CN102764637A - Method for preparing load type zero valent iron for water processing - Google Patents
Method for preparing load type zero valent iron for water processing Download PDFInfo
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- CN102764637A CN102764637A CN201210287643XA CN201210287643A CN102764637A CN 102764637 A CN102764637 A CN 102764637A CN 201210287643X A CN201210287643X A CN 201210287643XA CN 201210287643 A CN201210287643 A CN 201210287643A CN 102764637 A CN102764637 A CN 102764637A
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- valent iron
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Abstract
The invention provides a method for preparing load type zero valent iron for water processing. The method comprises the steps of 1), stirring a trivalence iron solution in a water bath, adding a weak base solution into the solution dropwise, enabling that OH-: Fe3+=(1:1)-(1:1.2), stirring continuously after addition, and aging to obtain a hydroxy iron pillar solution; 2), extracting the iron carbonyl column supporting liquid, adding dry ground mineralized garbage with landfill age of 8-15 years, stirring, aging, cleaning precipitates with water, drying and grinding to obtain powder; and 3), adding the powder into deionized water, under protective gases, stirring, a KBH4 solution or a NaBH4 solution is added into a stirred powder solution, and stirring continuously for 30-40 min; and 4), separating the solution, cleaning by using deoxidized deionized water, and under the protection of protective gases, drying at the constant temperature of 60-70 DEG C for 5-6 h to obtain the load type zero valent iron for waste water processing.
Description
Technical field
The present invention relates to environmental pollution control field of new, relate in particular to a kind of preparation method who is used for the support type Zero-valent Iron of water treatment.
Background technology
Nano zero valence iron shows superior performance on a series of environmental problems such as the pollution of solution organic matter, heavy metal pollution and environmental pollution reparation.The nano zero valence iron reducing activity is very strong, and unstable chemcial property is prone to oxidized.But because the effect of the surface of nano zero valence iron particle self ability is prone to cause reunion, reduced the adsorption site position of nano zero valence iron particle, reduced with the effective contact area of pollutant, degradation efficiency descends; Simultaneously, the nano zero valence iron of dispersion is difficult to Separation of Solid and Liquid after in waste water, handling.Therefore, exploitation nano zero valence iron support materials and technology are significant to suppressing nanoparticle agglomerates, raising particle stability and the enhancing nano zero valence iron aspects such as removal efficient to environmental pollutants in environment.Comprehensive achievement in research in recent years has materials such as clay, molecular sieve and active carbon with the nano zero valence iron particulate load to the used carrier of solid carrier.Active carbon is more expensive relatively, and zeolite molecular sieve also is will be through artificial synthetic, and clay class mineral need be seen mining site content, and the low area that distributes of some rare mineral content is few, needs long-distance transport.
Mineralized waste is meant in landfill yard landfill (in Shanghai generally at least more than 8-10, northern area is more than 10 years) for many years, reaches stabilisation basically, can exploit the rubbish of utilization.Existing tens health of China and accurate sanitary city household refuse landfill sites and general stockyard have been inserted or several ten million tons of heap garbages.Some central rubbish have reached stabilization of state basically, thereby have been called as mineralized waste after the degraded of 8-10.In Shanghai City, this mineralized waste has 4,000 ten thousand tons (nearly 2,000 ten thousand tons of over the years stockyard of 2,000 ten thousand tons of old port refuse landfills, urban district and suburb, Jiang Zhen stockyards etc.) at least.The mineralized waste that store up in cities such as Beijing, Tianjin, Guangzhou estimates also there are several ten million tons.Therefore the resource of these mineralized wastes is very sufficient, and it is wide to distribute, and all there is refuse landfill in each big city basically, and through degraded for a long time, some can be exploited, and can think the new material of getting of using not to the utmost without cease.
Summary of the invention
The objective of the invention is deficiency, a kind of preparation method who is used for the support type Zero-valent Iron of water treatment is provided for the carrier of the nano zero valence iron that overcomes prior art.
The technical scheme that the present invention adopts is in turn include the following steps:
1) with ferric salt solution 60 ~ 65 ℃ of stirred in water bath, in solution, drip weak caustic solution simultaneously, weak caustic solution slowly ionization generates OH
-, the final OH that generates
-The molar concentration relation of molar concentration and iron ion is: OH
-: Fe
3+=1:1 ~ 1:1.2 is added dropwise to complete the back and under 60 ~ 65 ℃ identical water bath condition, continues to stir 2 ~ 2.5h, and aging then 24h ~ 48h obtains the pillared liquid of iron carbonyl;
2) get the pillared liquid of above-mentioned iron carbonyl; Dry to wherein adding, as to pulverize 60 ~ 150 mesh sieves landfill is the mineralized waste in 8 ~ 15 years age, and the amount of the pillared liquid of the required above-mentioned iron carbonyl of every gram mineralized waste is 1 ~ 3mL, stirs 6 ~ 8h; Aging 24h ~ 48h; With distilled water washing and precipitating thing, 105-120 ℃ was dried by the fire 3-4 hour down, and milling makes powder;
3) get above-mentioned powder and join in the deionized water, every 100mL deionized water adds above-mentioned powder 10 ~ 15g, under protective gas, stirs, and in the powder solution that stirs, adding concentration again is the KBH of 0.5 ~ 1mol/L
4Or NaBH
4Solution, the above-mentioned powder of every gram adds KBH
4Or NaBH
4The amount of solution is 3 ~ 5mL, continues to stir 30 ~ 40min;
4) separate above-mentioned solution, use the deoxidation washed with de-ionized water, under protective gas protection, 60 ~ 70 ℃ of freeze-day with constant temperature 5 ~ 6h promptly obtain being used for the support type Zero-valent Iron of wastewater treatment.
Fe in the ferric salt solution described in the step 1)
3+Concentration is 0.4 ~ 0.8mol/L, and concentration is crossed conference and generated ferric hydroxide precipitate easily, too smallly then wastes water, and increases the water yield synthetic the time.
Trivalent iron salt described in the step 1) is a water-soluble trivalent ferric salt, has not so satisfied not Fe in the solution
3+Concentration requirement comprises FeCl
3Or Fe (NO
3)
3
The quick ionization of highly basic produces the rapid and iron generation deposition of hydroxyl meeting, leads to the failure, and therefore, the weak base described in the step 1) is Na
2CO
3
Step 3) and 4) protective gas described in is N
2
The centrifugation mode is adopted in separation described in the step 4).
Compare with general soil, mineralized waste has that unit weight is less, porosity is high, the content of organic matter is high, cation exchange capacity (CEC) is big, absorption and the strong characteristics of exchange capacity.Cation exchange capacity particularly, the cation exchange capacity of mineralized waste exceed tens of times (Tongji University's journals: natural science edition, the 34th the 10th phase of volume, 1360 pages) especially up to more than the 0.068mol/100g than common sand.Through cation exchange, can be in the amount of the catalyst of its area load than only the carriers such as active carbon through the Van der Waals force effect are big.Its porosity is high in addition, and specific area is big, is a kind of desirable carrier, and Zero-valent Iron is carried on mineralized waste can become a kind of novel effective water treatment agent.
Advantage of the present invention is the mineralized waste that adopts discarded rubbish behind long-time landfill, to obtain, and low price is rich and easy to get.The effect of the polymerization Tie Tong being crossed cation exchange at first loads to the mineralized waste surface, passes through KBH again
4Or NaBH
4Reduction, can obtain zero-valent iron particle on the mineralized waste surface, the treatment of wastes with processes of wastes against one another.
The specific embodiment
Embodiment 1
With concentration is 0.8mol/L FeCl
3Solution drips Na simultaneously 65 ℃ of stirred in water bath in solution
2CO
3Solution makes OH
-: Fe
3+=1.0 (mol ratios) are added dropwise to complete the back and under the same terms of 65 ℃, continue to stir 2.5h, and aging then 24h obtains the pillared liquid of iron carbonyl; Get the pillared liquid of above-mentioned iron carbonyl; Dry to wherein adding, as to pulverize 150 mesh sieves landfill is the mineralized waste in 15 years age, and the amount of the pillared liquid of the required above-mentioned iron carbonyl of every gram mineralized waste is 3mL, stirs 8h; Aging 24h; With distilled water washing and precipitating thing 5 times, 120 ℃ of bakings 4 hours down, milling makes powder; Get above-mentioned powder and join in the deionized water, every 100mL deionized water adds above-mentioned powder 15g, at N
2Protection is stirred down, adds the KBH that concentration is 1mol/L again
4Solution joins in the powder solution of stirring, and the above-mentioned powder of every gram adds KBH
4The amount of solution is 3mL, continues to stir 40min; Separate above-mentioned solution, use the deoxidation washed with de-ionized water, under nitrogen protection, 70 ℃ of freeze-day with constant temperature 6h promptly obtain being used for the support type Zero-valent Iron of wastewater treatment, and utilizing the icp analysis iron content is 27.1%.
1g support type Zero-valent Iron is joined in the 4-chlorophenol solution that 100mL concentration is 10mg/L, and 4-chlorophenol clearance is 98.5%, through deposition, Separation of Solid and Liquid rapidly.Compare the synthetic activated carbon supported Zero-valent Iron that makes under the same terms, mineralized waste can not considered cost basically, saves a lot of costs at the carriers such as angle specific activity charcoal of economy; The iron content of the activated carbon supported Zero-valent Iron that analysis obtains is merely 12.6%, causes the same contaminant degradation efficiency relatively lowly, has only 78.2%.
Embodiment 2
With concentration is 0.4mol/L Fe (NO
3)
3Solution drips Na simultaneously 60 ℃ of stirred in water bath in solution
2CO
3Solution makes OH
-: Fe
3+=1:1.2 (mol ratio) is added dropwise to complete the back and under the same terms of 60 ℃, continues to stir 2h, and aging then 48h obtains the pillared liquid of iron carbonyl; Get the pillared liquid of above-mentioned iron carbonyl, dry to wherein adding, as to pulverize 60 mesh sieves landfill is the mineralized waste in 8 years age, and the amount of the pillared liquid of the required above-mentioned iron carbonyl of every gram mineralized waste is 1mL; Stir 6h, aging 48h is with distilled water washing and precipitating thing 3 times; 105 ℃ were dried by the fire 3 hours down, and milling makes powder; Get above-mentioned powder and join in the deionized water, every 100mL deionized water adds above-mentioned powder 10g, at N
2Protection is stirred down, adds the NaBH that concentration is 0.5mol/L again
4Solution joins in the powder solution of stirring, and the above-mentioned powder of every gram adds NaBH
4The amount of solution is 5mL, continues to stir 30min; Separate above-mentioned solution, use the deoxidation washed with de-ionized water, under nitrogen protection, 60 ℃ of freeze-day with constant temperature 5h promptly obtain being used for the support type Zero-valent Iron of wastewater treatment, and utilizing the icp analysis iron content is 25.6%.
1g support type Zero-valent Iron is joined in the sodium nitrate solution that 100mL concentration is 20mg/L, and the nitrate anion clearance is 99.1%, through deposition, Separation of Solid and Liquid rapidly.Compare the synthetic activated carbon supported Zero-valent Iron that makes under the same terms, mineralized waste can not considered cost basically, saves a lot of costs at the carriers such as angle specific activity charcoal of economy; The iron content of the activated carbon supported Zero-valent Iron that analysis obtains is merely 15.8%, causes the same contaminant degradation efficiency relatively lowly, has only 73.5%.
Embodiment 3
With concentration is 0.5mol/L Fe (NO
3)
3Solution drips Na simultaneously 65 ℃ of stirred in water bath in solution
2CO
3Solution makes OH
-: Fe
3+=1.0 (mol ratios) are added dropwise to complete the back and under the same terms of 65 ℃, continue to stir 2.5h, and aging then 24h obtains the pillared liquid of iron carbonyl; Get the pillared liquid of above-mentioned iron carbonyl; Dry to wherein adding, as to pulverize 150 mesh sieves landfill is the mineralized waste in 10 years age, and the amount of the pillared liquid of the required above-mentioned iron carbonyl of every gram mineralized waste is 3mL, stirs 8h; Aging 48h; With distilled water washing and precipitating thing 5 times, 120 ℃ of bakings 4 hours down, milling makes powder; Get above-mentioned powder and join in the deionized water, every 100mL deionized water adds above-mentioned powder 15g, at N
2Protection is stirred down,, add the NaBH that concentration is 1mol/L again
4Solution joins in the powder solution of stirring, and the above-mentioned powder of every gram adds KBH
4The amount of solution is 4mL, continues to stir 40min; Separate above-mentioned solution, use the deoxidation washed with de-ionized water, under nitrogen protection, 70 ℃ of freeze-day with constant temperature 6h promptly obtain being used for the support type Zero-valent Iron of wastewater treatment, and utilizing the icp analysis iron content is 25.9%.
1g support type Zero-valent Iron is joined in the copper-bath that 100mL concentration is 20mg/L, and the copper ion clearance is 99.5%, through deposition, Separation of Solid and Liquid rapidly.Compare the synthetic activated carbon supported Zero-valent Iron that makes under the same terms, mineralized waste can not considered cost basically, saves a lot of costs at the carriers such as angle specific activity charcoal of economy; The iron content of the activated carbon supported Zero-valent Iron that analysis obtains is merely 15.8%, causes the same contaminant degradation efficiency relatively lowly, has only 73.8%.
Claims (6)
1. preparation method who is used for the support type Zero-valent Iron of water treatment, it is characterized in that: step is following:
1) with ferric salt solution 60 ~ 65 ℃ of stirred in water bath, in solution, drip weak caustic solution simultaneously, make OH
-With Fe
3+Mol ratio is 1:1 ~ 1:1.2, is added dropwise to complete the back and under 60 ~ 65 ℃ identical water bath condition, continues to stir 2 ~ 2.5h, and aging then 24h ~ 48h obtains the pillared liquid of iron carbonyl;
2) get the pillared liquid of above-mentioned iron carbonyl; Dry to wherein adding, as to pulverize 60 ~ 150 mesh sieves landfill is the mineralized waste in 8 ~ 15 years age, and the amount of the pillared liquid of the required above-mentioned iron carbonyl of every gram mineralized waste is 1 ~ 3mL, stirs 6 ~ 8h; Aging 24h ~ 48h; With distilled water washing and precipitating thing, 105-120 ℃ was dried by the fire 3-4 hour down, and milling makes powder;
3) get above-mentioned powder and join in the deionized water, every 100mL deionized water adds above-mentioned powder 10 ~ 15g, under protective gas, stirs, and in the powder solution that stirs, adding concentration again is the KBH of 0.5 ~ 1mol/L
4Or NaBH
4Solution, the above-mentioned powder of every gram adds KBH
4Or NaBH
4The amount of solution is 3 ~ 5mL, continues to stir 30 ~ 40min;
4) separate above-mentioned solution, use the deoxidation washed with de-ionized water, under protective gas protection, 60 ~ 70 ℃ of freeze-day with constant temperature 5 ~ 6h promptly obtain being used for the support type Zero-valent Iron of wastewater treatment.
2. the preparation method who is used for the support type Zero-valent Iron of water treatment according to claim 1 is characterized in that: Fe3+ concentration is 0.4 ~ 0.8mol/L in the ferric salt solution described in the step 1).
3. the preparation method who is used for the support type Zero-valent Iron of water treatment according to claim 1, it is characterized in that: the trivalent iron salt described in the step 1) comprises FeCl
3Or Fe (NO
3)
3
4. the preparation method who is used for the support type Zero-valent Iron of water treatment according to claim 1 is characterized in that: the weak base described in the step 1) is Na
2CO
3
5. the preparation method who is used for the support type Zero-valent Iron of water treatment according to claim 1 is characterized in that: the protective gas step 3) and 4) is N
2
6. the preparation method who is used for the support type Zero-valent Iron of water treatment according to claim 1 is characterized in that: the centrifugation mode is adopted in the separation described in the step 4).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105688817A (en) * | 2016-04-01 | 2016-06-22 | 同济大学 | Metal cation adsorption filter column and preparation method thereof as well as metal cation recycling system |
| CN106111048A (en) * | 2016-07-12 | 2016-11-16 | 成都理工大学 | One is used for removing phosphatic eggshell loaded nano-iron material and preparation method thereof in water |
| CN107930629A (en) * | 2017-11-15 | 2018-04-20 | 南京理工大学 | The preparation method of support type charcoal catalysis material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613081A (en) * | 2009-07-20 | 2009-12-30 | 江苏工业学院 | Be used to handle the preparation method of the nano iron-carbon micro-electrolytic material of organic wastewater |
| CN102274716A (en) * | 2011-07-26 | 2011-12-14 | 常州大学 | Preparing method for compound modified and mineralized rubbish from water treatment materials |
-
2012
- 2012-08-13 CN CN201210287643XA patent/CN102764637A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613081A (en) * | 2009-07-20 | 2009-12-30 | 江苏工业学院 | Be used to handle the preparation method of the nano iron-carbon micro-electrolytic material of organic wastewater |
| CN102274716A (en) * | 2011-07-26 | 2011-12-14 | 常州大学 | Preparing method for compound modified and mineralized rubbish from water treatment materials |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105688817A (en) * | 2016-04-01 | 2016-06-22 | 同济大学 | Metal cation adsorption filter column and preparation method thereof as well as metal cation recycling system |
| CN106111048A (en) * | 2016-07-12 | 2016-11-16 | 成都理工大学 | One is used for removing phosphatic eggshell loaded nano-iron material and preparation method thereof in water |
| CN107930629A (en) * | 2017-11-15 | 2018-04-20 | 南京理工大学 | The preparation method of support type charcoal catalysis material |
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Application publication date: 20121107 |