CN108160047B - Preparation method of modified zeolite loaded with nano zero-valent iron for removing lead from coal-fired flue gas - Google Patents

Preparation method of modified zeolite loaded with nano zero-valent iron for removing lead from coal-fired flue gas Download PDF

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CN108160047B
CN108160047B CN201810002357.1A CN201810002357A CN108160047B CN 108160047 B CN108160047 B CN 108160047B CN 201810002357 A CN201810002357 A CN 201810002357A CN 108160047 B CN108160047 B CN 108160047B
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valent iron
zeolite
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胡静龄
刘勇
胡小吐
钟璐
杨颖欣
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Guangdong Jiade Environmental Protection Technology Co Ltd
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Abstract

The invention discloses a preparation method of nano zero-valent iron-loaded modified zeolite for removing lead from coal-fired flue gas, which comprises the following steps: pretreating, preparing nano iron, synthesizing modified zeolite loaded with nano zero-valent iron, drying and washing. The nano zero-valent iron prepared by the method not only utilizes the high reducibility of the zero-valent iron, but also combines and improves the high adsorption property of zeolite and the chelating adsorption effect of chitosan on lead, and can adsorb elemental Pb and compound PbCl in coal-fired flue gas2The Pb in the form of the lead-free acid can remove heavy metal pollution in coal-fired flue gas to the maximum extent.

Description

Preparation method of modified zeolite loaded with nano zero-valent iron for removing lead from coal-fired flue gas
Technical Field
The invention relates to the field of coal-fired flue gas purification, in particular to a preparation method of modified zeolite loaded with nano zero-valent iron for removing lead from coal-fired flue gas.
Background
Lead is a heavy metal, one of the earliest metals used by human beings, and can be used as part of alloy of materials such as buildings, lead-acid storage batteries, bullets, shells, welding materials, fishing tools, fishery tools, radiation-proof materials, trophies, sulfuric acid corrosion resistance, ionizing radiation resistance, storage batteries and the like, and the alloy can be used as a type, a bearing, a cable sheath and the like, and can also be used as a lead ball of sports equipment and the like. Lead is a toxic heavy metal which is extremely harmful to human bodies, so that lead and compounds thereof can cause damage to a plurality of systems such as nerves, hematopoiesis, digestion, kidneys, cardiovascular system, endocrine system and the like after entering the organism, and lead poisoning can be caused if the content of lead is too high. Lead cannot be degraded anymore and remains toxic for a long time once discharged into the environment. Lead has been included as a strong pollutant because of its long-term persistence in the environment and its strong potential toxicity to many living tissues.
Coal-fired power plants are one of the major sources of heavy metal pollution. According to estimation, the total mass of lead discharged from thermal power production enterprises every year in China is 97.2-168.2 t. The lead in the coal is mainly present or combined in sulfide, and the lead in the coal has obvious positive correlation with the sulfur. Lead in the coal is volatilized in the combustion process and is in the form of simple substance Pb and compound PbCl2Etc. to be released into the atmosphere in the form of submicron lead particles and a gaseous phase. The average value of lead in the Chinese coal is 13.0 mu g/g, the content difference of Pb in different coal forming areas is large, and three different classification standards of low-lead coal (Pb20 mu g/g), medium-lead coal (Pb20 mu g/g-40 mu g/g) and high-lead coal (Pb40 mu g/g) are divided according to the difference of the content of Pb in the coal. The concentration of lead and its compounds must not exceed 0.7mg/m, as stipulated in the emission Standard of atmospheric pollutants (GB116297-1996)3. The removal of lead in the coal-fired flue gas has important environmental protection significance and is beneficial to protecting the ecological environment and the human health.
The nano zero-valent iron particles have higher specific surface area and excellent surface adsorption and chemical reaction activity, and can be used for reducing and repairing a plurality of pollutants such as halogenated torches, polychlorinated biphenyl (PCB), organochlorine pesticides, insecticides, dyes, heavy metal ions, nitrates, nameates, gronates and the like in the environment; the zeolite is used as a natural mineral material with wide distribution and large reserve, has larger specific surface area and charge performance, and can have various catalytic and adsorption performances after modification treatment; the loading technology generally loads the generated nano zero-valent iron particles on a solid carrier through high-temperature calcination or ion exchange, so that the agglomeration can be reduced, the migration capability of nano iron in the environment is enhanced, and the remediation of soil, underground water and polluted rivers is facilitated. Therefore, those skilled in the art have conducted studies on environmental protection applications of the modified zeolite loaded with nano zero-valent iron.
