CN110280213B - Nano magnetic composite iron-copper oxide dearsenization adsorbent and preparation method and application thereof - Google Patents

Nano magnetic composite iron-copper oxide dearsenization adsorbent and preparation method and application thereof Download PDF

Info

Publication number
CN110280213B
CN110280213B CN201910562100.6A CN201910562100A CN110280213B CN 110280213 B CN110280213 B CN 110280213B CN 201910562100 A CN201910562100 A CN 201910562100A CN 110280213 B CN110280213 B CN 110280213B
Authority
CN
China
Prior art keywords
adsorbent
arsenic
temperature
nano
copper oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910562100.6A
Other languages
Chinese (zh)
Other versions
CN110280213A (en
Inventor
刘志楼
李子良
徐志峰
张溪
昝苗苗
谷丽果
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangxi University of Science and Technology
Original Assignee
Jiangxi University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangxi University of Science and Technology filed Critical Jiangxi University of Science and Technology
Priority to CN201910562100.6A priority Critical patent/CN110280213B/en
Publication of CN110280213A publication Critical patent/CN110280213A/en
Application granted granted Critical
Publication of CN110280213B publication Critical patent/CN110280213B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—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 physical properties
    • B01J20/28009—Magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/55—Compounds of silicon, phosphorus, germanium or arsenic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a nano magnetic composite iron-copper oxide de-arsenic adsorbent which is of a multilayer core-shell structure and is prepared by using magnetic nano Fe3O4As core, in magnetic nano Fe3O4The surface of the carbon layer is coated with an intermediate carbon layer, and the surface of the carbon layer is coated with an iron-copper oxide layer. The invention also discloses a preparation method and application of the dearsenic adsorbent. The nano magnetic composite iron-copper oxide arsenic removal adsorbent can realize the direct capture of gas-phase arsenic in a larger temperature range, the adsorption rate and the adsorption capacity of the arsenic are both kept at 0.8mg/g/min and more than 18mg/g, the stability of the adsorbed arsenic is higher, the arsenic can not be dissociated and released within 1200 ℃, and the secondary pollution of the arsenic is reduced.

