CN108624329A - A kind of preparation method of new soil heavy metal fixative - Google Patents

A kind of preparation method of new soil heavy metal fixative Download PDF

Info

Publication number
CN108624329A
CN108624329A CN201810626581.8A CN201810626581A CN108624329A CN 108624329 A CN108624329 A CN 108624329A CN 201810626581 A CN201810626581 A CN 201810626581A CN 108624329 A CN108624329 A CN 108624329A
Authority
CN
China
Prior art keywords
heavy metal
attapulgite clay
silica gel
obtains
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201810626581.8A
Other languages
Chinese (zh)
Inventor
裘友玖
邓博
陈帅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Foshan Ling Chao New Material Co Ltd
Original Assignee
Foshan Ling Chao New Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Foshan Ling Chao New Material Co Ltd filed Critical Foshan Ling Chao New Material Co Ltd
Priority to CN201810626581.8A priority Critical patent/CN108624329A/en
Publication of CN108624329A publication Critical patent/CN108624329A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • 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
    • 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 present invention relates to technical field of soil remediation, more particularly to a kind of preparation method of new soil heavy metal fixative.Activated silica gel and r-chloropropyl trimethoxyl silane hybrid reaction are obtained the silica gel of chloromethylation by the present invention,High-purity attapulgite clay and green-vitriol are mixed,Sodium borohydride solution reduction be used in combination that Zero-valent Iron is made to be carried on attapulgite clay,New soil heavy metal fixative is obtained to Bio-sil pressurization filtering and washing with the water slurry of the attapulgite clay of load Zero-valent Iron,It is interacted using shearing force and cavitation minimizing electrostatic gravitation and hydrogen bond,Realize the dissociation of stick crystalline substance beam,With metal ion complexing occurs for hydroxyl,Electrostatic interaction can occur when being contacted with positively charged heavy metal ion,The adsorption activity of heavy metal contaminants is improved,Metallic iron core has good reduction or electronics base strength,The effective surface area of nano particle can be increased and enhance active site,To improve adsorption efficiency,It has broad application prospects.

