CN104525123A - Porous composite material for removing heavy metals in soil and preparation method thereof - Google Patents
Porous composite material for removing heavy metals in soil and preparation method thereof Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/08—Aluminium compounds, e.g. aluminium hydroxide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
Abstract
The invention discloses a preparation method of a porous composite material for removing heavy metals in soil, which comprises the following steps: mixing an inorganic material and an organic material, molding, drying, sintering and the like to prepare a porous material substrate; activating the porous material with acid; and finally, in an organic or inorganic solution, treating the porous material with a silane coupling agent or any other organic molecule with adsorption, complexing and chemical linkage function on heavy metals to obtain a functional molecular layer, thereby obtaining the required porous composite material. The porous composite material has the characteristics of high selectivity for heavy metals and high adsorption efficiency when being used for remediating heavy-metal-containing soil. The porous material has the advantages of low consumption and long service life (up to 3-5 years). The technique can be widely used for remediating farmland or cultivated soil without influencing the normal cultivation and production of crops.
Description
Technical field
The present invention relates to soil incubation technical field in agricultural production, be specifically related to a kind of application and remove the composite porous and preparation method thereof of heavy metal in soil.
Background technology
The seriousness of 1.1 " cadmium rice " and harmfulness
2013 Hunan statistical yearbook displays, Hunan the whole province grain acreage 493.7 ten thousand hectares in 2012, rice yield 2,631 ten thousand tons, accounts for national rice yield 12.9%, is national maximum paddy rice main producing region.But the disturbance in recent years, about cadmium rice emerges in an endless stream.As far back as 2002, the rice security Examined display that the Ministry of Agriculture does, cadmium exceeding standard rate is 10.3%, zhuzhou,hunan in 2006 is produced cadmium rice and is exceeded standard and cause villager uncomfortable, and Chengdu, Sichuan in 2008 detects cadmium rice and exceeds standard, 2011, Agricultural University Of Nanjing professor Pan Genxing announces 170 the sample detection exceeding standard rate done for 2007 and is also about 10%, and the sample investigation display of Guangdong Province's announcement in 2013, the rice up to 44.4% and rice made products exceed standard, and Hunan is then the vortex of cadmium rice disturbance.In Hunan " cadmium rice " event of Guangdong report in 2013, the content of cadmium reaches as high as per kilogram 1.005 milligrams, and almost the regional rice produced maintains an equal level this numerical value with Japan's " high cadmium ".The cadmium that Department of Qulity Supervision of Guangdong Province announces exceeds standard list display, and the Zhuzhou in Hunan, Hengyang, Chenzhou, Yiyang, Changde are called " cadmium rice " severely afflicated area, are especially very with the Youxian County of Zhuzhou subordinate area.
Zuo Xiongjian passes through different times, the detected next heavy metals exceeding standard situation of Rice Samples of different regions is analyzed, the rice heavy metal pollution in result display Hunan Province is mainly based on cadmium pollution, heavy-metal residual exceeding standard rate rises to 47.3% at 2010-2011 from 33.9%, and East Hunan is the comparatively serious area of heavy metal pollution.Hunan Rice residues of pesticides and heavy metals exceeding standard present situation and control way research, Zuo Xiongjian
" cadmium rice " has not only dampened the transaction of Hunan Grain, more threatens the healthy of Hunan people.Rice is one of staple food of eating of the mankind, therefore, rice is as the important step of in food chain, most probable brings cadmium into human body, and cadmium is once enter human body, substantially there is no the half-life, and there temporarily do not have specific drug to be got rid of to be external, the pain disease that cannot retrieve will be brought to human body, even dead.
1.2 Cadmium Pollution in Soils present situations
" cadmium rice " is mainly derived from the soil by cadmium pollution.In year December in April, 2005 to 2013, China has carried out national Soil Pollution Investigation first.Adjust the display of difference result, national soil environment situation totally allows of no optimist, and some areas soil pollution is heavier, and arable soil environmental quality causes anxiety, industry and mining discarded ground soil environment outstanding problem.Soil total exceeding standard rate in the whole nation is 16.1%, and wherein slightly, slightly, moderate and serious pollution point position ratio be respectively 11.2%, 2.3%, 1.5% and 1.1%.Pollution type is based on inorganic type, and a figure place that exceeds standard accounts for 82.8% of all super punctuation bits.Cadmium pollution object point position exceeding standard rate is the highest, reaches 7.0%.
