CN109078609A - The preparation method and products obtained therefrom of a kind of porous silica silicon materials containing Pidolidone that can be adsorbed and fix zinc ion and application - Google Patents
The preparation method and products obtained therefrom of a kind of porous silica silicon materials containing Pidolidone that can be adsorbed and fix zinc ion and application Download PDFInfo
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- CN109078609A CN109078609A CN201810802421.4A CN201810802421A CN109078609A CN 109078609 A CN109078609 A CN 109078609A CN 201810802421 A CN201810802421 A CN 201810802421A CN 109078609 A CN109078609 A CN 109078609A
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- pidolidone
- porous silica
- zinc ion
- silicon materials
- silica silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The preparation method and products obtained therefrom of the invention discloses a kind of porous silica silicon materials containing Pidolidone and absorption and the application of immobilization zinc ion.This method is using butylamine as catalyst, using ethyl alcohol as cosolvent, under conditions of ethyl orthosilicate hydrolyzes in water, Pidolidone is added, the porous silica gel rubber material containing Pidolidone is prepared for using sol-gel method.Reaction system of the present invention is simple, carries out at normal temperature, and preparation cost is low, and Pidolidone is closely bonded with porous silica in resulting materials, and can not only adsorb zinc ion in water can also reduce the zinc ion immobilization of absorption it and be precipitated again, forms secondary pollution.
Description
Technical field
The present invention relates to a kind of preparations of porous silica silicon materials containing Pidolidone that can be adsorbed and fix zinc ion
Method and products obtained therefrom and application.
Background technique
Contain a large amount of metal ion in industrial wastewater, wherein zinc ion causes serious pollution to water body soil and endangers
Human health.The processing method of zinc ion mainly has chemical precipitation method, oxidation-reduction method, electrolysis method, membrane separation process, absorption at present
Method etc..But above-mentioned processing method, which exists, generates a large amount of solid waste, and higher cost can not secondary use, it is difficult to industrialization promotion
The problems such as use.Absorption method has broad application prospects because of the simple advantage at low cost of its easy recovery process.Wherein nanometer two
Because of its large specific surface area, the advantages that stable physicochemical properties and simple preparation method, is made silicon oxide adsorbing material extensively
With.But silica adsorbent material belongs to physical absorption to the absorption of zinc ion, adsorbed zinc ion adsorbent meet water again after
Zinc ion is easy to be precipitated, and generates secondary pollution, is not easy to carry out subsequent processing.
Summary of the invention
The present invention provides a kind of porous silica silicon materials containing Pidolidone to solve the deficiency of the above material
Preparation method.
The present invention is achieved by the following measures:
Using butylamine as catalyst, using ethyl alcohol as cosolvent, under the hydrolysising condition of water and ethyl orthosilicate, L- paddy ammonia is added
Acid is prepared for Pidolidone earth silicon material using sol-gal process.
The method of the present invention specific steps are as follows:
(1) obtained mixed solution is mixed evenly in water and ethyl alcohol in proportion；
(2) butylamine is added in above-mentioned mixed solution, continues to stir evenly；
(3) ethyl orthosilicate is added in above-mentioned homogeneous solution, is stirred to react；
(4) Pidolidone is added in the mixed liquor of above-mentioned steps (3), stirring to Pidolidone is dissolved, and milky to appear is muddy
It is turbid, stop stirring, stands gelation；
(5) after gel aging, it is placed in baking oven drying, obtains the porous silica silicon materials containing Pidolidone.
In the above method, the mixing time in step (1) and (2) is respectively 10min and 30min, the stirring of step (3)
Time is 1min, and step (5) ageing time is 1h, through 80oPidolidone silica dioxide gel can be obtained in C oven drying.
In above-mentioned experimentation, water: ethyl alcohol: butylamine: ethyl orthosilicate: the molar ratio of Pidolidone is 12.33:
30.37 : 1.67 : 1: 0.03~0.17。
Resulting materials of the present invention are the porous silica silicon materials containing Pidolidone, wherein contain glutamic acid 4.99 ~ 24.97%,
Specific surface area is 334 ~ 370 m2/ g, aperture are 1.58 ~ 3.0 nm, 0.43 ~ 0.84 cm of Kong Rongwei3/g。
By isothermal nitrogen adsorption test show be added Pidolidone after sample specific surface area and Pidolidone is not added
Porous silica obtained is compared and has dropped 49.7 ~ 54.6%, but porous silica made from the Pidolidone of Different adding amount
Silicon sample surface area is 334 ~ 370 m2/ g, variation are little；Test result is also shown that the macropore of sample after addition Pidolidone
It is obviously reduced.
The present invention also provides the applications that resulting materials are used to adsorb and fix the zinc ion in water, provide for wastewater treatment
Thinking.
Specific steps are as follows:
(1) the zinc ion solution for the use of configuration concentration after white vitriol dissolution being 20mg/L.
