CN106215860B - One kind synthesizing fluorine ion absorber ZrO by phonochemistry method2-Al2O3The method of/GO - Google Patents

One kind synthesizing fluorine ion absorber ZrO by phonochemistry method2-Al2O3The method of/GO Download PDF

Info

Publication number
CN106215860B
CN106215860B CN201610632383.3A CN201610632383A CN106215860B CN 106215860 B CN106215860 B CN 106215860B CN 201610632383 A CN201610632383 A CN 201610632383A CN 106215860 B CN106215860 B CN 106215860B
Authority
CN
China
Prior art keywords
zro
fluorine ion
ethyl alcohol
phonochemistry
zrocl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610632383.3A
Other languages
Chinese (zh)
Other versions
CN106215860A (en
Inventor
陈萍华
蒋华麟
田磊
刘军
周敬松
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanchang Hangkong University
Original Assignee
Nanchang Hangkong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanchang Hangkong University filed Critical Nanchang Hangkong University
Priority to CN201610632383.3A priority Critical patent/CN106215860B/en
Publication of CN106215860A publication Critical patent/CN106215860A/en
Application granted granted Critical
Publication of CN106215860B publication Critical patent/CN106215860B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0211—Compounds of Ti, Zr, Hf
    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds

Abstract

The present invention discloses a kind of by phonochemistry method synthesis fluorine ion absorber ZrO2‑Al2O3The method of/GO, this method is by ZrOCl2 .8H2O、F127、AlCl3.6H2O、MgSO4Dissolving forms colourless transparent solution in ethanol, after adding graphene oxide, after phonochemical reaction occurs by sonic oscillation, and separating, washing and drying and processing, obtained ZrO2‑Al2O3/ GO crude products flow back in Soxhlet extractor, and reaction product separating, washing and drying and processing again obtain fluorine ion absorber ZrO2‑Al2O3/GO.Reaction time of the invention is short, easy to operate, and efficiently, energy consumption is few, at low cost, gained ZrO2‑Al2O3/ GO products have higher Adsorption effect to fluorine ion, can be used for the improvement of a wide range of fluoride pollution waste water.