Description

Nano magnetic composite iron-copper oxide dearsenization adsorbent and preparation method and application thereof
Technical Field
The invention belongs to the field of adsorbents, and particularly relates to an arsenic adsorbent suitable for high-sulfur high-temperature arsenic-containing flue gas generated in an industrial coal high-temperature process and a preparation method thereof.
Background
In the high-temperature combustion process, most of arsenic element in the fuel or ore volatilizes and enters the flue gas in the form of arsenic trioxide, and how to control the content of arsenic in the high-temperature flue gas is the key point of arsenic pollution control. At present, a synergistic removal process is mainly adopted for removing arsenic in the traditional coal-fired flue gas, namely, the synergistic removal is carried out in the treatment processes of flue gas waste heat recovery, dust removal, flue gas desulfurization and the like. In the process of treatment, arsenic is dispersed in media such as flue gas, smoke dust and desulfurization solution, so that arsenic emission nodes and subsequent control difficulty are increased. Achieving efficient capture and selective separation of gaseous arsenic is therefore the main direction of research in controlling arsenic contamination. At present, arsenic adsorbents are mainly concentrated on adsorption of arsenic in solution, and the adsorption of arsenic in flue gas is less, Chinese patent 201711220671.9 discloses a preparation method of a flue gas dearsenic adsorbent, which is prepared by uniformly mixing calcium oxide, metallurgical slag, zeolite and fly ash, granulating, heating and other processes; chinese patent ZL201810285567.6 discloses an arsenic adsorbent and a preparation method and application thereof, wherein an alumina carrier is impregnated by using iron element and is roasted at high temperature to prepare a gas-phase arsenic adsorbent. Although the adsorbent can realize the adsorption of gas-phase arsenic, the adsorbent has low resistance to sulfur dioxide, the adsorbed arsenic is difficult to be controllably separated from smoke dust, and the adsorbent faces the problem of secondary pollution of arsenic. In addition, the traditional adsorption material has low adsorption capacity and adsorption rate to gas-phase arsenic, and is difficult to meet the requirements of actual industry. Therefore, the development of a new stable, efficient and easily recyclable adsorption material to meet the requirement of arsenic adsorption in flue gas is urgently needed.
Disclosure of Invention
The invention aims to solve the technical problems, overcome the defects and defects in the background art and provide the arsenic removal adsorbent which has high capture efficiency and controllable separation of gas-phase arsenic and is environment-friendly, and the preparation method and the application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a nano-magnetic composite iron-copper oxide de-arsenic adsorbent is of a multilayer core-shell structure, and the de-arsenic adsorbent is magnetic nano-Fe3O4As an inner core, in the magnetic nano Fe3O4The surface of the carbon layer is coated with an intermediate carbon layer, and the surface of the intermediate carbon layer is coated with an iron-copper oxide layer (outer surface layer).
As a general inventive concept, the present invention also provides a preparation method of the above-mentioned nano magnetic composite iron-copper oxide dearsenic adsorbent, comprising the following steps:
(1) will be magneticNano Fe3O4Soaking in a carbon source solution, performing ultrasonic mixing uniformly, and drying to obtain a sample A;
(2) sintering the sample A at a high temperature to obtain a sample B;
(3) adding ammonia water and the sample B into a polyethylene glycol solution containing soluble ferric salt, soluble copper salt and dodecyl dimethyl ammonium bromide, and ultrasonically mixing to obtain a suspension;
(4) transferring the suspension to a hydrothermal synthesis reaction kettle for hydrothermal reaction, and filtering, washing and drying to obtain a sample C;
(5) and roasting and activating the sample C in a nitrogen atmosphere to obtain the nano magnetic composite iron-copper oxide arsenic removal adsorbent.
In the above preparation method, preferably, in the step (5), the calcination activation is a gradual temperature rise treatment process: firstly heating to 200-250 ℃ under the nitrogen protection atmosphere, keeping the temperature for 1-2.5 h, then heating to 400-500 ℃, and keeping the temperature for 3-6 h.
In the preparation method, preferably, in the step (4), the hydrothermal reaction temperature is 180-200 ℃, and the reaction time is 10-18 h.
In the preparation method, preferably, in the step (2), the temperature of high-temperature sintering is 600-700 ℃, and the temperature is kept for 3-5 hours; the high-temperature sintering is carried out under the protection of nitrogen.
In the preparation method, preferably, the heating rate in the sintering process is 5-10 ℃/min, and the nitrogen flow rate is 0.3-0.5L/min.
In the above preparation method, preferably, in the step (1), the nano-Fe3O4The size is 10-100 nm; the soluble ferric salt is one or more of ferric chloride, ferric nitrate and ferric sulfate; the soluble copper salt is one or more of copper chloride, copper nitrate and copper sulfate; the carbon source solution is a sucrose solution with the concentration of 5-40 mmol/L.
In the preparation method, preferably, in the step (3), the concentration of iron ions in the suspension is 5-15 g/L, the concentration of copper ions is 1.2-3.6 g/L, the addition amount of dodecyl dimethyl ammonium bromide is 0.8-1.2 g/L, the addition amount of the sample A is 15-25 g/L, and the addition amount of ammonia water is 1 mL/L.
