CN104324684A - Preparation method of mesoporous flower-cluster-shaped [gamma]-TiP and fluorine-removing application method - Google Patents

Preparation method of mesoporous flower-cluster-shaped [gamma]-TiP and fluorine-removing application method Download PDF

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CN104324684A
CN104324684A CN201410502347.6A CN201410502347A CN104324684A CN 104324684 A CN104324684 A CN 104324684A CN 201410502347 A CN201410502347 A CN 201410502347A CN 104324684 A CN104324684 A CN 104324684A
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tip
mesoporous
fluorine
preparation
gamma
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CN104324684B (en
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彭秋明
张庆瑞
吴文诗
邹国栋
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Yanshan University
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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
    • B01J20/0203—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
    • B01J20/28—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
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Medicinal Preparation (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

A preparation method of mesoporous flower-cluster-shaped [gamma]-TiP and a fluorine-removing application method. The mesoporous flower-cluster-shaped [gamma]-TiP has a chemical formula of Ti(HPO4)2.2H2O. The preparation method of the mesoporous flower-cluster-shaped [gamma]-TiP mainly includes following stpes: (1) blending butyl titanate with a purity being 99% and alcohol with the purity being 99% according to a volume ratio of 1:150-300 to obtain a mixed solution; and (2) dropwisely adding the mixed solution to a phosphate buffering solution with a mass ratio of the mixed solution to the phosphate buffering solution being 1:5, performing mechanical stirring for 12-24 h, and performing separation and drying to obtain the mesoporous flower-cluster-shaped [gamma]-TiP. The fluorine-removing application method includes following steps: (1) adding the mesoporous flower-cluster-shaped [gamma]-TiP to fluorine-containing water with the pH value of the fluorine-containing water being controlled to be seven; and (2) performing shaker vibration at 25 DEG C at 180 r/min for 24h. The preparation method is simple. The [gamma]-TiP is large in specific surface area, is uniform in particle size, is high in stability and is 90-110.6 mg/g in fluorine ion adsorption capacity.

Description

The preparation method of a kind of mesoporous flowers shape γ-TiP with except fluorine application process
Technical field
The present invention relates to the preparation method of phosphoeptide and remove fluorine application process.
Background technology
Along with the quickening of urbanization process and the fast development of industrial or agricultural, a large amount of municipal refuse, industrial wastewater and atmospheric fallout constantly enter in water, and the content of fluoride ion in water body is sharply raised.Drink the fluorine-containing water exceeded standard for a long time can cause den tal fluorosis, textured bone, pain, even paralyse.Therefore find the fluorine element in a kind of suitable material processed water extremely urgent.
Titanium phosphate has the ion-exchange performance as ion exchange resin, and have again the adsorption selection as zeolite and catalytic performance, be a kind of good sorbing material simultaneously.Have α, beta, gamma three kinds of crystal formations, wherein γ-TiP interfloor distance is large, so can adion wider range.Current main preparation methods is hydro-thermal method (Allulli S, Ferragina C, et al.Journal of Inorganic and Nuclear Chemistry, 1977), is by amorphous titanium phosphate and 10mol/L H 3pO 448h is reacted under 300 DEG C of conditions.But this preparation method's reaction temperature is high, and the time is long, preparation method is complicated.
Chinese invention patent application numbers 201310646042.8 discloses a kind of Titanium phosphate nano material and preparation method thereof and application.Titanium-containing compound and phosphorus-containing compound are stirred in alcohols solvent and evenly carry out metathesis reaction, obtain Titanium phosphate nano material.Reaction time is 36 ~ 60h. reaction temperature when being 50 DEG C, and products therefrom is the mixture that α and γ TiP forms.Reaction time is after 84h, obtains γ phase.Although the method reduces reaction temperature, preparation time is oversize, and the γ phase titanium phosphate purity obtained is not high.
Chinese invention patent application numbers 201210550027.9 discloses a kind of preparation method of flower-shaped micro-/ nano Titanium pyrophosphate.Joined in absolute ethyl alcohol in phytic acid and titanium source and obtain presoma after 180 ~ 220 DEG C of insulation reaction 6 ~ 12h are separated drying, then calcine 1 ~ 6h under 680 ~ 800 DEG C of conditions, obtaining product is Titanium pyrophosphate (TiP 2o 7).This preparation process is complicated, and temperature is too high, is unfavorable for large-scale production.
Chinese invention patent application numbers 201310342141.7 discloses a kind of composite of deep purifying Micro fluoride and preparation and purification method.Sorbing material described in this invention is with nanometer titanium phosphate for inorganic functional adsorbent, and conventional strong-base anion-exchange resin is the resin-base nano titanium phosphate composite of carrier.Although this composite can make water outlet heavy ion be reduced to below Drinking Water control criterion, adsorbance is not high.
Summary of the invention:
The object of the present invention is to provide the preparation method of the mesoporous flowers shape γ-TiP that a kind of preparation method is simple, purity is high, adsorbance is large and remove fluorine application process.
The chemical formula of mesoporous flowers shape γ-TiP of the present invention is Ti (HPO 4) 22H 2o.
The preparation method of above-mentioned mesoporous flowers shape γ-TiP:
By purity be 99% butyl titanate and purity be 99% alcohol 1:150 ~ 300 are blended by volume, again in above-mentioned mixed liquor: the mass ratio of PBS is the ratio of 1:5, above-mentioned mixed liquor being slowly added drop-wise to bovine serum albumin content is in the PBS of 0.1mg/ml, mechanical agitation 12 ~ 24h, obtains mesoporous flowers shape γ-TiP after separation, drying.
Above-mentioned mesoporous flowers shape γ-TiP removes fluorine application process:
The ratio of the mesoporous flowers shape γ-TiP500mg of above-mentioned preparation is added in often liter of fluorinated water, it is in the fluorinated water of 50 ~ 90mg/L that the mesoporous flowers shape γ-TiP of above-mentioned preparation is added concentration, control the pH value of fluorinated water 7,25 DEG C, adopt shaking table to shake 24h under the condition of 180r/min after, recording Adsorption of fluoride ion capacity is 90 ~ 110.6mg/g.
The present invention compared with prior art tool has the following advantages:
1, preparation technology is simple, and raw material is cheap, and reaction temperature is moderate, simple to operate.
2, the γ-TiP powder diameter prepared is even, and purity is high, and specific area is large, good biocompatibility, heat and chemical stability high.
3, adsorbance is large, can effectively except the fluorine in anhydrating, and protection of the environment is cheap, is applicable to large industrial production.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the mesoporous flowers shape γ-TiP that the embodiment of the present invention 1 obtains.
Fig. 2 is the XRD figure of the mesoporous flowers shape γ-TiP that the embodiment of the present invention 2 obtains.
Fig. 3 be the obtained mesoporous flowers shape γ-TiP of the embodiment of the present invention 3 except fluorine dynamics figure.
Detailed description of the invention:
Embodiment 1
15mg bovine serum albumin is joined in 150ml PBS and stirs, by 0.1ml butyl titanate and 30ml alcohol is blended is slowly added drop-wise in above-mentioned PBS afterwards, continue at room temperature mechanical agitation 12h, after last centrifugal drying, obtain Ti (HPO 4) 22H 2o white powder and mesoporous flowers shape γ-TiP.
It is in the fluorinated water of 50mg/L that above-mentioned for 100mg mesoporous flowers shape γ-TiP is joined 200ml mass concentration, control the pH value of fluorine water 7,25 DEG C, adopt shaking table isothermal vibration 24h under the condition of 180r/min after, measuring residual fluorine mass of ion concentration in solution is 5mg/L.
As shown in Figure 1, can find out that the pattern of the γ-TiP prepared is the mesoporous flowers shape combined by sheet.Particle diameter is greatly about 8 ~ 9 μm.Fluorine ion adsorption capacity is 90mg/g.
Embodiment 2
15mg bovine serum albumin is joined in 150ml PBS and stirs, by 0.2ml butyl titanate and 30ml alcohol is blended is slowly added drop-wise in above-mentioned PBS afterwards, continue stirred at ambient temperature 24h again, after last centrifugal drying, obtain Ti (HPO 4) 22H 2o white powder and mesoporous flowers shape γ-TiP.
It is in the fluorinated water of 90mg/L that above-mentioned for 100mg mesoporous flowers shape γ-TiP is joined 200ml mass concentration, control the pH value of fluorine water 7,25 DEG C, adopt shaking table isothermal vibration 24h under the condition of 180r/min after, measuring residual fluorine mass of ion concentration in solution is 31.95mg/L.
As shown in Figure 2, can find out that the TiP material prepared is pure γ phase.Fluorine ion adsorption capacity is 116.1mg/g.
Embodiment 3
15mg bovine serum albumin is joined in 150ml PBS and stirs, by 0.15ml butyl titanate and 30ml alcohol is blended is slowly added drop-wise in above-mentioned PBS afterwards, continue stirred at ambient temperature 20h again, after last centrifugal drying, obtain Ti (HPO 4) 22H 2o white powder and mesoporous flowers shape γ-TiP.
It is in the fluorinated water of 70mg/L that mesoporous for 100mg flowers shape γ-TiP is added 200ml mass concentration respectively, the pH value controlling fluorine water is 7,25 DEG C, adopt shaking table isothermal vibration 0.1h, 0.2h, 0.5h, 1h, 2h, 4h, 6h, 8h, 12h, 16h, 20h, 24h under the condition of 180r/min after to measure residual fluorine mass of ion concentration in solution be 65mg/L, 50mg/L, 45mg/L, 35mg/L, 32.5mg/L, 30mg/L, 27.5mg/L, 25mg/L, 22.5mg/L, 20.5mg/L, 19mg/L, 18.25mg/L.
As shown in Figure 3, when can find out that the maximum fluoride removing quantity of γ-TiP material prepared is 103mg/g, 24h, absorption reaches capacity.

Claims (3)

1. a New Type of Mesoporous flowers shape γ-TiP, is characterized in that: it chemical formula be Ti (HPO 4) 22H 2o.
2. the preparation method of the mesoporous flowers shape γ-TiP described in the claims 1, is characterized in that:
By purity be 99% butyl titanate and purity be 99% alcohol 1:150 ~ 300 are blended by volume, again in above-mentioned mixed liquor: the mass ratio of PBS is the ratio of 1:5, above-mentioned mixed liquor being slowly added drop-wise to bovine serum albumin content is in the PBS of 0.1mg/ml, mechanical agitation 12 ~ 24h, obtains mesoporous flowers shape γ-TiP after separation, drying.
3. the mesoporous flowers shape γ-TiP described in the claims 1 removes fluorine application process, it is characterized in that: the ratio adding the mesoporous flowers shape γ-TiP500mg of above-mentioned preparation in often liter of fluorinated water, it is in the fluorinated water of 50 ~ 90mg/L that the mesoporous flowers shape γ-TiP of above-mentioned preparation is added concentration, control the pH value of fluorinated water 7,25 DEG C, adopt shaking table to shake 24h under the condition of 180r/min after, recording Adsorption of fluoride ion capacity is 90 ~ 110.6mg/g.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107892361A (en) * 2017-11-07 2018-04-10 燕山大学 A kind of method of heavy metal in titanium phosphate nano flower coating material high depth purified water
CN108557793A (en) * 2018-02-12 2018-09-21 西北工业大学 A kind of flower-shaped titanium phosphate microballoon and preparation method thereof of nanometer sheet assembling

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001064003A (en) * 1999-08-26 2001-03-13 Tayca Corp Interlayer compound of titanium phosphate base
CN102976301A (en) * 2012-12-17 2013-03-20 山东轻工业学院 Preparation method for titanium pyrophosphate with flower-like micron/nanometre structure
CN103464086A (en) * 2013-08-07 2013-12-25 燕山大学 Composite material for deep purifying trace fluorine in water, preparation and purification method
CN103626145A (en) * 2013-12-04 2014-03-12 中国科学院化学研究所 Titanium phosphate nano material as well as preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001064003A (en) * 1999-08-26 2001-03-13 Tayca Corp Interlayer compound of titanium phosphate base
CN102976301A (en) * 2012-12-17 2013-03-20 山东轻工业学院 Preparation method for titanium pyrophosphate with flower-like micron/nanometre structure
CN103464086A (en) * 2013-08-07 2013-12-25 燕山大学 Composite material for deep purifying trace fluorine in water, preparation and purification method
CN103626145A (en) * 2013-12-04 2014-03-12 中国科学院化学研究所 Titanium phosphate nano material as well as preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
C.FERRAGINA ET AL: "γ-ZrP and γ-TiP palladium intercalation compounds:synthesis and characterization by X-ray diffraction and thermal analyses", 《MATERIALS RESEARCH BULLETIN》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107892361A (en) * 2017-11-07 2018-04-10 燕山大学 A kind of method of heavy metal in titanium phosphate nano flower coating material high depth purified water
CN107892361B (en) * 2017-11-07 2021-03-19 燕山大学 Method for deeply purifying heavy metals in water by using titanium phosphate nanoflower coating material
CN108557793A (en) * 2018-02-12 2018-09-21 西北工业大学 A kind of flower-shaped titanium phosphate microballoon and preparation method thereof of nanometer sheet assembling

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