" China's quality of rice security status and developing countermeasure research " that China Paddy Rice Inst and Ministry of Agriculture's rice and quality of item supervision and inspection center issue for 2010 claims, the arable land of China 1/5 is by heavy metal pollution, and wherein cadmium pollution is ploughed and related to 11 province, 25 areas.Area on the south the Changjiang river such as Hunan, Jiangxi, this problem is more outstanding.
The end of the year 2012, the Hu-nan's agriculture Room once disclosed in the whole province's farmland quality work meeting, and the rapid test paper heavy metal pollution of current Hunan Province has totally presented from slight pollution to severe compound pollution development, developed from local pollution to regional pollution, from city suburbs to the trend of vast rural development.Mainly concentrate on the areal of industrial concentration of the Xiangjiang River basins such as Zhuzhou, Hengyang, Loudi, Chenzhou, industrial and mineral mining area and surrounding area.The contaminated by heavy metals arable land of Hunan the whole province accounts for 25% of the whole province's cultivated area.Point out in the urban-rural integration blue books in 2012 that the Chinese Academy of Social Sciences issues, according to the result of agricultural sector's nearly 5 years agricultural environment policy position monitors, only the Xiangjiang River basin grain place of production has exceeded 1,180,000 mu by the area of heavy metal pollution.About 190,000 mu of wherein serious pollution, account for 16%, major pollutants are cadmium, arsenic etc., and especially serious with the pollution of cadmium, the exceeding standard rate of Cadmium in Soil is up to 64%.And in " the Heavy Metal Pollution international cooperation forum " that initiated by dawn environmental protection on January 11st, 2014, also mention " 2012; the paddy rice place of production, Hunan the whole province key area has 78.1% to be subject to the heavy metal pollutions such as cadmium; wherein serious pollution is 44.4%, and slight pollution is 33.7% " from the graduate Huang Shunhong president of Hunan Province's non-ferrous metal.In the news briefing that in March, 2014 holds in government of Hunan Province, the responsible persons such as land resources in Hunan province Room chief describe " Hunan Province second time land investigation key data achievement " interesting cases, investigation result shows, Chang-Zhu-Tan Delta Region, Hunan south area have part plough be subject in, serious pollution, should not cultivate.
Cadmium, in the harm of soil, is once contaminated, and returning to state of depolluting needs for a long time.Also do not have specific antidote available at present, and enter into the cadmium of human body, reach 10 ~ 30 years biological half life.
1.3 Cadmium Pollution in Soils preventive measure and recovery techniques
1.3.1 Cadmium Pollution in Soils preventive measure
The source of cadmium in agricultural land soil, mainly by following three kinds of modes: 1) aerosol deposition: the cadmium aerosol that particle is less can be carried within the specific limits by air-flow, and settles down; 2) sewage irrigation: irrigation water cadmium exceeds standard, and crop has the inspissation of hundred times to cadmium; 3) pollution that brings of sludge composting and chemical fertilizer: fertilizer itself containing certain Cd, the several years use the accumulation that may bring heavy metal.Therefore, the cadmium pollution of agricultural land soil be prevented, must do from gas, irrigation water and farmland management.
Cadmium aerosol, is mainly derived from the metallurgical industry that Hunan is numerous, administers metallurgical industry, weakens cadmium and other heavy metal to the pollution of environment from source.
Irrigation water, namely requires that the water source to entering farmland is administered.From heavy metal Treatment process aspect, heavy metal process in aqueous phase easily will process many compared with the heavy metal in soil, therefore, as important pollution sources of farmland cadmium pollution, to the cadmium of irrigation water and the prevention of other heavy metal or to administer be a very important aspect.
The method that in aqueous phase, heavy metal is administered is numerous, and at present, conventional processing method has three classes: the first kind is that in aqueous phase, heavy metal ion is by the method for chemical reaction removing occurs, and concrete grammar has the precipitation method, chemical reduction method, electrochemical reducing etc.; Equations of The Second Kind is the method making the heavy metal in aqueous phase carry out absorption under the condition not changing its chemical form, concentrate, be separated, and concrete grammar has zeolite adsorption, the absorption of many tuberculosis ore deposit, ocean, bentonite adsorption, solvent extraction, ion-exchange; 3rd class removes the method for heavy metal in aqueous phase, and concrete grammar has bio-flocculation process, biosorption process, phytoremediation method etc.
(3) fertilizer, containing more heavy metal Hg, Cd, As, Zn, Pb in general perphosphate, phosphate fertilizer takes second place, nitrogenous fertilizer and potash fertilizer content lower, but in nitrogenous fertilizer, lead content is higher, and wherein As and Cd is seriously polluted.Rational Application chemical fertilizer is required, but uses the excessive pollution that also can cause soil or underground water.
1.3.2 Cadmium Pollution in Soils recovery technique
Current, countries in the world take much count of heavy metal pollution amelioration technique study, and carry out research work widely.The approach that repairing heavy metal in soil pollutes mainly contains two kinds, and one is change the existing forms of heavy metal in soil, make it fix, and reduces its animal migration in the environment and bioavailability; Two is removal heavy metals from soil.Repair approach around these two kinds, correspondingly propose respective physics, chemistry and bioremediation technology.
(1) peripheral doses technology
Peripheral doses technology comprises: 1) soil moved in improve the original, and contaminated soil adds untainted new soil; Soil removal and replacement, will remove with contaminated soil, change untainted new soil; Dig, the table soil of pollution is turned over to lower floor; Remove table soil, the table soil mud of pollution is gone.1975, Japan repaired by the soil of cadmium pollution, employs displacement soil, and cadmium soil is buried to 25 centimetres of dark undergrounds.But in past 40 years, victim still lives in uneasiness, and Japanese society has also paid huge economic cost, and the shade of land pollution is eliminated not yet for this reason.
2) elution method, with leacheate or the water added containing heavy metal certain chemical substance water miscible can be improved, pollutant is rushed to root outer exactly, use the compound containing certain ligand or anion and heavy metal to form more stable complex compound or generate again to precipitate, to prevent polluted underground water.Elution method is better for the serious pollution effect of hydrocarbon, nitrate and heavy metal, is suitable for light soil, but investment is comparatively large, easily causes underground water pollution and loss of soil nutrient, soil sex change.
3) heat treating process is heated by contaminated soil, and the volatile contaminant in soil (Hg) is volatilized and collects to carry out reclaiming or processing, the method is only applicable to volatile heavy metal, limited to the removal of cadmium.
4) electrolysis is that heavy metal in soil is removed at male or female under the effect of electrolysis, electromigration, electric osmose and electrophoresis etc., but repairing effect and soil pH, shock-absorbing capacity, soil constitution and to pollute metal species correlation large.On the whole, these class methods have the advantages such as effect is thorough, stable, but implement complexity, a large amount of manpowers and financial resources need be spent, the soil swapped out is existed to the possibility of seepage and secondary pollution, simultaneously recover soil texture and fertility required time longer, and comparatively large by natural conditions restriction, the output of crops can be reduced, reduce economic benefit.
(2) chemical remediation technology
Chemical redemption is exactly drop into modifying agent, inhibitor to contaminated soil, increase the content of the soil organism, cation exchange capacity and clay, change the physicochemical property such as pH, Eh and conductance, heavy metal-polluted soil is oxidized, reduces, precipitate, adsorb, suppress and the effect such as antagonism, to reduce the biological effectiveness of heavy metal.Chemical redemption mainly contains the precipitation method, organic method, absorption method etc.
Conventional modifying agent has: the organic substance of lime, zeolite, calcium carbonate, phosphate, silicate and promotion reduction.The alkaline matter such as liming, slag, or the alkaline fertilizer such as calcium magnesium phosphate, can reduce the absorption of plant heavy metal.The impact of activity usually by soil ph of Cd is very large, [the N aidu R such as Naidu, KookanaR S, SumnerM E. Cadm ium sorp2 tion and transport in variab le charge soils [J]. Environ.Qua.l, 1997,26:602) 617.] by Cd contaminated soil liming 750kg/hm2, heavy metal in soil bio-available Zn concentration can be made to reduce about 15%, thus effectively suppress crop to the absorption of Cd.
Cd and Zn normally association, have similar chemical property and geochemical behaviour, thus Zn has the characteristic that antagonism Cd is absorbed by plants.By adding appropriate Zn in Cd contaminated soil, regulating Cd/Zn ratio, plant can be suppressed the absorption of Cd, the enrichment of Cd in plant can be reduced.In addition, the enrichment of paddy rice to cadmium can also be reduced adding of some inhibitor.Chen Taos etc. spray dinitrophenol dinitrophenolate cadmium inhibitor in cadmium pollution soil, and in conjunction with waterflooding, rice cadmium drops to 0.40mg/kg by 1.10mg/kg, reduce 64% [Chen Tao, Wu Yanyu, Kong Qingxin etc. agriculture cadmium pollution and control. state magazine, 1985 (2): 24-30].
The effectiveness comparison of chemical redemption is desirable and expense is little, but stability is not strong, there is the problem of heavy metal reactivation.According to the feature of heavy metal in soil, it easily reacts with some complexes and forms stable complex compound, and easy and number acid radical ion reacts to be formed and precipitates.In contaminated soil, add some complex compounds or acid ion, the pH value environment of soil is changed, to make the heavy metal in soil so stable that to exist, then carry out clear water drip washing.These class methods are not suitable for large-area pollution plot.
(3) bioremediation technology
Biological restoration be utilize some special plant, microorganism and animal, by metabolism, absorb the heavy metal removed in soil or Heavy Metals transformed, reducing the toxicity of heavy metal, purify soil.Mainly contain the technology such as animal reparation, microorganism remediation, phytoremediation.Animal repairs the heavy metal in the absorption soil such as some lower animal earthworm, the muroid mainly utilized in soil; Microorganism remediation is that the heavy metal such as the certain micro-organisms utilized in soil have the effects such as absorption, precipitation, oxidation and reduction, reduces the toxicity of heavy metal in soil.
Phytoremediation utilizes certain plants can restrain oneself with the characteristic of excessive accumulaiton heavy metal species to remove the heavy metal in soil.The Chen Tongbin researcher of geographical institute of the Chinese Academy of Sciences finds for 2009 can the super rich plant-ciliate desert-grass amassing cadmium, but but do not obtain large-area field application, its reason comprises: it is longer that this technology administers the cycle relatively, need time several years, peasant can not till the land in the meantime, such peasant will bear the economic loss of reparation and crops, this is that they are unacceptable, although therefore this technology is by the green environmental protection technique of praising highly as most market potential, but large-area application cannot be obtained.
Bioremediation technology is implemented simple, invest less, but governance process is longer.Situation about should pollute according to reality in the selection of removing pollutant by these class methods and determining, due to the effect of food chain, should avoid edible class, in order to avoid be detrimental to health during the choosing of these methods as far as possible.
1.3.4 brief summary
Although heavy metal, subsides are not that the soil remediation method of cadmium is numerous, and most method is still in laboratory batch experiment and simulated test stage, and the maturation method having reached on-the-spot level of application is little.Current research lays particular emphasis on that to seek governance efficiency high, the method that control expense is low and site operative is strong.
Hu-nan's agriculture expert introduction, Hunan is the maximum province of current national soil acidification area, and the whole province has 2/3rds to there is acidification phenomenon in various degree in ploughing.The direct impact that soil acidification brings, is increase the activity of cadmium in soil to make it more easily absorbed by crops, exacerbates the harm of cadmium pollution to a certain extent.Therefore, for the difference of each Polluted paddy soil proterties in Hunan, in conjunction with various heavy metal-polluted soil recovery technique, research and the integrated heavy metal recovery technique being suitable for each rice soil type in Hunan, to the being significant property of national economy in the whole province and even the whole nation.
Summary of the invention
The present invention, in order to solve the above-mentioned deficiency of prior art, proposes the composite porous preparation method that heavy metal in soil is removed in a kind of application.
In order to solve the problems of the technologies described above, the present invention by the following technical solutions: the composite porous preparation method of heavy metal in soil is removed in a kind of application, comprises the steps:
1) take the former material of a certain amount of porous material and put into ball grinder, then add water, dispersant, and insert abrading-ball, allow composite material carry out ball milling in ball grinder;
2) screen cloth crossed by the slurry after taking out ball milling, loads in stainless steel disc, then puts into baking oven together and dry;
3) the mud powder that drying completes is carried out shaping balling-up by extruder, ball is put into oven drying, and dry moisture, lower than 0.8%, finally uses electric furnace in reduction or oxidizing atmosphere, sinter at the temperature of 500-1000 DEG C, thus obtain porous material matrix;
4) the porous material matrix obtained through step 3) being immersed in concentration is in the dilute acid soln of 0.5-5%, transfers set to 0 .1-5 hour the temperature of 50-90 DEG C, then dry at the temperature of 80-150 DEG C;
5) product obtained through step 4) is dropped in organic liquid or the aqueous solution again, react at the temperature of 50-150 DEG C with silane coupler or organic molecule solution, thus synthesizing porous composite.
Preferably, the former material of porous material in described step 1) is one or more the mixture in potassic feldspar, bentonite, silica flour, calcite, talcum powder, graphite powder, gangue, coal dust, bauxite, calcite, organic polymer material.
Preferably, the dispersant in described step 1) is sodium phosphate trimer, and the weight ratio of the former material of porous material, water, abrading-ball and dispersant in ball grinder is 1: 0.8: 2: 0.003.
Preferably, the dilute acid soln in described step 4) is dilute sulfuric acid, watery hydrochloric acid or dust technology.
Preferably, the organic liquid in described step 5) is the one in benzene,toluene,xylene, methyl alcohol, ethanol, isopropyl alcohol, acetone, espeleton, methyl acetate, ethyl acetate and propyl acetate.
Preferably, the silane coupler in described step 5 is the one in gamma-amino propyl group front three (second) TMOS, γ-Mercaptopropyltriethoxysilane and N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane.
Preferably, described organic molecule solution is can play the organic molecule solution of complexing and chemical reaction with heavy metal element containing carboxylic acid group, alcohol radical, amino.
Preferably, obtained composite porous particle diameter is 1-2000mm, and porosity is 20-80%, and aperture is 5nm-800nm, and specific area is 0.1-1000 ㎡/g.
This is composite porous is graininess, and the one dimension length of particle is 0.5-100mm, is fine particulate when composite porous reality uses, and fine grained is wrapped in mesh bag to be convenient to pull out from mud or mud again.
Composite porous can in the paddy field being incorporated into by heavy metal pollution of Direct Uniform.The consumption of invention material is according to the calculation of total (guaranteeing the heavy metal adsorbing at least 80%) of heavy metal contained in the mud of field.This material sieve is pulled out in the mud of farmland to facilitate by the coarse granule fine grained of plastic wire parcel (or for) that 1 dimension length of material granule can be 1-100cm.Then normal farming and crops plantation are implemented to this plot.This plot can Planting Crops 3-5 season identifies validity of the present invention and persistence continuously.After multipass crops have been gathered in, earth is softened this farmland irrigating full water and has carried out the cultivated rake of appropriateness to pull composite porous coarse granule (or fine grained of the plastic wire parcel) sieve having adsorbed heavy metal out reach permanent removal heavy metal object.
Composite material granular of the present invention can blending in the planting soil of crops and to soil property without destruction, do not affect cultivating and the normal plantation of crop and growth of soil, (0.5-5) heavy metal can there is suction-operated for a long time, and adsorbed this of heavy metal composite porous in content of beary metal be the 2-100 of neighbouring soil doubly, adsorbed heavy metal material can by solubility be 4-12% solubility hydrochloric acid or 1-5% EDTA solution clean out.This after cleaning is composite porous can continue Adsorption of Heavy Metals in addition.
Compared with prior art, beneficial effect of the present invention is: of the present invention being applied to removes that heavy metal-polluted soil is composite porous has the high selectivity of heavy metal and adsorption efficiency is high, the chemical stability of material own is good, mechanical strength is high, have the feature of long service life, do not affect soil texture and characteristic, do not hinder normal farming and the plantation in soil, and the removal of heavy metal is permanent, the reparation of heavy metal pollution farmland and soil can be widely used in.Heavy metal in soil after process can reduce year by year and the content of beary metal of crops produced during using the porous material of this invention can be reduced to the national standard (in rice, cadmium is lower than 0.1mg/kg) of safe edible.
Detailed description of the invention
Below in conjunction with embodiment, invention is described in detail.
Embodiment 1:
Composite porous preparation: take potassic feldspar 1 kilogram, bentonite 55 kilograms, silica flour 2 kilograms, 0.5 kilogram, calcite, talcum powder 0.5 kilogram, graphite powder 2.5 kilograms, add water again, ball, dispersant, dispersant is sodium phosphate trimer, their proportionings are material: water: ball: dispersant=1: 0.8: 2: 0.003, then put into together inside ball grinder and carry out ball milling 18 hours; The slurry that ball milling completes is crossed 300 eye mesh screens, pours in stainless steel disc, then put into baking oven together and dry; The mud powder that drying completes is carried out shaping balling-up by extruder, ball is put into oven drying, dry moisture, lower than 0.8%, uses electric furnace to burn till; The material fired being immersed in concentration is in the dilution heat of sulfuric acid of 0.5-5%, transfers set to 0 .1-3 hour the temperature of 50-90 DEG C, then dry at the temperature of 80-150 DEG C; Drop into again afterwards in xylene solution, react with γ-Mercaptopropyltriethoxysilane at the temperature of 50-150 DEG C, thus synthesizing porous composite.
Embodiment 2:
Take embodiment 1 material 20 g (one dimension length is 1cm), join 10 kilograms containing in the agricultural land soil of cadmium, then add 19 kg of water, stir 2h, this mixture is contained in the container of a sealing, the container that this mixture is housed slowly is overturn (1 turn per minute) 180 days.Should containing the agricultural land soil of cadmium measured before mix with embodiment 1 material be 1.1mg/L containing cadmium concentration, earth saved by the container opening sealing after 180 days and the cadmium concentration result analyzed contained by earth is as shown in table 1.Pull out in the embodiment 1 material earth of particle 1cm simultaneously, earth is rinsed out with water, then embodiment 1 material rinsed well is put into 50ml 1%EDTA solution, shake this solution 5 hours, filter out embodiment 1 material subsequently and dilute example 1 material with the washing of 50ml deionized water, wash water and EDTA soak are merged, what analyze this amalgamation liquid is 3.0mg containing cadmium total amount.This illustrates that embodiment 1 material adsorbs and is enriched 3.0mg cadmium metal from earth, and this is that the content of total cadmium in the earth analyzed with table 1 is reduced to 0.94mg[(1.1mg/ kilogram of-0.94 mg/ kilogram from 1.1mg) * 20.0 kilograms=3.2mg] consistent.
Containing cadmium analysis result before and after the earth process of table 1 farmland
| Before process | After process | Cadmium removal efficiency percentage | |
| Active cadmium, mg/ kilogram | 0.28 | 0.13 | 53.6% |
| Total cadmium, mg/ kilogram | 1.10 | 0.94 | 14.5% |
As can be seen from Table 1, the material of embodiment 1 can remove the heavy metal cadmium of in soil 53.6%.These removed cadmiums from soil are all enriched in embodiment 1 material.The material of this Adsorption of Heavy Metals can separate the object reaching permanent removal heavy metal in soil from earth.
Embodiment 3:
Take embodiment 1 material 20 g (one dimension length is 20mm and is divided in four nylon net bags), join 10 kilograms containing in the agricultural land soil of cadmium, add 20 kg of water again, stir 2h, this mixture is contained in the container of a sealing, the container that this mixture is housed slowly is overturn (1 turn per minute) 200 days.Should containing the agricultural land soil of cadmium measured before mix with embodiment 1 material be 1.1mg/L containing cadmium concentration, earth saved by the container opening sealing after 200 days and the cadmium concentration result analyzed contained by earth is as shown in table 2.
Containing cadmium analysis result before and after the earth process of table 2 farmland
| Before process | After process | Cadmium removal efficiency percentage | |
| Active cadmium, mg/ kilogram | 0.30 | 0.11 | 63.3% |
| Total cadmium, mg/ kilogram | 1.20 | 0.90 | 25.0% |
As can be seen from Table 2, the material of embodiment 1 can remove the heavy metal cadmium of in soil 63.3%.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Above-described embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, patent of the present invention and protection domain should be as the criterion with appended claims.
Claims (9)
1. apply the composite porous preparation method removing heavy metal in soil, it is characterized in that, comprise the steps:
1) take the former material of a certain amount of porous material and put into ball grinder, then add water, dispersant, and insert abrading-ball, allow composite material carry out ball milling in ball grinder;
2) screen cloth crossed by the slurry after taking out ball milling, loads in stainless steel disc, then puts into baking oven together and dry;
3) the mud powder that drying completes is carried out shaping balling-up by extruder, ball is put into oven drying, and dry moisture, lower than 0.8%, finally uses electric furnace in reduction or oxidizing atmosphere, sinter at the temperature of 500-1000 DEG C, thus obtain porous material matrix;
4) the porous material matrix obtained through step 3) being immersed in concentration is in the dilute acid soln of 0.5-5%, transfers set to 0 .1-5 hour the temperature of 50-90 DEG C, then dry at the temperature of 80-150 DEG C;
5) product obtained through step 4) is dropped in organic liquid or the aqueous solution again, react at the temperature of 50-150 DEG C with silane coupler or organic molecule solution, thus synthesizing porous composite.
2. the composite porous preparation method of heavy metal in soil is removed in application as claimed in claim 1, it is characterized in that: the former material of the porous material in described step 1) is one or more the mixture in potassic feldspar, bentonite, silica flour, calcite, talcum powder, graphite powder, gangue, coal dust, bauxite, calcite, organic polymer material.
3. the composite porous preparation method of heavy metal in soil is removed in application as claimed in claim 1, it is characterized in that: the dispersant in described step 1) is sodium phosphate trimer, and the weight ratio of the former material of porous material, water, abrading-ball and dispersant in ball grinder is 1: 0.8: 2: 0.003.
4. the composite porous preparation method of heavy metal in soil is removed in application as claimed in claim 1, it is characterized in that: the dilute acid soln in described step 4) is dilute sulfuric acid, watery hydrochloric acid or dust technology.
5. the composite porous preparation method of heavy metal in soil is removed in application as claimed in claim 1, it is characterized in that: the organic liquid in described step 5) is the one in benzene,toluene,xylene, methyl alcohol, ethanol, isopropyl alcohol, acetone, espeleton, methyl acetate, ethyl acetate and propyl acetate.
6. the composite porous preparation method of heavy metal in soil is removed in application as claimed in claim 1, it is characterized in that: the silane coupler in described step 5 is the one in gamma-amino propyl group front three (second) TMOS, γ-Mercaptopropyltriethoxysilane and N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane.
7. the composite porous preparation method of heavy metal in soil is removed in application as claimed in claim 1, it is characterized in that: described organic molecule solution is can play the organic molecule solution of complexing and chemical reaction with heavy metal element containing carboxylic acid group, alcohol radical, amino.
8. composite porous by prepared by claim 1 preparation method, it is characterized in that: obtained composite porous particle diameter is 1-2000mm, porosity is 20-80%, and aperture is 5nm-800nm, and specific area is 0.1-1000 ㎡/g.
9. composite porous as claimed in claim 8, it is characterized in that: this is composite porous is graininess, and the one dimension length of particle is 0.5-100mm.
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