CN110801803B - Method for preparing mercury removal adsorbent by utilizing wet zinc smelting oxygen pressure acid leaching residue - Google Patents

Method for preparing mercury removal adsorbent by utilizing wet zinc smelting oxygen pressure acid leaching residue Download PDF

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CN110801803B
CN110801803B CN201911192039.7A CN201911192039A CN110801803B CN 110801803 B CN110801803 B CN 110801803B CN 201911192039 A CN201911192039 A CN 201911192039A CN 110801803 B CN110801803 B CN 110801803B
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zinc
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oxygen pressure
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刘志楼
李子良
徐志峰
严康
张溪
昝苗苗
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Jiangxi University of Science and Technology
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
    • B01D53/02—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
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    • B01D2257/00—Components to be removed
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    • B01D2257/602—Mercury or mercury compounds
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
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Abstract

The invention discloses a method for preparing a mercury removal adsorbent by utilizing wet zinc smelting oxygen pressure acid leaching slag, which comprises the following steps: (1) uniformly mixing zinc oxide ores and oxygen pressure acid leaching residues to obtain a premix, and dissolving soluble sulfide salt in an organic solution to obtain a sulfide salt solution; (2) mixing the premix obtained in the step (1) with a sulfide solution, ultrasonically stirring the mixture into a suspension, heating the suspension to perform hydrothermal reaction, and collecting a product to obtain a zinc polysulfide compound; (3) and (3) mixing the zinc polysulfide compound obtained in the step (2) with ferric salt, and uniformly grinding to obtain the demercuration adsorbent. The invention uses the wet-process zinc smelting oxygen pressure acid leaching residue as a raw material to prepare the mercury removal adsorbent, reduces the environmental hazard of the oxygen pressure acid leaching residue, can realize the full-scale resource utilization of the oxygen pressure acid leaching residue, and has high mercury removal efficiency which can reach more than 90 percent for removing various forms of mercury in flue gas and waste liquid.

Description

Method for preparing mercury removal adsorbent by utilizing wet zinc smelting oxygen pressure acid leaching residue
Technical Field
The invention belongs to the field of adsorption materials, and particularly relates to a preparation method of a mercury removal adsorbent.
Background
Along with the increasing exhaustion of high-grade zinc concentrate and the increasing strictness of environmental protection requirements, the direct wet-method zinc smelting under pressure or normal pressure by oxygen enrichment has been paid more and more attention because the direct wet-method zinc smelting under pressure or normal pressure has the advantages of suitability for processing refractory minerals such as high-iron sphalerite, lead-containing zinc concentrate and the like, no acid making process, small environmental pollution and the like. So far, a plurality of sets of oxygen pressure leaching full-wet zinc smelting systems are established in China. In oxygen pressure leaching, zinc sulfide in zinc concentrate is directly oxidized into soluble zinc sulfate, and elements such as sulfur, lead, iron and the like in the raw materials are retained in slag to form acid leaching high-sulfur slag. At present, a thermal filtration method is usually adopted for treating high-sulfur slag, when the high-sulfur slag is heated to 130-160 ℃, the elemental sulfur in the slag is changed into liquid sulfur with good fluidity and low viscosity, and then the separation of the sulfur-containing material and the elemental sulfur in the acid leaching slag is directly realized by a filtration method. Although the primary separation of elemental sulfur can be realized by hot filtration, the obtained sulfur-containing slag still contains a large amount of elemental sulfur and is difficult to directly utilize. Therefore, the high-sulfur slag is mostly used as waste slag to be placed in a special slag yard for storage, which causes huge environmental protection pressure.
In the roasting process of the nonferrous metal ores, mercury in the concentrate enters flue gas in the form of gaseous mercury, is dispersed in a subsequent flue gas treatment system to form mercury-containing waste liquid or waste gas, and is finally discharged into the environment, so that the nonferrous metal smelting industry is one of the main sources of mercury discharge in China. At present, the traditional flue gas demercuration method mainly adopts the Boleton method as a main method. In the process of absorbing mercury by the Borlington, highly corrosive chlorine needs to be introduced, and a separate mercury removal device needs to be established, so that the introduction cost is high, and the application of the mercury removal device in the mercury removal purification of nonferrous smelting flue gas is difficult. The non-ferrous smelting mercury-containing waste liquid is mainly acidic solution, the removal of mercury is mainly carried out by sulfide precipitation and ferric salt adsorption, a large amount of mercury-containing waste residues are formed, and the difficulty of subsequent treatment is very high. Therefore, in the nonferrous smelting industry, the removal of mercury in flue gas and the removal of mercury in waste liquid are both very headache and problems to be solved urgently.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background technology, and provide a method for preparing a mercury removal adsorbent by utilizing wet zinc smelting oxygen pressure acid leaching residue, wherein the method can realize resource utilization of the oxygen pressure acid leaching residue and reduce the cost of flue gas mercury removal. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for preparing a mercury removal adsorbent by utilizing wet zinc smelting oxygen pressure acid leaching slag comprises the following steps:
(1) uniformly mixing zinc oxide ore (subjected to fine grinding) and oxygen pressure acid leaching slag to obtain a premix, and dissolving soluble sulfide salt in an organic solution to obtain a sulfide salt solution;
(2) mixing the premix obtained in the step (1) with a sulfide solution, ultrasonically stirring the mixture into a suspension, heating the suspension to perform hydrothermal reaction (under a closed condition), and collecting a product to obtain a zinc polysulfide;
(3) and (3) mixing the zinc polysulfide compound obtained in the step (2) with ferric salt, and uniformly grinding to obtain the demercuration adsorbent.
In the above method for preparing the mercury removal adsorbent, preferably, the zinc oxide ore is zinc oxide concentrate or zinc sulfide concentrate after oxidation roasting, and the oxygen pressure acid leaching residue is high sulfur residue obtained after direct oxygen pressure acid leaching of the zinc sulfide concentrate or tailings obtained after hot filtering of the high sulfur residue. According to the invention, the demercuration adsorbent is prepared by mixing zinc oxide ore and oxygen pressure acid leaching residue, and the high-value demercuration adsorbent is directly prepared from zinc ore and waste residue, so that the waste can be efficiently utilized, and the method is green, environment-friendly and high in economic value.
In the above method for preparing the mercury removal adsorbent, preferably, the mass ratio of the zinc oxide ore to the oxygen pressure acid leaching slag is (3-8): 1. the mass ratio of the zinc oxide ore to the oxygen pressure acid leaching slag needs to be reasonably limited, incomplete vulcanization can be caused by excessive usage of the zinc oxide ore, zinc polysulfide is not favorably formed, sulfur exists after reaction due to low usage of the zinc oxide ore, the activity of the sulfur in the oxygen pressure acid leaching slag is low, and an adsorbent is wrapped in the subsequent grinding process, so that the demercuration performance is reduced.
In the above method for preparing a demercuration adsorbent, preferably, the organic solution is a mixed solution of water and at least one of methanol, ethanol or ethylene glycol, and the volume ratio of organic matters to water in the organic solution is (1-1.5): 1, adding the soluble sulfide salt to control the concentration of the soluble sulfide salt to be 0.01-0.05 mol/L. The volume ratio of the organic matter to the water can ensure a better vulcanization effect.
In the above method for preparing the demercuration adsorbent, preferably, the mass solid-to-liquid ratio of the premix to the sulfide solution is (0.2-0.5): 1. the purpose of the addition of sulphide salts is to promote the formation of polysulphides, and high amounts of premix are detrimental to the formation of polysulphides.
In the above method for preparing the demercuration adsorbent, preferably, the reaction temperature of the hydrothermal reaction is 150-. The hydrothermal reaction time and the reaction temperature have great influence on the reaction process of the zinc polysulfide compound, and the reaction time and the reaction temperature can ensure the complete reaction.
In the above method for preparing a demercuration adsorbent, preferably, the mass ratio of the zinc polysulfide to the iron salt is 1: (0.01-0.03). The addition of the ferric salt ensures that active sulfur and short-chain polysulfide are formed on the surface of the zinc polysulfide, and the addition of the ferric salt is controlled, so that the full reaction can be ensured, and the influence of redundant ferric salt on demercuration is avoided.
In the method for preparing the demercuration adsorbent, preferably, the iron salt is one or more of ferric chloride, ferric sulfate and ferric nitrate.
In the above method for preparing the demercuration adsorbent, preferably, the zinc oxide ore has a particle size of not more than 150 μm.
In the above method for preparing the demercuration adsorbent, preferably, the grinding is performed by mechanical ball milling, and the ball milling time is 30-60 min.
In the invention, the addition of the sulfide salt and the ferric salt mainly has the following functions:
1. the purpose of the addition of the sulphide salt is to promote the formation of polysulphides and to promote the reaction of sulphur in the acid leach with the zinc oxidised ore to form zinc polysulphides. The main part in the hydrothermal reaction is the sulfur in the added zinc oxide concentrate and the acid-base slag, S2-The main reaction processes of forming zinc polysulfide in the existing solution are as follows:
ZnO+S+S2-→ZnSx。
2. the activation of iron salt is to promote the formation of active sulfur sites on the surface of zinc polysulfide compound by using Fe3+The oxidizing property of the zinc polysulfide compound forms active sulfur on the surface of the zinc polysulfide compound, and converts low-activity long-chain polysulfide compound into high-activity short-chain sulfur, thereby promoting the adsorption of mercury. The local surface temperature is raised during the mixing and grinding process of the zinc polysulfide and the iron salt, and the iron salt and the zinc polysulfide are promoted to react, so that active sites are formed.
The invention provides a method for utilizing pressurized acid slag in zinc smelting, which utilizes the characteristic that pressurized acid slag contains a large amount of sulfur and metal sulfides, directly prepares zinc polysulfide by mixing with zinc oxide ore in a certain proportion and carrying out hydrothermal vulcanization reaction in a solution containing sulfur ions with a certain concentration, and forms a large amount of high-activity S, S on the surface of the zinc polysulfide by adopting iron salt activation2 2-、HS-And the active sites are equal, so that the mercury-containing composite material has extremely high adsorption capacity on mercury in gas phase and liquid phase.
Compared with the prior art, the invention has the advantages that:
1. the method takes the wet zinc smelting oxygen pressure acid leaching residue as the raw material to prepare the mercury removal adsorbent, reduces the environmental hazard of the oxygen pressure acid leaching residue, and can realize the full-scale resource utilization of the oxygen pressure acid leaching residue.
2. The process for preparing the demercuration adsorbent has the characteristics of simple operation, low cost, environmental friendliness and the like, and is easy to realize industrialization.
3. The adsorbent prepared by the invention has high mercury removal efficiency, the removal efficiency of removing various forms of mercury in flue gas and waste liquid can reach more than 90%, and the adsorbent can be directly applied to the existing treatment process and has wide application range.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 shows the mass ratio of Hg between different high-sulfur slag and zinc oxide concentrate in example 10The influence of the removal efficiency.
FIG. 2 shows the mass ratio of Hg between different tailings and zinc oxide concentrates in example 20The influence of the removal efficiency.
FIG. 3 is a graph of different hydrothermal reaction times vs. Hg for example 30The influence of the removal efficiency.
FIG. 4 shows the amount of ferric chloride added versus Hg in example 40The influence of the removal efficiency.
FIG. 5 shows the mercury removal adsorbent for Hg in the mercury-containing solution at different reaction times in example 52+The removal efficiency of (a).
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a method for preparing a mercury removal adsorbent by utilizing wet zinc smelting oxygen pressure acid leaching slag comprises the following steps:
(1) sieving finely ground zinc oxide ore (zinc oxide concentrate) by a 100-mesh sieve to obtain zinc oxide ore particles with the particle size of less than 150 mu m, and then respectively taking 40g, 60g, 80g, 100g, 120g, 140g, 160g and 180g of the zinc oxide ore and 20g of pressurized oxidation acid leaching slag (namely high-sulfur slag) to be uniformly mixed to obtain different premixes;
(2) according to the following steps: 1 preparing mixed solution of ethanol and water, andadding sodium sulfide into mixed solution of ethanol and water to enable S in the solution to be in solution2-The concentration of the ions is 0.02mol/L, and a sulfide solution is obtained;
(3) mixing different premixes obtained in the step (1) with the sulfide solution obtained in the step (2) respectively, wherein the mass solid-liquid ratio is controlled to be 0.3: 1, ultrasonically stirring for 10min to form a suspension, then adding the suspension into a closed hydrothermal reaction kettle, reacting for 6h at 180 ℃, naturally cooling after the reaction is finished, filtering and drying to obtain a zinc polysulfide compound;
(4) and (3) uniformly mixing 30g of the zinc polysulfide compound obtained in the step (3) with 0.5g of ferric chloride, and then carrying out mechanical ball milling on the mixture for 30min to obtain the demercuration adsorbent.
In the above embodiment, the mass fraction of zinc oxide in the zinc oxide ore is 52.3%, the mass fraction of zinc in the pressure oxidation acid slag is 6.24%, and the mass fraction of elemental sulfur is 62.4%.
And (3) taking the prepared demercuration adsorbent, placing the demercuration adsorbent in a fixed bed, and evaluating the demercuration performance of the flue gas of the demercuration adsorbent. The specific process is as follows: fixing 1g of the prepared demercuration adsorbent on a fixed bed, wherein the gas flow is 0.6L/min, and the smoke component is 5 v% SO2+8v％O2+87v％N2+480μg/m3Hg0The reaction temperature is controlled at 100 ℃, and the Hg in the final flue gas0The removal efficiency of (a) is shown in fig. 1.
As can be seen from the figure 1, the mass ratio of the zinc oxide ores to the acid leaching residues is (3-8): 1 range of Hg in flue gas0The removal efficiency of the catalyst is kept above 80%.
Example 2:
a method for preparing a mercury removal adsorbent by utilizing wet zinc smelting oxygen pressure acid leaching slag comprises the following steps:
(1) sieving finely ground zinc oxide ore (zinc oxide concentrate) by a 100-mesh sieve to obtain zinc oxide ore particles with the particle size of less than 150 mu m, and then respectively taking 40g, 60g, 80g, 100g, 120g, 140g, 160g and 180g of the zinc oxide ore and 20g of pressurized oxidation acid leaching slag to be uniformly mixed with tailings (namely high-sulfur slag after thermal filtration) obtained after thermal filtration to obtain different premixes;
(2) - (4) is the same as steps (2) to (4) of example 1.
In the high-sulfur slag after the hot filtration, the mass fraction of zinc is 10.24 percent, and the mass fraction of elemental sulfur is 38.63 percent.
And (3) taking the prepared demercuration adsorbent, placing the demercuration adsorbent in a fixed bed, and evaluating the demercuration performance of the flue gas of the demercuration adsorbent. The specific process is as follows: fixing 1g of the prepared demercuration adsorbent on a fixed bed, wherein the gas flow is 0.6L/min, and the smoke component is 5 v% SO2+8v％O2+87v％N2+480μg/m3Hg0The reaction temperature is controlled at 100 ℃, and the Hg in the final flue gas0The removal efficiency of (a) is shown in fig. 2.
As can be seen from FIG. 2, the mass ratio of the zinc oxide ore to the high-sulfur slag after hot filtration is (3-8): 1 range of Hg in flue gas0The removal efficiency of the catalyst is kept above 80%.
Example 3:
a method for preparing a mercury removal adsorbent by utilizing wet zinc smelting oxygen pressure acid leaching slag comprises the following steps:
(1) sieving finely ground zinc oxide ore (zinc oxide concentrate) by a 100-mesh sieve to obtain zinc oxide ore particles with the particle size of less than 150 mu m, and then respectively taking 100g of the zinc oxide ore and 20g of pressurized oxidation acid leaching slag to be uniformly mixed to obtain a premix;
(2) according to the following steps: 1 preparing mixed solution of ethanol and water, and adding sodium sulfide into the mixed solution of ethanol and water to ensure that S in the solution is dissolved2-The concentration of the ions is 0.02mol/L, and a sulfide solution is obtained;
(3) mixing the premix obtained in the step (1) with the sulfide salt solution obtained in the step (2), wherein the mass solid-liquid ratio is controlled to be 0.3: 1, ultrasonically stirring for 10min to form a suspension, then adding the suspension into a closed hydrothermal reaction kettle, taking a plurality of groups to react for 2h, 4h, 6h, 8h, 10h, 12h and 14h at 180 ℃, naturally cooling after the reaction is finished, filtering and drying to obtain different zinc polysulfide compounds;
(4) and (3) uniformly mixing 30g of different zinc polysulfide compounds obtained in the step (3) with 0.5g of ferric chloride, and then carrying out mechanical ball milling on the mixture for 30min to obtain the demercuration adsorbent.
In the above embodiment, the mass fraction of zinc oxide in the zinc oxide ore is 52.3%, the mass fraction of zinc in the pressure oxidation acid slag is 6.24%, and the mass fraction of elemental sulfur is 62.4%.
And (3) taking the prepared demercuration adsorbent, placing the demercuration adsorbent in a fixed bed, and evaluating the demercuration performance of the flue gas of the demercuration adsorbent. The specific process is as follows: fixing 1g of the prepared demercuration adsorbent on a fixed bed, wherein the gas flow is 0.6L/min, and the smoke component is 5 v% SO2+8v％O2+87v％N2+480μg/m3Hg0The reaction temperature is controlled at 100 ℃, and the Hg in the final flue gas0The removal efficiency of (a) is shown in fig. 3.
As can be seen from FIG. 3, the lower hydrothermal reaction time is detrimental to Hg0The optimal hydrothermal reaction time is 6-10h, at the time of Hg0The removal efficiency of the catalyst is over 85 percent.
Example 4:
a method for preparing a mercury removal adsorbent by utilizing wet zinc smelting oxygen pressure acid leaching slag comprises the following steps:
(1) sieving finely ground zinc oxide ore (zinc oxide concentrate) by a 100-mesh sieve to obtain zinc oxide ore particles with the particle size of less than 150 mu m, and then respectively taking 100g of the zinc oxide ore and 20g of pressurized oxidation acid leaching slag to be uniformly mixed to obtain a premix;
(2) according to the following steps: 1 preparing mixed solution of ethanol and water, and adding sodium sulfide into the mixed solution of ethanol and water to ensure that S in the solution is dissolved2-The concentration of the ions is 0.02mol/L, and a sulfide solution is obtained;
(3) mixing the premix obtained in the step (1) with the sulfide salt solution obtained in the step (2), wherein the mass solid-liquid ratio is controlled to be 0.3: 1, ultrasonically stirring for 10min to form a suspension, then adding the suspension into a closed hydrothermal reaction kettle, reacting for 6h at 180 ℃, naturally cooling after the reaction is finished, filtering and drying to obtain a zinc polysulfide compound;
(4) and (3) taking 30g of the zinc polysulfide compound obtained in the step (3), respectively and uniformly mixing with 0g, 0.1g, 0.3g, 0.5g, 0.7g, 0.9g and 1.1g of ferric chloride to obtain mixtures with different ferric chloride adding amounts, and then carrying out mechanical ball milling on the mixtures for 30min to obtain different demercuration adsorbents.
In the above embodiment, the mass fraction of zinc oxide in the zinc oxide ore is 52.3%, the mass fraction of zinc in the pressure oxidation acid slag is 6.24%, and the mass fraction of elemental sulfur is 62.4%.
And (3) taking the prepared demercuration adsorbent, placing the demercuration adsorbent in a fixed bed, and evaluating the demercuration performance of the flue gas of the demercuration adsorbent. The specific process is as follows: fixing 1g of the prepared demercuration adsorbent on a fixed bed, wherein the gas flow is 0.6L/min, and the smoke component is 5 v% SO2+8v％O2+87v％N2+480μg/m3Hg0The reaction temperature is controlled at 100 ℃, and the Hg in the final flue gas0The removal efficiency of (a) is shown in fig. 4.
As can be seen from fig. 4, the addition of ferric chloride significantly increased the Hg-pair of the demercuration agent0The effect of desorption, the effect of promotion is not greatly influenced when the addition exceeds 0.9g, and the optimal addition mass ratio is 1: (0.01-0.03), and the most preferable mass ratio is 30g (zinc polysulfide): 0.5g (ferric chloride).
Example 5:
a method for preparing a mercury removal adsorbent by utilizing wet zinc smelting oxygen pressure acid leaching slag comprises the following steps:
(1) sieving finely ground zinc oxide ore (zinc oxide concentrate) by a 100-mesh sieve to obtain zinc oxide ore particles with the particle size of less than 150 mu m, and then respectively taking 100g of the zinc oxide ore and 20g of pressurized oxidation acid leaching slag to be uniformly mixed to obtain a premix;
(2) according to the following steps: 1 preparing mixed solution of ethanol and water, and adding sodium sulfide into the mixed solution of ethanol and water to ensure that S in the solution is dissolved2-The concentration of the ions is 0.02mol/L, and a sulfide solution is obtained;
(3) mixing the premix obtained in the step (1) with the sulfide salt solution obtained in the step (2), wherein the mass solid-liquid ratio is controlled to be 0.3: 1, ultrasonically stirring for 10min to form a suspension, then adding the suspension into a closed hydrothermal reaction kettle, reacting for 6h at 180 ℃, naturally cooling after the reaction is finished, filtering and drying to obtain a zinc polysulfide compound;
(4) and (3) uniformly mixing 30g of different zinc polysulfide compounds obtained in the step (3) with 0.5g of ferric chloride, and then carrying out mechanical ball milling on the mixture for 30min to obtain the demercuration adsorbent.
In the above embodiment, the mass fraction of zinc oxide in the zinc oxide ore is 52.3%, the mass fraction of zinc in the pressure oxidation acid slag is 6.24%, and the mass fraction of elemental sulfur is 62.4%.
Taking the prepared demercuration adsorbent, placing the demercuration adsorbent in a fixed bed, and evaluating the performance of the demercuration adsorbent on the mercury-containing waste liquid, wherein the specific process comprises the following steps: adding 3g of demercuration adsorbent into a solution containing 50mg/L of mercury, stirring at a rotation speed of 100r/min to form a suspension, keeping the adsorption temperature at 40 ℃, and finally obtaining Hg in the solution2+The results of the change in adsorption efficiency with time are shown in FIG. 5. As can be seen from FIG. 5, Hg in the solution was present after a reaction time of more than 30min2+The removal efficiency of the mercury removal adsorbent is more than 90 percent, which shows that the mercury removal adsorbent prepared by pressure oxidation acid leaching residue can be used for removing Hg in the solution2+The removal effect is better.
Comparative example 1:
a method for preparing a mercury removal adsorbent by utilizing wet zinc smelting oxygen pressure acid leaching slag comprises the following steps:
(1) sieving finely ground zinc oxide ore (zinc oxide concentrate) by a 100-mesh sieve to obtain zinc oxide ore particles with the particle size of less than 150 mu m, and then respectively taking 100g of the zinc oxide ore and 20g of pressurized oxidation acid leaching slag to be uniformly mixed to obtain a premix;
(2) according to the following steps: 1 preparing a mixed solution of ethanol and water, but adding no sulfide salt into the solution;
(3) mixing the premix obtained in the step (1) with the sulfide salt solution obtained in the step (2), wherein the mass solid-liquid ratio is controlled to be 0.3: 1, ultrasonically stirring for 10min to enable the solution to become suspension, then adding the suspension into a closed hydrothermal reaction kettle, reacting for 6h at 180 ℃, naturally cooling after the reaction is finished, filtering and drying;
(4) and (3) uniformly mixing 30g of the product obtained in the step (3) with 0.5g of ferric chloride, and then carrying out mechanical ball milling on the mixture for 30min to obtain the demercuration adsorbent.
In the comparative example, the mass fraction of zinc oxide in the zinc oxide ore was 52.3%, the mass fraction of zinc in the pressure oxidation acid slag was 6.24%, and the mass fraction of elemental sulfur was 62.4%.
Taking the prepared demercuration adsorbent, placing the demercuration adsorbent in a fixed bed, and evaluating the adsorption performance of mercury-containing flue gas on the demercuration adsorbent, wherein the specific process comprises the following steps: fixing 1g of the prepared demercuration adsorbent on a fixed bed, wherein the gas flow is 0.6L/min, and the smoke component is 5 v% SO2+8v％O2+87v％N2+480μg/m3 Hg0The reaction temperature is controlled at 100 ℃, and the Hg in the final flue gas0The removal efficiency is 62.45%, and the removal efficiency is far lower than the effect of adding the sulfide salt solution in the embodiment, which shows that the addition of the sulfide salt in the preparation of the demercuration adsorbent by utilizing the pressurized acid-base residue is beneficial to the improvement of the demercuration performance.

Claims (9)

1. A method for preparing a mercury removal adsorbent by utilizing wet zinc smelting oxygen pressure acid leaching slag is characterized by comprising the following steps:
(1) uniformly mixing zinc oxide ores and oxygen pressure acid leaching residues to obtain a premix, and dissolving soluble sulfide salt in an organic solution to obtain a sulfide salt solution;
(2) mixing the premix obtained in the step (1) with a sulfide solution, ultrasonically stirring the mixture into a suspension, heating the suspension to perform hydrothermal reaction, and collecting a product to obtain a zinc polysulfide compound;
(3) mixing the zinc polysulfide compound obtained in the step (2) with ferric salt, and uniformly grinding to obtain a demercuration adsorbent;
the zinc oxide ore is zinc oxide concentrate or zinc sulfide concentrate after oxidation roasting, and the oxygen pressure acid leaching slag is high-sulfur slag obtained after the zinc sulfide concentrate is directly subjected to oxygen pressure acid leaching or tailings obtained after the high-sulfur slag is subjected to heat filtration.
2. The method for preparing the mercury-removing adsorbent according to claim 1, wherein the mass ratio of the zinc oxide ore to the oxygen pressure acid leaching slag is (3-8): 1.
3. the method for preparing the demercuration adsorbent according to claim 1, wherein the organic solution is a mixed solution of water and at least one of methanol, ethanol or ethylene glycol, and the volume ratio of organic matters to water in the organic solution is (1-1.5): 1, adding the soluble sulfide salt to control the concentration of the soluble sulfide salt to be 0.01-0.05 mol/L.
4. The method for preparing a demercuration adsorbent according to any one of claims 1 to 3, wherein the mass solid-to-liquid ratio of the premix to the sulfide solution is (0.2-0.5): 1.
5. the method for preparing the demercuration adsorbent according to any one of claims 1 to 3, wherein the hydrothermal reaction is carried out at a reaction temperature of 150 ℃ and 200 ℃ for a reaction time of 6 to 10 hours.
6. The method for preparing a demercuration adsorbent according to any one of claims 1 to 3, wherein the mass ratio of the zinc polysulfides to the iron salt is 1: (0.01-0.03).
7. The method for preparing a demercuration adsorbent according to any one of claims 1 to 3, wherein the iron salt is one or more of ferric chloride, ferric sulfate and ferric nitrate.
8. The method for preparing a demercuration adsorbent according to any one of claims 1 to 3, wherein the zinc oxide ore has a particle size of not more than 150 μm.
9. The method for preparing the demercuration adsorbent according to any one of claims 1 to 3, wherein the grinding is performed by mechanical ball milling for 30 to 60 min.
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