CN107583945A - A kind of method of organic polluted soil production fired brick - Google Patents
A kind of method of organic polluted soil production fired brick Download PDFInfo
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- CN107583945A CN107583945A CN201711040207.1A CN201711040207A CN107583945A CN 107583945 A CN107583945 A CN 107583945A CN 201711040207 A CN201711040207 A CN 201711040207A CN 107583945 A CN107583945 A CN 107583945A
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Abstract
The invention discloses a kind of method of organic polluted soil production fired brick, belong to contaminated soil remediation and recycling field.After contaminated soil is crushed, sieved by the present invention, a certain amount of catalytic oxidant is put into contaminated soil, cuts down total amount of organic, a certain amount of cleaning brick-making raw material is added again, humidification stirring ageing is carried out again, then carries out base, drying, sintering, and fired brick is made.The present invention makes full use of brickmaking technology equipment, the total amount of organic in oxidant reduction soil is added before brickmaking, so as to reduce the environmental risk of tail gas, while in the sintering process of adobe, the organic matter of residual is desorbed or is pyrolyzed, so as to which organic matter thoroughly be removed；The present invention realizes the recycling of soil while contaminated soil is handled.
Description
Technical field
The invention belongs to contaminated soil remediation and recycling field, and in particular to a kind of organic polluted soil produces fired brick
Method.
Background technology
As country " moves back two to enter the issue of three " policies and implement, substantial amounts of contaminating enterprises move out city, leave lower substantial amounts of
Contaminated site, wherein comprising the substantial amounts of organic contamination place of production, main polluted factors are total petroleum hydrocarbon (TPHs), volatile organic matter
And semi-volatile organic matter (SVOCs) (VOCs).
Organically-pollutedsoil soil remediation method mainly have cement kiln synergic processing, soil vapor extraction technology, thermal desorption technology,
Chemical oxidation techniques, microorganism remediation technology, phytoremediation technology, Barrier Technology in situ, Landfill etc..Move back two and enter three and leave
Contaminated site largely will be planned to residential land, business take etc., such region usually require carry out infrastructure construction, need
Place is excavated, and soil is transferred to other regions and banked up, substantial amounts of soil will be taken.
Cement rotary kiln incineration technology is mainly stopped for a long time using the high temperature in cement rotary kiln, gas, thermal capacity is big,
Heat endurance is good, alkaline environment, without waste sludge discharge the features such as, while clinker is produced, burning disposal contaminated soil.Have
Machine thing contaminated soil enters cement rotary kiln from kiln exit gas room, and gas phase temperature reaches as high as 1800 DEG C in kiln, and temperature of charge is about
For 1450 DEG C, under the hot conditions of cement kiln, the organic pollution in contaminated soil is converted into inorganic compound, high temperature gas flow
Alkaline material (CaO, the CaCO being distributed with high fineness, high concentration, high adsorption, high uniformity3Deng) fully contact, effectively press down
The discharge of acidic materials processed so that sulphur and chlorine etc. change into inorganic salts and is fixed up.Cement kiln synergic processing can have been realized
The innoxious and recycling of machine contaminated soil, but cement industry is in the state of production capacity surplus at this stage, and the market of cement is deposited
Certain the problem of.
Soil vapor extraction technology is the reparation for volatile organic matter and part semi-volatile organic matter contaminated soil
Method, soil vapor extraction technology are to extract soil air using horizontal or vertical well to cause barometric gradient in contaminated soil to become
Change, and then make nonaqueous phase liquid in soil and the pollutant volatilization being dissolved in interstitial water enhancing, soil surface pollutant
Desorption rate improve, volatile organic contaminant is extracted to ground, and it is collected and handled, to realize Polluted Soil
The purpose of earth reparation, gas phase extraction technique are typically carried out in the original location, have that remediation efficiency is low, repairing efficiency is longer, it is difficult to thoroughly
The features such as removing pollutant, and the features such as China's contaminated site recovery project existence time is tight at this stage, task weight, gaseous phase of soil
Extraction technique can not meet to require.
Organic polluted soil thermal desorption technology is under vacuum or when being passed through carrier gas, passes through directly or indirectly heat and hands over
Change, the organic pollution in soil be heated to enough temperature so that organic pollution be able to volatilize from pollution medium or
Separation, into the process of gas handling system.The technology repairing efficiency is short, can thoroughly remove pollutant, but its cost is higher.
Chemical oxidation techniques are the oxidation susceptibilities using oxidant, make pollutant oxidation Decomposition, are changed into nontoxic or toxicity
Less material, so as to eliminate the pollutant in soil.Contain substantial amounts of organic matter in soil, organic matter consumable can aoxidize
Agent, improve chemical oxidation recovery technique cost.
Microorganism remediation technology be it is a kind of using indigenous microorganism or the microorganism with specific function of domestication,
Under the conditions of control environment, by the metabolism of itself, reduce noxious pollutant activity in soil or be degraded into innocuous substance
Recovery technique, microorganism remediation technology application cost is relatively low, to soil fertility and metabolic activity negative effect it is small, can avoid because
Pollutant shift and to human health and environmental effects；Phytoremediation technology is to utilize green plants and its symbiotic microorganism
Extraction, transfer, absorb, decompose, the organic or inorganic pollutant in conversion or fixing soil, pollutant is removed from soil,
The purpose of so as to reach removal, reduction or stable pollutant, or reduce pollutant toxicity.Microorganism and phytoremediation technology reparation
Efficiency is low, the cycle is longer, it is generally the case that it is difficult to be timely completed the duration.