As a general inventive concept, the invention also provides an application of the arsenic removal adsorbent or the arsenic removal adsorbent prepared by the preparation method in high-temperature flue gas, the arsenic removal adsorbent is sprayed into the flue gas at the front end of a flue gas dust collection process, the adsorbent after arsenic adsorption and the smoke dust in the flue gas enter a dust removal system together to form arsenic-containing mixed smoke dust, and the arsenic-containing nano magnetic core-shell structure adsorbent is recovered from the arsenic-containing mixed smoke dust through magnetic separation.
In the application, preferably, the flue gas temperature of the adsorbent for adsorbing arsenic is 400-1000 DEG C
The nano magnetic composite iron-copper oxide dearsenization adsorbent can realize gas-phase As in high-temperature flue gas in complex atmosphere2O3The selective capture and the magnetic separation can realize the effective separation of arsenic in the flue gas. The reaction mechanism of the composite adsorbent for realizing the separation of gas-phase arsenic in high-temperature flue gas is as follows: with nano-magnetic Fe3O4The iron-copper composite oxide is a core, a carbon film is coated on the surface of the core, a carbon shell with a loose and porous surface is formed after high-temperature carbonization, the surface of the carbon layer is rich in various functional groups such as hydroxyl, carboxyl and the like in the high-temperature carbonization process, finally, iron-copper chemical substances are loaded on the porous carbon shell through hydrothermal reaction, and finally, high-activity composite oxide is formed through high-temperature activation, namely the final product is Fe3O4A magnetic nano material which takes the inner core, takes the porous carbon as an interlayer and takes the iron-copper active substance as the shell. Magnetic Fe3O4The core is favorable for magnetic separation of the composite adsorbent, the iron-copper active substance loaded on the porous carbon has higher adsorption rate and adsorption capacity to gas-phase arsenic, and finally the arsenic is mainly fixed on the adsorbent in a stable arsenate form, so that direct selective capture and separation of the gas-phase arsenic in the high-temperature flue gas can be realized.
And the traditional arsenic adsorbents such as calcium oxide and metallurgical slag are sprayed into the smoke and finally mixed with the smoke, so that the arsenic content in the smoke is increased, the secondary utilization of the smoke is influenced, and the obtained arsenic-containing smoke still needs to be treated additionally. Aiming at the problem, the nano magnetic composite iron-copper oxide dearsenifying adsorbent synthesized by the invention can be efficiently separated from the mixed smoke dust through simple magnetic separation, so that the recovery of the adsorbent can be realized, and the separation of arsenic and smoke dust can also be realized. In addition, porous carbon is introduced into the nano magnetic composite iron-copper oxide dearsenization adsorbent, so that the adsorbent has a very large specific surface area, and the copper-iron composite oxide has high adsorption activity in a high-sulfur atmosphere, so that the arsenic in high-temperature smelting flue gas can be efficiently and quickly captured, and the problems of low adsorption rate and low adsorption capacity caused by the fact that the traditional adsorbents such as calcium oxide are easily poisoned by sulfur dioxide and have low adsorption activity on arsenic are solved.
Compared with the prior art, the invention has the advantages that:
(1) the nano magnetic composite iron-copper oxide arsenic removal adsorbent can realize the direct capture of gas-phase arsenic in a larger temperature range, the adsorption rate and the adsorption capacity of the arsenic are both kept at 0.8mg/g/min and more than 18mg/g, the stability of the adsorbed arsenic is higher, the arsenic can not be dissociated and released within 1200 ℃, and the secondary pollution of the arsenic is reduced.
(2) The nano magnetic composite iron-copper oxide arsenic removal adsorbent can be widely applied to the field of industrial coal-fired flue gas arsenic removal, is wide in application range, can be directly applied to existing flue gas treatment equipment, and does not need to change the existing treatment process.
(3) The preparation method has the characteristics of simple process, less equipment investment, environmental friendliness and the like.
(4) The nano magnetic composite iron-copper oxide dearsenifying adsorbent can be recycled after desorption, the adsorption efficiency of the adsorbent on arsenic is kept above 50% after 5 times of recycling, the saturated adsorption capacity is still above 16mg/g, and the separation cost of arsenic is reduced.
Drawings
FIG. 1 is a TEM image of the nano-magnetic composite iron-copper oxide dearsenifying adsorbent prepared in example 1 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Comparative example 1:
taking 40mgFe3O4As adsorbent, it was placed in a quartz tube placed in a muffle furnace, the muffle furnace was heated to 600 deg.C, and then 100mg/m gaseous arsenic was introduced at a flow rate of 0.6L/min3The content of arsenic in the adsorbent was detected after 20min of reaction with the simulated gas to obtain the arsenic capture efficiency, and the results are shown in table 1.
Comparative example 2:
magnetic nano Fe3O4Soaking in 10mg/L sucrose solution, drying in vacuum drying oven, and carbonizing at 650 deg.C for 3h under nitrogen atmosphere to obtain porous carbon-coated adsorbent (denoted as Fe)3O4@C)。
Taking 40mgFe3O4@ C adsorbent, which is placed in a quartz tube placed in a muffle furnace, the muffle furnace is heated to 600 deg.C, and then 100mg/m gaseous arsenic is introduced at a flow rate of 0.6L/min3The content of arsenic in the adsorbent was detected after 20min of reaction with the simulated gas to obtain the arsenic capture efficiency, and the results are shown in table 1.
Comparative example 3:
adding copper sulfate and dodecyl dimethyl ammonium bromide into polyethylene glycol solution to obtain mixed solution with copper ion concentration of 2g/L and dodecyl dimethyl ammonium bromide concentration of 1g/L, and adding Fe in comparative example 2 into the mixed solution3O4The addition amounts of the @ C adsorbent and the ammonia water are respectively 20g/L and 1mL/L,and (4) carrying out ultrasonic dispersion to obtain a suspension.
Adding the suspension into a hydrothermal reaction kettle, and reacting at 180 ℃ for 10 hours to obtain the copper oxide magnetic adsorbent.
Heating the obtained copper oxide magnetic adsorbent to 200 ℃ under the nitrogen protection atmosphere, keeping the temperature for 1.5h, then heating to 450 ℃, keeping the temperature for 4h, and finally obtaining the activated adsorbent (marked as Fe)3O4@C@CuO)。
Taking 40mgFe3O4@ C @ CuO adsorbent, which is filled in a quartz tube arranged in a muffle furnace, the muffle furnace is heated to 600 ℃, and then 100mg/m of gaseous arsenic is introduced at the flow rate of 0.6L/min3The content of arsenic in the adsorbent was detected after 20min of reaction with the simulated gas to obtain the arsenic capture efficiency, and the results are shown in table 1.
Comparative example 4:
adding ferric chloride and dodecyl dimethyl ammonium bromide into polyethylene glycol solution to prepare mixed solution with the ferric ion concentration of 10g/L and the dodecyl dimethyl ammonium bromide concentration of 1g/L, and then adding the Fe in the comparative example 2 into the mixed solution3O4The @ C adsorbent and ammonia water are added in the amount of 20g/L and 1mL/L respectively, and suspension is obtained through ultrasonic dispersion.
Adding the suspension into a hydrothermal reaction kettle, and reacting at 180 ℃ for 10 hours to obtain the iron oxide magnetic adsorbent.
Firstly heating the obtained iron oxide magnetic adsorbent to 200 ℃ under the nitrogen protection atmosphere, preserving the heat for 1.5h, then heating to 450 ℃, preserving the heat for 4h, and finally obtaining the activated adsorbent (marked as Fe)3O4@C@Fe2O3)。
Taking 40mgFe3O4@C@Fe2O3Adsorbent, which is filled in a quartz tube placed in a muffle furnace, the muffle furnace is heated to 600 ℃, and then 100mg/m of gaseous arsenic is introduced at the flow rate of 0.6L/min3The content of arsenic in the adsorbent was detected after 20min of reaction with the simulated gas to obtain the arsenic capture efficiency, and the results are shown in table 1.
Comparative example 5:
adding ferric chloride, copper sulfate and dodecyl dimethyl ammonium bromide into polyethylene glycol solution to prepare mixed solution with the iron ion concentration of 10g/L, the copper ion concentration of 1.5g/L and the dodecyl dimethyl ammonium bromide concentration of 1g/L, and then adding the Fe in the comparative example 2 into the mixed solution3O4The @ C adsorbent and ammonia water are added in the amount of 20g/L and 1mL/L respectively, and suspension is obtained through ultrasonic dispersion.
Adding the suspension into a hydrothermal reaction kettle, and reacting at 180 ℃ for 10h to obtain the composite iron-copper oxide magnetic adsorbent (Fe) without activation3O4@C@x(CuO)·y(Fe2O3))。
40mg of unactivated Fe3O4@C@x(CuO)·y(Fe2O3) Adsorbent, which is filled in a quartz tube placed in a muffle furnace, the muffle furnace is heated to 600 ℃, and then 100mg/m of gaseous arsenic is introduced at the flow rate of 0.6L/min3The arsenic content in the adsorbent was detected after 20min of reaction with the simulated gas to obtain the arsenic capture efficiency, and the results are shown in table 1.
Example 1:
heating the composite iron-copper oxide magnetic adsorbent obtained in the comparative example 5 under the nitrogen protective atmosphere to 200 ℃, keeping the temperature for 1.5h, then heating to 450 ℃, keeping the temperature for 4h, and finally obtaining activated Fe3O4@C@ x(CuO)·y(Fe2O3) The TEM image of the adsorbent is shown in FIG. 1, and the dearsenic adsorbent is magnetic nano Fe as can be seen from FIG. 13O4As an inner core, in the magnetic nano Fe3O4The surface of the carbon layer is coated with an intermediate carbon layer, and the surface of the carbon layer is coated with an iron-copper oxide layer.
Taking 40mg of activated Fe3O4@C@x(CuO)·y(Fe2O3) Adsorbent, which is filled in a quartz tube placed in a muffle furnace, the muffle furnace is heated to 600 ℃, and then 100mg/m of gaseous arsenic is introduced at the flow rate of 0.6L/min3The arsenic content in the adsorbent is detected after the reaction is carried out for 20min, the capture efficiency of the arsenic is obtained,the results are shown in Table 1.
TABLE 1 comparison of arsenic adsorption Performance by different adsorbents
Figure BDA0002108553090000051
