CN106492744B - Tetrathio hydrazino calcium formate complex ion method for preparing modified bentonite - Google Patents
Tetrathio hydrazino calcium formate complex ion method for preparing modified bentonite Download PDFInfo
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Abstract
The invention discloses a kind of tetrathio hydrazino calcium formate complex ion method for preparing modified bentonite.It is mainly by tetrathio hydrazino formic acid and Ca2+The complex ion of formation is that column-supporting agent prepares modified alta-mud.Physical absorption or chemisorption occur for a large amount of active sites and molecule-type or ionic organic pollutant of tetrathio hydrazino calcium formate complex ion modified alta-mud interlayer prepared by the present invention, can dispel heavy metal ion and organic pollutant simultaneously.Compared with organic macromolecule modifying agent, adsorption capacity increases, and stable and firm, and energy permanent locking heavy metal ion, the sustainable time is longer, has saved cost to a certain extent.
Description
Technical field
The invention belongs to field of environment protection, and in particular to a kind of tetrathio hydrazino calcium formate complex ion modified alta-mud
Preparation method.
Background technique:
Bentonite with stronger adsorption capacity and ion-exchange capacity due to being valued by people, and it belongs to non-gold
Belong to mineral products, have the characteristics that it is widely distributed, bury shallow and easy excavation.Bentonite has special water imbibition, hydroplasticity, caking property
And stronger ion-exchange capacity and be widely used in that processing, mining, slag disposition, battery manufacture etc. is electroplated with much money
Belong to seriously polluted field.But natural montmorillonite is since active site is occupied, interlamellar spacing is small, cannot due to limited sorption capacity etc.
Meet the actual demand of people.Directly use the mesh that dosage is more, effect is poor, and guarantee effect is not achieved, saves resource, protect environment
's.Processing is modified to it can substantially improve its interlayer structure and absorption property.
Bentonitic main active is aqueous layer aluminosilicate mineral, clips one layer by two layers of oxygen-octahedron
Alumina octahedral is constituted, and belongs to 2:1 type three-layer clay mineral, such as Fig. 1.Bentonite has stronger ion-exchange capacity, one
Under fixed physical and chemical condition, can and Fe3+、Ca2+、Mg2+、Na+、K+Etc. being exchanged with each other.The bentonite after cation-modified
Large specific surface area, absorption property are good, can effectively remove the pollutant in waste water.Common inorganic cation mainly has multicore golden
Belong to cation and polymerization hydroxy metal cation etc., common organic cation includes alkyl quaternary ammonium salts, alkane base quaternary alkylphosphonium salt, alkyl
The hydrochloride etc. of amine.Modified bentonite, interlamellar spacing obtain different degrees of raising, and adsorption capacity is obviously changed
It is kind.
CN200910248679.5 organic modified bentonite and preparation method thereof；CN201010121822.7 is organically-modified swollen
Moisten the preparation method of soil；A kind of method using organobentonite processing waste water of CN201110307128.9, the above patent introduction
Organic modifiers handle bentonitic technology, for modified alta-mud, although the pillared effect due to modifying agent increases
Interlamellar spacing and adsorption capacity, but since the agent that has been modified of ion activity point occupies, so modified alta-mud is to heavy metal ion
Absorption mainly becomes weaker electrostatic interaction from the electrostatic interaction of original moderate strength, and adsorption obviously subtracts
It is weak, the purpose of permanent locking heavy metal ion is not achieved, and be easy to cause secondary pollution.
Summary of the invention
The purpose of the present invention is to provide a kind of tetrathio hydrazino calcium formate complex ion method for preparing modified bentonite.
It realizes the technical scheme is that a kind of preparation side of tetrathio hydrazino calcium formate complex ion modified alta-mud
Method includes the following steps:
(1) handle bentonite original soil (raw ore): take a certain amount of bentonite original soil to dry at 100-120 DEG C, then by its
It crushes, grinding, sieves for subsequent use；
(2) preparation of bentonite suspension: by above-mentioned bentonite and water 1:(10-35 in mass ratio) it mixes, it is heated to 60-
100 DEG C of stirrings are no less than 60min, obtain suspension；
(3) Na the preparation of sodium bentonite: is added in bentonite suspension2CO3Solution stirs it at 60-100 DEG C
It mixes and is heated to being uniformly mixed, obtain sodium bentonite suspension；
(4) preparation of tetrathio hydrazino calcium formate complex ion: the mixing that carbon disulfide is dissolved in hexamethylene and acetone is molten
In agent, which is slowly dropped in hydrazine hydrate, obtained solid is made into tetrathio after filtering after being stirred to react, being dry
Hydrazino formic acid solution, and and CaCl2Solution mixes to obtain tetrathio hydrazino calcium formate complex ion solution, set aside for use；
(5) by the sodium bentonite suspension by volume 1 of the complex ion solution of step (4) preparation and step (3) preparation:
(5-12) mixing, and not higher than being stirred in 100 DEG C of waters bath with thermostatic control, centrifugal drying is ground up, sieved, and finally obtains product.
In step (1), ground 100-200 mesh.
In step (3), the Na2CO3The concentration of solution is 0.1mol/L, bentonite suspension and Na2CO3Solution
Volume ratio is 20:1, and the agitating and heating time is not less than 60min.
In step (4), temperature control is stirred to react at 30-35 DEG C, is stirred to react the time not less than 2h；The quality of hydrazine hydrate
Score is 80wt%, carbon disulfide, hexamethylene, acetone and hydrazine hydrate volume ratio be 9.06:1:4.09:9.33.
In step (4), CaCl2The concentration of solution and tetrathio hydrazino formic acid solution is 0.01mol/L, CaCl2Solution
Volume ratio with tetrathio hydrazino formic acid solution is 1:2-1:4.
In step (5), the agitating and heating time is no less than 60min, and drying temperature is not higher than 120 DEG C, and 100-200 is crossed after grinding
Mesh.
Compared with prior art, the invention has the advantages that
(1) compared with traditional inorganic modified alta-mud and organic modified bentonite, tetrathio hydrazine prepared by the present invention
Base calcium formate complex ion modified alta-mud heavy-metal ion removal performance is more excellent, and it is seriously polluted to be used for heavy metal ion
Waste water in, the removal rate of heavy metal ion is larger.
(2) a large amount of active sites of tetrathio hydrazino calcium formate complex ion modified alta-mud interlayer and molecule-type or ionic
Physical absorption or chemisorption occur for organic pollutant, can dispel heavy metal ion and organic pollutant simultaneously.With organic big point
Sub- modifying agent is compared, and adsorption capacity increases, and stable and firm, and energy permanent locking heavy metal ion, the sustainable time is longer, from one
Determine to have saved cost in degree.
(3) preparation process of the present invention is simple, easy to operate, and cost is relatively low.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of active constituent in bentonite in the prior art.
Fig. 2 is tetrathio hydrazino calcium formate complex ion pillared modified montmorillonite structural schematic diagram of the present invention.
Fig. 3 is process flow chart of the invention.
Specific embodiment
Fig. 2 is tetrathio hydrazino calcium formate complex ion pillared modified montmorillonite structural schematic diagram of the present invention, weak in Fig. 2
Stable tetrathio hydrazino calcium formate complex ion as column-supporting agent to bentonite carry out pillared modification, with heavy metal ion
In effect, since the internal layer d track of heavy metal ion participates in hydridization, complex energy generated is lower, stability is more preferable, because
This heavy metal ion is by the central ion Ca with former complex2+Exchange reaction occurs, generates new heavy metal ion complex, weight
Metal ion is thus adsorbed and locks, furthermore a large amount of active sites of modified alta-mud interlayer and molecule-type or the organic dirt of ionic
It contaminates object and physical absorption or chemisorption occurs, heavy metal ion and organic pollutant can be dispelled simultaneously.
Technical solution of the present invention is further elaborated with reference to the accompanying drawings and examples.
Such as Fig. 3, a heavy metal species permanent locking agent of the invention is prepared by the following steps:
Embodiment 1:
It takes 50g bentonite original soil in 105 DEG C of drying in oven, then is crushed with ball mill, grinding, then sieve with 100 mesh sieve, by it
Obtained product is mixed with water 1:15 in mass ratio, is heated to 80 DEG C, and obtained suspension is sufficiently stirred.In 200mL suspension
10mL, the Na of 0.1mol/L is added2CO3Solution is uniformly mixed, and by it, to obtain sodium base swollen by agitating and heating 60min in 80 DEG C of water-baths
Moisten native suspension.
At 30-35 DEG C, 30mL carbon disulfide is dissolved in the in the mixed solvent of 20mL hexamethylene and acetone, cyclohexane
The carbon disulfide mixed solution of formation is slowly dropped in 31mL 80% (wt%) hydrazine hydrate, is stirred to react 2h, instead by 3.4mL
Answer product through filtering, filter cake is washed with dehydrated alcohol, and the tetrathio hydrazino formic acid crystal of white can be obtained after dry.Upper
The tetrathio hydrazino formic acid stated is made into the solution of 0.01mol/L, takes the tetrathio hydrazino formic acid of 40mL0.01mol/L
Middle addition 20mL, the CaCl of 0.01mol/L2Solution obtains tetrathio hydrazino calcium formate complex ion solution after being sufficiently stirred, quiet
It sets stand-by.
By it after 1:8 is mixed by volume with sodium bentonite suspension, the agitating and heating 60min in 80 DEG C of water-baths,
Centrifugal drying, grinding sieve with 100 mesh sieve again, and product is made.
Embodiment 2:
It takes in the tetrathio hydrazino formic acid of 60mL 0.01mol/L and 20mL, the CaCl of 0.01mol/L is added2Solution fills
Tetrathio hydrazino calcium formate complex ion solution is obtained after dividing stirring, other steps and formula are the same as embodiment 1.
Embodiment 3:
It takes in the tetrathio hydrazino formic acid of 80mL 0.01mol/L and 20mL, the CaCl of 0.01mol/L is added2Solution fills
Tetrathio hydrazino calcium formate complex ion solution is obtained after dividing stirring, other steps and formula are the same as embodiment 1.
Comparison example 1
It selects Wuxi that company's waste water is electroplated, measures Zn2+Concentration 5.14mg/L, Ni2+Concentration 4.88mg/L, Cr6+Concentration
4.91mg/L is separately added into tetramethyl-ammonium modified alta-mud, lauryl sodium sulfate and the embodiment of 5g in every liter of waste water
Product in 1-3, stirring rate 30r/min, mixing time 10min, measure heavy metal ion concentration and place half a year after from
Sub- concentration is shown in Table 1.Be added example product after heavy metal ion reach national emission standard GB8978-1996 (country allow
Maximum blowdown flow rate: primary standard Zn2+2.0mg/L,Ni2+1.0mg/L,Cr6+0.5mg/L), and it is long placed in rear concentration of heavy metal ion
There is no increase, illustrate that the sustainable time for locking heavy metal ion is longer.
The concentration and ion concentration after placement half a year of 1 heavy metal ion of table
| Substance 1 | Substance 2 | Example 1 | Example 2 | Example 3 | |
| Zn2+/(mg/L) | 1.12 | 0.99 | 0.92 | 0.89 | 0.88 |
| Ni2+/(mg/L) | 0.98 | 0.93 | 0.79 | 0.74 | 0.73 |
| Cr6+/(mg/L) | 0.68 | 0.50 | 0.36 | 0.33 | 0.34 |
| Zn after half a year2+/(mg/L) | 1.43 | 1.09 | 0.92 | 0.90 | 0.88 |
| Ni after half a year2+/(mg/L) | 1.06 | 0.96 | 0.79 | 0.74 | 0.74 |
| Cr after half a year6+/(mg/L) | 0.75 | 0.54 | 0.37 | 0.33 | 0.34 |
Comparison example 2:
The board wastewater for selecting Suzhou company, measures Cu2+Concentration 127.70mg/L, pH 5.2, in every liter of waste water
It is separately added into product in tetramethyl-ammonium modified alta-mud, lauryl sodium sulfate and the embodiment 1-3 of 5g, with 30r/min speed
Rate stirring, stands, Cu in above-mentioned clear liquid after reacting 10min2+Concentration and it is long placed in Cu after half a year2+Concentration is shown in Table 2, using in example
Product finds Cu2+Concentration reaches national emission standard GB8978-1996 (the maximum blowdown flow rate that country allows: primary standard Cu2+
2.0mg/L), and it is long placed in rear Cu2+Concentration is not significantly increased.
The variation of Cu in waste water ion concentration and copper ion concentration after standing half a year after substance is added in table 2
| Substance 1 | Substance 2 | Example 1 | Example 2 | Example 3 | |
| Cu2+/(mg/L) | 1.75 | 1.43 | 0.26 | 0.25 | 0.25 |
| Cu after half a year2+/(mg/L) | 3.78 | 2.56 | 0.27 | 0.25 | 0.25 |
Comparison example 3:
The production waste water for selecting Nanjing cell manufacturer, measures Zn2+Concentration 6.23mg/L, Mn2+Concentration 5.41mg/L,
Hg2+Concentration 1.67mg/L, tetramethyl-ammonium modified alta-mud, lauryl sodium sulfate and the implementation that 5g is added in every liter of waste water are real
Product in example 1-3 is stood, after measuring effects of ion concentration and being long placed in half a year with the stirring of 30r/min rate after reacting 10min
Ion concentration is shown in Table 3.Reach national emission standard GB8978-1996 (state using heavy metal ion in product wastewater in example
The maximum blowdown flow rate that family allows: primary standard Zn2+2.0mg/L,Mn2+2.0mg/L,Hg2+0.05mg/L), and it is long placed in rear heavy metal
Ion concentration is not significantly increased.
The concentration and ion concentration after placement half a year of 3 heavy metal ion of table
| Substance 1 | Substance 2 | Example 1 | Example 2 | Example 3 | |
| Zn2+/(mg/L) | 1.18 | 0.99 | 0.96 | 0.95 | 0.93 |
| Mn2+/(mg/L) | 0.76 | 0.63 | 0.41 | 0.40 | 0.40 |
| Hg2+/(mg/L) | 0.68 | 0.51 | 0.37 | 0.35 | 0.35 |
| Zn after half a year2+/(mg/L) | 1.43 | 1.09 | 0.97 | 0.95 | 0.94 |
| Mn after half a year2+/(mg/L) | 0.97 | 0.77 | 0.41 | 0.41 | 0.40 |
| Hg after half a year2+/(mg/L) | 0.75 | 0.63 | 0.37 | 0.35 | 0.35 |
Claims (6)
1. a kind of tetrathio hydrazino calcium formate complex ion method for preparing modified bentonite, which is characterized in that including walking as follows
It is rapid:
(1) it handles bentonite original soil: taking bentonite original soil to dry at 100-120 DEG C, then crushed, ground, be sieved, it is standby
With；
(2) preparation of bentonite suspension: by above-mentioned bentonite and water 1:(10-35 in mass ratio) it mixes, it is heated to 60-100
DEG C stirring be no less than 60min, obtain suspension；
(3) Na the preparation of sodium bentonite: is added in bentonite suspension2CO3It is stirred at 60-100 DEG C and is added by solution
Heat obtains sodium bentonite suspension to being uniformly mixed；
(4) carbon disulfide: being dissolved in the in the mixed solvent of hexamethylene and acetone by the preparation of tetrathio hydrazino calcium formate complex ion,
The mixed solution is slowly dropped in hydrazine hydrate, obtained solid is made into tetrathio hydrazine after filtering after being stirred to react, being dry
Base formic acid solution, and and CaCl2Solution mixes to obtain tetrathio hydrazino calcium formate complex ion solution, set aside for use；
(5) by the sodium bentonite suspension 1:(5- by volume of the complex ion solution of step (4) preparation and step (3) preparation
12) it mixes, and not higher than stirring in 100 DEG C of waters bath with thermostatic control, centrifugal drying is ground up, sieved, and finally obtains product.
2. tetrathio hydrazino calcium formate complex ion method for preparing modified bentonite as described in claim 1, feature exist
In, in step (1), ground 100-200 mesh.
3. tetrathio hydrazino calcium formate complex ion method for preparing modified bentonite as described in claim 1, feature exist
In, in step (3), the Na2CO3The concentration of solution is 0.1mol/L, bentonite suspension and Na2CO3The volume ratio of solution
For 20:1, the agitating and heating time is not less than 60min.
4. tetrathio hydrazino calcium formate complex ion method for preparing modified bentonite as described in claim 1, feature exist
In being stirred to react temperature control at 30-35 DEG C, be stirred to react the time not less than 2h in step (4)；The mass fraction of hydrazine hydrate
For 80wt%, carbon disulfide, hexamethylene, acetone and hydrazine hydrate volume ratio be 9.06:1:4.09:9.33.
5. tetrathio hydrazino calcium formate complex ion method for preparing modified bentonite as described in claim 1, feature exist
In, in step (4), CaCl2The concentration of solution and tetrathio hydrazino formic acid solution is 0.01mol/L, volume ratio 1:
2-1:4.
6. tetrathio hydrazino calcium formate complex ion method for preparing modified bentonite as described in claim 1, feature exist
In in step (5), the agitating and heating time is no less than 60min, and drying temperature is not higher than 120 DEG C, and 100-200 mesh is crossed after grinding.
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