CN109233859A - A kind of porous sustained-release composite passivant and the preparation method and application thereof for heavy metal-polluted soil passivation - Google Patents
A kind of porous sustained-release composite passivant and the preparation method and application thereof for heavy metal-polluted soil passivation Download PDFInfo
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- CN109233859A CN109233859A CN201811266303.2A CN201811266303A CN109233859A CN 109233859 A CN109233859 A CN 109233859A CN 201811266303 A CN201811266303 A CN 201811266303A CN 109233859 A CN109233859 A CN 109233859A
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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Abstract
The invention discloses under certain condition, using biomass, bentonite as raw material, prepared by charcoal to biomass heating by microwave and loads ferro element, obtaining the modified biological carbon materials of iron can targetedly heavy metal-passivated As (V), Cd (II)；Bentonite is modified by grafting copolymerization process, prepares chitin modified bentonite clay material, it can targetedly heavy metal-passivated Cu (II), Zn (II)；Chitin modified bentonite clay material is wrapped in the modified biological carbon materials outer layer of iron by binder, obtains iron modification biological charcoal-chitin modified bentonite composite passivant of porous sustained-release.Composite passivant prepared by the present invention, which has, is rapidly and efficiently passivated heavy metal-polluted soil As (V), Cd (II), Cu (II), Zn (II), it is long to be passivated the duration, good stability, resource circulation utilization does not cause secondary pollution to soil, operates the advantages that convenient.
Description
Technical field
The present invention relates to a kind of composite passivants for heavy metal pollution of soil passivation, belong to field of environment protection, have
Body is a kind of porous sustained-release composite passivant and the preparation method and application thereof for heavy metal-polluted soil passivation.
Background technique
Heavy metal pollution of soil, which refers to, brings the heavy metal substances such as cadmium, mercury, arsenic, lead and chromium into soil due to mankind's activity,
The phenomenon that keeping heavy metal content in soil significantly higher compared to Natural Background Values, and then destroying ecological environment.Heavy metal-polluted soil is dirty
Dye will enter human body by plant absorption, livestock enrichment and eventually by food chain, and then induce various diseases, and it is strong to endanger the mankind
Health.China there are about 1.5 hundred million mu arable land by heavy metal pollution, and therefore caused by grain drop in production every year up to 1 000 ten thousand tons with
On, heavy metals exceeding standard " poison " grain produced every year causes up to 20,000,000,000 yuan of direct economy to damage every year up to more than 1 000 ten thousand tons
It loses.It administers and restoration of soil polluted by heavy metal is to preserving the ecological environment, ensures that human health is of great significance, while and people
The challenge and huge challenge that class faces.
Carrying out chemical stabilization reparation using passivator is that heavy metal pollution of soil administers the both economical effective reparation of reparation
Technology, currently used passivator has cement, lime, slag, modified cellulose, organic clay, organic fertilizer etc., using single
Passivator is weak to the soil applicability of Compound Heavy Metals, and the duration is short, stability is poor for the passivation of above-mentioned passivator, outside
The heavy metal being passivated under the influence of portion's environment is easily reactivated and is absorbed by plants.Therefore, it needs to develop a kind of compound, sustained release
Passivator solves the problems, such as that current heavy metal pollution of soil administers recovery technique.
The present invention passes through microwave first and prepares charcoal to biomass straw heating and load ferro element, obtains what iron was modified
Biological carbon materials, can targetedly heavy metal-passivated As (V), Cd (II)；Then again using grafting copolymerization process to bentonite
It is modified, prepares chitin modified bentonite composite material, it can targetedly heavy metal-passivated Cu (II), Zn
(II)；Slow-release material is finally prepared, and is wrapped in what iron was modified by binder with chitin modified bentonite composite material
Biological carbon materials outer layer obtains iron modification biological charcoal-chitin modified bentonite composite passivant of porous sustained-release.The passivator
Not only to heavy metal As (V), Cd (II), Cu (II), Zn (II) good passivation effect, but also passivation time is long, good stability, and energy
Realize recycling, secondary pollution not caused to soil and had high economic benefit for resource.It is modified to yet there are no iron
The chitin modified bentonite porous sustained-release composite passivant relevant report of charcoal-.
Summary of the invention
The purpose of the present invention is to provide a kind of iron modification biological charcoal-for heavy metal-polluted soil passivation is chitin modified swollen
Moisten native porous sustained-release composite passivant preparation method, has for heavy metal in soil As (V), Cd (II), Cu (II), Zn (II)
The characteristics of adsorbing deactivation function and passivation duration length, passivation effect good stability.
A kind of porous sustained-release composite passivant for heavy metal-polluted soil passivation proposed by the present invention, including iron modification biological
Carbon Materials and chitin modified bentonite clay material, the porous passivator are iron modification biological Carbon Materials, are located at composite passivated
The kernel of agent, the sustained release passivator are chitin modified bentonite clay material, and positioned at the outer layer of composite passivant, described is compound
Passivator is made of iron modification biological Carbon Materials and chitin modified bentonite clay material, and iron modification biological Carbon Materials are located at kernel,
Chitin modified bentonite clay material wraps up iron modification biological Carbon Materials by binder and is located at composite passivant outer layer.
To achieve the above object, the invention adopts the following technical scheme:
A kind of porous sustained-release composite passivant and preparation method thereof for heavy metal-polluted soil passivation, comprising the following steps:
Step (1), the preparation of iron modification biological Carbon Materials:
A. after biomass straw removal of impurities, being crushed, be dry, the pyrolysis charring 40- in 400-600 DEG C of microwave reactor
50min, taking-up is cooled to 25 DEG C, obtains charcoal, spare；
B. by charcoal obtained by step a with after HCl solution Immersion treatment 12h, filtering takes filter residue, is washed to neutrality with distillation, and 75
DEG C drying, grinding, cross 10 meshes, obtain pretreated charcoal, it is spare, HCl solution concentration be 1mol/L；
C. pretreated charcoal obtained by step b is subjected to basification with NaOH solution, after impregnating 12h, filtering takes filter residue,
Modification biological charcoal is obtained, it is spare；NaOH solution concentration is 2mol/L；
D. modification biological charcoal obtained by step c is immersed into FeSO4In solution, it is stirred to react 0.5-2h, adds NaOH solution adjusting
PH is neutrality, and after impregnating reaction 22-26h, filtering takes filter residue, is cleaned with deionized water to colourless, 75 DEG C of drying change to get iron
Property biomaterial, it is spare；FeSO4Solution concentration is 1-2mol/L, and NaOH solution concentration is 2mol/L.
Step (2), the preparation of chitin modified bentonite clay material:
E. it dissolves the chitosan in acetic acid solution, obtains chitosan solution；By chitosan solution slurry at 85-95 DEG C constant temperature
5h is cooled to 60 DEG C, uses N2Purge 30min；Ammonium persulfate aqueous solution is added and is cooled to 45- in 60 DEG C of isothermal reaction 20min
55 DEG C, acrylic acid, N, N- methylene-bisacrylamide, sodium bentonite, under continuous stirring condition, in 65-75 DEG C of constant temperature is added
3h is reacted, graft polymerization reaction is completed, obtains chitin modified bentonite solution；
Wherein, the solid-to-liquid ratio of chitosan and acetic acid solution is 1:56-60, and acetic acid solution concentration is 1%(w/v)；Chitosan and over cure
The solid-to-liquid ratio of acid ammonium solution is 1:18-22, and ammonium persulfate solution concentration is 10%(w/v)；The weight ratio of chitosan and acrylic acid is
1:60-65；Chitosan and N, the weight ratio of N- methylene-bisacrylamide are 1:1-1.2, the weight of chitosan and sodium bentonite
Amount is than being 1:4.8-5；The sodium bentonite is 10% that the sodium chloride solution of 0.25mol/L is added drop-wise to deionized water preparation
(w/v) in bentonite suspension to get；
F. NaOH solution is added to adjust pH to bentonite solution chitin modified obtained by step e is neutrality, and filtering takes filter residue,
It is washed with deionized, 75 DEG C of drying are ground, sieved with 100 mesh sieve, obtain dry chitin modified bentonite clay material；NaOH solution
Concentration is 2mol/L；
Step (3), the preparation of porous iron modification biological charcoal-sustained release chitin modified bentonite composite passivant:
G. chitin modified bentonite clay material obtained by step (2) is uniformly mixed with methylcellulose, deionized water, silane is added
Coupling agent kh-570 mixes, and is stirred to react 30min in 90-120 DEG C of water bath with thermostatic control, is cooled to room temperature, and filters, takes filter residue, will filter
Slag for 24 hours, is cooled to room temperature in 55 DEG C of dryings, must be sustained chitin modified bentonite clay material, spare；It is wherein sustained chitin modified
Bentonite clay material raw material includes: methylcellulose chitin modified bentonite clay material 50-70 parts obtained by step (2) by weight
8-15 parts, 10-20 parts of Silane coupling reagent KH-570；
H. it will be sustained chitin modified bentonite clay material obtained by step g and is heated to 170-200 DEG C, keep the temperature 20-40min, wrap while hot
It is rolled in iron modification biological Carbon Materials outer layer obtained by step (1), is cooled to room temperature to obtain porous iron modification biological charcoal-sustained release chitosan
Modified alta-mud composite passivant；Porous iron modification biological Carbon Materials and the weight ratio of the chitin modified bentonite clay material of sustained release are
1:1-2；
A kind of porous sustained-release composite passivant for heavy metal-polluted soil passivation is obtained prepared by above-mentioned preparation method.
Concrete application method of the invention: the soil of heavy metal As, Cd, Cu, Zn combined pollution is taken, 0.1mol/L is used
CaCl2Extraction, icp ms measure heavy metal in soil As, Cd, Cu, Zn bio-available Zn concentration；Soil wind
Dry, ground 10 mesh nylon mesh takes 100g to be placed in beaker, and the weight ratio by soil and porous sustained-release composite passivant is
100:2-5 is added composite passivant and is uniformly mixed, and it is 30% that deionized water, which is added, and keeps soil moisture content, is placed in room temperature (25
DEG C) culture, and sampling analysis heavy metal-polluted soil As, Cd, Cu, Zn bio-available Zn concentration when 15d, 60d, calculate its passivation effect
Rate.
The beneficial effects of the present invention are:
(1) present invention uses biomass straw, bentonite to prepare heavy metal deactivator for basic material, and raw material is agriculture waste
Object and natural mineral matter, it is from a wealth of sources, cheap, environmental-friendly, it is able to achieve recycling, two not caused to soil for resource
Secondary pollution；
(2) present invention prepares the charcoal of high porosity by microwave to biomass heating, and it is modified to obtain iron after load ferro element
Biological carbon materials, can targetedly heavy metal-passivated As, Cd；Bentonite is modified using grafting copolymerization process, prepares shell
The modified bentonite composite material of glycan, can targetedly be passivated Cu, Zn；And two kinds of modified materials progress are compound, formation " has
Machine-is inorganic " intersect the porous sustained-release composite passivant combined, which can not only a huge sum of money in passivation soil rapidly and efficiently
Belong to, and is passivated duration length, good stability；
(3) porous sustained-release composite passivant preparation method prepared by the present invention is relatively easy, easy to use.
Specific embodiment
Specific embodiments of the present invention will be further explained below.It should be noted that for these implementations
The explanation of mode is used to help understand the present invention, but and does not constitute a limitation of the invention.In addition, invention described below
Technical characteristic involved in each embodiment can be combined with each other as long as they do not conflict with each other.
Embodiment 1:
By the pretreated biomass straw of 100g in 450 DEG C of charing 45min, 25 DEG C are cooled to after taking-up；Then 1mol/L is used
HCl solution submerges charcoal and handles 12h, and filtering takes filter residue, is washed to neutrality, 75 DEG C of drying with distillation, 10 meshes are crossed in grinding；
2mol/L NaOH solution Immersion treatment 12h is used again, and filtering takes filter residue；Finally use 1mol/L FeSO4Solution is submerged and is stirred anti-
Answer 1h, it is neutrality that NaOH solution, which is added, and adjusts pH, and after impregnating reaction for 24 hours, filtering takes filter residue, and deionized water is cleaned to colourless, 75
DEG C drying, obtain iron modification biological Carbon Materials；
5 grams of chitosans are dissolved in 280mL 1%(w/v) in acetic acid, prepare chitosan solution；Slurry is maintained at 5h at 90 DEG C,
After being cooled to 60 DEG C, N is used2Purge 30 min；0.1g/mL ammonium persulfate aqueous solution 20mL is added, is reacted at a temperature of 60 DEG C
20min；After being cooled to 50 DEG C, the mixed of 300mL acrylic acid, 5g N, N- methylene-bisacrylamide and 25g sodium bentonite is added
Object is closed, is stirred to react 3h at a temperature of 70 DEG C；It is neutrality that NaOH solution, which is added, and adjusts pH, and filtering takes filter residue, is washed with deionized water
It washs, 75 DEG C of drying are ground, sieved with 100 mesh sieve, obtain dry chitin modified bentonite clay material；
50 parts of chitin modified bentonite clay materials are uniformly mixed with deionized water, 10 parts of methylcellulose, 10 parts of silane are added
Coupling agent kh-570 mixes, and is stirred to react 30min in 110 DEG C of waters bath with thermostatic control, is cooled to room temperature, and filters, takes filter residue, by filter residue in
55 DEG C of dryings for 24 hours, are cooled to room temperature, must be sustained chitin modified bentonite clay material；By 1 part of chitin modified bentonite material of sustained release
Material is heated to 180 DEG C, keeps the temperature 30min, is wrapped in 1 part of iron modification biological Carbon Materials outer layer while hot, obtains porous iron modification biological charcoal-
It is sustained chitin modified bentonite composite passivant；
It takes 100g through air-dried, ground 10 mesh nylon mesh and has measured the compound dirt of heavy metal As, Cd, Cu, Zn bio-available Zn concentration
Soil is contaminated, 3g porous sustained-release composite passivant is added and is uniformly mixed, it is 30% that deionized water, which is added, and keeps soil moisture content, is placed in
(25 DEG C) of room temperature cultures, 15d, 60d 0.1mol/L CaCl2Extraction, icp ms are surveyed in soil
Heavy metal As, Cd, Cu, Zn bio-available Zn concentration；Calculating 15d is 28.68% to the deactivation rate of As, and the deactivation rate to Cd is
44.30%, the deactivation rate to Cu is 33.50%, and the deactivation rate to Zn is 18.59%；60d is 28.29% to the deactivation rate of As, right
The deactivation rate of Cd is 45.27%, and the deactivation rate to Cu is 32.15%, and the deactivation rate to Zn is 17.98%.
Embodiment 2:
By the pretreated biomass straw of 100g in 450 DEG C of charing 45min, 25 DEG C are cooled to after taking-up；Then 1mol/L is used
HCl solution submerges charcoal and handles 12h, and filtering takes filter residue, is washed to neutrality, 75 DEG C of drying with distillation, 10 meshes are crossed in grinding；
2mol/L NaOH solution Immersion treatment 12h is used again, and filtering takes filter residue；Finally use 2mol/L FeSO4Solution is submerged and is stirred anti-
Answer 1h, it is neutrality that NaOH solution, which is added, and adjusts pH, and after impregnating reaction for 24 hours, filtering takes filter residue, and deionized water is cleaned to colourless, 75
DEG C drying, obtain iron modification biological Carbon Materials；
5 grams of chitosans are dissolved in 290mL 1%(w/v) in acetic acid, prepare chitosan solution；Slurry is maintained at 5h at 90 DEG C,
After being cooled to 60 DEG C, N is used2Purge 30 min；0.1g/mL ammonium persulfate aqueous solution 20mL is added, is reacted at a temperature of 60 DEG C
20min；After being cooled to 50 DEG C, the mixed of 310mL acrylic acid, 5g N, N- methylene-bisacrylamide and 25g sodium bentonite is added
Object is closed, is stirred to react 3h at a temperature of 70 DEG C；It is neutrality that NaOH solution, which is added, and adjusts pH, and filtering takes filter residue, is washed with deionized water
It washs, 75 DEG C of drying are ground, sieved with 100 mesh sieve, obtain dry chitin modified bentonite clay material；
50 parts of chitin modified bentonite clay materials are uniformly mixed with deionized water, 10 parts of methylcellulose, 10 parts of silane are added
Coupling agent kh-570 mixes, and is stirred to react 30min in 110 DEG C of waters bath with thermostatic control, is cooled to room temperature, and filters, takes filter residue, by filter residue in
55 DEG C of dryings for 24 hours, are cooled to room temperature, must be sustained chitin modified bentonite clay material；By 2 parts of chitin modified bentonite materials of sustained release
Material is heated to 180 DEG C, keeps the temperature 30min, is wrapped in 1 part of iron modification biological Carbon Materials outer layer while hot, obtains porous iron modification biological charcoal-
It is sustained chitin modified bentonite composite passivant；
It takes 100g through air-dried, ground 10 mesh nylon mesh and has measured the compound dirt of heavy metal As, Cd, Cu, Zn bio-available Zn concentration
Soil is contaminated, 5g porous sustained-release composite passivant is added and is uniformly mixed, it is 30% that deionized water, which is added, and keeps soil moisture content, is placed in
(25 DEG C) of room temperature cultures, 15d, 60d 0.1mol/L CaCl2Weight in soil is surveyed in extraction, icp ms
Metal As, Cd, Cu, Zn bio-available Zn concentration；Calculating 15d is 31.35% to the deactivation rate of As, and the deactivation rate to Cd is 49.28%,
Deactivation rate to Cu is 35.21%, and the deactivation rate to Zn is 20.31%；60d is 32.57% to the deactivation rate of As, to the blunt of Cd
Rate is 50.61%, and the deactivation rate to Cu is 34.89%, and the deactivation rate to Zn is 22.41%.
Embodiment 3:
By the pretreated biomass straw of 100g in 550 DEG C of charing 45min, 25 DEG C are cooled to after taking-up；Then 1mol/L is used
HCl solution submerges charcoal and handles 12h, and filtering takes filter residue, is washed to neutrality, 75 DEG C of drying with distillation, 10 meshes are crossed in grinding；
2mol/L NaOH solution Immersion treatment 12h is used again, and filtering takes filter residue；Finally use 1mol/L FeSO4Solution is submerged and is stirred anti-
Answer 1h, it is neutrality that NaOH solution, which is added, and adjusts pH, and after impregnating reaction for 24 hours, filtering takes filter residue, and deionized water is cleaned to colourless, 75
DEG C drying, obtain iron modification biological Carbon Materials；
5 grams of chitosans are dissolved in 300mL 1%(w/v) in acetic acid, prepare chitosan solution；Slurry is maintained at 5h at 90 DEG C,
After being cooled to 60 DEG C, N is used2Purge 30 min；0.1g/mL ammonium persulfate aqueous solution 20mL is added, is reacted at a temperature of 60 DEG C
20min；After being cooled to 50 DEG C, the mixed of 320mL acrylic acid, 5g N, N- methylene-bisacrylamide and 25g sodium bentonite is added
Object is closed, is stirred to react 3h at a temperature of 70 DEG C；It is neutrality that NaOH solution, which is added, and adjusts pH, and filtering takes filter residue, is washed with deionized water
It washs, 75 DEG C of drying are ground, sieved with 100 mesh sieve, obtain dry chitin modified bentonite clay material；
50 parts of chitin modified bentonite clay materials are uniformly mixed with deionized water, 10 parts of methylcellulose, 10 parts of silane are added
Coupling agent kh-570 mixes, and is stirred to react 30min in 110 DEG C of waters bath with thermostatic control, is cooled to room temperature, and filters, takes filter residue, by filter residue in
55 DEG C of dryings for 24 hours, are cooled to room temperature, must be sustained chitin modified bentonite clay material；By 1 part of chitin modified bentonite material of sustained release
Material is heated to 180 DEG C, keeps the temperature 30min, is wrapped in 1 part of iron modification biological Carbon Materials outer layer while hot, obtains porous iron modification biological charcoal-
It is sustained chitin modified bentonite composite passivant；
It takes 100g through air-dried, ground 10 mesh nylon mesh and has measured the compound dirt of heavy metal As, Cd, Cu, Zn bio-available Zn concentration
Soil is contaminated, 3g porous sustained-release composite passivant is added and is uniformly mixed, it is 30% that deionized water, which is added, and keeps soil moisture content, is placed in
(25 DEG C) of room temperature cultures, 15d, 60d 0.1mol/L CaCl2Weight in soil is surveyed in extraction, icp ms
Metal As, Cd, Cu, Zn bio-available Zn concentration；Calculating 15d is 30.28% to the deactivation rate of As, and the deactivation rate to Cd is 48.12%,
Deactivation rate to Cu is 34.90%, and the deactivation rate to Zn is 20.58%；60d is 28.27% to the deactivation rate of As, to the blunt of Cd
Rate is 47.85%, and the deactivation rate to Cu is 33.58%, and the deactivation rate to Zn is 19.98%.
Embodiment 4:
By the pretreated biomass straw of 100g in 550 DEG C of charing 45min, 25 DEG C are cooled to after taking-up；Then 1mol/L is used
HCl solution submerges charcoal and handles 12h, and filtering takes filter residue, is washed to neutrality, 75 DEG C of drying with distillation, 10 meshes are crossed in grinding；
2mol/L NaOH solution Immersion treatment 12h is used again, and filtering takes filter residue；Finally use 2mol/L FeSO4Solution is submerged and is stirred anti-
Answer 1h, it is neutrality that NaOH solution, which is added, and adjusts pH, and after impregnating reaction for 24 hours, filtering takes filter residue, and deionized water is cleaned to colourless, 75
DEG C drying, obtain iron modification biological Carbon Materials；
5 grams of chitosans are dissolved in 300mL 1%(w/v) in acetic acid, prepare chitosan solution；Slurry is maintained at 5h at 95 DEG C,
After being cooled to 60 DEG C, N is used2Purge 30 min；0.1g/mL ammonium persulfate aqueous solution 20mL is added, is reacted at a temperature of 60 DEG C
20min；After being cooled to 55 DEG C, the mixed of 320mL acrylic acid, 5g N, N- methylene-bisacrylamide and 25g sodium bentonite is added
Object is closed, is stirred to react 3h at a temperature of 75 DEG C；It is neutrality that NaOH solution, which is added, and adjusts pH, and filtering takes filter residue, is washed with deionized water
It washs, 75 DEG C of drying are ground, sieved with 100 mesh sieve, obtain dry chitin modified bentonite clay material；
50 parts of chitin modified bentonite clay materials are uniformly mixed with deionized water, 10 parts of methylcellulose, 10 parts of silane are added
Coupling agent kh-570 mixes, and is stirred to react 30min in 110 DEG C of waters bath with thermostatic control, is cooled to room temperature, and filters, takes filter residue, by filter residue in
55 DEG C of dryings for 24 hours, are cooled to room temperature, must be sustained chitin modified bentonite clay material；By 2 parts of chitin modified bentonite materials of sustained release
Material is heated to 180 DEG C, keeps the temperature 30min, is wrapped in 1 part of iron modification biological Carbon Materials outer layer while hot, obtains porous iron modification biological charcoal-
It is sustained chitin modified bentonite composite passivant；
It takes 100g through air-dried, ground 10 mesh nylon mesh and has measured the compound dirt of heavy metal As, Cd, Cu, Zn bio-available Zn concentration
Soil is contaminated, 5g porous sustained-release composite passivant is added and is uniformly mixed, it is 30% that deionized water, which is added, and keeps soil moisture content, is placed in
(25 DEG C) of room temperature cultures, 15d, 60d 0.1mol/L CaCl2Weight in soil is surveyed in extraction, icp ms
Metal As, Cd, Cu, Zn bio-available Zn concentration；Calculating 15d is 33.57% to the deactivation rate of As, and the deactivation rate to Cd is 51.84%,
Deactivation rate to Cu is 37.41%, and the deactivation rate to Zn is 24.50%；60d is 31.28% to the deactivation rate of As, to the blunt of Cd
Rate is 52.48%, and the deactivation rate to Cu is 38.40%, and the deactivation rate to Zn is 26.67%.
Claims (7)
1. a kind of porous sustained-release composite passivant and preparation method thereof for heavy metal-polluted soil passivation, which is characterized in that including
Kernel porous iron modification biological Carbon Materials and outer layer are sustained chitin modified bentonite clay material, include the following steps:
(1) chitin modified bentonite clay material is uniformly mixed with methylcellulose, deionized water, silane coupling agent KH- is added
570 mix, and are stirred to react 30min in 90-120 DEG C of water bath with thermostatic control, are cooled to room temperature, and filter, take filter residue, and filter residue is dry in 55 DEG C
It is dry to be cooled to room temperature for 24 hours, chitin modified bentonite clay material must be sustained；
(2) chitin modified bentonite clay material will be sustained and be heated to 170-200 DEG C, 20-40min is kept the temperature, be wrapped in iron while hot and change
Property biological carbon materials outer layer is cooled to room temperature to obtain porous iron modification biological charcoal-chitin modified bentonite of sustained release composite passivated
Agent.
2. a kind of porous sustained-release composite passivant and its preparation side for heavy metal-polluted soil passivation according to claim 1
Method, which is characterized in that the weight ratio of porous iron modification biological Carbon Materials and the chitin modified bentonite clay material of sustained release is 1:1-2,
Be sustained chitin modified bentonite clay material raw material includes: chitin modified bentonite clay material 50-70 parts by weight, Methyl cellulose
It is 8-15 parts plain, 10-20 parts of Silane coupling reagent KH-570.
3. a kind of porous sustained-release composite passivant and its preparation side for heavy metal-polluted soil passivation according to claim 1
Method, which is characterized in that the preparation of kernel porous iron modification biological Carbon Materials includes the following steps:
(1) after biomass straw removal of impurities, being crushed, be dry, the pyrolysis charring 40- in 400-600 DEG C of microwave reactor
50min, taking-up are cooled to 25 DEG C, obtain charcoal；
(2) by gained charcoal with after HCl solution Immersion treatment 12h, filtering takes filter residue, is washed to neutrality, 75 DEG C of bakings with distillation
Dry, 10 meshes are crossed in grinding, obtain pretreated charcoal；
(3) the pretreated charcoal of gained is subjected to basification with NaOH solution, after impregnating 12h, filtering takes filter residue, must change
Property charcoal；
(4) gained modification biological charcoal is immersed into FeSO4In solution, it is stirred to react 0.5-2h, NaOH solution is added and adjusts during pH is
Property, after impregnating reaction 22-26h, filtering takes filter residue, is cleaned with deionized water to colourless, 75 DEG C of drying, obtains iron modification biological material
Material.
4. the preparation of kernel porous iron modification biological Carbon Materials according to claim 3, which is characterized in that HCl solution is dense
Degree is 1mol/L, and NaOH solution concentration is 2mol/L, FeSO4Solution concentration is 1-2mol/L.
5. a kind of porous sustained-release composite passivant and its preparation side for heavy metal-polluted soil passivation according to claim 1
Method, which is characterized in that the preparation of outer layer chitosan modified alta-mud material includes the following steps:
(1) it dissolves the chitosan in acetic acid solution, obtains chitosan solution；By chitosan solution slurry at 85-95 DEG C constant temperature
5h is cooled to 60 DEG C, uses N2Purge 30min；Ammonium persulfate aqueous solution is added and is cooled to 45- in 60 DEG C of isothermal reaction 20min
55 DEG C, acrylic acid, N, N- methylene-bisacrylamide, sodium bentonite, under continuous stirring condition, in 65-75 DEG C of constant temperature is added
3h is reacted, graft polymerization reaction is completed, obtains chitin modified bentonite solution；
(2) NaOH solution is added to adjust pH to the chitin modified bentonite solution of gained is neutrality, and filtering takes filter residue, spends
Ion water washing, 75 DEG C of drying, grinds, sieves with 100 mesh sieve, obtain dry chitin modified bentonite clay material.
6. the preparation of outer layer chitosan modified alta-mud material according to claim 5, which is characterized in that chitosan and second
The solid-to-liquid ratio of acid solution is 1:56-60, and acetic acid solution concentration is 1%(w/v)；The solid-to-liquid ratio of chitosan and ammonium persulfate solution is
1:18-22, ammonium persulfate solution concentration are 10%(w/v)；The weight ratio of chitosan and acrylic acid is 1:60-65；Chitosan and N,
The weight ratio of N- methylene-bisacrylamide is 1:1-1.2, and the weight ratio of chitosan and sodium bentonite is 1:4.8-5；It is described
Sodium bentonite be the sodium chloride solution of 0.25mol/L is added drop-wise to deionized water preparation 10%(w/v) bentonite suspension
In to get.
7. a kind of porous sustained-release for heavy metal-polluted soil passivation that preparation method according to claim 1 is prepared is multiple
Close passivator, it is characterised in that porous sustained-release composite passivant is 20-50g/kg for the dosage of soil heavy metal ion removal.
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| CN111974353A (en) * | 2020-08-28 | 2020-11-24 | 桂林理工大学 | Method for preparing hydrophobic biochar by using silane coupling agent KH-570 |
| CN113372919A (en) * | 2020-04-02 | 2021-09-10 | 汤彪 | Slow-release repairing agent for soil pollution |
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| CN115287074B (en) * | 2022-06-30 | 2024-04-05 | 中南林业科技大学 | Efficient nickel-polluted soil passivating agent and preparation method and application thereof |
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Address after: 650000 218-2, two A building, phase 1520, Haiyuan Road, Kunming hi tech Development Zone, Yunnan. Applicant after: Shengqing Environmental Protection Co., Ltd. Address before: 650000 218-2, two A building, phase 1520, Haiyuan Road, Kunming hi tech Development Zone, Yunnan. Applicant before: YUNNAN SHENGQING ENVIRONMENTAL PROTECTION SCIENCE AND TECHNOLOGY CO., LTD. |
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Application publication date: 20190118 |