CN104383890B - A kind of soil heavy mental ion adsorption agent and its preparation method - Google Patents
A kind of soil heavy mental ion adsorption agent and its preparation method Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
Abstract
The open a kind of soil heavy mental ion adsorption agent of the present invention and its preparation method. Described soil heavy mental ion adsorption agent is become for the ratio mixed preparing of 2:5:3 with potassium humate in mass ratio by the kaolin of the maize straw of modification, modification; The maize straw of described modification mainly by oven dry, alkaline purification, acid treatment, oven dry and become; The kaolin of described modification mainly adds sodium polyphosphate roasting and becomes. Adopt soil heavy mental ion adsorption agent of the present invention can significantly strengthen the adsorptive power of soil heavy metal, decrease the migration of heavy metal in soil to farm crop. Test shows: plumbous average reduction amplitude 15.63% in corn kernel, cadmium on average reduces amplitude 12.15%, and arsenic on average reduces amplitude 7.62%. Plumbous average reduction amplitude 17.8% in rice, cadmium on average reduces amplitude 17.27%, and arsenic on average reduces amplitude 21.84%, ensure that the quality safety of farm crop Leaf-feeding insects.
Description
Technical field
The present invention relates to the planting technology field of heavy metal pollution of soil reparation and crop production safety quality control.
Technical background
Along with the development of process of industrialization nearly decades, the leach liquor of the waste water that various industry produces such as mining industry, Metallurgy Industry, chemical industry etc. and solid waste directly enters water body, along with the distribution of water system and agricultural irrigation water need enter farm environment. Soil is the direct carrier that agricultural-food are produced, chemical substance in soil is absorbed by farm crop in agriculture production and enters agricultural-food, whether soil is polluted and pollution level directly affect agricultural-food quality and yield (Zhou Qixing edits. healthy soil science soil health quality and agricultural product security .2005, Beijing: scientific publication society), therefore, agricultural product quality and safety and soil pollution are in close relations. First heavy metal-polluted soil produces Cumulate Sum by agricultural-food root absorption and moves in plant materials, when polluting the maximum acceptable concentration that content exceedes farm crop, the edible safety of agricultural-food just is difficult to be protected, agricultural product quality enquiry data display in 2011, there is cadmium pollution in China's 10% rice, the long-term edible generation that can cause human body " itai-itai disease ". Therefore, soil, sewage heavy metal contamination seriously endanger health and the existence of the various life entities comprising the mankind. Soil, heavy metals pollute and have persistence, and bioconcentration and amplification etc. act on, how effectively to administer heavy metal wastewater thereby pollute and soil pollution by heavy metal oneself become the problem that the mankind pay close attention to jointly.
At present, China is by nearly 20,000,000 hm of cultivated area of the heavy metal contaminations such as Cd, As and Pb2, account for the 1/5 of total cultivated area, nearly 1.33 ten thousand hm of cultivated area wherein polluted by Cd2Relate to 11 and economize 25 areas, every year because heavy metal contamination causes grain drop in production more than 1,000 ten thousand tons, the contaminated by heavy metals grain that can not eat reaches 1,200 ten thousand tons of (Wei Chaoyang etc., heavy metal super-enriched plant and phytoremediation technology research progress, ecological journal, 2001,21 (7): 1196-1203), the whole nation has many areas to develop into the degree of production " cadmium rice ". Within 2000, the whole nation 2.2 hundred million ton-grain food investigation being found, in grain, heavy metal Pb, Cd, Hg and As exceeding standard rate reach 10%. 2002, Ministry of Agriculture's rice and quality of item supervision and inspection center thereof are to the rice security Examined display of market, the whole nation, exceed standard in rice the most seriously Pb, exceeding standard rate is 28.4%, next is Cd, exceeding standard rate is 10.3%, As and Hg exceeding standard rate is relatively low, it is respectively 2.8% and 3.4%, and present certain combined pollution phenomenon (Cheng Wang great etc., the kind of the heavy metal content such as arsenic, cadmium, chromium, nickel, lead and Grain position effect in evening japonica rice seed grain, rice in China science, 2005,19 (3): 273-279).
Repair the difference of control techniques principle according to heavy-metal contaminated soil, common heavy metal pollution of soil treatment process is broadly divided into three kinds, i.e. chemical method, physico-chemical processes and biological process. Chemical Treatment heavy-metal contaminated soil mainly comprises chemical precipitation method and electrolytic process, is mainly applicable to the process containing higher concentration heavy metal ion mine tailing storehouse soil. Physico-chemical processes process heavy-metal contaminated soil comprises ion exchange method and membrane separation technique, is applicable to the process containing low concentration heavy metal ion soil. Biological process mainly refers to plant restoration method, and the method refers to and utilizes plant to act on, by absorb, precipitate and enrichment etc., the heavy metal content reducing contaminated soil or surface water, to reach the object of pollution administration, repairing environment. Bioremediation comprises bio-flocculation process, biosorption process. Biological absorption be exactly organism and derivative thereof to the adsorption of heavy metal in medium, comprise the complexing of the different sites heavy metal ion of cell, ion-exchange, absorption and inorganic microdeposit etc. Biosorption process is a kind of brand-new heavy metal contamination administering method in recent years, and efficient with it, cheap advantage causes the interest of people gradually. The research of external this respect from the eighties, the nineties, development was very fast, biosorption process has compared with other heavy-metal contaminated soil treatment process can reduce farm crop to the absorption enriching quantity of heavy metal in soil, and working cost is low, can reclaim heavy metal and not have the advantage of secondary pollution. And biogenic has easy immobilization, and special biological adsorption agent can be made as required and Reusability. Therefore, biosorption process has good agricultural environment heavy metal contamination to administer application prospect.
