CN109745962A - A kind of mixed and modified organo montmorillonite and its synthetic method and application - Google Patents
A kind of mixed and modified organo montmorillonite and its synthetic method and application Download PDFInfo
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- CN109745962A CN109745962A CN201910197900.2A CN201910197900A CN109745962A CN 109745962 A CN109745962 A CN 109745962A CN 201910197900 A CN201910197900 A CN 201910197900A CN 109745962 A CN109745962 A CN 109745962A
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a kind of mixed and modified organo montmorillonite and its synthetic method and the applications in efficient degradation perfluorochemical, belong to persistent pollutant degradation field.The present invention first using poly- 4-vinylpridine styrene to montmorillonite carry out it is organically-modified, reuse cetyl trimethyl ammonia bromide to the phenylethene modified montmorillonite of poly- 4-vinylpridine carry out it is organically-modified, obtain mixed and modified organo montmorillonite；The mixed and modified organo montmorillonite has the advantages that increase absorption and protection aqueous electron to aqueous electron predecessor heteroauxin, can be realized the fast degradation to PFOA and defluorinate, and the method for the degrading perfluorinated compound of the present invention is not by pH value of solution, NO3 ‑、SO4 2‑And the influence of dissolved oxygen, application value with higher.
Description
Technical field
The invention belongs to persistent pollutant degradation fields, more specifically to a kind of mixed and modified organo montmorillonite
And its synthetic method and application.
Background technique
Since last century the fifties, perfluorochemical is extensive due to fabulous physics and chemical stability
Applied to industrial different field, as coating, fire proofing material, Macroscopic single crystal and polishing agent (Renner, R.,
Evidence of toxic effects and environmental impacts has sent researchers
scrambling to obtain more data.Environmental science&technology 2001,35,(7),
154A-160A.Schultz,M.M.；Barofsky,D.F.；Field,J.A.,Fluorinated alkyl
surfactants.Environmental Engineering Science 2003,20,(5),487-501.Giesy,J.P.；
Kannan,K.,Perfluorochemical surfactants in the environment.Environmental
science&technology 2002,36,(7),146A-152A).In a series of perfluorochemical, perfluoro caprylic acid be by
The highest perfluorochemical of content, recent years receive significant attention (Rahman, M.F. in the environment detected；Peldszus,
S.；Anderson,W.B.,Behaviour and fate of perfluoroalkyl and polyfluoroalkyl
substances(PFASs)in drinking water treatment:a review.Water research 2014,50,
318-40).Scientific research before confirms that perfluoro caprylic acid can cause the growth and development of embryo slow.In addition to this, it also grinds
Study carefully discovery for 5 to 18 years old youngsters and childrens, the hyperactivity of perfluoro caprylic acid concentration in blood and children, which are presented, to be positively correlated
Relationship.(Koustas,E.；Lam,J.；Sutton,P.；Johnson,P.I.；Atchley,D.S.；Sen,S.；Robinson,
K.A.；Axelrad,D.A.；Woodruff,T.J.,The Navigation Guide-evidence-based medicine
meets environmental health:systematic review of nonhuman evidence for PFOA
effects on fetal growth.Environmental health perspectives 2014,122,(10),1015-
27.Stein,C.R.；Savitz,D.A.,Serum Perfluorinated Compound Concentration and
Attention Deficit/Hyperactivity Disorder in Children 5-18Years of
Age.Environmental health perspectives 2011,119,(10),1466-1471)。
PFOA is the compound that hydrogen atom all in a kind of sad carbochain is all replaced by fluorine atoms.Since fluorine atom is strong
Electronegativity, carbon-fluorine bond is considered as strongest chemical bond (carbon-fluorine bond bond energy 485kJ/mol), and there are also very strong anti-oxidant
Ability, this shows compared to oxidative degradation technology, and PFOA is easier to be reduced degradation.(Rahman,M.F.；Peldszus,S.；
Anderson,W.B.,Behaviour and fate of perfluoroalkyl and polyfluoroalkyl
substances(PFASs)in drinking water treatment:a review.Water research 2014,50,
318-40.Arvaniti,O.S.；Stasinakis,A.S.,Review on the occurrence,fate and
removal of perfluorinated compounds during wastewater treatment.The Science
of the total environment 2015,524-525,81-92.Park,H.；Vecitis,C.D.；Cheng,J.；
Choi,W.；Mader,B.T.；Hoffmann,M.R.,Reductive Defluorination of Aqueous
Perfluorinated Alkyl Surfactants:Effects of Ionic Headgroup and Chain
Length.Journal of Physical Chemistry A 2009,113,(4),690-696).In a recent study,
The methods of many reduction PFOA are reported, including direct ultraviolet illumination, ultraviolet/sulphite, ultraviolet/potassium iodide, ultraviolet/light are urged
The technical methods such as agent (Lyu, X.J.；Li,W.W.；Lam,P.K.；Yu,H.Q.,Insights into
perfluorooctane sulfonate photodegradation in a catalyst-free aqueous
solution.Scientific reports 2015,5,9353.Gu,Y.；Dong,W.；Luo,C.；Liu,T.,Efficient
Reductive Decomposition of Perfluorooctanesulfonate in a High Photon Flux UV/
Sulfite System.Environmental science&technology 2016,50,(19),10554-10561.Qu,
Y.；Zhang,C.；Li,F.；Chen,J.；Zhou,Q.,Photo-reductive defluorination of
perfluorooctanoic acid in water.Water research 2010,44,(9),2939-47.Lin,H.；
Niu,J.；Xu,J.；Huang,H.；Li,D.；Yue,Z.；Feng,C.,Highly efficient and mild
electrochemical mineralization of long-chain perfluorocarboxylic acids(C9-
C10)by Ti/SnO2-Sb-Ce,Ti/SnO2-Sb/Ce-PbO2,and Ti/BDD electrodes.Environmental
science&technology 2013,47,(22),13039-46.Li,X.；Zhang,P.；Jin,L.；Shao,T.；Li,Z.；
Cao,J.,Efficient photocatalytic decomposition of perfluorooctanoic acid by
indium oxide and its mechanism.Environmental science&technology 2012,46,(10),
5528-34.Tang,H.；Xiang,Q.；Lei,M.；Yan,J.；Zhu,L.；Zou,J.,Efficient degradation of
perfluorooctanoic acid by UV–Fenton process.Chemical Engineering Journal
2012,184,156-162.Liu,Y.；Chen,S.；Quan,X.；Yu,H.；Zhao,H.；Zhang,Y.,Efficient
Mineralization of Perfluorooctanoate by Electro-Fenton with H2O2Electro-
generated on Hierarchically Porous Carbon.Environmental science&technology
2015,49,(22),13528-33).In these methods, reduction activation species such as aqueous electron, carbon dioxide anion from
Main function is played by base and light induced electron.In addition to this, these researchs also indicate that free compared to carbon dioxide anion
Base and light induced electron, the strong reducing power of aqueous electron can be by the complete defluorinate of PFOA, therefore this method is with higher answers
Use prospect.But aqueous electron needs more harsh reaction condition (such as anaerobic environment, height during deoxidization, degradation PFOA
PH), harsh reaction condition increases the not applicability of this method in practical applications.Therefore, a kind of low energy consumption, degradation
High-efficient, the strong method of applicability is urgently developed.
It is found through retrieval, Chinese Patent Application No. 201510981853.2, data of publication of application is the special of on May 4th, 2016
Sharp application documents disclose a kind of method of efficient degradation perfluorochemical, use 254nm ultraviolet light heteroauxin (IAA)
Solution generates aqueous electron, and the deoxidization, degradation PFCs under aerobic condition, by being added, cetyl trimethylammonium bromide is organic to be changed
The montmorillonite of property provides reaction microcell, substantially increases degradation and defluorination effect of the aqueous electron to PFCs, and this method
It is not influenced by pH value of solution and dissolved oxygen, substantially overcomes the defect of existing aqueous electron deoxidization, degradation PFCs method.The invention
Principle be use cetyl trimethylammonium bromide ion (HDTMA+Ion) balance montmorillonite interlayer negative electrical charge, had
Machine modified montmorillonoid, and utilize HDTMA+Longer C chain, make organo montmorillonite have hydrophobicity, to increase it to perfluor
The absorption of compound and heteroauxin, under ultraviolet lighting, the heteroauxin for being adsorbed onto interlayer occurs photoionization and generates water
Electronics is closed, these aqueous electrons can degrade perfluorochemical by way of restoring defluorinate.But the technology is to perfluor chemical combination
The degradation efficiency of object is limited, to improve degradation efficiency, needs to be further improved organic modification montmonrillonite.
Summary of the invention
1. solving the problems, such as
For existing aqueous electron deoxidization, degradation perfluorochemical technology there are severe reaction conditions, applicability it is poor,
Aqueous electron utilization rate and degradation efficiency need the problem of being further increased, and the present invention provides a kind of mixed and modified organic illiteracy is de-
Soil and its synthetic method and application；The present invention is first organically-modified to montmorillonite progress using poly- 4-vinylpridine styrene, then
It is organically-modified to poly- 4-vinylpridine phenylethene modified montmorillonite progress using cetyl trimethyl ammonia bromide, it is mixed
Close modified organo montmorillonite.Using the mixed and modified organo montmorillonite as catalytic media, in the aqueous solution containing heteroauxin,
Degrade PFOA under ultraviolet lighting.The mixed and modified organo montmorillonite has the absorption increased to aqueous electron predecessor heteroauxin
The advantages of with protection aqueous electron, so as to realize fast degradation and the defluorinate under aerobic and acid condition to PFOA.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:
A kind of method synthesizing mixed and modified organo montmorillonite of the invention, comprising the following steps:
S1, using poly- 4-vinylpridine styrene (PVPcoS) to montmorillonite (MMT) carry out it is organically-modified, obtain poly-
The phenylethene modified montmorillonite of 4-vinylpridine (PVPcoS-MMT)；
S2, using cetyl trimethyl ammonia bromide (HDTMA) to poly- 4-vinylpridine benzene second obtained in step S1
The progress of alkene modified montmorillonoid is organically-modified again, obtains mixed and modified organo montmorillonite (MOM-MMT).
Preferably, the total amount of the poly- 4-vinylpridine styrene in the step S1 is exchanged with the cation of montmorillonite
(CEC) total amount is consistent.
Preferably, the total amount of the cetyl trimethyl ammonia bromide in the step S2 is less than the cation exchange of montmorillonite
Total amount.
Preferably, the total amount of the cetyl trimethyl ammonia bromide in the step S2 is that the cation exchange of montmorillonite is total
0.6~0.8 times of amount.
Preferably, organically-modified specific steps are carried out to montmorillonite in the step S1 are as follows:
(1) na montmorillonite is distributed in water, obtains montmorillonite dispersion solution；
(2) the poly- 4-vinylpridine styrene solution of acidification is added into the montmorillonite of step (1) dispersion solution, stirs
It mixes；
(3) it is centrifuged after stirring in step (2), discards supernatant liquid, obtain sediment；
(4) sediment obtained in step (3) is washed with water, the phenylethene modified montmorillonite of poly- 4-vinylpridine is obtained.
Preferably, the phenylethene modified montmorillonite of poly- 4-vinylpridine is carried out in the step S2 organically-modified again
Specific steps are as follows:
(1) the phenylethene modified montmorillonite of poly- 4-vinylpridine is distributed in water, obtains poly- 4-vinylpridine benzene
Ethylene modified montmorillonite disperses solution；
(2) cetyl three is added into the phenylethene modified montmorillonite dispersion solution of the poly- 4-vinylpridine of step (1)
Methyl bromide ammonium salt solution, stirring；
(3) it is centrifuged after stirring in step (2), discards supernatant liquid, obtain sediment；
(4) sediment obtained in step (3) is washed with water, mixed and modified organo montmorillonite is obtained.
Preferably, carrying out jitter time in organically-modified specific steps (1) to montmorillonite in the step S1 is 8 small
When.
Preferably, montmorillonite cleaned in organically-modified specific steps (4) with deionized water in the step S1
Sediment 10 times.
A kind of mixed and modified organo montmorillonite of the invention, using the method for the above-mentioned mixed and modified organo montmorillonite of synthesis
Synthesis obtains.
A kind of method using mixed and modified organo montmorillonite efficient degradation perfluorochemical of the invention, including following step
It is rapid:
(i) heteroauxin solution and perfluorochemical solution are uniformly mixed；
(ii) above-mentioned mixed and modified organo montmorillonite is distributed in the mixed solution of step (i), obtains reaction solution；
(iii) light reaction is carried out with degrading perfluorinated compound to reaction solution obtained in step (ii) using mercury lamp.
Preferably, the step (ii) further includes adjusting the pH value of reaction solution to 4.0~10.0.
Preferably, the specific steps of the step (iii) are as follows: stir reaction solution obtained in step (ii) 30 minutes
After be transferred in crystal reaction tube, under aerobic environment, mercury lamp is immersed into reaction solution and carries out degradation reaction；Wherein, always
Reaction solution volume is 300mL, and at 25 ± 2 DEG C, mercury lamp is 36W low pressure mercury lamp for reaction temperature control, and the reaction time is 14 hours.
3. beneficial effect
Compared with the prior art, the invention has the benefit that
(1) a kind of method for synthesizing mixed and modified organo montmorillonite of the invention, including poly- 4- vinylpyridine is used first
Pyridine styrene is organically-modified to montmorillonite progress, reuses cetyl trimethyl ammonia bromide to poly- 4-vinylpridine benzene second
The progress of alkene modified montmorillonoid is organically-modified to obtain mixed and modified organo montmorillonite, has surprisingly found that mixed and modified organo montmorillonite energy
The adsorption efficiency to heteroauxin molecule is enough greatly increased, more aqueous electron precursors is promoted to generate in interlayer, thus
The utilization rate in reaction process to aqueous electron is improved, promotes the degradation of PFOA, therefore use poly- 4-vinylpridine styrene
Montmorillonite is carried out organically-modified for the first time；
(2) a kind of mixed and modified organo montmorillonite of the invention successively passes through poly- 4-vinylpridine styrene, 16
The modification of alkyl trimethyl ammonia bromide obtains, which is adsorbed with poly- 4-vinylpridine benzene simultaneously
Ethylene and cetyl trimethyl ammonia bromide protect the photoproduction largely generated to be hydrated while increasing to heteroauxin absorption
Electronics is not quenched by oxygen and proton, so that degradation reaction be allow to occur under aerobic and acid condition, and passes through control
The amount of modified poly- 4-vinylpridine styrene used, cetyl trimethyl ammonia bromide twice, makes mixed and modified organic illiteracy
De- native degradation with higher to perfluorochemical and defluorinate efficiency；
(3) a kind of method using mixed and modified organo montmorillonite efficient degradation perfluorochemical of the invention, in use
For the mixed and modified organo montmorillonite stated as catalytic media, the presence of the mixed and modified organo montmorillonite plays a micro- reaction
Efficient degradation PFOA is realized in the effect of device；
(4) montmorillonite and heteroauxin used in the present invention are all the substances that nature is widely present, will not be to environment
It pollutes, the poly- 4-vinylpridine styrene of used organic modifiers and cetyl trimethyl ammonia bromide can be by
It fixes well, will not can be discharged into environment and cause secondary pollution, realize green environment close friend.
Detailed description of the invention
Fig. 1 is the schematic diagram that PFOA degrades in mixed and modified montmorillonite in the present invention；
Fig. 2 is the schematic diagram of PFOA degradation mechanism in the present invention；
Fig. 3 a is organic modification montmonrillonites different in the present invention to the Adsorption thermodynamics curve graph of IAA；
Fig. 3 b is organic modification montmonrillonites different in the present invention to the Adsorption thermodynamics curve graph of PFOA；
Fig. 4 is organic modification montmonrillonites different in the present invention to the degradation figure of PFOA；
Fig. 5 a and 5b are the dynamic curve diagram that aqueous electron degrades to PFOA under different atmosphere in the present invention；
Fig. 5 c and 5d are the dynamic curve diagram that aqueous electron degrades to PFOA under condition of different pH in the present invention；
Fig. 6 is the intermediate product dynamic curve diagram that aqueous electron degrades to PFOA in the present invention；
Fig. 7 is the dynamic curve diagram that aqueous electron degrades to PFOA in the presence of different anions in the present invention；
Fig. 8 is the electron paramagnetic resonance spectrum figure of aqueous electron in different montmorillonite systems in the present invention.
Specific embodiment
The present invention is further described below combined with specific embodiments below.
Hereafter to the detailed description of exemplary embodiment of the present invention with reference to attached drawing, although these exemplary embodiment quilts
Sufficiently describe in detail so that those skilled in the art can implement the present invention, it is to be understood that can realize other embodiments and
Can without departing from the spirit and scope of the present invention to the present invention various changes can be made.Hereafter to the embodiment of the present invention
More detailed description is not limited to required the scope of the present invention, and just to be illustrated and do not limit pair
The description of the features of the present invention and feature to propose to execute best mode of the invention, and is sufficient to make those skilled in the art
It can implement the present invention.Therefore, the scope of the invention is only defined by the appended claims.
A kind of method synthesizing mixed and modified organo montmorillonite of the invention, comprising the following steps:
S1, na montmorillonite is distributed in water, stirring obtains montmorillonite dispersion solution for 8 hours；Disperse again to montmorillonite molten
The poly- 4-vinylpridine styrene that acidification is added in liquid carries out organically-modified, the poly- 4-vinylpridine of addition to montmorillonite
The total amount of styrene is consistent with the cation exchange total amount of montmorillonite, stirs 24 hours, and centrifugation discards supernatant liquid, is precipitated
Object, and clean sediment 10 times with deionized water water and obtain the phenylethene modified montmorillonite of poly- 4-vinylpridine；
S2, the phenylethene modified montmorillonite of poly- 4-vinylpridine will be obtained in step S1 be distributed in water, stir 1 hour；
The cetyl trimethyl ammonia bromide for being less than montmorillonite cation exchange total amount is stirring evenly and then adding into poly- 4-vinylpridine
Phenylethene modified montmorillonite progress is organically-modified again, and the total amount for the cetyl trimethyl ammonia bromide being usually added into is montmorillonite
0.6~0.8 times of cation exchange total amount, is stirred 24 hours, and centrifugation discards supernatant liquid, obtains sediment, and use deionization
Water water cleans sediment 10 times and obtains mixed and modified organo montmorillonite.
It is worth noting that the poly- 4-vinylpridine styrene that acidification is added in step S1 is poly- in order to be easier to carry out
4-vinylpridine is phenylethene modified, carries out organically-modified to montmorillonite using poly- 4-vinylpridine styrene so that covering de-
Soil can greatly increase the adsorption efficiency to heteroauxin molecule, and more aqueous electron precursors is promoted to generate in interlayer,
Promote the degradation of PFOA.
It further illustrates, a kind of mixed and modified organo montmorillonite of the invention successively uses poly- 4-vinylpridine
Styrene, cetyl trimethyl ammonia bromide carry out modification twice and obtain, the total amount of poly- 4-vinylpridine styrene with illiteracy
The cation exchange total amount of de- soil is consistent, and the total amount of cetyl trimethyl ammonia bromide is the cation exchange total amount of montmorillonite
0.6~0.8 times, by controlling the amount of poly- 4-vinylpridine styrene, cetyl trimethyl ammonia bromide and montmorillonite, make
It is with higher to perfluorochemical while heteroauxin adsorption capacity with higher to obtain mixed and modified organo montmorillonite
Degradation and defluorinate efficiency.
A kind of method using mixed and modified organo montmorillonite efficient degradation perfluorochemical of the invention, including following step
It is rapid:
(i) heteroauxin solution and perfluorochemical solution are uniformly mixed；
(ii) above-mentioned mixed and modified organo montmorillonite is distributed in the mixed solution of step (i), uses NaOH or HCl
The pH value of reaction solution is adjusted to 4.0~10.0, obtains reaction solution；
(iii) reaction solution obtained in step (ii) is stirred 30 minutes using magnetic agitation, it will be anti-after stirring
It answers solution to be transferred in crystal reaction tube, under aerobic environment, mercury lamp is immersed into reaction solution and carries out degradation reaction；Its
In, overall reaction liquid product is 300mL, and at 25 ± 2 DEG C, mercury lamp is 36W low pressure mercury lamp for reaction temperature control, and the reaction time is 14 small
When.
The present invention uses the principle of mixed and modified organo montmorillonite efficient degradation perfluorochemical are as follows: montmorillonite mineral are one
The mineral material of kind layer structure, interlayer have negative electrical charge, can be modified by the organic modifiers with positive charge.It is cationic
Polymer (poly- 4-vinylpridine styrene) modified organo montmorillonite is increased to aqueous electron predecessor heteroauxin
Absorption, aqueous electron can be protected sudden not by oxygen and proton by the modified montmorillonite of cetyl trimethyl ammonia bromide
It goes out.Therefore, organically-modified by using poly- 4-vinylpridine styrene to carry out montmorillonite first, reuse cetyl
Trimethyl ammonia bromide carries out organically-modified obtained mixed and modified organic illiteracy to the phenylethene modified montmorillonite of poly- 4-vinylpridine
De- soil, can not only increase adsorb to aqueous electron predecessor heteroauxin in this way, improve aqueous electron utilization rate, and can
Protect aqueous electron, do not quenched by oxygen and proton, thus realize under aerobic and acid condition to the fast degradation of PFOA and
Defluorinate.
Embodiment 1
The present embodiment measures suction of the different organic modification montmonrillonites to perfluorooctane carboxylic acid (PFOA) and heteroauxin (IAA)
Attached rate, the steps include:
(1) 200g montmorillonite (being purchased from Zhejiang Feng Hong montmorillonite Chemical Co., Ltd.) is dispersed in 4L water, is added
0.4mol solid NaCl is saturated 8h, and centrifugation discards supernatant liquid, obtains sediment；Sediment is redispersed in 4L water, so weight
It operates 6 times again.Sediment is cleaned with deionized water, is washed till with AgNO3Solution detection is generated without precipitating.Freeze-drying is satisfied
The Na of sum+Montmorillonite；
(2) Na that will be prepared+Montmorillonite is placed in water stirring 8 hours, keeps montmorillonite evenly dispersed.To scattered illiteracy
Total amount of electric charge is added in de- soil solution and exchanges the consistent poly- 4-vinylpridine benzene second of total amount with the cation of montmorillonite in solution
Alkene (is dissolved in 5mol/L H2SO4) aqueous solution 50mL, it stirs 24 hours, centrifugation obtains sediment, washes with water sediment, obtains
Poly- 4-vinylpridine styrene montmorillonite (PVPcoS-MMT)；
(3) the phenylethene modified montmorillonite of poly- 4-vinylpridine is dispersed in water, is stirred 1 hour.It stirs evenly
Afterwards, 0.2CEC, 0.4CEC, 0.6CEC, 0.8CEC are separately added into scattered poly- 4-vinylpridine styrene montmorillonite
The cetyl trimethyl bromination ammonia solution of amount stirs 24 hours, and centrifugation obtains sediment, washes with water sediment, is mixed
It closes modified organo montmorillonite (0.2MOM-MMT, 0.4MOM-MMT, 0.6MOM-MMT, 0.8MOM-MMT)；
(4) Na that will be prepared+Montmorillonite is placed in water stirring 8 hours, keeps montmorillonite evenly dispersed.To scattered illiteracy
The cetyl trimethyl bromination ammonia spirit of 1CEC is added in de- soil solution, stirs 24 hours, centrifugation obtains sediment, spends
Ionized water water cleans sediment, obtains cetyl trimethyl ammonia bromide modified montmorillonoid (HDTMA-MMT)；
(5) prepare PFOA aqueous solution each 10mL of the initial concentration from 0 to 1000mg/L, be separately added into 22mg Na+Montmorillonite
Or organic modification montmonrillonite, 10h is shaken at room temperature, and centrifuging and taking supernatant measures the concentration of PFOA, quasi- using langmuir model
Close the adsorption isotherm to PFOA, model Qe=(KL×Cmax×Ce)/(1+KL×Ce), PFOA is obtained in different montmorillonites
Maximal absorptive capacity be respectively Qe(mmol/kg)=8.199, PFOA is in HDTMA+Maximal absorptive capacity Q in montmorillonitee(mmol/
Kg)=277.312.Similarly, prepare IAA aqueous solution each 10mL of the initial concentration from 17.52 to 525.6mg/L, be separately added into
22mg Na+Montmorillonite or organic modification montmonrillonite shake 4h at room temperature, and centrifuging and taking supernatant measures the concentration of IAA, use
Adsorption isotherm of the langmuir models fitting to IAA, model Qe=(KL×Cmax×Ce)/(1+KL×Ce), it obtains IAA and exists
Maximal absorptive capacity in different montmorillonites is respectively Qe(mmol/kg)=156, IAA is in HDTMA+Maximal absorptive capacity in montmorillonite
Qe(mmol/kg)=277.
It follows that: the absorption to IAA is greatly facilitated in organic modification montmonrillonite, as mixed and modified cover takes off
The increase of poly- 4-vinylpridine styrene-content in soil, modified montmorillonoid increase IAA adsorbance, as shown in Figure 3a.It is surprised
Discovery compared with HDTMA- montmorillonite, mixed and modified montmorillonite reduces PFOA adsorbance, as shown in Figure 3b.
Embodiment 2
A kind of method of efficient degradation perfluorochemical of the present embodiment, the steps include:
(1) 200g montmorillonite (being purchased from Zhejiang Feng Hong montmorillonite Chemical Co., Ltd.) is dispersed in 4L water, is added
0.4mol solid NaCl is saturated 8h, and centrifugation discards supernatant liquid, obtains sediment；Sediment is redispersed in 4L water, so weight
It operates 6 times again.Sediment is cleaned with deionized water, is washed till with AgNO3Solution detection is generated without precipitating.Freeze-drying is satisfied
The Na of sum+Montmorillonite；
(2) Na that will be prepared+Montmorillonite is placed in water stirring 8 hours, keeps montmorillonite evenly dispersed.To scattered illiteracy
Total amount of electric charge is added in de- soil solution and exchanges the consistent poly- 4-vinylpridine benzene second of total amount with the cation of montmorillonite in solution
Alkene (is dissolved in 5mol/L H2SO4) aqueous solution 50mL, it stirs 24 hours, centrifugation obtains sediment, washes with water sediment, obtains
Poly- 4-vinylpridine styrene montmorillonite (PVPcoS-MMT)；
(3) the phenylethene modified montmorillonite of poly- 4-vinylpridine is dispersed in water, is stirred 1 hour.It stirs evenly
Afterwards, 0.2CEC, 0.4CEC, 0.6CEC, 0.8CEC are separately added into scattered poly- 4-vinylpridine styrene montmorillonite
The cetyl trimethyl bromination ammonia solution of amount stirs 24 hours, and centrifugation obtains sediment, washes with water sediment, is mixed
It closes modified organo montmorillonite (0.2MOM-MMT, 0.4MOM-MMT, 0.6MOM-MMT, 0.8MOM-MMT)；
(4) Na that will be prepared+Montmorillonite is placed in water stirring 8 hours, keeps montmorillonite evenly dispersed.To scattered illiteracy
The cetyl trimethyl bromination ammonia spirit of 1CEC is added in de- soil solution, stirs 24 hours, centrifugation obtains sediment, spends
Ionized water water cleans sediment, obtains cetyl trimethyl ammonia bromide modified montmorillonoid (HDTMA-MMT)；
(5) before carrying out deoxidization, degradation reaction, IAA solution and PFOA solution (are chosen into PFOA as perfluorochemical first
Representative substances) be uniformly mixed.Above-mentioned different montmorillonites are distributed in the mixed solution of IAA and PFOA, obtain IAA,
PFOA and the content of montmorillonite are respectively the reaction solution of 2mM, 10mg/L and 2.2g/L.Then the NaOH and HCl of 0.1mM are used
The pH to 7.0 for adjusting reaction solution stirs reaction solution 30 minutes using magnetic agitation, turns reaction solution after stirring
It moves to and is equipped in the light reaction instrument of 500W high-pressure sodium lamp, turn on light and carry out degradation reaction, total reaction volume 30mL, reaction temperature
At 25 ± 2 DEG C, the reaction time is 6 hours for control.Sampling and testing after 6 hours, sample are divided into two parts, the second of a 2 times of volumes
Residue PFOA content is measured with high performance liquid chromatography (HPLC) after nitrile extraction, with ion chromatography (IC) measurement life after another filtering
At F ion content, the degradation rate and defluorinate rate of PFOA are calculated with this, specific degradation and defluorinate curve are as shown in Figure 4.
From this it can be concluded that the deoxidization, degradation of PFOA is greatly promoted in the case where being added to organo montmorillonite
, wherein the mixed and modified organo montmorillonite of 0.6MOM-MMT shows highest defluorinate and degradation efficiency.
Embodiment 3
A kind of method of efficient degradation perfluorochemical of the present embodiment, the steps include:
(1) 200g montmorillonite (being purchased from Zhejiang Feng Hong montmorillonite Chemical Co., Ltd.) is dispersed in 4L water, is added
0.4mol solid NaCl is saturated 8h, and centrifugation discards supernatant liquid, obtains sediment；Sediment is redispersed in 4L water, so weight
It operates 6 times again.Sediment is cleaned with deionized water, is washed till with AgNO3Solution detection is generated without precipitating.Freeze-drying is satisfied
The Na of sum+Montmorillonite；
(2) Na that will be prepared+Montmorillonite is placed in water stirring 8 hours, keeps montmorillonite evenly dispersed.To scattered illiteracy
Total amount of electric charge is added in de- soil solution and exchanges the consistent poly- 4-vinylpridine benzene second of total amount with the cation of montmorillonite in solution
Alkene (is dissolved in 5mol/L H2SO4) aqueous solution 50mL, it stirs 24 hours, centrifugation obtains sediment, washes with water sediment, obtains
Poly- 4-vinylpridine styrene montmorillonite (PVPcoS-MMT)；
(3) the phenylethene modified montmorillonite of poly- 4-vinylpridine is dispersed in water, is stirred 1 hour.It stirs evenly
Afterwards, 0.2CEC, 0.4CEC, 0.6CEC, 0.8CEC are separately added into scattered poly- 4-vinylpridine styrene montmorillonite
The cetyl trimethyl bromination ammonia solution of amount stirs 24 hours, and centrifugation obtains sediment, washes with water sediment, is mixed
It closes modified organo montmorillonite (0.2MOM-MMT, 0.4MOM-MMT, 0.6MOM-MMT, 0.8MOM-MMT)；
(4) Na that will be prepared+Montmorillonite is placed in water stirring 8 hours, keeps montmorillonite evenly dispersed.To scattered illiteracy
The cetyl trimethyl bromination ammonia spirit of 1CEC is added in de- soil solution, stirs 24 hours, centrifugation obtains sediment, spends
Ionized water water cleans sediment, obtains cetyl trimethyl ammonia bromide modified montmorillonoid (HDTMA-MMT)；
(5) the case where aqueous electron degrades to PFOA under different atmosphere is investigated:
Before carrying out deoxidization, degradation reaction, IAA solution and PFOA solution are uniformly mixed first, then by 0.6MOM-MMT points
It is scattered in the mixed solution of IAA and PFOA, the content for obtaining IAA, PFOA and montmorillonite is respectively 2mM, 10mg/L and 2.2g/L
Reaction solution.Then the pH to 7.0 that reaction solution is adjusted using the NaOH and HCl of 0.1mM, it is molten to reaction using magnetic agitation
Liquid stirs 30 minutes, and reaction solution is transferred in crystal reaction tube after stirring, and overall reaction liquid product is 300ml, by one
Small cup 36W mercury lamp is immersed into reaction solution, is turned on light and is carried out degradation reaction.Reaction temperature control is at 25 ± 2 DEG C, the reaction time 14
Hour.It is tested in the environment for exposing nitrogen, not being aerated, exposing air respectively, aeration speed 4L/min.Sample time sets respectively
It is set to 0h, 0.5h, 1.5h, 2.5h, 3.5h, 4.5h, 6h, 8h, 11h, 14h.Sample is divided into two parts, the second of a 2 times of volumes
Residue PFOA content is measured with high performance liquid chromatography (HPLC) after nitrile extraction, with ion chromatography (IC) measurement life after another filtering
At F ion content, the degradation rate and defluorinate rate of PFOA are calculated with this, specific degradation and defluorinate curve are as shown in figure 5a and 5b.
From this it can be concluded that defluorinate rate and degradation rate are basic in the case where exposing nitrogen and the experiment condition not being aerated
Constant, the experimental group degradation rate for exposing air improves, and defluorinate rate only has seldom reduction, therefore it can be concluded that mixed and modified illiteracy
De- soil has good closure, can protect aqueous electron and not quenched by oxygen, improve the utilization rate of aqueous electron.
Embodiment 4
The basic content of the present embodiment is with embodiment 3, the difference is that the efficient degradation perfluorochemical of the present embodiment
Step (5) in method is to investigate the case where aqueous electron degrades to PFOA under condition of different pH, concrete operation step are as follows:
Before carrying out deoxidization, degradation reaction, IAA solution and PFOA solution are uniformly mixed first, then by 0.6MOM-MMT points
It is scattered in the mixed solution of IAA and PFOA, the content for obtaining IAA, PFOA and montmorillonite is respectively 2mM, 10mg/L and 2.2g/L
Reaction solution.Then the pH of reaction solution is adjusted respectively to 4.0,7.0,10.0 using the NaOH and HCl of 0.1mM.Use magnetic
Reaction solution is stirred in power stirring 30 minutes, reaction solution is transferred in crystal reaction tube after stirring, overall reaction liquid
Product is 300ml, and a 36W mercury lamp is immersed into reaction solution, turns on light and carries out degradation reaction.Reaction temperature is controlled 25 ± 2
DEG C, the reaction time is 14 hours.Sample time be respectively set to 0h, 0.5h, 1.5h, 2.5h, 3.5h, 4.5h, 6h, 8h, 11h,
14h.Sample is divided into two parts, and is contained after the acetonitrile extraction of a 2 times of volumes with high performance liquid chromatography (HPLC) measurement residue PFOA
Amount, the F ion content generated after another filtering with ion chromatography (IC) measurement, degradation rate and the defluorinate of PFOA are calculated with this
Rate, specific degradation and defluorinate curve are as shown in figures 5 c and 5d.
From this it can be concluded that the degradation and defluorinate of PFOA are hardly influenced by pH value of solution in reaction.
Embodiment 5
The basic content of the present embodiment is with embodiment 3, the difference is that the efficient degradation perfluorochemical of the present embodiment
Step (5) in method specifically:
Before carrying out deoxidization, degradation reaction, IAA solution and PFOA solution are uniformly mixed first, then by 0.6MOM-MMT points
It is scattered in the mixed solution of IAA and PFOA, the content for obtaining IAA, PFOA and montmorillonite is respectively 2mM, 10mg/L and 2.2g/L
Reaction solution.Then the pH to 7.0 that reaction solution is adjusted using the NaOH and HCl of 0.1mM, it is molten to reaction using magnetic agitation
Liquid stirs 30 minutes, and reaction solution is transferred in crystal reaction tube after stirring, and overall reaction liquid product is 300ml, by one
Small cup 36W mercury lamp is immersed into reaction solution, is turned on light and is carried out degradation reaction.Reaction temperature control is at 25 ± 2 DEG C, the reaction time 14
Hour.Sample time is respectively set to 0h, 0.5h, 1.5h, 2.5h, 3.5h, 4.5h, 6h, 8h, 11h, 14h.Sample passes through SPE
In-between product is detected and quantifies using LC/MS/MS after column processing, it is as shown in Figure 6 that intermediate product changes over time curve.
From this it can be concluded that the intermediates of PFOA mainly include the perfluorocarboxylic acid of different chain length in the system
And acetic acid methane.
Embodiment 6
The basic content of the present embodiment is with embodiment 3, the difference is that the efficient degradation perfluorochemical of the present embodiment
Step (5) in method is the case where aqueous electron degrades to PFOA in the presence of investigating different anions, concrete operation step are as follows:
Before carrying out deoxidization, degradation reaction, IAA solution and PFOA solution are uniformly mixed first, then by 0.6MOM-MMT points
It is scattered in the mixed solution of IAA and PFOA, the content for obtaining IAA, PFOA and montmorillonite is respectively 2mM, 10mg/L and 2.2g/L
Reaction solution.Then the pH to 7.0 that reaction solution is adjusted using the NaOH and HCl of 0.1mM, is added in two groups of experiments respectively
1mM NO3 -And SO4 2-.Reaction solution is stirred 30 minutes using magnetic agitation, reaction solution is transferred to quartz after stirring
In reaction tube, overall reaction liquid product is 300ml, and a 36W mercury lamp is immersed into reaction solution, turns on light and carries out degradation reaction.
At 25 ± 2 DEG C, the reaction time is 14 hours for reaction temperature control.Sample time be respectively set to 0h, 0.5h, 1.5h, 2.5h,
3.5h,4.5h,6h,8h,11h,14h.Sample is divided into two parts, with high performance liquid chromatography after the acetonitrile extraction of a 2 times of volumes
(HPLC) residue PFOA content is measured, the F ion content generated after another filtering with ion chromatography (IC) measurement is calculated with this
The degradation rate and defluorinate rate of PFOA, specific degradation and defluorinate curve are as shown in Figure 7.
From this it can be concluded that the presence of water body nitrate anion and sulfate radical does not almost have an impact the reaction.
Embodiment 7
A kind of method of efficient degradation perfluorochemical, the steps include:
(1) 200g montmorillonite (being purchased from Zhejiang Feng Hong montmorillonite Chemical Co., Ltd.) is dispersed in 4L water, is added
0.4mol solid NaCl is saturated 8h, and centrifugation discards supernatant liquid, obtains sediment；Sediment is redispersed in 4L water, so weight
It operates 6 times again.Sediment is cleaned with deionized water, is washed till with AgNO3Solution detection is generated without precipitating.Freeze-drying is satisfied
The Na of sum+Montmorillonite；
(2) Na that will be prepared+Montmorillonite is placed in water stirring 8 hours, keeps montmorillonite evenly dispersed.To scattered illiteracy
Total amount of electric charge is added in de- soil solution and exchanges the consistent poly- 4-vinylpridine benzene second of total amount with the cation of montmorillonite in solution
Alkene (is dissolved in 5mol/L H2SO4) aqueous solution 50mL, it stirs 24 hours, centrifugation obtains sediment, washes with water sediment, obtains
Poly- 4-vinylpridine styrene montmorillonite (PVPcoS-MMT)；
(3) the phenylethene modified montmorillonite of poly- 4-vinylpridine is dispersed in water, is stirred 1 hour.It stirs evenly
Afterwards, 0.2CEC, 0.4CEC, 0.6CEC, 0.8CEC are separately added into scattered poly- 4-vinylpridine styrene montmorillonite
The cetyl trimethyl bromination ammonia solution of amount stirs 24 hours, and centrifugation obtains sediment, washes with water sediment, is mixed
It closes modified organo montmorillonite (0.2MOM-MMT, 0.4MOM-MMT, 0.6MOM-MMT, 0.8MOM-MMT)；
(4) Na that will be prepared+Montmorillonite is placed in water stirring 8 hours, keeps montmorillonite evenly dispersed.To scattered illiteracy
The cetyl trimethyl bromination ammonia spirit of 1CEC is added in de- soil solution, stirs 24 hours, centrifugation obtains sediment, spends
Ionized water water cleans sediment, obtains cetyl trimethyl ammonia bromide modified montmorillonoid (HDTMA-MMT)；
(5) it is transferred in 20ml glass tube, uses after first mixing prepared heteroauxin solution and montmorillonite
The NaOH and HCl of 0.1mM adjusts the pH to 7.0 of solution, is added aqueous electron capturing agent dimethyl pyridine N-oxide (DMPO).
Reaction total volume is 10mL, and wherein the concentration of heteroauxin and DMPO are respectively 2mM and 20mM, and montmorillonite concentration is 2.2g/L.
After 180W Hg lamp irradiation 3.5min, 20 μ L of sampling, which are put into electron paramagnetic resonance (EPR), detects Free Radical Signal, specific as schemed
Shown in 8.
From this it can be concluded that the active specy in solution is mainly hydroxyl in the presence of without montmorillonite, na montmorillonite
Free radical, therefore can't detect the signal of aqueous electron in sample, after being added to organo montmorillonite, is removed in sample and detect hydroxyl
Outside base free radical, while also detecting that the signal of aqueous electron, it is mixed and modified in HDTMA modified montmorillonite and 0.6MOM
Stronger water and electronic signal are all detected in montmorillonite.In the modified montmorillonite of PVPcoS, hydroxyl free is detected
Base signal and weaker aqueous electron signal.This illustrates that the presence of HDTMA protects aqueous electron not quenched by oxygen, therefore
Promote degradation and defluorinate of the aqueous electron to perfluorochemical.
Claims (10)
1. a kind of method for synthesizing mixed and modified organo montmorillonite, comprising the following steps:
S1, using poly- 4-vinylpridine styrene to montmorillonite carry out it is organically-modified, obtain poly- 4-vinylpridine benzene second
Alkene modified montmorillonoid；
S2, it is taken off using cover phenylethene modified to poly- 4-vinylpridine obtained in step S1 of cetyl trimethyl ammonia bromide
Soil progress is organically-modified again, obtains mixed and modified organo montmorillonite.
2. a kind of method for synthesizing mixed and modified organo montmorillonite according to claim 1, it is characterised in that: the step
The total amount of poly- 4-vinylpridine styrene in S1 is consistent with the cation exchange total amount of montmorillonite.
3. a kind of method for synthesizing mixed and modified organo montmorillonite according to claim 1, it is characterised in that: the step
The total amount of cetyl trimethyl ammonia bromide in S2 is less than the cation exchange total amount of montmorillonite.
4. a kind of method for synthesizing mixed and modified organo montmorillonite according to claim 1, it is characterised in that: the step
The total amount of cetyl trimethyl ammonia bromide in S2 is 0.6~0.8 times of the cation exchange total amount of montmorillonite.
5. a kind of method for synthesizing mixed and modified organo montmorillonite according to claim 1, it is characterised in that: the step
Organically-modified specific steps are carried out in S1 to montmorillonite are as follows:
(1) na montmorillonite is distributed in water, obtains montmorillonite dispersion solution；
(2) the poly- 4-vinylpridine styrene solution of acidification, stirring are added into the montmorillonite of step (1) dispersion solution；
(3) it is centrifuged after stirring in step (2), discards supernatant liquid, obtain sediment；
(4) sediment obtained in step (3) is washed with water, the phenylethene modified montmorillonite of poly- 4-vinylpridine is obtained.
6. a kind of method for synthesizing mixed and modified organo montmorillonite according to claim 1, it is characterised in that: the step
Organically-modified specific steps are carried out again in S2 to the phenylethene modified montmorillonite of poly- 4-vinylpridine are as follows:
(1) the phenylethene modified montmorillonite of poly- 4-vinylpridine is distributed in water, obtains poly- 4-vinylpridine styrene
Modified montmorillonoid disperses solution；
(2) cetyl trimethyl is added into the phenylethene modified montmorillonite dispersion solution of the poly- 4-vinylpridine of step (1)
Ammonium bromide solution, stirring；
(3) it is centrifuged after stirring in step (2), discards supernatant liquid, obtain sediment；
(4) sediment obtained in step (3) is washed with water, mixed and modified organo montmorillonite is obtained.
7. a kind of mixed and modified organo montmorillonite, it is characterised in that: mixed using synthesis described in claim 1~6 any one
The method for closing modified organo montmorillonite synthesizes to obtain.
8. a kind of method using mixed and modified organo montmorillonite efficient degradation perfluorochemical, comprising the following steps:
(i) heteroauxin solution and perfluorochemical solution are uniformly mixed；
(ii) mixed and modified organo montmorillonite as claimed in claim 7 is distributed in the mixed solution of step (i), is reacted
Solution；
(iii) light reaction is carried out with degrading perfluorinated compound to reaction solution obtained in step (ii) using mercury lamp.
9. a kind of method of efficient degradation perfluorochemical according to claim 8, it is characterised in that: the step (ii)
It further include adjusting the pH value of reaction solution to 4.0~10.0.
10. a kind of method of efficient degradation perfluorochemical according to claim 8, it is characterised in that: the step
(iii) specific steps are as follows: it is transferred in crystal reaction tube after stirring reaction solution obtained in step (ii) 30 minutes,
Under aerobic environment, mercury lamp is immersed into reaction solution and carries out degradation reaction, reaction temperature is controlled at 25 ± 2 DEG C.
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