CN113769701A - Preparation method and application of magnetic renewable mercury removing agent - Google Patents

Preparation method and application of magnetic renewable mercury removing agent Download PDF

Info

Publication number
CN113769701A
CN113769701A CN202110969036.0A CN202110969036A CN113769701A CN 113769701 A CN113769701 A CN 113769701A CN 202110969036 A CN202110969036 A CN 202110969036A CN 113769701 A CN113769701 A CN 113769701A
Authority
CN
China
Prior art keywords
mercury
magnetic
renewable
demercuration
agent
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.)
Granted
Application number
CN202110969036.0A
Other languages
Chinese (zh)
Other versions
CN113769701B (en
Inventor
李海龙
孟凡悦
杨建平
屈文麒
杨泽群
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.)
Central South University
Original Assignee
Central South University
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 Central South University filed Critical Central South University
Priority to CN202110969036.0A priority Critical patent/CN113769701B/en
Publication of CN113769701A publication Critical patent/CN113769701A/en
Application granted granted Critical
Publication of CN113769701B publication Critical patent/CN113769701B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0288—Halides of compounds other than those provided for in B01J20/046
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention discloses a preparation method and application of a magnetic renewable mercury removing agent. The method comprises the steps of roasting natural iron minerals at a high temperature to remove partial sulfur, then converting the natural iron minerals into magnetic iron minerals, adding copper chloride for modification treatment, and mechanically grinding and activating to obtain the magnetic renewable mercury removing agent with excellent mercury removing performance. The magnetic demercuration agent is placed in a fixed bed, a fluidized bed or a wet flue gas purification system or is sprayed into flue gas to contact with mercury in the flue gas, gaseous mercury is converted into a stable compound, the gaseous mercury is solidified and removed, the demercuration agent loaded with mercury is separated out after magnetic separation, and the demercuration agent can be recycled after high-temperature mercury desorption. The magnetic renewable demercuration agent disclosed by the invention has the advantages of natural and easily-obtained raw materials, abundant reserves, simple preparation method, large mercury adsorption capacity, high adsorption rate, renewable recycling, obvious reduction of demercuration cost and good practical value.

Description

Preparation method and application of magnetic renewable mercury removing agent
Technical Field
The invention belongs to the technical field of environmental pollution prevention and purification, and particularly relates to a preparation method and application of a magnetic renewable mercury removing agent.
Background
Mercury is a heavy metal pollutant which exists in the environment for a long time and has global migration and diffusivity, has extreme toxicity, durability, high corrosivity and volatility, and brings serious harm to human health and the water-land ecological environment. The water guarantee official (water guarantee official) about mercury in 10.10.2013 is signed by the Japanese bear, and the water guarantee official (water guarantee official) about mercury in 2017 is officially effective in more than 100 countries all over the world, marking that the problem of mercury pollution control not only becomes the key point of environmental pollution control in China, but also can be restrained by the international environmental policy to bear the corresponding performance responsibility.
The currently common techniques for removing mercury from flue gas include condensation, absorption, adsorption, etc. The adsorption method is a common method for capturing and recovering mercury in flue gas. At present, the more researched adsorbents mainly comprise activated carbon, metal sulfides, metal oxides, modified fly ash, calcium adsorbent, precious metals and the like, the activated carbon is used in the field of coal-fired flue gas demercuration, but the demercuration effect is greatly influenced by working conditions, the use amount is large, the cost is high, the activated carbon adsorbing mercury is difficult to separate from the fly ash and cannot be recycled, and the resource utilization of the fly ash quality is seriously reduced due to the mixing of the activated carbon; cheap adsorbents such as metal oxide, modified fly ash and calcium adsorbent have limited adsorption capacity, have low demercuration efficiency and are not suitable for purifying flue gas with high mercury concentration; the metal sulfide has excellent demercuration activity, is considered to be the most potential material for replacing the traditional activated carbon adsorbent, but natural metal sulfide minerals almost have no demercuration capacity, the metal sulfide adsorbent with high demercuration efficiency needs to be strictly controlled and accurately synthesized by complex precursors and additives, the process is complex, the cost is high, the metal sulfide adsorbent cannot be regenerated and reused generally, the cost is greatly improved, the operation cost is increased, and the industrial production and application of the metal sulfide adsorbent are hindered.
The total dosage of the adsorbent can be reduced by regenerating the adsorbent for cyclic use, so that the demercuration cost is remarkably reduced, the treatment capacity of the waste adsorbent can be greatly reduced, the resource consumption is reduced, the cyclic utilization of the resource is realized, the requirement of green chemistry is met, and the adsorbent has double values of economy and environmental protection. The natural pyrite mineral has rich reserves, and some natural pyrite has excellent magnetization characteristics after simple treatment, so that the material can be easily separated out by magnetic separation for cyclic regeneration and utilization. Therefore, the natural pyrite is modified to have excellent mercury removal performance and realize recycling, the outstanding problems of high cost, small capacity, difficult recovery and the like of the existing mercury removal agent can be solved, and a new thought is provided for the development and utilization of the mercury removal agent.
Disclosure of Invention
In order to solve the defects and problems of the existing demercuration agent, obviously improve the demercuration efficiency, reduce the cost and realize the renewable recycling, the invention aims to provide a preparation method and application of a magnetic renewable demercuration agent.
The technical scheme of the invention is specifically introduced as follows:
the invention relates to a preparation method of a magnetic renewable mercury removing agent, which comprises the following steps: roasting natural pyrite mineral in a protective atmosphere to obtain a roasted product, mixing the roasted product with copper chloride to obtain a mixture, and mechanically grinding, activating, drying and screening the mixture to obtain the magnetic renewable mercury removing agent.
Preferably, the natural pyrite mineral is subjected to crushing, drying and screening treatment, and then the screened natural pyrite mineral is roasted, wherein the drying temperature is 100-120 ℃, and the drying time is 0.5-2 h.
Preferably, in the natural pyrite mineral, the mass fraction (wB%) of iron is more than or equal to 15%, and the mass fraction (wB%) of sulfur is more than or equal to 10%
Preferably, the natural pyrite mineral is selected from at least one of pyrite, pyrrhotite, pentlandite, and pyrrhotite.
Preferably, the protective atmosphere is selected from a nitrogen atmosphere. In the actual operation, after the roasting is finishedN2Naturally cooling in the atmosphere, taking out after cooling to room temperature, and sealing for storage.
Preferably, the roasting temperature is 550-750 ℃, and the roasting time is 20-180 min.
The inventor finds that the roasting temperature is controlled within the range, the obtained roasted product has optimal magnetism, the active sites are most abundant, and the mercury removal effect of the finally obtained magnetic renewable mercury removal agent is optimal.
Further preferably, the roasting temperature is 550-650 ℃, and the roasting time is 60-120 min.
Preferably, the mass ratio of the roasted product to the copper chloride is 1-10: 1-3.
Further preferably, the mass ratio of the roasted product to the copper chloride is 1-4: 1.
preferably, the temperature of the mechanical grinding activation is 25-90 ℃ and the time is 5-30 min.
Further preferably, the temperature of the mechanical grinding activation is 50-75 ℃, and the time is 15-30 min.
The inventors have found that grinding activation is carried out at this temperature, and the properties of the finally obtained mercury removing agent are optimal.
Preferably, the drying temperature is 60-180 ℃, and the drying time is 2-12 h.
Preferably, the sieve is a standard sieve which passes through 200 meshes, and undersize is taken.
The invention relates to an application of a magnetic renewable mercury removing agent, which applies the magnetic renewable mercury removing agent to the purification and removal of mercury in mercury-containing flue gas or mercury-containing wastewater.
Preferably, the application process comprises the steps of contacting the magnetic renewable demercuration agent with mercury-containing flue gas or placing the magnetic renewable demercuration agent in mercury-containing wastewater, performing demercuration reaction, performing magnetic separation, collecting the demercuration agent loaded with mercury in a centralized manner, performing thermal treatment to desorb mercury to obtain pure mercury and a recovered demercuration agent, mixing the recovered demercuration agent with copper chloride, and finally performing grinding and activation to obtain the regenerated magnetic renewable demercuration agent.
Further preferably, the temperature of the demercuration reaction is 5-220 ℃. In the present invention, mercury in the elemental, free and/or compound state can be removed.
Preferably, the temperature for desorbing the mercury by the heat treatment is 250-550 ℃, and the time for desorbing the mercury by the heat treatment is 30-120 min.
In the practical application process, the magnetic renewable demercuration agent is placed in a fixed bed, a fluidized bed, a wet flue gas purification system and a demercuration agent injection device for demercuration, and can be used for mercury purification of mercury-containing flue gas or wastewater in the processes of coal burning, metal smelting, garbage incineration, cement production, natural gas production and the like.
In the practical application process, the magnetic mercury removing agent loaded with mercury is placed in an electric control distillation furnace for desorption at high temperature, and mercury vapor escapes to enter a circulating condensation system to form liquid metal mercury, and then the liquid metal mercury is collected and stored in a concentrated manner.
Principles and advantages
The natural iron mineral has rich reserves, but has compact structure, large particle size, small specific surface area, complex impurity components, unexposed chemical active groups and no demercuration capability. After natural iron minerals are roasted at high temperature under the oxygen-free condition, partial sulfur in crystal lattices volatilizes to generate pyrrhotite with magnetism, and the equation reaction is as follows:
(1-x)FeS2(s)→Fe1-xS(s)+(2-3x)S(s)(1-1)
after high-temperature roasting, partial sulfur escapes, the structure becomes loose, the specific surface area is increased, the particle size is reduced, and the exposure of active sites is increased; the strong interaction force between mercury and sulfur atoms forms a large vacancy in the roasted iron mineral, a saturated sulfur site is converted into an unsaturated sulfur site, the unsaturated sulfur site has stronger low-temperature reaction activity on mercury than the saturated sulfur site, and the separated elemental sulfur also has promotion significance on mercury removal; the magnetic material with fully exposed sulfur sites reacts with copper chloride to spontaneously generate CuS on the surface of the magnetic material, mercury is captured by copper in the CuS to generate metal amalgam, and then the metal amalgam reacts with sulfur to be converted into stable mercury sulfide, the metal copper and iron sites also have oxidation performance, and Hg is converted into stable mercury sulfide in the presence of chlorine active sites0Converted into mercury chloride. So that the surface active site number and the activity of the modified iron mineral are obviously increasedAnd has excellent demercuration performance. The modified material has magnetism, is placed in an electric control distillation furnace for high-temperature desorption after being collected in a centralized manner, and the desorbed mercury is condensed to form liquid metal mercury for collection and storage, so that the mercury can be recycled, and the desorbed mercury removing agent can be regenerated and recycled by adding a small amount of copper chloride for grinding and activation.
Compared with the prior art, the technical scheme of the invention has the advantages that:
(1) the magnetic renewable mercury removing agent has high efficiency, large capacity and large application temperature range, mercury forms a stable compound on the mercury removing agent, the re-release of mercury is avoided, and the magnetic renewable mercury removing agent has great environmental benefit.
(2) The natural iron mineral has rich reserves, easily obtained raw materials and lower cost.
(3) The modification treatment process is simple, and the promotion range of the demercuration performance is large.
(4) Has excellent magnetism, and can be easily separated by magnetic separation
(5) The mercury on the mercury removing agent can be recovered as an economic product after being desorbed after the mercury is carried, and the economic benefit is improved.
(6) The mercury removing agent after mercury desorption can be regenerated and recycled by a simple method, and is economic and environment-friendly.
Detailed Description
The technical solution of the present invention is further described by the following specific examples. The examples are not intended to limit the scope of protection.
Example 1
Crushing natural pyrite (Fe 44 WB% and S51 WB%), drying, sieving, placing the sieved pyrite in a tube furnace, heating to 650 ℃ under the atmosphere of nitrogen, preserving heat for 60min, naturally cooling to room temperature, and taking out. Mixing the roasted sample with copper chloride according to the mass ratio of 2:1, mechanically grinding and activating in a ball mill at 50 ℃ for 15min, drying at 100 ℃ for 2h after activation is finished, and screening through a standard sieve of 200 meshes after drying is finished to obtain the magnetic reproducible mercury removing agent, wherein the measured coercive force is 28 mT. Weighing 5mg of demercuration agent, placing in a simulated fixed bed reactor, generating elemental mercury through a mercury permeation tube, and performing real-time mercury concentration by using an RA-915 mercury determinatorMeasuring, wherein the mass flow meter accurately controls the gas flow of each component to simulate the components of the smoke, the total gas flow is 1L/min, and the initial Hg is0The concentration was 100. + -. 1. mu.g/m 3, the reaction temperature was 75 ℃. Pure N2Hg in 1h under atmosphere0The removal rate is 98.1 percent; n is a radical of2+200ppm SO2Hg in 1h under atmosphere0The removal rate is 97.5 percent; n is a radical of2+5％O2+200ppm SO2Hg in 1h under atmosphere0The removal rate was 97.1%.
Example 2
Crushing natural pentlandite (Fe 30 WB% and S32 WB%), drying, sieving, placing the sieved pentlandite in a tube furnace, heating to 600 deg.C under nitrogen atmosphere, keeping the temperature for 120min, naturally cooling to room temperature, and taking out. Mixing the roasted sample with copper chloride according to the mass ratio of 1:1, mechanically grinding and activating in a ball mill at 75 ℃ for 30min, drying at 120 ℃ for 8h after activation is finished, and screening through a standard sieve of 200 meshes after drying is finished to obtain the magnetic reproducible mercury removing agent, wherein the measured coercive force is 24 mT. Weighing 20mg of demercuration agent, placing the demercuration agent in a simulated fixed bed reactor, generating elemental mercury through a mercury penetration tube, performing real-time measurement of mercury concentration by using an RA-915 mercury meter, accurately controlling the gas flow of each component by using a mass flow meter to simulate the components of flue gas, wherein the total gas flow is 1L/min, and the initial Hg is0The concentration was 500. + -. 5. mu.g/m 3, and the reaction temperature was 175 ℃. Pure N2Hg in 1h under atmosphere0The removal rate was 97.5%.
Example 3
The magnetic mercury removing agent prepared in the embodiment 1 is tested in a small-sized zinc smelting plant, the zinc smelting amount is 8t/h, and the smoke gas amount is 20000-3H Hg behind the Electrostatic precipitator0The discharge amount is 3-3.5mg/m3Adding a magnetic demercuration agent in a fixed bed manner, wherein the addition amount of the demercuration agent is 1.5kg, the demercuration efficiency in 1h is higher than 92.5%, carrying out magnetic separation after fully carrying mercury, separating the demercuration agent, intensively collecting, placing in an electric control distillation furnace for desorption at high temperature, wherein the desorption temperature is 500 ℃, the desorption time is 60min, mercury vapor escapes, enters a circulating condensation system to form liquid metal mercury, then intensively collecting and storing, and recovering mercuryThe purity is higher than 99.9%.
Example 4
Mixing the mercury removing agent subjected to mercury desorption in the embodiment 3 with copper chloride according to the mass ratio of 3:1, mechanically grinding and activating for 30min in a ball mill at 25 ℃, drying for 2h at 120 ℃ after activation is completed, and sieving through a standard sieve of 200 meshes after drying is completed to obtain the regenerated magnetic mercury removing agent, wherein the coercive force is measured to be 26 mT. The regenerated demercuration agent is placed in a fixed bed as in example 3, and the smoke amount is 20000-3/h，Hg0The discharge amount is 3-3.5mg/m3The addition amount of the demercuration agent is 1.5kg, and the demercuration efficiency in 1 hour is higher than 90.8 percent. The mercury removing agent is subjected to three adsorption, desorption and regeneration processes, and the mercury removing efficiency is respectively 90.8%, 90.2% and 89.3% under the same flue gas condition.
Example 5
Crushing natural pyrite (Fe 37 WB% and S42 WB%), drying, sieving, placing the sieved pyrite in a tube furnace, heating to 550 ℃ under the atmosphere of nitrogen, preserving heat for 120min, naturally cooling to room temperature, and taking out. Mixing the roasted sample with copper chloride according to a mass ratio of 4:1, mechanically grinding and activating in a ball mill at 75 ℃ for 15min, drying at 150 ℃ for 4h after activation is finished, screening through a standard sieve of 200 meshes after drying is finished to obtain the magnetic reproducible mercury removing agent, measuring the saturation magnetization intensity to be 13.1emu/g, spraying 50mg of mercury removing agent into a volume of 1m3In pilot injection column of (2), Hg0Has an initial concentration of 60 mu g/m3 and a flue gas flow of 1.5m3Min, temperature 125 deg.C, pure N2Hg under an atmosphere0The removal rate was 98.2%.
Example 6
Adding the magnetic renewable mercury removal agent obtained in the embodiment 5 into a simulated flue gas washing device, wherein the temperature of washing liquid is 50 ℃, the addition amount of the mercury removal agent is 2g/L to the washing liquid, the pH value of the simulated washing liquid is 4, elemental mercury is generated through a mercury penetration tube, real-time measurement of mercury concentration is performed by using an RA-915 mercury meter, the components of flue gas are simulated by accurately controlling the gas flow of each component through a mass flow meter, the total gas flow is 1L/min, and the initial Hg is initially added0The concentration is 200 +/-2 mu g/m3. Pure N2Hg in 1h under atmosphere0The removal rate was 92%.
Comparative example 1
Crushing natural pyrite (Fe 44 WB% and S51 WB%), drying, sieving, placing the sieved pyrite in a tube furnace, heating to 650 ℃ under the atmosphere of nitrogen, preserving heat for 60min, naturally cooling to room temperature, and taking out. Weighing 5mg of natural pyrite, placing the natural pyrite in a simulated fixed bed reactor, generating elemental mercury through a mercury penetration tube, carrying out real-time measurement on mercury concentration by using an RA-915 mercury detector, accurately controlling the gas flow of each component by using a mass flow meter to simulate the components of flue gas, wherein the total gas flow is 1L/min, and the initial Hg is0The concentration was 100. + -. 1. mu.g/m 3, the reaction temperature was 75 ℃. Pure N2Hg in 1h under atmosphere0The removal rate is 7.1%; n is a radical of2+200 ppm SO2Hg in 1h under atmosphere0The removal rate is 6.5 percent; n2+ 5% O2+200ppm SO2Hg in 1h under atmosphere0The removal rate was 4.1%.
Comparative example 2
Crushing natural pentlandite (Fe 30 WB% and S32 WB%), drying, sieving, placing the sieved pentlandite in a tube furnace, heating to 800 deg.C under nitrogen atmosphere, keeping the temperature for 120min, naturally cooling to room temperature, and taking out. Mixing the roasted sample with copper chloride according to the mass ratio of 1:1, mechanically grinding and activating in a ball mill at 75 ℃ for 30min, drying at 120 ℃ for 8h after activation is finished, and screening through a standard sieve of 200 meshes after drying is finished to obtain the magnetic reproducible mercury removing agent. Weighing 20mg of demercuration agent, placing the demercuration agent in a simulated fixed bed reactor, generating elemental mercury through a mercury permeation tube, carrying out real-time measurement on mercury concentration by using an RA-915 mercury meter, accurately controlling the gas flow of each component by using a mass flow meter to simulate the components of flue gas, wherein the total gas flow is 1L/min, and the initial Hg is0The concentration was 500. + -. 5. mu.g/m 3, and the reaction temperature was 175 ℃. Pure N2Hg in 1h under atmosphere0The removal rate was 28.5%.
Comparative example 3
Weighing the magnetic renewable demercuration agent obtained in example 1, placing the weighed agent in a simulated fixed bed reactor, and generating elemental mercury through a mercury permeation tube to ensure thatThe real-time measurement of the mercury concentration is carried out by using an RA-915 mercury detector, the mass flow meter accurately controls the gas flow of each component to simulate the components of the flue gas, the total gas flow is 1L/min, and the initial Hg is0The concentration was 1000. + -. 1. mu.g/m 3, the reaction temperature was 250 ℃. Pure N2Hg in 1h under atmosphere0The removal rate was 10.2%.
The above embodiments are illustrative of the present invention, and are not intended to limit the present invention, and any modifications of the present invention are possible and fall within the scope of the present invention.