Table 1 shows the comparison of the performance of the adsorbents in comparative examples 1-5 and example 1 in capturing arsenic, and it can be seen from the table that the efficiency of capturing gas-phase arsenic by single ferroferric oxide is not high, while the efficiency of capturing arsenic can be improved by certain precipitation of porous carbon load, and particularly Fe is obtained after the metal of copper and iron is oxidized and loaded2O3The arsenic capture efficiency (72.3%) can be obviously improved. Loading composite iron-copper oxide on core-shell structure Fe3O4After @ C and activation treatment, the capture efficiency of arsenic is obviously improved to 83.8%, the adsorption efficiency and the adsorption capacity of arsenic are respectively 1.257mg/g/min and 25.14mg/g, which are obviously superior to those of single iron or copper oxide, so that the composite iron-copper oxide has a synergistic effect on the capture of arsenic. Moreover, the material can avoid the metal compound with hydroxyl and SO in high-sulfur smoke after being activated at high temperature2The corresponding sulfate is formed through reaction, so that the adsorption effect on arsenic is reduced; meanwhile, the material can form stable iron-copper composite oxide through the roasting and activating process, and the capture effect of the material on arsenic is better.
To evaluate Fe after adsorption3O4@C@x(CuO)·y(Fe2O3) The high-temperature stability of arsenic in the adsorbent is realized by taking 100g of the adsorbent after adsorption (the arsenic adsorption amount is 19.4mg/g), adding the adsorbent into an alumina crucible, placing the alumina crucible in a closed tube furnace, heating the alumina crucible to 1200 ℃ at the speed of 5 ℃/min, and preserving the heat for 1 h. During the heating, nitrogen was continuously introduced at a rate of 1L/min, and the off-gas was treated with a 1mol/L NaOH solution at the outlet. After the reaction is finished, the arsenic content in the tail absorption liquid is not detected, and the arsenic content in the adsorbent is kept unchanged, which shows that the arsenic on the adsorbent has high stability within 1200 ℃, and is difficult to dissociate and release at high temperature, so that the high-efficiency adsorption of the adsorbent on the arsenic at high temperature is ensured.
In this embodiment, the recycling performance of the adsorbent is also studied, that is, arsenic on the adsorbent is desorbed in a high-concentration alkali solution, then the desorbed adsorbent is obtained through high-temperature activation treatment, the treated adsorbent is subjected to a gaseous arsenic adsorption experiment under the same conditions, and the recycling performance is recycled for 5 times, and the recycling performance results are shown in table 2 below. As can be seen from the table, Fe3O4@C@x(CuO)·y(Fe2O3) After 5 cycles, the adsorbent keeps the adsorption efficiency of arsenic above 50%, and the adsorption capacity of arsenic above 16mg/g, namely the prepared adsorbent has excellent recycling performance.
TABLE 2 Fe3O4@C@x(CuO)·y(Fe2O3) Cyclic use properties of adsorbents
Figure BDA0002108553090000061
Application example 1:
40mg of the activated Fe prepared in example 1 were taken3O4@C@x(CuO)·y(Fe2O3) Adsorbent, which is filled in a quartz tube placed in a muffle furnace, the temperature is kept at 500 ℃, simulated gas is introduced at the flow rate of 0.6L/min, and SO in the simulated flue gas is2Concentration of 0.5%, O2 concentration of 5%, gas phase As2O3Is 100ppm, the balance is N2. And detecting the arsenic content in the adsorbent after reaction to obtain the arsenic capture efficiency.
Application example 2:
40mg of activated Fe prepared in example 1 were taken3O4@C@x(CuO)·y(Fe2O3) Adsorbent, which is filled in a quartz tube placed in a muffle furnace, the temperature is kept at 500 ℃, simulated gas is introduced at the flow rate of 0.6L/min, and SO in the simulated flue gas is2Concentration of 5% O25% concentration of gas phase As2O3Is 100ppm, the balance is N2. And detecting the arsenic content in the adsorbent after reaction to obtain the arsenic capture efficiency.
Application example 3:
40mg of the activated Fe prepared in example 1 were taken3O4@C@x(CuO)·y(Fe2O3) Adsorbent, which is filled in a quartz tube placed in a muffle furnace, the temperature is maintained at 700 ℃, simulated gas is introduced at the flow rate of 0.6L/min, and SO in the simulated flue gas is2Concentration of 0.5%, O25% concentration of gas phase As2O3Is 100ppm, the balance is N2. And detecting the arsenic content in the adsorbent after reaction to obtain the arsenic capture efficiency.
Application example 4:
40mg of the activated Fe prepared in example 1 were taken3O4@C@x(CuO)·y(Fe2O3) Adsorbent, which is filled in a quartz tube placed in a muffle furnace, the temperature is maintained at 900 ℃, simulated gas is introduced at the flow rate of 0.6L/min, and SO in the simulated flue gas is2Concentration of 0.5%, O25% concentration of gas phase As2O3Is 100ppm, the balance is N2. And detecting the arsenic content in the adsorbent after reaction to obtain the arsenic capture efficiency.
Table 3 shows the sulfur resistance and the gas-phase arsenic capture efficiency at different temperatures of the composite iron-copper oxide adsorbent with a nano magnetic core-shell structure. Comparison of application examples 1 and 2 it can be seen that SO is present in flue gas2The concentration has little influence on the capture efficiency of the adsorbent, namely the adsorbent has higher sulfur resistance, and can realize the high-efficiency capture of gas-phase arsenic in the atmosphere of high sulfur dioxide. Comparing application examples 1, 3 and 4, it can be seen that the capture efficiency of gas-phase arsenic is reduced with the increase of temperature, but all the arsenic is kept above 80%, and the adsorption capacity of arsenic is kept above 24mg/L, namely Fe under different atmospheres and stable conditions3O4@C@x(CuO)·y(Fe2O3) The adsorbent can still maintain efficient capture of gas-phase arsenic.
TABLE 3 Sulfur resistance and arsenic Capture Performance of the sorbents at different temperatures
Figure BDA0002108553090000071