CN 104722279A discloses a method for removing heavy metals in water by uranium alginate/gelatin coated nano zero-valent ironThe method for isolating metal and lead pollutants specifically discloses the following preparation steps: stirring and dissolving sodium alginate and gelatin in a water bath at 50-65 ℃, and performing ultrasonic deaeration for 10-20min to obtain a uranium alginate/gelatin mixed solution; under the protection of nitrogen, the freshly prepared nano Fe0Mixing the particles with uranium alginate/gelatin solution, and ultrasonically dispersing for 10-20min to obtain nano Fe0With uranium alginate/gelatin blend the blend is added dropwise to CaC1 by dropper or via peristaltic pump2In the solution, crosslinking reaction is carried out for 30-60min under the condition of magnetic stirring, and black SA/Gel coated nano zero-valent iron Gel balls are obtained. However, the load synergy effect is not outstanding enough, and a good adsorption effect is difficult to obtain.
CN 105148885A discloses a method for removing Br03And Cl04The nanometer hammer modified zeolite and its preparation and application specifically disclose the following preparation method, firstly, the natural clinoptilolite is crushed, sieved and pretreated by acid and alkali, and then the zeolite and FeC1 are put into polyglycol liquid at the temperature of 120-3、MnS04Mixing and adding according to the weight ratio, stirring uniformly, reacting for 10-20min, adding NaOH solution into the mixed solution until the black suspended matter is not increased, reacting for 20-30min, filtering and leaching the mixture, and drying the solid to constant weight to obtain the Br-removing 03And C104The nano ferro-manganese modified zeolite. However, the method can only be applied to the field of sewage treatment, and cannot be applied to the adsorption of gaseous Pb simple substance.
In conclusion, the prior art still lacks a modified zeolite capable of adsorbing lead and lead compounds existing in a gas environment.
Disclosure of Invention
The invention aims to provide a preparation method of modified zeolite loaded with nano zero-valent iron for removing lead from coal-fired flue gas, and the prepared modified zeolite not only utilizes the high reducibility of the zero-valent iron, but also improves the high adsorption property of the zeolite and the chelating adsorption effect of chitosan on lead, and can adsorb simple substance Pb and ion Pb in the coal-fired flue gas2+So as to remove heavy metal pollutants in the coal-fired flue gas to the maximum extent.
The technical scheme adopted by the invention is as follows.
A preparation method of modified zeolite loaded with nano zero-valent iron for removing lead from coal-fired flue gas comprises the following steps:
(1) pretreatment: using 1-5mol/L HNO to zeolite3Stirring the solution for 8-12 hours, pickling to remove impurities, washing with deionized water for several times, and drying; natural zeolites tend to contain other mineral impurities, by HNO3Cleaning;
(2) preparing nano iron: adding the zeolite pretreated in the step (1) into deionized water, and then adding FeSO4·7H2Using HNO in combination with O3Adjusting the pH value of the solution to 2-5, then adding a reducing agent solution, and stirring at room temperature for 20-60 minutes to synthesize the zeolite loaded with the nano zero-valent iron;
(3) synthesizing the modified zeolite loaded with the nano zero-valent iron: adding a high molecular adsorbent and a surfactant into the solution obtained in the step (2), and stirring for 30-60 minutes under an ultrasonic condition at the temperature of 20-60 ℃ to obtain black spherical particles;
(4) drying and washing: and (4) standing the black spherical particles obtained in the step (3) for 12-24 hours, carrying out vacuum filtration to obtain a solid product, then washing with deionized water for several times, and carrying out vacuum drying to obtain the modified zeolite loaded with the nano zero-valent iron.
Preferably, FeSO is used in the step (2)4·7H2The mass ratio of O to zeolite is 1-3: 10.
Preferably, the stirring speed in the step (2) is 600-900 r/min; the reducing agent solution is prepared from NaBH4 and deionized water, and the quality of the reducing agent and the FeSO4·7H2The mass ratio of O is 3-6: 10.
In this step (2), the reaction equation exists as: fe2++2BH4 -+6H2O→Fe0+2B(OH)3+7H2。
Preferably, the polymeric adsorbent in step (3) is chitosan, and the added mass of the chitosan is equal to that of the FeSO4·7H2The mass ratio of O is 0.01-0.1: 1.
