CN109248549B - Method for washing and removing elemental mercury in mercury-containing gas by using superfine nano sulfur solution - Google Patents

Method for washing and removing elemental mercury in mercury-containing gas by using superfine nano sulfur solution Download PDF

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CN109248549B
CN109248549B CN201811347443.2A CN201811347443A CN109248549B CN 109248549 B CN109248549 B CN 109248549B CN 201811347443 A CN201811347443 A CN 201811347443A CN 109248549 B CN109248549 B CN 109248549B
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mercury
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sulfur
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CN109248549A (en
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刘恢
颜旭
谢小峰
陈昊
陈志军
杨姝
刘操
柴立元
杨志辉
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Central South University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/64—Heavy metals or compounds thereof, e.g. mercury
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    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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Abstract

The invention discloses a method for washing and removing simple substance mercury in mercury-containing gas by using superfine nano sulfur solution, which is to wash and remove mercury-containing gas0Gas and ultra-fine nano-meterThe sulfur solution is subjected to gas-liquid mixing reaction to remove Hg0Elemental mercury in the gas; the method has the characteristics of simple process, low price and environmental protection, and can realize the high-efficiency purification of the elemental mercury.

Description

Method for washing and removing elemental mercury in mercury-containing gas by using superfine nano sulfur solution
Technical Field
The invention relates to a treatment method of mercury-containing gas, in particular to a method for removing simple substance mercury in mercury-containing gas by using a superfine nano sulfur solution wet washing method, and belongs to the technical field of mercury vapor pollution control and emission reduction.
Background
Mercury is a highly toxic pollutant, and a series of environmental and health problems caused by mercury have become one of global concerns. Therefore, the twentieth conference of the twelfth congress Committee of the representative of the people in China, which is determined by the 10 th and 10 th annual meeting in 2016, approves the water guarantee grant about mercury signed by the bear in the 10 th and 10 th days in 2013, and the 16 th day in 2017 has been officially validated, a series of measures aiming at controlling the mercury pollution and reducing the emission are synchronously implemented, and the pollution control and the emission reduction of the mercury-containing flue gas are promoted to be climax.
The sulfur and mercury have interaction, and can react with mercury in mercury-containing gas to generate stable mercury sulfide, so the sulfur is regarded as a good mercury capture agent. However, since sulfur has a low mercury capture rate at low temperature, sulfur is often used for treating high-temperature mercury-containing flue gas, for example, chinese patent CN201510210205.7 discloses a method for purifying mercury in high-temperature flue gas by pre-adsorbing elemental sulfur on the particle surface and in part of microporous pores of fly ash. However, sulfur is volatile at high temperature, which seriously affects the stability of the material for catching mercury and even causes adverse effect on rear-end procedures and equipment. Therefore, wet scrubbing is a more suitable way for efficient mercury capture by sulfur materials. However, the sulfur has poor hydrophilicity and poor dispersibility in an aqueous solution, so that the sulfur has poor capability of trapping elemental mercury in a washing process, low mercury removal efficiency and small mercury trapping capacity. Thus, the use of sulfur to trap elemental mercury in gases has been limited.
Disclosure of Invention
In order to solve the problems of poor capture capacity, small adsorption capacity, low mercury removal efficiency and the like of the sulfur on gaseous mercury caused by poor hydrophilicity and dispersibility of the sulfur, the method has the characteristics of simple process, low price, environmental friendliness and the like, and can realize high-efficiency purification of the elemental mercury in the flue gas by carrying out nanocrystallization on the sulfur particles to improve the hydrophilicity and the dispersibility of the sulfur in an aqueous solution, simultaneously improve the activity of the sulfur, improve the surface property of the sulfur particles, improve the complexing reaction capacity of the sulfur particles on the gaseous elemental mercury and realize high-efficiency removal of the elemental mercury in the gas by a wet method.
In order to realize the technical purpose, the invention provides a method for washing and removing simple substance mercury in mercury-containing gas by using an ultrafine nano sulfur solution, which comprises the step of washing and removing Hg-containing gas0Gas and liquid mixed reaction is carried out on the gas and the superfine nano sulfur solution to remove Hg content0Hg in gas0。
