CN104478031A - Preparation method of aluminum polychloride/hydroxyapatite copolymeric material - Google Patents
Preparation method of aluminum polychloride/hydroxyapatite copolymeric material Download PDFInfo
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- CN104478031A CN104478031A CN201410743901.XA CN201410743901A CN104478031A CN 104478031 A CN104478031 A CN 104478031A CN 201410743901 A CN201410743901 A CN 201410743901A CN 104478031 A CN104478031 A CN 104478031A
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Abstract
The invention discloses a preparation method of an aluminum polychloride/hydroxyapatite copolymeric material. The preparation method comprises the following steps of preparing an aluminum polychloride semi-finished product, preparing a hydroxyapatite semi-finished product and preparing the copolymeric material and synthesizing the aluminum polychloride/hydroxyapatite copolymerization network structure material by virtue of a copolymerization method. Compared with the conventional fluorine-removal material, the fluoride removal capacity of the aluminum polychloride/hydroxyapatite copolymeric material is four times that of a single hydroxyapatite fluoride removal filter and is six times that of an active aluminum oxide fluoride removal filter; the network structure of the material facilitates has the effects of facilitating net capturing of aluminum ions and hydroxyapatite powder in a water body, and the problems of excessive aluminum ions and water clarity in the water body are solved; and meanwhile, by polyaluminum chloride active ingredient in the copolymeric material, the continuous regeneration of hydroxyapatite can be promoted and the service life of the material is prolonged.
Description
Technical field
The present invention relates to the preparation method of a kind of polymerize aluminum chloride/hydroxyapatite copolymeric material, especially a kind of preparation method being applicable to the polymerize aluminum chloride/hydroxyapatite copolymeric material removing in tap water the fluorine that exceeds standard.
Background technology
Fluorine is one of the widest element of earth surface distribution, and the fluorine in human body is mainly from tap water.Drink the fluorosis that water of high fluorine content causes and relate to worldwide endemy, China is one of country that fluorosis is the most serious in the world, and except Shanghai City, spread all over the country each province.The World Health Organization specifies that in tap water, the content of fluorine is no more than 1.5mg/L.Absorption method is drinking water defluorination method the most frequently used both at home and abroad at present.De-fluoridation adsorbent kind is more, and as zeolite, clay, gac, activated alumina, bone carbon and hydroxyapatite etc., but consider difficulty or ease, the cost of renovation process and remove fluorine capacity, many sorbent materials do not obtain practical application.
The mid-80, activated alumina is once prevalent at the time, but during owing to utilizing Defluorination of Formation Mater By Adsorption On Activated Alumina, need reduce the pH value of former water, defluorinating agent easily hardens, and work-ing life is short, and aluminium stripping such as to exceed standard at the problem, and is stopped use.
Hydroxyapatite is a kind of defluorinating agent that at present research is more, as patent of invention number for ZL200610029366.7 discloses a kind of preparation method of the hydroxy apatite powder through improvement; Patent of invention number discloses a kind of production method of drinking water defluoridation filtering material for ZL201010264616.1, and this defluoridation filter material is porous spherical hydroxyapatite; Patent of invention number discloses the production method of attapulgite loaded hydroxyapatite composite defluorination filter bulb for ZL201110311033.4.The powder specific surface area of the hydroxyapatite in above-mentioned patent is large, except fluorine capacity is high, but not easily retains in water body; The ball material of hydroxyapatite has the advantages such as regeneration is easy, water outlet is smooth, but it is lower to remove fluorine capacity relative.
Polymerize aluminum chloride is the flocculation agent that water treatment industry is commonly used, but in potable water applications, should be noted the problem that aluminium content easily exceeds standard.
Summary of the invention
Technical problem: the object of the invention is the weak point overcome in prior art, utilize the height of powdery hydroxyapatite to remove the throwing out of fluorine capacity and polymerize aluminum chloride, provide a kind of except fluorine capacity is high, the preparation method of Synthesis and applications technique simple polymerize aluminum chloride/hydroxyapatite copolymeric material.