Preferably, the surfactant in the step (3) is 4-nonylphenol ethoxylate, and the added mass of the 4-nonylphenol ethoxylate is equal to the mass of the FeSO4·7H2The mass ratio of O is 0.001-0.01: 1.
Preferably, the reaction temperature in the step (3) is controlled to 40 ℃.
In addition, the invention also provides the modified zeolite loaded with the nano zero-valent iron prepared by the preparation method.
In addition, the invention also provides the application of the modified zeolite in the lead removal of coal-fired flue gas.
The invention has the beneficial effects that:
(1) according to the technical scheme, the reasonable nano iron load material is adopted, the high-molecular adsorbent is combined to realize the synergistic adsorption capacity, and the surfactant is used for dispersing the nano particles, so that the modified zeolite loaded with the nano zero-valent iron can reduce lead ions, increase the surface tension of the modified zeolite and effectively adsorb elemental lead.
(2) The technical scheme adopts reasonable proportion, and specific temperature and pH value to control reaction conditions, thereby realizing optimization of the modified zeolite loaded with the nano zero-valent iron.
Detailed Description
The following further illustrates embodiments of the invention:
example 1 preparation of a modified Zeolite A1 supporting Nano zero valent iron
(1) Pretreatment: 50 g of zeolite was treated with 1mol/L HNO3Stirring the solution for 12 hours, pickling to remove impurities, washing with deionized water for three times, and drying;
(2) preparing nano iron: adding the zeolite pretreated in the step (1) into 200 g of deionized water, and then adding FeSO4·7H2O and using 1mol/L HNO3The solution is brought to a pH of 2-5 and then 4 g of NaBH are added450ml of reducing agent solution is prepared and stirred for 60 minutes at room temperature to synthesize the zeolite loaded with the nano zero-valent iron;
(3) synthesizing the modified zeolite loaded with the nano zero-valent iron: adding 10 g of chitosan and 1 g of 4-nonylphenol ethoxylate into the solution obtained in the step (2), and stirring for 60 minutes at 60 ℃ under ultrasonic conditions to obtain black spherical particles;
(4) drying and washing: and (4) standing the black spherical particles obtained in the step (3) for 24 hours, carrying out vacuum filtration to obtain a solid product, then washing with deionized water for three times, and carrying out vacuum drying to obtain the modified zeolite A1 loaded with the nano zero-valent iron.
Example 2 preparation of a modified Zeolite A2 supporting Nano zero valent iron
(1) Pretreatment: 50 g of zeolite was treated with 1mol/L HNO3Stirring the solution for 12 hours, pickling to remove impurities, washing with deionized water for three times, and drying;
(2) preparing nano iron: adding the zeolite pretreated in the step (1) into 200 g of deionized water, and then adding FeSO4·7H2O and using 1mol/L HNO3The solution is brought to a pH of 2-5 and then 4 g of NaBH are added450ml of reducing agent solution is prepared and stirred for 60 minutes at room temperature to synthesize the zeolite loaded with the nano zero-valent iron;
(3) synthesizing the modified zeolite loaded with the nano zero-valent iron: adding 2 g of chitosan and 0.2 g of 4-nonylphenol ethoxylate into the solution obtained in the step (2), and stirring for 60 minutes at a temperature of 60 ℃ under ultrasonic conditions to obtain black spherical particles;
(4) drying and washing: and (4) standing the black spherical particles obtained in the step (3) for 24 hours, carrying out vacuum filtration to obtain a solid product, then washing with deionized water for three times, and carrying out vacuum drying to obtain the modified zeolite A2 loaded with the nano zero-valent iron.
Example 3 preparation of a modified Zeolite A3 supporting Nano zero valent iron
(1) Pretreatment: 50 g of zeolite was treated with 1mol/L HNO3Stirring the solution for 12 hours, pickling to remove impurities, washing with deionized water for three times, and drying;
(2) preparing nano iron: adding the zeolite pretreated in the step (1) into 200 g of deionized water, and then adding FeSO4·7H2O and using 1mol/L HNO3The solution is brought to a pH of 2-5 and then 4 g of NaBH are added450ml of reducing agent solution was prepared and stirred at room temperatureSynthesizing the zeolite loaded with the nano zero-valent iron within 60 minutes;
(3) synthesizing the modified zeolite loaded with the nano zero-valent iron: adding 1 g of chitosan and 0.1 g of 4-nonylphenol ethoxylate into the solution obtained in the step (2), and stirring for 60 minutes at a temperature of 60 ℃ under ultrasonic conditions to obtain black spherical particles;
(4) drying and washing: and (4) standing the black spherical particles obtained in the step (3) for 24 hours, carrying out vacuum filtration to obtain a solid product, then washing with deionized water for three times, and carrying out vacuum drying to obtain the modified zeolite A3 loaded with the nano zero-valent iron.
Example 4 preparation of a modified Zeolite A4 supporting Nano zero valent iron
(1) Pretreatment: 50 g of zeolite was treated with 1mol/L HNO3Stirring the solution for 12 hours, pickling to remove impurities, washing with deionized water for three times, and drying;
(2) preparing nano iron: adding the zeolite pretreated in the step (1) into 200 g of deionized water, and then adding FeSO4·7H2O and using 1mol/L HNO3The solution is brought to a pH of 2-5 and then 4 g of NaBH are added450ml of reducing agent solution is prepared and stirred for 60 minutes at room temperature to synthesize the zeolite loaded with the nano zero-valent iron;
(3) synthesizing the modified zeolite loaded with the nano zero-valent iron: adding 0.9 g of chitosan and 0.09 g of 4-nonylphenol ethoxylate into the solution obtained in the step (2), and stirring for 60 minutes at a temperature of 60 ℃ under ultrasonic conditions to obtain black spherical particles;
(4) drying and washing: and (4) standing the black spherical particles obtained in the step (3) for 24 hours, carrying out vacuum filtration to obtain a solid product, then washing with deionized water for three times, and carrying out vacuum drying to obtain the modified zeolite A4 loaded with the nano zero-valent iron.
Example 5 preparation of a modified Zeolite A5 supporting Nano zero valent iron
(1) Pretreatment: 50 g of zeolite was treated with 1mol/L HNO3Stirring the solution for 12 hours, pickling to remove impurities, washing with deionized water for three times, and drying;
(2) preparing nano iron: adding 20 of the zeolite pretreated in the step (1)0 g of deionized water, then FeSO4·7H2O and using 1mol/L HNO3The solution is brought to a pH of 2-5 and then 4 g of NaBH are added450ml of reducing agent solution is prepared and stirred for 60 minutes at room temperature to synthesize the zeolite loaded with the nano zero-valent iron;
(3) synthesizing the modified zeolite loaded with the nano zero-valent iron: adding 0.8 g of chitosan and 0.08 g of 4-nonylphenol ethoxylate into the solution obtained in the step (2), and stirring for 60 minutes under ultrasonic conditions at a temperature of 60 ℃ to obtain black spherical particles;
(4) drying and washing: and (4) standing the black spherical particles obtained in the step (3) for 24 hours, carrying out vacuum filtration to obtain a solid product, then washing with deionized water for three times, and carrying out vacuum drying to obtain the modified zeolite A5 loaded with the nano zero-valent iron.
Example 6 preparation of a modified Zeolite A6 supporting Nano zero valent iron
(1) Pretreatment: 50 g of zeolite was treated with 1mol/L HNO3Stirring the solution for 12 hours, pickling to remove impurities, washing with deionized water for three times, and drying;
(2) preparing nano iron: adding the zeolite pretreated in the step (1) into 200 g of deionized water, and then adding FeSO4·7H2O and using 1mol/L HNO3The solution is brought to a pH of 2-5 and then 4 g of NaBH are added450ml of reducing agent solution is prepared and stirred for 60 minutes at room temperature to synthesize the zeolite loaded with the nano zero-valent iron;
(3) synthesizing the modified zeolite loaded with the nano zero-valent iron: adding 0.7 g of chitosan and 0.07 g of 4-nonylphenol ethoxylate into the solution obtained in the step (2), and stirring for 60 minutes under ultrasonic conditions at a temperature of 60 ℃ to obtain black spherical particles;
(4) drying and washing: and (4) standing the black spherical particles obtained in the step (3) for 24 hours, carrying out vacuum filtration to obtain a solid product, then washing with deionized water for three times, and carrying out vacuum drying to obtain the modified zeolite A6 loaded with the nano zero-valent iron.
Example 7 preparation of a modified Zeolite A7 supporting Nano zero valent iron
(1) Pretreatment: 50 g of zeoliteWith 1mol/L HNO3Stirring the solution for 12 hours, pickling to remove impurities, washing with deionized water for three times, and drying;
(2) preparing nano iron: adding the zeolite pretreated in the step (1) into 200 g of deionized water, and then adding FeSO4·7H2O and using 1mol/L HNO3The solution is brought to a pH of 2-5 and then 4 g of NaBH are added450ml of reducing agent solution is prepared and stirred for 60 minutes at room temperature to synthesize the zeolite loaded with the nano zero-valent iron;
(3) synthesizing the modified zeolite loaded with the nano zero-valent iron: adding 0.6 g of chitosan and 0.06 g of 4-nonylphenol ethoxylate into the solution obtained in the step (2), and stirring for 60 minutes under ultrasonic conditions at a temperature of 60 ℃ to obtain black spherical particles;
(4) drying and washing: and (4) standing the black spherical particles obtained in the step (3) for 24 hours, carrying out vacuum filtration to obtain a solid product, then washing with deionized water for three times, and carrying out vacuum drying to obtain the modified zeolite A7 loaded with the nano zero-valent iron.
Example 8 preparation of a modified Zeolite A8 supporting Nano zero valent iron
(1) Pretreatment: 50 g of zeolite was treated with 1mol/L HNO3Stirring the solution for 12 hours, pickling to remove impurities, washing with deionized water for three times, and drying;
(2) preparing nano iron: adding the zeolite pretreated in the step (1) into 200 g of deionized water, and then adding FeSO4·7H2O and using 1mol/L HNO3The solution is brought to a pH of 2-5 and then 4 g of NaBH are added450ml of reducing agent solution is prepared and stirred for 60 minutes at room temperature to synthesize the zeolite loaded with the nano zero-valent iron;
(3) synthesizing the modified zeolite loaded with the nano zero-valent iron: adding 0.5 g of chitosan and 0.05 g of 4-nonylphenol ethoxylate into the solution obtained in the step (2), and stirring for 60 minutes at a temperature of 60 ℃ under ultrasonic conditions to obtain black spherical particles;
(4) drying and washing: and (4) standing the black spherical particles obtained in the step (3) for 24 hours, carrying out vacuum filtration to obtain a solid product, then washing with deionized water for three times, and carrying out vacuum drying to obtain the modified zeolite A8 loaded with the nano zero-valent iron.
Example 9 preparation of a modified Zeolite A9 supporting Nano zero valent iron
(1) Pretreatment: 50 g of zeolite was treated with 1mol/L HNO3Stirring the solution for 12 hours, pickling to remove impurities, washing with deionized water for three times, and drying;
(2) preparing nano iron: adding the zeolite pretreated in the step (1) into 200 g of deionized water, and then adding FeSO4·7H2O and using 1mol/L HNO3The solution is brought to a pH of 2-5 and then 4 g of NaBH are added450ml of reducing agent solution is prepared and stirred for 60 minutes at room temperature to synthesize the zeolite loaded with the nano zero-valent iron;
(3) synthesizing the modified zeolite loaded with the nano zero-valent iron: adding 0.4 g of chitosan and 0.04 g of 4-nonylphenol ethoxylate into the solution obtained in the step (2), and stirring for 60 minutes at a temperature of 60 ℃ under ultrasonic conditions to obtain black spherical particles;
(4) drying and washing: and (4) standing the black spherical particles obtained in the step (3) for 24 hours, carrying out vacuum filtration to obtain a solid product, then washing with deionized water for three times, and carrying out vacuum drying to obtain the modified zeolite A9 loaded with the nano zero-valent iron.
Example 10 preparation of a modified Zeolite A10 supporting Nano zero valent iron
(1) Pretreatment: 50 g of zeolite was treated with 1mol/L HNO3Stirring the solution for 12 hours, pickling to remove impurities, washing with deionized water for three times, and drying;
(2) preparing nano iron: adding the zeolite pretreated in the step (1) into 200 g of deionized water, and then adding FeSO4·7H2O and using 1mol/L HNO3The solution is brought to a pH of 2-5 and then 4 g of NaBH are added450ml of reducing agent solution is prepared and stirred for 60 minutes at room temperature to synthesize the zeolite loaded with the nano zero-valent iron;
(3) synthesizing the modified zeolite loaded with the nano zero-valent iron: adding 0.3 g of chitosan and 0.03 g of 4-nonylphenol ethoxylate into the solution obtained in the step (2), and stirring for 60 minutes at a temperature of 60 ℃ under ultrasonic conditions to obtain black spherical particles;
(4) drying and washing: and (4) standing the black spherical particles obtained in the step (3) for 24 hours, carrying out vacuum filtration to obtain a solid product, then washing with deionized water for three times, and carrying out vacuum drying to obtain the modified zeolite A10 loaded with the nano zero-valent iron.
Example 11 preparation of a modified Zeolite A11 supporting Nano zero valent iron
(1) Pretreatment: 50 g of zeolite was treated with 1mol/L HNO3Stirring the solution for 12 hours, pickling to remove impurities, washing with deionized water for three times, and drying;
(2) preparing nano iron: adding the zeolite pretreated in the step (1) into 200 g of deionized water, and then adding FeSO4·7H2O and using 1mol/L HNO3The solution is brought to a pH of 2-5 and then 4 g of NaBH are added450ml of reducing agent solution is prepared and stirred for 60 minutes at room temperature to synthesize the zeolite loaded with the nano zero-valent iron;
(3) synthesizing the modified zeolite loaded with the nano zero-valent iron: adding 0.2 g of chitosan and 0.02 g of 4-nonylphenol ethoxylate into the solution obtained in the step (2), and stirring for 60 minutes at a temperature of 60 ℃ under ultrasonic conditions to obtain black spherical particles;
(4) drying and washing: and (4) standing the black spherical particles obtained in the step (3) for 24 hours, carrying out vacuum filtration to obtain a solid product, then washing with deionized water for three times, and carrying out vacuum drying to obtain the modified zeolite A11 loaded with the nano zero-valent iron.
Example 12 preparation of a modified Zeolite A12 supporting Nano zero valent iron
(1) Pretreatment: 50 g of zeolite was treated with 1mol/L HNO3Stirring the solution for 12 hours, pickling to remove impurities, washing with deionized water for three times, and drying;
(2) preparing nano iron: adding the zeolite pretreated in the step (1) into 200 g of deionized water, and then adding FeSO4·7H2O and using 1mol/L HNO3The solution is brought to a pH of 2-5 and then 4 g of NaBH are added450ml of reducing agent solution is prepared and stirred for 60 minutes at room temperature to synthesize the zeolite loaded with the nano zero-valent iron;
(3) synthesizing the modified zeolite loaded with the nano zero-valent iron: adding 0.1 g of chitosan and 0.01 g of 4-nonylphenol ethoxylate into the solution obtained in the step (2), and stirring for 60 minutes at a temperature of 60 ℃ under ultrasonic conditions to obtain black spherical particles;
(4) drying and washing: and (4) standing the black spherical particles obtained in the step (3) for 24 hours, carrying out vacuum filtration to obtain a solid product, then washing with deionized water for three times, and carrying out vacuum drying to obtain the modified zeolite A12 loaded with the nano zero-valent iron.
Example 13 preparation of a modified Zeolite A13 supporting Nano zero valent iron
(1) Pretreatment: 50 g of zeolite was treated with 1mol/L HNO3Stirring the solution for 12 hours, pickling to remove impurities, washing with deionized water for three times, and drying;
(2) preparing nano iron: adding the zeolite pretreated in the step (1) into 200 g of deionized water, and then adding FeSO4·7H2O and using 1mol/L HNO3The solution is brought to a pH of 2-5 and then 4 g of NaBH are added450ml of reducing agent solution is prepared and stirred for 60 minutes at room temperature to synthesize the zeolite loaded with the nano zero-valent iron;
(3) synthesizing the modified zeolite loaded with the nano zero-valent iron: adding 0.05 g of chitosan and 0.005 g of 4-nonylphenol ethoxylate into the solution obtained in the step (2), and stirring for 60 minutes under ultrasonic conditions at a temperature of 60 ℃ to obtain black spherical particles;
(4) drying and washing: and (4) standing the black spherical particles obtained in the step (3) for 24 hours, carrying out vacuum filtration to obtain a solid product, then washing with deionized water for three times, and carrying out vacuum drying to obtain the modified zeolite A13 loaded with the nano zero-valent iron.
Example 14 preparation of a modified Zeolite A14 supporting Nano zero valent iron
(1) Pretreatment: 50 g of zeolite was treated with 1mol/L HNO3Stirring the solution for 12 hours, pickling to remove impurities, washing with deionized water for three times, and drying;
(2) preparing nano iron: adding the zeolite pretreated in the step (1) into 200 g of deionized water, and then adding FeSO4·7H2O and using 1mol/L HNO3The solution is brought to a pH of 2-5 and then 4 g of NaBH are added450ml of reducing agent solution is prepared and stirred for 60 minutes at room temperature to synthesize the zeolite loaded with the nano zero-valent iron;
(3) synthesizing the modified zeolite loaded with the nano zero-valent iron: adding 0.01 g of chitosan and 0.001 g of 4-nonylphenol ethoxylate into the solution obtained in the step (2), and stirring for 60 minutes under ultrasonic conditions at a temperature of 60 ℃ to obtain black spherical particles;
(4) drying and washing: and (4) standing the black spherical particles obtained in the step (3) for 24 hours, carrying out vacuum filtration to obtain a solid product, then washing with deionized water for three times, and carrying out vacuum drying to obtain the modified zeolite A13 loaded with the nano zero-valent iron.
Comparative example 1 preparation of modified zeolite B1 loaded with nano-zero valent iron without chitosan
(1) Pretreatment: 50 g of zeolite was treated with 1mol/L HNO3Stirring the solution for 12 hours, pickling to remove impurities, washing with deionized water for three times, and drying;
(2) preparing nano iron: adding the zeolite pretreated in the step (1) into 200 g of deionized water, and then adding FeSO4·7H2O and using 1mol/L HNO3The solution is brought to a pH of 2-5 and then 4 g of NaBH are added450ml of reducing agent solution is prepared and stirred for 60 minutes at room temperature to synthesize the zeolite loaded with the nano zero-valent iron;
(3) synthesizing the modified zeolite loaded with the nano zero-valent iron: adding 0.1 g of 4-nonylphenol ethoxylate into the solution obtained in step (3), and stirring for 60 minutes under ultrasonic conditions at a temperature of 60 ℃ to obtain black spherical particles;
(4) drying and washing: and (3) standing the black spherical particles obtained in the step (3) for 24 hours, carrying out vacuum filtration to obtain a solid product, then washing with deionized water for several times, and carrying out vacuum drying to obtain a product, namely the chitosan-free modified zeolite B1 loaded with nano zero-valent iron.
Comparative example 2 preparation of nano zero-valent iron-loaded modified zeolite B2 free of 4-nonylphenol ethoxylate
(1)Pretreatment: 50 g of zeolite was treated with 1mol/L HNO3Stirring the solution for 12 hours, pickling to remove impurities, washing with deionized water for three times, and drying;
(2) preparing nano iron: adding the zeolite pretreated in the step (1) into 200 g of deionized water, and then adding FeSO4·7H2O and using 1mol/L HNO3The solution is brought to a pH of 2-5 and then 4 g of NaBH are added450ml of reducing agent solution is prepared and stirred for 60 minutes at room temperature to synthesize the zeolite loaded with the nano zero-valent iron;
(3) synthesizing the modified zeolite loaded with the nano zero-valent iron: adding 1 g of chitosan into the solution obtained in the step (3), and stirring for 60 minutes under the ultrasonic condition and at the temperature of 60 ℃ to obtain black spherical particles;
(4) drying and washing: and (3) standing the black spherical particles obtained in the step (3) for 24 hours, carrying out vacuum filtration to obtain a solid product, then washing the solid product with deionized water for a plurality of times, and carrying out vacuum drying to obtain a product, namely the modified zeolite B2 loaded with the nano zero-valent iron and not containing the 4-nonylphenol ethoxylate.
Comparative example 3 preparation of nano zero-valent iron-loaded modified zeolite B3 free of chitosan and 4-nonylphenol ethoxylate
(1) Pretreatment: 50 g of zeolite was treated with 1mol/L HNO3Stirring the solution for 12 hours, pickling to remove impurities, washing with deionized water for three times, and drying;
(2) preparing nano iron: adding the zeolite pretreated in the step (1) into 200 g of deionized water, and then adding FeSO4·7H2O and using 1mol/L HNO3The solution is brought to a pH of 2-5 and then 4 g of NaBH are added450ml of reducing agent solution is prepared and stirred for 60 minutes at room temperature to synthesize the zeolite loaded with the nano zero-valent iron;
(3) drying and washing: standing the product obtained in the step (2) for 24 hours, carrying out vacuum filtration to obtain a solid product, then washing the solid product with deionized water for a plurality of times, and carrying out vacuum drying to obtain a product, namely the modified zeolite B3 loaded with nano zero-valent iron and not containing chitosan and 4-nonylphenol ethoxylate.
