CN106082155A - Utilize the method that fishbone prepares hydroxyapatite - Google Patents
Utilize the method that fishbone prepares hydroxyapatite Download PDFInfo
- Publication number
- CN106082155A CN106082155A CN201610401774.4A CN201610401774A CN106082155A CN 106082155 A CN106082155 A CN 106082155A CN 201610401774 A CN201610401774 A CN 201610401774A CN 106082155 A CN106082155 A CN 106082155A
- Authority
- CN
- China
- Prior art keywords
- fishbone
- hydroxyapatite
- calcining
- temperature
- 70min
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a kind of method utilizing fishbone to prepare hydroxyapatite, fishbone is processed into fishbone powder be placed in temperature be 40～60 DEG C, concentration be 0.8～1.2mol/L Na2CO3Solution soaks 4～6h, with water, fishbone powder is cleaned to neutral, dry 3～4 hours for 45～65 DEG C, carry out stagewise calcining subsequently, first it is rapidly heated to 280～320 DEG C of calcinings 50～70min, then raises temperature to 400～500 DEG C of calcinings 50～70min, then be warming up to 700～800 DEG C of calcinings 50～70min, air cooling, to room temperature, obtains hydroxyapatite.The present invention is with fishbone as raw material, simple and easy to do, the shortest, can shorten more than 60% than method preparation time maximums such as Hydrothermal Synthesiss, improve production efficiency, reduce energy consumption, purer hydroxyapatite can be obtained simultaneously, 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 one utilizes fishbone to prepare
The method of hydroxyapatite.
Background technology
China has the abundant stock of fish, in addition to daily eating, is also used for the numerous food processing such as frozen fillet.?
Producing a large amount of by-product during this, wherein fishbone accounts for more than the 30% of Fish sole mass.If can not process further
Or it is used, will result in the waste of large number of biological matter, and cause environmental pollution.Due to fishbone be mainly composed of protein,
Organic matter and hydroxyapatite (hydroxyatite, chemical formula Ca such as fat10(PO4)6(OH)2) etc. containing calcium phosphate, suitable root
It is used according to its composition characteristic.
Hydroxyapatite is the host inorganic compounds in various animal skeleton and tooth.Its crystal is hexagonal crystal system, brilliant
The ligancy that in born of the same parents, two calcium ions are different makes to be formed in parallel with in whole crystal structure the larger passage of major axis, makes calcium ion
It is prone to by other ion substitution.Therefore hydroxyapatite can with absorption heavy metal ion exchange, can be used for process waste water,
The heavy metal pollution of soil etc..Owing to the adsorptivity of hydroxyapatite heavy metal ion is strong, during desorption, release rate is relatively low, is difficult to
Form secondary pollution.
Prior art utilizes fishbone to carry out hydro-thermal reaction to prepare hydroxyapatite and have the shortcoming time-consuming long, energy consumption is big.Fish
Squama is currently used primarily in and extracts the collagen protein that economic worth is bigger, decalcification in the way of soluble-salt before extracting, and generally uses
Calcination method fish scale prepares hydroxyapatite can lose again collagen protein, it is difficult to extract collagen protein and hydroxyapatite, institute simultaneously
Be not suitable for calcination method with fish scale and prepare hydroxyapatite.Therefore, need that a kind of low cost, energy consumption be little, simple and fast at present badly
Utilize the method that fishbone prepares hydroxyapatite.
Summary of the invention
It is an object of the invention to solve at least the above, and the advantage that at least will be described later is provided.
It is a still further object of the present invention to provide a kind of method utilizing fishbone to prepare hydroxyapatite, be former with fishbone
Material, simple and easy to do, the shortest, more than 60% can be shortened than method preparation time maximums such as Hydrothermal Synthesiss, improve production efficiency,
Reduce energy consumption, purer hydroxyapatite can be obtained simultaneously, 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, it is provided that one utilizes fishbone to prepare hydroxy-apatite
The method of stone, fishbone is processed into fishbone powder be placed in temperature be 40～60 DEG C, concentration be 0.8～1.2mol/L Na2CO3Molten
Liquid soaks 4～6h, with water, fishbone powder is cleaned to neutral, dry 3～4 hours in 45～65 DEG C, carry out stagewise calcining, first
First it is rapidly heated to 280～320 DEG C of calcinings 50～70min, then raises temperature to 400～500 DEG C of calcinings 50～70min, then heat up
To 700～800 DEG C of calcinings 50～70min, air cooling, to room temperature, obtains hydroxyapatite.