Description

A kind of preparation method of new soil heavy metal fixative
Technical field
The present invention relates to technical field of soil remediation, more particularly to a kind of preparation side of new soil heavy metal fixative Method.
Background technology
Soil refers to one layer of loose substance of earth surface, by various particulate minerals, organic substance, moisture, sky The compositions such as gas, microorganism, can growing plant.Soil composition is substantially：Air and water respectively account for 25%, solid and account for 45%, is organic Matter accounts for 3%~4%, microorganism and accounts for 1% or so, this ratio is once lacked of proper care, as unhealthy soil.They are interknited, and are made mutually About, required goods and materials condition is provided for plant growth.
In recent years, with the growth of people's environmental consciousness, the secondary pollution that is generated in recycling of WEEE processing procedure It is widely paid close attention to, especially heavy metal pollution of soil and organic contamination situation causes anxiety.Heavy metal generally refers to proportion and exists 5.0g/cm3 the about 45 kinds of above elements.Heavy metal in Study on environmental pollution is primarily referred to as Pb, Cd, Hg, Cr and eka-gold Belong to the significant elements of bio-toxicities such as As, further includes the elements such as the heavy metal Zn with certain toxicity, Cu, Co, Ni and Sn.
Have scholar for electronic waste to bed mud in river and heavy metal pollution of soil the study found that in bed mud and soil Cd, Cr, Cu, Pb are more than《Standard of soil environment quality》（GB15618-2008）Secondary standard.Electronic waste is released into environment Put persistence organic pollutant（POPs）, wherein relatively conventional and concerned POPs mainly has PAHs, PBDEs, PCBs etc..This A little organic pollutions can enter in air, water body and soil through a variety of ways, by a series of Transport And Transformations, to organism with Health forms potential threat.In order to ensure the health of ecological environment and human body, the soil of destruction is repaired and has been become Problem to be solved too impatient to wait.
Currently used heavy metal-polluted soil recovery technique includes mainly excavation, stabilisation/solidification, chemical leaching, air lift, heat Processing, biological prosthetic etc..Wherein curing/stabilizing technology is a kind of technology of waste disposal of comparative maturity, has been applied to soil The engineering field of earth heavy metal reparation.Heavy metal-polluted soil curing/stabilizing recovery technique refers to will with method physically or chemically Toxic heavy metal in soil is fixed up, or heavy metal is converted to the inactive form of chemical property, prevents it in ring In border migrate, spread etc. processes, to reduce heavy metal murder by poisoning degree recovery technique.Curing/stabilizing technology and other Recovery technique is compared, and has the advantages such as processing time is short, the scope of application is wider.
Currently, conventional soil heavy metal fixative has the disadvantage that：
（1）Organic fixative production process itself discharges pollutants, and for there are secondary pollutions when repairing；
（2）Inorganic fixative is as lime fixative by so that heavy metal is formed hydroxide or carbonate precipitation Cured, the following deacidification rain once environmental condition changes, heavy metal is easy to discharge again；
（3）It is big to soil disturbance, expensive, fixed effect is poor, lasting passivation time is short.
Therefore, preparing good solidification effect, non-secondary pollution, cheap heavy metal curing agent becomes heavy metal pollution The key technology of soil remediation is explored and is repaiied as heavy-metal contaminated soil by raw material preparation heavy metal curing agent of natural minerals Multiple important research direction.
Invention content
Present invention mainly solves the technical issues of, in current organic heavy metal-polluted soil fixative production process itself Discharge pollutants, and for when repairing there are secondary pollution, and inorganic fixative as lime fixative by making weight Metal forms hydroxide or carbonate precipitation and is cured, and heavy metal is easy to discharge again in acid condition, adsorbs Effect is affected by soil pH, is led to the defect that adsorption rate is low, is provided a kind of preparation of new soil heavy metal fixative Method.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
A kind of preparation method of new soil heavy metal fixative, it is characterised in that specifically preparation process is：
（1）It takes 100~120mL sodium silicate solutions to pour into the three-necked flask with blender, adjusts pH with salt slow acid, start Blender stirs 30~40min with the rotating speed of 350~400r/min, and microwave oscillation handles 3~5min, obtains nano-sized hydrosol, Nano-sized hydrosol is put into heat temperature raising in baking oven, is dried to obtain nanometer silica gel；
（2）It weighs 200~220g nanometer silica gels to be placed in 400~450mL Loprazolam aqueous solutions, controls certain temperature, stirring 20~30min obtains activated silica gel, and activated silica gel is mixed in mass ratio with r-chloropropyl trimethoxyl silane, obtains reactant Material, 200~250g reaction masses are placed in 400~420mL dimethylbenzene and are reacted, the silica gel of chloropropylation is obtained, spare；
（3）By attapulgite clay salt acid dip 2~3 days, the then sonic oscillation in supersound process machine, filtering removes filtrate, The clay activated, then rinsed to cleaning solution and be in neutrality repeatedly with deionized water, it is subsequently placed into drying in baking oven, sieving obtains To high-purity attapulgite clay；
（4）High-purity attapulgite clay and green-vitriol are added in the conical flask equipped with deionized water, changed after mechanical agitation With magnetic stirrer, and it is passed through nitrogen protection, 4~5g sodium borohydrides is taken to be dissolved in prepare in 500mL deionized waters and obtain Above-mentioned sodium borohydride solution dropping funel is added in conical flask sodium borohydride solution, and reduction reaction obtains reduzate；
（5）Above-mentioned reduzate is placed in supercentrifuge the rotating speed with 4500~5000r/min to centrifuge, collects lower layer Solid, with absolute ethyl alcohol washs 3~4 times by obtained solid and is placed in vacuum drying chamber and be dried in vacuo, and is sieved, obtains load zero The attapulgite clay of valence iron；
（6）The silica gel of chloropropylation is immersed in polyethylenimine solution, is impregnated, filtering removal filtrate obtains Bio-sil, will Bio-sil is laid down on sand core funnel, and the attapulgite clay for loading Zero-valent Iron is configured to 500~600mL water slurries, then Filtering and washing is carried out to Bio-sil with water slurry, obtains new soil heavy metal fixative.
Step（1）The mass fraction of the sodium silicate solution is 30%, and the mass fraction of hydrochloric acid is 10%, adjusts pH to 6 ~7, microwave oscillation power is set as 700~800W, and oven temperature is 80~85 DEG C, and drying time is 3~4h.
Step（2）The mass fraction of the Loprazolam aqueous solution is 40%, controlled at 50~55 DEG C, activates silicon Glue is 2 ︰ 1 with r-chloropropyl trimethoxyl silane mixing quality ratio, and the reaction time is 40~45min.
Step（3）The mass fraction of the hydrochloric acid be 5%, 25~30kHz of supersonic frequency, duration of oscillation be 20~ 30min sets oven temperature as 200~300 DEG C, and drying time is 3~4h, and be sieved specification is 200 mesh.Step（4）It is described High-purity attapulgite clay and green-vitriol mixing quality ratio be 2 ︰ 5, the mechanical agitation time be 20~25min, control dropping liquid Dripping speed is 4~5mL/min, and the reduction reaction time is 40~45min.Step（5）The vacuum drying chamber set temperature It it is 50~60 DEG C, vacuum drying time is 6~7h, and be sieved specification is 200 mesh.
Step（6）The mass fraction of the polyethylenimine solution is 20%, and soaking time is 10~12min, is laid thick Degree is 3~5mm, and the mass fraction of water slurry is 5%, and pressure is 0.15~0.20MPa when suction filtration.
The beneficial effects of the invention are as follows：
（1）The present invention prepares nanometer silica gel in a manner of microwave oscillation, then uses Loprazolam activated in water solution nanometer silica gel, will Activated silica gel and r-chloropropyl trimethoxyl silane hybrid reaction, carry out chloromethylation, the silica gel of chloromethylation are obtained, by concave convex rod Sonic oscillation processing is carried out after clay hydrochloric acid impregnating active, washs and is dried to obtain high-purity attapulgite clay, it then will be high-purity Attapulgite clay and green-vitriol mixing, are used in combination sodium borohydride solution reduction that Zero-valent Iron is made to be carried on attapulgite clay, by chlorine The silica gel of propylated immerses in polyethylenimine solution, obtains Bio-sil, and the water with the attapulgite clay of load Zero-valent Iron is outstanding Supernatant liquid pressurizes filtering and washing to Bio-sil, is prepared new soil heavy metal fixative, natural attapulgite clay crystal by It interacts in electrostatic attraction and hydrogen bond, it is difficult to which dissociation and dispersion are modified by acid and are slightly carried to increase its surface area, utilize ultrasound It vibrates the shearing force generated and cavitation minimizing electrostatic gravitation and hydrogen bond interacts, realize the dissociation of stick crystalline substance beam, concave convex rod Clay itself is to be arranged as brilliant beam by bar-like single crystal close parallel, and mutually aggregation forms attapulgite clay particle to brilliant beam again, Surface forming part hole, the high-purity attapulgite clay monocrystalline arrangement more independent dispersion obtained after slightly carrying, surface porosity is porous, This is because after peracid treatment, the impurity such as removal dolomite, calcium carbonate weaken original intermolecular bonding force, duct is dredged It is logical, equally distributed gap is formd on surface, good environment is provided for load Zero-valent Iron；
（2）The silica gel of chloropropylation is soaked in polyethylenimine solution by the present invention can obtain chelate adsorption, polyethylene Imines is a kind of water-soluble polyamine, possesses a large amount of amido atom in linear macromolecule chain, polyethyleneimine is tightly adsorbed on silicon Glue internal pore surface can generate very strong chelation to metal ion, and Bio-sil is coated on load after filtering and washing The attapulgite clay surface of Zero-valent Iron constitutes nanofiltration membrane, can adsorb and combine with the heavy metal cation of other in solution, make weight Metal ion by adsorptive concentration, can efficient absorption heavy metal ion, and organic pollution will not be discharged, since concave convex rod is viscous There are a large amount of hydroxy functional groups in soil, when the heavy metal fixative of the present invention is imposed in the soil containing heavy metal ion, hydroxyl With metal ion complexing occurs for base, and there are a large amount of NA for attapulgite clay interlayer+、K+、Mg2+Commutative inorganic cation quilt Ion exchange occurs for metal ion substitution, or carries out adsorption reaction on its surface, and fixation principle is adsorbed with lime fixative Difference, influenced by soil pH it is smaller, attapulgite clay pass through modified, the Si in tetrahedral structure4+By Al3+Displacement is substituted, is led It causes attapulgite clay negatively charged, electrostatic interaction can occur when being contacted with positively charged heavy metal ion, to heavy metal pollution The adsorption activity of object improves, and Zero-valent Iron of the present invention is by the material of appearance iron oxide shell coated metal iron core, metallic iron core The heart can reduce electron-withdrawing group strength, and surface iron hydroxide provides coordination and electrostatic attraction and absorption charged ion function, possesses Have the shortcomings that deficient in stability while fine grain and high surface area and easily reunite, influences the using effect of Zero-valent Iron, in order to The reunion for avoiding particle distributes it to solid supported in attapulgite clay, can increase the effective surface area of nano particle simultaneously Enhance active site, strengthening electronic transfer to improve adsorption efficiency, has broad application prospects.
Specific implementation mode
It is that 30% sodium silicate solution pours into the three-necked flask with blender to take 100~120mL mass fractions, uses matter Measure score be 10% salt slow acid adjust pH to 6~7, start blender, with 350~400r/min rotating speeds stirring 30~ 40min, microwave oscillation handle 3~5min, set microwave oscillation power as 700~800W, obtain nano-sized hydrosol, by nanometer water Colloidal sol, which is put into baking oven, is heated to 80~85 DEG C, and dry 3~4h obtains nanometer silica gel；Weigh 200~220g nanometer silica gels It is placed in the Loprazolam aqueous solution that 400~450mL mass fractions are 40%, controlled at 50~55 DEG C, stirring 20~ 30min obtains activated silica gel, and activated silica gel is mixed for 2 ︰ 1 in mass ratio with r-chloropropyl trimethoxyl silane, obtains reactant 200~250g reaction masses are placed in 40~45min of reaction in 400~420mL dimethylbenzene, obtain the silica gel of chloropropylation by material, It is spare；The salt acid dip 2~3 days for being 5% by attapulgite clay mass fraction, then with 25~30kHz in supersound process machine Frequency ultrasound vibrate 20~30min, filtering removal filtrate, the clay activated, then rinsed repeatedly with deionized water to washing It washs liquid to be in neutrality, is subsequently placed into dry 3~4h in the baking oven that set temperature is 200~300 DEG C, crosses 200 mesh sieve, obtain high-purity recessed Convex stick clay；According to mass ratio it is 2 ︰ 5 by high-purity attapulgite clay and green-vitriol, is added to the taper equipped with deionized water In bottle, magnetic stirrer is used after 20~25min of mechanical agitation instead, and be passed through nitrogen protection, 4~5g sodium borohydrides is taken to dissolve It is prepared in 500mL deionized waters and obtains sodium borohydride solution, conical flask is added in above-mentioned sodium borohydride solution dropping funel In, control dropping funel drop speed is 4~5mL/min, and 40~45min of reduction reaction obtains reduzate；By above-mentioned reduzate It is placed in supercentrifuge rotating speed with 4500~5000r/min to centrifuge, collects lower layer's solid, by obtained solid with anhydrous Ethyl alcohol washs 3~4 times and is placed on 6~7h of vacuum drying in the vacuum drying chamber that set temperature is 50~60 DEG C, crosses 200 mesh sieve, Obtain the attapulgite clay of load Zero-valent Iron；The silica gel of chloropropylation is immersed into the polyethylenimine solution that mass fraction is 20% In, 10~12min is impregnated, filtering removal filtrate obtains Bio-sil, Bio-sil is laid down on sand core funnel, lays thick Degree is 3~5mm, and the attapulgite clay for loading Zero-valent Iron is configured to the water slurry that 500~600mL mass fractions are 5%, then Filtering and washing is carried out to Bio-sil with the pressure of 0.15~0.20MPa with water slurry, new soil heavy metal is obtained and fixes Agent.
It is that 30% sodium silicate solution pours into the three-necked flask with blender to take 100mL mass fractions, uses mass fraction PH to 6 is adjusted for 10% salt slow acid, starts blender, 30min is stirred with 350r/min rotating speeds, microwave oscillation handles 3min, Microwave oscillation power is set as 700W, obtains nano-sized hydrosol, nano-sized hydrosol is put into baking oven and is heated to 80 DEG C, is done Dry 3h, obtains nanometer silica gel；It weighs 200g nanometer silica gels to be placed in the Loprazolam aqueous solution that 400mL mass fractions are 40%, control Temperature processed is 50 DEG C, stirs 20min, obtains activated silica gel, be in mass ratio with r-chloropropyl trimethoxyl silane by activated silica gel 2 ︰ 1 are mixed, and obtain reaction mass, 200g reaction masses are placed in 400mL dimethylbenzene and react 40min, obtain chloropropylation Silica gel, it is spare；The salt acid dip 2 days for being 5% by attapulgite clay mass fraction, then with 25kHz's in supersound process machine Frequency ultrasound vibrates 20min, filtering removal filtrate, the clay activated, then is rinsed repeatedly to cleaning solution with deionized water and be in Neutrality is subsequently placed into dry 3h in the baking oven that set temperature is 200 DEG C, crosses 200 mesh sieve, obtain high-purity attapulgite clay；It will be high Pure attapulgite clay and green-vitriol are 2 ︰ 5 according to mass ratio, are added in the conical flask equipped with deionized water, mechanical agitation It uses magnetic stirrer after 20min instead, and is passed through nitrogen protection, take 4g sodium borohydrides to be dissolved in 500mL deionized waters and match Sodium borohydride solution is made, above-mentioned sodium borohydride solution dropping funel is added in conical flask, control dropping funel drop speed Reduzate is obtained for 4mL/min, reduction reaction 40min；Above-mentioned reduzate is placed in supercentrifuge with 4500r/ The rotating speed of min centrifuges, and collects lower layer's solid, and it is 50 that obtained solid is washed 3 times to be placed on set temperature with absolute ethyl alcohol DEG C vacuum drying chamber in be dried in vacuo 6h, cross 200 mesh sieve, obtain the attapulgite clay of load Zero-valent Iron；By chloropropylation Silica gel immerses in the polyethylenimine solution that mass fraction is 20%, impregnates 10min, and filtering removal filtrate obtains Bio-sil, Bio-sil is laid down on sand core funnel, laying thickness is 3mm, and the attapulgite clay for loading Zero-valent Iron is configured to 500mL Mass fraction is 5% water slurry, then carries out filtering and washing to Bio-sil with water slurry with the pressure of 0.15MPa, obtains New soil heavy metal fixative.
It is that 30% sodium silicate solution pours into the three-necked flask with blender to take 110mL mass fractions, uses mass fraction PH to 6 is adjusted for 10% salt slow acid, starts blender, 35min is stirred with 380r/min rotating speeds, microwave oscillation handles 4min, Microwave oscillation power is set as 750W, obtains nano-sized hydrosol, nano-sized hydrosol is put into baking oven and is heated to 83 DEG C, is done Dry 3h, obtains nanometer silica gel；It weighs 210g nanometer silica gels to be placed in the Loprazolam aqueous solution that 420mL mass fractions are 40%, control Temperature processed is 53 DEG C, stirs 25min, obtains activated silica gel, be in mass ratio with r-chloropropyl trimethoxyl silane by activated silica gel 2 ︰ 1 are mixed, and obtain reaction mass, 220g reaction masses are placed in 410mL dimethylbenzene and react 43min, obtain chloropropylation Silica gel, it is spare；The salt acid dip 2 days for being 5% by attapulgite clay mass fraction, then with 27kHz's in supersound process machine Frequency ultrasound vibrates 25min, filtering removal filtrate, the clay activated, then is rinsed repeatedly to cleaning solution with deionized water and be in Neutrality is subsequently placed into dry 3h in the baking oven that set temperature is 250 DEG C, crosses 200 mesh sieve, obtain high-purity attapulgite clay；It will be high Pure attapulgite clay and green-vitriol are 2 ︰ 5 according to mass ratio, are added in the conical flask equipped with deionized water, mechanical agitation It uses magnetic stirrer after 23min instead, and is passed through nitrogen protection, take 4g sodium borohydrides to be dissolved in 500mL deionized waters and match Sodium borohydride solution is made, above-mentioned sodium borohydride solution dropping funel is added in conical flask, control dropping funel drop speed Reduzate is obtained for 4mL/min, reduction reaction 43min；Above-mentioned reduzate is placed in supercentrifuge with 4750r/ The rotating speed of min centrifuges, and collects lower layer's solid, and it is 55 that obtained solid is washed 3 times to be placed on set temperature with absolute ethyl alcohol DEG C vacuum drying chamber in be dried in vacuo 6h, cross 200 mesh sieve, obtain the attapulgite clay of load Zero-valent Iron；By chloropropylation Silica gel immerses in the polyethylenimine solution that mass fraction is 20%, impregnates 11min, and filtering removal filtrate obtains Bio-sil, Bio-sil is laid down on sand core funnel, laying thickness is 4mm, and the attapulgite clay for loading Zero-valent Iron is configured to 550mL Mass fraction is 5% water slurry, then carries out filtering and washing to Bio-sil with water slurry with the pressure of 0.17MPa, obtains New soil heavy metal fixative.
It is that 30% sodium silicate solution pours into the three-necked flask with blender to take 120mL mass fractions, uses mass fraction PH to 7 is adjusted for 10% salt slow acid, starts blender, 40min is stirred with 400r/min rotating speeds, microwave oscillation handles 5min, Microwave oscillation power is set as 800W, obtains nano-sized hydrosol, nano-sized hydrosol is put into baking oven and is heated to 85 DEG C, is done Dry 4h, obtains nanometer silica gel；It weighs 220g nanometer silica gels to be placed in the Loprazolam aqueous solution that 450mL mass fractions are 40%, control Temperature processed is 55 DEG C, stirs 30min, obtains activated silica gel, be in mass ratio with r-chloropropyl trimethoxyl silane by activated silica gel 2 ︰ 1 are mixed, and obtain reaction mass, 250g reaction masses are placed in 420mL dimethylbenzene and react 45min, obtain chloropropylation Silica gel, it is spare；The salt acid dip 3 days for being 5% by attapulgite clay mass fraction, then with 30kHz's in supersound process machine Frequency ultrasound vibrates 30min, filtering removal filtrate, the clay activated, then is rinsed repeatedly to cleaning solution with deionized water and be in Neutrality is subsequently placed into dry 4h in the baking oven that set temperature is 300 DEG C, crosses 200 mesh sieve, obtain high-purity attapulgite clay；It will be high Pure attapulgite clay and green-vitriol are 2 ︰ 5 according to mass ratio, are added in the conical flask equipped with deionized water, mechanical agitation It uses magnetic stirrer after 25min instead, and is passed through nitrogen protection, take 5g sodium borohydrides to be dissolved in 500mL deionized waters and match Sodium borohydride solution is made, above-mentioned sodium borohydride solution dropping funel is added in conical flask, control dropping funel drop speed Reduzate is obtained for 5mL/min, reduction reaction 45min；Above-mentioned reduzate is placed in supercentrifuge with 5000r/ The rotating speed of min centrifuges, and collects lower layer's solid, and it is 60 that obtained solid is washed 4 times to be placed on set temperature with absolute ethyl alcohol DEG C vacuum drying chamber in be dried in vacuo 7h, cross 200 mesh sieve, obtain the attapulgite clay of load Zero-valent Iron；By chloropropylation Silica gel immerses in the polyethylenimine solution that mass fraction is 20%, impregnates 12min, and filtering removal filtrate obtains Bio-sil, Bio-sil is laid down on sand core funnel, laying thickness is 5mm, and the attapulgite clay for loading Zero-valent Iron is configured to 600mL Mass fraction is 5% water slurry, then carries out filtering and washing to Bio-sil with water slurry with the pressure of 0.20MPa, obtains New soil heavy metal fixative.
The heavy metal-polluted soil fixative that comparative example is produced with Lu'an City company is as a comparison case to produced by the present invention Heavy metal-polluted soil fixative in new soil heavy metal fixative and comparative example is detected, and testing result is as shown in table 1：
Test method：
Each 100g of Cd, Pb, Cu contaminated soil is weighed, 3g new soil heavy metal fixatives produced by the present invention and right are separately added into Heavy metal-polluted soil fixative in ratio, stirs evenly, and adds the mixture 30%（Weight ratio）Tap water, fully stir 5min is mixed, is uniformly mixed, stands 3 days, it is spare.Natural air drying soil after 3 days is crushed sampling, respectively basis《Toxicity from solid waste Leaching method sulfonitric method》（Environmental protection professional standard HJ/T299-2007）With《The measurement of soil pH》（Agricultural industry mark Quasi- NY/T1377-2007）Measure toxicity of lixivium and soil pH value.
1 performance measurement result of table
According to data in table 1 it is found that new soil heavy metal fixative produced by the present invention, have to heavy metal more efficient, more Lasting fixed effect, and non-secondary pollution, it is simple for process, it is cheap, it can also to enter the plant cultivated in the soil In content of beary metal be significantly reduced, have wide prospect of the application.

Claims (7)

1. a kind of preparation method of new soil heavy metal fixative, it is characterised in that specifically preparation process is：
（1）It takes 100~120mL sodium silicate solutions to pour into the three-necked flask with blender, adjusts pH with salt slow acid, start Blender stirs 30~40min with the rotating speed of 350~400r/min, and microwave oscillation handles 3~5min, obtains nano-sized hydrosol, Nano-sized hydrosol is put into heat temperature raising in baking oven, is dried to obtain nanometer silica gel；
（2）It weighs 200~220g nanometer silica gels to be placed in 400~450mL Loprazolam aqueous solutions, controls certain temperature, stirring 20~30min obtains activated silica gel, and activated silica gel is mixed in mass ratio with r-chloropropyl trimethoxyl silane, obtains reactant Material, 200~250g reaction masses are placed in 400~420mL dimethylbenzene and are reacted, the silica gel of chloropropylation is obtained, spare；
（3）By attapulgite clay salt acid dip 2~3 days, the then sonic oscillation in supersound process machine, filtering removes filtrate, The clay activated, then rinsed to cleaning solution and be in neutrality repeatedly with deionized water, it is subsequently placed into drying in baking oven, sieving obtains To high-purity attapulgite clay；
（4）High-purity attapulgite clay and green-vitriol are added in the conical flask equipped with deionized water, changed after mechanical agitation With magnetic stirrer, and it is passed through nitrogen protection, 4~5g sodium borohydrides is taken to be dissolved in prepare in 500mL deionized waters and obtain Above-mentioned sodium borohydride solution dropping funel is added in conical flask sodium borohydride solution, and reduction reaction obtains reduzate；
（5）Above-mentioned reduzate is placed in supercentrifuge the rotating speed with 4500~5000r/min to centrifuge, collects lower layer Solid, with absolute ethyl alcohol washs 3~4 times by obtained solid and is placed in vacuum drying chamber and be dried in vacuo, and is sieved, obtains load zero The attapulgite clay of valence iron；
（6）The silica gel of chloropropylation is immersed in polyethylenimine solution, is impregnated, filtering removal filtrate obtains Bio-sil, will Bio-sil is laid down on sand core funnel, and the attapulgite clay for loading Zero-valent Iron is configured to 500~600mL water slurries, then Filtering and washing is carried out to Bio-sil with water slurry, obtains new soil heavy metal fixative.
2. a kind of preparation method of new soil heavy metal fixative according to claim 1, it is characterised in that：Step （1）The mass fraction of the sodium silicate solution is 30%, and the mass fraction of hydrochloric acid is 10%, adjusts pH to 6~7, sets microwave Hunting power is 700~800W, and oven temperature is 80~85 DEG C, and drying time is 3~4h.
3. a kind of preparation method of new soil heavy metal fixative according to claim 1, it is characterised in that：Step （2）The mass fraction of the Loprazolam aqueous solution is 40%, controlled at 50~55 DEG C, activated silica gel and chloropropyl three Methoxy silane mixing quality ratio is 2 ︰ 1, and the reaction time is 40~45min.
4. a kind of preparation method of new soil heavy metal fixative according to claim 1, it is characterised in that：Step （3）The mass fraction of the hydrochloric acid is 5%, 25~30kHz of supersonic frequency, and duration of oscillation is 20~30min, sets baking oven temperature Degree is 200~300 DEG C, and drying time is 3~4h, and be sieved specification is 200 mesh.
5. a kind of preparation method of new soil heavy metal fixative according to claim 1, it is characterised in that：Step （4）High-purity attapulgite clay and green-vitriol mixing quality ratio is 2 ︰ 5, and the mechanical agitation time is 20~25min, control Dropping funel drop speed processed is 4~5mL/min, and the reduction reaction time is 40~45min.
6. a kind of preparation method of new soil heavy metal fixative according to claim 1, it is characterised in that：Step （5）The vacuum drying chamber set temperature is 50~60 DEG C, and vacuum drying time is 6~7h, and be sieved specification is 200 mesh.
7. a kind of preparation method of new soil heavy metal fixative according to claim 1, it is characterised in that：Step （6）The mass fraction of the polyethylenimine solution is 20%, and soaking time is 10~12min, and laying thickness is 3~5mm, The mass fraction of water slurry is 5%, and pressure is 0.15~0.20MPa when suction filtration.
CN201810626581.8A 2018-06-19 2018-06-19 A kind of preparation method of new soil heavy metal fixative Withdrawn CN108624329A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810626581.8A CN108624329A (en) 2018-06-19 2018-06-19 A kind of preparation method of new soil heavy metal fixative

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810626581.8A CN108624329A (en) 2018-06-19 2018-06-19 A kind of preparation method of new soil heavy metal fixative

Publications (1)

Publication Number Publication Date
CN108624329A true CN108624329A (en) 2018-10-09

Family

ID=63691865

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810626581.8A Withdrawn CN108624329A (en) 2018-06-19 2018-06-19 A kind of preparation method of new soil heavy metal fixative

Country Status (1)

Country Link
CN (1) CN108624329A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114133462A (en) * 2021-12-16 2022-03-04 江苏暨之阳环保科技有限公司 Heavy metal treatment agent for petroleum-polluted soil and preparation method thereof
CN115215621A (en) * 2022-08-06 2022-10-21 安徽美琛生态科技有限公司 Method for preparing non-sintered ceramsite from electroplating sludge

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114133462A (en) * 2021-12-16 2022-03-04 江苏暨之阳环保科技有限公司 Heavy metal treatment agent for petroleum-polluted soil and preparation method thereof
CN114133462B (en) * 2021-12-16 2022-09-06 江苏暨之阳环保科技有限公司 Heavy metal treatment agent for petroleum-polluted soil and preparation method thereof
CN115215621A (en) * 2022-08-06 2022-10-21 安徽美琛生态科技有限公司 Method for preparing non-sintered ceramsite from electroplating sludge

Similar Documents

Publication Publication Date Title
Suganya et al. Computation of adsorption parameters for the removal of dye from wastewater by microwave assisted sawdust: theoretical and experimental analysis
CN107983300B (en) The charcoal composite material and preparation method and application of manganese dioxide modification
CN109880629A (en) A kind of preparation method of soil remediation material
CN105709699B (en) A kind of soil heavy mental adsorbent and preparation method thereof
CN110639943B (en) Remediation method for organic matter contaminated soil
CN105236507B (en) The method that the adsorbent being combined using beta cyclodextrin chitosan and walnut shell charcoal removes the Cr VI in waste water
CN105036355B (en) A kind of biological cleaning carrier for wastewater treatment
CN106966456A (en) A kind of preparation method and application of ferrous sulfide/biology carbon composite
CN101920191B (en) Application of activated carbon modified material and application in removing arsenic from water
CN104031651A (en) Passivation improver for heavy metal pollution farmland and using method thereof
Yadav et al. Biogenic silica nanoparticles from agro-waste: Properties, mechanism of extraction and applications in environmental sustainability
CN113171766B (en) Preparation method and application of ternary magnetic nano graphite phase carbon nitride material integrating oil absorption/adsorption of metal ions/photocatalysis
CN105056891B (en) Biological carbon composite of graphene modified and its preparation method and application
Sricharoen et al. Ultrasonic-assisted recycling of Nile tilapia fish scale biowaste into low-cost nano-hydroxyapatite: Ultrasonic-assisted adsorption for Hg2+ removal from aqueous solution followed by “turn-off” fluorescent sensor based on Hg2+-graphene quantum dots
CN108339521A (en) A kind of sodium alginate-MOFs complex microsphere preparation methods of absorption heavy metal arsenic
CN108624329A (en) A kind of preparation method of new soil heavy metal fixative
CN109663583A (en) A kind of material and preparation method thereof of adsorbing separation heavy metal ions in soil
CN109967033A (en) A kind of modified rice husk biomass carbon and preparation method thereof
CN103011328A (en) Novel efficient grapheme loaded nano-iron material for adsorbing phosphorus in water
CN102002367B (en) Eluent for soil polluted by organochlorine pesticides and repair method by using same
CN111203187A (en) Repair material for removing pollutants in underground water, preparation method and application thereof
CN114832778A (en) Shaddock peel biochar for adsorbing arsenic as well as preparation method and application thereof
He et al. Adsorption enhancement of Congo red dye from wastewater based on edamame shell originated activated carbon by the cations: Experimental and theoretical studies
CN107838433A (en) A kind of crape myrtle fruit prepares the method with slow releasing function nano zero valence iron
CN108480393B (en) Magnetic aminated hollow microsphere soil remediation agent, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20181009