CN109078612B - Carbon-based nano zero-valent iron composite material prepared from low-rank coal and method - Google Patents
Carbon-based nano zero-valent iron composite material prepared from low-rank coal and method Download PDFInfo
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- CN109078612B CN109078612B CN201810987013.0A CN201810987013A CN109078612B CN 109078612 B CN109078612 B CN 109078612B CN 201810987013 A CN201810987013 A CN 201810987013A CN 109078612 B CN109078612 B CN 109078612B
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- 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
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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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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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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- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The invention discloses a carbon-based nano zero-valent iron composite material prepared by using low-rank coal and a method thereof, wherein the carbon-based nano zero-valent iron composite material is prepared by deashed low-rank coal and FeSO4Solution according to FeSO4The weight ratio of the low-rank coal to the low-rank coal is 1:20, and the low-rank coal is directly calcined at high temperature in nitrogen atmosphere after water bath, oscillation, filtration and vacuum drying. The invention simultaneously utilizes the adsorptivity of the low-rank coal and the reducibility of related substances to realize the one-step synthesis of required materials, thereby saving the step of adding a reducing agent in the prior art and also avoiding adding an organic solvent, and having simple operation, short and long time consumption, low cost and no pollution to the environment.
Description
Technical Field
The invention relates to the field of material preparation, in particular to a preparation method of a carbon-based nano zero-valent iron composite material for purifying pollutants in water.
Background
With the development of economy, the problem of water pollution is increasingly prominent, and the life health of human beings is threatened. The nano zero-valent iron has small particles, large specific surface area and high reaction activity, and is considered as a novel purification material. Especially has objective effect in the purification of heavy metal wastewater and refractory organic matters. However, the nano zero-valent iron is easy to agglomerate and often cannot be fully contacted with pollutants in water, so that the efficiency is reduced.
A carbon-based material represented by activated carbon is a widely used adsorbent, which has a large specific surface area and high adsorption efficiency, but has poor selective adsorption ability. If the nano zero-valent iron is loaded on the material, the application of the material is more targeted, and the problem that the nano zero-valent iron is easy to agglomerate is solved, so that the adsorption efficiency is improved.
The method for loading the nano zero-valent iron on the activated carbon mainly comprises a physical method and a chemical method, and the chemical method is related to the invention.
Chinese patent application No. 2016111827977 discloses a preparation method and application of a nano zero-valent iron composite material, which comprises the steps of firstly preparing corn straw biochar, soaking the biochar in nitric acid for modification, washing to neutrality, and drying for later use; FeSO is reduced by liquid phase reduction method in nitrogen environment4·7H2Reducing O into simple substance iron, and loading the simple substance iron on the biochar; and carrying out solid-liquid separation on the solution after the reaction to obtain the biochar loaded nano zero-valent iron composite material. According to the method, not only is the activated carbon prepared firstly, but also a reducing agent KBH4 is additionally added in the system, and in order to improve the dispersion degree of the nano zero-valent iron composite material on the activated carbon, a dispersing agent polyvinylpyrrolidone (PVP) and an ethanol solvent organic material are introduced, so that the preparation steps are complex, the time consumption is long, the cost is high, and the environmental pollution is caused.
In order to simplify the preparation process and reduce the pollution to the environment, the article "preparation of carbon-supported zero-valent iron by one-step reduction roasting method and removal of Cr (VI) in water" is disclosed in the 10 th (2016 (10 months, authors, Wujinhua, Zhongwein, etc.) "of environmental engineering journal, which selects activated carbon as a reducing agent and prepares the carbon-supported zero-valent iron material by one-step roasting. Although the process is simplified, the manufacturing cost is greatly increased, and the carbon-supported zero-valent iron material obtained by one-step reduction roasting cannot be popularized in a large area. The cost is high for three reasons: firstly, activated carbon is directly used as a reducing agent, as is known in the art, activated carbon is an artificial material, and most commonly used activated carbon in the adsorption field are coal-based carbon (taking anthracite, long-flame coal, weakly caking coal, non-caking coal, lignite and the like as raw materials) and biomass carbon (taking sawdust, shells and the like as raw materials) which are generally selected as raw materials with high carbon content, and the raw materials are treated by adopting a physical/chemical process, so that the main problems of complex preparation process and high energy consumption exist. Therefore, if the carbon-supported zero-valent iron material is prepared by only utilizing the reducibility of the activated carbon, the material is obviously large and small; secondly, because the activated carbon is solid, during calcination, the reduction of iron is a solid-phase reaction, and the reaction only occurs at the contact surface of a zero-valent iron precursor (ferric nitrate in the text) and the activated carbon, which results in low reaction efficiency, and thus requires an increase in calcination temperature and an extension of calcination time, as evidenced by the calcination temperature of 1000 ℃ and the calcination time of 4 hours disclosed in the document; thirdly, because the activated carbon is obtained by manual treatment, the reaction is single when the activated carbon is used as a reducing agent, only carbon element participates in the reaction, and in order to ensure the adsorbability of the finally prepared material, more zero-valent iron precursor is required to be added during calcination, in the document, 0.025 mol of iron is required per gram of carrier (activated carbon), under the condition of using the large amount of reagent, the removal efficiency of the finally prepared carbon-loaded zero-valent iron material to Cr (VI) in 50mg/L water is 86.8%, and the cost and the obtained benefit are completely unequal. For the above reasons, the technology provided by the document is still available as a research paper, and it is not practical to popularize the technology in a large area in industry.
The low-rank coal is coal in a low metamorphic stage, has the characteristics of large moisture, low heat productivity and high volatile content, is difficult to store and transport in a long distance, and is not suitable to be used as fuel. However, because the low-rank coal has abundant surface functional groups, a developed pore structure can be formed under certain conditions, and the low-rank coal can be used as a filter and an adsorbent for treating wastewater besides being used as a fuel, a fuel cell, a catalyst or a carrier. At present, in the aspect of wastewater treatment, low-rank coal is mainly subjected to physical or chemical activation treatment to prepare activated carbon, and the sewage is purified by utilizing the adsorption performance of the activated carbon, but the adsorption capacity of the activated carbon prepared from the low-rank coal is poor, so that the large-scale development and utilization of the activated carbon are restricted. Therefore, the realization of high added value utilization is a more urgent technical problem at present.
Disclosure of Invention
In order to overcome the technical defects of high cost and low adsorption efficiency of the existing carbon-loaded zero-valent iron composite material prepared by roasting activated carbon by one-step method, the invention provides a carbon-based nano zero-valent iron composite material prepared by using low-rank coal.
The invention also provides a method for preparing the carbon-based nano zero-valent iron composite material
In order to achieve the purpose, the invention adopts the technical scheme that:
The carbon-based nano zero-valent iron composite material prepared by using low-rank coal is characterized by comprising the low-rank coal after deashing and FeSO4Solution according to FeSO4And (3) performing water bath oscillation, filtration and vacuum drying on the low-rank coal in a mass ratio of 1:20, and directly calcining the mixture at the high temperature of 800 ℃ for 1h in a nitrogen atmosphere.
The method for preparing the carbon-based nano zero-valent iron composite material by using the low-rank coal comprises the following steps:
the first step is as follows: deashing of low-rank coal by using pickle liquor
Sieving the crushed and dried low-rank coal, washing and deashing the pickle liquor, fully washing with distilled water, and drying for later use;
further: the pickle liquor is prepared from distilled water, 37 wt% of hydrochloric acid and 40 wt% of hydrofluoric acid according to a volume ratio of 5: 3: 2, and (2).
The second step is that: one-step method for preparing carbon-based nano zero-valent iron composite material
At a concentration of 1g/L of FeSO4Adding the deashed low-rank coal into the solution to obtain FeSO4The mass ratio of the low-rank coal to the low-rank coal is 1:20, the low-rank coal is filtered after being fully oscillated in a water bath, and the solid to be treated is obtained through vacuum drying; the solid to be treated is placed in a nickel boat in pure N2Heating to 800 ℃ in the atmosphere, calcining for 1h at constant temperature, and then continuing to calcine in pure N2And naturally cooling in the atmosphere to obtain the final product.
Further vacuum drying at 70-90 deg.C for 10-14 h.
The advantages of the solution according to the invention are illustrated below on the basis of the reaction mechanism.
1. The invention directly puts the low-rank coal after deashing into FeSO4In the solution, in the process, the low-rank coal is used for directly reacting on FeSO4Adsorbing the solution, oscillating in water bath, and adding FeSO4Adsorbing the FeSO on the pores and the surfaces of the low-rank coal, filtering and drying in vacuum to obtain the FeSO adsorbed4The carbon-based material is reacted in the nitrogen atmosphere, and reducing gases CO and H released in the low-rank coal pyrolysis process are utilized2And the reducibility of the carbon, and reacting Fe at high temperature2+Reduction to Fe0Thereby preparing the carbon-based material-nano zero-valent iron composite material (after the reaction formula is attached). In the whole process, by simultaneously utilizing the adsorptivity of the low-rank coal and the reducibility of related substances, the reduction of iron comprises a solid-phase reduction reaction on the surface of solid carbon and a gas-solid-phase reduction reaction caused by carbon monoxide and hydrogen, the reaction rate and the efficiency are obviously higher, the required material is synthesized by a one-step method, and in the invention, the required iron per gram of carrier is only 3.29 multiplied by 10-4The mol ratio of the raw materials is reduced, the production cost is reduced, the adsorption rate of the prepared material to 50mg/L hexavalent chromium solution reaches 100%, more importantly, a new way is opened up for the comprehensive utilization of low-rank coal, and the method can be used for industrial production and large-area popularization.
The chemical reaction formula of the invention is as follows:
2FeSO4＝Fe2O3+SO2↑+SO3↑
Fe2O3+3C＝2Fe+3CO↑
Fe2O3+3CO＝2Fe+3CO2↑
Fe2O3+3H2＝2Fe+3H2O↑
drawings
FIG. 1 is an X-ray diffraction diagram of a carbon-based nano zero-valent iron composite material synthesized by the method of the invention;
FIG. 2 is a graph showing the adsorption effect of the carbon-based nano zero-valent iron composite material synthesized by the method of the present invention on hexavalent chromium in a solution;
FIG. 3 is a comparison graph of the adsorption effect of the carbon-based nano zero-valent iron composite material and unmodified low-rank coal on hexavalent chromium in a solution.
Detailed Description
The preparation method of the carbon-based nano zero-valent iron composite material of the invention is further illustrated by the following examples
The first step is as follows: deashing of low-rank coal by using pickle liquor
Sieving the crushed and dried low-rank coal by a 80-mesh sieve, and mixing distilled water, 37% hydrochloric acid and 40% hydrofluoric acid according to a volume ratio of 5: 3: 2 preparing mixed acid, and adding the sieved low-rank coal into the mixed acid. Heating and stirring at 60 ℃ for 4h, deashing, fully washing with distilled water, and drying for later use.
The second step is that: one-step method for preparing carbon-based nano zero-valent iron composite material
Preparing 1g/L FeSO4Aqueous solution of 1LFeSO4Adding 20g of deashed low-rank coal into the aqueous solution, oscillating in water bath for 12h, filtering, vacuum drying at 80 ℃ for 12h to obtain a solid to be treated, putting the solid in a nickel boat, and purifying with pure N 2Heating to 800 deg.C at a rate of 10 deg.C/min under atmosphere, maintaining the temperature for 1h, and continuing to maintain the temperature in pure N2And naturally cooling the atmosphere to obtain a final product, wherein the product representation is shown in figure 1, and the adsorption effect is shown in figure 2.
In order to verify the effect of the invention, the carbon-based nano zero-valent iron composite material synthesized by the invention and the unmodified low-rank coal in the same batch are respectively subjected to an adsorption efficiency detection test on Cr (VI) simulated wastewater.
Firstly, preparing hexavalent chromium solutions with the concentrations of 50, 100, 200, 300, 400 and 500mg/L respectively, putting 40mL into a 100mL conical flask respectively, then adding 0.2g of the composite material, reacting for 12 hours in a water bath oscillator under the conditions of pH 2, 25 ℃ and the rotating speed of 150r/min, and measuring the concentration of the residual hexavalent chromium in the solution by adopting a dibenzoyl dihydrazide spectrophotometry (GBT 7466-. The same batch of unmodified low-rank coal was used for comparison in the same way. The comparison results are shown in FIG. 3.
As can be seen from fig. 3, the adsorption efficiencies of the present invention for hexavalent chromium in the above-mentioned solution are 100%, 97.9%, 90.1%, 81.2%, 69.5%, 58.2%, respectively, while the adsorption efficiencies of unmodified low-rank coal for hexavalent chromium in the above-mentioned solution are 85.2%, 69.7%, 47.3%, 32.1%, 16.5%, 9.8%, respectively. Compared with the unmodified low-rank coal in the same batch, the loaded material has higher adsorption efficiency, and the efficiency reduction amplitude of the loaded material is obviously smaller than that of the unmodified low-rank coal under high concentration.
Claims (3)
1. A method for preparing a carbon-based nano zero-valent iron composite material by using low-rank coal is characterized by comprising the following steps:
the first step is as follows: deashing of low-rank coal by using pickle liquor
Sieving the crushed and dried low-rank coal, washing and deashing the pickle liquor, fully washing with distilled water, and drying for later use;
the second step is that: one-step method for preparing carbon-based nano zero-valent iron composite material
At a concentration of 1g/L of FeSO4Adding the deashed low-rank coal into the solution to obtain FeSO4The mass ratio of the low-rank coal to the low-rank coal is 1:20, the low-rank coal is filtered after being fully oscillated in a water bath, and the solid to be treated is obtained through vacuum drying; the solid to be treated is placed in a nickel boat in pure N2Heating to 800 ℃ in the atmosphere, calcining for 1h at constant temperature, and then continuing to calcine in pure N2And naturally cooling in the atmosphere to obtain the final product.
2. The method for preparing carbon-based nano zero-valent iron composite material according to claim 1, wherein the acid leaching solution in the first step is prepared from distilled water, 37 wt% hydrochloric acid, 40 wt% hydrofluoric acid according to a volume ratio of 5: 3: 2, and (2).
3. The method for preparing carbon-based nano zero-valent iron composite material according to claim 1, wherein the temperature of the vacuum drying in the second step is 70-90 ℃ and the time is 10-14 h.
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