(2) above-mentioned material prepared is placed in the Zn of 20mg/L by 8 grams every liter2+In solution, concussion absorption 4 hours.
(3) material after absorption is placed in 80o3h is dried in C baking oven, is recycled.
Although the porous silica sample of the surface area ratio addition Pidolidone of the porous silica of Pidolidone is not added
Product are much larger, but the latter is 86.69 ~ 91.91% to the removal rate of zinc ion, the porous silica without adding Pidolidone
Removal rate is only 74.81%,.After the sample absorption zinc ion for more importantly adding Pidolidone, then dissolution rate is decreased obviously,
Zinc ion is adsorbed afterwards together with the carboxyl secure bond on Pidolidone, zinc ion thus by well be fixed on gel
In, it is not easy to be precipitated again and environmental pollution generates secondary pollution.
The utility model has the advantages that process of the present invention reaction condition is mild, it need to only carry out at room temperature, preparation flow is simple, raw
It produces at low cost；Pidolidone is closely bonded with silicon dioxide skeleton, is not easy nature isolation；Resulting materials not only adsorb zinc in waste water
Ion efficiency is high, and zinc ion immobilization can be reduced it and be precipitated again and generate secondary pollution.
Detailed description of the invention
Fig. 1 is comparative example, the porous silica silicon materials prepared by embodiment 1 without Pidolidone, contains Pidolidone
Porous silica silicon materials and embodiment 1 adsorb zinc after the infrared spectrogram of sample and raw material Pidolidone.
Specific embodiment
Invention is further described in detail for specific embodiment with reference to the accompanying drawing, and following embodiment is only used for more clear
Illustrate to Chu the technical solution of this patent, and not intended to limit the protection scope of the present invention.
Sample N is measured using isothermal nitrogen adsorption instrument (Autosorb iQ-C)2Adsorption isothermal curve, according to BET model
Specific surface area is calculated, according to BJH model calculated hole diameters distribution curve, the value of curve highest point is taken as aperture.Using zincon point
Light photometer measuring method detects initial C0 and remaining zinc ion concentration C1 zinc ion concentration.It is dense that remaining zinc ion is obtained by standard curve
C1 is spent, removal rate is calculated by formula W=(C0-C1)/C0*100%.
Adsorption sample after taking drying, is placed in 50ml distilled water, shakes 4h, is detected by zincon spectrophotometer method
Zinc ion concentration C2 is dissolved out, dissolution rate is measured by the calculating of formula T=C2/ (C0-C1) * 100%.
The content of Pidolidone is obtained by thermogravimetric analysis calculated result in sample.
The following are specific embodiments:
Example 1
(1) 10 min are mixed in 12.33mol water and 30.37mol ethyl alcohol, uniform mixed solution is made；
(2) 1.67mol butylamine is added in above-mentioned mixed solution, continues to stir 30 min；
(3) 1mol ethyl orthosilicate is added in the homogeneous solution of above-mentioned (2), is stirred to react 1 min；
(4) 0.1mol Pidolidone is added in the mixed liquor of above-mentioned (3), stirring to Pidolidone is dissolved, milky to appear
Muddiness stops stirring, stands；
(5) after solution age 1h, 80 are placed inoC baking oven dries 4h, obtains the silicon materials of porous silica containing Pidolidone.
Show that the sample specific surface area is 370 m through isothermal nitrogen adsorption detection20.84 cm of/g, Kong Rongwei3/ g, aperture are
3nm。
The 0.4g sample is taken to be placed in the Zn of 50ml 0.8mg/L2+In solution, zinc ion absorption is gone in concussion absorption 4 hours
Except rate is 91.91%.Sample 80 after absorptionoC dries 3h, is placed in 50ml distilled water, measures Zn after shaking 4h2+Dissolution rate is
8.80%。
Example 2
(1) 10 min are mixed in 12.33mol water and 30.37mol ethyl alcohol in proportion, uniform mixed solution is made；
(2) 1.67mol butylamine is added in above-mentioned mixed solution, continues to stir 30 min；
(3) 1mol ethyl orthosilicate is added in above-mentioned homogeneous solution, is stirred to react 1 min；
(4) 0.07mol Pidolidone is added in above-mentioned mixed liquor, stirring to Pidolidone is dissolved, and milky to appear is muddy
It is turbid, stop stirring, stands；
(5) after solution age 1h, 80 are placed inoC baking oven dries 4h, obtains Pidolidone porous silica silicon materials.
Show that the sample specific surface area is 345 m through isothermal nitrogen adsorption detection2/ g, hole hold 0.57 cm3/ g, aperture are
2.14nm。
The 0.4g sample is taken to be placed in the Zn of 50ml 0.8mg/L2+In solution, concussion is adsorbed 4 hours, and eliminating rate of absorption is
86.69%。
Embodiment 3
(1) 10 min are mixed in 12.33mol water and 30.37mol ethyl alcohol in proportion, uniform mixed solution is made；
(2) 1.67mol butylamine is added in above-mentioned mixed solution, continues to stir 30 min；
(3) 1mol ethyl orthosilicate is added in above-mentioned homogeneous solution, is stirred to react 1 min；
(4) 0.17mol Pidolidone is added in above-mentioned mixed liquor, stirring to Pidolidone is dissolved, and milky to appear is muddy
It is turbid, stop stirring, stands；
(5) after solution age 1h, 80 are placed inoC baking oven dries 4h, obtains Pidolidone porous silica silicon materials.
Show that the sample specific surface area is 334 m through isothermal nitrogen adsorption detection2/ g, hole hold 0.43 cm3/ g, aperture are
1.58nm。
Comparative example
(1) obtained mixed solution is mixed evenly in 12.33mol water and 30.37mol ethyl alcohol in proportion；
(2) 1.67mol butylamine is added in above-mentioned mixed solution, continues to stir evenly；
(3) 1mol ethyl orthosilicate is added in above-mentioned homogeneous solution, is stirred to react, occur muddy, stopping stirring to solution,
It stands；
(4) after solution age 1h, 80 are placed inoC baking oven dries 4h, obtains porous silica silicon materials.
The sample is free of Pidolidone, show that the sample specific surface area is 736 m through isothermal nitrogen adsorption detection2/ g, hole
Diameter is 30nm.
The 0.4g sample is taken to be placed in the Zn of 50ml 0.8mg/L2+In solution, concussion absorption 4 hours, to zinc ion adsorption rate
It is 74.81%.Sample 80 after absorptionoC dries 3h, is placed in 50ml distilled water, measures Zn after shaking 4h2+Dissolution rate is 65.91%.
Fig. 1 is the ammonia of paddy containing L- of the porous silica silicon materials without Pidolidone of comparative example preparation, the preparation of embodiment 1
Acid porous silica silicon materials, embodiment 1 adsorb zinc after sample and raw material Pidolidone infrared spectrogram.As it can be seen that
Compared to the infrared spectroscopy of Pidolidone raw material, in adding porous silica silicon materials made from Pidolidone, Pidolidone exists
1280 to 1560 cm-1Between the obvious red shift of characteristic peak, show that Pidolidone is chemically bonded with silica.And add L-
Porous silica silicon materials made from glutamic acid less add 1630 cm of porous silica silicon materials made from Pidolidone-1Place
Si-OH base absorption peak obviously weakens, while corresponding carboxyl absorption peak is not compared to pure Pidolidone herein for Pidolidone
There is enhancing, the Si-OH base junction of the carboxyl and silica that show Pidolidone is closed.After adsorbing zinc ion, containing the more of Pidolidone
1280 to 1630 cm of hole earth silicon material-1Between characteristic peak obviously weaken or disappear, show zinc ion and Pidolidone
Bonding, to realize zinc ion immobilization.
Claims (8)
1. a kind of preparation method of the porous silica silicon materials containing Pidolidone, the specific steps of which are as follows:
Obtained mixed solution is mixed evenly in water and ethyl alcohol in proportion；
Butylamine is added in above-mentioned mixed solution, continues to stir evenly；
Ethyl orthosilicate is added in above-mentioned homogeneous solution, is stirred to react；
Pidolidone being added in the mixed liquor of above-mentioned steps (3), stirring to Pidolidone is dissolved, milky turbidity to appear,
Stop stirring, stands gelation；
After gel aging, it is placed in baking oven drying, obtains the porous silica silicon materials containing Pidolidone.
2. according to the method described in claim 1, it is characterized in that: water: ethyl alcohol: butylamine: ethyl orthosilicate: mole of Pidolidone
Than being 12.33: 30.37: 1.67: 1:0.03 ~ 0.17.
3. according to the method described in claim 1, it is characterized in that: the mixing time in step (1) and (2) be respectively 10min and
30min。
4. according to the method described in claim 1, it is characterized in that: step (3) mixing time is 1min.
5. according to the method described in claim 1, it is characterized in that: step (5) ageing time is 1h.
6. according to the method described in claim 1, it is characterized in that: drying temperature is 80oC, time 4h.
7. it is a kind of by the resulting porous silica silicon materials containing Pidolidone of claim 1 the method, it is characterized in that: described
Material contains glutamic acid 4.99 ~ 24.97%, and specific surface area is 334 ~ 370 m2/ g, aperture be 1.58 ~ 3.0 nm, Kong Rongwei 0.43 ~
0.84 cm3/g。
8. the porous silica silicon materials described in a kind of claim 7 containing Pidolidone are in terms of adsorbing with immobilization zinc ion
Using.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112467234A (en) * | 2020-12-24 | 2021-03-09 | 国家纳米科学中心 | Electrolyte for zinc secondary battery and preparation method and application thereof |
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