Preferably, the described method utilizing fishbone to prepare hydroxyapatite, the granularity of fishbone powder is less than 100 mesh.
Preferably, the described method utilizing fishbone to prepare hydroxyapatite, the method that fishbone is processed into fishbone powder
For: fishbone is heated in boiling water 15～30min, is placed in 45～65 DEG C of environment drying 3～4h, is crushed to below 100 mesh sieves,
Obtain fishbone powder.
Preferably, the described method utilizing fishbone to prepare hydroxyapatite, fishbone powder is placed in temperature be 50 DEG C, dense
Degree is the Na of 1mol/L2CO3Solution soaks 5h.
Preferably, the described method utilizing fishbone to prepare hydroxyapatite, stagewise calcining includes: the most quickly rise
Temperature, 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.
Preferably, the described method utilizing fishbone to prepare hydroxyapatite, stagewise calcining is carried out in Muffle furnace.
The present invention at least includes following beneficial effect:
The first, the present invention is with fishbone as raw material, simple and easy to do, the shortest, more maximum than method preparation times such as Hydrothermal Synthesiss
More than 60% can be shortened, improve production efficiency, reduce energy consumption, purer hydroxyapatite can be obtained simultaneously, and have
Preferably granularity, the adsorptivity of heavy metal ion is strong；
The second, Na2CO3Solution soaking is conducive to adding absorption hydroxyl for the calcium containing compound in fishbone, compensates hydroxyl phosphorus
Lime stone composition hydroxyl in calcination process comes off, and in minimizing calcination process, hydroxyapatite is because being converted into the damage that calcium phosphate brings
Losing, dissolution of calcium carbonate degree is less than calcium hydroxide, compares and directly uses sodium hydroxide, potassium hydroxide etc. only to contain alkali hydroxy,
Have in the solution of a large amount of carbonate, can effectively reduce dissolution and the loss of calcium ion in fishbone；After fishbone is pulverized, add surface
Long-pending, during firing, it is uniformly heated, Organic substance can preferably burn removals, decreases cementing phenomenon, improves finally
The dispersion of the hydroxyapatite obtained；Stagewise calcining is for the moisture in progressively and abundant removing fishbone powder and various to have
Machine compound；First stage calcines, absorption water, water of crystallization and the water of coordination that main removal fishbone powder contains, and part low burn
Point and the Organic substance of volatilization point, including part collagen protein and connective tissue protein etc., second stage calcining is removed in fishbone powder
Guanine compounds and other high burning-point organic；Phase III calcining remove remnant organic matter, and make other calcic without
Machine compound is converted into hydroxyapatite；
3rd, fishbone heats 15～30min in boiling water and takes off residual meat and remove the clearly visible organic matters such as surface residual meat, and 700
The ratio of the calcium of DEG C product prepared by calcining heat and the content of phosphorus and hydroxyapatite closest to, calcining heat is too high or forges
Burning time lengthening, all can cause hydroxyapatite generation decomposed, content decreases.
Part is embodied by the further advantage of the present invention, target and feature by description below, and part also will be by this
Invention research and practice and be understood by the person skilled in the art.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopy of the hydroxyapatite that embodiments of the invention 4 obtain；
Fig. 2 is the infrared spectrogram of the hydroxyapatite that embodiments of the invention 4 obtain；
Fig. 3 be the hydroxyapatite that obtains of embodiments of the invention 4 in sour environment to three kinds of heavy metal ion Pb2 +、Cd2+And Ni2+The design sketch (concentration of metal ions total in solution is 30mg/L) of Adsorption respectively.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, to make those skilled in the art with reference to description
Word can be implemented according to this.
Should be appreciated that used herein such as " have ", " comprising " and " including " term do not allot one or many
Other element individual or the existence of a combination thereof or interpolation.
It should be noted that experimental technique described in following embodiment, if no special instructions, it is conventional method, institute
State reagent and material, if no special instructions, the most commercially obtain.
<embodiment 1>
A kind of method utilizing fishbone to prepare hydroxyapatite, fishbone powder is broken into fishbone powder be placed in temperature be 40 DEG C,
Concentration is the Na of 0.8mol/L2CO3Solution soaks 4h, cleans to neutral with water, dry 3 hours, carry out in Muffle furnace for 45 DEG C
Stagewise is calcined, and is first rapidly heated to 280 DEG C of calcining 50min, then raises temperature to 400 DEG C of calcining 50min, then is warming up to 700
DEG C calcining 50min, air cooling, to room temperature, obtains hydroxyapatite.
<embodiment 2>
A kind of method utilizing fishbone to prepare hydroxyapatite, fishbone powder is broken into fishbone powder be placed in temperature be 60 DEG C,
Concentration is the Na of 1.2mol/L2CO3Solution soaks 6h, cleans to neutral with water, dry 4 hours, carry out in Muffle furnace for 65 DEG C
Stagewise is calcined, and is first rapidly heated to 320 DEG C of calcining 70min, then raises temperature to 500 DEG C of calcining 70min, then is warming up to 800
DEG C calcining 70min, air cooling, to room temperature, obtains hydroxyapatite.
<embodiment 3>
A kind of method utilizing fishbone to prepare hydroxyapatite, fishbone powder is broken into fishbone powder be placed in temperature be 50 DEG C,
Concentration is the Na of 1mol/L2CO3Solution soaks 5h, cleans to neutral with water, dry 3 hours for 55 DEG C, carry out in Muffle furnace point
Segmentation is calcined, and is first 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
Calcining 60min, air cooling, to room temperature, obtains hydroxyapatite.
<embodiment 4>
A kind of method utilizing fishbone to prepare hydroxyapatite, heats fishbone 20min in boiling water, is placed in 55 DEG C of environment
Middle drying 3h, is crushed to below 100 mesh sieves, it is thus achieved that fishbone powder, fishbone powder is placed in temperature be 50 DEG C, concentration be 1mol/L's
Na2CO3Solution soaks 5h, cleans to neutral with water, dry 3 hours, Muffle furnace carries out stagewise calcining, first for 55 DEG C
It is rapidly heated 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 calcining 60min, air cooling
To room temperature, obtain hydroxyapatite.
The infrared spectrogram of the hydroxyapatite that embodiment 4 obtains is as in figure 2 it is shown, have the characteristic peak of hydroxyapatite；
Scanning electron microscopy as it is shown in figure 1, as can be seen from Figure 1 hydroxyapatite be graininess, particle diameter is 50～100nm, relatively
The hydroxyapatite prepared in hydro-thermal method has bigger specific surface area.
<comparative example>
Preparation process and parameter example 4 simultaneously, the difference is that, in stagewise is calcined, final calcining sections is respectively
Being warming up to 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, calcine 60min, air cooling, to room temperature, obtains comparative example 1, comparative example 2, contrast
Example 3, the hydroxyapatite of comparative example 4, and carry out the test of calcium-phosphorus ratio, 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 the biggest difference, 700 DEG C of calcining institutes
Product, the ratio of the content of its calcium and phosphorus and hydroxyapatite closest to, for optimum temperature, calcining heat is too high, can lead
Causing hydroxyapatite and a small amount of decomposition occurs, content decreases.
<absorbability test>
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, and the process time is 1h, and period is stirred continuously, at the end of under the conditions of 10000g centrifugal 20min take
Clear mensuration residual heavy metal ion concentration.
Experimental result is as it is shown on 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, hydroxy-apatite prepared by fishbone powder
Stone regulates through 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 described herein and treatment scale are used to the explanation of the simplification present invention.To the application of the present invention,
Modifications and variations will be readily apparent to persons skilled in the art.
Although embodiment of the present invention are disclosed as above, but it is not restricted in description and embodiment listed
Using, it can be applied to various applicable the field of the invention completely, for those skilled in the art, and can be easily
Realizing other amendment, therefore under the general concept limited without departing substantially from claim and equivalency range, the present invention does not limit
In specific details with shown here as the embodiment with description.
Claims (6)
1. one kind utilizes the method that fishbone prepares hydroxyapatite, it is characterised in that fishbone is processed into fishbone powder and is placed in temperature
The Na that degree is 40～60 DEG C, concentration is 0.8～1.2mol/L2CO3Solution soaks 4～6h, in being cleaned extremely by fishbone powder with water
Property, in 45～65 DEG C dry 3～4 hours, carry out stagewise calcining, be first rapidly heated to 280～320 DEG C calcining 50～
70min, then raises temperature to 400～500 DEG C of calcinings 50～70min, then is warming up to 700～800 DEG C of calcinings 50～70min, air cooling
To room temperature, obtain hydroxyapatite.
Utilize the method that fishbone prepares hydroxyapatite the most as claimed in claim 1, it is characterised in that the granularity of fishbone powder is low
In 100 mesh.
Utilize the method that fishbone prepares hydroxyapatite the most as claimed in claim 2, it is characterised in that fishbone is processed adult fish
The method of bone meal is: fishbone heats in boiling water 15～30min, is placed in 45～65 DEG C of environment drying 3～4h, is crushed to
Below 100 mesh sieves, obtain fishbone powder.
Utilize the method that fishbone prepares hydroxyapatite the most as claimed in claim 1, it is characterised in that fishbone powder is placed in temperature
Degree is 50 DEG C, concentration is the Na of 1mol/L2CO3Solution soaks 5h.
Utilize the method that fishbone prepares hydroxyapatite the most as claimed in claim 1, it is characterised in that stagewise calcining bag
Include: be first rapidly heated to 300 DEG C of calcining 60min, then raise temperature to 450 DEG C of calcining 60min, then be warming up to 700 DEG C of calcinings
60min。
6. utilize, as according to any one of Claims 1 to 5, the method that fishbone prepares hydroxyapatite, it is characterised in that point
Segmentation calcining is carried out in Muffle furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610401774.4A CN106082155B (en) | 2016-06-07 | 2016-06-07 | The method that hydroxyapatite is prepared using fish-bone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610401774.4A CN106082155B (en) | 2016-06-07 | 2016-06-07 | The method that hydroxyapatite is prepared using fish-bone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106082155A true CN106082155A (en) | 2016-11-09 |
| CN106082155B CN106082155B (en) | 2018-04-06 |
Family
ID=57228060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610401774.4A Expired - Fee Related CN106082155B (en) | 2016-06-07 | 2016-06-07 | The method that hydroxyapatite is prepared using fish-bone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106082155B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517130A (en) * | 2016-12-27 | 2017-03-22 | 合肥学院 | Method for preparing iron hydroxyphosphate micro-nano powder material from phosphorus-rich biomass |
| 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 |
| 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 |
| CN110408409A (en) * | 2018-04-29 | 2019-11-05 | 上海绅涪生物科技有限公司 | A kind of soil surface renovation agent, preparation method and the usage |
| CN115028150A (en) * | 2022-07-15 | 2022-09-09 | 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 |
| JP7373330B2 (en) | 2018-09-25 | 2023-11-02 | Ｄｏｗａエコシステム株式会社 | Method for manufacturing hydroxyapatite |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544318A (en) * | 2003-11-21 | 2004-11-10 | 陕西科技大学 | Nanometer hydroxyapatite powder preparation method |
| CN101264871A (en) * | 2008-03-27 | 2008-09-17 | 上海交通大学 | Method for preparing tetracalcium phosphate from natural bone powder |
| CN101462707A (en) * | 2007-12-18 | 2009-06-24 | 孙炜 | Natural high-purity nano hydroxylapatite leaching technology |
| CN102145193A (en) * | 2011-04-14 | 2011-08-10 | 李亚屏 | Cuttlebone conversion series porous biological ceramics |
| CN102274737A (en) * | 2010-06-13 | 2011-12-14 | 宁波大学 | Method for preparing macroporous material loaded with silver nanometer particles |
| CN104692347A (en) * | 2015-01-30 | 2015-06-10 | 福建永宸生物科技开发有限公司 | Synthesis method of carbonate hydroxyapatite with reducing function |
| CN105460912A (en) * | 2015-12-08 | 2016-04-06 | 福州大学 | Method for preparing hydroxyapatite with high specific surface area by utilizing fishbone |
-
2016
- 2016-06-07 CN CN201610401774.4A patent/CN106082155B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544318A (en) * | 2003-11-21 | 2004-11-10 | 陕西科技大学 | Nanometer hydroxyapatite powder preparation method |
| CN101462707A (en) * | 2007-12-18 | 2009-06-24 | 孙炜 | Natural high-purity nano hydroxylapatite leaching technology |
| CN101264871A (en) * | 2008-03-27 | 2008-09-17 | 上海交通大学 | Method for preparing tetracalcium phosphate from natural bone powder |
| CN102274737A (en) * | 2010-06-13 | 2011-12-14 | 宁波大学 | Method for preparing macroporous material loaded with silver nanometer particles |
| CN102145193A (en) * | 2011-04-14 | 2011-08-10 | 李亚屏 | Cuttlebone conversion series porous biological ceramics |
| CN104692347A (en) * | 2015-01-30 | 2015-06-10 | 福建永宸生物科技开发有限公司 | Synthesis method of carbonate hydroxyapatite with reducing function |
| CN105460912A (en) * | 2015-12-08 | 2016-04-06 | 福州大学 | Method for preparing hydroxyapatite with high specific surface area by utilizing fishbone |
Non-Patent Citations (1)
| Title |
|---|
| JAYACHANDRAN VENKATESAN ET AL.: ""Effect of temperature on isolation and characterization of hydroxyapatite from tuna（thunnus obesus）bone"", 《MATERIALS》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517130A (en) * | 2016-12-27 | 2017-03-22 | 合肥学院 | Method for preparing iron hydroxyphosphate micro-nano powder material from phosphorus-rich biomass |
| CN110408409A (en) * | 2018-04-29 | 2019-11-05 | 上海绅涪生物科技有限公司 | A kind of soil surface renovation agent, preparation method and the usage |
| 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 |
| CN115028150A (en) * | 2022-07-15 | 2022-09-09 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106082155B (en) | 2018-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106082155A (en) | Utilize the method that fishbone prepares hydroxyapatite | |
| CN106478996A (en) | A kind of method and its application for preparing calcium carbonate chitin composite granule with crab shell as raw material | |
| CN103751850A (en) | Three-dimensional graphene/hydroxyapatite hydrogel material | |
| CN104211036A (en) | Hydroxyapatite and preparation method thereof | |
| CN104857914A (en) | Method for preparing nanometer titanate adsorbent through modified chicken manure | |
| CN106862585A (en) | It is a kind of to prepare CaCO by template of egg-shell meal3The method of Ag composites | |
| CN104607144A (en) | Structure self-growing aqueous phase phosphate radical adsorbing material and preparation method and application thereof | |
| Budiatin et al. | The characterization of bovine bone-derived hydroxyapatite isolated using novel non-hazardous method | |
| CN102671630B (en) | Method for preparing printing dye adsorbent by taking eggshells as matrix and treatment method | |
| JP6351008B2 (en) | Hydroxyapatite derived from fish bone | |
| CN107007862A (en) | A kind of pig manure deodorant and preparation method thereof | |
| CN110395743B (en) | Method for synthesizing analcite by illite microwave heating solid-phase steam conversion method | |
| CN104556168B (en) | A kind of method by aluminum oxide activating dissolution in flyash | |
| CN101597103B (en) | Preparation method for drinking water magnesian defluorinating agent | |
| CN104026652A (en) | Preparing method of food grade marine-organism-sourced shell micro powder | |
| CN112841569A (en) | Practical nutritional fish scale biological calcium compound chewable tablet and preparation method thereof | |
| KR101624665B1 (en) | Natural liquid fertilizer containing ginseng and method of manufacturing the same | |
| CN114735669B (en) | Method for extracting hydroxyapatite from fish bones and obtained hydroxyapatite | |
| CN106432540A (en) | Chitin micro-powder preparation method | |
| CN102887823A (en) | Method for preparing calcium lactate by eggshell vacuum neutralization | |
| CN105126176B (en) | A kind of oyster shell bio-compatible biomimetic material and preparation method for femur reparation | |
| CN105688865A (en) | Bio-adsorbent prepared by modifying ball-milled tea residues and preparation method and application of bio-adsorbent | |
| CN105192252A (en) | High-protein feed meat meal premix easy to absorb and preparation method thereof | |
| CN104084149A (en) | Fluorine adsorbing material carrying out alkali modification on peanut shells | |
| CN104399426A (en) | Production method of aluminum-doped hydroxyapatite defluorinating filter material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180406 Termination date: 20190607 |