CN106745628A - A kind of production method of carbon doping hydroxyapatite defluoridation filter material - Google Patents
A kind of production method of carbon doping hydroxyapatite defluoridation filter material Download PDFInfo
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- CN106745628A CN106745628A CN201611178081.XA CN201611178081A CN106745628A CN 106745628 A CN106745628 A CN 106745628A CN 201611178081 A CN201611178081 A CN 201611178081A CN 106745628 A CN106745628 A CN 106745628A
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- phosphoric acid
- hydrogen carbonate
- ammonium hydrogen
- filter material
- calcium nitrate
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- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A kind of production method of carbon doping hydroxyapatite defluoridation filter material, including：Calcium nitrate, phosphoric acid, ammoniacal liquor and the ammonium hydrogen carbonate for using technical grade are raw material；Synthesis carbon doping hydroxyapatite filtrate, wherein ammoniacal liquor play a part of to regulate and control pH value of reaction system, to ensure the purity and fluorine removal capacity of product；Ammonium hydrogen carbonate doping is few, due to CO3 2‑Doping the lattice of hydroxyapatite can be caused to be distorted, the vacancy concentration on surface accordingly increases, structure becomes loose, chemical mobility of the surface also strengthens accordingly, so as to improve its fluorine removal ability, the hydroxyapatite defluoridation filter material that the overall fluorine removal Capacity Ratio of filtrate is single improves 34 times, and specific activity aluminum oxide defluoridation filter material at least improves more than 7 times.Its method is simple, and defluorination effect is steady in a long-term, and production efficiency is higher.
Description
Technical field
The present invention relates to a kind of production method of defluoridation filter material, especially a kind of carbon doping hydroxyl suitable for defluoridation filter material
The production method of apatite defluoridation filter material.
Background technology
It is to be related to worldwide endemic disease to drink the fluorine poisoning that high-fluorine water causes, and the lighter causes den tal fluorosis, and severe one can draw
Play fluorosis of bone.The World Health Organization specifies that the content of fluorine in drinking water is no more than 1.5mg/L.Because high-fluorine water is mainly distributed on ring
Border is severe, with a varied topography, the few electricity of water shortage, have inconvenient traffic, it is backward in economy, take in rural area, pastoral area not high, therefore absorption method is mesh
Preceding drinking water defluorination method the most frequently used both at home and abroad.The crucial part of absorption method seeks to choose suitable adsorbent.
Adsorbent kind is more both at home and abroad at present, such as zeolite, clay, activated carbon, activated alumina and bone black, but considers
To environmental pollution, the difficulty or ease of renovation process, cost and fluorine removal capacity, many adsorbents do not obtain practical application.
Hydroxyapatite (abbreviation HAP) is a kind of Novel defluoridation filter material, and powder body material has synthesis convenient, and fluoride removing rate is high etc.
Calcium ion in advantage, and its structure is easily replaced by other ions, especially divalent heavy metal ions, in addition with economic hair
Exhibition there is a growing awareness that the importance of environmental protection, so the Study on adsorption properties in recent years to hydroxyapatite is more.
As patent of invention number for ZL201010264616.1 is disclosed a kind of production method of drinking water defluoridation filtering material, this defluoridation filter material
It is porous spherical hydroxyapatite；Patent of invention number discloses attapulgite loaded hydroxyapatite for ZL201110311033.4
The production method of composite defluorination filter bulb；A kind of patent of invention number aluminium doped hydroxyapatite for ZL201410742909.4 is disclosed
The production method of defluoridation filter material.Based on hydroxyapatite in above-mentioned patent document, progressively it is modified to reach
The purpose of depth fluorine removal, but the cost of material is still of a relatively high, and fluorine removal capacity needs further to improve.And improve fluorine removal appearance
Amount, reduces cost, the security for improving application is the modified eternal theme of defluorinating agent.
The content of the invention
Technical problem：The purpose of the present invention is to overcome weak point of the prior art, proposes a kind of carbon doping hydroxyl phosphorus
The production method of lime stone defluoridation filter material.
