CN106586994A - Technological method for preparing hydroxyapatite by using phosphating waste water as raw material - Google Patents
Technological method for preparing hydroxyapatite by using phosphating waste water as raw material Download PDFInfo
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- CN106586994A CN106586994A CN201611169871.1A CN201611169871A CN106586994A CN 106586994 A CN106586994 A CN 106586994A CN 201611169871 A CN201611169871 A CN 201611169871A CN 106586994 A CN106586994 A CN 106586994A
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- waste water
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- hydroxyapatite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/321—Methods for converting an alkaline earth metal ortho-phosphate into another ortho-phosphate
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to a technological method for preparing hydroxyapatite by using phosphating waste water as a raw material. Aiming at high concentration phosphating waste water, the method is used for disposing the high concentration phosphating waste water with NaOH as a regulator and Ca(OH)2 as a precipitant, and preparing hydroxyapatite at the same time. Fractional precipitation and a product morphology control method are adopted to ensure the purity of the hydroxyapatite and improve the quality of the hydroxyapatite. Simple in process and operation, the method can not only remove most PO4<3-> and heavy metal ions in phosphating waste water to make effluent quality up to an emission standard but also recycle the by-products, so that the method has good economic benefits and application prospects.
Description
Technical field
The invention belongs to environmental conservation water process and resource regeneration field, and in particular to one kind is with phosphorized waste water as raw material system
The process of standby hydroxyapatite.
Background technology
Bonderizing is to form a kind of insoluble phosphate film in metal surface using phosphoric acid or phosphatic solution
Process, be Technology that Treatment of Metal Surface is generally adopted.General parkerizing process includes alkali cleaning oil removing, acid pickling and rust removing, phosphorus
Change and Passivation Treatment, produce substantial amounts of pollutant in the process, such as oil emulsion, surfactant and phosphate etc., especially with phosphorus
The discharge capacity of hydrochlorate is larger, exceeded serious, and as the species of pollutant is various, brings suitable difficulty to wastewater treatment.With
The fast development of auto manufacturing, communications service manufacturing industry etc., China produces substantial amounts of high concentration phosphorized waste water every year, if
Less than rationally effectively improvement, it will cause great environmental pollution and ecological disruption.At present, dephosphorization technique both domestic and external is with biology
Based on method and chemical method, but high concentration phosphatization wastewater biodegradability is poor, should not adopt Biochemical method, therefore chemical method is place
The robust techniques of reason high concentration phosphorized waste water.In chemical method dephosphorization technique, the sedimentation method are with extensive the characteristics of its efficient, simplicity
Using.
Chinese Patent Application No. 201410651110.4, date of application are disclosed for the patent application document of 2014.11.17
A kind of medicament hydrated calcium chloroaluminate suitable for high-density phosphorus agricultural chemicals waste water dephosphorization, Phosphorus From Wastewater clearance is up to 99%.Should
The shortcoming of invention be hydrated calcium chloroaluminate as a kind of dephosphorization agent, it is unobvious to the removal effect of heavy metal ion in solution, and
Many industrial trade phosphorus-containing wastewaters contain plurality of heavy metal ion, therefore the invention is for many industrial trade phosphorus-containing wastewaters not
It is suitable for.
Chinese Patent Application No. 201410296901.X, date of application are disclosed for the patent application document of 2014.06.28
A kind of adsorption treatment material suitable for high-concentration phosphorus-containing wastewater, with good absorbability.The shortcoming of the invention is that institute is public
The adsorbing material composition opened is numerous, and proportioning is complicated.
Although the dephosphorization technique that major part Application Number (patent) is announced at present can effectively reduce waste water phosphorus content with technique,
It is unobvious to the removal effect of heavy metal ion in solution, and fails to solve sludge problem, produced sludge components is complicated, main
Heavy metallic salt to be included, calcium phosphate, calcium hydrogen phosphate, dalcium biphosphate etc., it is big using difficulty, easily cause secondary pollution and resource
Waste.The present invention is controlled with product form by fractional precipitation, is capable of achieving pollutant shunting, is reclaimed high-purity hydroxyapatite.
