CN105218698B - A kind of method for preparing hydroxyapatite and shitosan as raw material with shrimp and crab shells - Google Patents
A kind of method for preparing hydroxyapatite and shitosan as raw material with shrimp and crab shells Download PDFInfo
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Abstract
The present invention provides a kind of method for preparing hydroxyapatite and shitosan as raw material with shrimp and crab shells, solves the problem that can not be made full use of to shrimp and crab shells at present.The present invention is to simplify shrimp and crab shells pre-treating technology and can simultaneously make full use of active principle --- calcium carbonate and chitin in shrimp and crab shells, only need to carry out raw material simple pretreatment, reacted using the method for step alkalization microwave, protein and lipid solubilization that the alkali added during microwave reaction will can be remained in shrimp and crab shells, and the de- albumen of such as soda boiling, the complicated of acidleach decalcification need not be carried out and pre-processed, effectively shorten the reaction time（2 ~ 12h was tapered to by 10 days）, and can effectively reduce reaction energy barrier.And recycling is carried out to the liquid after microwave reaction, the protein and grease remained in shrimp and crab shells can be made full use of, so as to production cost, high-efficiency environment friendly can be reduced.
Description
Technical field
The invention belongs to chemical technology field, more particularly to one kind prepares hydroxyapatite and shell using shrimp and crab shells as raw material
The method of glycan.
Background technology
Hydroxyapatite is a kind of alkalescent (pH=7~9) synthos for being slightly soluble in water.The use of hydroxy apatite powder
Way is very wide, can be by being heated to 800~1200 DEG C of prepared hydroxylapatite ceramics, or the complex phase pottery based on hydroxyapatite
Porcelain, for the hard tissue repair of human body；Can also be combined with macromolecular material, such as PLA, collagen, poly- phthalein amine, so as to change
The biocompatibility of kind material；It is also used as the metallic implant surface spraying hydroxyapatite such as joint prosthesis, tooth implant
The raw material of coating.Hydroxyapatite is increasingly valued by people as a kind of important bioactive materials.
Shitosan is the general name that formed soluble chitin after a certain amount of acetyl degree is taken off by chitin, and shitosan is certainly
A kind of biodegradable positively charged alkaline polysaccharide in right boundary, the biological functionality and compatibility of this natural polymer, blood
The premium properties such as liquid phase capacitive, security, microbic resolvability, are applied to medicine, food, chemical industry, cosmetics, water process, gold
The numerous areas such as category is extracted and reclaimed, biochemical and biomedical engineering.Chitin is widely present in the crusts such as shrimp, crab, insect and moves
The shell of thing.Chitin is typically closely linked simultaneously with protein or calcium carbonate or both, as complex compound, by acid
Alkali process can remove the impurity such as calcium salt and protein, and shrimp, crab shell also have pigment, can be removed by redox.Chitin is
Poly- 2- acetamidos -2- deoxidation-D- glucopyranoses, are a kind of linear neutral macromolecule polysaccharides, are processed through concentrated base and remove acetyl group
Obtain chitosan, i.e. shitosan.
Shrimp and crab shells are all the byproducts of ocean aquatic products, and its main inorganic composition is calcium carbonate and chitin, and has uniqueness
Biological evolution micro-structural.But the utilization of current shrimp and crab shells is limited, and majority is processed as rubbish, in the course of time to ring
Border have it is potentially hazardous, and produce resource serious waste；The method that part is recycled to crab shell is also merely with crab
Calcium carbonate conversion hydroxyapatite in shell, or only convert shitosan by active ingredient of chitin, it is impossible to make full use of crab shell
In active ingredient.If profit can be subject to the calcium carbonate in crab shell and chitin simultaneously by simple and effective transform mode
With, and the protein and grease remained in energy effective recycling shrimp and crab shells, the pollution to environment can have both been reduced, money can be realized again
Effective utilization in source, realizes environmental protection.