Technical scheme: the preparation method of polymerize aluminum chloride of the present invention/hydroxyapatite copolymeric material, comprises the steps:
A. the half-finished preparation of polymerize aluminum chloride
(1) adopt crystal aluminum chloride to be raw material, grinding evenly;
(2) take crystal aluminum chloride and put into crucible, preheating is carried out to retort furnace;
(3) control in-furnace temperature, when to reach temperature be 200-300 DEG C to temperature, crucible is put into retort furnace roasting, stir once every 5-6min, roasting 20-30min;
(4) take out crucible, in crucible, add water, amount of water according to every 10g crystal aluminum chloride add water 2-5mL calculate, stir, obtain the polymerize aluminum chloride work in-process of viscous resin shape;
B. the half-finished preparation of hydroxyapatite
(1) adopt calcium hydroxide, phosphoric acid to be raw material, that determines calcium hydroxide and phosphoric acid according to calcium phosphorus mol ratio 1.45-1.75 adds quality;
(2) add 5 times add quality water to calcium hydroxide in the reactor, be heated to 60 DEG C-90 DEG C, and keep water temperature;
(3) will determine the calcium hydroxide cold water furnishing pasty state adding quality, add in reactor by pasty state calcium hydroxide, limit edged is stirred to evenly;
(4) phosphoric acid is joined 3 times in the water of phosphoric acid volume, be mixed with phosphoric acid solution;
(5) phosphoric acid solution be mixed with is dripped in reactor, control rate of addition and be about 200mL/h, drip while stir, until phosphoric acid solution adds, obtain hydroxyapatite work in-process;
C. the preparation of copolymeric material
(1) in hydroxyapatite work in-process, add polymerize aluminum chloride work in-process, add-on is 5-8:1 according to the mass ratio of material crystal aluminum chloride and calcium hydroxide;
(2) continue to stir, keep temperature 60 C-90 DEG C, reaction 1-2h;
(3) naturally cool to room temperature, take out product, carry out dewatering, wash, dry, pulverizing, obtain polymerize aluminum chloride/hydroxyapatite copolymeric material.
Beneficial effect: the present invention is by copolymerization process synthesized polymer aluminum chloride/hydroxyapatite copolymerization network structured material, compared with existing defluorination material, current material is only the single defluorination material of effect, if polymerize aluminum chloride is a kind of inorganic polymer flocculation agent, there are the performances such as absorption, cohesion, precipitation, almost there is no effect for tap water eliminating minute fluorine separately, and there is the problem of aluminium content overproof in water body; Although the fluorine capacity that removes of hydroxyapatite is higher than common defluorination material, powder not easily retains, and it is lower that ball material removes fluorine capacity relative.Polymerize aluminum chloride/hydroxyapatite copolymerization network structured material has synergistic function, and the hydroxyapatite defluoridation filter material single except fluorine volume ratio improves 3 times, and specific activity aluminum oxide defluoridation filter material improves 5 times; The network structure of material is conducive to the effect that net catches aluminum ion and hydroxy apatite powder in water body, solves aluminum ion in water body and exceeds standard and the problem of water body clarity; Polymerize aluminum chloride active ingredient simultaneously in copolymeric material can impel hydroxyapatite constantly to regenerate, and improves the work-ing life of material.Major advantage is as follows:
1, product except fluorine capacity high, compared with the prior art, product improve 3-5 doubly except fluorine capacity;
2, material lifetime is long, does not need regeneration in operational process, and defluorination effect is steady in a long-term;
3, use simply, there is no the problem of filtrate whole updating;
4, the potential safety hazard that the aluminium composition that there is not common aluminium base material for water treatment existence exceeds standard.
