CN106082155B - The method that hydroxyapatite is prepared using fish-bone - Google Patents
The method that hydroxyapatite is prepared using fish-bone Download PDFInfo
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- CN106082155B CN106082155B CN201610401774.4A CN201610401774A CN106082155B CN 106082155 B CN106082155 B CN 106082155B CN 201610401774 A CN201610401774 A CN 201610401774A CN 106082155 B CN106082155 B CN 106082155B
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- hydroxyapatite
- calcining
- fish
- bone
- fishbone dust
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention discloses a kind of method that hydroxyapatite is prepared using fish-bone, and fish-bone is processed into fishbone dust and is placed in the Na that temperature is 40~60 DEG C, concentration is 0.8~1.2mol/L2CO34~6h is soaked in solution, fishbone dust is cleaned to neutrality with water, 45~65 DEG C dry 3~4 hours, then carry out segmented calcining, it is rapidly heated first to 280~320 DEG C of 50~70min of calcining, then raises temperature to 400~500 DEG C of 50~70min of calcining, then is warming up to 700~800 DEG C of 50~70min of calcining, room temperature is air-cooled to, produces hydroxyapatite.The present invention is simple and easy to do, time-consuming short using fish-bone as raw material, and preparation time maximum can shorten more than 60% the methods of than Hydrothermal Synthesiss, production efficiency is improved, reduces energy consumption, while purer hydroxyapatite can be obtained, and there is preferable granularity, the adsorptivity of heavy metal ion is strong.
Description
Technical field
The present invention relates to the utilization of fish processing byproduct.It is more particularly related to a kind of prepared using fish-bone
The method of hydroxyapatite.
Background technology
China possesses the abundant stock of fish, in addition to daily consumption, is also used for the processing of the numerous foods such as frozen fillet.
A large amount of accessory substances are produced during this, wherein fish-bone accounts for more than the 30% of fish sole mass.If can not further it handle
Or be used, a large amount of biomass will be caused to waste, and cause environmental pollution.Due to fish-bone main component for protein,
The organic matters such as fat and hydroxyapatite (hydroxyatite, chemical formula Ca10(PO4)6(OH)2) etc. contain calcium phosphate, suitable root
It is used according to its composition characteristic.
Hydroxyapatite is the host inorganic compounds in various animal skeletons and tooth.Its crystal is hexagonal crystal system, brilliant
Two different ligancies of calcium ion cause the larger passage that major axis is formed in parallel with whole crystal structure in born of the same parents, make calcium ion
It is easy to by other ion substitutions.Therefore hydroxyapatite can exchange with the heavy metal ion of absorption, available for processing waste water,
The heavy metal pollution of soil etc..Because the adsorptivity of hydroxyapatite heavy metal ion is strong, release rate is relatively low during desorption, is not easy
Form secondary pollution.
Prior art prepares hydroxyapatite using fish-bone progress hydro-thermal reaction has the shortcomings that time-consuming, energy consumption is big.Fish
Squama is currently used primarily in the larger collagen of extraction economic value, the decalcification in a manner of soluble-salt before extracting, and generally uses
Calcination method fish scale prepares hydroxyapatite can lose collagen again, it is difficult to while collagen and hydroxyapatite are extracted, institute
Calcination method is not suitable for fish scale and prepares hydroxyapatite.Therefore, need that a kind of cost is low, energy consumption is small, simple and fast badly at present
The method that hydroxyapatite is prepared using fish-bone.
The content of the invention
It is an object of the invention to solve at least the above, and provide the advantages of at least will be described later.
It is a still further object of the present invention to provide a kind of method that hydroxyapatite is prepared using fish-bone, using fish-bone as original
Material, simple and easy to do, time-consuming short, preparation time maximum can shorten more than 60% the methods of than Hydrothermal Synthesiss, improve production efficiency,
Energy consumption is reduced, while purer hydroxyapatite can be obtained, and there is preferable granularity, the adsorptivity of heavy metal ion
By force.
In order to realize according to object of the present invention and further advantage, there is provided one kind prepares hydroxy-apatite using fish-bone
The method of stone, fish-bone is processed into fishbone dust and is placed in the Na that temperature is 40~60 DEG C, concentration is 0.8~1.2mol/L2CO3It is molten
4~6h is soaked in liquid, is cleaned fishbone dust to neutrality with water, is dried 3~4 hours in 45~65 DEG C, carries out segmented calcining, it is first
First it is rapidly heated to 280~320 DEG C of 50~70min of calcining, then raises temperature to 400~500 DEG C of 50~70min of calcining, then heat up
To 700~800 DEG C of 50~70min of calcining, room temperature is air-cooled to, produces hydroxyapatite.
Preferably, the method that hydroxyapatite is prepared using fish-bone, the granularity of fishbone dust are less than 100 mesh.
Preferably, the method that hydroxyapatite is prepared using fish-bone, the method that fish-bone is processed into fishbone dust
For：Fish-bone is heated into 15~30min in boiling water, 3~4h of drying in 45~65 DEG C of environment is placed in, is crushed to below 100 mesh sieves,
Produce fishbone dust.
Preferably, the method that hydroxyapatite is prepared using fish-bone, by fishbone dust be placed in temperature for 50 DEG C, it is dense
Spend the Na for 1mol/L2CO35h is soaked in solution.
Preferably, the method that hydroxyapatite is prepared using fish-bone, segmented calcining are included：It is quick first to rise
Temperature then raises temperature to 450 DEG C of calcining 60min, then be warming up to 700 DEG C of calcining 60min to 300 DEG C of calcining 60min.
Preferably, the method that hydroxyapatite is prepared using fish-bone, segmented calcining are carried out in Muffle furnace.
The present invention comprises at least following beneficial effect：
Firstth, the present invention is simple and easy to do, time-consuming short using fish-bone as raw material, and preparation time is maximum the methods of than Hydrothermal Synthesiss
More than 60% can be shortened, improve production efficiency, reduce energy consumption, while purer hydroxyapatite can be obtained, and had
Preferable granularity, the adsorptivity of heavy metal ion are strong；
Secondth, Na2CO3Solution adsorbs hydroxyl immersed with beneficial to for the calcium containing compound addition in fish-bone, compensates hydroxyl phosphorus
Hydroxyl of the lime stone composition in calcination process comes off, and reduces the damage that hydroxyapatite is brought because being converted into calcium phosphate in calcination process
Losing, dissolution of calcium carbonate degree be less than calcium hydroxide, compared to directly only containing alkali hydroxy using sodium hydroxide, potassium hydroxide etc.,
In the solution for there are a large amount of carbonates, the dissolution and loss of calcium ion in fish-bone can be effectively reduced；After fish-bone crushes, surface is added
Product, during firing, is uniformly heated, and organic matter can preferably burn removals, reduce cementing phenomenon, improves finally
The decentralization of the hydroxyapatite of acquisition；Segmented calcining is for the moisture progressively and fully in removing fishbone dust and various had
Machine compound；First stage calcines, main absorption water, the crystallization water and the water of coordination for removing fishbone dust and containing, and part low burn
The organic matter of point and volatilization point, including part collagen and connective tissue protein etc., second stage calcining are removed in fishbone dust
Guanine class compound and other high-flash organic matters；Phase III calcining remove remnant organic matter, and make other calcics without
Machine compound is converted into hydroxyapatite；
3rd, fish-bone, which heats 15~30min in boiling water and takes off residual meat, removes the clearly visible organic matters such as the residual meat in surface, and 700
The ratio and hydroxyapatite of the calcium of product prepared by DEG C calcining heat and the content of phosphorus are closest, and calcining heat is too high or forges
Time lengthening is burnt, can all cause hydroxyapatite that decomposed occurs, content decreases.
Further advantage, target and the feature of the present invention embodies part by following explanation, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Brief description of the drawings
Fig. 1 is the scanning electron microscopy for the hydroxyapatite that embodiments of the invention 4 obtain；
Fig. 2 is the infrared spectrogram for the hydroxyapatite that embodiments of the invention 4 obtain；
Fig. 3 be the obtained hydroxyapatite of embodiments of the invention 4 in sour environment to three kinds of heavy metal ion Pb2 +、Cd2+And Ni2+The design sketch of Adsorption respectively (total concentration of metal ions is 30mg/L in solution).
