CN110586026A - Adsorbent for removing heavy metal arsenic and preparation method and application thereof - Google Patents
Adsorbent for removing heavy metal arsenic and preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/06—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds
- B01D53/10—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds with dispersed adsorbents
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- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- 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
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/55—Compounds of silicon, phosphorus, germanium or arsenic
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- B01D2258/00—Sources of waste gases
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- B01D2258/0283—Flue gases
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Abstract
The invention discloses an adsorbent for removing heavy metal arsenic, a preparation method and application thereof. The preparation method comprises the following steps: waste cationic resin is taken as raw material and directly mixed and impregnated with iron-containing wastewater to obtain Fe3+And calcining the @ resin composite material at high temperature to obtain the hollow ferric oxide microspheres. The adsorbent for removing heavy metal arsenic is fed into the combustion furnace and the tail flue thereof in an injection mode, so that arsenic can be removed in a high-temperature environment. The hollow iron oxide microspheres have good high-temperature sintering resistance, can keep the stability of the shape and the structure under the high-temperature condition, and provide more reaction area and activity for the reaction of the hollow iron oxide microspheres and arsenic compoundsThe sexual locus promotes the reaction process of ferric oxide and arsenic, and effectively improves the trapping effect of the adsorbent on gaseous arsenic compounds in high-temperature flue gas.
Description
Technical Field
The invention relates to an adsorbent for removing heavy metal arsenic and a preparation method and application thereof, belonging to the technical field of solid waste recycling.
Background
The arsenic-containing compound is one of the most harmful substances in the current environment, can enter human bodies through respiratory tracts, skins, digestive tracts and the like, and can damage human body cells to cause various diseases, such as toxic neurasthenia, polyneuritis, skin cancer and the like. Coal combustion, waste incineration, metal smelting, and the like are the main sources of arsenic-containing waste gas. In 2014, the proportion of coal in primary energy consumption of China reaches 66%, more than 51% of coal is used for combustion, and the arsenic concentration in the atmospheric environment is increased rapidly. Gaseous arsenic compounds can be condensed in phase or out of phase at low temperature to form larger solid particles, and most of arsenic compounds can be collected and recovered by adopting equipment such as a cyclone dust collector and the like. However, the actual temperature of the coal-fired flue gas is higher, the temperature in the furnace is more generally over 1000 ℃, arsenic mostly exists in the form of gaseous oxide under the condition, and the conventional dust removal equipment is difficult to play a role, so that a large amount of arsenic-containing flue gas is dissipated into the atmospheric environment, and the serious threat is caused to the health of people.
In recent decades, domestic and foreign scholars carry out a series of researches on the occurrence state and migration and transformation rules of arsenic in coal, and the research results provide a certain theoretical basis for removing arsenic from coal-fired flue gas. The existing arsenic pollution control means mainly comprise three aspects of coal dearsenification, arsenic control in combustion and arsenic removal in coal-fired flue gas, wherein, arsenic removal technologies such as coal washing, flotation and the like can effectively reduce the arsenic content in the coal, but can generate a large amount of high-toxicity waste water, easily cause secondary pollution and limit the application of the waste water; the arsenic removal from the arsenic control and coal-fired flue gas during combustion is mainly realized by adding an inorganic mineral adsorbent into the combustion furnace or tail flue gas to promote the adsorption and conversion of arsenic so as to achieve the purpose of reducing the emission of arsenic pollutants, and is a current research hotspot. The related literature shows that calcium oxide, aluminum oxide and iron oxide show better affinity to gas-phase arsenic in a plurality of inorganic minerals, and arsenic can be physically/chemically adsorbed in coal-fired flue gas, converted into stable arsenate and fixed in a product, so that arsenic removal of the flue gas is realized.
The existing research on arsenic removal of flue gas focuses on medium and low temperature areas, and has certain guiding significance for removing arsenic from tail flue gas with lower temperature. However, it is difficult to control the arsenic compounds in the flue gas to a low level only by tail gas treatment, so that the combined removal of the arsenic compounds in the coal-fired furnace and tail flue gas is considered. The actual temperature in a common combustion furnace of a coal-fired power plant is generally high, and under the condition, the conventional adsorbent material is easy to have a serious sintering inactivation phenomenon, so that the arsenic trapping effect is seriously reduced. The existing conventional adsorbent material is only suitable for medium-low temperature areas, and the preparation or modification method is complicated and complex, so that the requirement of arsenic removal of flue gas in the coal-fired power plant furnace is difficult to meet. Therefore, the development of new arsenic adsorbents having both high activity and sintering resistance is a very important research direction.
Sulfonated polystyrene resin is a high molecular material with ion exchange function, and is commonly used in the fields of hard water softening, acid catalysis and the like. After the resin is used for a long time, impurities adsorbed on the surface are gradually accumulated, so that the efficiency is reduced, the water quality treatment requirement is difficult to meet, in this case, the material needs to be renewed, and the original resin is discarded. A large amount of waste resin generated in use is generally subjected to incineration treatment, the cost is about 3000-4000 yuan/ton, the cost is high, and the environment is seriously polluted. In addition, a large amount of iron-containing acidic wastewater is generated in the production and processing process of steel plants, and the purification process of the wastewater is complicated, time-consuming and labor-consuming. A method for effectively utilizing these two waste resources is needed.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems that the conventional adsorbent material in the prior art is not suitable for dearsenification in a high-temperature furnace, the flue gas dearsenification effect in the high-temperature furnace is limited and the like, the invention provides an adsorbent for removing heavy metal arsenic, a preparation method of the adsorbent and application of the adsorbent for dearsenification in a high-temperature environment.
The technical scheme is as follows: the invention relates to an adsorbent for removing heavy metal arsenic, which is an iron oxide microsphere with a hollow structure.
The preparation method of the adsorbent for removing heavy metal arsenic comprises the following steps:
(1) washing the waste sulfonated polystyrene resin, drying and sealing for later use;
(2) mixing and soaking the pretreated waste sulfonated polystyrene resin and the iron-containing wastewater, filtering out the resin after magnetically stirring for 6-10 h, washing and drying; and then roasting the dried resin at high temperature to obtain the hollow iron oxide microspheres.
In the step (1), the waste sulfonated polystyrene resin can be waste sulfonated polystyrene resin in chemical plants and laboratories. Preferably, the drying conditions after washing are: the drying temperature is 40-60 ℃, and the time is 4-5 h.
Preferably, in the step (2), the pretreated waste sulfonated polystyrene resin and the iron-containing wastewater are mixed according to the mass volume ratio of 3-10 g: mixing and soaking 100-200 ml. Further, the conditions of high-temperature roasting are as follows: the high-temperature roasting temperature is 500-700 ℃, and the time is 4-6 h.
The adsorbent is applied to dearsenization in a high-temperature environment, wherein the high-temperature environment is a temperature environment of more than 1000 ℃. Preferably, the application method comprises the following steps: the adsorbent for removing the heavy metal arsenic is delivered into a combustion furnace and a tail flue thereof in a spraying mode. The arsenic oxide can be efficiently captured and fixed in the adsorbent by fully mixing the adsorbent with the high-temperature coal-fired flue gas through injection; and then the temperature is reduced by a combustion furnace heat exchanger, and an arsenic adsorbent is separated by a cyclone dust collector and the like, so that the arsenic in the high-temperature coal-fired flue gas is removed.
Has the advantages that: compared with the prior art, the invention has the advantages that: (1) the hollow structure of the adsorbent can provide a higher specific surface area and abundant surface active sites, and is beneficial to improving the arsenic trapping efficiency of ferric oxide; the adsorbent can maintain the structure and the appearance of the hollow sphere at high temperature, and particularly the stability and the integrity of the inner surface of the hollow sphere; in addition, the hollow spheres are stacked in a spherical manner in the adsorbent bed layer, so that the contact area between the particles is small, namely, the region where the agglomeration action can occur at high temperature is reduced, thereby being beneficial to reducing the agglomeration degree of iron oxide at high temperature, maintaining higher specific surface area and improving the sintering resistance of the adsorbent; (2) the method adopts the waste sulfonated polystyrene resin as a template and takes the ferric salt in the wastewater of the steel plant as an iron source to prepare the hollow ferric oxide microspheres, the raw materials are easy to obtain, the price is low, the preparation method is simple and easy to operate, and the prepared hollow sphere material has good adsorption effect on arsenic in high-temperature flue gas in a furnace; moreover, a feasible solution is provided for the treatment and disposal of the waste resin and the iron-containing wastewater, and the reutilization of waste resources is effectively realized.
Drawings
FIG. 1 is a flow chart of the preparation process of the hollow iron oxide microsphere adsorbent of the present invention;
FIG. 2 is a topographical view of hollow iron oxide microspheres prepared in example 1;
fig. 3 is a schematic diagram showing the injection position of the adsorbent of the present invention in practical use.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
The invention relates to an adsorbent for removing heavy metal arsenic, which is an iron oxide microsphere with a hollow structure.
The method adopts the waste sulfonated polystyrene resin as a template and takes ferric salt in the wastewater of an iron and steel plant as an iron source to prepare the ferric oxide microsphere with the hollow structure, and as shown in figure 1, the method specifically comprises the following steps:
(1) pretreatment of waste sulfonated polystyrene resin
And washing the waste sulfonated polystyrene resin, drying and sealing for later use. The waste sulfonated polystyrene resin can be waste sulfonated polystyrene resin in chemical plants and laboratories. Washing and drying at 40-60 ℃ for 4-5 h.
(2) Preparation of hollow structure iron oxide
Mixing and soaking the pretreated waste sulfonated polystyrene resin and the iron-containing wastewater, filtering out the resin after magnetically stirring for 6-10 h, washing and drying; then roasting the dried resin at high temperature to obtain hollow ferric oxide microspheres; the diameter of the prepared hollow ferric oxide microsphere is generally 0.1-0.5 mm.
The mass volume ratio of the pretreated waste sulfonated polystyrene resin to the iron-containing wastewater is 3-10 g: mixing and soaking 100-200 ml. And after drying, roasting at a high temperature of 500-700 ℃ for 4-6 h.
Fig. 3 shows a high-temperature flue gas treatment system of a coal-fired power plant, wherein the adsorbent of the invention is injected into a furnace and a tail flue, so that the adsorbent can be fully mixed with high-temperature coal-fired flue gas, arsenic oxide can be efficiently captured and fixed in the adsorbent, and the arsenic-containing adsorbent can be subsequently cooled by a heat exchanger and separated by a cyclone dust collector and the like, so that arsenic removal of the high-temperature coal-fired flue gas can be realized.
Example 1
(1) Weighing 20g of waste sulfonated polystyrene resin, washing with deionized water, filtering, drying in an oven at 40 ℃ for 4h, and sealing for later use;
(2) weighing 10g of spare resin, and adding the spare resin into 200ml of iron-containing wastewater, wherein the iron-containing wastewater comes from a certain iron and steel plant in Henan province, the pH value of the solution is 1, and the total iron content is about 2500 mg/L; after magnetic stirring for 6h, filtering out the resin, washing and drying, then placing the resin in a tube furnace, and roasting for 6h at 500 ℃ to obtain the hollow iron oxide microspheres, wherein the surface appearance of the hollow iron oxide microspheres is shown in figure 2, and the particle size of the hollow iron oxide microspheres is 0.5 mm.
Respectively placing the prepared hollow ferric oxide microspheres and 0.5g of purchased analytically pure calcium oxide, ferric oxide and aluminum oxide in a high-temperature fixed bed reactor, respectively heating to 600 ℃ and 1200 ℃ at the speed of 10 ℃/min, and then introducing gas-phase As mixed with the hollow ferric oxide microspheres2O3Simulated coal-fired flue gas (As)2O3Concentration of 100ppm, N2The ratio was (86 v/v%), O2The ratio was (6 v/v%), H2The ratio of O to SO was (8 v/v%)2The concentration is 1000ppm, the NO concentration is 500ppm, the total gas flow is 1000ml/min), and the adsorption reaction time is 10 min. And measuring the adsorption capacity of different materials to arsenic at the temperature of 600 ℃ and 1200 ℃ by an atomic absorption spectrometer.
The results show that the adsorption capacity of the hollow-structure iron oxide microspheres, analytically pure iron oxide, calcium oxide and aluminum oxide to arsenic at 600 ℃ is respectively 10.6mg/g, 8.02mg/g, 4.52mg/g and 4.2 mg/g; 9.72mg/g, 3.129mg/g, 1.093mg/g and 1.42mg/g at 1200 ℃.
Example 2
(1) Weighing 20g of waste sulfonated polystyrene resin, washing with deionized water, filtering, drying in an oven at 50 ℃ for 5h, and sealing for later use;
(2) weighing 3g of the spare resin, adding the resin into 100ml of iron-containing wastewater, wherein the iron-containing wastewater comes from a certain iron and steel plant in Henan province, the pH value of the solution is 1, and the total iron content is about 2500 mg/L; and after magnetically stirring for 8 hours, filtering out the resin, washing and drying, then placing the resin in a tubular furnace, and roasting at 600 ℃ for 5 hours to obtain the hollow iron oxide microspheres.
Respectively placing the prepared hollow ferric oxide microspheres and 0.5g of purchased analytically pure calcium oxide, ferric oxide and aluminum oxide in a high-temperature fixed bed reactor, respectively heating to 600 ℃ and 1200 ℃ at the speed of 10 ℃/min, and then introducing gas-phase As mixed with the hollow ferric oxide microspheres2O3Simulated coal-fired flue gas (As)2O3Concentration of 100ppm, N2The ratio was (86 v/v%), O2The ratio was (6 v/v%), H2The ratio of O to SO was (8 v/v%)2The concentration is 1000ppm, the NO concentration is 500ppm, the total gas flow is 1000ml/min), and the adsorption reaction time is 10 min. And measuring the adsorption capacity of different materials to arsenic at the temperature of 600 ℃ and 1200 ℃ by an atomic absorption spectrometer.
The results show that the adsorption capacity of the hollow-structure iron oxide microspheres, analytically pure iron oxide, calcium oxide and aluminum oxide to arsenic at 600 ℃ is respectively 9.8mg/g, 8.1mg/g, 4.7mg/g and 4.04 mg/g; the adsorption amounts of arsenic at 1200 ℃ were 8.9mg/g, 3.3mg/g, 1.3mg/g and 1.33mg/g, respectively.
Example 3
(1) Weighing 20g of waste sulfonated polystyrene resin, washing with deionized water, filtering, drying in an oven at 50 ℃ for 5h, and sealing for later use;
(2) weighing 7g of the spare resin, adding the spare resin into 160ml of iron-containing wastewater, wherein the iron-containing wastewater comes from a certain iron and steel plant in Henan province, the pH value of the solution is 1, and the total iron content is about 2500 mg/L; and after magnetically stirring for 10 hours, filtering out the resin, washing and drying, then placing the resin in a tubular furnace, and roasting at 700 ℃ for 4 hours to obtain the hollow ferric oxide microspheres.
Respectively placing the prepared hollow ferric oxide microspheres and 0.5g of purchased analytically pure calcium oxide, ferric oxide and aluminum oxide in a high-temperature fixed bed reactor, respectively heating to 600 ℃ and 1200 ℃ at the speed of 10 ℃/min, and then introducing gas-phase As mixed with the hollow ferric oxide microspheres2O3Simulated coal-fired flue gas (As)2O3Concentration of 100ppm, N2The ratio was (86 v/v%), O2The ratio was (6 v/v%), H2The ratio of O to SO was (8 v/v%)2The concentration is 1000ppm, the NO concentration is 500ppm, the total gas flow is 1000ml/min), and the adsorption reaction time is 10 min. And measuring the adsorption capacity of different materials to arsenic at the temperature of 600 ℃ and 1200 ℃ by an atomic absorption spectrometer.
The results show that the adsorption capacity of the hollow-structure iron oxide microspheres, analytically pure iron oxide, calcium oxide and aluminum oxide to arsenic at 600 ℃ is respectively 10.2mg/g, 7.9mg/g, 4.3mg/g and 4.1 mg/g; the adsorption amounts of arsenic at 1200 ℃ were 9.3mg/g, 3.1mg/g, 1.1mg/g and 1.41mg/g, respectively.
The experimental results show that the four samples have higher arsenic adsorption capacity at low temperature, but iron oxide, calcium oxide and aluminum oxide particles obtained by purchase are influenced by high-temperature sintering along with the rise of temperature, the activity is gradually reduced, and the adsorption capacity is obviously reduced; the hollow-structure iron oxide microsphere adsorbent still has a strong arsenic trapping effect at a high temperature of 1200 ℃, and the adsorption quantity of the adsorbent is not obviously changed compared with that of the adsorbent at a temperature of 600 ℃, which shows that the hollow-structure iron oxide microsphere adsorbent has a good arsenic trapping effect and high-temperature sintering resistance.
Claims (8)
1. An adsorbent for removing heavy metal arsenic, which is characterized in that the adsorbent is an iron oxide microsphere with a hollow structure.
2. The preparation method of the adsorbent for removing heavy metal arsenic, which is disclosed by claim 1, is characterized by comprising the following steps of:
(1) washing the waste sulfonated polystyrene resin, drying and sealing for later use;
(2) mixing and soaking the pretreated waste sulfonated polystyrene resin and the iron-containing wastewater, filtering out the resin after magnetically stirring for 6-10 h, washing and drying; and then roasting the dried resin at high temperature to obtain the hollow iron oxide microspheres.
3. The method for preparing the adsorbent for removing heavy metal arsenic according to claim 2, wherein in the step (1), the waste sulfonated polystyrene resin is waste sulfonated polystyrene resin in chemical plants and laboratories.
4. The method for preparing the adsorbent for removing heavy metal arsenic according to claim 2, wherein in the step (1), the drying conditions are as follows: the drying temperature is 40-60 ℃, and the drying time is 4-5 h.
5. The preparation method of the adsorbent for removing heavy metal arsenic according to claim 2, wherein in the step (2), the mass-to-volume ratio of the pretreated waste sulfonated polystyrene resin to the iron-containing wastewater is 3-10 g: 100 to 200 ml.
6. The method for preparing the adsorbent for removing the heavy metal arsenic according to claim 2, wherein in the step (2), the high-temperature roasting conditions are as follows: the high-temperature roasting temperature is 500-700 ℃, and the time is 4-6 h.
7. Use of the sorbent of claim 1 for arsenic removal in a high temperature environment, wherein the high temperature environment is a temperature environment of 1000 ℃ or higher.
8. The use of claim 7, wherein the sorbent for heavy metal arsenic removal is fed into the furnace and its back flue by injection.
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Cited By (1)
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| CN113797894A (en) * | 2021-10-08 | 2021-12-17 | 华中科技大学 | Supported porous carbon material, preparation method thereof and application thereof in flue gas dearsenification |
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Application publication date: 20191220 |