Claims (10)

1. A preparation method of a magnetic renewable mercury removing agent is characterized by comprising the following steps: the method comprises the following steps: roasting the natural pyrite object under the protective atmosphere to obtain a roasted product, mixing the roasted product with copper chloride to obtain a mixture, and mechanically grinding, activating, drying and screening the mixture to obtain the magnetic renewable mercury removing agent.
2. The preparation method of the magnetic renewable mercury removing agent according to claim 1, characterized in that: the natural sulfur-iron ore is firstly crushed, dried and screened, and then the screened natural iron ore is roasted, wherein the drying temperature is 100-120 ℃, and the drying time is 0.5-2 h.
3. The preparation method of the magnetic renewable mercury removing agent according to claim 1, characterized in that: the natural pyrite mineral comprises iron with a mass fraction of more than or equal to 15% and sulfur with a mass fraction of more than or equal to 10%, and is selected from at least one of pyrite, pyrrhotite, pentlandite and pyrrhotite.
4. The preparation method of the magnetic renewable mercury removing agent according to claim 1, characterized in that: the protective atmosphere is selected from nitrogen atmosphere, the roasting temperature is 550-750 ℃, and the roasting time is 20-180 min.
5. The preparation method of the magnetic renewable mercury removing agent according to claim 1, characterized in that: the mass ratio of the roasted product to the copper chloride is 1-10: 1-3.
6. The preparation method of the magnetic renewable mercury removing agent according to claim 1, characterized in that: the temperature of the mechanical grinding activation is 25-90 ℃, the time is 5-30min, the drying temperature is 60-180 ℃, and the drying time is 2-12 h.
7. Use of a magnetic regenerable mercury removing agent prepared according to the preparation method of any one of claims 1 to 6, wherein: the magnetic renewable mercury removal agent is applied to the mercury purification and removal of mercury-containing flue gas or mercury-containing wastewater.
8. The application of the magnetic renewable demercuration agent according to claim 7, wherein the application process comprises the steps of contacting the magnetic renewable demercuration agent with mercury-containing flue gas or placing the magnetic renewable demercuration agent in mercury-containing wastewater, performing demercuration reaction, performing magnetic separation, collecting the demercuration agent loaded with mercury in a centralized manner, performing thermal treatment to desorb mercury to obtain pure mercury and recover the demercuration agent, mixing the recovered demercuration agent with copper chloride, and finally performing grinding and activation to obtain the regenerated magnetic renewable demercuration agent.
9. Use of a magnetic regenerable mercury removing agent according to claim 7, wherein: the temperature of the demercuration reaction is 5-220 ℃.
10. Use of a magnetic regenerable mercury removing agent according to claim 7, wherein: the temperature for desorbing mercury by heat treatment is 250-550 ℃, and the time for desorbing mercury by heat treatment is 30-120 min.
CN202110969036.0A 2021-08-23 2021-08-23 Preparation method and application of magnetic renewable mercury removing agent Active CN113769701B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110969036.0A CN113769701B (en) 2021-08-23 2021-08-23 Preparation method and application of magnetic renewable mercury removing agent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110969036.0A CN113769701B (en) 2021-08-23 2021-08-23 Preparation method and application of magnetic renewable mercury removing agent