Description

One kind synthesizing fluorine ion absorber ZrO by phonochemistry method2-Al2O3The method of/GO
Technical field
The present invention relates to one kind synthesizing fluorine ion absorber ZrO by phonochemistry method2-Al2O3The method of/GO, particularly belongs to Phonochemistry technical field.
Background technology
Influence of the ultrasonication to compound is found in nineteen twenty-seven earliest, since then, sonic oscillation effect just by with In the synthesis of organic matter and inorganic matter, it is referred to as phonochemistry synthetic method.In comparison, ultrasonic wave is more safer than microwave, because Its frequency is lower.Nowadays, for ultrasonic wave as effective energy source, it is chemical anti-to accelerate to change the chemical property of substrate The effect answered is widely known.When ul-trasonic irradiation is in aqueous media, due to the sound wave expansion and compression lasting to solution Ringing generates continue alternate positive/negative-pressure in the solution.This behavior causes to generate a series of minute bubbles, these are stingy Bubble is filled with vaporized steam.These minute bubbles are the accumulations of sound wave energy in radiative process, therefore these minute bubbles meetings Rapidly expansion reaches a critical point, before they cave in, it may appear that of short duration hole.When caving in, each minute bubbles are One heat generating spot, can generate very high temperature（5500℃）And pressure（Thousands of a atmospheric pressure）, chemical bond can be interrupted, is generated Free radical, to cause a series of phonochemical reaction.Phonochemistry synthetic method has the characteristics that the time is short, consumes energy less, is efficient, It receives significant attention.
Fluorine ion is a kind of serious pollutant, and excessive fluorine can cause organism serious harm.At present in the world There are Fluorine of Drinking Water excessive problems in many places, administer the focus that Fluorine of Drinking Water pollution has become current environment pollution control Problem.For absorption method because its is at low cost, easy to operate become applies to obtain one of most commonly used fluoride pollution Treatment process.Absorption at present The preparation method of agent mainly has the precipitation method, and hydro-thermal method, calcination method etc., often there is reaction time length, energy consumption are big, cumbersome The problems such as.In order to solve this series of problems, the preparation method for developing new adsorbent is imperative.
Under this technical background, we have developed a kind of by phonochemistry method synthesis fluorine ion absorber ZrO2-Al2O3/GO Method.Need to only ultrasonic wave be utilized to act on 5min to raw material, so that it may which rush brings it about chemical reaction and generates product.The method letter Less, products obtained therefrom has efficient Adsorption performance to fluorine ion for single, efficient, energy consumption.
Invention content
The purpose of the present invention is to provide one kind synthesizing fluorine ion absorber ZrO by phonochemistry method2-Al2O3The side of/GO Method, this method comprises the following steps：
（1）By ZrOCl2 .8H2O、F127（Polyoxyethylene/polyoxypropylene/polyoxyethylene amphiphilic block copolymer）、 AlCl3.6H2O、MgSO4Dissolving forms colourless transparent solution in ethanol；The ZrOCl2 .8H2O and AlCl3.6H2Mole of O Than being 1：2 to 1：0.5.
（2）Graphene oxide is added into the solution obtained by step (1), after phonochemical reaction occurs by ultrasonic wave, then Mechanical agitation 15min；The graphene oxide and stepZrOCl2 .8H2The mass ratio of O is 1:2.4.
（3）It is 1 that volume ratio is added into step (2) products therefrom：5 deionized water and the mixed liquor of ethyl alcohol, continue to stir Suction filtration separation is carried out after mixing 1h, then each washing of gained filter cake ethyl alcohol, deionized water alternating 3 times is dried overnight, i.e., in 50 DEG C Obtain ZrO2-Al2O3/ GO crude products.
(4) ZrO2-Al2O3/ GO crude products are 150 with volume ratio in Soxhlet extractor:2.3 ethyl alcohol and concentrated hydrochloric acid Mixed liquor flow back at 95 DEG C 48h, followed by filter separation, each washing of gained filter cake ethyl alcohol, deionized water alternating 3 times, It is dried overnight at 50 DEG C again, obtains ZrO2-Al2O3/GO。
In step (2), the ultrasonic power that the phonochemical reaction uses is 250W, and the ultrasonication time is 5min.
Advantages of the present invention：Reaction time is short, easy to operate, and efficiently, energy consumption is few, and at low cost, products obtained therefrom is to fluorine ion With higher Adsorption effect, it can be used for the improvement of a wide range of fluoride pollution waste water.
Description of the drawings
Fig. 1 is fluorine ion absorber ZrO obtained by the embodiment of the present invention 12-Al2O3Adsorption isotherms of/the GO to fluorine ion Figure.
Specific implementation mode
The embodiment of the present invention is described in further detail below, but the present embodiment is not intended to restrict the invention.
Embodiment 1
Graphene oxide is prepared in the method for the regular oxidation graphite of report（GO）.
By 0.48g ZrOCl2 .8H2O、0.1 g F127、0.72g AlCl3.6H2O、0.36g MgSO4It is dissolved in 100 ml second Alcohol forms clear solution（ZrOCl2 .8H2O and AlCl3.6H2The molar ratio of O is 1:2）.0.2 g GO are added later, with 250W's 5 min of power ultrasonic action-reaction, then 15 min of mechanical agitation.Then it is slowly added into the volume of 100 ml deionized waters and ethyl alcohol Than being 1:5 mixed solution continues after stirring 1 h, filters separation solid.Obtained solid is each with ethyl alcohol, deionized water alternating Washing 3 times, then 50 DEG C it is drying over night, obtain ZrO2-Al2O3/ GO crude products.
By the ZrO of gained2-Al2O3/ GO crude products Soxhlet extractor is in the mixed of 150 ml ethyl alcohol and 2.30 ml concentrated hydrochloric acids In solution, 95 DEG C of 48 h of reflux.Each washing of taking-up ethyl alcohol, deionized water alternating 3 times after having reacted, then 50 DEG C of dryings one Evening is to get final product.It is 57.4mg/g to the maximal absorptive capacity of fluorine ion.
Embodiment 2
Graphene oxide is prepared in the method for the regular oxidation graphite of report（GO）.
By 0.48g ZrOCl2 .8H2O、0.1 g F127、0.36g AlCl3.6H2O、0.36g MgSO4It is dissolved in 100 ml second Alcohol forms clear solution（ZrOCl2 .8H2O and AlCl3.6H2The molar ratio of O is 1:1）.0.2 g GO are added later, with 250W's 5 min of power ultrasonic action-reaction, then 15 min of mechanical agitation.Then it is slowly added into the volume of 100 ml deionized waters and ethyl alcohol Than being 1:5 mixed solution continues after stirring 1 h, filters separation solid.Obtained solid is each with ethyl alcohol, deionized water alternating Washing 3 times, then 50 DEG C it is drying over night, obtain ZrO2-Al2O3/ GO crude products.
By the ZrO of gained2-Al2O3/ GO crude products Soxhlet extractor is in the mixed of 150 ml ethyl alcohol and 2.30 ml concentrated hydrochloric acids In solution, 95 DEG C of 48 h of reflux.Each washing of taking-up ethyl alcohol, deionized water alternating 3 times after having reacted, then 50 DEG C of dryings one Evening is to get final product.It is 57.3mg/g to the maximal absorptive capacity of fluorine ion.
Embodiment 3
Graphene oxide is prepared in the method for the regular oxidation graphite of report（GO）.
By 0.48g ZrOCl2 .8H2O、0.1 g F127、0.18g AlCl3.6H2O、0.36g MgSO4It is dissolved in 100 ml second Alcohol forms clear solution（ZrOCl2 .8H2O and AlCl3.6H2The molar ratio of O is 1:0.5）.0.2 g GO are added later, with 250W 5 min of power ultrasonic action-reaction, then 15 min of mechanical agitation.Then it is slowly added into the body of 100 ml deionized waters and ethyl alcohol Product is than being 1:5 mixed solution continues after stirring 1 h, filters separation solid.Obtained solid is replaced with ethyl alcohol, deionized water Each washing 3 times, then 50 DEG C it is drying over night, obtain ZrO2-Al2O3/ GO crude products.
By the ZrO of gained2-Al2O3/ GO crude products Soxhlet extractor is in the mixed of 150 ml ethyl alcohol and 2.30 ml concentrated hydrochloric acids In solution, 95 DEG C of 48 h of reflux.Each washing of taking-up ethyl alcohol, deionized water alternating 3 times after having reacted, then 50 DEG C of dryings one Evening is to get final product.It is 102mg/g to the maximal absorptive capacity of fluorine ion.