Claims (10)

1. The nano magnetic composite iron-copper oxide dearsenic adsorbent applied to high-temperature flue gas is characterized in that the dearsenic adsorbent is of a multilayer core-shell structure, and the dearsenic adsorbent is magnetic nano Fe3O4As an inner core, in the magnetic nano Fe3O4The surface of the intermediate carbon layer is coated with an iron-copper oxide layer, and the dearsenization adsorbent is a nano magnetic composite iron-copper oxide dearsenization adsorbent which is subjected to roasting activation treatment in a nitrogen atmosphere.
2. The preparation method of the nano magnetic composite iron-copper oxide dearsenifying adsorbent as claimed in claim 1, characterized by comprising the following steps:
(1) magnetic nano Fe3O4Soaking in a carbon source solution, performing ultrasonic mixing uniformly, and drying to obtain a sample A;
(2) sintering the sample A at a high temperature to obtain a sample B;
(3) adding ammonia water and the sample B into a polyethylene glycol solution containing soluble iron salt, soluble copper salt and dodecyl dimethyl ammonium bromide, and ultrasonically mixing to obtain a suspension;
(4) transferring the suspension to a hydrothermal synthesis reaction kettle for hydrothermal reaction, and filtering, washing and drying to obtain a sample C;
(5) and roasting and activating the sample C in a nitrogen atmosphere to obtain the nano magnetic composite iron-copper oxide dearsenic adsorbent.
3. The method according to claim 2, wherein in the step (5), the calcination activation is a stepwise temperature rise treatment process: firstly heating to 200-250 ℃ under the nitrogen protection atmosphere, keeping the temperature for 1-2.5 h, then heating to 400-500 ℃, and keeping the temperature for 3-6 h.
4. The preparation method according to claim 2, wherein in the step (4), the hydrothermal reaction temperature is 180 to 200 ℃ and the reaction time is 10 to 18 hours.
5. The preparation method according to claim 2, wherein in the step (2), the temperature of the high-temperature sintering is 600-700 ℃, and the temperature is kept for 3-5 hours; the high-temperature sintering is carried out under the protection of nitrogen.
6. The method according to claim 5, wherein the temperature rise rate during the sintering process is 5 to 10 ℃/min, and the nitrogen flow rate is 0.3 to 0.5L/min.
7. The method according to any one of claims 2 to 6, wherein in the step (1), nano Fe3O4The size is 10-100 nm; the soluble ferric salt is one or more of ferric chloride, ferric nitrate and ferric sulfate; the soluble copper salt is one or more of copper chloride, copper nitrate and copper sulfate; the carbon source solution is a sucrose solution with the concentration of 5-40 mmol/L.
8. The method according to any one of claims 2 to 6, wherein in the step (3), the concentration of iron ions in the suspension is 5 to 15g/L, the concentration of copper ions is 1.2 to 3.6g/L, the addition amount of dodecyl dimethyl ammonium bromide is 0.8 to 1.2g/L, the addition amount of the sample B is 15 to 25g/L, and the addition amount of ammonia water is 1 mL/L.
9. The application of the arsenic removal adsorbent according to claim 1 or the arsenic removal adsorbent prepared by the preparation method according to any one of claims 2 to 8 in high-temperature flue gas is characterized in that the arsenic removal adsorbent is sprayed into the flue gas at the front end of a flue gas dust collection process, the adsorbent adsorbing arsenic enters a dust removal system together with smoke dust in the flue gas to form arsenic-containing mixed smoke dust, and the arsenic-containing nano magnetic core-shell structure adsorbent is recovered from the arsenic-containing mixed smoke dust through magnetic separation.
10. The use according to claim 9, wherein the adsorbent adsorbs arsenic at a temperature of 400 to 1000 ℃.
CN201910562100.6A 2019-06-26 2019-06-26 Nano magnetic composite iron-copper oxide dearsenization adsorbent and preparation method and application thereof Active CN110280213B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910562100.6A CN110280213B (en) 2019-06-26 2019-06-26 Nano magnetic composite iron-copper oxide dearsenization adsorbent and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910562100.6A CN110280213B (en) 2019-06-26 2019-06-26 Nano magnetic composite iron-copper oxide dearsenization adsorbent and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN110280213A CN110280213A (en) 2019-09-27
CN110280213B true CN110280213B (en) 2022-06-07

Family

ID=68006194

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910562100.6A Active CN110280213B (en) 2019-06-26 2019-06-26 Nano magnetic composite iron-copper oxide dearsenization adsorbent and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN110280213B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112176195B (en) * 2020-09-18 2022-05-10 中南大学 Method for removing arsenic from arsenic-containing smoke dust

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101591552B (en) * 2008-05-30 2013-09-11 北京三聚环保新材料股份有限公司 Preparation method of normal temperature composite desulfurating and dearsenic agent
US9822296B2 (en) * 2011-06-15 2017-11-21 The Frazer And Cruickshank Living Trust Proppants for removal of contaminants from fluid streams and methods of using same
CN102688760B (en) * 2012-06-07 2014-04-02 北京科技大学 Fe3O4/CuO/pSiO2 catalyst and preparation method thereof
CN102790217B (en) * 2012-07-26 2014-07-09 天津大学 Carbon cladded ferriferrous oxide negative electrode material of lithium ion battery and preparation method thereof
CN103877931A (en) * 2012-12-19 2014-06-25 上海工程技术大学 Metal compound-type arsenic removal agent, preparation method and application thereof
CN103464089B (en) * 2013-09-11 2015-10-28 清华大学 Magnetic arsenic adsorbent and preparation method thereof and application
CN104549131A (en) * 2013-10-29 2015-04-29 中国石油化工股份有限公司 Adsorption desulfurization additive, as well as preparation method and desulfurization system thereof
CN103599737B (en) * 2013-11-20 2015-10-14 北京化工大学 One has carbon shell magnetic Nano material and preparation method
CN105214599B (en) * 2014-07-03 2018-06-08 中国石油化工股份有限公司 Sulphur arsenic adsorbent and preparation method thereof
CN104275150A (en) * 2014-10-16 2015-01-14 广州博能能源科技有限公司 Deep smoke purifying material, and preparation method and use method thereof
CN105797728B (en) * 2016-04-14 2018-04-03 同济大学 A kind of magnetic Nano CuxO‑Fe2O3The preparation method and applications of ozone catalyst
CN107999024B (en) * 2017-12-13 2020-07-31 江西理工大学 Preparation method and application of efficient sulfur-resistant copper-based demercuration adsorbent
CN107983295B (en) * 2018-01-12 2019-09-20 湖南大学 Core-shell structure iron-copper bi-metal material and its preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
水热法制备铜_铁氧化物纳米材料及其在环境处理和能源存储中的应用_孟德海;孟德海;《中国优秀博硕士学位论文全文数据库（硕士） 工程科技Ⅰ辑》;20140415(第4期);第1-108页 *

Also Published As

Publication number Publication date
CN110280213A (en) 2019-09-27

Similar Documents

Publication Publication Date Title
Dong et al. Elemental mercury removal from coal-fired flue gas using recyclable magnetic Mn-Fe based attapulgite sorbent
Yang et al. Preparation of magnetic Co-Fe modified porous carbon from agricultural wastes by microwave and steam activation for mercury removal
Shan et al. Preparation of microwave-activated magnetic bio-char adsorbent and study on removal of elemental mercury from flue gas
Yang et al. Mercury removal from flue gas by magnetic iron-copper oxide modified porous char derived from biomass materials
Yang et al. Removal of elemental mercury from flue gas using red mud impregnated by KBr and KI reagent
Xie et al. Novel regenerable sorbent based on Zr–Mn binary metal oxides for flue gas mercury retention and recovery
Zhou et al. Effect of flue gas component and ash composition on elemental mercury oxidation/adsorption by NH4Br modified fly ash
Yang et al. Development of selenized magnetite (Fe3O4− xSey) as an efficient and recyclable trap for elemental mercury sequestration from coal combustion flue gas
CN110252255B (en) Preparation method and application of gaseous mercury adsorbent
CN110420640B (en) Flue gas catalyst, and device and method for cooperatively treating multiple pollutants in flue gas
Xie et al. In-situ preparation of zinc sulfide adsorbent using local materials for elemental mercury immobilization and recovery from zinc smelting flue gas
CN103623772A (en) Absorbent for removing and recovering liquid-phase mercury as well as preparation method and using method thereof
JP2019193926A (en) Manufacturing method of magnetic hydrothermal charcoal, and application thereof
CN103920461A (en) Magnetic biochar quantum dot composite adsorbent as well as preparation method and using method thereof
CN102553526B (en) Method for removing mercury ions from water by using silver-modified magnetic carbon nanotube and regeneration method
Wu et al. Development of iron oxide sorbents for Hg0 removal from coal derived fuel gas: Sulfidation characteristics of iron oxide sorbents and activity for COS formation during Hg0 removal
Liang et al. Inexpensive metal oxides nanoparticles doped Na2CO3 fibers for highly selective capturing trace HCl from HCl/CO2 mixture gas at low temperature
Guo et al. Coupling mechanism of activated carbon mixed with dust for flue gas desulfurization and denitrification
Cui et al. Study of the properties of adsorption of SO2–thermal regeneration cycle of activated coke modified by oxidization
CN110280213B (en) Nano magnetic composite iron-copper oxide dearsenization adsorbent and preparation method and application thereof
He et al. Highly efficient sorption and immobilization of gaseous arsenic from flue gas on MnO2/attapulgite composite with low secondary leaching risks
Xu et al. Simultaneous removal of NO and elemental mercury from coal-fired flue gas using natural ferruginous manganese ore at low temperature
Hou et al. The mechanism of CO regeneration on V2O5/AC catalyst and sulfur recovery
AU2020203664B2 (en) Magnetic selenium doped iron-sulfur composite and preparation method and application thereof
CN109200792B (en) Comprehensive treatment method and system for sintering flue gas of iron and steel plant

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant