CN106423081B - Chitin modified sodium bentonite, preparation method and application - Google Patents
Chitin modified sodium bentonite, preparation method and application Download PDFInfo
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- CN106423081B CN106423081B CN201610976257.XA CN201610976257A CN106423081B CN 106423081 B CN106423081 B CN 106423081B CN 201610976257 A CN201610976257 A CN 201610976257A CN 106423081 B CN106423081 B CN 106423081B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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Abstract
The invention discloses a kind of chitin modified sodium bentonite, preparation method and applications, belong to modified bentonite adsorbent and water-treatment technology field.The present invention is in chemical reactive synthesis method, by chloroacetic bridge linking effect by chitosan loaded on sodium bentonite surface, i.e., is first carried out to natural sodium bentonite with monoxone organically-modified, then obtains chitin modified sodium bentonite with chitosan reaction after alkalization.Compare traditional mechanical mixture, chemical modification increases the degree of roughness of material, O, N atom number of chemisorption can be generated by increasing, increase adsorption surface area, so that modified sodium bentonite has superior absorption property and hot property, 99.8% is reached as high as to the adsorption rate of chrome azurol S under room temperature, can be used as adsorbent for the wastewater treatment containing color developing agent or dyestuff.
Description
Technical field
The present invention relates to a kind of chitin modified sodium bentonites, also relate to the preparation side of the modification sodium bentonite
Method and application belong to modified bentonite adsorbent and water-treatment technology field.
Background technology
Chitosan (Chitosan) is also known as chitosan, and the chitin (Chitin) being widely present by nature is through de-
Acetyl effect obtains, and chemical name is Chitosan (1-4) -2- amino-B-D glucose.Chitosan is a kind of alkalinity sugar, tool
There are good adsorptivity, film forming, permeability, fibre forming property, hygroscopicity and moisture retention, is applied in fields such as medicine, chemical industry, food
Extensively.Contain a large amount of free amine group and hydroxyl in chitosan molecule, it can be with the formation such as heavy metal ion, rare earth ion
Stable chelate can be used for the processing of contents of many kinds of heavy metal ion waste water.But the density of chitosan is smaller, is in suspend in water
State is not easy to solution and is sufficiently mixed.
Bentonite is a kind of with montmorillonite clay mineral as main component, is in layer structure, large specific surface area, adsorptivity
Can be good, there is potential application prospect in waste water, exhaust-gas treatment.But hygroscopic expansion and dispersion are outstanding in water for bentonite
It is floating, and solid- liquid separation speed is slow, flocculation dewatering effect is poor, this limits its application to a certain extent.Also, single swelling
Soil is undesirable to the removal effect of pollutant, though and chitosan treatment effect is preferable, cost is higher, therefore less individually makes
With.Have document report to be combined chitosan for wastewater treatment with bentonite, however chitosan is a kind of macromolecule polysaccharide,
Molecular weight directly mixes chitosan solution with bentonite mostly 100,000 or more, it is difficult to make the two fully reaction or absorption, thus
The absorption property of material cannot be effectively improved.The patent of invention of publication No. CN101475187A discloses a kind of chitosan swelling
Soil is that the bentonite suspension of high degree of dispersion is added in the dilute acetic acid solution of chitosan to be mixed to prepare.Compare chitosan
Solution is simply mixed with bentonitic, and bentonitic interlamellar spacing can be expanded to 1.9nm by this method, and chitosan is made to can smoothly enter into
Between bentonite bed, to improve the absorption property of material.But its absorption specific aim is still to be improved.
Chrome azurol S (abbreviation CAS) is a kind of triphenylmethane dye, is red-brown powder, is dissolved in water (being in brown color), micro-
Ethyl alcohol (being in rufous) is dissolved in be widely used in experimental study as a kind of highly sensitive color developing agent or complex compound indicator, change
The fields such as work, environmental monitoring.Increase however as its application, more and more chromazurine waste liquids are discharged into water body, to environmental ecology
Balance produces adverse effect.Currently, having caused the very big concern of people to the processing of chromazurine waste liquid.Publication No.
The patent of invention of CN103464113A discloses a kind of composite modified bentonite, is prepared by following steps：1) sodium base is swollen
Profit soil is dispersed in water, and is made into the suspension A of concentration 10%；2) it under 60~80 DEG C of water bath conditions, is slowly added in suspension A
1~4mL ethylenediamines, it is stirring while adding, obtain mixed liquid B；3) 1~2g chitosans are weighed, the acetic acid of mass concentration 2% is dissolved in
In solution, it is made into the chitosan solution C of concentration 1%~2%；Under 80 DEG C of water bath conditions, chitosan solution C is slowly dropped to mixed
It closes in liquid B, loads 2h；Cooling, washing, filtering, take filtration cakes torrefaction, be ground up, sieved to get.It is original that this method, which is with bentonite,
Material, heavy metal chelant ethylenediamine and chitosan are prepared by modifying agent reaction, and wherein ethylenediamine can increase original soil interlamellar spacing, help
Between chitosan enters bentonite bed and it is supported on its surface, so as to improve material to the absorption property of heavy metal, but is not had
Processing for waste water from dyestuff.
Invention content
The object of the present invention is to provide a kind of chitin modified sodium bentonites, exist to the adsorption rate of chrome azurol S in waste water
98% or more.
Meanwhile the present invention also provides a kind of preparation methods of chitin modified sodium bentonite.
Finally, the present invention provides a kind of application of chitin modified sodium bentonite in the treatment of waste water again.
In order to achieve the goal above, the technical solution adopted in the present invention is：
Chitin modified sodium bentonite, is prepared by following steps：
1) sodium bentonite is scattered in isopropanol, one in the concentrated sulfuric acid and monoxone, chloropropionic acid is added after mixing
Kind, it is heated to reflux to the reaction was complete, isolates product, drying for standby；
2) chitosan is scattered in isopropanol, product in step 1) is added after quaternization, it is anti-at 30~50 DEG C
Answer 5~7h to get.
Isopropanol is reaction dissolvent in step 1), is used as tertiary alcohols chemistries torpescence, polarity is small, solvation
Act on it is weak, it is small to the active inhibiting effect of negative oxygen ion, be not easy to cause side reaction, to make esterification fully carry out, obtain
Higher degree of substitution.70~120mL isopropanols are added per 0.5g sodium bentonites.
Sodium bentonite and chloroacetic mass ratio are 1 in step 1):9~11.
The effect of the concentrated sulfuric acid is to be catalyzed the esterification of sodium alkoxide and carboxylic acid in step 1), and 3 are added per 0.5g sodium bentonites
~4 drop concentrated sulfuric acids.Monoxone is preferably added to monoxone with chloropropionic acid, cheap, more common.
The temperature reacted in step 1) is 70~90 DEG C, 4~6h of time.
The method that suction filtration can be used is detached in step 1), and solid is collected after suction filtration, it is dry (dry such as at 50~70 DEG C
4~6h), you can.
The same step 1) of the effect of isopropanol in step 2).Dosage is that 70~120mL isopropanols are added per 0.5g chitosans.
In step 2) quaternization be hydroxyl on chitosan reacted with highly basic generation chitosan alkali (reaction principle referring to
《The progress of Chemical Modifying of Chitosan》, leather chemical industry, 2005).By taking NaOH as an example, reaction synthesis schematic diagram is shown in Fig. 1.Alkalization
Reaction finishes, and chitosan alkali reacts the modified sodium bentonite of generation with product in step 1) again.NaOH, KOH etc. can be used in highly basic,
180~220g/L of concentration.The temperature of quaternization is 40~50 DEG C, 50~70min of time.
The mass ratio of chitosan and product in step 1) is 1 in step 2):0.8~1.2.
Second step reaction finishes in step 2), and chitin modified sodium bentonite is washed with isopropanol, is dried (such as after filtering
Dry 3~5h at 50~70 DEG C), you can.
The preparation method of chitin modified sodium bentonite, includes the following steps：
1) sodium bentonite is scattered in isopropanol, monoxone and the concentrated sulfuric acid is added after mixing, is heated to reflux to reaction
Completely, product, drying for standby are isolated；
2) chitosan is scattered in isopropanol, product in step 1) is added after quaternization, it is anti-at 30~50 DEG C
Answer 5~7h to get.
70~120mL isopropanols are added per 0.5g sodium bentonites in step 1).
Sodium bentonite and chloroacetic mass ratio are 1 in step 1):9~11.The concentrated sulfuric acid is the catalyst of esterification,
3~4 drop concentrated sulfuric acids are added per 0.5g sodium bentonites.
The temperature reacted in step 1) is 70~90 DEG C, 4~6h of time.
The method that suction filtration can be used is detached in step 1), is dried after suction filtration, you can.
In step 2) quaternization be chitosan on hydroxyl reacted with highly basic generation chitosan alkali, chitosan alkali again with step
It is rapid 1) in product reaction generate modified sodium bentonite.NaOH, KOH etc., 180~220g/L of concentration can be used in highly basic.Alkalization is anti-
The temperature answered is 40~50 DEG C, 50~70min of time.
The mass ratio of chitosan and product in step 1) is 1 in step 2):0.8~1.2.
Second step reaction finishes in step 2), and chitin modified sodium bentonite is washed with isopropanol, dry after filtering, i.e.,
It can.
Application of the above-mentioned chitin modified sodium bentonite in the wastewater treatment containing color developing agent or dyestuff.Specifically,
Contain the dyestuffs such as chrome azurol S in waste water.
Beneficial effects of the present invention：
The present invention is in the method for chemical reactive synthesis, by chloroacetic bridge linking effect by chitosan loaded in Na-bentonite
Native surface first carries out natural sodium bentonite with monoxone organically-modified then swollen with the sodium base after chitin modified acidification
Profit soil, obtains chitin modified sodium bentonite.Traditional mechanical mixture is compared, chemical modification can increase the coarse journey of material
Degree increases O, N atom number for generating chemisorption, increases adsorption surface area, so that modified sodium bentonite is had more excellent
Absorption property and hot property.Chitin modified sodium bentonite reaches as high as 99.8% to the adsorption rate of chrome azurol S at normal temperatures,
Adsorbent be can be used as the wastewater treatment containing color developing agent or dyestuff.
The preparation process of chitin modified sodium bentonite is simple, easy to operate in the present invention, and reaction condition is mild and former
Material is easy to get, and is suitable for scale industrial production and application.
Description of the drawings
Fig. 1 is that the reaction of chitin modified sodium bentonite in the present invention synthesizes schematic diagram；
The infrared spectrum of Fig. 2 sodium bentonites, chloroethene acidification sodium bentonite and modified sodium bentonite；
Fig. 3 is the thermogravimetric curve of sodium bentonite and modified sodium bentonite；
Fig. 4 is the scanning electron microscope (SEM) photograph of sodium bentonite and modified sodium bentonite.
Specific implementation mode
Only invention is further described in detail for following embodiments, but does not constitute any limitation of the invention.
Embodiment 1
Chitin modified sodium bentonite, is prepared by following steps：
1) preparation of intermediate product
0.5g sodium bentonites are scattered in 70mL isopropanols, 30min is stirred, 5g monoxones are added and 3 drops are dense
Sulfuric acid, back flow reaction 5h at 80 DEG C are filtered, and collect solid, and dry 4h is spare at 60 DEG C；
2) preparation of modified sodium bentonite
0.5g chitosans are scattered in 70mL isopropanols, the KOH aqueous solutions of 1mL concentration 200g/L are added, are stirred,
And warming-in-water is to 40 DEG C, quaternization 70min；Product in 0.5g steps 1) is added, is stirred, and the constant temperature at 40 DEG C
React 6h, reaction finishes, and product is washed with isopropanol, filter 23, at 60 DEG C dry 4h to get.
Embodiment 2
Chitin modified sodium bentonite, is prepared by following steps：
1) preparation of intermediate product
0.5g sodium bentonites are scattered in 100mL isopropanols, 30min is stirred, 4.5g monoxones and 4 drops is added
The concentrated sulfuric acid, back flow reaction 6h at 70 DEG C are filtered, and collect solid, and dry 5h is spare at 50 DEG C；
2) preparation of modified sodium bentonite
0.5g chitosans are scattered in 70mL isopropanols, the KOH aqueous solutions of 1mL concentration 180g/L are added, are stirred,
And warming-in-water is to 45 DEG C, quaternization 1h；Product in 0.4g steps 1) is added, is stirred, and constant temperature is anti-at 30 DEG C
Answer 7h, reaction to finish, product is washed with isopropanol, filter 23 time, at 50 DEG C dry 5h to get.
Embodiment 3
Chitin modified sodium bentonite, is prepared by following steps：
1) preparation of intermediate product
0.5g sodium bentonites are scattered in 120mL isopropanols, 30min is stirred, 5.5g monoxones and 4 drops is added
The concentrated sulfuric acid, back flow reaction 4h at 90 DEG C are filtered, and collect solid, and dry 3h is spare at 70 DEG C；
2) preparation of modified sodium bentonite
0.5g chitosans are scattered in 70mL isopropanols, the KOH aqueous solutions of 1mL concentration 220g/L are added, are stirred,
And warming-in-water is to 50 DEG C, quaternization 50min；Product in 0.6g steps 1) is added, is stirred, and the constant temperature at 50 DEG C
React 5h, reaction finishes, and product is washed with isopropanol, filter 23, at 70 DEG C dry 3h to get.
Embodiment 4
Modification sodium bentonite 0.06g prepared by embodiment 1 is added to by the application of chitin modified sodium bentonite
In the chrome azurol S waste water of 10mL concentration 300mg/L (pH 6.0), separation is staticly settled after stirring and adsorbing 4h.Measure chromium in waste water
The removal rate of reddish black S is 99.2%.
Test example
1, the performance characterization of chitin modified sodium bentonite
The infrared spectrum analysis spectrogram of sodium bentonite, chloroethene acidification sodium bentonite and modified sodium bentonite is shown in Fig. 2,
Curve a is sodium bentonite in figure, and b is that chloroethene is acidified sodium bentonite, and c is modified sodium bentonite.In curve a, wave number
3626cm-1Place's absorption peak has apparent Al (OH)3(or A12O3·3H2O-OH stretching vibration absorption peaks)；Wave number 3449cm-1
For the absorption peak of-OH, 980cm-1And 1040cm-1The absorption peak at place is Al (OH)3(or A12O3·3H2O-OH deformation vibrations)；
521cm-1And 793cm-1Place's absorption peak is A1O6Octahedron vibration band.In curve b, wave number 3627cm-1And 3449cm-1It inhales at place
It is essentially unchanged to receive peak, 2919cm-1、2850cm-1The absorption peak for methyl, methylene occur shows that monoxone is sent out with sodium bentonite
Raw reaction synthesis first step product chloroethene is acidified sodium bentonite.In curve c, 1680cm-1The height of place's absorption peak is basically unchanged,
But width becomes larger, 1086~1045cm-1Place is Si-O-Si absorption peaks.Comparison curves a, b, c are also found that in curve a, b
In, wave number is respectively 3437cm-1、3449cm-1And 3627cm-1Place is respectively there are one absorption peak, and in curve c and at a peak,
For 3417cm-1, which is the merging of-OH and-NH vibration absorption peaks, shows that chitosan carries out the sodium bentonite after activation
Success is modified.
The thermal gravimetric analysis curve of sodium bentonite and modified sodium bentonite is shown in Fig. 3, and a is sodium bentonite in figure, and b is to change
Property sodium bentonite.Sodium bentonite before modified only has distant weightlessness in 31~70 DEG C of temperature ranges, for institute
Containing losing for a small amount of moisture.And modified sodium bentonite has clearly in 32~84 DEG C and 245~290 DEG C of temperature ranges
Weightlessness, the wherein first stage is that contained humidity losing, and second stage is weightless caused by chitosan chain oxidative degradation.
It can also be seen that the hot property of modified sodium bentonite is obviously improved than before by the collection of illustrative plates comparison after before modified.
The scanning electron microscope (SEM) photograph of sodium bentonite and modified sodium bentonite is shown in Fig. 4, and a is sodium bentonite in figure, and b is to be modified
Sodium bentonite.There are larger difference, modified sodium bentonite to have obviously by the appearance form both known to electron microscopic picture
Irregular laminated structure, degree of roughness and fluffy degree increase compared with sodium bentonite, and between slab-like set block also
Clip some thinner powdery little particles.Modified sodium bentonite surface has more loose lamella to stack, and shows chitosan
Expand material internal hole, hole number increases and more coarse, and material specific surface area increases, and is conducive to carrying for absorption property
It is high.The variation of material appearance pattern shows that chitosan has successfully been modified sodium bentonite in electron microscope.
2, adsorption cleaning of the chitin modified sodium bentonite to chromazurine waste water
1) the chitin modified sodium bentonite for taking 0.1g sodium bentonites and embodiment 1 to prepare respectively, is added to concentration
In the chrome azurol S waste liquid (15mL) of 500mg/L (pH 6.0), separation is staticly settled at 20 DEG C after stirring and adsorbing 4h, takes upper layer clear
Liquid centrifuges 5min (rotating speed 50rpm), then takes supernatant liquor, using the concentration of chrome azurol S in determined by ultraviolet spectrophotometry clear liquid.
The results show that sodium bentonite does not adsorb chrome azurol S, and it is modified sodium bentonite and the adsorption rate of chrome azurol S is reached
99.6%, adsorbance 74.7mg/g.
2) the chitin modified sodium bentonite for taking 0.1g sodium bentonites and embodiment 2 to prepare respectively, is added to concentration
In the chrome azurol S waste liquid (15mL) of 500mg/L (pH 4.0), stirring and adsorbing 4h at 20 DEG C, the survey of separation of the supernatant and chrome azurol S
Method is determined with 1).The results show that sodium bentonite does not adsorb chrome azurol S, and it is modified suction of the sodium bentonite to chrome azurol S
Attached rate is up to 98.1%, adsorbance 73.6mg/g.
3) the chitin modified sodium bentonite for taking 0.08g sodium bentonites and embodiment 3 to prepare respectively, is added to concentration
In the chrome azurol S waste liquid (10mL) of 500mg/L (pH 6.0), stirring and adsorbing 1h at 20 DEG C, the survey of separation of the supernatant and chrome azurol S
Method is determined with 1).The results show that sodium bentonite does not adsorb chrome azurol S, and it is modified suction of the sodium bentonite to chrome azurol S
Attached rate is up to 99.8%, adsorbance 62.4mg/g.
Claims (3)
1. chitin modified sodium bentonite, it is characterised in that：It is prepared by following steps：
1）Sodium bentonite is scattered in isopropanol, monoxone and the concentrated sulfuric acid are added after mixing, is heated to reflux to the reaction was complete,
Isolate product, drying for standby；
2）Chitosan is scattered in isopropanol, step 1 is added after quaternization）Middle product, at 30 ~ 50 DEG C react 5 ~
7h to get；
Step 1）Middle sodium bentonite is 1 with chloroacetic mass ratio:9~11；
Step 1）The temperature of middle reaction is 70 ~ 90 DEG C, 4 ~ 6h of time；
Step 2）Middle quaternization is that the hydroxyl on chitosan reacts generation chitosan alkali with highly basic, and highly basic is NaOH or KOH；
Step 2）Middle chitosan and step 1）The mass ratio of middle product is 1:0.8~1.2.
2. the preparation method of chitin modified sodium bentonite, it is characterised in that：Include the following steps：
1）Sodium bentonite is scattered in isopropanol, monoxone and the concentrated sulfuric acid are added after mixing, is heated to reflux to the reaction was complete,
Isolate product, drying for standby；
2）Chitosan is scattered in isopropanol, step 1 is added after quaternization）Middle product, at 30 ~ 50 DEG C react 5 ~
7h to get；
Step 1）Middle sodium bentonite is 1 with chloroacetic mass ratio:9~11；
Step 1）The temperature of middle reaction is 70 ~ 90 DEG C, 4 ~ 6h of time；
Step 2）Middle quaternization is that the hydroxyl on chitosan reacts generation chitosan alkali with highly basic, and highly basic is NaOH or KOH；
Step 2）Middle chitosan and step 1）The mass ratio of middle product is 1:0.8~1.2.
3. application of the modified sodium bentonite in handling the waste water containing chrome azurol S as described in claim 1.
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| CN108057428A (en) * | 2017-12-26 | 2018-05-22 | 刘春丽 | A kind of modified material for handling heavy metal containing sewage and its preparation method and application |
| CN109337453A (en) * | 2018-10-24 | 2019-02-15 | 厦门理工学院 | A kind of environmental protection coating material and its preparation method and application |
| CN114849657B (en) * | 2022-04-27 | 2023-09-29 | 南昌市国昌环保科技有限公司 | Preparation of efficient amphiphilic chitosan-loaded bentonite adsorbent and application of efficient amphiphilic chitosan-loaded bentonite adsorbent in coking wastewater |
| CN115634668A (en) * | 2022-10-31 | 2023-01-24 | 同济大学 | Preparation and use methods of sodium bentonite-loaded chitosan heavy metal stabilizing agent |
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