Claims (2)

1. a kind of synthesizing fluorine ion absorber ZrO by phonochemistry method2-Al2O3The method of/GO, it is characterised in that：The side Method includes the following steps：
（1）By ZrOCl2 .8H2O、F127、AlCl3.6H2O、MgSO4Dissolving forms colourless transparent solution in ethanol；Described ZrOCl2 .8H2O and AlCl3.6H2The molar ratio of O is 1：2 to 1：0.5；
（2）To step（1）Graphene oxide is added in the solution of gained, after phonochemical reaction occurs by ultrasonic wave, then machinery Stir 15min；The graphene oxide and stepZrOCl2 .8H2The mass ratio of O is 1:2.4；
（3）To step（2）It is 1 that volume ratio is added in products therefrom：5 deionized water and the mixed liquor of ethyl alcohol continue to stir 1h After carry out suction filtration separation, each washing of gained filter cake ethyl alcohol, deionized water alternating 3 times, be then dried overnight in 50 DEG C to get ZrO2-Al2O3/ GO crude products；
（4）ZrO2-Al2O3/ GO crude products are 150 with volume ratio in Soxhlet extractor:The mixing of 2.3 ethyl alcohol and concentrated hydrochloric acid Liquid flows back 48h at 95 DEG C, followed by filters separation, each washing of gained filter cake ethyl alcohol, deionized water alternating 3 times, then 50 It is dried overnight at DEG C, obtains ZrO2-Al2O3/GO。
2. one kind according to claim 1, which passes through phonochemistry method, synthesizes fluorine ion absorber ZrO2-Al2O3The method of/GO, It is characterized in that：In step (2), ultrasonic power that the phonochemical reaction uses is 250W, and the ultrasonication time is 5min。
CN201610632383.3A 2016-08-05 2016-08-05 One kind synthesizing fluorine ion absorber ZrO by phonochemistry method2-Al2O3The method of/GO Active CN106215860B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610632383.3A CN106215860B (en) 2016-08-05 2016-08-05 One kind synthesizing fluorine ion absorber ZrO by phonochemistry method2-Al2O3The method of/GO

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610632383.3A CN106215860B (en) 2016-08-05 2016-08-05 One kind synthesizing fluorine ion absorber ZrO by phonochemistry method2-Al2O3The method of/GO

Publications (2)

Publication Number Publication Date
CN106215860A CN106215860A (en) 2016-12-14
CN106215860B true CN106215860B (en) 2018-09-11

