CN106833651A - Active medical stone soil heavy mental ion adsorption passivator and preparation method thereof - Google Patents
Active medical stone soil heavy mental ion adsorption passivator and preparation method thereof Download PDFInfo
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- CN106833651A CN106833651A CN201611190029.6A CN201611190029A CN106833651A CN 106833651 A CN106833651 A CN 106833651A CN 201611190029 A CN201611190029 A CN 201611190029A CN 106833651 A CN106833651 A CN 106833651A
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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
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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
- C09K17/04—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only applied in a physical form other than a solution or a grout, e.g. as granules or gases
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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
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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
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
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Abstract
Active medical stone soil heavy mental ion adsorption passivator and preparation method thereof belongs to soil remediation and field of environment protection or heavy metal ion adsorbing material field; exceeded to solve farmland soil heavy metals cadmium (Cd), chromium (Cr), copper (Cu), zinc (Zn), nickel (Ni), lead (Pb), agricultural land soil is unable to the problem that safety continuous are utilized.Meanwhile, the absorption passivator can reduce the enrichment of crop heavy metal.The preparation method of passivator quality is：Medical stone original ore powder+clay+humic acid ratio in mass ratio is 80:5:5:Mix and stir；After material is mixed and stirred for uniformly in proportion, adding citric acid activate and then carries out dries pulverizing, and heavy metal-polluted soil absorption passivator is obtained.
Description
Technical field
The present invention relates to heavy metal ion adsorbed passivator of active medical stone and preparation method thereof, belong to heavy metal ion suction
Enclosure material field.
Background technology
Since more than 40 years of China's reform, rapid economic development, material progress and cultural and ideological progress is enriched constantly, the people
Living standard is significantly improved, and overall national strength is greatly enhanced.However, along with large-scale industrialization in a short time, urbanization and agriculture
Industry intensivization development, the problem of environmental pollution of China also becomes increasingly conspicuous, and big gas and water, soil, noise pollution event frequently occur,
There is report during environmental hazard, environmental pollution has turned into the bottleneck problem of restriction China economic development.
Soil is the material base of the sustainable development of socio-economy.Currently, China's soil environment situation totally allows of no optimist,
Press《National Soil Pollution Investigation publication》(on April 17th, 2014), the total exceeding standard rate of national soil is 16.1%, wherein gently
Micro-, slight, moderate and serious pollution point position ratio are respectively 11.2%, 2.3%, 1.5% and 1.1%.Arable soil environment matter
Amount causes anxiety, soil point position exceeding standard rate be 19.4%, wherein slightly, slightly, moderate and serious pollution point position ratio be respectively
13.7%th, 2.8%, 1.8% and 1.1%, major pollutants are cadmium, nickel, copper, arsenic, mercury, lead, DDT and polycyclic aromatic hydrocarbon.
Chemical pollutant enters water body and soil with number of ways, health and ecological environment is generated direct or latent
Harm, wherein with the industrial processes such as mining and metallurgy, machine-building, chemical industry, electronics, instrument produce heavy metal ion
(chromium, cadmium, copper, mercury, nickel, zinc etc.) environmental pollution is the most serious.Heavy metal ion toxicity is big, does not degrade in the environment,
Conversion is difficult, not only soil and earth's surface, body of groundwater are polluted, also can be with the accumulation of organism, by food chain pair
Health constitutes harm.
At present, the method for the treatment of soil heavy metal ion pollutant mainly includes ion-exchange, adduct process, burning
Method, soil moved in improve the original displacement method, electrodynamics method, absorption method etc..From from the aspect of purification efficiency and economic benefit, it is desirable to adsorb
Method.The material such as activated carbon and zeolite has large specific surface area, is often used for heavy metal-polluted water or soil as sorbing material
The improvement of earth.Meanwhile, clay mineral has that cheap, porosity is high, surface texture is various, absorption affinity is strong, ion exchange energy
Performance and the features such as power protrusion, therefore, adsorb, lock and be passivated dirt using little particle clay mineral or modified (activation) mineral
Heavy metal ion in dye soil has become the new focus administered with repairing heavy metal in soil pollution.At present, the country has applied
Clay pit species soil passivator patent include：
A kind of preparation of soil heavy metal passivant and the passivating method -201210196956.4 to P in soil b；
102746849B
Main classification number：C09K17/02(2006.01)I
Summary:A kind of preparation of the present invention for soil heavy metal passivant and the passivating method to P in soil b, first, by alkali
Ultrasonic disperse stirs into muddy during flyash after liquid and sieving is proportionally added into reactor, and reactor is placed in baking oven and carries out
Hydrothermal crystallizing reacts；By reacted product cooling, centrifugation, be washed with deionized, dry, grind after obtain final product synthetic zeolite
Powder, secondly, normal pressure burns rice husk and produces rice hull ash, by powder of straw, flyash, synthetic zeolite powder, rice hull ash by weight percentage
It is well mixed, obtain final product heavy metal deactivator；By adjusting soil pH value, soil moisture content, passivator quality, passivation time, blunt
Change the conditions such as temperature, the passivation effect of loess agricultural land soil Pb can be improved, the method is with low cost, easy to operate, practicality
By force, security is good, easy to spread, can be passivated heavy metal-polluted soil while improved soil property, in heavy metal pollution of soil
Reparation aspect has potential application value.
Charcoal mixed matching soil heavy metal passivant for facilities vegetable field and preparation method thereof -201210299639.5；
102807872B Main classifications number：C09K17/40(2006.01)I.Summary:The present invention relates to soil amelioration techniques and environmental protection
Technology, specially charcoal mixed matching soil heavy metal passivant for facilities vegetable field and preparation method thereof.By weight percentage, soil
Earth heavy metal deactivator is：Charcoal 50~60%, medical stone powder 5~10%, diatomite in powder 5~10%, lignite 10~20%
With flyash 10~20%.The preparation method of soil heavy metal passivant：The medical stone powder of 80 mesh sieves will first be crossed, 80 mesh sieves are crossed
Diatomite in powder mixes with the flyash of lignite and 80 mesh sieves excessively, stirs, then mixes with the charcoal for crossing 20 mesh sieves, fully
Stirring, after being well mixed, is made soil heavy metal passivant.Preparation method of the present invention is simple, by the synergy of each composition,
Passivation protected horticultural vegetable field soil heavy metal is reached, crop can be using the effect of state content of beary metal in reducing soil.
Chinese patent CN1669634A discloses " the preparation side of montmorillonite loading nano titanium dioxide heavy metal adsorbent
Method ", heavy metal ion adsorbed rate is improved by load nano-titanium dioxide.Chinese patent CN102274717A discloses " a kind of
The preparation method of thio-modified sepiolite heavy metal absorbent ", with natural clay sepiolite as matrix, is added by high-speed stirred
Mercapto propyl silane modification sepiolite, improves the adsorption capacity of sepiolite.The above-mentioned method cost for preparing clay base adsorbent
Of a relatively high, and preparation process is complex, it is sometimes higher that the field of adsorbent is added or used to ratio, thus may result in
Original soil physico-chemical property changes.Therefore, consider from economics point and practicality, still need to put forth effort research and development low
Cost, high efficiency, environment-friendly soil heavy mental ion adsorption passivator.
The content of the invention
It is high for existing adsorbent production cost, the defect such as preparation process complexity, it is an object of the invention to provide work
Property medical stone soil heavy mental ion adsorption agent and preparation method thereof, the adsorbent heavy metal ion have preferably absorption and
Passivation effect.There is the preparation method of the adsorbent raw material to be easy to get, and process is simple is with low cost, it is easy to Industry Promotion
Advantage.
The purpose of the present invention is realized by following technical scheme：
(1) medical stone raw ore obtains D through 300 DEG C of drying into high pressure pulverizer milling50No more than 125 μm, D90Less
In 250 μm of original ore powder；Wherein, D50And D90When the cumulative particle sizes percentile of respectively adsorbent reaches 50% and 90%
Corresponding particle diameter；
(2) in mass ratio it is 80 according to medical stone original ore powder+clay+humic acid:5:5, mix and stir；
(3) on the basis of step (2), citric acid soln is sprayed while stirring, carry out priming reaction, citric acid in solution
Content is 1.5mol/L.PH value is adjusted to 5.2, and soak time is 5min；Citric acid soln addition is submergence enough；
4) the mixed material heating drying for obtaining step (3), temperature is 300 DEG C -- 500 DEG C, the time is 8min, after drying
Obtain active medical stone mixed dry material；
(5) machine is carried out to the medical stone mixed dry material after drying using the high speed disintegrator of 1200 revs/min of the speed of mainshaft
Tool is crushed, and grinding time is 30~90s, obtains passivator.
Medical stone obtains specific surface area not less than 1.7m after being milled into high pressure pulverizer2The original ore powder of/g.
Further, the mass content of montmorillonite is more than 90% in the clay.
Further, quality of organic matter content is 80%-90% in humic acid.
According to passivator prepared by methods described.
Clay as additive, with good dispersiveness and plasticity.
Beneficial effect
There is the preparation method of adsorbent of the present invention raw material to be easy to get, process is simple, low cost, it is easy to Industry Promotion
Advantage, prepared absorption passivator centering, the heavy metal ion of low concentration include：Cadmium, chromium, copper, zinc, nickel, lead have compared with
Good absorption passivation effect, the enrichment of crop heavy metal can be reduced effectively.
(7) when identical to contaminated soil addition, through to common medical stone, ordinary fly ash, activation medical stone in basin
Cultivation is made in the soil contrast test of heavy metal pollution.
Common medical stone is 10.5-18% to the adsorption rate of cadmium metal (Cd), and active medical stone is 18-36%, adsorption rate
Improve 90%.
Common medical stone is 1.8-17.3% to the adsorption rate of metallic lead (Pb), and active medical stone is 6-22%, adsorption rate
Improve 30%.
Common medical stone is 20.0-36.2% to the adsorption rate of metallic arsenic (As), and active medical stone is 38.4-52.1%,
Adsorption rate improves 44%.
Conclusion is the medical stone (referred to as active medical stone) after activation, due to common medical stone in the absorption of heavy metal.
Brief description of the drawings
Fig. 1 adds influence of the passivator to pakchoi plant height
Fig. 2 adds influence of the passivator to rape plant height
Fig. 3 adds influence of the passivator to spinach plant height
Fig. 4 adds influence of the passivator to pakchoi dry weight
Fig. 5 adds influence of the passivator to rape dry weight
Fig. 6 adds influence of the passivator to spinach dry weight
Specific embodiment
Embodiment 1
Active medical stone is D50No more than 125 μm (60 mesh), D90No more than 250 μm (120 mesh), specific surface area is not less than
1.7m2The active medical stone powder of/g；Wherein, D50And D90The cumulative particle sizes percentile of respectively adsorbent reaches 50% He
Corresponding particle diameter when 90%.
The preparation method of the passivator, step is as follows：
(1) medical stone raw ore obtains D through 300 DEG C of drying of low temperature into high pressure pulverizer milling50No more than 125 μm (60
Mesh), D90The no more than 250 μm original ore powders of (120 mesh)；The main motor current 30Kw of high pressure pulverizer, rotating speed 740/ minute；Analysis
Power of motor 3Kw, 960 revs/min of rotating speed；Supercharging blower motor 22Kw, 1470 revs/min of rotating speed.It is 3 ton hours to produce
(2) medical stone original ore powder+clay+humic acid is 80 in mass ratio:5:5:Mix and stir；Medical stone
Specific surface area is obtained not less than 1.7m after into high pressure pulverizer milling2The original ore powder of/g.The mass content of montmorillonite in clay
More than 90%.
Quality of organic matter content is 80%-90% in humic acid.
(3) on the basis of step (2), citric acid soln is sprayed while stirring, carry out priming reaction, citric acid in solution
Content is 1.5mol/L.PH value is adjusted to 5.2, and the stir-activating time is 5min；
(4) the mixed material heating drying for obtaining step (3), temperature is 300 DEG C -- 500 DEG C, to accelerate reaction, the time is
8min；Active medical stone mixed dry material is obtained after drying；
(5) mechanical crushing being carried out to the medical stone mixed dry material after drying using high speed disintegrator, grinding time is 30~
90s, obtains the active medical stone soil heavy mental ion adsorption passivator.1200 revs/min of the speed of mainshaft of high speed disintegrator
Clock；Power of motor 30KW. production capacities are 5 tons/h.
(6) activated medical stone passivator, in activation, citric acid reacts with medical stone, obtains sodium citrate, lemon
The compounds such as sour iron, potassium citrate, calcium citrate, in mercury pressure ratio surface area test, specific surface area has 1.2m2/ g brings up to
2.1m2/ g, micropore is expanded.
The effect of the active heavy metal-passivated contaminated soil in medical stone field
Test site is located at Daxing district, Beijing, China vegetables production base.Experimental plot soil is light by heavy metals such as cadmiums (Cd)
Degree pollution, content of beary metal (total amount) cadmium (Cd)：0.54~0.62mg/kg, chromium (Cr)：31.05~42.93mg/kg, lead
(Pb)：7.08~9.51mg/kg, copper (Cu)：15.94~19.61mg/kg, nickel (Ni)：11.47~15.64mg/kg, zinc
(Zn)：59.04~74.97mg/kg.
In addition to control group cell, each treatment group cell (2m × 2m) addition medical stone adsorbs passivator, and addition is
6.8Kg/ cells (about the 0.5% of topsoil soils mass fraction), mixing of being turned over after addition, smooth and isolation strip making ridge.Passivation
One week (7d) is balanced after agent addition, then starts sowing plantation pakchoi (grinding fast dish 2 in capital), rape (capital oil 605) and spinach
(vegetable spinach 1), aerial part is harvested after experiment 47d carries out biomass and content of beary metal measure.The every cell of soil sampling (2m ×
3 sampled points 2m) are set, topsoil (0~20cm) soil biased sample is gathered using 5 methods, contained for heavy metal-polluted soil available state
The measure of amount and soil physico-chemical property (pH).
Sample detection is performed according to following standard method：
(1) measure of topsoil soils pH value presses ISO 10390-2005 standard tests
(2) topsoil soils content of beary metal is determined and presses People's Republic of China's state environment protecting standard soils and sediments
Measure chloroazotic acid extraction/inductively coupled plasma mass spectrometry (exposure draft) of metallic element is determined
(3) measure of topsoil soils heavy metal available state is effective by People's Republic of China's state environment protecting standard soil
The measure triethylene pentaacetic acid of element/inductively coupled plasma mass spectrometry (exposure draft) is determined
(4) Zeeman GFAAS presses national food safety standard cadmium in foods, chromium, copper, zinc, nickel, lead, arsenic, the measure of mercury
Inductively coupled plasma mass spectrometry (exposure draft)
1 is shown in Table without with addition passivator heavy metal in soil bio-available Zn concentration measurement result.As can be seen that prepared
Active medical stone adsorbent for heavy metal have preferable adsorption effect to different heavy metal ion, can obviously reduce soil
The content of heavy metal available state in earth, reduced rate is between 6-41%.
Table 1 changes without with addition passivator heavy metal in soil bio-available Zn concentration
Influence of the addition passivator to content of beary metal in vegetables (pakchoi, rape, spinach) overground part tissue determines knot
Fruit is shown in Table 2.From table 2, absorption reduction by 18% of the pakchoi to Cd can be made using medical stone, the absorption reduction by 16% to Cr,
Absorption reduction by 12% to Pb, the absorption reduction by 62% to Cu, the absorption reduction by 39% to Ni, the absorption reduction by 15% to Zn.
Absorption reduction by 21% of the rape to Cr can be made using medical stone, the absorption reduction by 12% to Pb, the absorption reduction by 26% to Cu is right
The absorption reduction by 42% of Ni, the absorption reduction by 31% to Zn.Also can effectively be reduced using medical stone spinach to Cd, Cr, Pb,
The absorption of Cu, Ni and Zn.Wherein, to the absorption reduction by 25% of Cd, the absorption reduction by 24% to Cr, the absorption reduction to Pb
11%, the absorption reduction by 58% to Cu, the absorption reduction by 44% to Ni, the absorption reduction by 32% to Zn.
Content of beary metal in the vegetables of table 2 (pakchoi, rape, spinach) overground part tissue
Addition passivator Fig. 1-3 are seen to the influence measurement result of pakchoi, rape, spinach plant height, to pakchoi, rape,
The influence measurement result of spinach yield (dry weight) is shown in Fig. 4-6.As can be seen that using passivator to pakchoi, rape and spinach
Growth (with plant height and biological gauge) is substantially without significant impact, or even it can be promoted to grow, such as pakchoi, rape and spinach
Plant height increased 11%, 11% and 21% respectively, the yield (dry weight) of pakchoi and spinach also increased 17% He respectively
11%.
Meanwhile, influence of the addition passivator to soil property (pH value) in soil also measured were, find 0.5% addition water
Flat lower passivator does not produce significant impact to soil pH value.
The present invention include but is not limited to above example, it is every carried out under inventive concept and principle it is any equivalent
Replace or local improvement, all will be regarded as within protection scope of the present invention.
Claims (5)
1. the preparation method of active medical stone soil heavy mental ion adsorption passivator, it is characterised in that step is as follows：
(1) medical stone raw ore obtains D through 300 DEG C of drying into high pressure pulverizer milling50No more than 125 μm, D90No more than 250 μ
The original ore powder of m；Wherein, D50And D90The cumulative particle sizes percentile of respectively adsorbent reaches corresponding when 50% and 90%
Particle diameter；
(2) in mass ratio it is 80 according to medical stone original ore powder+clay+humic acid:5:5, mix and stir；
(3) on the basis of step (2), citric acid soln is sprayed while stirring, carry out priming reaction, citron acid content in solution
It is 1.5mol/L；PH value is adjusted to 5.2, and soak time is 5min；Citric acid soln addition is submergence enough；
4) the mixed material heating drying for obtaining step (3), temperature is 300 DEG C -- 500 DEG C, the time is 8min, is obtained after drying
Active medical stone mixed dry material；
(5) mechanical powder is carried out to the medical stone mixed dry material after drying using the high speed disintegrator of 1200 revs/min of the speed of mainshaft
Broken, grinding time is 30~90s, obtains passivator.
2. preparation method according to claim 1, it is characterised in that medical stone is compared after being milled into high pressure pulverizer
Surface area is not less than 1.7m2The original ore powder of/g.
3. preparation method according to claim 1, it is characterised in that the mass content of montmorillonite is more than in the clay
90%.
4. preparation method according to claim 1, it is characterised in that quality of organic matter content is 80%- in humic acid
90%.
5. the passivator for being prepared according to claim 1-4 methods describeds.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109097052A (en) * | 2018-08-31 | 2018-12-28 | 哈密国家农业科技园区管委会 | A kind of natural medical stone agricultural soil heavy metal deactivator and preparation method thereof |
| CN111500292A (en) * | 2020-04-23 | 2020-08-07 | 中国建筑第二工程局有限公司 | Composite type soil material and application thereof in preparing greening planting soil from river and lake dredging mud |
| CN112574754A (en) * | 2020-12-19 | 2021-03-30 | 四川大学 | Passivator for repairing heavy metal polluted farmland soil and application method |
| CN113800973A (en) * | 2021-09-27 | 2021-12-17 | 浙江益壤环保科技有限公司 | Soil conditioner suitable for acidic farmland and preparation method thereof |
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| CN109097052A (en) * | 2018-08-31 | 2018-12-28 | 哈密国家农业科技园区管委会 | A kind of natural medical stone agricultural soil heavy metal deactivator and preparation method thereof |
| CN111500292A (en) * | 2020-04-23 | 2020-08-07 | 中国建筑第二工程局有限公司 | Composite type soil material and application thereof in preparing greening planting soil from river and lake dredging mud |
| CN112574754A (en) * | 2020-12-19 | 2021-03-30 | 四川大学 | Passivator for repairing heavy metal polluted farmland soil and application method |
| CN113800973A (en) * | 2021-09-27 | 2021-12-17 | 浙江益壤环保科技有限公司 | Soil conditioner suitable for acidic farmland and preparation method thereof |
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