hydrothermal reaction process, part of calcium ions in the ceramsite are activated and react with sodium hydroxide, so that the surface alkalinity of the ceramsite is enhanced, and the adsorbability of heavy metal ions is enhanced.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. The modified ceramsite capable of efficiently removing manganese is characterized by being prepared from the following raw materials in parts by weight: 40-60 wt% of papermaking white mud, 40-60 wt% of fly ash and 0-10 wt% of kaolin.
2. The preparation method of the modified ceramsite capable of removing manganese efficiently according to the claim 1, is characterized by comprising the following steps:
(1) mixing the raw materials uniformly according to a ratio, and making into green pellets by a centrifugal pelletizer, wherein the particle size of the green pellets is controllable within the range of 2-20 mm;
(2) naturally curing the green pellets prepared in the step (1) for 20-24h, drying at 105 ℃, and finally calcining to obtain ceramsite;
(3) and (3) mixing the ceramsite obtained in the step (2) with a NaOH solution for hydrothermal reaction, filtering, repeatedly washing the ceramsite by using deionized water until the pH value of the washing liquor is about 7, and finally drying to obtain the final modified ceramsite.
3. The method for preparing the modified ceramsite capable of efficiently removing manganese according to claim 2, wherein in the step (1), the main raw materials comprise papermaking white mud and fly ash, and the additive comprises kaolin, wherein the papermaking white mud accounts for 40-60 wt%, the fly ash accounts for 40-60 wt%, and the kaolin accounts for 0-10 wt%.
4. The method for preparing modified ceramsite with high efficiency for removing manganese according to claim 2, wherein the calcination temperature in step (2) is 1000-1200 ℃, and the holding time is 0-2 h.
5. The method for preparing modified ceramsite with high manganese removal efficiency according to claim 2, wherein the ceramsite obtained in the step (2) takes anorthite and gehlenite as main mineral phases.
6. The method for preparing the modified ceramsite capable of efficiently removing manganese according to the claim 2, wherein in the step (3), the concentration of NaOH solution is 2-4mol/L, and the solid-to-liquid ratio is 1: 20-30 (solid unit g, liquid unit mL).
7. The method for preparing modified ceramsite with high efficiency for removing manganese according to claim 2, wherein in the step (3), the ceramsite is subjected to hydrothermal reaction with NaOH solution, wherein the temperature of the oven is 100 ℃ and 160 ℃, and the heat preservation time is 8-12 h.
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