The content of the invention
The shortcoming of prior art, prepares it is an object of the invention to provide one kind by raw material of shrimp and crab shells in view of the above
The method of hydroxyapatite and shitosan, solves the problem that can not be made full use of to shrimp and crab shells at present.
In order to achieve the above objects and other related objects, the present invention uses following technical scheme：
A kind of method for preparing hydroxyapatite and shitosan as raw material with shrimp and crab shells, comprises the following steps：
(1) simple pretreatment：Shrimp and crab shells are directly dried, is crushed, obtain shrimp and crab shells raw material powder；
(2) heating response：Step (1) gained shrimp and crab shells raw material powder is weighed, a certain amount of diammonium hydrogen phosphate and phosphoric acid is added
Ammonium dihydrogen, plus deionized water stirs, with diluted alkaline adjust pH value to 10.0~13.0, be heated to 80-150 DEG C react 2~
12 hours, by the cleaning of gained product, dry, obtain final product hydroxyapatite-shitosan composite granule；
(3) product is separated：The hydroxyapatite that step (2) is obtained-shitosan composite granule, adds deionized water, with
Dilute acid for adjusting pH value stirs 30min~24h to 3.5~6.5, and separation of solid and liquid, resulting solid is washed with deionized into
Property, be dried to obtain pure ha powder, by the liquid after resulting separation of solid and liquid add diluted alkaline adjust pH value to 8.0~
11.0, the solid of precipitation is collected, is dried, that is, obtain chitosan powder body.
Preferably, in step (2), the shrimp and crab shells powder, diammonium hydrogen phosphate, the mass ratio of ammonium dihydrogen phosphate are 20:1.6-
3.6:1.4-3.1, more preferably 20:2.4-3.2:2.1-2.8.
Preferably, in step (2), the diluted alkaline is the NaOH aqueous solution that mass percent is 5~20wt% or quality hundred
Fraction is the ammonia spirit of 5~20wt%.
Preferably, being heating using microwave reaction in step (2), the heating is carried out in microwave reaction kettle, more preferably, micro-
The microwave reaction power of ripple reactor is 200~800W.
Preferably, in step (3), the diluted acid is aqueous hydrochloric acid solution or volume basis that percent by volume is 5~15%
Than the aqueous acetic acid for 5~15%.
Preferably, in step (3), the diluted alkaline is the NaOH aqueous solution that mass percent is 5~20wt% or quality hundred
Fraction is the ammonia spirit of 5~20wt%.
Beneficial effects of the present invention are：
(1) it is material that the present invention uses the marine biomass discarded object shrimp and crab shells of rich reserves, while producing hydroxy-apatite
Stone and shitosan, and hydroxyapatite and the total yield of shitosan may be up to 92.37%, adequately achieve to the effective of raw material
Comprehensive utilization.
(2) present invention is to simplify shrimp and crab shells pre-treating technology and can simultaneously make full use of working substance in shrimp and crab shells
Matter --- calcium carbonate and chitin, it is only necessary to which raw material are carried out with simple pretreatment, the method for the microwave that alkalized using a step
Reacted, protein and lipid solubilization that the alkali added during microwave reaction will can be remained in shrimp and crab shells, and need not be carried out such as
Soda boiling takes off the complicated pretreatment of albumen, acidleach decalcification, effectively shortens the reaction time (tapering to 2~12h by 10 days), and can be effective
Reduce reaction energy barrier.So as to production cost, high-efficiency environment friendly can be reduced.
(3) hydroxyapatite is converted merely with the calcium carbonate in shrimp and crab shells in the present invention and prior art, or only with first
Shell element is compared for active ingredient conversion shitosan, and advantage is to take full advantage of the various active principle (calcium carbonate in shrimp and crab shells
And chitin), simultaneous reactions generation hydroxyapatite and shitosan, and realize nanometer hydroxyapatite-shitosan powder
Efficiently separate, process is simple and utilization rate is high.
(4) method of the present invention is simple to operate, process stabilization, is adapted to large-scale batch production.
(5) another advantage is that shrimp and crab shells typically all contain grease and albumen, and treatment not in time all can be smelly.Carried in tradition
During taking chitin, isolating protein and grease are gone using alkali cleaning.In our method, can quickly process these and give up
Material, and the liquid after microwave reaction is reclaimed using saponification etc. of saltouing, completely using these greases and protein.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum of the hydroxyapatite obtained by prepared by embodiment 1.
Fig. 2 is the infrared spectrogram of the shitosan obtained by prepared by embodiment 1.
Fig. 3 is the X ray diffracting spectrum of the shitosan obtained by prepared by embodiment 1.
Specific embodiment
Embodiments of the present invention are illustrated below by way of specific instantiation, those skilled in the art can be by this specification
Disclosed content understands other advantages of the invention and effect easily.The present invention can also be by specific realities different in addition
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
In addition, it is to be understood that one or more method and steps mentioned in the present invention do not repel before and after the combination step
Can also there is other method step or other method step can also be inserted between the step of these are specifically mentioned, unless separately
It is described.
Embodiment 1
(1) shrimp shell pretreatment：The direct dries pulverizing of shrimp shell is stand-by into powder.
(2) microwave reaction：40g shrimp shell raw material powder is weighed to be put into microwave reaction kettle, add 4.67g diammonium hydrogen phosphates and
4.07g ammonium dihydrogen phosphates and 2.5L deionized waters, stir, and are existed with the sodium hydrate aqueous solution regulation pH value of 10wt%
10.0, by adjusting microwave reaction power 400w controlling reaction temperatures at 90 DEG C, the reaction time is 4h, the product after microwave reaction
To obtain nanometer hydroxyapatite-shitosan powder 16.8520g after deionized water cleaning, drying.
(3) product is separated：16.8520g nanometer hydroxyapatites that step (2) is obtained-shitosan powder add go from
Sub- water, the watery hydrochloric acid regulation pH value for being slowly added into 10wt% while stirring at room temperature is 4.0, and solid-liquid point after 2h is stirred at normal temperatures
From the solid for obtaining is washed with deionized to neutrality, is dried to obtain 10.2713g pure ha powders；By separation of solid and liquid
The liquid of collection, the NaOH regulation pH value for being slowly added into 10wt% while stirring at room temperature is 11.0, the solid that will be separated out
Drying is collected, that is, obtains chitosan powder body 5.2174g.
Phase structure test is carried out to gained hydroxy apatite powder using X-ray diffractometer (XRD), as a result such as Fig. 1 institutes
Show that (JCPDS standard card 09-0432) consistent with the standard diagram of hydroxyapatite does not have the diffraction maximum of other impurities phase, table
Bright use the method obtains high-purity pure ha powder after separating, and its crystal structure meets standard hydroxyapatite
Space hexagonal crystallographic texture.There is the characteristic peak of hydroxyapatite, and (002) crystal face in crystal faces such as (002) (300) (222)
Characteristic peak is very sharp, illustrates that hydroxyapatite crystal has had the trend along c-axis direction preferential growth.
Structural characterization is carried out as shown in Fig. 2 3428.45cm to shitosan powder using infrared spectrometer (IR)-1Left and right, be
Formed hydrogen bond association-the OH stretching vibration absworption peaks multi-absorption peak Chong Die and broadening with the stretching vibration absworption peak of-NH.
Existed in chitosan molecule in substantial amounts of chain, interchain hydrogen bond, because of the length of hydrogen bond and strong and weak, make its flexible peak one compared with
In frequency range wide.In 2922.62cm-1And 2857.41cm-1Place is respectively two stretching vibration absworption peaks of C-H.
1637.48cm-1There are stronger acid amides I absworption peaks, 1597.18cm-1It is the absworption peak of acid amides II to locate.=CH2Bending and-CH3Deformation
Absworption peak is in 1423.12cm-1Place, C-H bendings and-CH3Symmetrical deformation vibration absworption peak is in 1381.66cm-1Place.
