CN107583945B - Method for producing sintered bricks from organic contaminated soil - Google Patents
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- CN107583945B CN107583945B CN201711040207.1A CN201711040207A CN107583945B CN 107583945 B CN107583945 B CN 107583945B CN 201711040207 A CN201711040207 A CN 201711040207A CN 107583945 B CN107583945 B CN 107583945B
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Abstract
The invention discloses a method for producing sintered bricks by using organic contaminated soil, belonging to the field of contaminated soil remediation and recycling. The method comprises the steps of crushing and screening the polluted soil, adding a certain amount of catalytic oxidant into the polluted soil to reduce the total amount of organic matters, adding a certain amount of clean brick making raw materials, humidifying, stirring and aging, and then performing blank making, drying and sintering to prepare the sintered brick. According to the invention, brick making process equipment is fully utilized, the total amount of organic matters in soil is reduced by adding the oxidant before brick making, so that the environmental risk of tail gas is reduced, and meanwhile, in the sintering process of green bricks, residual organic matters are desorbed or pyrolyzed, so that the organic matters are thoroughly removed; the invention realizes the resource utilization of the soil while treating the polluted soil.
Description
Technical Field
The invention belongs to the field of polluted soil restoration and recycling, and particularly relates to a method for producing sintered bricks by using organic polluted soil.
Background
With the release and implementation of the national policy of 'two-in-three' return, a large number of polluted enterprises move out of urban areas, and a large number of polluted sites are left, wherein the polluted sites contain a large number of organic polluted production sites, and main pollution factors are Total Petroleum Hydrocarbons (TPHs), Volatile Organic Compounds (VOCs) and semi-volatile organic compounds (SVOCs).
The organic contaminated soil remediation method mainly comprises cement kiln cooperative treatment, a soil vapor extraction technology, a thermal desorption technology, a chemical oxidation technology, a microorganism remediation technology, a plant remediation technology, an in-situ barrier technology, a landfill technology and the like. The majority of the two-in-three-left polluted site is planned to be residential land, business land and the like, and such areas usually need infrastructure construction, need to be excavated, and transfer soil to other areas to be stacked, so that a large amount of land is occupied.
The rotary cement kiln incineration technology mainly utilizes the characteristics of high temperature, long-time gas retention, large heat capacity, good thermal stability, alkaline environment, no waste residue discharge and the like in the rotary cement kiln, and incinerates and treats the polluted soil while producing cement clinker. The organic contaminated soil enters the cement rotary kiln from a kiln tail flue gas chamber, the temperature of a gas phase in the kiln can reach 1800 ℃ at most, the temperature of materials is about 1450 ℃, organic contaminants in the contaminated soil are converted into inorganic compounds under the high-temperature condition of the cement kiln, and high-temperature gas flow and alkaline materials (CaO, CaCO) with high fineness, high concentration, high adsorbability and high uniformity are distributed3Etc.) to effectively inhibit the discharge of acidic substances, so that sulfur, chlorine, etc. are converted into inorganic salts to be fixed. Harmlessness and reclamation of organic polluted soil can be realized by the cooperative treatment of the cement kiln, but the cement industry is in the current stageThe excess capacity state and the sale of cement have certain problems.
The soil vapor extraction technology is a method for repairing soil polluted by volatile organic compounds and partial semi-volatile organic compounds, and is characterized in that the pressure gradient change in the polluted soil is caused by utilizing a vertical or horizontal well to extract soil air, so that the volatilization of non-aqueous phase liquid and pollutants dissolved in interstitial water in the soil is enhanced, the desorption rate of the pollutants on the surface of the soil is increased, the volatile organic pollutants are extracted to the ground and collected and processed, and the aim of repairing the polluted soil is fulfilled.
The thermal desorption technique for organic contaminated soil is a process of heating organic contaminants in soil to a sufficient temperature by direct or indirect heat exchange under vacuum condition or when carrier gas is introduced, so that the organic contaminants are volatilized or separated from a contaminated medium and enter a gas treatment system. The technology has short repairing period, can thoroughly remove pollutants, but has higher cost.
The chemical oxidation technology is to utilize the oxidizing property of oxidant to oxidize and decompose pollutant into non-toxic or less toxic matter to eliminate pollutant in soil. The soil contains a large amount of organic matters, and the organic matters can consume the oxidant, so that the cost of the chemical oxidation remediation technology is increased.
The microbial remediation technology is a remediation technology which utilizes indigenous microorganisms or artificially domesticated microorganisms with specific functions to reduce the activity of harmful pollutants in soil or degrade harmful substances under the proper environmental conditions through the metabolism of the microorganisms, has low application cost and small negative influence on the fertility and the metabolic activity of the soil, and can avoid the influence on human health and environment caused by pollutant transfer; the phytoremediation technology is to utilize green plants and their symbiotic microorganisms to extract, transfer, absorb, decompose, transform or fix organic or inorganic pollutants in soil and remove the pollutants from the soil, so as to achieve the purposes of removing, reducing or stabilizing the pollutants, or reducing the toxicity of the pollutants and the like. The repair efficiency of microorganism and plant repair technology is low, the period is long, and the construction period is difficult to complete on time under normal conditions.
The photolysis process is a process for decomposing organic waste gas under irradiation of light directly or through a certain photocatalyst, mainly including ultraviolet light decomposition process and photocatalytic oxidation process, and is a new technology for treating several organic compounds which are difficult to degrade and have low concentration, and can make the structure and physicochemical properties of target pollutant change and produce H2O、CO2And other small molecule substances. The photocatalyst is pollution-free, has high efficiency on partial organic matters, but can cause the catalyst to lose activity when the concentration of the organic matters on the surface of the catalyst is too high, so that the method is suitable for indoor air purification with low concentration and small air quantity and is not suitable for large-scale industrial application.
The in-situ barrier technology is mainly characterized in that the polluted soil is placed in an anti-seepage barrier landfill, or a barrier layer is laid to block the way of migration and diffusion of pollutants in the soil, so that the polluted soil is isolated from the surrounding environment, and the pollutants are prevented from contacting human bodies and migrating along with rainfall or underground water to further cause harm to the human bodies and the surrounding environment. According to the implementation mode, the method can be divided into in-situ barrier covering and ex-situ barrier filling. The pollution in the polluted soil by the technology is not thoroughly removed, and the environmental risk still exists.
Various problems exist with a single soil remediation method, and therefore, more and more research is being focused on the mixed use of multiple remediation technologies to overcome the disadvantages of a single technology.
Disclosure of Invention
Aiming at the problems of the existing organic contaminated soil remediation method, the invention provides a method for producing sintered bricks by using organic contaminated soil, the method comprises the steps of oxidizing organic matters in the polluted soil by using a photocatalytic oxidant, reducing the total amount of organic pollutants, reproducing sintered bricks, under high-temperature combustion, organic pollutants in the polluted soil are converted into inorganic compounds through a photocatalytic oxidant, the organic pollutants in the polluted soil are thoroughly removed, the restoration and the resource utilization of the organic polluted soil are realized, due to the introduction of the photocatalytic oxidant, the usage amount of the oxidant in the process of combustion is reduced, and simultaneously, in the high-temperature combustion process, the organic pollutants attached to the photocatalytic oxidant are converted into inorganic matters by the noble metal oxide, in the early photocatalytic process, the titanium dioxide which loses catalytic activity due to the adsorption of organic matters regenerates the photocatalytic activity.
The invention provides a method for producing sintered bricks by using organic contaminated soil, which comprises the following steps:
firstly, crushing and screening polluted soil, and conveying the polluted soil to a stirrer;
secondly, adding a certain amount of oxidant into the polluted soil, fully stirring, mixing, turning, oxidizing by light, and standing for 2-3 days;
thirdly, adding clean brick making raw materials into the oxidized polluted soil, adding water, stirring, mixing and aging;
and fourthly, feeding the aged stirred material into brick making process equipment, and sequentially performing blank making, drying and sintering to prepare the sintered brick.
Wherein the oxidant is WO3-CeO2Titanium dioxide-graphene.
Wherein the titanium dioxide is rutile titanium dioxide.
Wherein, the oxidant WO3-CeO2The preparation method of the titanium dioxide-graphene comprises the following steps:
firstly, preparing graphene oxide; uniformly mixing 5g of graphite powder and 35g of potassium permanganate, weighing 300mL of concentrated sulfuric acid and 37g of potassium nitrate, mixing, placing in an ice bath environment, adding a mixture consisting of the graphite powder and the potassium permanganate under the condition of magnetic stirring at a slow adding speed, keeping the temperature of the ice bath, keeping the reaction mixed solution at the temperature of a 60-DEG C water bath kettle after the addition is finished, stirring for 24 hours, placing in the ice bath environment for cooling, slowly adding 20mL of hydrogen peroxide after the temperature is reduced to 5 ℃, continuing stirring for 25 minutes after the reaction solution is completely changed into yellow brown, obtaining a yellow brown turbid solution, centrifugally dewatering, washing with 10 mass percent hydrochloric acid and deionized water to be neutral, and obtaining graphene oxide.
And secondly, preparing a mixed carrier, namely adding 150ml of deionized water and 600ml of isopropanol into a reaction container, then placing the reaction container in an ice bath environment, dropwise adding concentrated hydrochloric acid while stirring to adjust the pH value of the reaction solution to be 1-3, adding the graphene oxide prepared in the first step, and adding the graphene oxide in a suspension of the deionized water at a concentration of 0.5 mg/ml-1The addition amount is 200-400ml, and then the concentration is 0.5 mol.L-1Of TiCl (A) to (B)4300ml of aqueous solution, adjusting the pH value of the reaction solution to 7-8 after the dropwise addition is finished, transferring the reaction solution into a polytetrafluoroethylene-lined stainless steel autoclave, heating to 700-900 ℃ in an argon atmosphere for reaction, raising the temperature to 700-900 ℃ at a rate of 2 ℃/min, and keeping the temperature for 2 hours to obtain a graphene-rutile titanium dioxide mixed carrier;
the third step, catalyst preparation, is the reaction of tungsten nitrate (W (NO)3)3) And cerium nitrate (Ce (NO)3)3) Mixing according to a certain ratio, adding water to obtain a solution with a concentration of 2 g/ml-1(in WO)3Mass meter), placing the mixed carrier prepared in the second step into a reaction vessel, adding deionized water to prepare into 2 g/ml-1The aqueous solution of the metal oxide prepared above was added dropwise to the aqueous solution of the mixed carrier in an amount of WO35-8 percent of the mass ratio, stirring uniformly after the dropwise addition, performing ultrasonic treatment for 1 hour, then placing the mixture at the temperature of 60 ℃ for stirring reaction for 1 hour, standing the mixture overnight, filtering the mixture, washing the mixture by deionized water, drying the obtained filter cake in an oven at the temperature of 80 ℃, then placing the dried filter cake into a muffle furnace for roasting at the temperature of 2 ℃ for min-1The temperature rising speed reaches 500 ℃, the temperature is kept for 2 hours, and the catalyst is taken out after being cooled and ground to obtain the required catalyst.
Wherein the tungsten nitrate (W (NO)3)3) And cerium nitrate (Ce (NO)3)3) The mass ratio of the substances is 3: 1-2: 1.
Wherein the polluted soil is crushed and sieved to have a particle size of less than 20 mm.
Wherein the volume ratio of the polluted soil to the clean brick making raw materials is more than 1: 1, and the preferred volume ratio is 3-5: 1.
Wherein, the baked brick is a perforated brick or a hollow brick.
Wherein the drying temperature of the green brick is 50-200 ℃, and the sintering temperature is 800-1000 ℃.
Wherein, each 1m3The dosage of the oxidant used by the polluted soil is 5 kg-25 kg.
The invention has the following characteristics and advantages:
(1) before the brick blanks are formed, the organic pollutants in the soil are reduced through photocatalytic oxidation, the amount of dioxin formed by burning the organic pollutants in the brick making process is reduced, the organic matter content in the brick making tail gas is reduced, and the environmental risk of the tail gas is reduced;
(2) the invention utilizes chemical combustion oxidation catalysis technology, removes organic pollutants by utilizing the catalytic effect of the bimetallic oxide in a specific ratio under the load of a compound carrier formed by rutile type titanium dioxide-graphene in the process of sintering and brickmaking, and the combustion oxidation process completely oxidizes the organic pollutants attached to the rutile type titanium dioxide to recover the catalytic effect of the rutile type titanium dioxide, and can still utilize the photocatalytic effect after the brickmaking is finished;
(3) the invention fully utilizes the existing sintered brick production process equipment, uses the humidifying stirring tank as an oxidation reactor, and does not need to greatly change the sintered brick process;
(4) the invention fully utilizes the heat in the production process of the baked bricks, realizes the desorption and pyrolysis of organic pollutants while the green bricks are baked, and thoroughly removes the pollutants;
(5) the invention realizes the restoration and reclamation of the polluted soil and can generate certain economic benefit.
Drawings
FIG. 1: graphene-titanium dioxide X-ray powder diffraction analysis diagram.
Detailed Description
The invention provides a method for producing sintered bricks by using organic contaminated soil, which comprises the following steps:
firstly, crushing and screening polluted soil, and conveying the polluted soil to a stirrer;
secondly, adding a certain amount of oxidant into the polluted soil, fully stirring, mixing and oxidizing, and standing for 2-3 days;
thirdly, adding a clean brick making raw material into the oxidized polluted soil, adding water, stirring, mixing and aging for 12-24 hours, wherein the clean brick making raw material is coal gangue or a mixture of coal and one or more of clay, building garbage and industrial solid waste;
and fourthly, feeding the aged stirred material into brick making process equipment, and sequentially carrying out blank making, drying for 12-24 hours and sintering for 24-48 hours to prepare the sintered brick.
And crushing and screening the polluted soil until the particle size is less than 20 mm.
The volume ratio of the polluted soil to the clean brick making raw materials is more than 1: 1, and the preferred volume ratio is 3-5: 1.
The baked brick is a perforated brick or a hollow brick.
The drying temperature of the green brick is 50-200 ℃, and the sintering temperature is 800-1000 ℃.
Every 1m3The dosage of the oxidant used by the polluted soil is 5 kg-25 kg.
The oxidant adopted in the second step of the invention is a bimetallic oxide catalyst taking rutile type titanium dioxide-graphene as a carrier. Titanium dioxide is a high-efficiency photocatalyst, can oxidize most of organic compounds which are difficult to degrade, and has good catalytic degradation effect on volatile organic waste gas. Titanium dioxide has three crystal structures in nature, wherein an anatase phase and a brookite phase belong to a low-temperature phase and are unstable, and a rutile phase is a high-temperature stable phase.
Compared with anatase titanium dioxide, the rutile titanium dioxide has a lower specific surface area, so that the catalytic performance and the capacity of loading other catalysts are influenced, and graphene is a two-dimensional planar nano material, has outstanding mechanical, optical and thermal properties, high thermal conductivity, large specific surface area and excellent mechanical performance, and a lot of researches show that the photocatalytic performance of titanium dioxide can be improved by wrapping titanium dioxide with graphene. In the application, the graphene-rutile titanium dioxide composite material is prepared, the specific surface area of rutile titanium dioxide during loading is increased by adding graphene, the high-efficiency photocatalytic performance before high-temperature sintering is realized, and volatile organic compounds are removed better.
Because the electron-hole recombination rate of the titanium dioxide is high, the photocatalytic quantum efficiency is low. The noble metal is loaded on the surface of the titanium dioxide, so that the photo-generated electrons and holes can be effectively separated, and the photo-degradation reaction efficiency of the titanium dioxide is improved. Therefore, the titanium dioxide and graphene composite material is considered as a carrier, and the precious metal compound is deposited on the carrier, so that the photocatalytic effect of the titanium dioxide can be further improved.
In addition, titanium dioxide and graphene are good carriers of noble metal oxide catalysts, and are commonly used in a high-temperature chemical combustion oxidation technology for removing organic pollutants to prepare efficient catalysts. Particularly, the metal oxide particles are loaded on the titanium dioxide, the loaded metal oxide particles can not be agglomerated under the high-temperature reaction condition, so that the catalyst can not be deactivated, and the titanium dioxide can disperse the particles of the metal oxide catalyst when being used as a carrier, so that the contact area of the metal oxide and a reactant is enlarged, and the oxidation catalytic reaction is promoted.
The noble metal catalyst, which is the most effective method for degrading organic wastes in the catalytic combustion process and has good degradation activity, has been much studied on the selection of the noble metal catalyst, among which cerium oxide (CeO)2) Is a very efficient combustion catalyst. And further selecting other noble metals to form bimetal or ternary with cerium oxideThe metal catalyst can effectively improve the catalytic activity, the oxygen storage capacity and the transfer performance of surface active oxygen of the cerium oxide, thereby improving the efficiency of the whole combustion catalysis process. Among the numerous noble metal oxide catalysts which are associated with cerium oxide, tungsten oxide is used in the supported system according to the invention (WO)3) The catalyst has the best catalytic effect when forming a bimetallic oxide catalyst with cerium oxide. Therefore, in the present application, a composite material formed by rutile titanium dioxide and graphene is used as a carrier, tungsten oxide and cerium oxide are used to form a bimetallic oxide catalyst with a proper proportion, and organic contaminated soil is sintered into bricks, so that an optimal organic contaminant removal method is obtained, and the optimal organic contaminant removal method is preferably selected from bimetallic oxides.
The preparation method of the bimetallic oxide catalyst provided by the application comprises the following steps:
firstly, preparing graphene oxide; uniformly mixing 5g of graphite powder and 35g of potassium permanganate, weighing 300mL of concentrated sulfuric acid and 37g of potassium nitrate, mixing, placing in an ice bath environment, adding a mixture consisting of the graphite powder and the potassium permanganate under the condition of magnetic stirring at a slow adding speed, keeping the temperature of the ice bath, keeping the reaction mixed solution at the temperature of a 60-DEG C water bath kettle after the addition is finished, stirring for 24 hours, placing in the ice bath environment for cooling, slowly adding 20mL of hydrogen peroxide after the temperature is reduced to 5 ℃, continuing stirring for 25 minutes after the reaction solution is completely changed into yellow brown, obtaining a yellow brown turbid solution, centrifugally dewatering, washing with 10 mass percent hydrochloric acid and deionized water to be neutral, and obtaining graphene oxide.
And secondly, preparing a mixed carrier, namely adding 150ml of deionized water and 600ml of isopropanol into a reaction container, then placing the reaction container in an ice bath environment, dropwise adding concentrated hydrochloric acid while stirring to adjust the pH value of the reaction solution to be 1-3, adding the graphene oxide prepared in the first step, and adding the graphene oxide in a suspension of the deionized water at a concentration of 0.5 mg/ml-1The addition amount is 200-400ml, and then the concentration is 0.5 mol.L-1Of TiCl (A) to (B)4300ml of aqueous solution, adjusting the pH value of the reaction solution to 7-8 after the dropwise addition is finished, and transferring the reaction solution to the inner lining poly-tetra-polyHeating the mixture to 700-900 ℃ in an argon atmosphere in a fluoroethylene stainless steel high-pressure kettle for reaction, raising the temperature to 700-900 ℃ at the rate of 2 ℃/min, and preserving the heat for 2 hours to obtain a graphene-rutile titanium dioxide mixed carrier;
the third step, catalyst preparation, is the reaction of tungsten nitrate (W (NO)3)3) And cerium nitrate (Ce (NO)3)3) Mixing according to a certain ratio, adding water to obtain a solution with a concentration of 2 g/ml-1(in WO)3Mass meter), placing the mixed carrier prepared in the second step into a reaction vessel, adding deionized water to prepare into 2 g/ml-1The aqueous solution of the metal oxide prepared above was added dropwise to the aqueous solution of the mixed carrier in an amount of WO35-8 percent of the mass ratio, stirring uniformly after the dropwise addition, performing ultrasonic treatment for 1 hour, then placing the mixture at the temperature of 60 ℃ for stirring reaction for 1 hour, standing the mixture overnight, filtering the mixture, washing the mixture by deionized water, drying the obtained filter cake in an oven at the temperature of 80 ℃, then placing the dried filter cake into a muffle furnace for roasting at the temperature of 2 ℃ for min-1The temperature rising speed reaches 500 ℃, the temperature is kept for 2 hours, and the catalyst is taken out after being cooled and ground to obtain the required catalyst.
Preferably the tungsten nitrate (W (NO)3)3) And cerium nitrate (Ce (NO)3)3) The mass ratio of the substances is 3: 1-2: 1.
The invention will be described in more detail with reference to the following figures and embodiments, but the scope of the invention is not limited thereto.
Example 1 preparation of graphene oxide
Uniformly mixing 5g of graphite powder and 35g of potassium permanganate, weighing 300mL of concentrated sulfuric acid and 37g of potassium nitrate, mixing, placing in an ice bath environment, adding a mixture consisting of the graphite powder and the potassium permanganate under the condition of magnetic stirring at a slow adding speed, keeping the temperature of the ice bath, keeping the reaction mixed solution at the temperature of a 60-DEG C water bath kettle after the addition is finished, stirring for 24 hours, placing in the ice bath environment for cooling, slowly adding 20mL of hydrogen peroxide after the temperature is reduced to 5 ℃, continuing stirring for 25 minutes after the reaction solution is completely changed into yellow brown, obtaining a yellow brown turbid solution, centrifugally dewatering, washing with 10 mass percent hydrochloric acid and deionized water to be neutral, and obtaining graphene oxide.
Example 2 preparation of graphene-rutile titanium dioxide Mixed support
Adding 150ml of deionized water and 600ml of isopropanol into a reaction vessel, then placing the reaction vessel in an ice bath environment, dropwise adding concentrated hydrochloric acid while stirring to adjust the pH value of the reaction solution to about 2, adding the graphene oxide prepared in example 1, and adding the graphene oxide in a form of suspension of deionized water, wherein the concentration of the graphene oxide is 0.5 mg/ml-1300ml of the solution was added, followed by slowly dropping the solution at a concentration of 0.5 mol. L-1Of TiCl (A) to (B)4300ml of aqueous solution, adjusting the pH value of the reaction solution to 7 after the dropwise addition is finished, transferring the reaction solution into a polytetrafluoroethylene-lined stainless steel autoclave, heating the reaction solution to 700 ℃ in an argon atmosphere for reaction, raising the temperature at a rate of 2 ℃/min to 700 ℃, and keeping the temperature for 2 hours to obtain the graphene-rutile titanium dioxide mixed carrier.
Comparative example 1 preparation of graphene-titanium dioxide 1 Mixed support
Adding 150ml of deionized water and 600ml of isopropanol into a reaction vessel, then placing the reaction vessel in an ice bath environment, dropwise adding concentrated hydrochloric acid while stirring to adjust the pH value of the reaction solution to about 2, adding the graphene oxide prepared in example 1, and adding the graphene oxide in a form of suspension of deionized water, wherein the concentration of the graphene oxide is 0.5 mg/ml-1300ml of the solution was added, followed by slowly dropping the solution at a concentration of 0.5 mol. L-1Of TiCl (A) to (B)4300ml of aqueous solution, adjusting the pH value of the reaction solution to 7 after the dropwise addition is finished, transferring the reaction solution into a polytetrafluoroethylene-lined stainless steel autoclave, heating the reaction solution to 200 ℃ in an argon atmosphere for reaction, raising the temperature to 200 ℃ at a rate of 2 ℃/min, and keeping the temperature for 2 hours to obtain the graphene-rutile titanium dioxide mixed carrier.
Comparative example 2 preparation of graphene-titanium dioxide 2 Mixed Carrier
Adding 150ml of deionized water and 600ml of isopropanol into a reaction vessel, then placing the reaction vessel in an ice bath environment, dropwise adding concentrated hydrochloric acid while stirring to adjust the pH value of the reaction solution to about 2, adding the graphene oxide prepared in example 1, and adding the graphene oxideAdding deionized water to form suspension with concentration of 0.5 mg/ml-1300ml of the solution was added, followed by slowly dropping the solution at a concentration of 0.5 mol. L-1Of TiCl (A) to (B)4300ml of aqueous solution, adjusting the pH value of the reaction solution to 7 after the dropwise addition is finished, transferring the reaction solution into a polytetrafluoroethylene-lined stainless steel autoclave, heating the reaction solution to 500 ℃ in an argon atmosphere for reaction, raising the temperature at a rate of 2 ℃/min to 500 ℃, and keeping the temperature for 2 hours to obtain the graphene-rutile titanium dioxide mixed carrier.
X-ray powder diffraction analysis (XRD) is adopted for judging the crystal form of the graphene-rutile type titanium dioxide. The method is the method for testing the most mature crystalline state appearance and the most widely applied powder. The crystal structure was analyzed by the shape of a distinctive diffraction peak appearing in correspondence with the X-ray irradiation, and the type of the crystal was determined by comparison with a powder diffraction card (JCPDS No. 21-1272).
As shown in fig. 1, example 2(B) obtained by adding graphene material showed a (110) crystal plane diffraction peak at 27.55 ° and a 27.55 ° crystal plane diffraction peak in the composite graphene material was stronger than that of pure commercially available rutile titanium dioxide (a), while graphene (002) exhibited a characteristic absorption peak at about 26 ° and was too close to that of rutile titanium dioxide, and thus no separately apparent peak was observed, which occurred in the same case in pure commercially available anatase titanium dioxide (E), and the carriers prepared in comparative examples 1(D) and 2(C) exhibited a (101) crystal plane diffraction peak at 25.40 ° and was too close to that of graphene (002) at 26 °, so that the single peak of graphene was not observed, and the composite carrier was enhanced at 25.40 ° peak surface, while C, D and B exhibited two peaks between 25 ° and 27 °, a mixture of anatase and rutile is illustrated.
EXAMPLE 3 preparation of bimetallic oxidant
Mixing tungsten nitrate (W (NO)3)3) And cerium nitrate (Ce (NO)3)3) Mixing at a ratio of 2: 1, adding water to obtain a solution with a concentration of 2 g/ml-1(in WO)3Mass meter), the carrier prepared in example 2 was placed in a reaction vessel, and deionized water was added to prepare a concentrationIs 2 g.ml-1The aqueous solution of the metal oxide prepared above was added dropwise to the aqueous solution of the mixed carrier in an amount of WO3The mass ratio is 6 percent, the mixture is stirred uniformly after the dropwise addition, ultrasonic treatment is carried out for 1 hour, then the mixture is placed at the temperature of 60 ℃ for stirring reaction for 1 hour, then the mixture is placed still overnight, filtered and washed by deionized water, the obtained filter cake is dried in an oven at the temperature of 80 ℃, and then the filter cake is placed in a muffle furnace for roasting at the temperature of 2 ℃ for min-1The temperature rising speed reaches 500 ℃, the temperature is kept for 2 hours, and the catalyst is taken out after being cooled and ground to obtain the required catalyst.
As shown in FIG. 1, it can be seen from the X-ray powder diffraction analysis chart of comparative example 2 and example 3 that the characteristic diffraction peaks are of rutile titanium dioxide-graphene carrier, and WO is not detected in the spectrum3And CeO2Indicating that the two oxides are highly dispersed in the rutile titanium dioxide-graphene carrier.
Comparative example 3 preparation of bimetallic oxidant 2
Mixing tungsten nitrate (W (NO)3)3) And cerium nitrate (Ce (NO)3)3) Mixing at a ratio of 2: 1, adding water to obtain a solution with a concentration of 2 g/ml-1(in WO)3Mass basis), the carrier prepared in comparative example 1 was placed in a reaction vessel, and deionized water was added to prepare a solution having a concentration of 2 g/ml-1The aqueous solution of the metal oxide prepared above was added dropwise to the aqueous solution of the mixed carrier in an amount of WO3The mass ratio is 6 percent, the mixture is stirred uniformly after the dropwise addition, ultrasonic treatment is carried out for 1 hour, then the mixture is placed at the temperature of 60 ℃ for stirring reaction for 1 hour, then the mixture is placed still overnight, filtered and washed by deionized water, the obtained filter cake is dried in an oven at the temperature of 80 ℃, and then the filter cake is placed in a muffle furnace for roasting at the temperature of 2 ℃ for min-1The temperature rising speed reaches 500 ℃, the temperature is kept for 2 hours, and the catalyst is taken out after being cooled and ground to obtain the required catalyst.
The catalytic degradation of volatile organic compounds benzene and xylene by bimetallic oxides using rutile titanium dioxide as a carrier is compared through experiments, the catalysts respectively measured are the two catalysts given in example 3 and comparative example 3, and the adopted determination technology is chromatographic technologyThe chromatograph used was a GC-2010 gas chromatograph (shimadzu corporation, japan), and the degradation rates of benzene and xylene after catalysis were determined by measuring the chromatographic peak areas of benzene and xylene in the sample by using a chromatographic technique. Setting conditions: the column temperature is 55 ℃, the temperature of the detection chamber and the gasification chamber is 250 ℃, the gas flow is 80ml/min, the pressure is 100kPa, the degradation rate is (initial time chromatographic peak area-measuring time chromatographic peak area/initial time chromatographic peak area) multiplied by 100 percent, and the initial benzene and xylene concentrations are both 0.02mg/m3The reactions were carried out for 100min each, and were tested at 50min, 70min and 100min, respectively.
The experimental process comprises the following steps: A350W xenon lamp (with the wavelength range of 390-760 nm) is used as a visible light source, a certain amount of benzene is added into a 1L closed container by a static method to volatilize automatically, and a catalyst is placed in a reaction container. After the reaction was started, 5mL of gas was withdrawn from the reactor at regular intervals by means of a syringe and the photocatalytic degradation effect was analyzed. In order to ensure the accuracy of the experiment, after each degradation, zero-order air is introduced into the reactor to replace residual gas, so that the influence of residual benzene on the experimental result is avoided, and the experimental result is shown in table 1.
TABLE 1
As can be seen from table 1, when the carrier of the bimetallic oxide catalyst is formed by rutile titanium dioxide and graphene, the catalytic effect is better than the photocatalytic performance of the bimetallic oxide formed by anatase titanium dioxide and graphene as the carrier in the process of photocatalytic degradation of volatile organic compounds, i.e., benzene and xylene.
Comparative example 4 preparation of bimetallic oxidant 3
Mixing tungsten nitrate (W (NO)3)3) And cerium nitrate (Ce (NO)3)3) Mixing at a ratio of 2: 1, adding water to obtain a solution with a concentration of 2 g/ml-1(in WO)3Mass meter), the carrier prepared in comparative example 2 was placed in a reaction vessel, and deionized water was added to prepare a solution having a concentration of 2 g/ml-1Prepared from the aboveIs added dropwise to the mixed carrier aqueous solution in an amount of WO3The mass ratio is 6 percent, the mixture is stirred uniformly after the dropwise addition, ultrasonic treatment is carried out for 1 hour, then the mixture is placed at the temperature of 60 ℃ for stirring reaction for 1 hour, then the mixture is placed still overnight, filtered and washed by deionized water, the obtained filter cake is dried in an oven at the temperature of 80 ℃, and then the filter cake is placed in a muffle furnace for roasting at the temperature of 2 ℃ for min-1The temperature rising speed reaches 500 ℃, the temperature is kept for 2 hours, and the catalyst is taken out after being cooled and ground to obtain the required catalyst.
Example 4
The embodiment is targeted to the soil polluted by petroleum hydrocarbon in a certain site, wherein the concentration of the petroleum hydrocarbon (less than C16) is 560-4890 mg/kg, and the concentration of the petroleum hydrocarbon (more than C16) is 6240-169920 mg/kg. The method for producing the baked bricks by using the polluted soil comprises the following steps:
(1) will be 30m3Crushing and screening the polluted soil to 15 +/-5 mm soil particles, and conveying the soil particles to a stirrer;
(2) adding 30kg of bimetallic oxidant into the polluted soil, fully stirring, mixing, turning and throwing, oxidizing by visible light, and standing for 2 days;
(3) adding 20m into the oxidized contaminated soil3Cleaning a brick making raw material coal gangue, adding water, stirring, mixing and aging for 24 hours;
(4) entering normal brick making process equipment, entering a blank making system to prepare a porous brick blank, then drying and sintering the porous brick blank in a drying and sintering system, wherein the drying temperature is 60 +/-5 ℃, the drying time is 24 hours, the sintering temperature is 900 +/-10 ℃, and the sintering time is 24 hours to prepare the porous sintered brick.
The quality and performance of the sintered porous brick tested according to the wall brick test rule (JC/T466-.
The concentration of petroleum hydrocarbon in leachate prepared by the sintered porous brick according to a solid waste leaching toxicity leaching method sulfuric acid-nitric acid method (HJ/T299-2007) should meet the water limit value (less than or equal to 0.05mg/L) of class III of surface water environment quality standard (GB3838-2002), and the total petroleum hydrocarbon of the porous sintered brick meets the residential ground standard (total petroleum hydrocarbon (less than C16) < 230mg/kg, total petroleum hydrocarbon (greater than C16) < 10000mg/kg) in site soil environment risk evaluation screening value (DB 11/811-2011).
TABLE 2 Total amount of sintered masonry hydrocarbons and leach concentrations
As can be seen from Table 2, the more rutile type titanium dioxide is present in the catalyst carrier, the better the performance of the catalyst in catalyzing and oxidizing petroleum hydrocarbons as a whole, while the anatase type titanium dioxide is used as the carrier, which affects the performance of the catalyst.
Preparation of the double Metal oxide catalyst according to the preparation of example 3, tungsten nitrate (W (NO)3)3) And cerium nitrate (Ce (NO)3)3) The mass ratio of the substances is 3: 1, 2: 1 and 1: 2 in sequence.
TABLE 3 influence of the metal catalyst ratio on the total amount of petroleum hydrocarbons and the leaching concentration
As can be seen from table 3, the more tungsten nitrate is used in the bimetallic catalyst, the better the catalytic performance, while the more cerium nitrate is used, the less the catalytic oxidation of petroleum hydrocarbons.
Example 5
The target of the embodiment is the benzene series (benzene and xylene) polluted soil of a certain site, the concentration range of the benzene is 14.87-920.54 mg/kg, and the concentration range of the xylene is 267.32-765.14 mg/kg. The method for producing the baked bricks by using the polluted soil comprises the following steps:
(1) will be 40m3Crushing and screening the polluted soil to 15 +/-5 mm soil particles, and conveying the soil particles to a stirrer;
(2) adding 40kg of bimetallic oxidant into the polluted soil, fully stirring, mixing, turning, oxidizing by visible light, and standing for two days;
(3) adding 10m into the oxidized polluted soil3Cleaning a brick making raw material coal gangue, adding water, stirring, mixing and aging for 24 hours;
(4) entering normal brick making process equipment, entering a blank making system to prepare a porous brick blank, and then entering a drying and sintering system, wherein the drying temperature is 60 +/-5 ℃, and the sintering temperature is 1000 +/-10 ℃ to prepare the porous sintered brick.
The quality and performance of the sintered porous brick tested according to the wall brick test rule (JC/T466-.
The concentrations of benzene and xylene in a leaching solution prepared by the sintered porous brick according to a solid waste leaching toxicity leaching method sulfuric acid-nitric acid method (HJ/T299-2007) meet the specific project standard limits (benzene is less than or equal to 0.01mg/L and xylene is less than or equal to 0.5mg/L) of a surface water environment quality standard (GB3838-2002) of a centralized domestic drinking water surface water source, and the benzene and the xylene of the sintered porous brick meet the residential land standard (benzene is less than 0.64mg/kg and xylene is less than 74mg/kg) in a site soil environment risk evaluation screening value (DB 11/811-one 2011).
TABLE 4 Total benzene and xylene content and leach concentration of the baked bricks
It can be seen from table 4 that the more rutile titania is present in the catalyst support, the better the overall catalytic oxidation of benzene and xylene is, while the use of anatase titania as a support affects the performance of the catalyst.
TABLE 5 influence of the metal catalyst ratio on the total benzene and xylene content and the leaching concentration
As can be seen from table 5, the more tungsten nitrate is used in the bimetallic catalyst, the better the catalytic performance, while the more cerium nitrate is used, the less the catalytic oxidation of benzene and xylene.
Example 6
The target of the embodiment is soil polluted by polycyclic aromatic hydrocarbons (benzene (a) pyrene, benzo (a) anthracene and benzo (b) fluoranthene) on a certain site, wherein the concentration of the benzene (a) pyrene is 0.9-4.58 mg/kg, the concentration of the benzo (a) anthracene is 4.22-22.98 mg/kg, and the concentration of the benzo (b) fluoranthene is 5.72-15.48 mg/kg. The method for producing the baked bricks by using the polluted soil comprises the following steps:
(1) 50m3Crushing and screening the polluted soil to 15 +/-5 mm soil particles, and conveying the soil particles to a stirrer;
(2) adding 5kg of bimetallic oxidant into the polluted soil, fully stirring, mixing, turning, oxidizing by visible light, and standing for two days;
(3) adding 10m into the oxidized polluted soil3Cleaning a brick making raw material coal gangue, adding water, stirring, mixing and aging for 24 hours;
(4) entering normal brick making process equipment, entering a blank making system to prepare a porous brick blank, and then entering a drying and sintering system, wherein the drying temperature is 150 +/-5 ℃, and the sintering temperature is 900 +/-10 ℃ to prepare the porous sintered brick.
The quality and performance of the sintered porous brick tested according to the wall brick test rule (JC/T466-.
The concentration of polycyclic aromatic hydrocarbon in leachate prepared by the sintered porous brick according to the solid waste leaching toxicity leaching method sulfuric acid-nitric acid method (HJ/T299-2007) should meet the specific project standard limit (benzene (a) pyrene is less than or equal to 2.8 multiplied by 10) of the surface water source of centralized domestic drinking water in the surface water environment quality standard (GB3838-2002)-6mg/L), the total petroleum hydrocarbon of the porous sintered brick meets the site soil environmental risk evaluation screening value (DB 11/811-2)011) Standard of living area (benzene (a) pyrene is less than 0.2mg/kg, benzene (a) pyrene is less than 0.5mg/kg, and benzo (b) fluoranthene is less than 0.5 mg/kg).
TABLE 6 Total amount of polycyclic aromatic hydrocarbons and leach concentration for the baked bricks
It can be seen from table 6 that the more rutile type titanium dioxide is present in the catalyst carrier, the better the performance of the catalyst in the overall catalytic oxidation of polycyclic aromatic hydrocarbons, while the anatase type titanium dioxide used as the carrier affects the performance of the catalyst.
TABLE 7 influence of the metal catalyst ratio on the total amount of polycyclic aromatic hydrocarbons and the leaching concentration
As can be seen from table 7, when the amount of tungsten nitrate used in the bimetallic catalyst is more, the catalytic performance is better, while the amount of cerium nitrate used is too much, the catalytic oxidation of the polycyclic aromatic hydrocarbon is reduced.
The foregoing is only a preferred embodiment of the present invention and is not intended to limit the invention; other modifications, substitutions, simplifications, improvements and the like which do not depart from the spirit and scope of the invention are deemed to be equivalent permutations and equivalents thereof.
Claims (7)
1. A method for producing a baked brick from organic contaminated soil is characterized by comprising the following steps:
firstly, crushing and screening polluted soil, and conveying the polluted soil to a stirrer;
secondly, adding a certain amount of catalytic oxidant into the polluted soil, fully stirring, mixing, turning, oxidizing by light, and standing for 2-3 days;
thirdly, adding clean brick making raw materials into the oxidized polluted soil, adding water, stirring, mixing and aging for 12-24 hours;
fourthly, feeding the aged stirred material into brick making process equipment, and sequentially performing blank making, drying and sintering to prepare a sintered brick;
the catalytic oxidant is WO3-CeO2Titanium dioxide-graphene;
the titanium dioxide is rutile titanium dioxide.
2. The method for producing a baked brick from an organic contaminated soil according to claim 1, wherein: said WO3-CeO2Titanium dioxide-graphene through tungsten nitrate (W (NO)3)3) And cerium nitrate (Ce (NO)3)3) Preparation of tungsten nitrate (W (NO)3)3) And cerium nitrate (Ce (NO)3)3) The mass ratio of the substances is 3: 1-2: 1.
3. The method for producing a sintered brick from an organic contaminated soil according to claim 1 or 2, wherein: and crushing and screening the polluted soil until the particle size is less than 20 mm.
4. The method for producing a sintered brick from an organic contaminated soil according to claim 1 or 2, wherein: the volume ratio of the polluted soil to the clean brick making raw material is more than 1: 1.
5. The method for producing a sintered brick from an organic contaminated soil according to claim 1 or 2, wherein: the baked brick is a perforated brick or a hollow brick.
6. The method for producing a sintered brick from an organic contaminated soil according to claim 1 or 2, wherein: the drying temperature of the green brick is 50-200 ℃, the drying time is 12-24 hours, the sintering temperature is 800-1000 ℃, and the sintering time is 24-48 hours.
7. The method for producing a sintered brick from an organic contaminated soil according to claim 1 or 2, wherein: every 1m3The dosage of the oxidant used by the polluted soil is 5 kg-25 kg.
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| CN110479757B (en) * | 2019-09-02 | 2024-02-09 | 河南工程学院 | Electric restoration device and restoration method for composite heavy metal contaminated soil |
| CN112845565B (en) * | 2020-12-23 | 2022-09-02 | 中骏生态环境(上海)有限公司 | Application of graphene-based nanocomposite in petroleum hydrocarbon contaminated soil remediation |
| CN115301714B (en) * | 2022-08-11 | 2023-12-01 | 徐州振丰新型墙体材料有限公司 | Method for making bricks by harmless sintering of polluted soil |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3804826A1 (en) * | 1988-02-17 | 1989-08-31 | Dietrich Kleinschmidt | Integrated process and apparatus for immobilising pollutants in waste materials |
| WO1999042382A1 (en) * | 1998-02-18 | 1999-08-26 | Rocky Mountain Remediation Services, L.L.C. | Method for treating wastes and preparing construction materials from waste |
| JP2004209314A (en) * | 2002-12-27 | 2004-07-29 | Kogi Corp | Treatment method and treatment apparatus of waste or the like by superheated steam |
| CN102764758A (en) * | 2012-08-02 | 2012-11-07 | 大连民族学院 | DDT (dichloro-diphenyl-trichloroethane) contaminated soil combined remediation method by ultraviolet rays, alfalfa and DDT degrading bacteria |
| CN103990451A (en) * | 2014-05-28 | 2014-08-20 | 南京理工大学 | Simple preparation method of efficient cerium tungsten oxide catalyst |
| CN107032757A (en) * | 2016-12-22 | 2017-08-11 | 北京北方节能环保有限公司 | A kind of method of the red water pollution soil remediations of TNT and recycling |
-
2017
- 2017-10-31 CN CN201711040207.1A patent/CN107583945B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3804826A1 (en) * | 1988-02-17 | 1989-08-31 | Dietrich Kleinschmidt | Integrated process and apparatus for immobilising pollutants in waste materials |
| WO1999042382A1 (en) * | 1998-02-18 | 1999-08-26 | Rocky Mountain Remediation Services, L.L.C. | Method for treating wastes and preparing construction materials from waste |
| JP2004209314A (en) * | 2002-12-27 | 2004-07-29 | Kogi Corp | Treatment method and treatment apparatus of waste or the like by superheated steam |
| CN102764758A (en) * | 2012-08-02 | 2012-11-07 | 大连民族学院 | DDT (dichloro-diphenyl-trichloroethane) contaminated soil combined remediation method by ultraviolet rays, alfalfa and DDT degrading bacteria |
| CN103990451A (en) * | 2014-05-28 | 2014-08-20 | 南京理工大学 | Simple preparation method of efficient cerium tungsten oxide catalyst |
| CN107032757A (en) * | 2016-12-22 | 2017-08-11 | 北京北方节能环保有限公司 | A kind of method of the red water pollution soil remediations of TNT and recycling |
Non-Patent Citations (2)
| Title |
|---|
| A superior Ce-W-Ti mixed oxide catalyst for the selective catalytic reduction of NOx with NH3;Wenpo Shan等;《Applied Catalysis B: Environmental》;20121231;第100-106页 * |
| WO3/TIO2-rGO复合材料的制备及其光催化性能;李翠霞等;《兰州理工大学学报》;20170630;第43卷(第3期);摘要 * |
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