CN109082277A - A kind of cadmium arsenic combined pollution renovation agent and the preparation method and application thereof - Google Patents
A kind of cadmium arsenic combined pollution renovation agent and the preparation method and application thereof Download PDFInfo
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- CN109082277A CN109082277A CN201810936188.9A CN201810936188A CN109082277A CN 109082277 A CN109082277 A CN 109082277A CN 201810936188 A CN201810936188 A CN 201810936188A CN 109082277 A CN109082277 A CN 109082277A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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Abstract
The present invention provides a kind of cadmium arsenic combined pollution renovation agents, including with the mixed calcium carbonate in 10 ~ 30:30 of weight ratio ~ 60:10 ~ 40:1 ~ 10, silicon-calcium-magnesium fertilizer, humic acid modified clay and Fe (OH)3；Wherein, humic acid modified clay through clay acidification, acid-treated clay alkali metal ion and humic acid modified is prepared.Invention further provides a kind of preparation methods of cadmium arsenic combined pollution renovation agent.The described method includes: (1) clay acid activation；(2) acid-treated clay alkali metal ion；(3) humic acid modified clay；(4) cadmium arsenic combined pollution renovation agent is prepared.The cadmium arsenic combined pollution renovation agent that invention provides can effectively lower the activity of cadmium, influence the dissolution of arsenic；It is good and can increase the soil organism to adsorb heavy metal-passivated effect, improves soil texture, promotes plant growth.
Description
Technical field
The invention belongs to agricultural environment child care and recovery technique field, and in particular to a kind of cadmium arsenic combined pollution renovation agent and
Preparation method and application.
Background technique
Soil acidification is a kind of form of expression of soil degradation, soil acidification not still one of soil fertility decline it is important
Reason, and an important factor for restriction sustainable development of agricultural production.According to statistics, so far from the eighties in last century, China's soil
Acidification situation is increasingly severe, and the land area of acidification has been expanded to 40% or more of China's cultivated area, and often has
There is a situation where especially in south China, due to soil slant acidity itself, rainwater is more, and soil acidification phenomenon is more serious in flakes.
Soil acidification can cause the activation of the heavy metals such as aluminium, manganese, chromium, cadmium, to influence the growth of plant, poisoning by aluminum, manganese such as occur
Phenomena such as poisoning, and activate heavy metal be absorbed by crops accumulation after, pass through the health of food chain harmful to human and animal body.
Adjusting soil acidification is a problem urgently to be solved in modern agriculture environmental protection.It is given through investigation: (1)
Improving soil pH can effectively reduce the activity of cadmium in soil, but when reaction is fierce, pH is excessively high, when soil pH larger fluctuation, arsenic quilt
Dissolution, the validity of arsenic are enhanced；(2) humic acid is the larger molecular organics matter being widely present in nature, and humic acid divides greatly
The basic structure of son is aromatic ring and alicyclic ring, and the functional groups such as carboxyl, hydroxyl, carbonyl, quinonyl, methoxyl group are connected on ring, alternative
Complexation heavy metal ion is adsorbed, but humic acid is generally not soluble in water, is dissolved in alkaline solution, limits it and passivation of heavy metal is imitated
Fruit；(3) organic matter can be carried on surface of clay by organically-modified by clay material, it is made to obtain preferably absorption heavy metal
Effect and adsorptive selectivity, but common such as chitosan and cetyl trimethylammonium bromide (CTMAB) price are higher, technique
Complexity, application are less.
Therefore, it is urgent to provide a kind of reaction milder, absorption heavy metal effect is good, validity of arsenic can be effectively reduced and
The simpler soil pollution renovation agent of product processes.
Summary of the invention
In view of the shortcomings of the prior art, it is an object of that present invention to provide a kind of cadmium arsenic combined pollution renovation agents and preparation method thereof
With application, cadmium arsenic combined pollution renovation agent provided by the invention can effectively lower the activity of cadmium, influence the dissolution of arsenic；Absorption passivation
Heavy metal effect is good and can increase the soil organism, improves soil texture, promotes plant growth.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of cadmium arsenic combined pollution renovation agent, which is characterized in that including with 10~30:30 of weight ratio~60:10~40:1
~10 mixed calcium carbonate, silicon-calcium-magnesium fertilizer, humic acid modified clay and Fe (OH)3；Wherein, humic acid modified clay is through clay acid
It activation, acid-activated clay sodium and humic acid modified is prepared.
Further, the humic acid modified clay preparation method specifically comprises the following steps:
The acidification of S1 clay
Clay material is added in acid solution, is filtered after acidified processing, stay first pass filtering acid solution it is spare, and with go from
Sub- water cleans filtering filter residue, until filtrate and NaOH do not generate precipitating, obtains acid-treated clay after filtering filter residue dries pulverizing；
S2 acid-treated clay alkali metal ion
Acid-treated clay obtained by S1 is added in lye, is filtered after alkali metal ionization processing, stays filtering lye spare,
Alkali metal ion clay is obtained after filtering filter residue dries pulverizing；
The humic acid modified clay of S3
Alkali metal ion clay obtained by S2 is added to containing in humic acid solution, is filtered after humic acid modified processing,
And filtering filter residue is cleaned with deionized water and adjusts filtering filter residue pH, humic acid modified clay is obtained after dries pulverizing.
Further, the Fe (OH)3It is prepared by following methods: ground hematite is added to the resulting first pass mistake of S1
It in acid filtering liquid, is filtered after fully reacting, takes filtrate spare；Gained filtrate is adjusted into pH to Fe with the resulting filtering lye of S23+It is complete
Full precipitating, filtering drying obtain Fe (OH) after crushing3。
Further, clay material described in S1 is one of sepiolite, zeolite, attapulgite, montmorillonite, kaolin etc.
Or it is a variety of.
Further, clay material partial size≤75 μm.
Further, the clay material and the mass ratio of acid solution are 1:1~20, the acid strength be 0.1mol/L~
10mol/L。
Further, the acid solution is one or more of sulfuric acid, nitric acid, hydrochloric acid.
Further, acidification temperature described in S1 is 10 DEG C~40 DEG C, and the activation processing time is 5~120min.
Further, the ratio of acid-treated clay described in S2 and the lye is 1:1~30；The concentration of lye is 0.5%
~10%.
Further, the lye is NaOH, KOH, Na2CO3、K2CO3One of or it is a variety of.
Further, the alkali metal ion treatment temperature is 10 DEG C~40 DEG C, and the alkali metal ionization handles the time
For 1min~30min.
Further, alkali metal ion clay described in S3 and the ratio containing humic acid solution are 1:1~30；It is described
Containing content of humic acid >=1% in humic acid solution.
Further, described containing humic acid solution is potassium humate, sodium humate, ammonium humate, one in nitro humus acid
Kind or the aqueous solution of a variety of preparations.
Further, the temperature of the humic acid modified processing is 10 DEG C~40 DEG C, and the processing time is 5min~120min.
Further, the humic acid modified clay pH is 8~12.
Further, iron content >=50% in the ground hematite；The ratio of the ground hematite and first pass filtering acid solution
For 1~20:100.
Further, CaCO in the calcium carbonate3Content >=90%；CaO content >=40% in the silicon-calcium-magnesium fertilizer, effectively
Silicone content >=30%, content of MgO >=5%.
Based on the same inventive concept, the present invention also provides a kind of preparation method of cadmium arsenic combined pollution renovation agent,
It is characterized in that, includes the following steps:
The acidification of S1 clay
Clay material is added in acid solution, is filtered after acidified processing, stay first pass filtering acid solution it is spare, and with go from
Sub- water cleans filtering filter residue, until filtrate and NaOH do not generate precipitating, obtains acid-treated clay after filtering filter residue dries pulverizing；
S2 acid-treated clay alkali metal ion
Acid-activated clay obtained by S1 is added in lye, is filtered after the processing of clay alkali metal ionization, stays filtering alkali
Liquid is spare, obtains alkali metal ion clay after filtering filter residue dries pulverizing；
The humic acid modified clay of S3
Alkali metal ionization obtained by S2 is added containing in humic acid solution, is filtered after humic acid modified processing, and to go
Ionized water cleaning filtering filter residue simultaneously adjusts filtering filter residue pH, obtains humic acid modified clay after dries pulverizing；
S4 prepares cadmium arsenic combined pollution renovation agent
By humic acid modified clay, Fe (OH) obtained by calcium carbonate, silicon-calcium-magnesium fertilizer, S33With weight ratio 10~30:30~60:
10~40:1~10 mix up to cadmium arsenic combined pollution renovation agent.
Further, the Fe (OH)3It is prepared by following methods: ground hematite is added to the resulting first pass mistake of S1
It in acid filtering liquid, is filtered after fully reacting, takes filtrate spare；Gained filtrate is adjusted into pH to Fe with the resulting filtering lye of S23+It is complete
Full precipitating, filtering drying obtain Fe (OH) after crushing3。
Further, in the preparation method, clay material described in S1 be sepiolite, zeolite, attapulgite, montmorillonite,
One of kaolin etc. is a variety of.Clay material partial size≤75 μm.The clay material and the mass ratio of acid solution are 1:1
~20, the acid strength is 0.1mol/L~10mol/L.The acid solution is one or more of sulfuric acid, nitric acid, hydrochloric acid.
Acidification temperature described in S1 is 10 DEG C~40 DEG C, and the activation processing time is 5~120min.Acid-treated clay described in S2 and institute
The ratio for stating lye is 1:1~30；The concentration of lye is 0.5%~10%.The lye is NaOH, KOH, Na2CO3、
K2CO3One of or it is a variety of.The alkali metal ion treatment temperature is 10 DEG C~40 DEG C, the alkali metal ionization processing
Time is 1min~30min.Alkali metal ion clay described in S3 and the ratio containing humic acid solution are 1:1~30；
It is described to contain content of humic acid >=1% in humic acid solution.The humic acid solution that contains is potassium humate, sodium humate, humic acid
One of ammonium, nitro humus acid or the aqueous solution of a variety of preparations.The temperature of the humic acid modified processing is 10 DEG C~40 DEG C,
The processing time is 5min~120min.The humic acid modified clay pH is 8~12.Iron content in the ground hematite >=
50%；The ratio of the ground hematite and first pass filtering acid solution is 1~20:100.CaCO in the calcium carbonate3Content >=
90%；CaO content >=40% in the silicon-calcium-magnesium fertilizer, available silicon content >=30%, content of MgO >=5%.
Based on the same inventive concept, the present invention also provides the application for having crossed a kind of above-mentioned cadmium arsenic combined pollution renovation agent,
The cadmium arsenic combined pollution renovation agent is applied to adjust acidification soil, especially adjusting acidification paddy soils and drought soil.It is preferred that
, the pH of the acidification soil is 4.5-6.0；Preferably, when the cadmium arsenic combined pollution renovation agent adjusts acid soil again
Amount of application be 100-200kg/ mus, preferably 150kg/ mus.
The research of the invention finds that improving soil pH can effectively reduce the activity of cadmium in soil, but when pH is excessively high, arsenic is molten
Out, the validity of arsenic is improved, therefore salt of weak acid is selected to promote soil pH, reaction speed is slower, the influence fluctuation to soil pH
It is smaller.In addition, the oxide and hydroxide of iron have single-minded adsorptivity to arsenic, the validity of arsenic can effectively reduce.Humic acid
It is a kind of macromolecular substances, alternative absorption complexation heavy metal ion.But humic acid is generally not soluble in water, and it is molten to be dissolved in alkalinity
Liquid limits its passivation effect to heavy metal.In addition, total amount of humic acid is surprisingly big, number is of the invention former in terms of trillion tons
The preferable source of material.
The invention has the benefit that
The present invention provides a kind of cadmium arsenic combined pollution renovation agent, advantages are as follows: (1) improves soil pH value, influence arsenic
Dissolution: calcium carbonate, calcium silicate fertilizer, modified humic acid clay in the present invention are alkaline matter and contain various nutrient elements, such as
Alkali displacement capacity can be improved in calcium, magnesium, silicon etc., so that soil pH value be made to increase, but reacts mild, not will cause soil pH compared with
Great fluctuation process reduces the validity of arsenic to influence the dissolution of arsenic；(2) heavy metal-passivated, reduce heavy metal validity: the present invention
In alkaline matter the free acid in soil can be neutralized by basic mineral, displace the hydrogen ion on manosil AS, and pass through
It supplements activated silica and increases absorption of the soil to cation, then promote the coprecipitated of anion and heavy metal by improving soil pH value
It forms sediment, reduces the biological effectiveness of heavy metal；Modified humic acid clay can Absorptive complex wave heavy metal, reduce its validity；Fe(OH)3
Can obligate arsenic-adsorbing, can effectively reduce the validity of arsenic；(3) increase the soil organism, improve soil texture, promote plant raw
Long: modified humic acid clay can be improved soil organic matter content in the present invention, reduce the soil weight, improve soil texture；Separately
Outside, it can promote plant growth containing various nutrient elements such as K, Ca, Mg needed for plant in the present invention.
Invention further provides a kind of preparation method of cadmium arsenic combined pollution renovation agent, advantages are as follows: (1) prepares
Humic acid modified adsorption by clay performance is good, easily settled, easy recycling, and prepares industry simply, low in cost: right first in this method
Clay carries out acidification, removes the cation between crystals of clay, increases clay specific surface area and micropore size, recycles alkali heat
Condition makes clay material adsorb humic acid molecule, is surface modified to clay, makes humic acid modified clay to heavy metal ion
With adsorption selectivity and higher adsorption capacity；Prepared humic acid Modified clay mineral adsorbent absorption property is good, easily
Sedimentation, easily recycling are suitable for Industrial Wastewater Treatment and soil remediation, and preparation industry is simple, low in cost；(2) present invention system
Standby Fe (OH)3Method advantage are as follows: using the lower Iron Ore Powder for the treatment of cost of waste liquor in production process to produce Fe (OH)3, increase
Add purity, improve its validity, and achievees the effect that waste utilization and reduce cost；(3) calcium carbonate, silicon-calcium-magnesium in this method
Fertile, humic acid modified clay and Fe (OH)3Compound prescription ratio obtained through testing repeatedly, and each component cooperate, collaboration
It plays a role.
Invention further provides a kind of cadmium arsenic combined pollution renovation agents to adjust the application on acidification soil, especially
It is to adjust acidification paddy soils and drought soil.It is tested in application effect of the cadmium arsenic combined pollution renovation agent of the present invention to pollution rice field
In, cadmium arsenic combined pollution renovation agent provided by the invention can effectively improve soil pH value, while reduce the cadmium in rice, arsenic
Content.In addition, also known by this experiment, it is compound to add 100~200kg cadmium arsenic of the present invention in acid soil per acre
Pollution amelioration agent is advisable；Preferably, cadmium arsenic combined pollution renovation agent described in 150kg is added in acid soil per acre.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..It is not specified in embodiment specific
Technology or conditions person, described technology or conditions according to the literature in the art, or carried out according to product description.It is used
Production firm person is not specified in reagent or instrument, is the conventional products that can be commercially available by regular distributor.
1 cadmium arsenic combined pollution renovation agent of embodiment
1) ratio by attapulgite with mass ratio for 1:10 is added in the sulfuric acid of 1mol/L, is activated at 25 DEG C
30min is filtered after activation, stays first pass filtering acid solution spare, and gained filter residue is cleaned repeatedly with deionized water, until
Gained washing lotion and NaOH do not generate precipitating (being washed till non-metallic ion), and dries pulverizing obtains acidification attapulgite；
2) viscous ratio of the attapulgite with mass ratio for 1:10 will be acidified to be added in the NaOH solution that concentration is 4%,
Modified 30min, is filtered after modified at 25 DEG C, stays filtering lye spare, filters filter residue dries pulverizing up to alkali metal ion
Change attapulgite；
3) ratio by alkali metal ion attapulgite with mass ratio for 1:20 is added to the potassium humate that concentration is 5%
In solution, modified 60min, is filtered after modified at 25 DEG C, is cleaned gained filter residue with deionized water, is adjusted pH to 10, dry
Dry grinding is up to humic acid modified attapulgite.
4) ratio by ground hematite with mass ratio for 8:100 is added in the resulting first pass filtering acid solution of step 1),
It is spare that filtrate is filtered to take after fully reacting；
5) to filter lye regulating step 4 obtained by step 2)) in filtrate pH to Fe3+Precipitating completely, filtering drying crush
It obtains Fe (OH)3；
6) by calcium carbonate, silicon-calcium-magnesium fertilizer, humic acid modified attapulgite, Fe (OH)3With the weight ratio of 20:50:25:5
Mixing is to get cadmium arsenic combined pollution renovation agent.
2 cadmium arsenic combined pollution renovation agent of embodiment
1) ratio by attapulgite with mass ratio for 1:10 is added in the sulfuric acid of 1mol/L, is activated at 25 DEG C
30min is filtered after activation, stays first pass filtering acid solution spare, and gained filter residue is cleaned repeatedly with deionized water, until
Gained washing lotion and NaOH do not generate precipitating (being washed till non-metallic ion), and dries pulverizing must be acidified attapulgite；
2) ratio of the attapulgite with mass ratio for 1:10 will be acidified to be added in the NaOH solution that concentration is 4%, 25
Modified 30min, is filtered after modified at DEG C, stays filtering lye spare, filters filter residue dries pulverizing up to alkali metal ion
Attapulgite.
3) ratio by alkali metal ion attapulgite with mass ratio for 1:20 is added to the potassium humate that concentration is 5%
In solution, modified 60min, is filtered after modified at 25 DEG C, is cleaned gained filter residue with deionized water, is adjusted pH to 10, dry
Dry grinding is up to humic acid modified attapulgite.
4) ratio by ground hematite with mass ratio for 8:100 is added in the resulting first pass filtering acid solution of step 1),
It is spare that filtrate is filtered to take after fully reacting；
5) to filter lye regulating step 4 obtained by step 2)) in filtrate pH to Fe3+Precipitating completely, filtering drying crush
It obtains Fe (OH)3；
6) by calcium carbonate, silicon-calcium-magnesium fertilizer, humic acid modified attapulgite, Fe (OH)3With the weight ratio of 30:50:15:5
Mixing is to get cadmium arsenic combined pollution renovation agent.
3 cadmium arsenic combined pollution renovation agent of embodiment
1) ratio by attapulgite with mass ratio for 1:10 is added in the sulfuric acid of 1mol/L, is activated at 25 DEG C
30min is filtered after activation, stays first pass filtering acid solution spare, and gained filter residue is cleaned repeatedly with deionized water, until
Gained washing lotion and NaOH do not generate precipitating (being washed till non-metallic ion), and dries pulverizing must be acidified attapulgite；
2) ratio of the attapulgite with mass ratio for 1:10 will be acidified to be added in the NaOH solution that concentration is 4%, 25
Modified 30min, is filtered after modified at DEG C, stays filtering lye spare, filters filter residue dries pulverizing up to alkali metal ion
Attapulgite.
3) ratio by alkali metal ion attapulgite with mass ratio for 1:20 is added to the potassium humate that concentration is 5%
In solution, modified 60min, is filtered after modified at 25 DEG C, is cleaned gained filter residue with deionized water, is adjusted pH to 10, dry
Dry grinding is up to humic acid modified attapulgite.
4) ratio by ground hematite with mass ratio for 8:100 is added the resulting first pass of step 1) and filters in acid solution, instead
It is spare that filtrate is filtered to take after answering completely；
5) to filter lye regulating step 4 obtained by step 2)) in filtrate pH to Fe3+Precipitating completely, filtering drying crush
It obtains Fe (OH)3；
6) by calcium carbonate, silicon-calcium-magnesium fertilizer, humic acid modified attapulgite, Fe (OH)3With the weight ratio of 24:50:25:1
Mixing is to get cadmium arsenic combined pollution renovation agent.
4 cadmium arsenic combined pollution renovation agent of embodiment
1) ratio by attapulgite with mass ratio for 1:10 is added in the hydrochloric acid of 0.1mol/L, is activated at 25 DEG C
30min is filtered after activation, stays first pass filtering acid solution spare, and gained filter residue is cleaned repeatedly with deionized water, until
Gained washing lotion and NaOH do not generate precipitating (being washed till non-metallic ion), and dries pulverizing obtains acidification attapulgite；
2) viscous ratio of the attapulgite with mass ratio for 1:10 will be acidified to be added in the NaOH solution that concentration is 1%,
Modified 30min, is filtered after modified at 25 DEG C, stays filtering lye spare, filters filter residue dries pulverizing up to alkali metal ion
Change attapulgite；
3) ratio by alkali metal ion attapulgite with mass ratio for 1:20 is added to the potassium humate that concentration is 1%
In solution, modified 60min, is filtered after modified at 25 DEG C, is cleaned gained filter residue with deionized water, is adjusted pH to 10, dry
Dry grinding is up to humic acid modified attapulgite.
4) ratio by ground hematite with mass ratio for 8:100 is added in the resulting first pass filtering acid solution of step 1),
It is spare that filtrate is filtered to take after fully reacting；
5) to filter lye regulating step 4 obtained by step 2)) in filtrate pH to Fe3+Precipitating completely, filtering drying crush
It obtains Fe (OH)3；
6) by calcium carbonate, silicon-calcium-magnesium fertilizer, humic acid modified attapulgite, Fe (OH)3With the weight ratio of 20:50:25:5
Mixing is to get cadmium arsenic combined pollution renovation agent.
5 cadmium arsenic combined pollution renovation agent of embodiment
1) ratio by attapulgite with mass ratio for 1:10 is added in the sulfuric acid of 1mol/L, is activated at 25 DEG C
30min is filtered after activation, stays first pass filtering acid solution spare, and gained filter residue is cleaned repeatedly with deionized water, until
Gained washing lotion and NaOH do not generate precipitating (being washed till non-metallic ion), and dries pulverizing obtains acidification attapulgite；
2) viscous ratio of the attapulgite with mass ratio for 1:10 will be acidified to be added in the NaOH solution that concentration is 4%,
Modified 30min, is filtered after modified at 25 DEG C, stays filtering lye spare, filters filter residue dries pulverizing up to alkali metal ion
Change attapulgite；
3) ratio by alkali metal ion attapulgite with mass ratio for 1:20 is added to the potassium humate that concentration is 5%
In solution, modified 60min, is filtered after modified at 25 DEG C, is cleaned gained filter residue with deionized water, is adjusted pH to 10, dry
Dry grinding is up to humic acid modified attapulgite.
6) by calcium carbonate, silicon-calcium-magnesium fertilizer, humic acid modified attapulgite, ground hematite with the weight ratio of 20:50:25:5
Mixing is to get cadmium arsenic combined pollution renovation agent.
The application effect of experimental example cadmium arsenic combined pollution renovation agent of the present invention is tested
The cadmium arsenic combined pollution renovation agent that Example 1,2,3 provides is tested.
1, test site: xiangtan, hunan province county Yang Jia bridge town.
2, test period: in June, 2017~2017 year October.
3, field experimental design: selection size is close, and the field that water system is independent of each other is tested.Test sets 6 processing,
Be respectively as follows: (1) control treatment 1: uncontaminated rice field does not deal with measure；；(2) control treatment 2: pollution rice field does not deal with and arranges
It applies；(3) test process 1: pollution rice field, 10 days 50kg/ mus of combined pollution renovation agent of the application cadmium arsenic before rice transplanting；(4) it tries
Test processing 2: pollution rice field, 10 days 100kg/ mus of combined pollution renovation agent of the application cadmium arsenic before rice transplanting；(5) test process 3:
Pollute rice field, 10 days 150kg/ mus of combined pollution renovation agent of the application cadmium arsenic before rice transplanting.(6) test process 4: pollution rice
Field, 10 days 200kg/ mus of combined pollution renovation agent of the application cadmium arsenic before rice transplanting.Each processing is normally ploughed by local Rice Cropping
It manages.After rice harves, rice yield, soil pH, rice arsenic content, rice cadmium content are measured.
4, test result:
Example 1,2,3,4,5 provide cadmium arsenic combined pollution renovation agent tested, be as a result shown in Table respectively 1, table 2,
Table 3, table 4, table 5.
Improved effect of 1 embodiment of table, the 1 cadmium arsenic combined pollution renovation agent to soil and rice
Improved effect of 2 embodiment of table, the 2 cadmium arsenic combined pollution renovation agent to soil and rice
Improved effect of 3 embodiment of table, the 3 cadmium arsenic combined pollution renovation agent to soil and rice
Improved effect of 4 embodiment of table, the 4 cadmium arsenic combined pollution renovation agent to soil and rice
Improved effect of 5 embodiment of table, the 5 cadmium arsenic combined pollution renovation agent to soil and rice
As table 1, table 2, table 3, table 4, shown in experimental result it is found that cadmium arsenic combined pollution renovation agent provided by the invention can
To effectively improve soil pH value, rice yield is improved, while reducing the cadmium in rice, arsenic content.In addition, also by this experiment
It is found that being advisable with adding 100~200kg cadmium arsenic combined pollution renovation agent of the present invention in acid soil per acre；Preferably,
Cadmium arsenic combined pollution renovation agent described in 150kg is added in acid soil per acre.It also knows, reduces Fe (OH) from table 33Ratio,
As a result visible rice arsenic handles high (embodiment 1,2 and 4) compared with other)；As known from Table 5, Fe (OH)3There is better reparation than miberal powder
Effect.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of cadmium arsenic combined pollution renovation agent, which is characterized in that including with 10~30:30 of weight ratio~60:10~40:1~
10 mixed calcium carbonate, silicon-calcium-magnesium fertilizer, humic acid modified clay and Fe (OH)3；Wherein, humic acid modified clay is through clay acid
Change, acid-treated clay alkali metal ion and humic acid modified be prepared.
2. cadmium arsenic combined pollution renovation agent according to claim 1, which is characterized in that the humic acid modified clay preparation
Method specifically comprises the following steps:
The acidification of S1 clay
Clay material is added in acid solution, is filtered after acidified processing, stays first pass filtering acid solution spare, and with deionized water
Filtering filter residue is cleaned, until filtrate and NaOH do not generate precipitating, obtains acid-treated clay after filtering filter residue dries pulverizing；
S2 acid-treated clay alkali metal ion
Acid-treated clay obtained by S1 is added in lye, is filtered after alkali metal ionization processing, stays filtering lye spare, filtering
Alkali metal ion clay is obtained after filter residue dries pulverizing；
The humic acid modified clay of S3
Alkali metal ion clay obtained by S2 is added to containing in humic acid solution, is filtered after humic acid modified processing, and with
Deionized water cleaning filtering filter residue simultaneously adjusts filtering filter residue pH, obtains humic acid modified clay after dries pulverizing.
3. cadmium arsenic combined pollution renovation agent according to claim 2, which is characterized in that the Fe (OH)3By following methods system
It is standby to form: ground hematite being added in the resulting first pass filtering acid solution of S1, is filtered after fully reacting, takes filtrate spare；It will
Gained filtrate adjusts pH to Fe with the resulting filtering lye of S23+Precipitating completely, filtering drying obtain Fe (OH) after crushing3。
4. cadmium arsenic combined pollution renovation agent according to claim 2, it is characterised in that: clay material described in S1 is Hai Pao
One of stone, zeolite, attapulgite, montmorillonite, kaolin etc. are a variety of；
Clay material partial size≤75 μm and/or；
And/or the clay material and the mass ratio of acid solution are 1:1~20, the acid strength is 0.1mol/L~10mol/
L；
And/or the acid solution is one or more of sulfuric acid, nitric acid, hydrochloric acid；
And/or acidification temperature described in S1 is 10 DEG C~40 DEG C, the activation processing time is 5~120min.
5. cadmium arsenic combined pollution renovation agent according to claim 2, it is characterised in that: acid-treated clay described in S2 with it is described
The ratio of lye is 1:1~30；The concentration of lye is 0.5%~10%；
And/or the lye is NaOH, KOH, Na2CO3、K2CO3One of or it is a variety of；
And/or the alkali metal ion treatment temperature is 10 DEG C~40 DEG C, the alkali metal ionization processing time is 1min
~30min.
6. cadmium arsenic combined pollution renovation agent according to claim 2, it is characterised in that: alkali metal ionization described in S3 is viscous
The native and ratio containing humic acid solution is 1:1~30；It is described to contain content of humic acid >=1% in humic acid solution；
And/or the humic acid solution that contains is one of potassium humate, sodium humate, ammonium humate, nitro humus acid or more
The aqueous solution that kind is prepared；
And/or the temperature of the humic acid modified processing is 10 DEG C~40 DEG C, the processing time is 5min~120min；
And/or the humic acid modified clay pH is 8~12.
7. cadmium arsenic combined pollution renovation agent according to claim 3, which is characterized in that iron content in the ground hematite >=
50%；The ratio of the ground hematite and first pass filtering acid solution is 1~20:100.
8. a kind of preparation method of cadmium arsenic combined pollution renovation agent, which comprises the steps of:
The acidification of S1 clay
Clay material is added in acid solution, is filtered after acidified processing, stays first pass filtering acid solution spare, and with deionized water
Filtering filter residue is cleaned, until filtrate and NaOH do not generate precipitating, obtains acid-treated clay after filtering filter residue dries pulverizing；
S2 acid-treated clay alkali metal ion
Acid-treated clay obtained by S1 is added to containing in soda lye, is filtered after alkali metal ionization processing, stays filtering lye spare,
Alkali metal ion clay is obtained after filtering filter residue dries pulverizing；
The humic acid modified clay of S3
Alkali metal ion clay obtained by S2 is added containing in humic acid solution, is filtered after humic acid modified processing, and to go
Ionized water cleaning filtering filter residue simultaneously adjusts filtering filter residue pH, obtains humic acid modified clay after dries pulverizing；
S4 prepares cadmium arsenic combined pollution renovation agent
By humic acid modified clay, Fe (OH) obtained by calcium carbonate, silicon-calcium-magnesium fertilizer, S33With 10~30:30 of weight ratio~60:10~
40:1~10 mix up to cadmium arsenic combined pollution renovation agent.
9. a kind of preparation method of cadmium arsenic combined pollution renovation agent according to claim 1, which is characterized in that the Fe
(OH)3It is prepared: ground hematite being added in the resulting first pass filtering acid solution of S1, mistake after fully reacting by following methods
Filter, takes filtrate spare；Gained filtrate is adjusted into pH to Fe with the resulting filtering lye of S23+Precipitating completely, after filtering drying crushes
It obtains Fe (OH)3。
10. any one of a kind of described in any item cadmium arsenic combined pollution renovation agents of the claim 1-7 or claim 8-9 side
The application of cadmium arsenic combined pollution renovation agent made from method, it is characterised in that: the cadmium arsenic combined pollution renovation agent is for adjusting acid
Property soil, especially adjusting acidification paddy soils and drought soil；Preferably, the pH of the acidification soil is 4.5-6.0；It is preferred that
, the amount of application when cadmium arsenic combined pollution renovation agent adjusts acid soil again is 100-200kg/ mus, preferably 150kg/
Mu.
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| CN114774130A (en) * | 2022-04-15 | 2022-07-22 | 哈尔滨工业大学 | Modified clay mineral for repairing arsenic-lead-antimony composite contaminated soil and preparation method and application thereof |
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