Hydroxyapatite be a kind of new, excellent performance medicine and environment functional material, wide application, added value
It is high.Hydroxyapatite is main inorganic composition part in human body and animal skeleton, in skeleton, occupies skeleton composition
6/10ths, and the content in dentary is up to 97%, the features such as which has nontoxic, nonirritant and mutability, bio-compatible
Property it is good, after implantation human body, the short period chemical bonding can occur with skeleton, with excellent bone conductibility.Hydroxyl phosphorus
Lime stone specific surface area is big, and surface duct is enriched, and with good absorption property, can be used to remove Heavy Metals in Waters, Organic substance
Deng multiple pollutant matter.In addition, the ion-exchange capacity of hydroxyapatite is very strong, for example phosphate anion is easily and the official such as sulfate radical
Can group exchange, easily and metal ion exchanged, displacement reaction in hydroxide ion and halide ion to calcium ion there is.
The content of the invention
The present invention is carried for existing sedimentation method treatment of phosphate coating wastewater process sludge yield is big, the problem that processing cost is high
For a kind of new phosphide method of wastewater treatment, i.e., hydroxyapatite is prepared by raw material of high concentration phosphorized waste water, can both reduce
Sludge yield during phosphorized waste water handling process, can reclaim high value added product hydroxyapatite again.
To solve above-mentioned technical problem, the technical scheme that the present invention is provided is：
A kind of process for preparing hydroxyapatite with phosphorized waste water as raw material, including fractional precipitation and product form control
Two parts processed, specifically comprise the steps of：
(1) add regulator in waste water, adjust pH value of solution, remove the heavy metal ion impurities in solution, including Ni2+、
Fe3+、Cu2+；Regulator is saved in supernatant backflow, increases heavy metal removing rate；
(2) add a certain amount of precipitant and regulator in the waste water after above-mentioned step process, stir at a certain temperature
Certain hour, then still aging a period of time at a certain temperature, then Jing are filtered, wash, are dried to obtain solid product；Finally
Gained solid product is sent in Muffle furnace, in air atmosphere Jing after uniform temperature calcining certain hour, you can needed for being obtained
Sample.
Wherein, in step (1), the regulator selects NaOH solution, and concentration is 1～2mol/L, and pH value of solution control is 7.4
～8.5.Supernatant reflux ratio is 20～30%.
Wherein, in step (2), the regulator selects NaOH solution, and concentration is 1～2mol/L；Precipitant selects Ca
(OH)2, and the amount ratio of calcium phosphorus substance, i.e. n (Ca)/n (P), is 1.5～3.Whipping temp is 40～60 DEG C, and stir speed (S.S.) is
1000～1500r/min, mixing time are 2～6h.The still aging time is 2～6h, and still aging temperature is 40～60 DEG C.Wash
Agent is washed for ethanol；Baking temperature is 80～115 DEG C.Calcining heat is 700～1000 DEG C, and heating rate is 0.5～20 DEG C/min,
A length of 2～10h during sintering soak.
Compared to prior art, the invention has the advantages that：
(1) fractional precipitation, first removes the heavy metal ion in phosphorized waste water, it is to avoid interference of the heavy metal ion to product,
Ensure the purity of product, reduce sludge product resource difficulty.
(2) product form control, controls phosphorized waste water processing procedure technological parameter, makes the orientation generation of sludge product have high returning
Receive the hydroxyapatite of value.
The present invention is controlled with product form by fractional precipitation, is capable of achieving pollutant shunting, is reclaimed high-purity hydroxy-apatite
Stone.Step-by-step precipitation method is first passed through, the Ni in phosphorized waste water is removed2+、Fe3+、Cu2+Etc. heavy metal ion, and Zn2+Then with [Zn
(OH)4]2-Form exists in solution, it is to avoid generate impact of the heavy phosphates precipitation to product purity；Pass through product shape again
State control methods, control calcium-phosphorus ratio, reaction temperature, whipping temp, Aging Temperature, calcining heat etc., it is to avoid Ca3(PO4)2、
CaHPO4Generation, it is ensured that Ca10(PO4)6(OH)2Yield.
The present invention prepares hydroxyapatite, can not only reduce pollution, protection ring with high concentration phosphorized waste water as raw material
Border, can also save phosphor resource, mitigate phosphorus ore recovery pressure, with good economic and social profit.
Description of the drawings
Fig. 1：The process chart of the present invention.
Specific embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1
Using process of the present invention process Hangzhou Stationery Factory phosphorized waste water (before workpiece phosphatization without pickling at
Reason, the phosphorous 254mg/L of waste water).First, add NaOH solution in waste water, adjust pH to 7.4, remove Fe in waste water2+、Ni2+、
Cu2+Etc. heavy metal ion impurities, standing is filtrated to get supernatant；Addition Ca (OH) in gained supernatant again2, holding n (Ca)/
N (P) is 1.5, and 2h is stirred at 40 DEG C, and the then still aging 6h at 40 DEG C, then Jing is filtered, washed, being dried to obtain solid product
Thing, finally sends into gained solid product in Muffle furnace, in air atmosphere 700 DEG C of calcining 4h of Jing.Phosphorized waste water dephosphorization efficiency
Up to 93.7%, hydroxyapatite purity 79% is obtained.
Embodiment 2
Jiangsu band large-scale metal surface treatment enterprise phosphorized waste water is processed using process of the present invention.First, to
Add NaOH solution in waste water, adjust pH to 7.8, remove Fe in waste water2+、Ni2+、Cu2+Etc. heavy metal ion impurities, stood
Filter obtains supernatant；Addition Ca (OH) in gained supernatant again2, keep n (Ca)/n (P) to be 2.0,4h is stirred at 50 DEG C,
Then the still aging 6h at 50 DEG C, then Jing is filtered, is washed, being dried to obtain solid product, is finally sent into gained solid product
In Muffle furnace, 800 DEG C of calcining 6h of Jing, are obtained hydroxyapatite in air atmosphere.Phosphorized waste water dephosphorization efficiency up to 95.1%,
Prepared hydroxyapatite purity 73%.
Embodiment 3
Hefei refrigerator factory phosphorized waste water is processed using process of the present invention.First, add NaOH in waste water
Solution, adjusts pH to 8.5, removes Fe in waste water2+、Ni2+、Cu2+Etc. heavy metal ion impurities, standing is filtrated to get supernatant；Again
Add Ca (OH) in gained supernatant2, keep n (Ca)/n (P) to be 3.0,6h stirred at 60 DEG C, then stand at 60 DEG C
6h is aged, then Jing is filtered, washed, being dried to obtain solid product, finally gained solid product is sent in Muffle furnace, in air gas
Under atmosphere, 1000 DEG C of calcining 8h of Jing, are obtained hydroxyapatite.Phosphorized waste water dephosphorization efficiency is obtained hydroxyapatite pure up to 90.8%
Degree 81%.
The above, is only presently preferred embodiments of the present invention, not makees any pro forma restriction to the present invention, any ripe
Professional and technical personnel is known, it is in the range of without departing from technical solution of the present invention, according to the technical spirit of the present invention, real to more than
Apply any simple modification, equivalent that example made and improve etc., still fall within technical solution of the present invention protection domain it
It is interior.
Claims (8)
1. a kind of process for preparing hydroxyapatite with phosphorized waste water as raw material, it is characterised in that：Including fractional precipitation and
Product form controls two parts, specifically comprises the steps of：
(1) add regulator in waste water, adjust pH value of solution, remove the heavy metal ion impurities in solution, including Ni2+、Fe3+、
Cu2+；Regulator is saved in supernatant backflow, increases heavy metal removing rate；
(2) add a certain amount of precipitant and regulator in the waste water after above-mentioned step process, stir certain at a certain temperature
Time, then still aging a period of time at a certain temperature, then Jing filter, wash, are dried to obtain solid product；Finally by institute
Obtain solid product to send in Muffle furnace, in air atmosphere Jing after uniform temperature calcining certain hour, you can sample needed for being obtained.
2. the process for preparing hydroxyapatite with phosphorized waste water as raw material according to claim 1, it is characterised in that：
In step (1), the regulator selects NaOH solution, and concentration is 1～2mol/L, and pH value of solution control is 7.4～8.5.
3. the process for preparing hydroxyapatite with phosphorized waste water as raw material according to claim 1, it is characterised in that：
In step (1), supernatant reflux ratio is 20～30%.
4. the process for preparing hydroxyapatite with phosphorized waste water as raw material according to claim 1, it is characterised in that：
In step (2), the regulator selects NaOH solution, and concentration is 1～2mol/L；Precipitant selects Ca (OH)2, and calcium phosphorus substance
Amount ratio, i.e. n (Ca)/n (P), is 1.5～3.
5. the process for preparing hydroxyapatite with phosphorized waste water as raw material according to claim 1, it is characterised in that：
In step (2), whipping temp is 40～60 DEG C, and stir speed (S.S.) is 1000～1500r/min, and mixing time is 2～6h.
6. the process for preparing hydroxyapatite with phosphorized waste water as raw material according to claim 1, it is characterised in that：
In step (2), the still aging time is 2～6h, and still aging temperature is 40～60 DEG C.
7. the process for preparing hydroxyapatite with phosphorized waste water as raw material according to claim 1, it is characterised in that：
In step (2), detergent is ethanol；Baking temperature is 80～115 DEG C.
8. the process for preparing hydroxyapatite with phosphorized waste water as raw material according to claim 1, it is characterised in that：
In step (2), calcining heat is 700～1000 DEG C, and heating rate is 0.5～20 DEG C/min, a length of 2～10h during sintering soak.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611169871.1A CN106586994A (en) | 2016-12-16 | 2016-12-16 | Technological method for preparing hydroxyapatite by using phosphating waste water as raw material |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611169871.1A CN106586994A (en) | 2016-12-16 | 2016-12-16 | Technological method for preparing hydroxyapatite by using phosphating waste water as raw material |
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| CN106586994A true CN106586994A (en) | 2017-04-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201611169871.1A Pending CN106586994A (en) | 2016-12-16 | 2016-12-16 | Technological method for preparing hydroxyapatite by using phosphating waste water as raw material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108217775A (en) * | 2018-02-05 | 2018-06-29 | 合肥市联任科技有限公司 | A kind of chlorine-contained wastewater inorganic agent and preparation method thereof |
| CN110280208A (en) * | 2019-07-11 | 2019-09-27 | 南京理工大学 | The method that hydroxyapatite is prepared by chemical industry recycling phosphate |
| CN111232941A (en) * | 2020-03-25 | 2020-06-05 | 江苏一夫科技股份有限公司 | Method for preparing hydroxyapatite based on phosphogypsum cleaning wastewater |
| CN112062115A (en) * | 2020-09-16 | 2020-12-11 | 北京天盾新材科技有限公司 | Recycling treatment method of acid waste liquid containing melamine and phosphorus |
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Patent Citations (2)
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| CN102826640A (en) * | 2011-06-17 | 2012-12-19 | 中国石油化工股份有限公司 | Method for treating organic phosphorus production wastewater |
| CN103739165A (en) * | 2014-01-08 | 2014-04-23 | 新疆德安环保科技有限公司 | Recycling treatment method for automobile coating wastewater |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108217775A (en) * | 2018-02-05 | 2018-06-29 | 合肥市联任科技有限公司 | A kind of chlorine-contained wastewater inorganic agent and preparation method thereof |
| CN110280208A (en) * | 2019-07-11 | 2019-09-27 | 南京理工大学 | The method that hydroxyapatite is prepared by chemical industry recycling phosphate |
| CN111232941A (en) * | 2020-03-25 | 2020-06-05 | 江苏一夫科技股份有限公司 | Method for preparing hydroxyapatite based on phosphogypsum cleaning wastewater |
| CN112062115A (en) * | 2020-09-16 | 2020-12-11 | 北京天盾新材科技有限公司 | Recycling treatment method of acid waste liquid containing melamine and phosphorus |
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Application publication date: 20170426 |