1320.87cm-1Locate to be coupled absworption peak with N-H deformations for acid amides C-N is flexible.In 1157.43cm-1It is the vibration of β-glycosidic bond to locate
Peak.From the point of view of the analysis of above vibration peak, it may be determined that product is shitosan.It is poly- to gained shell using X-ray diffractometer (XRD)
Icing Sugar body carries out phase structure test, as a result as shown in figure 3, occurring the point for belonging to shitosan near 2 θ=11 ° and 20 °
Sharp diffraction maximum, illustrates that it all has crystallinity very high, and this is the result that intramolecular has hydrogen bond.From near 2 θ=11 °
There is diffraction maximum to judge, the shitosan for being obtained belongs to α-type shitosan.
Embodiment 2
(1) shrimp shell pretreatment：The direct dries pulverizing of shrimp shell is stand-by into powder.
(2) microwave reaction：40g shrimp shell raw material powder is weighed to be put into microwave reaction kettle, add 4.67g diammonium hydrogen phosphates and
4.07g ammonium dihydrogen phosphates and 2.5L deionized waters, are stirred, and pH value is adjusted 12.0 with the sodium hydroxide solution of 15wt%,
Controlled at 100 DEG C by adjusting microwave reaction power 500w controlling reaction temperatures, the reaction time is 2h, the product after microwave reaction
To obtain nanometer hydroxyapatite-shitosan powder 15.9876g after deionized water cleaning, drying.
(3) product is separated：15.9876g nanometer hydroxyapatites that step (2) is obtained-shitosan powder add go from
Sub- water, the watery hydrochloric acid regulation pH value for being slowly added into 15wt% while stirring at room temperature is 6.5, and solid-liquid after 24h is stirred at normal temperatures
Separate, the solid for obtaining is washed with deionized to neutrality, is dried to obtain 9.5702g pure ha powders；By solid-liquid point
From the liquid collected, it is 10.0 to be slowly added into 10wt% ammoniacal liquor regulation pH value while stirring at room temperature, and the solid of precipitation is carried out
Drying is collected, that is, obtains chitosan powder body 4.8220g.
Gained hydroxy apatite powder and shitosan powder are carried out using X-ray diffractometer (XRD) and infrared spectrometer
Test, as a result shows that gained hydroxy apatite powder is high-purity space hexagonal crystallographic texture, and shitosan powder is with higher
Crystallinity α-type shitosan.
Embodiment 3
(1) crab shell pretreatment：The direct dries pulverizing of crab shell is stand-by into powder.
(2) microwave reaction：40g crab shell raw material powder is weighed to be put into microwave reaction kettle, add 6.34g diammonium hydrogen phosphates and
5.52g ammonium dihydrogen phosphates and 2.5L deionized waters, are stirred, and pH value is adjusted 8.0 with the sodium hydroxide solution of 5wt%, are led to
Overregulate microwave reaction power 400w controlling reaction temperatures control at 90 DEG C, the reaction time is 8h, the product after microwave reaction with
Nanometer hydroxyapatite-shitosan powder 18.9652g is obtained after deionized water cleaning, drying.
(3) product is separated：18.9652g nanometer hydroxyapatites that step (2) is obtained-shitosan powder add go from
Sub- water, the watery hydrochloric acid regulation pH value for being slowly added into 5wt% while stirring at room temperature is 4.0, and solid-liquid point after 6h is stirred at normal temperatures
From the solid for obtaining is washed with deionized to neutrality, is dried to obtain 13.4368g pure ha powders；By separation of solid and liquid
The liquid of collection, the NaOH regulation pH value for being slowly added into 5wt% while stirring at room temperature is 10.0, and the solid of precipitation is entered
Row collects drying, that is, obtain chitosan powder body 3.8177g.
Gained hydroxy apatite powder and shitosan powder are carried out using X-ray diffractometer (XRD) and infrared spectrometer
Test, as a result shows that gained hydroxy apatite powder is high-purity space hexagonal crystallographic texture, and shitosan powder is with higher
Crystallinity α-type shitosan.