Technical scheme：The production method of carbon doping hydroxyapatite defluoridation filter material of the invention,
Comprise the following steps：
(1) calcium nitrate, phosphoric acid, ammoniacal liquor and the ammonium hydrogen carbonate for using technical grade are raw material；
(2) quality is added according to what the carbon phosphorus mol ratio of ammonium hydrogen carbonate and phosphoric acid determined ammonium hydrogen carbonate and phosphoric acid；
(3) adding according to calcium nitrate molal quantity and the ratio-dependent calcium nitrate of ammonium hydrogen carbonate and the molal quantity sum of phosphoric acid
Amount；；
(4) ammonium hydrogen carbonate and calcium nitrate water that determine to add quality are tuned into pasty state, pasty state ammonium hydrogen carbonate and nitric acid
Calcium mixed liquor is added in reactor, is stirred while adding to uniform；
(5) it is 1 according to the volume ratio of phosphoric acid and water：3, prepare phosphoric acid solution；
(6) phosphoric acid solution that will be configured to is added drop-wise in reactor, and rate of addition is 200L/h；
(7) during phosphoric acid is added dropwise, while to the pH value that ammoniacal liquor adjustment reaction system is added dropwise in reactor；
(8) after treating that phosphoric acid is dripped, continue to be stirred under normal temperature；
(9) after reaction terminates, product is taken out, is dehydrated, washed, dried, crushed, obtained carbon doping hydroxyapatite and remove
Fluorine filtrate.
The carbon phosphorus mol ratio of the ammonium hydrogen carbonate and phosphoric acid is 0.02-0.1.
The calcium nitrate molal quantity is 1.2~1.5 with the molal quantity sum of ammonium hydrogen carbonate and phosphoric acid.
The pH value of the reaction system is maintained at the scope of 9-11 in real time.
After the phosphoric acid is dripped, the time that continuation is stirred at normal temperatures is 0.5-1.
Beneficial effect：In order to further improve hydroxyapatite Fluoride-Absorption Capacity, the present invention using the cheap calcium nitrate of technical grade,
Phosphoric acid, ammoniacal liquor and ammonium hydrogen carbonate are raw material, synthesize carbon doping hydroxyapatite filtrate, and wherein ammoniacal liquor plays regulation and control reaction system pH
The effect of value, to ensure the purity and fluorine removal capacity of product；Ammonium hydrogen carbonate doping is few, due to CO3 2-Doping can cause hydroxyl
The lattice of base apatite is distorted, and the vacancy concentration on surface accordingly increases, and structure becomes loose, and chemical mobility of the surface is also corresponding
Enhancing, so as to improve its fluorine removal ability, the hydroxyapatite defluoridation filter material that the overall fluorine removal Capacity Ratio of filtrate is single improves 3-4
Times, specific activity aluminum oxide defluoridation filter material at least improves more than 7 times；Mainly have the advantage that：
1st, the fluorine removal capacity of product is high, and compared with the prior art, the fluorine removal capacity of product improves 3-4 times, in running
In be not required to regeneration, defluorination effect is steady in a long-term；
2nd, produced using cheap technical grade material, prepared under normal temperature, produced and simple and easy to control using technique, equipment, favorably
In large-scale production and utilization and extention；
3rd, product crystal in preparation process has been formed, it is not necessary to which still aging again, production efficiency is higher.
Specific embodiment
The production method of carbon doping hydroxyapatite defluoridation filter material of the invention：
(1) calcium nitrate, phosphoric acid, ammoniacal liquor and the ammonium hydrogen carbonate for using technical grade are raw material；
(2) according to the ratio-dependent ammonium hydrogen carbonate and phosphoric acid that the carbon phosphorus mol ratio of ammonium hydrogen carbonate and phosphoric acid is 0.02-0.1
Add quality；
(3) it is 1.2-1.5 according to the ratio of calcium nitrate molal quantity and the molal quantity sum of ammonium hydrogen carbonate and phosphoric acid, determines nitre
The dosage of sour calcium；；
(4) ammonium hydrogen carbonate and calcium nitrate water that determine to add quality are tuned into pasty state, pasty state ammonium hydrogen carbonate and nitric acid
Calcium mixed liquor is added in reactor, is stirred while adding to uniform；
(5) it is 1 according to the volume ratio of phosphoric acid and water：3, prepare phosphoric acid solution；；
(6) phosphoric acid solution that will be configured to is added drop-wise in reactor, and rate of addition is 200L/h；
(7) during phosphoric acid is added dropwise, while to ammoniacal liquor is added dropwise in reactor, making the pH value of reaction system real-time
It is maintained at the scope of 9-11；
(8) after treating that phosphoric acid is dripped, continue to be stirred 0.5-1 hours under normal temperature；
(9) after reaction terminates, product is taken out, is dehydrated, washed, dried, crushed, obtained carbon doping hydroxyapatite and remove
Fluorine filtrate
The present invention is further described by the following embodiment：
By taking one ton of reactor as an example, technical grade nitric acid calcium content 99%, ammonium hydrogen carbonate is (with NH3Meter) content 21%~
22%, phosphorus acid content 85%, density is 1.7g/mL, ammoniacal liquor content 20%.
