CN114471460A - Demercuration adsorbent and preparation method thereof - Google Patents

Demercuration adsorbent and preparation method thereof Download PDF

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CN114471460A
CN114471460A CN202210031722.8A CN202210031722A CN114471460A CN 114471460 A CN114471460 A CN 114471460A CN 202210031722 A CN202210031722 A CN 202210031722A CN 114471460 A CN114471460 A CN 114471460A
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sludge
printing
zncl
raw material
demercuration adsorbent
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罗光前
吕敏
邹仁杰
孙瑞泽
方灿
兰萍
李显
姚洪
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Huazhong 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/25—Coated, impregnated or composite adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds
    • 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
    • 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
    • B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes

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  • Treatment Of Sludge (AREA)

Abstract

The invention belongs to the technical field related to environmental protection, and discloses a demercuration adsorbent and a preparation method thereof, wherein the method comprises the following steps: (1) carrying out filter pressing on the printing and dyeing sludge until the water content is lower than the preset water content, and sequentially drying, crushing, grinding and sieving to obtain a printing and dyeing sludge powder raw material; (2) mixing the printing and dyeing sludge powder raw material with ZnCl2The solution is soaked and aged at room temperature after being stirred and mixed, and then ZnCl is obtained2Modifying a sludge raw material; (3) reacting ZnCl2Pyrolyzing the modified sludge raw material in an oxygen-free atmosphere to obtain a printing and dyeing sludge pyrolytic coke; (4) and (3) placing the printing and dyeing sludge pyrolytic coke in air for oxidation to obtain oxidized sludge coke, namely the demercuration adsorbent. The invention achieves the aim of' producing with wasteThe purpose of waste is to realize resource utilization of the printing and dyeing sludge under the condition of adapting to and meeting the requirements of industrial development and environmental protection.

Description

Demercuration adsorbent and preparation method thereof
Technical Field
The invention belongs to the technical field related to environmental protection, and particularly relates to a demercuration adsorbent and a preparation method thereof.
Background
In recent years, with the improvement of living standard and the diversification of life style of people, the printing and dyeing industry is rapidly developed. As a typical high water consumption industry, the amount of printing and dyeing wastewater produced is rapidly increasing with the development of the industry. The treatment process of the printing and dyeing wastewater roughly comprises the processes of grating, regulation, oxidation, precipitation and the like, a large amount of sludge is generated in each stage, great pressure is brought to environmental protection, and the treatment of the printing and dyeing sludge becomes an important problem in the printing and dyeing industry. Due to the industrial particularity, the printing and dyeing production wastewater contains a large amount of dyes, fibers, mineral substances, chemical agents and the like, and a large amount of coagulants, flocculants and the like are added in the wastewater treatment process, and all the substances are transferred and concentrated into the sludge, so that the complexity and the pollution of the sludge are increased. Compared with common sludge, the printing and dyeing sludge has the advantages of high content of harmful substances (nickel, chromium, sulfur, iron and the like), high viscosity and high treatment difficulty, belongs to dangerous environment resources, and is classified as strictly-controlled substances in some regions.
At present, the treatment of the printing and dyeing sludge has no targeted scheme, and the traditional sludge treatment means is generally adopted for landfill or incineration. Patent CN104310884B discloses a curing agent for attapulgite reinforced printing and dyeing sludge treatment and a curing method thereof, which is characterized in that printing and dyeing sludge is mixed with attapulgite and composite additives (cement, fly ash and calcium chloride) in different proportions, then a formed block is prepared, and the formed block is cured at room temperature for 1-28 days to obtain a cured body of printing and dyeing sludge suitable for sanitary landfill; the printing and dyeing sludge solidified body prepared by the method has good mechanical strength and pollutant solidification effect, but needs a large amount of additional material investment and long maintenance time, increases the cost investment of printing and dyeing sludge treatment, and simultaneously leads to the waste of resources such as organic matters, mineral matters and the like in the sludge when the printing and dyeing sludge solidified body is buried. Patent CN103708691B reports an integrated treatment process for printing and dyeing sludge, which integrates sludge concentration, mechanical dehydration and sludge drying, and finally uses incineration as a sludge terminal treatment mode; the process realizes the synchronous operation of sludge filtration and drying, has larger sludge treatment capacity, but the printing and dyeing sludge contains a certain amount of acid, alkali residues and heavy metals, the release of pollutants such as dioxin, heavy metals and the like is increased while the volume reduction and the reduction of the sludge are realized by incineration, and in addition, the problems of slag bonding and corrosion of a boiler can be aggravated by ash and acid gases generated in the incineration process. Therefore, a new way for disposing and utilizing the printing and dyeing sludge needs to be found.
The pyrolysis technology is used as an organic solid waste treatment mode, can realize the aims of reducing, recycling and harmlessly treating waste, is applied to printing and dyeing sludge treatment, can retain carbon in organic matters as an active carbon component, and can further convert inorganic minerals into active components of the active carbon. In addition, the pyrolysis is carried out in an oxygen-less or oxygen-free atmosphere, and harmful gases such as SO can be reduced while promoting the decomposition of organic substances2、NOXCan also fix more heavy metals in the solid product and reduce the volatilization of the heavy metals. Patent CN103318889A discloses a method for preparing activated carbon by using printing and dyeing sludge, the method comprises the steps of drying, pyrolyzing, oxidizing and pickling with potassium permanganate with different concentrations and sulfuric acid to obtain the activated carbon, the activated carbon prepared by the method has a developed pore structure, but after pickling, part of active components in a solid product are dissolved, the chemical adsorption capacity of the active components is weakened, and the application of the active components is limited. In order to realize the high-efficiency and targeted utilization of the solid pyrolysis product of the printing and dyeing sludge, the pyrolysis process needs to be further optimized.
The preparation of activated carbon by utilizing the pyrolysis of organic wastes as an adsorbent for controlling pollutants in the atmosphere and water is widely concerned by researchers in recent years, and the research on the removal of the elemental mercury in the coal-fired flue gas is also frequently reported. As a global pollutant, mercury has strong toxicity, volatility, biological accumulation and long-distance transportation, poses serious threat to human health,whereas coal fired power plant mercury emissions are considered to be the largest source of anthropogenic mercury pollution. Activated carbon injection technology (ACI) is one of the mainstream mercury removal technologies, but activated carbon prepared by directly pyrolyzing organic waste has weak selectivity to mercury, usually needs further modification treatment, and researches show that S, ZnS and FeS are loaded2、Fe2O3The active carbon with equal components has good adsorption capacity to the elementary mercury. How to reduce the input of chemical reagents and prepare the adsorbent rich in the demercuration active component puts higher requirements on the selection of raw materials.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides the demercuration adsorbent and the preparation method thereof, the preparation method is suitable for the method for preparing the demercuration adsorbent by pyrolyzing the printing and dyeing sludge, the purpose of 'treating waste with waste' is achieved, and the resource utilization of the printing and dyeing sludge is realized under the condition of adapting to and meeting the requirements of industrial development and environmental protection.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a demercuration adsorbent, the method comprising the steps of:
(1) carrying out filter pressing on the printing and dyeing sludge until the water content is lower than the preset water content, and sequentially drying, crushing, grinding and sieving to obtain a printing and dyeing sludge powder raw material;
(2) mixing the printing and dyeing sludge powder raw material with ZnCl2The solution is soaked and aged at room temperature after being stirred and mixed, and then ZnCl is obtained2Modifying a sludge raw material;
(3) ZnCl is reacted with2Pyrolyzing the modified sludge raw material in an oxygen-free atmosphere to obtain a printing and dyeing sludge pyrolytic coke;
(4) and (3) placing the printing and dyeing sludge pyrolytic coke in air for oxidation to obtain oxidized sludge coke, namely the demercuration adsorbent.
Further, the predetermined water content is 50%.
Further, ZnCl2The concentration of the solution is 1 mol/L-3 mol/L.
Further, the printing and dyeing sludge powder raw material and ZnCl2The solid-liquid mass ratio of the mixed solution is 1:1～1:3。
further, the pyrolysis atmosphere is at least one of nitrogen, argon and helium.
Furthermore, the heating rate in the pyrolysis process is 10 ℃/min, the pyrolysis temperature is 400-700 ℃, and the pyrolysis time is 1 h.
Furthermore, the time of oxidation is 2-24 h.
Further, mixing the obtained printing and dyeing sludge powder raw material with ZnCl2After the solutions are uniformly mixed, the mixture is aged for 24 hours at room temperature, then the mixture is placed in a drying oven, modified sludge is dried to constant weight at 105 ℃, and the dried sludge is sequentially ground and crushed and sieved by a 80-mesh sieve to obtain ZnCl2Modifying the sludge raw material.
Further, in the pyrolysis process, the pyrolysis gas is firstly condensed and collected by a water bath device, and then is discharged after the acid gas is absorbed by the alkaline solution.
According to another aspect of the invention, a demercuration adsorbent is provided, and the demercuration adsorbent is prepared by the preparation method of the demercuration adsorbent.
Generally, compared with the prior art, the mercury removal adsorbent and the preparation method thereof provided by the invention have the following beneficial effects:
1. the invention adopts ZnCl2The dyeing sludge is subjected to impregnation modification, the porosity of the pyrolytic coke is effectively improved, the content of Cl in the sludge coke is increased, and the mode of impregnating firstly and then pyrolyzing is adopted to promote ZnCl2The hydrolysis product reacts with the sludge pyrolysis gas to further solidify sulfur in the sludge and generate mercury reaction sites with higher activity.
2. The air oxidation method adopted by the invention greatly reduces the modification cost and effectively improves the mercury removal efficiency of the sludge coke.
3. The invention combines the characteristics of sulfur (organic sulfur) enrichment of printing and dyeing sludge and needs to select Zncl as a demercuration active site2The solution realizes pore-forming, sulfur fixation and active site function increase.
4. The prepared pyrolytic coke is applied to removing elemental mercury in flue gas, converts the components of the printing and dyeing sludge into active sites, reduces the investment of chemical reagents, reduces the preparation cost of the mercury removal adsorbent, and realizes the aim of treating waste by waste.
5. The raw materials used in the invention are the printing and dyeing sludge, the yield is high, the source is wide, the components are complex, the adsorbent is prepared by pyrolysis and carbonization, mineral substances, inorganic salts, heavy metals and the like in the sludge are fixed in the pyrolysis coke, the release of pollutants is reduced, the resource utilization of the printing and dyeing sludge is realized, the overall process is simple, and the repeated operability is strong.
Drawings
FIG. 1 is a schematic flow diagram of a process for preparing a demercuration adsorbent according to the present invention;
FIG. 2 is an XRD analysis of the printing and dyeing sludge before and after pyrolysis;
FIG. 3 is an XRD analysis of the printing and dyeing sludge before and after thermal pyrolytic pyrooxidation;
FIG. 4 is a curve of the pyrolysis pyromercury removal rate prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Referring to fig. 1, the invention provides a preparation method of a mercury removal adsorbent, and the mercury removal adsorbent prepared by the preparation method is used for removing elemental mercury in coal-fired flue gas, so that double effects of sludge resource utilization and environmental protection are realized. The preparation method comprises the following steps:
step one, raw material pretreatment. Specifically, the collected printing and dyeing sludge is subjected to preliminary dehydration by using a filter press to reduce the water content to below 50%, then the printing and dyeing sludge is placed in a drying oven and dried at 105 ℃ to constant weight, and the dried sludge is crushed, ground and sieved by a 80-mesh sieve to obtain the printing and dyeing sludge powder raw material.
The printing and dyeing sludge is firstly subjected to filter pressing before drying, so that a large amount of moisture in the sludge is pressed out, and the moisture content of the sludge is reduced, thereby reducing the heat drying time and cost.
And step two, modifying the raw materials. Specifically, the obtained printing and dyeing sludge powder raw material and ZnCl with different concentrations (1-3 mol/L)2Uniformly mixing the solutions according to different solid-liquid mass ratios (1: 1-1: 3), aging at room temperature for 24 hours, then placing the mixture in a drying oven, drying the modified sludge to constant weight at 105 ℃, grinding and crushing the dried sludge, and sieving with a 80-mesh sieve to obtain ZnCl2Modifying the sludge raw material.
ZnCl is selected for chemical modification of printing and dyeing sludge2Impregnation process, on the one hand ZnCl2Can promote the conversion of organic matters, increase the volatile analysis in the pyrolysis process and load ZnCl on sludge2And the gasification and the migration at high temperature leave pores on the pyrolysis surface, so that the pore structure is improved, and the specific surface area is increased. On the other hand, ZnCl2Partial hydrolysis to Zn (OH) occurs during the dissolution process2The substance is decomposed in the pyrolysis process, the product can react with the gas generated by the pyrolysis of the sludge, more sulfur is retained in the solid product, the environmental pollution is reduced, and in addition, ZnCl2Chlorine in the mercury can form C-Cl bonds on carbon groups, and can be used for specifically oxidizing and adsorbing elemental mercury and promoting the removal of mercury.
Too high a concentration of ZnCl2The solution and the excessively high solid-liquid mixing ratio can cause the blockage of the pore structure of the pyrolytic coke to reduce the demercuration effect, and can also cause the waste of medicines.
And step three, pyrolyzing the sludge. In N2Under the atmosphere, ZnCl is obtained2Heating the modified sludge raw material to 400-700 ℃ at a heating rate of 10 ℃/min, then carrying out pyrolysis at the temperature for 1h, cooling, and taking out a solid product to obtain the printing and dyeing sludge pyrolytic coke.
In the pyrolysis process of the printing and dyeing sludge, the heating rate is controlled at 10 ℃/min, the yield of the sludge coke can be improved, and the cracking phenomenon of the pyrolysis coke is reduced, so that the pore structure of the pyrolysis coke is fully developed.
Lower pyrolysis temperature can make the volatile analysis go out incompletely, and the pyrolysis is not enough, and higher pyrolysis temperature can cause the collapse of pyrolysis burnt pore structure and reduce its demercuration efficiency, and too high pyrolysis temperature can also increase the volatilization of heavy metal in addition.
The printing and dyeing sludge is used as a secondary product for printing and dyeing wastewater treatment and is rich in elements such as sulfur, iron and the like, wherein the sulfur is mainly divided into sulfate, sulfide and organic sulfur, and the iron is mainly Fe2+、Fe3+In the presence of the compound, during the pyrolysis process, part of sulfides with poor thermal stability and organic sulfur are decomposed and transferred to sulfates with good stability and organic sulfur, and Fe3+The compound is partially reduced in a pyrolysis atmosphere to Fe2+The compound is transferred, so that the sulfur and the iron can be mostly remained in the solid product through pyrolysis, and the pollution is reduced.
Rich S and Fe elements in the printing and dyeing sludge can be used as active components for mercury removal adsorption, and in the pyrolysis process, the S and Fe elements are effectively retained in the pyrolysis coke to generate pyrite mineral, ZnCl2The impregnation modification can change the crystal component of the sludge pyrolytic coke, ZnCl2ZnO is generated in the hydrolysis product in the pyrolysis process, and H released by organic sulfur pyrolysis of the printing and dyeing sludge2The S reaction produces ZnS, fixing more sulfur in the pyrolytic coke. As shown in FIG. 2, the sludge raw material was compared without ZnCl2Impregnation modified sludge pyrolytic coke and ZnCl2The modified sludge pyrolytic coke has an X-ray diffraction (XRD) result, and can find that all the sludge original samples have impurity peaks, which indicates that no obvious crystal exists in the sludge original samples; without ZnCl2The dipping modified sludge pyrolytic coke contains pyrrhotite Fe1-xS crystal corresponds to a peak, which indicates that pyrolysis promotes Fe1-xS, crystal generation; through ZnCl2In the modified sludge pyrolytic coke, a strong ZnS crystal corresponding peak appears, and the original Fe1-xDisappearance of S crystal peak, indicating ZnCl2Not only promotes the fixation of sulfur in the pyrolysis gas, but also promotes Fe1-xAnd (4) decomposing S.
And step four, carrying out air oxidation on the pyrolysis coke. Specifically, the prepared pyrolytic coke is placed in air and oxidized for 2-24 hours at room temperature, and further air oxidized sludge coke, namely the demercuration adsorbent, is obtained.
The air is used as a cheap oxidant, so that on one hand, the oxidation of transition metal compounds in the sludge coke can be promoted, meanwhile, the oxygen-containing functional groups of the carbon-based adsorbent are increased, the oxidation of mercury is promoted, the mercury removal efficiency of the sludge coke is further enhanced, and on the other hand, the modification cost of the sludge coke is greatly reduced. As shown in FIG. 3, the intensity of the ZnS crystal response peak in the air-oxidized pyrolysis coke is weakened, which indicates that air causes partial oxidation of ZnS on the surface of the adsorbent, but the mercury removal experiment result indicates that the mercury removal efficiency of the air-oxidized sludge coke is greatly improved.
Too long an oxidation time in air can cause the pyrolysis coke to adsorb more water, produce sulfate and weaken the mercury removal capability of the pyrolysis coke.
The present invention is further illustrated in detail below with reference to several examples.
Example 1
The water content of the printing and dyeing sludge raw material adopted in the embodiment 1 of the invention is 83%, and the demercuration adsorbent is prepared according to the following steps:
(1) and (3) carrying out filter pressing on the sludge to reduce the water content to 45%, placing the obtained sludge cake in a drying oven, drying at 105 ℃ to constant weight, then crushing and grinding the sludge cake, and sieving the crushed sludge cake with a 80-mesh sieve to obtain the sludge raw material.
(2) Mixing the sludge raw material obtained in the step (1) with ZnCl with the concentration of 3mol/L2Mixing the solutions according to the solid-liquid mass ratio of 1:2, uniformly stirring, aging the obtained mixture for 24 hours at room temperature, then placing the mixture in a drying oven, drying the mixture at 105 ℃ to constant weight, grinding and crushing the dried mixture, and sieving the ground mixture with a 80-mesh sieve to obtain ZnCl2Modifying the sludge raw material.
(3) In N2ZnCl obtained from step (2) is reacted under an atmosphere2Heating the modified sludge material to 600 ℃ at a heating rate of 10 ℃/min, then preserving heat at the temperature for 1h for pyrolysis, cooling and taking out to obtain ZnCl2And (3) modifying the sludge coke.
(4) ZnC obtained in the step (3)l2And (3) placing the modified sludge coke in the air, and oxidizing for 12 hours at room temperature to obtain double modified sludge coke serving as a mercury removal adsorbent.
Carrying out an elemental mercury removal experiment in a fixed bed mercury removal device, wherein the experimental conditions are as follows: the dosage of the adsorbent is 100mg, and the atmosphere: high purity N2The reaction temperature: 110 ℃, total gas flow: 1L/min;
the mercury removal rate curve of the adsorbent prepared in example 1 of the present invention is shown in fig. 4, the adsorbent maintains a relatively stable mercury removal rate, the average mercury removal efficiency reaches 85% within 30min, and compared with the modified sludge coke which is not oxidized by air in the treatment mode, the mercury removal efficiency is increased by 30% and is 5 times higher than that of coconut shell activated carbon.
Example 2
The preparation process of the printing and dyeing sludge raw material and the adsorbent adopted in the embodiment 2 of the invention is the same as that of the embodiment 1, and certain process parameters in the preparation process are mainly changed, and the change steps and the parameters are as follows:
(3) in N2ZnCl obtained from step (2) is reacted under an atmosphere2Heating the modified sludge material to 400 ℃ at a heating rate of 10 ℃/min, then preserving heat at the temperature for 1h for pyrolysis, cooling and taking out to obtain ZnCl2And (3) modifying the sludge coke.
Other preparation process parameters and mercury removal experiment parameters are kept unchanged.
The average demercuration efficiency of the adsorbent prepared in the embodiment 2 of the invention reaches 55% within 30min, and compared with the modified sludge coke which is not oxidized by air in the treatment mode, the demercuration efficiency is increased by 46% and is 3 times of that of coconut shell activated carbon.
Example 3
The preparation process of the printing and dyeing sludge raw material and the adsorbent adopted in the embodiment 3 of the invention is the same as that of the embodiment 1, and certain process parameters in the preparation process are mainly changed, and the change steps and the parameters are as follows:
(2) mixing the sludge raw material obtained in the step (1) with ZnCl with the concentration of 2mol/L2The solution is mixed according to the solid-to-liquid ratio of 1:3, after being uniformly stirred, the mixture is aged for 24 hours at room temperature,then placing the mixture in a drying oven, drying the mixture at 105 ℃ to constant weight, grinding and crushing the dried mixture, and sieving the ground mixture with a 80-mesh sieve to obtain ZnCl2Modifying the sludge raw material.
(3) In N2ZnCl obtained from step (2) is reacted under an atmosphere2Heating the modified sludge material to 500 ℃ at a heating rate of 10 ℃/min, then preserving heat at the temperature for 1h for pyrolysis, cooling and taking out to obtain ZnCl2And (3) modifying the sludge coke.
(4) ZnCl obtained in the step (3)2And (3) placing the modified sludge coke in the air, and oxidizing for 2h at room temperature to obtain double modified sludge coke serving as a mercury removal adsorbent.
Other preparation process parameters and mercury removal experiment parameters are kept unchanged.
The average demercuration efficiency of the adsorbent prepared in the embodiment 3 of the invention reaches 75% within 30min, and compared with the modified sludge coke which is not oxidized by air in the treatment mode, the demercuration efficiency is increased by 27% and is 4 times of that of coconut shell activated carbon.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A preparation method of a demercuration adsorbent is characterized by comprising the following steps:
(1) carrying out filter pressing on the printing and dyeing sludge until the water content is lower than the preset water content, and sequentially drying, crushing, grinding and sieving to obtain a printing and dyeing sludge powder raw material;
(2) mixing the printing and dyeing sludge powder raw material with ZnCl2The solution is soaked and aged at room temperature after being stirred and mixed, and then ZnCl is obtained2Modifying a sludge raw material;
(3) ZnCl is reacted with2Pyrolyzing the modified sludge raw material in an oxygen-free atmosphere to obtain printing and dyeing sludge pyrolytic coke;
(4) and (3) placing the printing and dyeing sludge pyrolytic coke in air for oxidation to obtain oxidized sludge coke, namely the demercuration adsorbent.
2. The method for preparing the demercuration adsorbent according to claim 1, wherein: the predetermined water content is 50%.
3. The method for preparing the demercuration adsorbent according to claim 1, wherein: ZnCl2The concentration of the solution is 1 mol/L-3 mol/L.
4. The method for preparing the demercuration adsorbent according to claim 1, wherein: printing and dyeing sludge powder raw material and ZnCl2The solid-liquid mass ratio of the mixed solution is 1: 1-1: 3.
5. The method for preparing the demercuration adsorbent according to claim 1, wherein: the pyrolysis atmosphere is at least one of nitrogen, argon and helium.
6. The method for preparing the demercuration adsorbent according to claim 5, wherein: the heating rate in the pyrolysis process is 10 ℃/min, the pyrolysis temperature is 400-700 ℃, and the pyrolysis time is 1 h.
7. The method for preparing the demercuration adsorbent according to claim 1, wherein: the oxidation time is 2-24 h.
8. The method for preparing a demercuration adsorbent according to any one of claims 1 to 7, wherein: mixing the obtained printing and dyeing sludge powder raw material with ZnCl2After the solutions are uniformly mixed, the mixture is aged for 24 hours at room temperature, then the mixture is placed in a drying oven, modified sludge is dried to constant weight at 105 ℃, and the dried sludge is sequentially ground and crushed and sieved by a 80-mesh sieve to obtain ZnCl2Modifying the sludge raw material.
9. The method for preparing a demercuration adsorbent according to any one of claims 1 to 7, wherein: in the pyrolysis process, pyrolysis gas is firstly condensed and collected by a water bath device, and then is discharged after being absorbed by alkaline solution.
10. A demercuration adsorbent, characterized in that: the demercuration adsorbent is prepared by the preparation method of the demercuration adsorbent as defined in any one of claims 1-9.
CN202210031722.8A 2022-01-12 2022-01-12 Demercuration adsorbent and preparation method thereof Pending CN114471460A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116196725A (en) * 2023-04-04 2023-06-02 中南大学 Mercury adsorption and adsorbent regeneration device for coal-fired flue gas and mercury removal method

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104174360A (en) * 2014-09-17 2014-12-03 苏州新协力环保科技有限公司 Preparation method of sludge adsorbent applied to demercuration of smoke

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104174360A (en) * 2014-09-17 2014-12-03 苏州新协力环保科技有限公司 Preparation method of sludge adsorbent applied to demercuration of smoke

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
袁蓓: ""污泥衍生吸附剂脱除烟气中汞的实验研究"", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116196725A (en) * 2023-04-04 2023-06-02 中南大学 Mercury adsorption and adsorbent regeneration device for coal-fired flue gas and mercury removal method
CN116196725B (en) * 2023-04-04 2024-05-14 中南大学 Mercury adsorption and adsorbent regeneration device for coal-fired flue gas and mercury removal method

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