Photodissociation method is the method for decomposing organic exhaust gas directly or by certain photochemical catalyst under light illumination, is mainly had ultraviolet
Light decomposition method and photocatalytic oxidation, it is a variety of difficult degradations of processing, the new technology of low concentration organic compound, target stains can be made
Thing structure and physico-chemical property change, while generate H2O、CO2With other small-molecule substances.Photochemical catalyst is pollution-free, to part
Organic matter efficiency is very high, but when catalyst surface organic concentration is too high, catalyst can be caused to lose activity, therefore the party
Method is applied to low concentration, the indoor air purification of small tolerance, does not apply to large-scale commercial Application.
Contaminated soil is mainly placed in antiseepage barrier landfill yard by Barrier Technology in situ, or is blocked by laying barrier layer
The approach of pollutants in soil diffusion, makes contaminated soil isolate with surrounding environment, avoid pollutant and human contact and with
Precipitation or underground water migrate and then human body and surrounding environment are damaged.By embodiments thereof, barrier in situ can be divided into and covered
Lid and dystopy barrier landfill.Pollute in the technology contaminated soil and do not remove thoroughly, environmental risk is still present.
All there are various problems in single soil remediation method, therefore, increasing research begins to focus on a variety of repair
Recovering technology is used in mixed way, the defects of to overcome monotechnics to exist.
The content of the invention
Problem be present for existing Organically-pollutedsoil soil remediation method, the invention provides a kind of production of organic polluted soil
The method of fired brick, this method are aoxidized to organic matter in contaminated soil using photocatalyst first, cut down organic dirt
Thing total amount is contaminated, reproduction fired brick, under high-temp combustion, is turned the organic pollution in contaminated soil by photocatalyst
Inorganic compound is turned to, thoroughly removes organic pollution in contaminated soil, realizes reparation and the recycling of organic polluted soil, by
In the introducing of photocatalyst, the burned usage amount into middle oxidant is reduced, meanwhile, it is attached during high-temp combustion
The organic pollution on photocatalyst is converted into inorganic matter by metal oxide containing precious metals, in early stage photocatalytic process because
The titanium dioxide that organic matter absorption loses catalytic activity regenerates photocatalytic activity.
The present invention provides a kind of method of organic polluted soil production fired brick, comprises the following steps：
The first step, after contaminated soil is crushed, sieve, it is delivered in mixer；
Second step, a certain amount of oxidant is added in contaminated soil, and be thoroughly mixed and turn over throwing, see photooxidation, with
Static 2-3 days afterwards；
3rd step, addition cleaning brick-making raw material, adds water to be stirred and be aged in contaminated soil after oxidation；
4th step, the stirring material after ageing is sent into brickmaking technology equipment, base, drying and sintering is carried out successively, is made
Fired brick.
Wherein, the oxidant is WO3-CeO2/ titanium dioxide-graphene.
Wherein, the titanium dioxide is rutile titanium dioxide.
Wherein, the oxidant WO3-CeO2The preparation method of/titanium dioxide-graphene includes：
It is prepared by the first step, graphene oxide；Take 5g graphite powders and 35g potassium permanganate to be well mixed, weigh the 300mL concentrated sulfuric acids
It is put into reaction vessel, is placed in ice bath environment with the mixing of 37g potassium nitrate, in the case of magnetic agitation, starts to add graphite
The mixture that powder and potassium permanganate are formed, adding speed is slow, keeps ice bath temperature, protects reaction mixture after the completion of addition
The stirring reaction 24h under 60 DEG C of water-bath temperature conditionss is held, is put into ice bath environment and cools down, 5 DEG C is down to and once starts slowly
20ml hydrogen peroxide is added, after question response solution is changed into yellowish-brown completely, continues to stir 25min, obtains yellowish-brown turbid solution, centrifuge
Dehydration, then the chlorohydric acid pickling and adopting for using mass percentage concentration to be 10% are washed with deionized to neutrality, are obtained and are aoxidized stone
Black alkene.
Prepared by second step, mixed carrier, take 150ml deionized waters and 600ml isopropanols to be added in reaction vessel, then
It is placed in ice bath environment, the pH value that concentrated hydrochloric acid regulation reaction solution is added dropwise while stirring between 1 and 3, adds the first step and prepared
Graphene oxide, graphene oxide adds in a manner of the outstanding mixed liquid of deionized water, concentration 0.5mgml-1, addition is
200-400ml, it is 0.5molL that concentration, which is then slowly added dropwise,-1TiCl4Aqueous solution 300ml, regulation reaction is molten after being added dropwise
The pH value of liquid is transferred in inner liner polytetrafluoroethylene stainless steel autoclave between 7-8, in argon atmosphere, be heated to 700 DEG C-
900 DEG C of reactions, 2 DEG C/min of heating rate, it is warming up to 700 DEG C of -900 DEG C of insulations and obtains graphene-rutile titanium dioxide in 2 hours
Mixed carrier；
3rd step, the preparation of catalyst, by nitric acid tungsten (W (NO3)3) and cerous nitrate (Ce (NO3)3) according to certain material
Amount proportioning mixing, it is 2gml that the water of addition, which is configured to concentration,-1(with WO3Quality meter) aqueous solution, prepared by second step mixed
Close carrier to be placed in reaction vessel, it is 2gml to add deionized water to be configured to concentration-1, metal oxide prepared above is water-soluble
Drop is added in the mixed carrier aqueous solution, and dripping quantity is with WO3Quality accounting 5%-8% is defined, and is stirred after being added dropwise, and surpasses
Sound 1 hour, stirring reaction 1 hour, then stands overnight at a temperature of being subsequently placed at 60 DEG C, filtering, deionized water washing, obtains
Filter cake in 80 DEG C of baking oven dry, Muffle kiln roasting is subsequently placed into, with 2 DEG C of min-1Programming rate reach 500 DEG C,
Constant temperature 2 hours, takes out after cooling, grinds, and obtains required catalyst.