Embodiment 1：
1st, it is 0.02 according to the carbon phosphorus mol ratio of ammonium hydrogen carbonate and phosphoric acid, the quality that adds for determining ammonium hydrogen carbonate is
1.72kg, the volume that adds of phosphoric acid is 73L；
2nd, it is 1.3 according to the ratio of calcium nitrate molal quantity and the molal quantity sum of ammonium hydrogen carbonate and phosphoric acid, determines calcium nitrate
Dosage be 236kg,
3rd, calcium nitrate 236kg, ammonium hydrogen carbonate 1.72kg being weighed respectively, water being spent and is tuned into pasty state, pasty state mixed liquor is added
In reactor, stir while adding to uniform；
4th, according to the volume ratio 1 of phosphoric acid and water：3, by the water of the phosphoric acid addition 219L of 73L, stir wiring solution-forming；
5th, above-mentioned phosphoric acid solution is added drop-wise to reactor, it is 200L/h to control rate of addition；
6th, during phosphoric acid is added dropwise, while to being added dropwise over ammoniacal liquor in reactor, the pH value for adjusting reaction system is
9；
7th, continue to stir 0.5 hour after phosphoric acid is dripped, under normal temperature；
8th, after reaction terminates, product is taken out, is dehydrated, washed, dried, crushed, obtained carbon doping hydroxyapatite and remove
Fluorine filtrate.
Embodiment 2：
1st, it is 0.04 according to the carbon phosphorus mol ratio of ammonium hydrogen carbonate and phosphoric acid, the quality that adds for determining ammonium hydrogen carbonate is
3.44kg, the volume that adds of phosphoric acid is 73L；
2nd, it is 1.5 according to the ratio of calcium nitrate molal quantity and the molal quantity sum of ammonium hydrogen carbonate and phosphoric acid, determines calcium nitrate
Dosage be 268kg,
3rd, calcium nitrate 268kg, ammonium hydrogen carbonate 3.44kg are weighed respectively, pasty state is tuned into water, pasty state mixed liquor is added anti-
In answering kettle, stir while adding to uniform；
4th, according to the volume ratio 1 of phosphoric acid and water：, 3, stir wiring solution-forming in the water that the phosphoric acid of 73L is added 219L；
5th, above-mentioned phosphoric acid solution is added drop-wise to reactor, it is 200L/h to control rate of addition；
6th, during phosphoric acid is added dropwise, while to being added dropwise over ammoniacal liquor in reactor, the pH value for adjusting reaction system is
10；
7th, continue to stir 1 hour after phosphoric acid is dripped, under normal temperature；
8th, after reaction terminates, product is taken out, is dehydrated, washed, dried, crushed, obtained carbon doping hydroxyapatite and remove
Fluorine filtrate.
Embodiment 3：
1st, it is 0.08 according to the carbon phosphorus mol ratio of ammonium hydrogen carbonate and phosphoric acid, the quality that adds for determining ammonium hydrogen carbonate is
6.88kg, the volume that adds of phosphoric acid is 73L；
2nd, it is 1.2 according to the ratio of calcium nitrate molal quantity and the molal quantity sum of ammonium hydrogen carbonate and phosphoric acid, determines calcium nitrate
Dosage be 230kg,
3rd, calcium nitrate 230kg, ammonium hydrogen carbonate 6.88kg are weighed respectively, pasty state is tuned into water, pasty state mixed liquor is added anti-
In answering kettle, stir while adding to uniform；
4th, according to the volume ratio 1 of phosphoric acid and water：, 3, stir wiring solution-forming in the water that the phosphoric acid of 73L is added 219L；
5th, above-mentioned phosphoric acid solution is added drop-wise to reactor, it is 200L/h to control rate of addition；
6th, during phosphoric acid is added dropwise, while to being added dropwise over ammoniacal liquor in reactor, the pH value for adjusting reaction system is
11；
7th, continue to stir 1 hour after phosphoric acid is dripped, under normal temperature；
8th, after reaction terminates, product is taken out, is dehydrated, washed, dried, crushed, obtained carbon doping hydroxyapatite and remove
Fluorine filtrate.
Claims (5)
1. a kind of production method of carbon doping hydroxyapatite defluoridation filter material, it is characterised in that comprise the following steps：
（1）Calcium nitrate, phosphoric acid, ammoniacal liquor and the ammonium hydrogen carbonate for using technical grade are raw material；
（2）What the carbon phosphorus mol ratio according to ammonium hydrogen carbonate and phosphoric acid determined ammonium hydrogen carbonate and phosphoric acid adds quality；
（3）According to calcium nitrate molal quantity and the dosage of the ratio-dependent calcium nitrate of the molal quantity sum of ammonium hydrogen carbonate and phosphoric acid；
（4）The ammonium hydrogen carbonate and calcium nitrate water that determine to add quality are tuned into pasty state, pasty state ammonium hydrogen carbonate and calcium nitrate are mixed
Close during liquid adds reactor, stir while adding to uniform；
（5）Volume ratio according to phosphoric acid and water is 1：3, prepare phosphoric acid solution；；
（6）The phosphoric acid solution that will be configured to is added drop-wise in reactor, and rate of addition is 200L/h；
（7）During phosphoric acid is added dropwise, while to the pH value that ammoniacal liquor adjustment reaction system is added dropwise in reactor；（8）Treat
After phosphoric acid is dripped, continue to be stirred under normal temperature；
（8）After reaction terminates, product is taken out, be dehydrated, washed, dried, crushed, obtain the filter of carbon doping hydroxyapatite fluorine removal
Material.
2. the production method of a kind of carbon doping hydroxyapatite defluoridation filter material according to claim 1, it is characterised in that：Institute
The carbon phosphorus mol ratio for stating ammonium hydrogen carbonate and phosphoric acid is 0.02-0.1.
3. the production method of a kind of carbon doping hydroxyapatite defluoridation filter material according to claim 1, it is characterised in that：Institute
The ratio for stating the molal quantity sum of calcium nitrate molal quantity and ammonium hydrogen carbonate and phosphoric acid is 1.2 ~ 1.5.
4. the production method of a kind of carbon doping hydroxyapatite defluoridation filter material according to claim 1, it is characterised in that：Instead
The pH value of system is answered to be maintained at the scope of 9-11 in real time.
5. the production method of a kind of carbon doping hydroxyapatite defluoridation filter material according to claim 1, it is characterised in that：Institute
State after phosphoric acid drips, the time that continuation is stirred at normal temperatures is 0.5-1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111514846A (en) * | 2020-04-20 | 2020-08-11 | 西安斯威夫特环保科技有限公司 | Preparation method of defluorination filter material |
| CN115779856A (en) * | 2022-11-21 | 2023-03-14 | 煤炭科学技术研究院有限公司 | Hydroxyapatite/active carbon composite defluorination material and preparation method thereof |
| CN116371350A (en) * | 2023-03-20 | 2023-07-04 | 北京铭泽源环境工程有限公司 | Preparation method of hydroxyapatite-loaded defluorination adsorbent and defluorination adsorbent |
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| JPH01203206A (en) * | 1988-02-09 | 1989-08-16 | Nippon Chem Ind Co Ltd | Production of octacalcium phosphate |
| CN1415537A (en) * | 2002-11-19 | 2003-05-07 | 武汉化工学院 | Adulterated hydroxyapatite and its production method |
| CN101913584A (en) * | 2010-08-27 | 2010-12-15 | 江苏永冠给排水设备有限公司 | Method for producing filter material for removing fluorine from drinking water |
| CN102381691A (en) * | 2011-07-29 | 2012-03-21 | 沈阳大学 | Preparation method of nano hydroxylapatite adsorbent for absorbing heavy metal ions in waste water |
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2016
- 2016-12-19 CN CN201611178081.XA patent/CN106745628B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01203206A (en) * | 1988-02-09 | 1989-08-16 | Nippon Chem Ind Co Ltd | Production of octacalcium phosphate |
| CN1415537A (en) * | 2002-11-19 | 2003-05-07 | 武汉化工学院 | Adulterated hydroxyapatite and its production method |
| CN101913584A (en) * | 2010-08-27 | 2010-12-15 | 江苏永冠给排水设备有限公司 | Method for producing filter material for removing fluorine from drinking water |
| CN102381691A (en) * | 2011-07-29 | 2012-03-21 | 沈阳大学 | Preparation method of nano hydroxylapatite adsorbent for absorbing heavy metal ions in waste water |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111514846A (en) * | 2020-04-20 | 2020-08-11 | 西安斯威夫特环保科技有限公司 | Preparation method of defluorination filter material |
| CN115779856A (en) * | 2022-11-21 | 2023-03-14 | 煤炭科学技术研究院有限公司 | Hydroxyapatite/active carbon composite defluorination material and preparation method thereof |
| CN115779856B (en) * | 2022-11-21 | 2024-05-07 | 煤炭科学技术研究院有限公司 | Hydroxyapatite/activated carbon composite defluorination material and preparation method thereof |
| CN116371350A (en) * | 2023-03-20 | 2023-07-04 | 北京铭泽源环境工程有限公司 | Preparation method of hydroxyapatite-loaded defluorination adsorbent and defluorination adsorbent |
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