The successful enforcement of biosorption process, key depends on the development and application of sorbent material. Biological adsorption agent refers generally to adsorb the microbe of heavy metal, comprises algae, bacterium, fungi etc. Growing along with biosorption technology, biological adsorption agent is not only confined to microorganism, some abundant crude substance, particularly Mierocrystalline cellulose, is considered as having the biological adsorption agent of suitable potentiality. Mierocrystalline cellulose is the abundantest on the earth, it is possible to the natural resource of recovery, has inexpensive, degradable and environment is not produced the advantages such as pollution. But natural cellulose absorption heavy metal ability is also not bery strong, it is necessary to just can become sorbing material of good performance by modification. 2001, the research such as Liu Minghua showed, modified spherical Mierocrystalline cellulose is to Cr3+Adsorptive capacity is 28mg/g; 2009, the researchs such as king showed, modification sugarcane residue is to Cu2+Adsorptive capacity is up to 58.53mg/g. It may be seen that biological adsorption agent wide material sources, wide in variety, many biomaterials have superior absorption heavy metal ability. Agricultural crop straw is the agricultural wastes that biomass is huge in the world. Especially the crop straw rich cellulose composition such as corn, wheat, paddy rice, can play an important role in a lot of fields, but, the agricultural crop straw that existing utilization obstacle causes quite a few is used by low value and directly discarded, and the crop of developing into of agricultural wastes method of modifying and technology of preparing is prepared ion adsorbent and provides theoretical basis and research direction.
Summary of the invention
The technical problem to be solved in the present invention overcomes in original agricultural cultivation management mode owing to heavy metal-polluted soil background value is relatively high or sewage irrigation causes Regional Agricultural Products heavy metal content to exceed the safety problem of national food hygienic standard limitation. Therefore, the present invention provide a kind of can effectively solve crop production safety have the soil heavy mental ion adsorption agent to heavy metal-polluted soil efficacy of adsorption and preparation method, improve agricultural product security eating quality to reach, promote the object of the orderly development of agricultural environment and human health.
For solving the problems of the technologies described above and realize the object of the invention, the technical scheme of the present invention is as follows:
1. a soil heavy mental ion adsorption agent, it is characterised in that: by following A, B and potassium humate three groups of materials in A:B: the ratio that the mass ratio of potassium humate is 2:5:3 is obtained by mixing;
(1) A group material is the maize straw of modification, and the maize straw of described modification is obtained by following method:
1. the collection of stalk and pre-treatment
Collect the fresh straw of more than the plant root after harvest corn, cut and cut up with a hay cutter into section, the earth cleaning stalk surface attachment and sand and dust are rinsed with clear water, it is placed on shady and cool place nature air-dry, put into again constant temperature oven 50 DEG C dry to constant weight pulverize or nature sunlight under shine dry in the air be dried to constant weight after pulverize, cross 2-4 order sieve and obtain stalk particle;
2. straw modification
A, in stalk particle: concentration is the mass ratio of the NaOH solution of 1mol/L is the ratio of 1:50, adds the NaOH solution of stalk particle and 1mol/L in a reservoir, stirs after evenly, puts into Tempeerature-constant air shaking table, soaks 18 hours at 40 DEG C;
After B, immersion, taking out stalk particle, supernatant liquor is removed in centrifugation, and it is precipitated as through alkaline purification stalk particle;
C, by through alkaline purification stalk particle and vinyl cyanide according to alkaline purification stalk particle: the ratio that the mass ratio of vinyl cyanide is 1:10 is mixed to get mixture, and this mixture is put into another container, reacts 20-30min at 30 DEG C;
D, by step (1) 2. C wash 2-3 time through reacted stalk particle deionized water, then be 12g/L hydrochloric acid soak acid-cleaning by concentration, until the pH that stalk particle fully soaks into stalk particle be 7 or pH be 5��6.9;
E, taking-up, through the stalk particle of pickling, are washed until aqueous solution pH is 6.5��7 with deionized water, then stalk particle are put into constant temperature oven 50 DEG C oven dry to constant weight, obtain the maize straw of described modification;
(2) B group material is the kaolin of modification, and the kaolin of described modification is obtained by following method:
Get kaolinite original ore powder in container, in kaolinite original ore powder: the ratio that the mass ratio of sodium polyphosphate is 4:1 adds sodium polyphosphate, mix, add distilled water again and stir into pasty state, after leaving standstill half an hour, it is placed in constant temperature oven, start baking oven, setting top temperature is 100 DEG C, when oven temperature rises to 100 DEG C gradually, maintain 100 DEG C of constant temperature bakings and then move in retort furnace for l hour, open retort furnace and be warming up to 280 DEG C of roasting temperatures one hour, being come out of the stove by kaolin cool to room temperature, ground 2-4 order sieves and obtains the kaolin of modification.
2. soil heavy mental ion adsorption agent according to technical scheme 1, it is characterised in that: the cool room temperature described in room temperature of being come out of the stove by kaolin described in step (2) is 32 DEG C��15 DEG C.
3. the preparation method of a soil heavy mental ion adsorption agent, it is characterised in that, by following A, B and potassium humate three groups of materials in A:B: the ratio mixing that the mass ratio of potassium humate is 2:5:3 is described soil heavy mental ion adsorption agent:
(1) A group material is the maize straw of modification, and the maize straw of described modification is obtained by following method:
1. the collection of stalk and pre-treatment
Collect the fresh straw of more than the milpa root after harvest corn, cut and cut up with a hay cutter into section, the earth cleaning stalk surface attachment and sand and dust are rinsed with clear water, it is placed on shady and cool place nature air-dry, put into again constant temperature oven 50 DEG C dry to constant weight pulverize or nature sunlight under shine dry in the air be dried to constant weight after pulverize, cross 2-4 order sieve and obtain stalk particle;
2. straw modification
A, in stalk particle: concentration is the mass ratio of the NaOH solution of 1mol/L is the ratio of 1:50, adds the NaOH solution of stalk particle and 1mol/L in a reservoir, stirs after evenly, puts into Tempeerature-constant air shaking table, soaks 18 hours at 40 DEG C;
After B, immersion, taking out stalk particle, supernatant liquor is removed in centrifugation, and it is precipitated as through alkaline purification stalk particle;
C, by through alkaline purification stalk particle and vinyl cyanide according to alkaline purification stalk particle: the ratio that the mass ratio of vinyl cyanide is 1:10 is mixed to get mixture, and this mixture is put into another container, reacts 20-30min at 30 DEG C;
D, step (1) 2. C wash 2-3 time through reacted stalk particle deionized water, then be 12g/L hydrochloric acid soak acid-cleaning by concentration, until the pH that stalk particle fully soaks into stalk particle be 7 or pH be 5��6.9;
E, taking-up, through the stalk particle of pickling, are washed until aqueous solution pH is 6.5��7 with deionized water, then stalk particle are put into constant temperature oven 50 DEG C oven dry to constant weight, obtain the maize straw of described modification;
(2) B group material is the kaolin of modification, and the kaolin of described modification is obtained by following method:
Get kaolinite original ore powder in container, in kaolinite original ore powder: the ratio that the mass ratio of sodium polyphosphate is 4:1 adds sodium polyphosphate, mix, add distilled water again and stir into pasty state, after leaving standstill half an hour, it is placed in constant temperature oven, start baking oven, setting top temperature is 100 DEG C, when oven temperature rises to 100 DEG C gradually, maintain 100 DEG C of constant temperature bakings and then move in retort furnace for l hour, open retort furnace and be warming up to 280 DEG C of roasting temperatures one hour, being come out of the stove by kaolin cool to room temperature, ground 2-4 order sieves and obtains the kaolin of modification.
4. the preparation method of soil heavy mental ion adsorption agent according to technical scheme 3, the described cool room temperature described in room temperature of being come out of the stove by kaolin of step (2) is 32 DEG C��15 DEG C.
5. soil heavy mental ion adsorption agent described in technical scheme 1 or 2 is reducing the application of crop products heavy metal content.
Compared with the prior art, the invention has the beneficial effects as follows:
The present invention is in a large amount of Literature Consults and previous work basis, take corn stalk as raw material, adopt chemical separation method, fresh straw is carried out modification, sufficient mixed preparing is carried out with the modified kaolin of the blunt burning of high temperature and potassium humate, form soil heavy mental ion adsorption agent prescription of the present invention, by arranging the heavy-metal contaminated soil adsorption applications test of this formula, coupled ion absorption quantitative analysis and effect comparison, develop a kind of soil heavy mental ion adsorption agent that can effectively reduce crop heavy metal content, for ensureing that crop production safety provides significant technical guarantee.
The suitable soil heavy mental ion adsorption agent prescription of preparation measure that the present invention is suitable for and preparation, enhances the adsorptive power of soil heavy metal, decreases the migration of heavy metal in soil to farm crop, ensure that the quality safety of farm crop Leaf-feeding insects.
Compared with not adding soil heavy mental ion adsorption agent of the present invention, the adsorptive capacity increasing degree of rice soil heavy metal arsenic, lead, cadmium is respectively 50%, 49.1% and 16.7%; The adsorptive capacity increasing degree of red soil heavy metal arsenic, lead, cadmium is respectively 20.5%, 8.4% and 29.3%; The adsorptive capacity increasing degree of purple soil heavy metal arsenic, lead, cadmium is respectively 50%, 41.1% and 64.97%, effectively reduce the transfer of heavy metal in soil to the farm crop Leaf-feeding insects such as corn kernel, rice, heavy metal content in corn kernel is significantly reduced, wherein plumbous average reduction amplitude 15.63%, cadmium on average reduces amplitude 12.15%, and it is 7.62% that arsenic on average reduces amplitude. In rice, heavy metal content obtains significantly being reduced, wherein plumbous average reduction amplitude 17.8%, and cadmium on average reduces amplitude 17.27%, and arsenic on average reduces amplitude 21.84%.
Preparation method and the using method of soil heavy mental ion adsorption agent of the present invention are all easy and simple to handle, with low cost, draw materials conveniently, are suitable for planting wide popularization and application in industry development at green, non-polluted farm product.
Soil heavy mental ion adsorption agent provided by the present invention can be avoided burning, because of a large amount of, environmental pollution, the destruction eubiosis problem that straw causes every year simultaneously, and the efficient resource carrying out agricultural wastes utilizes.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but is only citing, is not construed as limiting the invention. Following examples material therefor is commercially available, is ordinary method without specified otherwise.
Embodiment 1 soil heavy mental ion adsorption agent of the present invention and its preparation method
A kind of soil heavy mental ion adsorption agent of the present invention, by following A, B and potassium humate three groups of materials in A:B: the ratio that the mass ratio of potassium humate is 2:5:3 is mixed:
(1) A group material is the maize straw of modification, and the maize straw of described modification is obtained by following method:
1. the collection of stalk and pre-treatment
Collect the fresh straw of more than the plant root after harvest corn, cut and cut up with a hay cutter into section, the earth cleaning stalk surface attachment and sand and dust are rinsed with clear water, it is placed on shady and cool place nature air-dry, put into again constant temperature oven 50 DEG C dry to constant weight pulverize or nature sunlight under shine dry in the air be dried to constant weight after pulverize, cross 3 orders sieve and obtain stalk particle;
2. straw modification
A, in stalk particle: concentration is the mass ratio of the NaOH solution of 1mol/L is the ratio of 1:50, adds the NaOH solution of stalk particle and 1mol/L in a reservoir, stirs after evenly, puts into Tempeerature-constant air shaking table, soaks 18 hours at 40 DEG C;
After B, immersion, taking out stalk particle, supernatant liquor is removed in centrifugation, and it is precipitated as through alkaline purification stalk particle;
C, by through alkaline purification stalk particle and vinyl cyanide according to alkaline purification stalk particle: the ratio that the mass ratio of vinyl cyanide is 1:10 is mixed to get mixture, and this mixture is put into another container, reacts 20min at 30 DEG C;
D, by step (1) 2. C wash 2 times through reacted stalk particle deionized water, it is 12g/L hydrochloric acid soak acid-cleaning by concentration again, until the pH that stalk particle fully soaks into stalk particle is 7 (measuring the pH value of stalk particle with reference to NY/T1121.2-2006);
E, taking-up, through the stalk particle of pickling, are washed until aqueous solution pH is 7 with deionized water, then stalk particle are put into constant temperature oven 50 DEG C oven dry to constant weight, obtain the maize straw of described modification;
(2) B group material is the kaolin of modification, and the kaolin of described modification is obtained by following method:
Get kaolinite original ore powder in container, in kaolinite original ore powder: the ratio that the mass ratio of sodium polyphosphate is 4:1 adds sodium polyphosphate, mix, add distilled water again and stir into pasty state, after leaving standstill half an hour, it is placed in constant temperature oven, start baking oven, setting top temperature is 100 DEG C, when oven temperature rises to 100 DEG C gradually, maintain 100 DEG C of constant temperature bakings and then move in retort furnace for l hour, open retort furnace and be warming up to 280 DEG C of roasting temperatures one hour, being come out of the stove by kaolin cool to room temperature 25 DEG C, ground 3 orders sieve and obtain the kaolin of modification.
The adsorption applications of embodiment 2 soil heavy mental ion adsorption agent of the present invention on soil type.
1, experiment is for examination material
1.1 participate in the experiment soil
Adsorption test soil picks up from different location, three, Yunnan Province, dissimilar arable soil. Gathering soil sample after naturally air-dry, preparation of milling, for the detection of heavy metal-polluted soil and physicochemical character index, soil basic condition of participating in the experiment sees the following form:
Table 1 is participated in the experiment the basic condition of soil
1.2 tests are arranged and heavy metal reagent
Heavy metal reagent that table 2 adsorption test adds and add-on
1.3 experimental technique
Adsorption test prepares two groups, and one group is comparison (CK), and one group is process. Three kinds of soil sample 1.00g that control group took 100 order sieves respectively are put in 100mL polyethylene centrifuge tube respectively, arrange three repetitions, totally 9 centrifuge tubes. Note: in table, each data are the mean value of three replications.
The soil heavy mental ion adsorption agent of the present invention described in embodiment 1 that treatment group also adds 1.00g except took three kinds of soil sample 1.00g of 100 order sieves according to control group except is put in 50mL centrifuge tube respectively. Three repetitions, totally 9 centrifuge tubes are set.
According to the concentration that arranges in table 2,18 centrifuge tubes of the control group and treatment group that have filled test materials are added three heavy metal species reagent respectively, and reagent solution is in advance by NaOH solution adjust ph to 5.0, and the add-on of often kind of reagent solution is 20mL. The centrifuge tube having added reagent is at room temperature vibrated and takes out centrifugal (6000r/min) 30 minutes after (200r/min) 24h, the supernatant liquor in centrifuge tube is filtered with quantitative paper (GB/T1914-93), solution after filtration is pressed GB/T17141-1997 method with atomic absorption spectrophotometer respectively and is measured plumbous, cadmium, press, by atomic absorption spectrometry, the concentration that GB/T22105.2-2008 measures arsenic, then calculate heavy metal adsorptive capacity.
1.3 heavy metal adsorptive capacitys calculate
Heavy metal adsorptive capacity calculates as follows:
Q=(Ci-Ce)��V/m
In formula, q attaches most importance to metal adsorption amount (mg/kg), Ci and Ce is respectively heavy metal initial soln concentration and balance solution weight metal concentration (mg/L), and V is balanced solution volume (mL), m is soil quality (g). Balanced solution heavy metal concentration refers to after absorption heavy metal heavy metal concentration in solution.
4, application result
Soil is as a kind of medium carrying heavy metal, inherently possesses certain heavy metal adsorption, contrasting (table 3) by the adsorption test of this test, the adsorptive power aggregate performance of three kinds of soil heavy metal of participating in the experiment is red soil > rice soil > purple soil; From heavy metal element, three class soil all easily adsorb lead, and the adsorptive power of arsenic is relatively weak. And add the soil heavy mental ion adsorption agent of the present invention's configuration, the adsorptive power of soil heavy metal is significantly strengthened, compared with the heavy metal adsorptive capacity not adding invention soil heavy mental ion adsorption agent, the absorption amplitude of rice soil arsenic, lead, cadmium increases by 50%, 49.1% and 16.7% respectively; The absorption amplitude of red soil arsenic, lead, cadmium increases by 20.5%, 8.4% and 29.3% respectively; Purple soil 50%, 41.1% and 64.97%.
Table 3 adsorption test balanced solution concentration
5, conclusion
Different soil ion adsorption test shows, soil heavy mental ion adsorption agent of the present invention can effectively increase the adsorptive capacity of the arsenic of soil heavy metal, lead, cadmium, three soil types participated in the experiment are by adding soil heavy mental ion adsorption agent of the present invention, and the loading capacity increasing degree of heavy metal arsenic, lead, cadmium is on average 49.7%, 32.86% and 36.99%.
Table 4 soil type and different treatment heavy metal-polluted soil adsorptive capacity
Embodiment 3 soil heavy mental ion adsorption agent of the present invention reduces the growth condition of corn kernel heavy metal content on heavy-metal contaminated soil.
1, experiment is for examination material
1.1 participate in the experiment soil
Soil of participating in the experiment picks up from Gejiu, Yunnan Province spends heavy-metal contaminated soil, and the basic physicochemical character of soil is in table 5:
Table 5 is participated in the experiment the basic condition of soil
1.2 participate in the experiment crop: Gejiu is when landlord plants blue or green food corn variety three, and variety name is good list 108, No. 3, red list and glutinous No. 8 of actions and spoken parts in classical Chinese drama.
2, test method
Arrange heavy-metal contaminated soil corn planting pot experiment in Gejiu, test soil is all taken from Zhang Jiazhai village, Datun Town, Gejiu and is closed Yulin corn planting ground soil. Test arrangement three kinds, two soil treatment, three test design repeated. Test basin adopts high 60cm, bore to be the plastic tub of 50cm, and every basin dress soil 40kg, amounts to dress soil 18 basins. The process adding sorbent material is that the every basin of topsoil soils adds according to the amount of 500g (1.25g sorbent material/kg soil) in control basis, and other control measures are consistent with comparison. Measure soil conventional index and heavy metal content before corn planting, the heavy metal content of different corn variety seed grain under the different soil treatment of detection respectively after corn planting.
3, test-results
Being got basin soil and derive from Zhang Jiazhai village, Datun Town, Gejiu, soil pH is 5.7, after testing, in table 6, basin soil heavy metal in soil arsenic, cadmium content is relatively high, exceeds the relevant limitation of " soil environment quality standard " (GB15618-1995), and integrated pollution evaluation is intermediate pollution.
Table 6 basin soil heavy metal analysis data
Through the plantation in a season, the absorption accumulation ability of different corn variety heavy metal shows certain difference. In table 7, the heavy metal adsorption in contaminated soil is had certain difference by three corn varieties itself. From corn variety heavy metal absorbed dose of participating in the experiment, plumbous, cadmium aggregate performance is the actions and spoken parts in classical Chinese drama glutinous No. 8 red lists of the > good lists 108 of No. 3 >, and lead, the cadmium in glutinous No. 8 corn kernels of actions and spoken parts in classical Chinese drama all exceeds China's " pollutants in food limitation " (GB2762-2012) standard limit index. The absorption of arsenic element is then slightly different, shows as good glutinous No. 8 of the list 108 red list of > No. 3 > actions and spoken parts in classical Chinese drama, and this may be relevant with the absorption characteristic of kind heavy metal.
Table 7 different treatment corn kernel heavy metal content detection data
Note: adding sorbent treatment in table 7 is the process adding soil heavy mental ion adsorption agent of the present invention.
The corn kernel heavy metal content of the native autochthonal length of basin with adding soil heavy mental ion adsorption agent of the present invention of comparative analysis original pollution basin, aggregate performance is for after application of soil heavy mental ion adsorption agent of the present invention, and the heavy metal content in corn kernel all has and significantly reduces. Wherein, reducing and be apparent that lead element the most, compared with comparison (CK), what reduction amplitude was bigger is No. 3, red list, and reduction amplitude is the plumbous average reduction amplitude of 20.44%, three kinds is 15.63%; Equally, what the amplitude that reduced by cadmium was bigger is also No. 3, red list, and the range of decrease is that on average to reduce amplitude be 12.15% to 15.21%, three kind cadmiums; By contrast, what reduction amplitude was less is arsenic element, although arsenic content overproof is more than 1 times in planting soil, but owing to dry farming crop is little to arsenic susceptibility, thus the arsenic content in corn kernel does not exceed national food hygienic standard limitation, but by adding soil heavy mental ion adsorption agent of the present invention in contaminated soil, transfer to the arsenic in corn kernel and certain minimizing has also occurred, what minimizing amplitude was maximum is glutinous No. 8 of actions and spoken parts in classical Chinese drama, minimum is No. 3, red list, and it is 7.62% that three corn variety arsenic on average reduce amplitude.
4, conclusion
, intermediate pollution soil slight at heavy metal adds a certain amount of soil heavy mental ion adsorption agent of the present invention, can effectively reduce the transfer of heavy metal in soil to corn kernel, three corn tested varieties by adding soil heavy mental ion adsorption agent of the present invention before contaminated soil corn planting, the corn kernel heavy metal content that in corn kernel, heavy metal content is relatively directly planted on contaminated soil is compared, all obtain reduction by a relatively large margin, plumbous average reduction amplitude is 15.63%, it is 12.15% that cadmium on average reduces amplitude, and it is 7.62% that arsenic on average reduces amplitude.
Embodiment 4 soil heavy mental ion adsorption agent of the present invention reduces the growth condition of rice Seed weight metal content on cadmium pollution soil.
1, experiment is for examination material
1.1 participate in the experiment soil
Soil of participating in the experiment picks up from Yiliang County, Kunming city, Yunnan Province Kuang Yuan town Bao Hong villagers' committee water paddy soil. The basic physicochemical character of soil is in table 8:
Table 8 is participated in the experiment the basic condition of soil
1.2 participate in the experiment crop: when landlord plants rice varieties two, variety name is respectively Chu and obstructs No. 28, excellent 20.
2, test method
Arrange the test of paddy rice planting pot in Yiliang County, test soil all takes from Yiliang County, Kunming city, the Yunnan Province Kuang Yuan town Bao Hong villagers' committee bright rice seedling bed of Li Hong. Test arrangement two kinds, two soil treatment, three test design repeated. Test tools adopts high 40cm, bore to be the plastic tank of 20cm, 20 kilograms, every basin dress soil, amounts to dress soil 12 basins. The process adding sorbent material is that the every basin of topsoil soils adds according to the amount of 25g (1.25g sorbent material/kg soil) in control basis, and other control measures are consistent with comparison. Measure soil conventional index and heavy metal content before rice transplanting, paddy rice heavy metal content of different rice varieties seed grain under the different soil treatment of detection respectively after planting.
3, test-results
Got test soil and derived from Yiliang County, Kunming city, Yunnan Province Kuang Yuan town Bao Hong villagers' committee rice terrace, soil pH is 6.9, after testing, in table 9, heavy metal in soil cadmium content is relatively high, exceeds the relevant limitation of " soil environment quality standard " (GB15618-1995).
Table 9 basin soil heavy metal analysis data
Through the plantation in a season, the absorption accumulation ability of different rice varieties heavy metal shows certain difference. In table 10, the heavy metal adsorption in contaminated soil is also had certain difference by two rice varieties itself. From rice varieties heavy metal absorbed dose of participating in the experiment, lead, cadmium, arsenic three heavy metal species Bulk elemental show as excellent 20 > Chu stalks 28, although lead and arsenic in two kind rice all exceed China's " pollutants in food limitation " (GB2762-2012) standard limit index, but adding soil heavy mental ion adsorption agent of the present invention in soil, lead and the content of arsenic in these two kind rice all obtain bigger reduction. And cadmium exceeds standard in soil, but the Cd concentration of brown rice of these two kinds does not exceed standard.
The paddy rice Seed weight metal content of comparative analysis primary soil, the soil-grown adding soil heavy mental ion adsorption agent of the present invention, aggregate performance is for after application of soil heavy mental ion adsorption agent of the present invention, three heavy metal species content in paddy rice seed grain all reduce significantly. Wherein, reduce and comparatively it is apparent that arsenic element, compared with comparison (CK), Chu's stalk 28 reduction amplitudes more greatly 28.86%, excellent 20 reduction amplitudes are 14.84%, and average reduction amplitude is 21.84%; And cadmium and plumbous reduction amplitude are more or less the same, wherein the reduction amplitude of cadmium is on average 17.27% by two kinds, is on average 17.8% to the reduction amplitude of lead.
4, conclusion
The single contaminated soil of heavy metal cadmium (this heavy metal in soil content only cadmium exceed standard, claim the single contaminated soil of cadmium) a certain amount of soil heavy mental ion adsorption agent of the present invention of middle interpolation, can effectively reduce the transfer of heavy metal in soil to paddy rice seed grain, two paddy rice tested varieties by adding soil heavy mental ion adsorption agent of the present invention before contaminated soil is planted, the paddy rice seed grain that in rice, heavy metal content is relatively directly planted on this cadmium pollution soil is compared, heavy metal content all obtains reduction by a relatively large margin, plumbous average reduction amplitude is 17.8%, it is 17.27% that cadmium on average reduces amplitude, it is 21.84% that arsenic on average reduces amplitude.
Table 10 different treatment paddy rice Seed weight metal content detection data
Note: adding sorbent treatment in table 10 is the process adding soil heavy mental ion adsorption agent of the present invention.
Each embodiment above, in soil, the mensuration of arsenic content presses GB/T22105.2-2008 method mensuration. In soil, the mensuration of lead content presses GB/T17141-1997 method mensuration. In soil, the mensuration of cadmium content presses GB/T17141-1997 method mensuration. The mensuration of mercury in soils content is pressed GB/T22105.1-2008 method and is measured. In soil, the mensuration of chromium content presses GB/T17137-1997 method mensuration. In corn kernel and paddy rice seed grain, the mensuration of lead content all measures by GB5009.12-2010 method, the mensuration of cadmium content all measures by GB/T5009.11-2003 method by the mensuration of GB/T5009.15-2003 method mensuration, total arsenic content.
Claims (5)
1. a soil heavy mental ion adsorption agent, it is characterised in that: by following A, B and potassium humate three groups of materials in A:B: the ratio that the mass ratio of potassium humate is 2:5:3 is obtained by mixing;
(1) A group material is the maize straw of modification, and the maize straw of described modification is obtained by following method:
1. the collection of stalk and pre-treatment
Collect the fresh straw of more than the plant root after harvest corn, cut and cut up with a hay cutter into section, the earth cleaning stalk surface attachment and sand and dust are rinsed with clear water, it is placed on shady and cool place nature air-dry, put into again constant temperature oven 50 DEG C dry to constant weight pulverize or nature sunlight under shine dry in the air be dried to constant weight after pulverize, cross 2-4 order sieve and obtain stalk particle;
2. straw modification
A, in stalk particle: concentration is the mass ratio of the NaOH solution of 1mol/L is the ratio of 1:50, adds the NaOH solution of stalk particle and 1mol/L in a reservoir, stirs after evenly, puts into Tempeerature-constant air shaking table, soaks 18 hours at 40 DEG C;
After B, immersion, taking out stalk particle, supernatant liquor is removed in centrifugation, and it is precipitated as through alkaline purification stalk particle;
C, by through alkaline purification stalk particle and vinyl cyanide according to alkaline purification stalk particle: the ratio that the mass ratio of vinyl cyanide is 1:10 is mixed to get mixture, and this mixture is put into another container, reacts 20-30min at 30 DEG C;
D, by step (1) 2. C wash 2-3 time through reacted stalk particle deionized water, then be 12g/L hydrochloric acid soak acid-cleaning by concentration, until the pH that stalk particle fully soaks into stalk particle be 7 or pH be 5��6.9;
E, taking-up, through the stalk particle of pickling, are washed until aqueous solution pH is 6.5��7 with deionized water, then stalk particle are put into constant temperature oven 50 DEG C oven dry to constant weight, obtain the maize straw of described modification;
(2) B group material is the kaolin of modification, and the kaolin of described modification is obtained by following method:
Get kaolinite original ore powder in container, in kaolinite original ore powder: the ratio that the mass ratio of sodium polyphosphate is 4:1 adds sodium polyphosphate, mix, add distilled water again and stir into pasty state, after leaving standstill half an hour, it is placed in constant temperature oven, start baking oven, setting top temperature is 100 DEG C, when oven temperature rises to 100 DEG C gradually, maintain 100 DEG C of constant temperature bakings and then move in retort furnace for l hour, open retort furnace and be warming up to 280 DEG C of roasting temperatures one hour, being come out of the stove by kaolin cool to room temperature, ground 2-4 order sieves and obtains the kaolin of modification.
2. soil heavy mental ion adsorption agent according to claim 1, it is characterised in that: the cool room temperature described in room temperature of being come out of the stove by kaolin described in step (2) is 32 DEG C��15 DEG C.
3. the preparation method of a soil heavy mental ion adsorption agent, it is characterised in that, by following A, B and potassium humate three groups of materials in A:B: the ratio mixing that the mass ratio of potassium humate is 2:5:3 is described soil heavy mental ion adsorption agent:
(1) A group material is the maize straw of modification, and the maize straw of described modification is obtained by following method:
1. the collection of stalk and pre-treatment
Collect the fresh straw of more than the milpa root after harvest corn, cut and cut up with a hay cutter into section, the earth cleaning stalk surface attachment and sand and dust are rinsed with clear water, it is placed on shady and cool place nature air-dry, put into again constant temperature oven 50 DEG C dry to constant weight pulverize or nature sunlight under shine dry in the air be dried to constant weight after pulverize, cross 2-4 order sieve and obtain stalk particle;
2. straw modification
A, in stalk particle: concentration is the mass ratio of the NaOH solution of 1mol/L is the ratio of 1:50, adds the NaOH solution of stalk particle and 1mol/L in a reservoir, stirs after evenly, puts into Tempeerature-constant air shaking table, soaks 18 hours at 40 DEG C;
After B, immersion, taking out stalk particle, supernatant liquor is removed in centrifugation, and it is precipitated as through alkaline purification stalk particle;
C, by through alkaline purification stalk particle and vinyl cyanide according to alkaline purification stalk particle: the ratio that the mass ratio of vinyl cyanide is 1:10 is mixed to get mixture, and this mixture is put into another container, reacts 20-30min at 30 DEG C;
D, step (1) 2. C wash 2-3 time through reacted stalk particle deionized water, then be 12g/L hydrochloric acid soak acid-cleaning by concentration, until the pH that stalk particle fully soaks into stalk particle be 7 or pH be 5��6.9;
E, taking-up, through the stalk particle of pickling, are washed until aqueous solution pH is 6.5��7 with deionized water, then stalk particle are put into constant temperature oven 50 DEG C oven dry to constant weight, obtain the maize straw of described modification;
(2) B group material is the kaolin of modification, and the kaolin of described modification is obtained by following method:
Get kaolinite original ore powder in container, in kaolinite original ore powder: the ratio that the mass ratio of sodium polyphosphate is 4:1 adds sodium polyphosphate, mix, add distilled water again and stir into pasty state, after leaving standstill half an hour, it is placed in constant temperature oven, start baking oven, setting top temperature is 100 DEG C, when oven temperature rises to 100 DEG C gradually, maintain 100 DEG C of constant temperature bakings and then move in retort furnace for l hour, open retort furnace and be warming up to 280 DEG C of roasting temperatures one hour, being come out of the stove by kaolin cool to room temperature, ground 2-4 order sieves and obtains the kaolin of modification.
4. the preparation method of soil heavy mental ion adsorption agent according to claim 3, the described cool room temperature described in room temperature of being come out of the stove by kaolin of step (2) is 32 DEG C��15 DEG C.
5. soil heavy mental ion adsorption agent described in claim 1 or 2 is reducing the application of crop products heavy metal content.
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| CN104941996B (en) * | 2015-06-09 | 2017-12-19 | 北京市环境保护科学研究院 | A kind of restorative procedure for chromium-polluted soil |
| CN104926567B (en) * | 2015-06-24 | 2018-03-02 | 黑龙江省科学院自然与生态研究所 | A kind of preparation and its application method for improveing farmland cadmium pollution |
| CN104998898B (en) * | 2015-06-24 | 2018-03-02 | 黑龙江省科学院自然与生态研究所 | A kind of method of maize straw collaboration weathered coal in-situ passivation soil in protected field heavy metal |
| CN105419810A (en) * | 2015-10-30 | 2016-03-23 | 云南省农业科学院质量标准与检测技术研究所 | Soil conditioner for reducing content of arsenic in panax notoginseng, method for preparing soil conditioner and application thereof |
| CN105598153A (en) * | 2015-12-23 | 2016-05-25 | 湖南德宝恒嘉环保生物科技有限公司 | Matched improver and method for controlling heavy metal and arsenic compound contaminated soil |
| CN106552579A (en) * | 2017-01-07 | 2017-04-05 | 北京源清益壤环保科技有限公司 | For removing modified kaolin adsorbent of lead in polluted-water and preparation method thereof |
| CN107486161A (en) * | 2017-08-14 | 2017-12-19 | 中国烟草总公司郑州烟草研究院 | A kind of adsorbent for heavy metal and its application |
| CN107837790A (en) * | 2017-11-13 | 2018-03-27 | 谢长溪 | A kind of kitchen waste oil adsorbent and preparation method thereof |
| CN108244459A (en) * | 2018-01-10 | 2018-07-06 | 山东青果食品有限公司 | A kind of method for removing vegetables heavy metal |
| CN108410474A (en) * | 2018-05-10 | 2018-08-17 | 张鑫 | Active soil conditioner of a kind of reduction heavy metal in soil and preparation method thereof |
| CN109534629B (en) * | 2018-12-18 | 2021-05-28 | 毅康科技有限公司 | Method for treating heavy metals in river sludge |
| CN110305664A (en) * | 2019-01-14 | 2019-10-08 | 深圳屹米达环保科技有限公司 | Soil conditioner and preparation method thereof and application method |
| CN110061210B (en) * | 2019-04-15 | 2021-08-31 | 深圳市高能达电池有限公司 | Preparation method and application of modified bagasse/sulfur composite material |
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