Wherein, the nitric acid tungsten (W (NO3)3) and cerous nitrate (Ce (NO3)3) material amount proportioning be 3: 1-2: 1.
Wherein, the contaminated soil crushing and screening to particle diameter is less than 20mm.
Wherein, the volume ratio of contaminated soil and cleaning brick-making raw material is more than 1: 1, further preferred 3~5: 1.
Wherein, the fired brick is porous brick or hollow brick.
Wherein, the brick bat drying temperature is 50~200 DEG C, and sintering temperature is 800~1000 DEG C.
Wherein, per 1m3The oxidizer that uses of contaminated soil be 5kg~25kg.
The present invention has following features and advantage：
(1) present invention cuts down the organic pollution in soil by photochemical catalytic oxidation, reduces brickmaking before adobe is formed
Process organic pollution burns to form the amount of bioxin, while reduces content of organics in brickmaking tail gas, reduces the environment of tail gas
Risk；
(2) present invention utilizes chemical combustion oxidation catalyst technologies, by the bimetallic oxide of specific proportioning in rutile
Under compounding that type titanium dioxide-graphene is formed is carrier loaded, by sintering urging using bimetallic oxide during brickmaking
Change effect, remove removal organic polluter, and organic dirt that this combustion oxidation process will be attached on rutile titanium dioxide
It is complete to contaminate thing oxidation, recovers the catalytic effect of rutile titanium dioxide, its photocatalysis can be still utilized after the completion of brickmaking
Effect；
(3) present invention takes full advantage of existing production sintering brick process equipment, will humidification tank diameter as oxidation reactor,
Larger change need not be made to sintering brick process；
(4) present invention takes full advantage of the heat in fired brick production process, while adobe sinters, realizes organic dirt
Desorption and the pyrolysis of thing are contaminated, thoroughly removes pollutant；
(5) present invention realizes reparation and the recycling of contaminated soil, and economic benefit certain caused by energy simultaneously.
Brief description of the drawings
Fig. 1：Graphene-titanium dioxide X-ray powder diffraction analysis chart.
Embodiment
The present invention provides a kind of method of organic polluted soil production fired brick, comprises the following steps：
The first step, after contaminated soil is crushed, sieve, it is delivered in mixer；
Second step, a certain amount of oxidant is added in contaminated soil, and be thoroughly mixed oxidation, static 2-3 days；
3rd step, addition cleaning brick-making raw material in contaminated soil after oxidation, add water to be stirred and be aged 12~24
Hour, cleaning brick-making raw material is gangue or coal and one or more mixing in clay, building waste, Industrial Solid Waste waste
Thing；
4th step, by after ageing stirring material be sent into brickmaking technology equipment, successively carry out base, dry 12~24 hours and
Sintering 24~48 hours, is made fired brick.
The contaminated soil crushing and screening to particle diameter is less than 20mm.
The volume ratio of contaminated soil and cleaning brick-making raw material is more than 1: 1, further preferred 3~5: 1.
The fired brick is porous brick or hollow brick.
The brick bat drying temperature is 50~200 DEG C, and sintering temperature is 800~1000 DEG C.
Per 1m3The oxidizer that uses of contaminated soil be 5kg~25kg.
The oxidant that the present invention uses in second step is the bimetallic using rutile titanium dioxide-graphene as carrier
Oxide catalyst.Titanium dioxide is a kind of efficient photochemical catalyst, can aoxidize the organic compound of most of difficult degradations, right
Volatile organic waste gas has good catalytic degradation effect.Three kinds of crystal structures in nature be present in titanium dioxide, wherein, it is sharp
Titanium ore phase and brookite belong to low temperature phase, unstable, and rutile phase is the phase of high-temperature stable, and in this application,
Need to be sintered in high temperature, if using Anatase and brookite, in high-temperature sintering process, phase changes,
Some organic pollutants can be wrapped in titanium dioxide crystal, influence the photocatalysis effect of titanium dioxide, and the light for suppressing the later stage is urged
Change and recycle, therefore, the titanium dioxide used in this application is rutile titanium dioxide.
Relative to anatase titanium dioxide, the specific surface area of rutile titanium dioxide is relatively low, influences its catalytic performance
And load the ability of other catalyst, and graphene is a kind of two dimensional surface nano material, have outstanding mechanics, optics and
Thermal property, high-termal conductivity, specific surface area are big, good mechanical performance, and existing many researchs show, dioxy is wrapped up using graphene
The photocatalysis performance of titanium dioxide can be improved by changing titanium.In this application, graphene-rutile titanium dioxide composite wood is prepared
Material, specific surface area when being loaded by the addition increase rutile titanium dioxide of graphene, is realized before high temperature sintering
High efficiency photocatalysis performance, preferably removes volatile organic matter.
Because the electron-hole recombination rate of titanium dioxide is high, photocatalysis quantum efficiency is low.Noble-metal-supported is in titanium dioxide
Surface is advantageous to efficiently separating for light induced electron and hole, improves the light degradation reaction efficiency of titanium dioxide.Therefore the application examines
Consider using titanium dioxide and graphene composite material as carrier, in deposited on supports precious metal chemical complex, can further improve
The photocatalysis effect of titanium dioxide.
In addition, titanium dioxide and graphene are all the carriers of good precious metal oxide catalyst, high temperature is commonly used in
Learn in combustion oxidation technology and remove removal organic polluter, prepare efficient catalyst and use.Especially metal oxide particle loads
Onto titanium dioxide, under the reaction condition of high temperature, the metal oxide particle loaded will not reunite, so as to lead
Catalyst inactivation is caused, and the particle of metal oxide catalyst can be disperseed when titanium dioxide is as carrier, increasing
The contact area of metal oxide and reactant, it may advantageously facilitate the progress of oxidation catalysis reaction.
Noble metal catalyst is a kind of maximally effective method of decomposing organic waste in Production by Catalytic Combustion Process, has good degraded
Activity, there are the selection that many research is directed to noble metal catalyst, wherein cerium oxide (CeO2) it is a kind of very efficient
Combustion catalyst.And further select other noble metals to form bimetallic or trimetallic catalyst with cerium oxide, can more have
The transfer performance of the raising catalytic activity of cerium oxide of effect, oxygen storage capacity and active oxygen, is urged so as to improve whole burning
The efficiency of change process.In numerous precious metal oxide catalysts being engaged with cerium oxide, under the load system of the present invention,
Using tungsten oxide (WO3) best with cerium oxide formation bi-metal oxide catalyst catalytic effect.Therefore, use in this application
The composite that rutile titanium dioxide and graphene are formed is formed properly mixed double as carrier with tungsten oxide and cerium oxide
Metal oxide catalyst, by sintering organic polluted soil into brick, optimal organic pollutant removal method is obtained, preferably
In bimetallic oxide.
The preparation method for the bi-metal oxide catalyst that the application provides includes：
It is prepared by the first step, graphene oxide；Take 5g graphite powders and 35g potassium permanganate to be well mixed, weigh the 300mL concentrated sulfuric acids
It is put into reaction vessel, is placed in ice bath environment with the mixing of 37g potassium nitrate, in the case of magnetic agitation, starts to add graphite
The mixture that powder and potassium permanganate are formed, adding speed is slow, keeps ice bath temperature, protects reaction mixture after the completion of addition
The stirring reaction 24h under 60 DEG C of water-bath temperature conditionss is held, is put into ice bath environment and cools down, 5 DEG C is down to and once starts slowly
20ml hydrogen peroxide is added, after question response solution is changed into yellowish-brown completely, continues to stir 25min, obtains yellowish-brown turbid solution, centrifuge
Dehydration, then the chlorohydric acid pickling and adopting for using mass percentage concentration to be 10% are washed with deionized to neutrality, are obtained and are aoxidized stone
Black alkene.
Prepared by second step, mixed carrier, take 150ml deionized waters and 600ml isopropanols to be added in reaction vessel, then
It is placed in ice bath environment, the pH value that concentrated hydrochloric acid regulation reaction solution is added dropwise while stirring between 1 and 3, adds the first step and prepared
Graphene oxide, graphene oxide adds in a manner of the outstanding mixed liquid of deionized water, concentration 0.5mgml-1, addition is
200-400ml, it is 0.5molL that concentration, which is then slowly added dropwise,-1TiCl4Aqueous solution 300ml, regulation reaction is molten after being added dropwise
The pH value of liquid is transferred in inner liner polytetrafluoroethylene stainless steel autoclave between 7-8, in argon atmosphere, be heated to 700 DEG C-
900 DEG C of reactions, 2 DEG C/min of heating rate, it is warming up to 700 DEG C of -900 DEG C of insulations and obtains graphene-rutile titanium dioxide in 2 hours
Mixed carrier；
3rd step, the preparation of catalyst, by nitric acid tungsten (W (NO3)3) and cerous nitrate (Ce (NO3)3) according to certain material
Amount proportioning mixing, it is 2gml that the water of addition, which is configured to concentration,-1(with WO3Quality meter) aqueous solution, prepared by second step mixed
Close carrier to be placed in reaction vessel, it is 2gml to add deionized water to be configured to concentration-1, metal oxide prepared above is water-soluble
Drop is added in the mixed carrier aqueous solution, and dripping quantity is with WO3Quality accounting 5%-8% is defined, and is stirred after being added dropwise, and surpasses
Sound 1 hour, stirring reaction 1 hour, then stands overnight at a temperature of being subsequently placed at 60 DEG C, filtering, deionized water washing, obtains
Filter cake in 80 DEG C of baking oven dry, Muffle kiln roasting is subsequently placed into, with 2 DEG C of min-1Programming rate reach 500 DEG C,
Constant temperature 2 hours, takes out after cooling, grinds, and obtains required catalyst.
It is preferred that the nitric acid tungsten (W (NO3)3) and cerous nitrate (Ce (NO3)3) material amount proportioning be 3: 1-2: 1.
The present invention is described in further detail with reference to the accompanying drawings and detailed description, but protection scope of the present invention
It is not limited to the content.
The preparation of the graphene oxide of embodiment 1
Take 5g graphite powders and 35g potassium permanganate to be well mixed, weigh the 300mL concentrated sulfuric acids and the mixing of 37g potassium nitrate is put into instead
Answer in container, be placed in ice bath environment, in the case of magnetic agitation, start to add the mixing that graphite powder and potassium permanganate are formed
Thing, adding speed is slow, keeps ice bath temperature, and reaction mixture is maintained to 60 DEG C of water-bath temperature strip after the completion of addition
Stirring reaction 24h under part, it is put into ice bath environment and cools down, is down to 5 DEG C and once starts to be slowly added 20ml hydrogen peroxide, question response is molten
After liquid is changed into yellowish-brown completely, continues to stir 25min, obtain yellowish-brown turbid solution, centrifugal dehydration, then using mass percentage concentration
Chlorohydric acid pickling for 10% and adopting is washed with deionized to neutrality, obtains graphene oxide.
The preparation of 2 graphenes of embodiment-rutile titanium dioxide mixed carrier
Take 150ml deionized waters and 600ml isopropanols to be added in reaction vessel, be subsequently placed in ice bath environment, side
Concentrated hydrochloric acid regulation reaction solution is added dropwise in side pH value is stirred 2 or so, graphene oxide prepared by embodiment 1 is added, aoxidizes stone
Black alkene is added in a manner of the outstanding mixed liquid of deionized water, concentration 0.5mgml-1, addition 300ml, then it is slowly added dropwise
Concentration is 0.5molL-1TiCl4Aqueous solution 300ml, the pH value of reaction solution is adjusted after being added dropwise 7, is transferred to liner
In polytetrafluoroethylene (PTFE) stainless steel autoclave, in argon atmosphere, 700 DEG C of reactions are heated to, 2 DEG C/min of heating rate, are warming up to 700
DEG C insulation obtains graphene-rutile titanium dioxide mixed carrier in 2 hours.
The preparation of the mixed carrier of 1 graphene of comparative example-titanium dioxide 1
Take 150ml deionized waters and 600ml isopropanols to be added in reaction vessel, be subsequently placed in ice bath environment, side
Concentrated hydrochloric acid regulation reaction solution is added dropwise in side pH value is stirred 2 or so, graphene oxide prepared by embodiment 1 is added, aoxidizes stone
Black alkene is added in a manner of the outstanding mixed liquid of deionized water, concentration 0.5mgml-1, addition 300ml, then it is slowly added dropwise
Concentration is 0.5molL-1TiCl4Aqueous solution 300ml, the pH value of reaction solution is adjusted after being added dropwise 7, is transferred to liner
In polytetrafluoroethylene (PTFE) stainless steel autoclave, in argon atmosphere, 200 DEG C of reactions are heated to, 2 DEG C/min of heating rate, are warming up to 200
DEG C insulation obtains graphene-rutile titanium dioxide mixed carrier in 2 hours.
The preparation of the mixed carrier of 2 graphenes of comparative example-titanium dioxide 2
Take 150ml deionized waters and 600ml isopropanols to be added in reaction vessel, be subsequently placed in ice bath environment, side
Concentrated hydrochloric acid regulation reaction solution is added dropwise in side pH value is stirred 2 or so, graphene oxide prepared by embodiment 1 is added, aoxidizes stone
Black alkene is added in a manner of the outstanding mixed liquid of deionized water, concentration 0.5mgml-1, addition 300ml, then it is slowly added dropwise
Concentration is 0.5molL-1TiCl4Aqueous solution 300ml, the pH value of reaction solution is adjusted after being added dropwise 7, is transferred to liner
In polytetrafluoroethylene (PTFE) stainless steel autoclave, in argon atmosphere, 500 DEG C of reactions are heated to, 2 DEG C/min of heating rate, are warming up to 500
DEG C insulation obtains graphene-rutile titanium dioxide mixed carrier in 2 hours.
Judgement for graphene-rutile titanium dioxide crystal formation is using X-ray powder diffraction analysis (X-ray
Diffraction, abbreviation XRD).This method is to test most ripe, the most widely used method of powder crystalline state looks.Pass through X ray
Irradiation, the shape for corresponding the characteristic diffraction maximum of appearance analyze its crystal structure, by with powder diffraction card
(JCPDS No.21-1272) is contrasted to determine the type of crystal.
As shown in figure 1, compared with pure commercially available rutile titanium dioxide (A), by adding grapheme material acquisition
Embodiment 2 (B), all there are (110) crystallographic plane diffraction peaks at 27.55 °, and 27.55 ° of crystal face in composite graphite alkene material spreads out
Penetrate that peak is stronger, and the characteristic absorption peak of graphene (002) is got too close at 26 ° or so with rutile titanium dioxide, therefore do not have
There is individually obvious peak, same case occurs in pure commercially available anatase titanium dioxide (E), comparative example 1 (D) and 2 (C) systems
Standby carrier (101) crystallographic plane diffraction peaks in 25.40 ° of appearance, excessively connect with the characteristic absorption peak of graphene (002) at 26 °
Closely, therefore the separate peak of graphene does not occur, and process is compound, and complex carrier strengthens in 25.40 ° of peak face, and c, d and b phases
Than occurring two peaks between 25 ° to 27 °, explanation is the mixing of Detitanium-ore-type and rutile-type.
The preparation of the bimetallic oxidant of embodiment 3
By nitric acid tungsten (W (NO3)3) and cerous nitrate (Ce (NO3)3) mixed according to the proportioning of the amount 2: 1 of material, the water of addition
It is 2gml to be configured to concentration-1(with WO3Quality meter) aqueous solution, carrier prepared by embodiment 2 is placed in reaction vessel, added
It is 2gml that ionized water, which is configured to concentration,-1, the metal oxide aqueous solution prepared above is added drop-wise in the mixed carrier aqueous solution,
Dripping quantity is with WO3Quality accounting 6% is defined, and is stirred after being added dropwise, and ultrasound 1 hour, is subsequently placed at a temperature of 60 DEG C
Stirring reaction 1 hour, is then stood overnight, filtering, and deionized water washing, obtained filter cake is dried in 80 DEG C of baking oven, with
After be put into Muffle kiln roasting, with 2 DEG C of min-1Programming rate reach 500 DEG C, constant temperature 2 hours, taken out after cooling, grind,
Catalyst required for obtaining.
As shown in figure 1, the X-ray powder diffraction analysis chart of comparing embodiment 2 and embodiment 3 can be seen that feature diffraction
Peak is all rutile titanium dioxide-graphene carrier, and WO is not detected in spectrogram3And CeO2Characteristic diffraction peak, show two
Individual oxide is highly dispersed in rutile titanium dioxide-graphene carrier.
The preparation of the bimetallic oxidant 2 of comparative example 3
By nitric acid tungsten (W (NO3)3) and cerous nitrate (Ce (NO3)3) mixed according to the proportioning of the amount 2: 1 of material, the water of addition
It is 2gml to be configured to concentration-1(with WO3Quality meter) aqueous solution, carrier prepared by comparative example 1 is placed in reaction vessel, added
It is 2gml that ionized water, which is configured to concentration,-1, the metal oxide aqueous solution prepared above is added drop-wise in the mixed carrier aqueous solution,
Dripping quantity is with WO3Quality accounting 6% is defined, and is stirred after being added dropwise, and ultrasound 1 hour, is subsequently placed at a temperature of 60 DEG C
Stirring reaction 1 hour, is then stood overnight, filtering, and deionized water washing, obtained filter cake is dried in 80 DEG C of baking oven, with
After be put into Muffle kiln roasting, with 2 DEG C of min-1Programming rate reach 500 DEG C, constant temperature 2 hours, taken out after cooling, grind,
Catalyst required for obtaining.
Rutile titanium dioxide is compared by experiment and is used as the bimetallic oxide of carrier to volatile organic matter benzene, two
The catalytic degradation of toluene, two kinds of catalyst that the catalyst measured respectively is embodiment 3 and comparative example 3 provides, used survey
It is chromatographic technique to determine technology, and the chromatograph used is GC-2010 types gas chromatograph (Japanese Shimadzu Corporation), using chromatographic technique
The chromatographic peak area of benzene and dimethylbenzene in sample is determined, so as to determine the degradation rate of benzene and dimethylbenzene after catalysis.Impose a condition：
55 DEG C of column temperature, sensing chamber and 250 DEG C, gas flow 80ml/min, pressure 100kPa of room temperature of gasification, degradation rate=(when initial
Carve chromatographic peak area-measure moment chromatographic peak area/initial time chromatographic peak area) × 100%, initial benzene and dimethylbenzene are dense
Degree is 0.02mg/m3, each carry out 100min is reacted, is tested respectively in 50min, 70min and 100min.
Experimentation：, will be certain using static method using 350W xenon lamps (390~760nm of wave-length coverage) as visible light source
The benzene of amount, which is added in 1L closed vessel, voluntarily to be volatilized, and catalyst is placed in reaction vessel.After reaction starts, when one section
Between with syringe extracts 5mL gas, analysis photocatalytic degradation effect from reactor.In order to ensure the accuracy of experiment, often
Secondary degraded is passed through in reactor with zero level air replaces remaining gas later, is avoided the benzene of residual and is influenceed experimental result, experiment
It the results are shown in Table 1.
Table 1
As it can be seen from table 1 the load of bi-metal oxide catalyst is formed using rutile titanium dioxide and graphene
Body, during photocatalytic degradation volatile organic matter benzene and dimethylbenzene, catalytic effect is better than anatase titanium dioxide
The photocatalysis performance of the bimetallic oxide formed with graphene as carrier.
The preparation of the bimetallic oxidant 3 of comparative example 4
By nitric acid tungsten (W (NO3)3) and cerous nitrate (Ce (NO3)3) mixed according to the proportioning of the amount 2: 1 of material, the water of addition
It is 2gml to be configured to concentration-1(with WO3Quality meter) aqueous solution, carrier prepared by comparative example 2 is placed in reaction vessel, added
It is 2gml that ionized water, which is configured to concentration,-1, the metal oxide aqueous solution prepared above is added drop-wise in the mixed carrier aqueous solution,
Dripping quantity is with WO3Quality accounting 6% is defined, and is stirred after being added dropwise, and ultrasound 1 hour, is subsequently placed at a temperature of 60 DEG C
Stirring reaction 1 hour, is then stood overnight, filtering, and deionized water washing, obtained filter cake is dried in 80 DEG C of baking oven, with
After be put into Muffle kiln roasting, with 2 DEG C of min-1Programming rate reach 500 DEG C, constant temperature 2 hours, taken out after cooling, grind,
Catalyst required for obtaining.
Embodiment 4
The present embodiment object is certain place petroleum hydrocarbon contaminated soil, and petroleum hydrocarbon (＜ C16) concentration is 560~4890mg/kg,
Petroleum hydrocarbon (＞ C16) concentration is 6240~16920mg/kg.The method of contaminated soil production fired brick is as follows：
(1) by 30m3Contaminated soil carries out soil particle that is broken and being sized to 15 ± 5mm, and is delivered in mixer；
(2) 30kg bimetallic oxidants are added in contaminated soil, and is thoroughly mixed and turns over throwing, see photooxidation, then
Static 2 days；
(3) 20m is added in contaminated soil after oxidation3Brick-making raw material gangue is cleaned, adds water to be stirred and be aged
24h；
(4) enter normal brickmaking technology equipment, porous adobe, re-dry and sintering system be made into base system,
Drying temperature is 60 ± 5 DEG C, and drying time is 24 hours, and sintering temperature is 900 ± 10 DEG C, and sintering time is 24 hours, is made
Porous baked brick.
Sintered perforated brick according to《Wall-building brick inspection rule》(JC/T 466-1992) and《Test methods for wall bricks》(GB/T
Its quality and performance 2542-2012) is examined to be satisfied by《Sintered perforated brick and porous building-brick》(GB13544-2011) require.
Sintered perforated brick according to《Solid waste Leaching leaching method sulfonitric method》(HJ/T299-2007) prepare
Leachate petroleum hydrocarbon concentration should meet《Water environment quality standard》(GB3838-2002) water environment quality standard
Group III water limit value (≤0.05mg/L), porous baked brick total petroleum hydrocarbon meet《Place soil environmental risk assessment screening value》
(DB11/811-2011) residential estate standard (total petroleum hydrocarbon (＜ C16) ＜ 230mg/kg, total petroleum hydrocarbon (＞ C16) ＜ in
10000mg/kg)。
The fired brick petroleum hydrocarbon total amount of table 2 and leaching concentration
From table 2 it can be seen that rutile titanium dioxide is more in the catalyst carrier, the overall catalysis oxidation of catalyst
Petroleum hydrocarbon performance is better, and can influence the performance of catalyst as carrier using anatase titanium dioxide.
Preparation method according to embodiment 3 prepares bi-metal oxide catalyst, used nitric acid tungsten (W (NO3)3) and
Cerous nitrate (Ce (NO3)3) material amount proportioning to be followed successively by 3: 1,2: 1,1: 2.
The metallic catalyst of table 3 is with the influence for comparing petroleum hydrocarbon total amount and leaching concentration
From table 3 it can be seen that when dosage is more in bimetallic catalyst for nitric acid tungsten, catalytic performance is better, and nitric acid
The dosage of cerium is excessive, can reduce the catalysis oxidation of petroleum hydrocarbon.
Embodiment 5
The present embodiment object is certain place benzene homologues (benzene and dimethylbenzene) contaminated soil, benzene concentration scope is 14.87~
920.54mg/kg, xylene concentration scope are 267.32~765.14mg/kg.The method of contaminated soil production fired brick is such as
Under：
(1) by 40m3Contaminated soil carries out soil particle that is broken and being sized to 15 ± 5mm, and is delivered in mixer；
(2) 40kg bimetallic oxidants are added in contaminated soil, and is thoroughly mixed and turns over throwing, see photooxidation, then
Stand two days；
(3) 10m is added in contaminated soil after oxidation3Brick-making raw material gangue is cleaned, adds water to be stirred and be aged
24h；
(4) enter normal brickmaking technology equipment, porous adobe, re-dry and sintering system be made into base system,
Drying temperature is 60 ± 5 DEG C, and sintering temperature is 1000 ± 10 DEG C, and porous baked brick is made.
Sintered perforated brick according to《Wall-building brick inspection rule》(JC/T 466-1992) and《Test methods for wall bricks》(GB/T
Its quality and performance 2542-2012) is examined to be satisfied by《Sintered perforated brick and porous building-brick》(GB13544-2011) require.
Sintered perforated brick according to《Solid waste Leaching leaching method sulfonitric method》(HJ/T299-2007) prepare
Leachate benzene and xylene concentration should meet《Water environment quality standard》(GB3838-2002) centralized Drinking Water
Earth surface water source ground specific project standard limited value (benzene≤0.01mg/L, dimethylbenzene≤0.5mg/L), porous baked brick benzene and dimethylbenzene
Meet《Place soil environmental risk assessment screening value》Residential estate standard in (DB11/811-2011) (benzene ＜ 0.64mg/kg,
Dimethylbenzene ＜ 74mg/kg).
The fired brick benzene of table 4 and dimethylbenzene total amount and leaching concentration
From table 4, it can be seen that rutile titanium dioxide is more in the catalyst carrier, the overall catalysis oxidation of catalyst
Benzene and dimethylbenzene performance are better, and can influence the performance of catalyst as carrier using anatase titanium dioxide.
The metallic catalyst of table 5 is with the influence for comparing benzene and dimethylbenzene total amount and leaching concentration
As can be seen from Table 5, when dosage is more in bimetallic catalyst for nitric acid tungsten, catalytic performance is better, and nitric acid
The dosage of cerium is excessive, can reduce the catalysis oxidation of benzene and dimethylbenzene.
Embodiment 6
The present embodiment object is certain place polycyclic aromatic hydrocarbon (benzene (a) and pyrene, benzo (a) anthracene and benzo (b) fluoranthene) Polluted Soil
Earth, benzene (a) and pyrene concentration are 0.9~4.58mg/kg, and benzo (a) anthracene concentration is 4.22~22.98mg/kg, benzo (b) fluoranthene
Concentration is 5.72~15.48mg/kg.The method of contaminated soil production fired brick is as follows：
(1) by 50m3Contaminated soil carries out soil particle that is broken and being sized to 15 ± 5mm, and is delivered in mixer；
(2) 5kg bimetallic oxidants are added in contaminated soil, and is thoroughly mixed and turns over throwing, see photooxidation, it is then quiet
Put two days；
(3) 10m is added in contaminated soil after oxidation3Brick-making raw material gangue is cleaned, adds water to be stirred and be aged
24h；
(4) enter normal brickmaking technology equipment, porous adobe, re-dry and sintering system be made into base system,
Drying temperature is 150 ± 5 DEG C, and sintering temperature is 900 ± 10 DEG C, and porous baked brick is made.
Sintered perforated brick according to《Wall-building brick inspection rule》(JC/T 466-1992) and《Test methods for wall bricks》(GB/T
Its quality and performance 2542-2012) is examined to be satisfied by《Sintered perforated brick and porous building-brick》(GB13544-2011) require.
Sintered perforated brick according to《Solid waste Leaching leaching method sulfonitric method》(HJ/T299-2007) prepare
Leachate polycyclic aromatic hydrocarbon concentration should meet《Water environment quality standard》(GB3838-2002) centralized Drinking Water
Table water head site specific project standard limited value (benzene (a) and pyrene≤2.8 × 10-6Mg/L), porous baked brick total petroleum hydrocarbon meets《Place
Soil environment risk assessment screening value》(DB11/811-2011) residential estate standard (benzene (a) and pyrene ＜ 0.2mg/kg, benzene in
(a) and pyrene ＜ 0.5mg/kg, benzo (b) fluoranthene ＜ 0.5mg/kg).
The fired brick polycyclic aromatic hydrocarbon total amount of table 6 and leaching concentration
As can be seen from Table 6, when in catalyst carrier rutile titanium dioxide it is more, the overall catalysis oxidation of catalyst
Polycyclic aromatic hydrocarbon performance is better, and can influence the performance of catalyst as carrier using anatase titanium dioxide.
The metallic catalyst of table 7 is with the influence for comparing polycyclic aromatic hydrocarbon total amount and leaching concentration
As can be seen from Table 7, when dosage is more in bimetallic catalyst for nitric acid tungsten, catalytic performance is better, and nitric acid
The dosage of cerium is excessive, can reduce the catalysis oxidation of polycyclic aromatic hydrocarbon.
Described above is only the preferred embodiments of the present invention, is not intended to limit the invention；Others are any not to depart from this
Modification that the principle and concept thereof of invention are made, replacement, simplification, improvement etc., should be regarded as equivalent substitute mode, in this hair
Within bright protection domain.
Claims (9)
- A kind of 1. method of organic polluted soil production fired brick, it is characterised in that comprise the following steps：The first step, after contaminated soil is crushed, sieve, it is delivered in mixer；Second step, a certain amount of catalytic oxidant is added in contaminated soil, and be thoroughly mixed and turn over throwing, see photooxidation, with Static 2-3 days afterwards；3rd step, addition cleaning brick-making raw material, adds water to be stirred and is aged 12~24 hours in contaminated soil after oxidation；4th step, the stirring material after ageing is sent into brickmaking technology equipment, base, drying and sintering is carried out successively, sintering is made Brick.
- 2. the method for organic polluted soil production fired brick as claimed in claim 1, it is characterised in that：The catalytic oxidant For WO3-CeO2/ titanium dioxide-graphene.
- 3. the method for organic polluted soil production fired brick as claimed in claim 1 or 2, it is characterised in that：The titanium dioxide Titanium is rutile titanium dioxide.
- 4. the method for the organic polluted soil production fired brick as described in claims 1 to 3, it is characterised in that：The WO3- CeO2/ titanium dioxide-graphene passes through nitric acid tungsten (W (NO3)3) and cerous nitrate (Ce (NO3)3) prepare, nitric acid tungsten (W (NO3)3) and Cerous nitrate (Ce (NO3)3) material amount proportioning be 3: 1-2: 1.
- 5. the method for the organic polluted soil production fired brick as described in Claims 1-4, it is characterised in that：The Polluted Soil Earth crushing and screening to particle diameter is less than 20mm.
- 6. the method for the organic polluted soil production fired brick as described in claim 1 to 5, it is characterised in that：Contaminated soil and The volume ratio for cleaning brick-making raw material is more than 1: 1, further preferred 3~5: 1.
- 7. the method for the organic polluted soil production fired brick as described in claim 1 to 6, it is characterised in that：The fired brick For porous brick or hollow brick.
- 8. the method for the organic polluted soil production fired brick as described in claim 1 to 7, it is characterised in that：The adobe is done Dry temperature is 50~200 DEG C, and drying time is 12~24 hours, and sintering temperature is 800~1000 DEG C, and sintering time is 24~48 Hour.
- 9. the method for the organic polluted soil production fired brick as described in claim 1 to 8, it is characterised in that：Per 1m3Pollution The oxidizer that soil uses is 5kg~25kg.
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| CN110171956A (en) * | 2019-05-22 | 2019-08-27 | 福道联合(天津)大数据有限公司 | The method for preparing revetment brick using low concentration oil-polluted soils |
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| CN115301714A (en) * | 2022-08-11 | 2022-11-08 | 徐州振丰新型墙体材料有限公司 | Method for making brick by harmless sintering of polluted soil |
| 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 |
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