Comparative example 4 preparation of Supported Chitosan Zeolite B4
(1) Pretreatment: 50 g of zeolite was treated with 1mol/L HNO3Stirring the solution for 12 hours, pickling to remove impurities, washing with deionized water for three times, and drying;
(2) adding 1 g of chitosan into the solution obtained in the step (2), and stirring for 60 minutes under the ultrasonic condition and at the temperature of 60 ℃ to obtain black spherical particles;
(3) drying and washing: and (3) standing the black spherical particles obtained in the step (2) for 24 hours, carrying out vacuum filtration to obtain a solid product, then washing with deionized water for several times, and carrying out vacuum drying to obtain a product, namely the chitosan-loaded zeolite B4.
Application examples
Preparing the product into a packing layer, filling the packing layer into a coal-fired flue gas adsorption tower, enabling the same batch of coal-fired flue gas to be measured to flow through the packing layer, and spraying slurry with the pH value of 4 on the packing layer to help the cooling and better adsorption of the packing layer. Subsequently, by measuring the lead concentration at the inlet and outlet of the coal-fired flue gas, the following test results were obtained, as shown in table 1.
TABLE 1
Figure BDA0001537316720000101
Figure BDA0001537316720000111
As can be seen from Table 1, the adsorption effect of the group A is better than that of the group B, and the effect of A3-A12 is far better than that of the group B, which indicates that the modified zeolite loaded with nano zero-valent iron prepared by the technical scheme has better adsorption effect by loading chitosan and 4-nonylphenol ethoxylate, and the chelation adsorption effect of chitosan on lead generates a synergistic effect with the high reducibility of nano zero-valent iron, so that the lead in the flue gas can be better adsorbed.
In addition, as can be seen from table 1, the effect of A3-a12 is far better than the adsorption effect of groups a1, a2, a13 and a14, which shows that when the content of chitosan and 4-nonylphenol ethoxylate is too high, the porosity of zeolite is easily blocked, and the adsorption effect is rather reduced, and when the concentration of chitosan and 4-nonylphenol ethoxylate is too low, no constituent molecules form a synergistic adsorption effect, so the mass ratio of A3-a12 can obtain a synergistic adsorption effect.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (6)

1. A preparation method of modified zeolite loaded with nano zero-valent iron for removing lead from coal-fired flue gas is characterized by comprising the following steps:
(1) pretreatment: using 1-5mol/L HNO to zeolite3Stirring the solution for 8-12 hours, pickling to remove impurities, washing with deionized water for several times, and drying;
(2) preparing nano iron: adding the zeolite pretreated in the step (1) into deionized water, and then adding FeSO4·7H2Using HNO in combination with O3Adjusting the pH value of the solution to 2-5, then adding a reducing agent solution, and stirring at room temperature for 20-60 minutes to synthesize the zeolite loaded with the nano zero-valent iron;
(3) synthesizing the modified zeolite loaded with the nano zero-valent iron: adding a high molecular adsorbent and a surfactant into the solution obtained in the step (2), and stirring for 30-60 minutes under an ultrasonic condition at the temperature of 20-60 ℃ to obtain black spherical particles;
the high molecular adsorbent is chitosan, and the added mass of the chitosan is equal to that of the FeSO4·7H2The mass ratio of O is 0.01-0.1: 1;
the surfactant is 4-nonylphenol ethoxylate, and the added mass of the 4-nonylphenol ethoxylate is equal to the FeSO4·7H2The mass ratio of O is 0.001-0.01:1；
(4) drying and washing: and (4) standing the black spherical particles obtained in the step (3) for 12-24 hours, carrying out vacuum filtration to obtain a solid product, then washing with deionized water for several times, and carrying out vacuum drying to obtain the modified zeolite loaded with the nano zero-valent iron.
2. The process according to claim 1, wherein in step (2), FeSO is used as the carrier4·7H2The mass ratio of O to zeolite is 1-3: 10.
3. The preparation method according to claim 2, wherein the stirring speed in step (2) is 600-900 r/min; the reducing agent solution is NaBH4A solution prepared with deionized water, the mass of the reducing agent and the FeSO4·7H2The mass ratio of O is 3-6: 10.
4. The method according to claim 3, wherein the temperature in the step (3) is 40 ℃.
5. A modified zeolite supporting nano zero-valent iron prepared by the preparation method of any one of claims 1 to 4.
6. Use of a modified zeolite according to claim 5 for lead removal from coal combustion flue gases.
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