Embodiment
With reference to embodiment, the present invention is described in further detail, to make those skilled in the art with reference to specification
Word can be implemented according to this.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more
The presence or addition of individual other elements or its combination.
It should be noted that experimental method described in following embodiments, is conventional method unless otherwise specified, institute
Reagent and material are stated, unless otherwise specified, is commercially obtained.
<Embodiment 1>
A kind of method that hydroxyapatite is prepared using fish-bone, by fish-bone be ground into fishbone dust be placed in temperature for 40 DEG C,
Concentration is 0.8mol/L Na2CO34h is soaked in solution, is cleaned with water to neutrality, 45 DEG C dry 3 hours, are carried out in Muffle furnace
Segmented is calcined, and is rapidly heated first to 280 DEG C of calcining 50min, then raises temperature to 400 DEG C of calcining 50min, then be warming up to 700
DEG C calcining 50min, be air-cooled to room temperature, produce hydroxyapatite.
<Embodiment 2>
A kind of method that hydroxyapatite is prepared using fish-bone, by fish-bone be ground into fishbone dust be placed in temperature for 60 DEG C,
Concentration is 1.2mol/L Na2CO36h is soaked in solution, is cleaned with water to neutrality, 65 DEG C dry 4 hours, are carried out in Muffle furnace
Segmented is calcined, and is rapidly heated first to 320 DEG C of calcining 70min, then raises temperature to 500 DEG C of calcining 70min, then be warming up to 800
DEG C calcining 70min, be air-cooled to room temperature, produce hydroxyapatite.
<Embodiment 3>
A kind of method that hydroxyapatite is prepared using fish-bone, by fish-bone be ground into fishbone dust be placed in temperature for 50 DEG C,
Concentration is 1mol/L Na2CO35h is soaked in solution, is cleaned with water to neutrality, 55 DEG C dry 3 hours, are divided in Muffle furnace
Segmentation is calcined, and is rapidly heated first to 300 DEG C of calcining 60min, then raises temperature to 450 DEG C of calcining 60min, then be warming up to 700 DEG C
60min is calcined, room temperature is air-cooled to, produces hydroxyapatite.
<Embodiment 4>
A kind of method that hydroxyapatite is prepared using fish-bone, 20min is heated by fish-bone in boiling water, is placed in 55 DEG C of environment
Middle drying 3h, is crushed to below 100 mesh sieves, obtain fishbone dust, by fishbone dust be placed in temperature be 50 DEG C, concentration be 1mol/L's
Na2CO35h is soaked in solution, is cleaned with water to neutrality, 55 DEG C dry 3 hours, segmented calcining are carried out in Muffle furnace, first
It is rapidly heated to 300 DEG C of calcining 60min, then raises temperature to 450 DEG C of calcining 60min, then is warming up to 700 DEG C of calcining 60min, air cooling
To room temperature, hydroxyapatite is produced.
The infrared spectrogram for the hydroxyapatite that embodiment 4 obtains is as shown in Fig. 2 the characteristic peak with hydroxyapatite；
Scanning electron microscopy is as shown in figure 1, hydroxyapatite is graininess as can be seen from Figure 1, and particle diameter is 50~100nm, relatively
There is bigger specific surface area in hydroxyapatite prepared by hydro-thermal method.
<Comparative example>
Preparation process and parameter while example 4, the difference is that, it is final to calcine section difference in segmented calcining
800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C are warming up to, 60min is calcined, is air-cooled to room temperature, obtains comparative example 1, comparative example 2, contrast
The hydroxyapatite of example 3, comparative example 4, and the test of calcium-phosphorus ratio is carried out, test result is as shown in the table：
| Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Temperature (DEG C) | 700 | 800 | 900 | 1000 | 1100 |
| Calcium-phosphorus ratio | 1.76 | 1.71 | 1.63 | 1.55 | 1.51 |
As seen from the above table, final calcination stage temperature is different, and the composition of products therefrom has very big difference, 700 DEG C of calcining institutes
Product, the ratio and hydroxyapatite of the content of its calcium and phosphorus are closest, are optimum temperature, calcining heat is too high, can lead
Cause hydroxyapatite that a small amount of decomposition occurs, content decreases.
<Adsorption capacity is tested>
Metal ion in solution (Pb2+、Cd2+And Ni2+) total concentration is 30mg/L, the hydroxyl that embodiments of the invention 4 obtain
Apatite inventory is 5g/L, processing time 1h, is during which stirred continuously, at the end of under the conditions of 10000g centrifugation 20min take
Clear measure residual heavy metal ion concentration.
Experimental result is as shown in figure 3, respectively illustrate hydroxyapatite that embodiment 4 obtains in sour environment to three kinds
Heavy metal ion Pb2+、Cd2+And Ni2+The effect of Adsorption respectively, under given condition, the hydroxy-apatite of fishbone dust preparation
Stone is adjusted by solution acidity, to Pb2+、Cd2+And Ni2+The adsorption removal rate of three kinds of ions is attained by more than 80%.
Number of devices and treatment scale described herein are the explanations for simplifying the present invention.To the present invention application,
Modifications and variations will be readily apparent to persons skilled in the art.
Although embodiment of the present invention is disclosed as above, it is not restricted in specification and embodiment listed
With it can be applied to various suitable the field of the invention completely, can be easily for those skilled in the art
Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, it is of the invention and unlimited
In specific details and shown here as the embodiment with description.
Claims (5)
- A kind of 1. method that hydroxyapatite is prepared using fish-bone, it is characterised in that fish-bone heats in boiling water to 15~ 30min, 3~4h of drying in 45~65 DEG C of environment is placed in, is crushed to below 100 mesh sieves, produces fishbone dust, fishbone dust is placed in temperature Spend the Na for being 0.8~1.2mol/L for 40~60 DEG C, concentration2CO34~6h is soaked in solution, is cleaned fishbone dust into water Property, in 45~65 DEG C dry 3~4 hours, carry out segmented calcining, be rapidly heated first to 280~320 DEG C calcining 50~ 70min, 400~500 DEG C of 50~70min of calcining are then raised temperature to, then be warming up to 700~800 DEG C of 50~70min of calcining, air cooling To room temperature, hydroxyapatite is produced.
- 2. the method for preparing hydroxyapatite using fish-bone as claimed in claim 1, it is characterised in that the granularity of fishbone dust is low In 100 mesh.
- 3. the method for preparing hydroxyapatite using fish-bone as claimed in claim 1, it is characterised in that fishbone dust is placed in temperature Spend the Na for being 1mol/L for 50 DEG C, concentration2CO35h is soaked in solution.
- 4. the method for preparing hydroxyapatite using fish-bone as claimed in claim 1, it is characterised in that segmented calcining bag Include：It is rapidly heated first to 300 DEG C of calcining 60min, then raises temperature to 450 DEG C of calcining 60min, then be warming up to 700 DEG C of calcinings 60min。
- 5. such as the method according to any one of claims 1 to 4 that hydroxyapatite is prepared using fish-bone, it is characterised in that point Segmentation calcining is carried out in Muffle furnace.
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| CN109110957A (en) * | 2018-08-28 | 2019-01-01 | 青岛理工大学 | A method of Pb In Exhausted Water is recycled using useless chicken bone |
| CN109174050A (en) * | 2018-08-28 | 2019-01-11 | 青岛理工大学 | A kind of preparation method of useless chicken bone adsorbent |
| JP7373330B2 (en) | 2018-09-25 | 2023-11-02 | Ｄｏｗａエコシステム株式会社 | Method for manufacturing hydroxyapatite |
| CN109264690A (en) * | 2018-12-06 | 2019-01-25 | 湖南三友环保科技股份有限公司 | A method of purifying fish waste Central Plains form hydroxyapatite |
| CN109621277A (en) * | 2018-12-06 | 2019-04-16 | 湖南三友环保科技股份有限公司 | A method of stablizing the Heavy Metals in domestic garbage incineration flyash using fish waste |
| CN115028150B (en) * | 2022-07-15 | 2023-07-04 | 中国地质大学（北京） | Preparation method and application of synthetic hydroxyapatite |
| CN115991976A (en) * | 2022-11-09 | 2023-04-21 | 成都理工大学 | Composite phase-change energy storage material taking animal bones as carrier and preparation method thereof |
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