Embodiment
Embodiment 1,
1. adopt crystal aluminum chloride to be raw material, take 800g and grind uniform crystal aluminum chloride and put into crucible, preheating is carried out to retort furnace, when to control in-furnace temperature be 250 DEG C, porcelain crucible put into stove roasting, stir once every 5min, roasting 30min;
2. in crucible, add 400mL water, stir, sample is polymerized, and obtains the polymerize aluminum chloride work in-process of viscous resin shape;
3. adopt calcium hydroxide, phosphoric acid to be raw material, that determines calcium hydroxide and phosphoric acid according to calcium phosphorus mol ratio 1.45-1.75 adds quality, adds 500mL water in the reactor, is heated to 60 DEG C, and keeps water temperature;
4. take 125g calcium hydroxide cold water furnishing pasty state, add in reactor, stir, obtain the polymerize aluminum chloride work in-process of viscous resin shape;
5. being added by 100g phosphoric acid in the water of 300g stirs is made into phosphoric acid solution;
6. the phosphoric acid solution of preparation is dripped in reactor, control rate of addition and be about 200mL/h, drip while stir, until
Phosphoric acid solution adds, and obtains hydroxyapatite work in-process;
7., after phosphoric acid solution adds, add polymerize aluminum chloride work in-process;
8. continue to stir, keep temperature 60 C, reaction 1.5h;
9. naturally cool to room temperature, take out product, carry out dewatering, wash, dry, pulverizing, obtain polymerize aluminum chloride/hydroxyapatite copolymeric material.
Embodiment 2,
1. adopt crystal aluminum chloride to be raw material, take 1000g and grind uniform crystal aluminum chloride and put into crucible, preheating is carried out to retort furnace, when to control in-furnace temperature be 290 DEG C, porcelain crucible put into stove roasting, stir once every 5min, roasting 30min;
2. in crucible, add 500mL water, stir, sample is polymerized, and obtains the polymerize aluminum chloride work in-process of viscous resin shape;
3. adopt calcium hydroxide, phosphoric acid to be raw material, that determines calcium hydroxide and phosphoric acid according to calcium phosphorus mol ratio 1.45-1.75 adds quality; Add 500mL water in the reactor, be heated to 75 DEG C, and keep water temperature;
4. take 125g calcium hydroxide cold water furnishing pasty state, add in reactor, stir;
5. 100g phosphoric acid is added in the water of 300g the wiring solution-forming that stirs;
6. the phosphoric acid solution of preparation is dripped in reactor, control rate of addition and be about 200mL/h, drip while stir.
7., after phosphoric acid solution adds, add polymerize aluminum chloride work in-process;
8. continue to stir, keep temperature 75 DEG C reaction 120min;
9. take out product, naturally cool to room temperature, carry out dewatering, wash, dry, pulverizing, obtain polymerize aluminum chloride/hydroxyapatite copolymeric material.
Embodiment 3:
1. take 625g to grind uniform crystal aluminum chloride and put into crucible, when to control in-furnace temperature be 200 DEG C, porcelain crucible put into stove roasting, stir once every 6min, roasting 20min;
2. in crucible, add 300mL water, stir, sample is polymerized, and forms the resinous substance of thickness.
3. add 500mL water in the reactor, be heated to 90 DEG C, and keep water temperature;
4. take 125g calcium hydroxide cold water furnishing pasty state, add in reactor, stir;
5. 100g phosphoric acid is added in the water of 300g the wiring solution-forming that stirs;
6. the phosphoric acid solution of preparation is dripped in reactor, control rate of addition and be about 200mL/h, drip while stir.
7., after phosphoric acid solution adds, add the resinous substance of PAC work in-process thickness;
8. continue to stir, keep temperature 90 DEG C reaction 60min;
9. take out product, naturally cool to room temperature, carry out dewatering, wash, dry, pulverizing, obtain polymerize aluminum chloride/hydroxyapatite copolymeric material.
Claims (1)
1. the preparation method of polymerize aluminum chloride/hydroxyapatite copolymeric material: it is characterized in that comprising the steps:
A. the half-finished preparation of polymerize aluminum chloride
(1) adopt crystal aluminum chloride to be raw material, grinding evenly;
(2) take crystal aluminum chloride and put into crucible, preheating is carried out to retort furnace;
(3) control in-furnace temperature, when temperature reaches 200-300 DEG C, crucible is put into retort furnace roasting, stir once every 5-6min, roasting 20-30min;
(4) take out crucible, in crucible, add water, amount of water according to every 10g crystal aluminum chloride add water 2-5mL calculate, stir, obtain the polymerize aluminum chloride work in-process of viscous resin shape;
B. the half-finished preparation of hydroxyapatite
(1) adopt calcium hydroxide, phosphoric acid to be raw material, that determines calcium hydroxide and phosphoric acid according to calcium phosphorus mol ratio 1.45-1.75 adds quality;
(2) add 5 times add quality water to calcium hydroxide in the reactor, be heated to 60 DEG C-90 DEG C, and keep water temperature;
(3) will determine the calcium hydroxide cold water furnishing pasty state adding quality, add in reactor by pasty state calcium hydroxide, limit edged is stirred to evenly;
(4) phosphoric acid is joined 3 times in the water of phosphoric acid volume, be mixed with phosphoric acid solution;
(5) phosphoric acid solution be mixed with is dripped in reactor, control rate of addition and be about 200mL/h, drip while stir, until phosphoric acid solution adds, obtain hydroxyapatite work in-process;
C. the preparation of copolymeric material
(1) in hydroxyapatite work in-process, add polymerize aluminum chloride work in-process, add-on is 5-8:1 according to the mass ratio of material crystal aluminum chloride and calcium hydroxide;
(2) continue to stir, keep temperature 60 C-90 DEG C, reaction 1-2h;
(3) naturally cool to room temperature, take out product, carry out dewatering, wash, dry, pulverizing, obtain polymerize aluminum chloride/hydroxyapatite copolymeric material.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110316872A (en) * | 2019-07-18 | 2019-10-11 | 贵州财经大学 | A kind of hydroxyapatite defluoridation filter material device and its technique |
| CN110523365A (en) * | 2019-08-17 | 2019-12-03 | 江苏长江水务股份有限公司 | A kind of efficient preparation method for removing the modified hydroxylapatite of fluoride in water body |
| 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 |
| CN115571963A (en) * | 2022-10-17 | 2023-01-06 | 西安西热水务环保有限公司 | Synchronous turbidity-reducing and fluorine-removing medicament and use method thereof |
| CN117085638A (en) * | 2023-09-14 | 2023-11-21 | 山东环瑞生态科技有限公司 | Efficient defluorination medicament suitable for lithium battery wastewater and application thereof |
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| JPS53125357A (en) * | 1977-04-06 | 1978-11-01 | Ataka Kensetsu Kougiyou Kk | Method of removing underwater fluorine ion |
| CN101862644A (en) * | 2009-04-17 | 2010-10-20 | 中国科学院生态环境研究中心 | Preparation method of Al-doped hydroxyapatite high-efficiency defluorinating adsorbent |
| 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 |
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2014
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Patent Citations (3)
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| JPS53125357A (en) * | 1977-04-06 | 1978-11-01 | Ataka Kensetsu Kougiyou Kk | Method of removing underwater fluorine ion |
| CN101862644A (en) * | 2009-04-17 | 2010-10-20 | 中国科学院生态环境研究中心 | Preparation method of Al-doped hydroxyapatite high-efficiency defluorinating adsorbent |
| 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 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110316872A (en) * | 2019-07-18 | 2019-10-11 | 贵州财经大学 | A kind of hydroxyapatite defluoridation filter material device and its technique |
| CN110523365A (en) * | 2019-08-17 | 2019-12-03 | 江苏长江水务股份有限公司 | A kind of efficient preparation method for removing the modified hydroxylapatite of fluoride in water body |
| 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 |
| CN115571963A (en) * | 2022-10-17 | 2023-01-06 | 西安西热水务环保有限公司 | Synchronous turbidity-reducing and fluorine-removing medicament and use method thereof |
| CN117085638A (en) * | 2023-09-14 | 2023-11-21 | 山东环瑞生态科技有限公司 | Efficient defluorination medicament suitable for lithium battery wastewater and application thereof |
| CN117085638B (en) * | 2023-09-14 | 2024-03-19 | 山东环瑞生态科技有限公司 | Efficient defluorination medicament suitable for lithium battery wastewater and application thereof |
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