Family

ID=57547507

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610632383.3A Active CN106215860B (en) 2016-08-05 2016-08-05 One kind synthesizing fluorine ion absorber ZrO by phonochemistry method2-Al2O3The method of/GO

Country Status (1)

Country Link
CN (1) CN106215860B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107413294A (en) * 2017-05-19 2017-12-01 西安石油大学 A kind of method that graphene-supported silver handles high Oil repellent domestic water
CN110614076A (en) * 2019-10-14 2019-12-27 西安工程大学 Preparation method of zirconium dioxide/aluminum oxide composite adsorption material
CN111644150A (en) * 2020-06-11 2020-09-11 南昌航空大学 Preparation method of phosphate adsorbent based on 3D rGO/zirconium dioxide composite material

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103861559A (en) * 2014-03-12 2014-06-18 陕西科技大学 Zirconia-modified graphene and method for removing fluorine ions in water

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61220787A (en) * 1985-03-25 1986-10-01 Miyoshi Oil & Fat Co Ltd Treatment of water

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103861559A (en) * 2014-03-12 2014-06-18 陕西科技大学 Zirconia-modified graphene and method for removing fluorine ions in water

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Fluoride removal from aqueous solution by Al(III)–Zr(IV) binary oxide adsorbent;Jiuya Zhu等;《Applied Surface Science》;20150903;第357 卷;第2.2-2.3节，摘要 *
Preparation, characterization and evaluation of fluoride adsorption efficiency from water of iron-aluminium oxide-graphene oxide composite material;Sarat Kanrar等;《Chemical Engineering Journal》;20160717;第306卷;第2.6，3.2，3.8节 *

Also Published As

Publication number Publication date
CN106215860A (en) 2016-12-14

Similar Documents

Publication Publication Date Title
CN106215860B (en) One kind synthesizing fluorine ion absorber ZrO by phonochemistry method2-Al2O3The method of/GO
CN108636357A (en) A kind of use in waste water treatment cross-linking type graphite oxide aerogel and preparation method thereof
CN108440322B (en) Star-shaped carboxylic acid group zwitterionic surfactant and preparation method and application thereof
CN103570948A (en) Preparation method and application of porous material with surface grafted beta-cyclodextrin
CN109772300A (en) A kind of MnOx-CeO2The preparation method of graphene aerogel catalyst material
CN109607739A (en) A kind of application of piezoelectric material barium titanate Ultrasound-activated persulfate in processing waste water
CN106582626A (en) Preparation method and application of novel silver ion doped TiO2 composite material
CN105597775A (en) Graphene /Cu-Mn-Ce compound catalyst, and preparation method and applications thereof
CN110479232A (en) A kind of preparation method of redox graphene base optic catalytic airsetting glue bead
RU2011149770A (en) WAYS TO REDUCE THE AMOUNT OF MONOFLUORACETATE IN THE PRODUCTION OF HYDROFLUOROLEPHINS
CN106563307A (en) Sewage filter material and preparation method thereof
RU2008131241A (en) METHOD FOR PRODUCING ALUMINUM-SILICON FLAGULANT-COAGULANT AND METHOD FOR CLEANING WITH ITS WATER
CN110339818A (en) A kind of preparation method of modified magnetic chitosan absorbent
CN105110406B (en) Application of the ion liquid functionalization silica gel in Phenol for Waste Water pollutant is removed
CN107892408A (en) A kind of farmland agricultural chemicals waste water purification method
CN106621556A (en) Filtering material used for sewage treatment
CN106560466A (en) Method for preparing halopropyl alcohol and propylene oxide
CN106518613B (en) A method of preparing halogen ethyl alcohol and ethylene oxide
CN108298721A (en) A kind of method of graphite oxide colloidal sol waste liquid cleaning treatment and recycling
CN107413169A (en) A kind of formaldehyde absorbent of the doped nano titanium dioxide containing Ternary copper and preparation method thereof
JP2017537059A (en) Method for purifying lignin by subjecting slurry containing lignin to an electric field
CN105772037B (en) A kind of ultraviolet catalytic removes material of bromate and preparation method thereof in water removal
CN109317111A (en) A kind of preparation method for the floatability type foamed absorbent carrying nano-photocatalyst
CN106518612B (en) A method of preparing halogen propyl alcohol and propylene oxide
CN108722367A (en) A kind of modified polyacrylamide scavenging material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant