CN101798092A - Polyferro-silicate, preparation method thereof and applications thereof in water treatment - Google Patents
Polyferro-silicate, preparation method thereof and applications thereof in water treatment Download PDFInfo
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- CN101798092A CN101798092A CN 201010155626 CN201010155626A CN101798092A CN 101798092 A CN101798092 A CN 101798092A CN 201010155626 CN201010155626 CN 201010155626 CN 201010155626 A CN201010155626 A CN 201010155626A CN 101798092 A CN101798092 A CN 101798092A
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Abstract
The invention relates to a polyferro-silicate, a preparation method thereof and applications thereof in water treatment, and belongs to the field of water pollution. The invention aims to provide a polyferro-silicate, a preparation method thereof and applications thereof in water treatment. The polyferro-silicte is prepared by reacting a soluble ferric salt water solution with an alkali metal silicate water solution. The preparation method comprises the following steps of: while continuously stirring, dropwise adding the alkali metal silicate water solution into the soluble ferric salt water solution until the pH value of the mixture solution is 8-9; and standing, activating, filtering, washing, drying, grinding and sieving for later use. The polyferro-silicate is used as a catalyst in heterogeneous-catalysis ozone-oxidation water treatment. The polyferro-silicate of the invention has the advantages of large specific area, favorable settleability, good catalytic effect, no toxic or side effect and easy recycling. The invention has the advantages of simple preparation method and abundant material source, thus preparation cost is low. The polyferro-silicate of the invention can promote the decomposition of ozone to generate hydroxyl free radicals, increase the generation rate and quantity of the free radicals in the water body and enhance the oxidizing property and the utilization ratio of ozone.
Description
Technical field
The invention belongs to water treatment field, be specifically related to a kind of Polyferro-silicate and preparation method thereof and its application.
Background technology
The O3 catalytic oxidation technology is a kind of as high-level oxidation technology, gets more and more people's extensive concerning in recent years.The O3 catalytic oxidation technology is a kind of novel method that at normal temperatures and pressures those is difficult to the oxidation operation of the independent oxidation of ozone.This technology mainly is divided into two big classes: utilize GOLD FROM PLATING SOLUTION to belong to ion for the homogeneous catalysis ozone oxidation of catalyzer with solid metal, metal oxide, gac or load on metal on the carrier or heterogeneous catalysis ozone oxidation that metal oxide is catalyzer.Because there is the problem of catalyst loss in the homogeneous catalysis ozone oxidation, and has introduced metal ion, has the removal problem of follow-up metal ion, so the application in water treatment has been subjected to certain restriction.And the heterogeneous catalysis oxidation technology is applied to actual production owing to it with respect to additive method is easier, so has caused many investigators' extensive interest, becomes the research focus in catalyzed oxidation field.Metal oxide (TiO
2, MnO
2, CeO
2, ZnOOH, FeOOH etc.) the existing report of pollutent in the catalytic ozonation degradation water.
The solid-state outward appearance of Polyferro-silicate is a sorrel, be slightly soluble in water and organic solvent, the report that is applied to sorbent material, filler and catalyzer has been arranged, but this kind Polyferro-silicate Preparation of catalysts method and its application in the water treatment of heterogeneous catalysis ozone oxidation yet there are no report.
Summary of the invention
The purpose of this invention is to provide preparation method and its application in water treatment of Polyferro-silicate.
Polyferro-silicate is that alkali metal silicate aqueous solution is added drop-wise in the soluble iron salt brine solution among the present invention, again through quiet heavy, activation, filter, washing, dry, grind and sieve and make; Wherein, dripping alkali metal silicate aqueous solution to pH value in the soluble iron salt brine solution is 8 ~ 9; Its preparation method is undertaken by following step: one, the stirring velocity with 100r/min ~ 300r/min constantly stirs the soluble iron salt brine solution, and dropwise dripping alkali metal silicate aqueous solution simultaneously is 8 ~ 9 until the pH value, obtains mixture; Two, with the quiet heavy 10 ~ 30min of the mixture of step 1 gained, under 30 ℃ ~ 80 ℃ conditions, activate 12 ~ 24h then, filter; Three, the throw out after will filtering, grinds then and sieves to the specific conductivity of supernatant liquor and the pH after drying that do not change with the deionized water repetitive scrubbing, promptly obtains Polyferro-silicate.
Polyferro-silicate is done the catalyzer application among the present invention in the water treatment of heterogeneous catalysis ozone oxidation.
Polyferro-silicate of the present invention is solid-state, armorphous, be sorrel, particle diameter is 0.1 ~ 0.5mm, and it leaves standstill sedimentation fully behind the 2min in water, and specific surface area is 339.0958m/g, (FeOOH specific surface area 98.6m/g) specific surface area is big than existing nano-level iron series catalysts, excellent catalytic effect, no side effects is easy to recycle.Preparation method of the present invention is simple, and raw material sources are abundant, so preparation cost is low.Polyferro-silicate of the present invention can promote ozone to decompose the generation hydroxyl radical free radical, increases the generating rate and the quantity of free radical in the water body, has improved the oxidisability and the utilization ratio of ozone.O3 catalytic oxidation improves 30 ~ 67 percentage points than independent ozone oxidation to the clearance of organic pollutant in the water.
Description of drawings
Fig. 1 is that the Polyferro-silicate of embodiment 18 preparations amplifies 40,000 times of scanning electronic microscope (SEM) figure; Fig. 2 is that the Polyferro-silicate of embodiment 18 preparations amplifies 3,000 times of scanning electronic microscope (SEM) figure; Fig. 3 is the design sketch that the contrast experiment removes organic pollutant parachloronitrobenzene in the water in the embodiment 18, among Fig. 3-■-expression adds the organic pollutant removal rate curve of ozone and catalyzer Polyferro-silicate, among Fig. 2-◆-expression only adds the organic pollutant removal rate curve of ozone; Among the figure-▲-represent that Polyferro-silicate is adsorbed with the organic pollutants curve; Fig. 4 is Polyferro-silicate x-ray photoelectron power spectrum (XPS) figure of embodiment 18 preparations.Fig. 5 is the XRD spectra of the Polyferro-silicate of embodiment 18 preparations.
Embodiment
Embodiment one: Polyferro-silicate of the present invention is that alkali metal silicate aqueous solution is added drop-wise in the soluble iron salt brine solution, again through quiet heavy, activation, filter, washing, dry, sieve after grinding and make; Wherein, dripping alkali metal silicate aqueous solution to pH value in the soluble iron salt brine solution is 8 ~ 9.
The described Polyferro-silicate of present embodiment is solid-state, armorphous, is sorrel, and particle diameter is 0.1 ~ 0.5mm, and it leaves standstill sedimentation fully behind the 2min in water, and specific surface area is 339.0958m/g.
Embodiment two: what present embodiment and embodiment one were different is: soluble ferric iron salt is iron nitrate, ferric sulfate or iron(ic) chloride in the described soluble iron salt brine solution.Other is identical with embodiment one.
Embodiment three: what present embodiment was different with embodiment one or two is: alkalimetal silicate is water glass, potassium silicate or Starso in the described alkali metal silicate aqueous solution.Other is identical with embodiment one or two.
Embodiment four: the preparation method of Polyferro-silicate is undertaken by following step in the present embodiment: one, the stirring velocity with 100r/min ~ 300r/min constantly stirs the soluble iron salt brine solution, simultaneously dropwise dripping alkali metal silicate aqueous solution is 8 ~ 9 until the pH value, obtains mixture; Two, with the quiet heavy 10 ~ 30min of the mixture of step 1 gained, under 30 ℃ ~ 80 ℃ conditions, activate 12 ~ 24h then, filter; Three, the throw out after will filtering, sieves after grinding then to the specific conductivity of supernatant liquor and the pH after drying that do not change with the deionized water repetitive scrubbing, promptly obtains Polyferro-silicate.
Present embodiment prepares Polyferro-silicate needs hermetically drying to preserve.
Embodiment five: present embodiment is different with embodiment four: described in the step 1 in the soluble iron salt brine solution soluble ferric iron salt be iron nitrate, ferric sulfate or iron(ic) chloride.Other step is identical with embodiment four with parameter.
Embodiment six: what present embodiment was different with embodiment four or five is: in the step 1 in the alkali metal silicate aqueous solution alkalimetal silicate be water glass, potassium silicate or Starso.Other step is identical with embodiment four or five with parameter.
Embodiment seven: what present embodiment was different with one of embodiment four to six is: the concentration of the described soluble iron salt brine solution of step 1 is 0.2mol/L ~ 2.0mol/L.Other step is identical with one of embodiment four to six with parameter.
Embodiment eight: what present embodiment and embodiment seven were different is: the concentration of the described soluble iron salt brine solution of step 1 is 0.5mol/L ~ 1.5mol/L.Other step is identical with embodiment seven with parameter.
Embodiment nine: what present embodiment and embodiment seven were different is: the concentration of the described soluble iron salt brine solution of step 1 is 1.0mol/L.Other step is identical with embodiment seven with parameter.
Embodiment ten: what present embodiment was different with one of embodiment four to nine is: the concentration of the described alkali metal silicate aqueous solution of step 1 is 0.25mol/L ~ 2.5mol/L.Other step is identical with one of embodiment four to nine with parameter.
Embodiment 11: what present embodiment and embodiment ten were different is: the concentration of the described alkali metal silicate aqueous solution of step 1 is 0.5mol/L ~ 2.0mol/L.Other step is identical with embodiment ten with parameter.
Embodiment 12: what present embodiment and embodiment ten were different is: the concentration of the described alkali metal silicate aqueous solution of step 1 is 1.0mol/L.Other step is identical with embodiment ten with parameter.
Embodiment 13: what present embodiment and embodiment ten were different is: the concentration of the described alkali metal silicate aqueous solution of step 1 is 1.5mol/L.Other step is identical with embodiment ten with parameter.
Embodiment 14: what present embodiment was different with one of embodiment four to 13 is: the step 2 activation temperature is 50 ℃ ~ 70 ℃.Other step is identical with one of embodiment four to 13 with parameter.
Embodiment 15: what present embodiment was different with one of embodiment four to 13 is: the step 2 activation temperature is 60 ℃.Other step is identical with one of embodiment four to 13 with parameter.
Embodiment 16: what present embodiment was different with one of embodiment four to 15 is: the described soak time of step 2 is 15 ~ 20h.
Embodiment 17: the present embodiment Polyferro-silicate in the water treatment of heterogeneous catalysis ozone oxidation as Application of Catalyst.
The Polyferro-silicate of present embodiment can promote ozone to decompose the generation hydroxyl radical free radical, increases the generating rate and the quantity of free radical in the water body, has improved the oxidisability and the utilization ratio of ozone.O3 catalytic oxidation improves 30 ~ 67 percentage points than independent ozone oxidation to the clearance of organic pollutant in the water.
Embodiment 18: the present embodiment Polyferro-silicate is to prepare according to the following steps: one, constantly stirring 150mL concentration with the stirring velocity of 100r/min is the 0.63mol/L iron nitrate aqueous solution, the sodium silicate aqueous solution that dropwise drips simultaneously concentration and be 0.89mol/L is 9 until pH value, the acquisition mixture; Two, with the quiet heavy 30min of the mixture of step 1 gained, under 60 ℃ of conditions, activate 24h then, filter; Three, the throw out after will filtering, sieves after grinding then to the specific conductivity of supernatant liquor and the pH after drying that do not change with the deionized water repetitive scrubbing, promptly obtains Polyferro-silicate (seeing Fig. 1, Fig. 2 and Fig. 4).
As shown in Figure 5, Polyferro-silicate is armorphous.
Employing simultaneous test checking parachloronitrobenzene of the present invention (
pCNB) removal effect:
In Continuous Flow test, remove respectively same concentrations in the water the organic pollutant parachloronitrobenzene (
pCNB), one group adds ozone separately, and concentration of liquid phase ozone is about 0.6mg/L; Another group adds ozone and catalyzer Polyferro-silicate, and concentration of liquid phase ozone is about 0.6mg/L, and catalyst amounts is 500mg; Parachloronitrobenzene in two groups of water (
pCNB) removal effect as shown in Figure 3.Wherein water inlet flow velocity and go out water flow velocity and be 6L/h in the test of two groups of Continuous Flow adopts the reactive mode of continuous water-inlet continuous water-outlet, in the water outlet of 20min sampling and measuring
pThe content of CNB.The adding of catalyzer makes parachloronitrobenzene clearance (reaction 20min) improve 65 percentage points, and Polyferro-silicate is adsorbed with, and organic pollutants (parachloronitrobenzene) amount is very little to be had only about 4%.The stripping of Fe ion is 0.246mg/L behind the operation 60min continuously, less than the requirement (0.3mg/L) of iron concentration in the national drinking water standard.Experimental data shows that prepared catalyst ozone oxidation is removed the active strong of organic pollutant, self stability height.
Claims (10)
1. Polyferro-silicate is characterized in that Polyferro-silicate is that alkali metal silicate aqueous solution is added drop-wise in the soluble iron salt brine solution, again through quiet heavy, activation, filter, washing, dry, grind and sieve and make; Wherein, dripping alkali metal silicate aqueous solution to pH value in the soluble iron salt brine solution is 8 ~ 9.
2. according to the described Polyferro-silicate of claim 1, it is characterized in that soluble ferric iron salt is iron nitrate, ferric sulfate or iron(ic) chloride in the described soluble iron salt brine solution.
3. according to claim 1 or 2 described Polyferro-silicates, it is characterized in that alkalimetal silicate is water glass, potassium silicate or Starso in the alkali metal silicate aqueous solution.
4. the preparation method of Polyferro-silicate according to claim 1, the preparation method who it is characterized in that Polyferro-silicate is undertaken by following step: one, the stirring velocity with 100r/min ~ 300r/min constantly stirs the soluble iron salt brine solution, simultaneously dropwise dripping alkali metal silicate aqueous solution is 8 ~ 9 until the pH value, obtains mixture; Two, with the quiet heavy 10 ~ 30min of the mixture of step 1 gained, under 30 ℃ ~ 80 ℃ conditions, activate 12 ~ 24h then, filter; Three, the throw out after will filtering, grinds then and sieves to the specific conductivity of supernatant liquor and the pH after drying that do not change with the deionized water repetitive scrubbing, promptly obtains Polyferro-silicate.
5. according to the preparation method of the described Polyferro-silicate of claim 4, it is characterized in that soluble ferric iron salt is iron nitrate, ferric sulfate or iron(ic) chloride in the salt brine solution of soluble iron described in the step 1.
6. according to the preparation method of claim 4 or 5 described Polyferro-silicates, it is characterized in that in the step 1 that alkalimetal silicate is water glass, potassium silicate or Starso in the alkali metal silicate aqueous solution.
7. according to the preparation method of the described Polyferro-silicate of claim 6, the concentration that it is characterized in that the described soluble iron salt brine solution of step 1 is 0.2mol/L ~ 2.0mol/L.
8. according to the preparation method of claim 4,5 or 7 described Polyferro-silicates, the concentration that it is characterized in that the described alkali metal silicate aqueous solution of step 1 is 0.25mol/L ~ 2.5mol/L.
9. according to the preparation method of the described Polyferro-silicate of claim 1, it is characterized in that the step 2 activation temperature is 50 ℃ ~ 70 ℃.
10. the application of Polyferro-silicate in water treatment according to claim 1, it is characterized in that Polyferro-silicate in the water treatment of heterogeneous catalysis ozone oxidation as Application of Catalyst.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068971A (en) * | 2010-12-03 | 2011-05-25 | 哈尔滨工业大学 | Preparation method of poly-aluminum silicate |
| CN103933980A (en) * | 2014-03-18 | 2014-07-23 | 中原工学院 | Preparation method and application of polyferric silicate doped hydroxy ferric oxide catalyst |
| CN103933960A (en) * | 2014-03-18 | 2014-07-23 | 中原工学院 | Preparation method and application of polyzinc silicate doped hydroxy zinc oxide catalyst |
| JP2014148433A (en) * | 2013-01-31 | 2014-08-21 | National Institute Of Advanced Industrial & Technology | Amorphous iron silicate and synthesis method thereof |
| CN109482187A (en) * | 2018-12-18 | 2019-03-19 | 黑龙江省科学院自然与生态研究所 | A kind of preparation method of the ferrosilicon binary oxide ozonisation catalyst of goethite structure |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1541951A (en) * | 2003-11-06 | 2004-11-03 | 同济大学 | One-step production method for coagulant solid polymerized silica ferric sulfate |
-
2010
- 2010-04-26 CN CN 201010155626 patent/CN101798092A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1541951A (en) * | 2003-11-06 | 2004-11-03 | 同济大学 | One-step production method for coagulant solid polymerized silica ferric sulfate |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068971A (en) * | 2010-12-03 | 2011-05-25 | 哈尔滨工业大学 | Preparation method of poly-aluminum silicate |
| CN102068971B (en) * | 2010-12-03 | 2013-06-19 | 哈尔滨工业大学 | Preparation method of poly-aluminum silicate |
| JP2014148433A (en) * | 2013-01-31 | 2014-08-21 | National Institute Of Advanced Industrial & Technology | Amorphous iron silicate and synthesis method thereof |
| CN103933980A (en) * | 2014-03-18 | 2014-07-23 | 中原工学院 | Preparation method and application of polyferric silicate doped hydroxy ferric oxide catalyst |
| CN103933960A (en) * | 2014-03-18 | 2014-07-23 | 中原工学院 | Preparation method and application of polyzinc silicate doped hydroxy zinc oxide catalyst |
| CN103933980B (en) * | 2014-03-18 | 2015-11-11 | 中原工学院 | The preparation method of Polyferro-silicate doping hydroxyl oxidize iron catalyst and application thereof |
| CN109482187A (en) * | 2018-12-18 | 2019-03-19 | 黑龙江省科学院自然与生态研究所 | A kind of preparation method of the ferrosilicon binary oxide ozonisation catalyst of goethite structure |
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Application publication date: 20100811 |