CN114700027B - Supported active sulfur group compound and preparation method and application thereof - Google Patents
Supported active sulfur group compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a supported active sulfur group compound and a preparation method and application thereof. Adding sulfur group elementary substance powder particles such as long-chain or annular inert sulfur powder, selenium powder, tellurium powder and the like into saturated reducing liquid, adding a chemical activator to form uniform slurry, diluting and adjusting the pH value to prepare an active dipping solution, dipping a carrier into the active solution, and drying to obtain the active sulfur group compound. The active sulfur group compound is contacted with elemental mercury in smoke or air to convert the mercury into a stable compound, so that the mercury is cured, removed or enriched. The strong reduction and the chemical excitation destroy and break the long chain or ring structure of the inert simple substance, the active site is fully exposed, and the activation energy of the reaction with mercury is obviously reduced. The mercury saturation adsorption capacity and the adsorption rate are improved by hundreds to thousands of times compared with the traditional sulfur powder, and the applicable temperature window range is obviously enlarged. The preparation process is simple, the cost is low, the demercuration product is environment-friendly and has no secondary pollution, and the method has good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of environmental pollution prevention and control and gas purification, and particularly relates to a supported active sulfur group compound and a preparation method and application thereof.
Background
Mercury has a strong affinity for chalcogens, which can immobilize and convert mercury into mercuric sulfide or mercuric selenide. The ancient process of refining pills is based on this principle. The "Shen Tong Qi", compiled by Wei Beryang in east Han dynasty, has recorded "the flowers and women on the river are very beautiful and the most spiritual, the fire flies, no dust appears, the ghost hides the dragon, the Mozhi exists, the yellow bud is root, the Wang is white, and the Zhu is produced". Here, the very beautiful flowers and girls on the river mean mercury, which is not evaporated when mercury is heated, yellow buds (sulfur powder) are added when mercury is fixed, and red cinnabar (mercuric sulfide) is generated after heating. The "Dan House mirror Source" of the Tang Dynasty book also records saying: lime sulfur, which may be dry mercury. The recipe is like in Yu: "this sulfur is seen as hardware but black, and mercury but red". In daily life, after the thermometer is broken, sulfur powder is generally scattered on mercury to convert the mercury into sulfur mercury (mercuric sulfide) which is not easy to volatilize and has reduced toxicity, and the chemical reaction is also applied.
The industries of smelting, coal-fired power generation, waste incineration, cement production, steel production, natural gas production and the like are main sources of artificial emission of mercury. Mercury has the characteristics of high toxicity, high volatility and easy migration and diffusivity, and serious harm can be caused to human health and ecological environment due to mercury pollution. The property that the sulfur group substances such as mercury, sulfur, selenium and the like have high affinity is applied to convert the mercury in a free state into the sulfur selenide, so that the mercury selenide can be used as a feasible path for controlling mercury pollution. Currently, sulfur-loaded activated carbon, metal sulfoselenide, has been studied for mercury removal. But the demercuration effect of the sulfur-loaded activated carbon is greatly improved compared with that of the conventional activated carbon, but the demercuration capacity is still low, and the cost is high; the synthesis process of the metal sulfoselenide adsorbent is complicated, the precursor is complex, the large-scale production difficulty is high, and the demercuration effect is poor when the temperature is higher than 80 ℃.
Hg (l) + S (S) = HgS (S). DELTA.H (298K) = -58.16KJ/mol the reaction can spontaneously proceed from the thermodynamic perspective, but elemental sulfur and selenium exist in long chain or ring forms, the structure is compact, the agglomeration is realized, the specific surface area is small, the contact chance of active sites on mercury and sulfur group elements is small, the activation energy required by the reaction of mercury and sulfur group elements is large, and the reaction rate of mercury and sulfur group elements is small at normal temperature. The industrial preparation of the mercury sulfide is carried out at high temperature or under the heating condition, and long-chain or annular sulfur group elementary substances are broken under the high temperature condition, so that the mercury reacts with the exposed active sites of the sulfur group elementary substances to generate the mercury sulfide. The saturated adsorption capacity and the adsorption rate of mercury are lower than the amount calculated theoretically by directly adopting sulfur powder or selenium powder and other sulfur group elementary substances as mercury adsorption materials, because the existing forms of most sulfur group elementary substances are inert, the number of the accessible sulfur group active sites is less. The method adopts a microbiological method and a process of simulating the generation of amino acid in a living body to convert selenium to prepare nano active sulfur and nano active selenium with higher specific surface area and more exposed active sites, the nano sulfur and nano selenium have higher mercury removal capacity than a chalcogen elementary substance with a compact structure, but the nano chalcogen elementary substance generally has better mercury removal effect at more than 100 ℃, and the mercury removal temperature window is smaller; the microbial method has low conversion rate and long period, and the process of generating the converted selenium by the amino acid has high cost and difficult acquisition of raw materials, and is not suitable for large-scale application.
Therefore, the method has important significance for simply treating the natural sulfur family simple substance which is easy to obtain and preparing the active sulfur family compound which has large mercury saturation adsorption capacity, high adsorption rate, large applicable temperature window, environmental friendliness, low cost and easy large-scale production.
Disclosure of Invention
In order to overcome the obvious defects of small adsorption capacity, low adsorption rate, high cost, complex preparation, small temperature window and the like of the conventional sulfur-based mercury adsorption material, the invention provides a load type active sulfur-based compound with large adsorption capacity and large demercuration temperature window, and a preparation method and application thereof.
The technical scheme of the invention is as follows:
the invention discloses a preparation method of a supported active sulfur group compound, which comprises the following steps:
mixing the sulfur family powder treated by acid with a solution containing a solid reducing agent or a liquid reducing agent, stirring for the first time to form a pasty material, then adding a solid chemical exciting agent into the pasty material, stirring for the second time to form slurry, then adding a diluent into the slurry, adjusting the pH to 8-13, aging to obtain an active impregnation solution, then impregnating a carrier into the active impregnation solution, reacting, and carrying out solid-liquid separation to obtain an active sulfur family compound;
the solid chemical activator is one or more of hydroxides, carbonates and bicarbonates of potassium, sodium, calcium and magnesium.
The preparation method comprises the steps of firstly carrying out acid pretreatment on the chalcogenide powder, cleaning and simultaneously improving the specific surface area, then reacting the chalcogenide powder with a reducing agent and a solid chemical activator in sequence to break the long chain or ring structure of the chalcogenide powder, reacting to form low-valence chalcogenide and short-chain active simple substance chalcogenide, then adding a diluent, aging to enable the reaction to be more thorough, and simultaneously enabling the chalcogenide active substance formed through the reaction to be uniformly dispersed on the surface of a carrier.
According to the preparation method, the obtained active sulfur group compound has the synergistic effect of the low-valence sulfur group substance and the short-chain active simple substance sulfur group element, so that the applicable demercuration temperature window is remarkably increased, and the active sulfur group compound has a very good adsorption effect when the temperature is as low as room temperature and is as high as more than 150 ℃.
Of course, the invention can also adjust the forming proportion of the low-valence sulfur group substance and the short-chain active simple substance sulfur group element, so that the sulfur group element has better adsorption performance at a certain temperature.
Preferably, the chalcogen powder is soaked in an acid solution for 3-12h, washed, dried, crushed and ground, and sieved by a 200-mesh sieve, and the sieved substance is taken out to obtain the acid-treated chalcogen powder.
Further preferably, the washing process is to rinse 3 times by turns with deionized water and ethanol.
Further preferably, the drying temperature is 80-120 ℃.
Preferably, the chalcogenide powder is selected from one or a combination of several of sulfur powder, selenium powder, tellurium powder, natural minerals containing sulfur, selenium and tellurium simple substances or industrial products.
Further preferably, the chalcogenide powder is selected from sulfur powder or selenium powder.
In the invention, the selected sulfur group powder simple substance comprises crystalline state and amorphous state, the sulfur group powder simple substance comprises nanometer size and non-nanometer size, and the sulfur group natural mineral has the simple substance content higher than 70%.
Preferably, the solution containing the solid reducing agent is prepared by dissolving a supersaturated amount of the solid reducing agent in an aqueous solution, and the solid reducing agent is selected from one of stannous chloride, sodium hydrosulfite, sodium borohydride, potassium borohydride and thiourea dioxide; preferably one of sodium borohydride, stannous chloride and thiourea dioxide,
the liquid reducing agent is selected from one of sulfinic acid, sulfurous acid and diammonium, and is preferably diammonium.
Preferably, the solid-liquid mass volume ratio of the chalcogenide powder to the solution containing the solid reducing agent is 0.1-2g:1mL; the solid-liquid mass volume ratio of the sulfur family powder to the liquid reducing agent is 0.1-2g:1mL.
Further preferably, the solid-liquid mass volume ratio of the chalcogenide powder to the solution containing the solid reducing agent is 0.2-0.8g:1mL; the solid-liquid mass volume ratio of the sulfur family powder to the liquid reducing agent is 0.3-1g:1mL.
Still more preferably, the solid-liquid mass volume ratio of the chalcogenide powder to the solution containing the solid reducing agent is 0.3 to 0.6g:1mL; the solid-liquid mass volume ratio of the chalcogenide powder to the liquid reducing agent is 0.3-0.6g:1mL.
More preferably, the solid-liquid mass volume ratio of the chalcogenide powder to the solution containing the solid reducing agent is 0.5-0.8g:1mL; the solid-liquid mass volume ratio of the chalcogenide powder to the liquid reducing agent is 0.5-0.8g:1mL.
Preferably, the time of the first stirring is 10-60min, and the temperature of the first stirring is 25-60 ℃. Temperature was provided by a thermostatic water bath.
Preferably, the solid-liquid mass volume ratio of the solid chemical excitant to the solution containing the solid reducing agent is 0.1-2g:1mL, wherein the solid-liquid mass volume ratio of the solution of the solid chemical excitant to the solution of the liquid reducing agent is 0.1-4g:1mL.
Further preferably, the solid-liquid mass volume ratio of the solid chemical excitant to the solution containing the solid reducing agent is 0.15-1g:1mL, wherein the solid-liquid mass volume ratio of the solution of the solid chemical excitant to the solution of the liquid reducing agent is 0.2-1.5g:1mL.
Still more preferably, the solid-liquid mass volume ratio of the solid chemical activator to the solution containing the solid reducing agent is 0.6-1g:1mL, wherein the solid-liquid mass volume ratio of the solution of the solid chemical excitant to the solution of the liquid reducing agent is 0.6-1g:1mL.
Still more preferably, the solid-liquid mass volume ratio of the solid chemical activator to the solution containing the solid reducing agent is 0.15-0.4g:1mL, wherein the solid-liquid mass volume ratio of the solution of the solid chemical excitant to the solution of the liquid reducing agent is 0.15-0.4g:1mL.
The inventors found that when the solid-liquid mass-to-volume ratio of the chalcogen powder to the solution containing the solid reducing agent or the liquid reducing agent (reducing agent) is controlled to be 0.3 to 0.6g:1mL, and the solid-liquid mass volume ratio of the solid chemical excitant to the reducing agent is 0.6-1g:1mL of the adsorbent still has a very excellent adsorption effect at a very low temperature of 25 to 75 ℃.
When the solid-liquid mass volume ratio of the sulfur family powder to the solution containing the solid reducing agent or the liquid reducing agent (reducing agent) is controlled to be 0.5-0.8g:1mL, and the solid-liquid mass volume ratio of the solid chemical exciting agent to the reducing agent is 0.15-0.4g: when the volume is 1mL, the adsorption effect is still very excellent at a high temperature of more than 100 ℃.
Preferably, the time of the second stirring is 10-120min, and the temperature of the second stirring is 25-60 ℃.
Preferably, the volume ratio of the slurry to the diluent is 1.
In the actual operation process, the diluent is prepared according to the pH value of the slurry, can be water, or is prepared by adding an acid-base pH regulator into water, and finally the pH value of the active impregnation solution is controlled to be 8-13, although the pH value of the active impregnation solution needs to be effectively controlled, if the pH value is too high, the reaction speed is too high, and finally agglomeration on the surface of the carrier is caused, so that the performance is influenced.
Preferably, the aging time is 1 to 3 hours.
Preferably, the carrier is selected from one of activated carbon, molecular sieve, zirconia, alumina, zeolite, silicon carbide, kaolin, red mud, metal organic framework material, sponge and organic polymer fiber.
Preferably, the mass ratio of the chalcogen powder to the carrier is 0.005 to 0.3, preferably 0.02 to 0.1.
Preferably, the reaction is carried out with continuous shaking for 3-24h.
After the reaction is finished, centrifugal separation or direct two-phase separation is carried out, the mixture is taken out, washed by deionized water for 1 to 3 times and dried for 3 to 18 hours at the temperature of between 80 and 125 ℃, and the active sulfur family compound is obtained.
The invention also provides the supported active sulfur group compound prepared by the preparation method.
The invention also provides application of the supported active sulfur group compound prepared by the preparation method, and the supported active sulfur group compound is used for removing elemental mercury in flue gas or adsorbing leaked liquid elemental mercury.
In the practical application process, the supported active sulfur group compound provided by the invention can be used in the processes of removing, enriching and recovering elemental mercury in flue gas in the industries of smelting, coal-fired power generation, waste incineration, cement production, steel production, natural gas production and the like; and the method can also be used for treating the leakage process of the liquid elemental mercury. The load type active sulfur group compound is contacted with flue gas or elemental mercury released into the air to convert the mercury into a stable compound, so that the solidification, removal and enrichment of the mercury are realized; the load type active sulfur group compound can be directly sprayed to any position in a flue, a demercuration tower, a fluidized bed or a wet flue gas purification system; or used at the outlet of a fixed bed system or a flue, or directly contacted with leaked liquid elemental mercury beads.
Principles and advantages
According to the invention, the long chain or ring structure of sulfur group elementary substance powder particles such as inert sulfur powder, selenium powder, tellurium powder and the like is broken and fractured through strong reduction and chemical excitation, active sites are fully exposed, the number of accessible active sites is remarkably increased, the active sites are uniformly loaded on a carrier, the active sites are fully dispersed, the agglomeration phenomenon is avoided, the opportunity of contact of mercury and the active sites is increased, and the migration and diffusion of mercury on the surface of a material are promoted under the synergistic effect of the sulfur group active sites and metal sites improved by a chemical exciting agent. The energy barrier required by the fracture of a long chain or ring structure is overcome when sulfur group elementary substance powder particles react with mercury, the chemical activation energy of the reaction with mercury is obviously reduced, and the active sulfur group compound can react with mercury at a lower temperature.
Partial low-valence sulfur group substances are generated on the active sulfur group compound, the low-valence sulfur group substances and short-chain active elemental sulfur group elements are in synergistic action, the applicable demercuration temperature window is remarkably increased, and the compound material suitable for various temperature conditions is prepared by adjusting the proportion of sulfur group elemental powder particles, a strong reducing agent and a chemical exciting agent and the proportion of active sites on the adjustable active sulfur group compound such as constant temperature, pH value, carrier loading capacity and the like, so that the application temperature range of the metal sulfur selenide and the nanometer sulfur group elemental sulfur is comprehensively covered. The active sulfur group compound contacts with elemental mercury in smoke or air to convert the mercury into a stable sulfur group mercury compound, so that the mercury is solidified, removed or enriched, and meanwhile, mercury adsorbed on the surface of the active sulfur group compound adsorbent can form a mercury active site to promote the subsequent conversion and adsorption of the mercury.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) Compared with the traditional sulfur group elemental sulfur powder and sulfur-loaded active carbon, the mercury saturation adsorption capacity and the adsorption rate of the loaded active sulfur group compound are greatly improved by hundreds or even thousands of times.
(2) Overcomes the defects of complex synthesis process, complex precursor, difficult large-scale synthesis and serious secondary pollution of the metal sulfoselenide and the load material thereof.
(3) The application temperature window is large, the environment is friendly, and no secondary pollution is generated.
(4) The synthesis is fast and efficient, the operation is simple, the raw material source is wide, the cost is low, and the large-scale production is easy.
(5) Water-proof and SO-proof 2 Excellent performance and high chemical stability.
Drawings
FIG. 1 is a graph of the mercury removal effect of the supported active chalcogenides obtained in example 1 at different temperatures.
Figure 2 XRD pattern of the supported active chalcogenide compound obtained in example 2.
Detailed Description
The technical solution of the present invention will be described in detail with reference to examples.
Example 1
Soaking industrial selenium powder (with purity of 98%) in dilute acid solution for 5h, rinsing with deionized water and ethanol in turn for 3 times, drying at 100 deg.C, crushing, grinding, sieving with 200 mesh sieve, and collecting undersize; preparing saturated reducing solution of sodium borohydride, dropwise adding the reducing solution onto the industrial selenium powder subjected to surface treatment according to the proportion of 0.4g/mL, fully wetting, uniformly mixing, continuously stirring for 30min in constant-temperature water bath at 30 ℃ until the mixture is pasty, continuously adding a sodium carbonate excitant according to the proportion of 0.7g/mL, and stirring for 60min to form uniform slurry; adding a large amount of acidic diluent into the slurry according to a volume ratio of 1; commercial activated carbon (with the mass ratio of 0.05g/g to industrial selenium powder) purchased is dipped into the active dipping solution, continuously shaken for 12h, centrifugally separated, washed with deionized water for 2 times, and dried at 100 ℃ for 8h to obtain the activated carbon-supported activated chalcogenide compound 1.
Weighing 10mg of the activated carbon loaded activated sulfur group compound 1, placing the activated carbon loaded activated sulfur group compound 1 in a simulation fixed bed reactor, generating elemental mercury through a mercury permeation tube, carrying out real-time measurement on mercury concentration by using a VM-3000 mercury photometer, 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 is 1L/min 0 The concentration is 1000 +/-5 mu g/m 3 . Pure N 2 Under the atmosphere, the demercuration efficiency is higher than 96.5% at 50-150 ℃, which shows that the active sulfur group compound has excellent demercuration effect in a wide temperature range; pure N 2 The saturated demercuration capacity is 48.5mg/g under the atmosphere.
Weighing 25mg of the activated carbon-loaded activated sulfur group compound 1 prepared in the embodiment 1, placing the activated carbon-loaded activated sulfur group compound 1 in a simulated flue gas washing and purifying reactor, generating elemental mercury through a mercury permeation tube, performing real-time measurement of mercury concentration by using a VM-3000 mercury photometer, 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 is 1L/min 0 The concentration is 200 +/-1 mu g/m 3 . Pure N 2 Under the atmosphere, the demercuration efficiency of the washing liquid is higher than 96.2% within the pH range of 1-9.
Mercury leakage treatment after the simulated thermometer is broken, the activated carbon loaded activated sulfur family compound 1 prepared in the example 1 is scattered on mercury beads, and Hg is obtained when the adding amount of the activated carbon loaded activated sulfur family compound 1 reaches 18mg 0 The volatilization rate continued to drop to about 0.1. Mu.g-min -1 。
Example 2
Soaking medicinal selenium powder (with purity of 99.9%) in dilute acid solution for 3h, rinsing with deionized water and ethanol for 3 times in turn, drying at 100 deg.C, crushing, grinding, sieving with 200 mesh sieve, and collecting undersize; dropwise adding the reducing solution onto the surface-treated industrial selenium powder according to the proportion of 0.32g/mL, fully wetting, uniformly mixing, continuously stirring in a constant-temperature water bath at 45 ℃ for 10min to obtain a paste, continuously adding a sodium hydroxide exciting agent according to the proportion of 0.2g/mL, and stirring for 20min to obtain uniform slurry; adding a large amount of acidic diluent into the slurry according to a volume ratio of 1; soaking sponge (0.03 g/g of industrial selenium powder) into the active soaking solution, continuously shaking for 6h, separating two phases, washing with deionized water for 2 times, and drying at 110 ℃ for 6h to obtain the sponge-loaded active chalcogenide compound 1.
Weighing 36.2mg of sponge-loaded active sulfur group compound 1, placing the compound in a simulated fixed bed reactor, generating elemental mercury through a mercury permeation tube, carrying out real-time measurement on mercury concentration by using a VM-3000 mercury photometer, 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 is 0 The concentration is 1200 +/-5 mu g/m 3 . Pure N 2 Under the atmosphere, the demercuration efficiency is higher than 99% within 6 h; pure N 2 Under the atmosphere, the saturated demercuration capacity is 58.52mg/g, and the saturated demercuration capacity of the unit activated chalcogenide selenide loaded with the active chalcogenide compound is calculated to be 1316.7mg/g.
Example 3
Soaking industrial sulfur powder (with purity of 98%) in dilute acid solution for 8h, rinsing with deionized water and ethanol for 3 times in turn, drying at 90 ℃, crushing and grinding, sieving with a 200-mesh sieve, and taking undersize; preparing saturated reducing liquid of stannous chloride, dropwise adding the reducing liquid onto the sulfur powder subjected to surface treatment according to the proportion of 1g/mL, fully wetting, uniformly mixing, continuously stirring in a constant-temperature water bath at 30 ℃ for 20min to be pasty, continuously adding a potassium hydroxide excitant according to the proportion of 0.8g/mL, and stirring for 20min to form uniform slurry; adding a large amount of acidic diluent into the slurry according to the volume ratio of 1; and (2) dipping the ZSM-5 molecular sieve (with the mass ratio of 0.1g/g to sulfur powder) into an active dipping solution, continuously shaking for 8h, centrifugally separating, washing for 2 times by deionized water, and drying for 9h at 110 ℃ to obtain the ZSM-5 molecular sieve loaded active sulfur family compound 1.
Weighing 100mg of ZSM-5 molecular sieve loaded active sulfur group compound1 injection volume of 1m 3 In the pilot-scale injection tower, elemental mercury is generated by a mercury generating device, the mercury concentration is measured in real time by using a VM-3000 mercury measuring instrument, and the gas flow and the Hg are controlled by a flue gas flow valve 0 Has an initial concentration of 125. Mu.g/m 3 Flue gas flow of 0.8m 3 Min, pure N 2 Hg under an atmosphere 0 The removal rate was 99.2%.
Example 4
Soaking amorphous selenium powder (purity 80%) in dilute acid solution for 8h, rinsing with deionized water and ethanol in turn for 3 times, drying at 100 deg.C, crushing, grinding, sieving with 200 mesh sieve, and collecting undersize; dropwise adding the reducing solution onto the surface-treated sulfur powder according to the proportion of 0.2g/mL, fully wetting and uniformly mixing, continuously stirring for 20min in a constant-temperature water bath at 30 ℃ to form a paste, continuously adding a sodium hydroxide exciting agent according to the proportion of 0.6g/mL, and stirring for 30min to form uniform slurry; adding a large amount of acidic diluent into the slurry according to a volume ratio of 1; dipping the alumina pellets (amorphous selenium powder in a mass ratio of 0.02 g/g) into an active dipping solution, continuously shaking for 12h, centrifugally separating, washing with deionized water for 2 times, and drying at 110 ℃ for 9h to obtain the alumina pellet-loaded active chalcogenide compound 1.
Weighing 25mg of alumina pellet loaded active sulfur group compound 1, placing the compound in a simulation fixed bed reactor, generating elemental mercury through a mercury permeation tube, carrying out real-time measurement on mercury concentration by using a VM-3000 mercury photometer, accurately controlling gas flow of each component by a mass flow meter to simulate components of flue gas, wherein the total gas flow is 1L/min, and the initial Hg is 0 The concentration is 100 +/-1 mu g/m 3 . Pure N 2 Under the atmosphere, the demercuration efficiency is higher than 99.3% at 100 ℃; n is a radical of hydrogen 2 +1000ppm SO 2 Hg under an atmosphere 0 The removal rate is 99.2%; n is a radical of 2 +8％H 2 O+1000ppm SO 2 Hg under an atmosphere 0 The removal rate is 96.8%; n is a radical of hydrogen 2 +10％SO 2 Hg under an atmosphere 0 The removal rate was 98.8%.
Example 5
Soaking medicine sulfur powder (purity 99.9%) in dilute acid solution for 5h, rinsing with deionized water and ethanol for 3 times in turn, drying at 110 deg.C, crushing, grinding, sieving with 200 mesh sieve, and collecting undersize; preparing saturated reducing solution of thiourea dioxide, dripping the reducing solution onto the sulfur powder subjected to surface treatment according to the proportion of 0.4g/mL, fully wetting, uniformly mixing, continuously stirring in a thermostatic water bath at 30 ℃ for 30min to be pasty, continuously adding a sodium hydroxide excitant according to the proportion of 0.8g/mL, and stirring for 20min to form uniform slurry; adding a large amount of acidic diluent into the slurry according to a volume ratio of 1; soaking zirconium oxide (0.12 g/g of chemical sulfur powder) into the active soaking solution, continuously shaking for 12h, centrifuging, washing with deionized water for 2 times, and drying at 110 ℃ for 10h to obtain the zirconium oxide loaded active sulfur family compound 1.
Weighing 40mg of zirconium oxide loaded active sulfur group compound 1, placing the zirconium oxide loaded active sulfur group compound in a simulation fixed bed reactor, generating elemental mercury through a mercury permeation tube, performing real-time measurement of mercury concentration by using a VM-3000 mercury measuring instrument, accurately controlling gas flow of each component by using a mass flow meter to simulate components of flue gas, wherein the total gas flow is 1L/min, and the initial Hg is 0 The concentration is 600 +/-5 mu g/m 3 . Pure N 2 The demercuration efficiency at 25 ℃ under the atmosphere is 100 percent.
Example 6
Soaking medicine sulfur powder (with purity of 99.9%) in dilute acid solution for 5h, rinsing with deionized water and ethanol in turn for 3 times, drying at 110 deg.C, crushing, grinding, sieving with 200 mesh sieve, and collecting undersize; preparing thiourea dioxide saturated reducing solution, dripping the reducing solution onto the sulfur powder subjected to surface treatment according to the proportion of 0.6g/mL, fully wetting and uniformly mixing, continuously stirring for 30min in constant-temperature water bath at 30 ℃ until the mixture is pasty, continuously adding a sodium hydroxide excitant according to the proportion of 0.2g/mL, and stirring for 20min to form uniform slurry; adding a large amount of acidic diluent into the slurry according to the volume ratio of 1; soaking zirconium oxide (0.12 g/g of chemical sulfur powder) in the active soaking solution, continuously shaking for 12h, centrifuging, washing with deionized water for 2 times, and drying at 110 deg.C for 10h to obtain zirconium oxide loaded active sulfur family compound 2.
Weighing 40mg of zirconium oxide loaded active sulfur group compound 1, placing the zirconium oxide loaded active sulfur group compound in a simulation fixed bed reactor, generating elemental mercury through a mercury permeation tube, performing real-time measurement of mercury concentration by using a VM-3000 mercury measuring instrument, accurately controlling gas flow of each component by using a mass flow meter to simulate components of flue gas, wherein the total gas flow is 1L/min, and the initial Hg is 0 The concentration is 600 +/-5 mu g/m 3 . Pure N 2 Under the atmosphere, the demercuration efficiency at 125 ℃ is 100 percent.
Comparative example 1
Weighing 10mg of purchased commercial activated carbon, placing the commercial activated carbon in a simulated fixed bed reactor, generating elemental mercury through a mercury penetration tube, carrying out real-time measurement on mercury concentration by using a VM-3000 mercury photometer, 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 is 0 The concentration is 1000 +/-5 mu g/m 3 . Pure N 2 The saturated demercuration capacity under the atmosphere is 0.13mg/g.
Weighing 10mg of sulfur-loaded activated carbon, placing the sulfur-loaded activated carbon in a simulated fixed bed reactor, generating elemental mercury through a mercury penetration tube, measuring the mercury concentration in real time by using a VM-3000 mercury photometer, 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 is 0 The concentration is 1000 +/-5 mu g/m 3 . Pure N 2 The saturated demercuration capacity is 0.45mg/g under the atmosphere.
Weighing 10mg of industrial selenium powder in a simulated fixed bed reactor, generating elemental mercury through a mercury permeation tube, measuring the mercury concentration in real time by using a VM-3000 mercury photometer, accurately controlling the gas flow of each component by a mass flow meter to simulate the components of flue gas, wherein the total gas flow is 1L/min, and the initial Hg is 0 The concentration is 1000 +/-5 mu g/m 3 . Pure N 2 The saturated demercuration capacity under the atmosphere is 3.16mg/g.
Comparative example 2
Weighing 50mg of sulfur powder in a simulated fixed bed reactor, generating elemental mercury through a mercury permeation tube, carrying out real-time measurement on mercury concentration by using a VM-3000 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 is 0 The concentration is 2000 +/-5 mu g/m 3 . Pure N 2 The saturated demercuration capacity is 2.01mg/g under the atmosphere and at normal temperature.
Mercury leakage treatment is carried out after the simulated thermometer is broken, sulfur powder is scattered on mercury beads, and Hg is generated when the adding amount of the activated carbon loaded active sulfur family compound 1 reaches 60mg 0 The volatilization rate is about 0.8 mu g min -1 ；Hg 0 The reduction value of the volatilization rate is about 0.1 mu g min -1 The dosage of the sulfur powder is 230mg, which is 12.7 times of the dosage of the activated carbon loaded activated sulfur family compound 1 in the example 1.
Comparative example 3
Soaking industrial selenium powder (with purity of 98%) in dilute acid solution for 5h, rinsing with deionized water and ethanol in turn for 3 times, drying at 100 deg.C, crushing, grinding, sieving with 200 mesh sieve, and collecting undersize; preparing saturated reducing solution of sodium borohydride, dropwise adding the saturated reducing solution onto the industrial selenium powder subjected to surface treatment according to the proportion of 0.4g/mL, fully wetting, uniformly mixing, and continuously stirring for 30min in constant-temperature water bath at 30 ℃ until the saturated reducing solution is pasty; adding a large amount of acidic diluent into the slurry according to a volume ratio of 1; commercially available activated carbon (in a mass ratio of 0.05g/g to industrial selenium powder) was immersed in the active impregnation solution, continuously shaken for 12 hours, centrifuged, washed 2 times with deionized water, and dried at 100 ℃ for 8 hours to obtain complex 2.
Weighing 10mg of the compound 2, placing the compound in a simulated fixed bed reactor, generating elemental mercury through a mercury permeation tube, carrying out real-time measurement on mercury concentration by using a VM-3000 mercury photometer, 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 is 0 The concentration is 1000 +/-5 mu g/m 3 . Pure N 2 Under the atmosphere, the demercuration efficiency at 100 ℃ is 36.3 percent.
Comparative example 4
Soaking industrial sulfur powder (with purity of 98%) in dilute acid solution for 8h, rinsing with deionized water and ethanol for 3 times in turn, drying at 90 ℃, crushing and grinding, sieving with a 200-mesh sieve, and taking undersize; dropwise adding deionized water onto the surface-treated sulfur powder in a ratio of 1g/mL, fully wetting, uniformly mixing, continuously stirring in a constant-temperature water bath at 30 ℃ for 20min to obtain a paste, continuously adding a potassium hydroxide activator in a ratio of 0.8g/mL, and stirring for 20min to obtain uniform slurry; adding a large amount of acidic diluent into the slurry according to the volume ratio of 1; and (2) dipping the ZSM-5 molecular sieve (with the mass ratio of 0.1g/g to sulfur powder) into an active dipping solution, continuously shaking for 8h, centrifugally separating, washing for 2 times by deionized water, and drying for 9h at 110 ℃ to obtain the ZSM-5 molecular sieve loaded active sulfur family compound 1.
Weighing 100mg of ZSM-5 molecular sieve loaded active sulfur group compound 1 and spraying the compound into the reactor with the volume of 1m 3 In the pilot-scale injection tower, elemental mercury is generated by a mercury generating device, the mercury concentration is measured in real time by using a VM-3000 mercury measuring instrument, and the gas flow and the Hg are controlled by a flue gas flow valve 0 The initial concentration of the flue gas is 125 mu g/m < 3 >, and the flue gas flow is 0.8m 3 Min, pure N 2 Hg under an atmosphere 0 The removal rate was 56.2%.
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 within the scope of the present invention.
Claims (9)
1. A preparation method of a supported active chalcogenide compound is characterized by comprising the following steps: the method comprises the following steps:
mixing the sulfur family powder treated by acid with a solution containing a solid reducing agent or a liquid reducing agent, stirring for the first time to form a pasty material, then adding a solid chemical exciting agent into the pasty material, stirring for the second time to form slurry, then adding a diluent into the slurry, adjusting the pH to 8-13, aging to obtain an active impregnation solution, then impregnating a carrier into the active impregnation solution, reacting, and carrying out solid-liquid separation to obtain an active sulfur family compound;
the sulfur family powder is selected from one or a combination of more of sulfur powder, selenium powder, tellurium powder, natural minerals containing sulfur, selenium and tellurium simple substances or industrial products;
the solid chemical excitant is selected from one or a combination of more of hydroxides and carbonates of potassium and sodium;
the carrier is selected from one of activated carbon, molecular sieve, zirconia, alumina, zeolite, silicon carbide, kaolin, red mud, metal organic framework material, sponge and organic polymer fiber;
the mass ratio of the sulfur family powder to the carrier is 0.005-0.3;
the reaction is carried out under continuous oscillation, and the reaction time is 3-24h.
2. The process for the preparation of a supported active chalcogen complex according to claim 1, wherein: soaking the chalcogenide powder in acid solution for 3-12h, cleaning, drying, crushing, grinding, sieving with 200 mesh sieve, and collecting the undersize product to obtain the acid-treated chalcogenide powder.
3. The process for the preparation of a supported active chalcogen complex according to claim 1, wherein: the solution containing the solid reducing agent is prepared by dissolving a supersaturated amount of the solid reducing agent in an aqueous solution, wherein the solid reducing agent is selected from one of stannous chloride, sodium hydrosulfite, sodium borohydride, potassium borohydride and thiourea dioxide; the liquid reducing agent is selected from one of sulfinic acid, sulfurous acid and hydrazine.
4. The process for the preparation of a supported active chalcogen complex according to claim 1, wherein: the solid-liquid mass volume ratio of the sulfur family powder to the solution containing the solid reducing agent is 0.1-2g:1mL; the solid-liquid mass volume ratio of the chalcogenide powder to the liquid reducing agent is 0.1-2g:1mL;
the first stirring time is 10-60min, and the first stirring temperature is 25-60 ℃;
the solid-liquid mass volume ratio of the solid chemical excitant to the solution containing the solid reducing agent is 0.1-2g:1mL, wherein the solid-liquid mass volume ratio of the solution of the solid chemical excitant to the solution of the liquid reducing agent is 0.1-4g:1mL;
the time of the second stirring is 10-120min, and the temperature of the second stirring is 25-60 ℃.
5. The method for preparing a supported active chalcogen complex according to claim 4, wherein said method comprises the steps of:
the solid-liquid mass volume ratio of the chalcogenide powder to the solution containing the solid reducing agent is 0.3-0.6g:1mL; the solid-liquid mass volume ratio of the sulfur family powder to the liquid reducing agent is 0.3-0.6g:1mL;
the solid-liquid mass volume ratio of the solid chemical excitant to the solution containing the solid reducing agent is 0.6-1g:1mL, wherein the solid-liquid mass volume ratio of the solution of the solid chemical excitant to the solution of the liquid reducing agent is 0.6-1g:1mL.
6. The method for preparing a supported active chalcogen complex according to claim 4, wherein said method comprises the steps of: the solid-liquid mass volume ratio of the chalcogenide powder to the solution containing the solid reducing agent is 0.5-0.8g:1mL; the solid-liquid mass volume ratio of the chalcogenide powder to the liquid reducing agent is 0.5-0.8g:1mL;
the solid-liquid mass volume ratio of the solid chemical excitant to the solution containing the solid reducing agent is 0.15-0.4g:1mL, wherein the solid-liquid mass volume ratio of the solution of the solid chemical excitant and the liquid reducing agent is 0.15-0.4g:1mL.
7. The process for the preparation of a supported active chalcogen complex according to claim 1, wherein: the volume ratio of the slurry to the diluent is 1; the aging time is 1-3h.
8. A supported active chalcogenide compound prepared by the process of any one of claims 1 to 7.
9. Use of a supported active chalcogen composite prepared by the preparation process according to any one of claims 1 to 7, characterized in that: the load type active sulfur group compound is used for removing elemental mercury in smoke or adsorbing leaked liquid elemental mercury.
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