Publications (2)

Publication Number Publication Date
CN113769701A true CN113769701A (en) 2021-12-10
CN113769701B CN113769701B (en) 2022-07-19

Family

ID=78838909

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110969036.0A Active CN113769701B (en) 2021-08-23 2021-08-23 Preparation method and application of magnetic renewable mercury removing agent

Country Status (1)

Country Link
CN (1) CN113769701B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114733344A (en) * 2022-05-05 2022-07-12 中南大学 Flue gas mercury circulating capture method and system

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114733344A (en) * 2022-05-05 2022-07-12 中南大学 Flue gas mercury circulating capture method and system

Also Published As

Publication number Publication date
CN113769701B (en) 2022-07-19

Similar Documents

Publication Publication Date Title
Quan et al. Study on the regenerable sulfur-resistant sorbent for mercury removal from nonferrous metal smelting flue gas
Li et al. Sulfur abundant S/FeS2 for efficient removal of mercury from coal-fired power plants
Liu et al. Recyclable CuS sorbent with large mercury adsorption capacity in the presence of SO2 from non-ferrous metal smelting flue gas
Shan et al. Preparation of microwave-activated magnetic bio-char adsorbent and study on removal of elemental mercury from flue gas
CN100340683C (en) Sorbents and methods for the removal of mercury from combustion gases
Yang et al. Development of selenized magnetite (Fe3O4− xSey) as an efficient and recyclable trap for elemental mercury sequestration from coal combustion flue gas
CN111330427A (en) Application of metal sulfide mercury removal agent in washing and removing mercury in flue gas
CN109012091B (en) Synergistic removal of Hg in flue gas0And Hg in the waste liquid2+Method (2)
Yang et al. Recyclable chalcopyrite sorbent for mercury removal from coal combustion flue gas
Zhang et al. Mercury oxidation and adsorption characteristics of potassium permanganate modified lignite semi-coke
CN103285711B (en) Method for purifying and recovering mercury in off gas
Liu et al. Co-doped ZnS with large adsorption capacity for recovering Hg 0 from non-ferrous metal smelting gas as a co-benefit of electrostatic demisters
CN103920461A (en) Magnetic biochar quantum dot composite adsorbent as well as preparation method and using method thereof
CN113769701B (en) Preparation method and application of magnetic renewable mercury removing agent
Wan et al. Removal of mercury from flue gas using coal gasification slag
Zhou et al. Template synthesis of sulfur-doped mesoporous carbon for efficiently removing gas-phase elemental mercury from flue gas
CN111266079A (en) Blast furnace gas dechlorination and dehumidification agent and preparation and use methods thereof
Pang et al. Selective uptake of gaseous sulfur trioxide and mercury in ZnO-CuS composite at elevated temperatures from SO2-rich flue gas
CN115715973A (en) In-situ nano-selenium carbon-based demercuration adsorption material and preparation method and application thereof
CN114835142B (en) Method for recovering carbon dioxide from industrial kiln tail gas and producing lithium carbonate
Zhou et al. Adsorption, regeneration and kinetic of gas phase elemental mercury capture on sulfur incorporated porous carbon synthesized by template method under simulated coal-fired flue gas
CN112403186A (en) Method for cooperatively treating multi-pollutant flue gas and recovering ammonium ferrous sulfite
CN111054297A (en) Preparation of manganese ferrite/porous graphite phase carbon nitride and method for treating low-concentration uranium-containing wastewater
CN110115975A (en) Modified carbon nitride adsorbent of a kind of manganese oxide and the preparation method and application thereof
Lin et al. Carbon dioxide sequestration by industrial wastes through mineral carbonation: Current status and perspectives

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