The invention adopts the superfine nano sulfur solution as the gaseous mercury cleaning solution, the superfine nano sulfur comprises nano sulfur particles, the surface performance of the nano sulfur particles is improved, the hydrophilicity is better compared with that of common sulfur particles, and the superfine nano sulfur solution has better dispersibility in water, as shown in figure 1, the superfine nano sulfur solution is a transparent solution; the surface activity of the nano sulfur particles is higher than that of the common sulfur particles, and the nano sulfur particles are Hg0High reaction activity and high mercury removing capacity.
In a preferable scheme, the superfine nano sulfur solution is synthesized by a liquid phase method. The nano sulfur particles prepared by the liquid phase method have good hydrophilicity and can be stably and uniformly dispersed in an aqueous solution.
In a more preferable scheme, the superfine nano sulfur solution is prepared by at least one sulfur source of sulfur dioxide, bisulfite or thiosulfate in a liquid phase by adopting an acid induction method.
The preferable scheme is. The acid induction method adopts weak organic acid as an inducer. Compared with the ultrafine nano sulfur solution prepared by inorganic strong acid, the ultrafine nano sulfur solution prepared by adopting organic weak acid as an inducer has more stable demercuration performance.
In a preferable scheme, the superfine nano sulfur solution contains nano sulfur particles with the particle size of not more than 10 nm.
In a preferred embodiment, the Hg content0The gas theoretically includes any Hg-containing gas0Of gas, e.g. pure Hg0Steam, containing Hg0Air, Hg content0Flue gas or Hg0Mixed gas of steam and other inert gases.
In the preferable scheme, the pH value of the superfine nano sulfur solution is controlled within the range of 0.5-3.6; preferably 0.5 to 2. Within the pH range, the reaction efficiency of the elemental mercury and the superfine nano sulfur is improved.
Preferred embodiment, contains Hg0The temperature of the superfine nano sulfur solution is lower than 60 ℃ in the process of gas-liquid mixing reaction of the gas and the superfine nano sulfur solution. When the temperature exceeds 60 ℃, the stability of the superfine nano sulfur solution is deteriorated, and the superfine nano sulfur solution is easy to aggregate into sulfur particles with larger particle size and precipitate.
In the preferred scheme, after the gas-liquid mixing reaction is finished, the solution is heated to more than 60 ℃ to form precipitate, and the sulfur-mercury compound is recovered by solid-liquid separation. The solution is heated to more than 60 ℃, so that the mercury-containing sulfur particles grow up to form precipitate, and the separation and recovery of valuable resources are easy to realize.
The method for removing the elemental mercury in the flue gas by using the superfine nano sulfur solution comprises the following specific processes: will contain Hg0Gas-liquid mixing is carried out on the flue gas and the superfine nano sulfur solution, and the elemental mercury in the flue gas can be efficiently purified by utilizing the strong chemical adsorption effect of the nano sulfur on the mercury; the waste washing liquid can be heated by heating the solutionThe temperature is higher than 60 ℃ to ensure that the sulfur particles containing mercury grow up to form precipitate, and the valuable resources are recovered through solid-liquid separation. The method has the characteristics of simple process, low price and environmental protection, and meets the industrial popularization requirement.
Compared with the prior art, the technical scheme of the invention has the advantages that:
(1) the superfine nano sulfur has good water-soluble hydrophilicity and dispersibility, can realize high-efficiency removal of elemental mercury in flue gas, and the removal rate of the elemental mercury can reach 73.4-89.4%.
(2) The mercury removing agent has excellent acid resistance and has efficient mercury removing performance in an acid environment with the pH range of 0.5-3.6.
(3) The preparation method of the demercuration solution is various, the most appropriate method can be flexibly selected according to the actual application requirement, and the demercuration agent which has the best demercuration under the specific application condition and is low in price can be simply prepared.
(4) The demercuration process does not need to add additional purification equipment and procedures, and can realize the demercuration of the mercury by only adding the nano demercuration solution into a washing device of the existing flue gas purification process, thereby reducing the cost and investment.
(5) The preparation of the demercuration solution and the demercuration process thereof are simple and environment-friendly, have no secondary pollution, and meet the requirements of industrial production.
Drawings
FIG. 1 is a diagram showing the dispersion effect of the ultra-fine nano sulfur solution, the general sulfur solution and the sublimed sulfur solution (on the left, middle and right sides, respectively);
FIG. 2 is a transmission electron microscope image of the ultra-fine nano sulfur.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Example 1
To a solution containing 100ml of Na at a concentration of 0.5 mol/L at room temperature2S2O33ml of saturated sodium dodecyl benzene sulfonate solution added into the solution is continuously used as a dispersing agentUltrasonically stirring, and dropwise adding formic acid to adjust the pH value of the solution to 1.2 to obtain the nano sulfur colloidal solution. At 0.3m3Gas flow rate of/min will gas (Hg)0The concentration is 0.35mg/m3The carrier gas is N2) Hg is added into a bubbling washer which is placed at room temperature and contains 75ml of superfine nano sulfur solution0The removal rate can reach 84.4 percent.
Example 2
To a solution containing 100ml of Na at a concentration of 0.5 mol/L at room temperature2S2O33ml of saturated sodium dodecyl benzene sulfonate solution added into the solution is used as a dispersing agent, ultrasonic stirring is continuously carried out, and concentrated sulfuric acid is dropwise added to adjust the pH value of the solution to 0.5, so that the nano sulfur colloidal solution is obtained. At 0.3m3Gas flow rate of/min will gas (Hg)0The concentration is 0.35mg/m3The carrier gas is N2) Hg is added into a bubbling washer which is placed at room temperature and contains 75ml of superfine nano sulfur solution0The removal rate can reach 79.2 percent.
Example 3
100ml of NaHSO with a concentration of 0.5 mol/L3Heating the solution in water bath at 100 ℃ for 4 hours under the action of selenium, adding 3ml of saturated sodium dodecyl benzene sulfonate solution as a dispersing agent, continuously carrying out ultrasonic stirring, and dropwise adding formic acid to adjust the pH value of the solution to 1.2 to obtain the nano sulfur colloidal solution. At 0.3m3Gas flow rate of/min will gas (Hg)0The concentration is 0.35mg/m3The carrier gas is N2) Hg is added into a bubbling washer which is placed at room temperature and contains 75ml of superfine nano sulfur solution0The removal rate can reach 71.7 percent.
Example 4
To a solution containing 100ml of Na at a concentration of 0.5 mol/L at room temperature2S2O33ml of saturated sodium dodecyl benzene sulfonate solution added into the solution is used as a dispersing agent, ultrasonic stirring is continuously carried out, and concentrated sulfuric acid is dropwise added to adjust the pH value of the solution to 1.2, so that the nano sulfur colloidal solution is obtained. At 0.3m3Gas flow rate of/min will gas (Hg)0The concentration is 0.35mg/m3The carrier gas is N2) Hg in a bubbling scrubber filled with 75ml of ultra-fine nano-sulfur solution at 45 DEG C0Removal rateCan reach 50.9 percent.
Example 5
To a solution containing 100ml of Na at a concentration of 0.5 mol/L at room temperature2S2O33ml of saturated sodium dodecyl benzene sulfonate solution added into the solution is used as a dispersing agent, ultrasonic stirring is continuously carried out, and concentrated sulfuric acid is dropwise added to adjust the pH value of the solution to 1.2, so that the nano sulfur colloidal solution is obtained. At 0.3m3Air flow Rate/min simulated Smoke (Hg) at a temperature of 150 deg.C0The concentration is 1.20mg/m3，O26% of SO20.1% of CO26% of carrier gas is N2) Hg in a bubbling scrubber filled with 75ml of ultra-fine nano-sulfur solution at 45 DEG C0The removal rate can reach 60.9 percent.
Comparative example 1
Adding 1.6g of sublimed sulfur into 100ml of deionized water at room temperature, continuously ultrasonically stirring, and dropwise adding concentrated sulfuric acid to adjust the pH of the solution to 1.2 to obtain a sulfur suspension. At 0.3m3Gas flow rate of/min will gas (Hg)0The concentration is 0.35mg/m3The carrier gas is N2) Hg is added into a bubbling washer which is placed at room temperature and contains 75ml of superfine nano sulfur solution0The removal rate is only 2.7%.
Comparative example 2
To a solution containing 100ml of Na at a concentration of 0.5 mol/L at room temperature2S2O3Concentrated sulfuric acid is directly added into the solution to adjust the pH of the solution to 1.2, and then the general sulfur solution is obtained. At 0.3m3Gas flow rate of/min will gas (Hg)0The concentration is 0.35mg/m3The carrier gas is N2) Hg is added into a bubbling washer which is placed at room temperature and contains 75ml of superfine nano sulfur solution0The removal rate is only 18.7%.
Comparative example 3
To a solution containing 100ml of Na at a concentration of 0.5 mol/L at room temperature2S2O33ml of saturated sodium dodecyl benzene sulfonate solution added into the solution is used as a dispersing agent, ultrasonic stirring is continuously carried out, and concentrated sulfuric acid is dropwise added to adjust the pH value of the solution to 5.0, so that the nano sulfur colloidal solution is obtained. At 0.3m3Min air flowFast-acting gas (Hg)0The concentration is 0.35mg/m3The carrier gas is N2) Hg is added into a bubbling washer which is placed at room temperature and contains 75ml of superfine nano sulfur solution0The removal rate was 5.1%.
Having described preferred and comparative embodiments of the present invention in detail, Table 1 is drawn below to compare the similarities and differences between the examples and comparative examples. It should be noted that the present invention is not limited to the specific details of the above-mentioned embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are included in the protection scope of the present invention.
Table 1 experimental conditions and mercury removal efficiencies of examples 1-5 and comparative examples 1-3.
Figure BDA0001864112000000051
Figure BDA0001864112000000061

Claims (3)

1. A method for washing and removing elemental mercury in mercury-containing gas by using a superfine nano sulfur solution is characterized by comprising the following steps: will contain Hg0Gas-liquid mixing reaction is carried out on the gas and the superfine nano sulfur solution, and Hg in the gas is removed0；
The superfine nano sulfur solution is prepared by at least one sulfur source of sulfur dioxide, bisulfite or thiosulfate by adopting an acid induction method; the acid induction method adopts weak organic acid as an inducer;
the superfine nano sulfur solution contains nano sulfur particles with the particle size not more than 10 nm;
containing Hg0The temperature of the superfine nano sulfur solution is lower than 60 ℃ in the gas-liquid mixed reaction process of the gas and the superfine nano sulfur solution, and the pH value is controlled within the range of 0.5-3.6.
2. The method of claim 1, wherein the washing with the ultra-fine nano sulfur solution is performedThe method for removing the elemental mercury in the mercury-containing gas by washing is characterized by comprising the following steps: said Hg-containing0The gas comprising pure Hg0Steam, containing Hg0Air, Hg content0Flue gas or Hg0Mixed gas of steam and other inert gases.
3. The method for removing elemental mercury from mercury-containing gas by washing with the ultrafine nano sulfur solution according to claim 1, wherein the method comprises the following steps: after the gas-liquid mixing reaction is finished, the solution is heated to more than 60 ℃ to form precipitate, and the sulfur-mercury compound is recovered through solid-liquid separation.
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DE2305522C2 (en) * 1973-02-05 1979-06-28 Preussag Ag Metall, 3380 Goslar Process for the extraction of mercury from roasting gases containing SO2
DE4123907A1 (en) * 1991-07-18 1993-01-21 Gea Wiegand Gmbh Sepn. of mercury@ and/or mercury cpds. from waste - comprises treatment with washing liq. contg. finely divided colloid and polysulphide additive
WO2014062438A2 (en) * 2012-10-16 2014-04-24 Novinda Corporation Solution-based mercury capture
CN106731559B (en) * 2015-11-23 2020-06-23 中国铝业股份有限公司 Mercury-containing flue gas wet-process mercury removal agent and mercury removal method
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