Embodiment 4
(1) crab shell pretreatment：The direct dries pulverizing of crab shell is stand-by into powder.
(2) microwave reaction：40g crab shell raw material powder is weighed to be put into microwave reaction kettle, add 6.34g diammonium hydrogen phosphates and
5.52g ammonium dihydrogen phosphates and 2.5L deionized waters, stir, with the ammoniacal liquor regulation pH value of 10wt% 12.0, by regulation
Microwave reaction power 600w controlling reaction temperatures are controlled at 115 DEG C, and the reaction time is 6h, and the product after microwave reaction is with deionization
Nanometer hydroxyapatite-shitosan powder 19.4302g is obtained after water cleaning, drying.
(3) product is separated：19.4302g nanometer hydroxyapatites that step (2) is obtained-shitosan powder add go from
Sub- water, the watery hydrochloric acid regulation pH value for being slowly added into 10wt% while stirring at room temperature is 4.0, solid after stirring 30min at normal temperatures
Liquid is separated, and the solid for obtaining is washed with deionized to neutrality, is dried to obtain 12.0331g pure ha powders；By solid-liquid
The liquid for separating and collecting, the ammoniacal liquor regulation pH value for being slowly added into 10wt% while stirring at room temperature is 10.0, the solid that will be separated out
Drying is collected, that is, obtains chitosan powder body 5.9146g.
Gained hydroxy apatite powder and shitosan powder are carried out using X-ray diffractometer (XRD) and infrared spectrometer
Test, as a result shows that gained hydroxy apatite powder is high-purity space hexagonal crystallographic texture, and shitosan powder is with higher
Crystallinity α-type shitosan.
Embodiment 5
(1) crab shell pretreatment：The direct dries pulverizing of crab shell is stand-by into powder.
(2) microwave reaction：40g crab shell raw material powder is weighed to be put into microwave reaction kettle, add 7.13g diammonium hydrogen phosphates and
6.21g ammonium dihydrogen phosphates and 3.0L deionized waters, are stirred, and pH value is adjusted 13.0 with the sodium hydroxide solution of 20wt%,
Controlled at 150 DEG C by adjusting microwave reaction power 800w controlling reaction temperatures, the reaction time is 12h, the product after microwave reaction
Thing with deionized water clean, dry after obtain nanometer hydroxyapatite-shitosan powder 20.3269g.
(3) product is separated：20.3269g nanometer hydroxyapatites that step (2) is obtained-shitosan powder add go from
Sub- water, the watery hydrochloric acid regulation pH value for being slowly added into 15wt% while stirring at room temperature is 4.0, and solid-liquid point after 1h is stirred at normal temperatures
From the solid for obtaining is washed with deionized to neutrality, is dried to obtain 11.8850g pure ha powders；By separation of solid and liquid
The liquid of collection, it is 11.0 to be slowly added into 10wt% ammoniacal liquor regulation pH value while stirring at room temperature, and the solid of precipitation is received
Collection drying, that is, obtain chitosan powder body 6.4335g.
Gained hydroxy apatite powder and shitosan powder are carried out using X-ray diffractometer (XRD) and infrared spectrometer
Test, as a result shows that gained hydroxy apatite powder is high-purity space hexagonal crystallographic texture, and shitosan powder is with higher
Crystallinity α-type shitosan.
The above, only presently preferred embodiments of the present invention, above-described embodiment only illustrative principle of the invention and
Its effect, and formal and substantial limitation not any to the present invention, it is noted that for the common skill of the art
Art personnel, on the premise of the inventive method is not departed from, can also make some improvement and supplement, and these improve and supplement
Should be regarded as protection scope of the present invention.All those skilled in the art, are not departing from the feelings of the spirit and scope of the present invention
Under condition, when the equivalent variations of a little variation, modification and evolution made using disclosed above technology contents, this is
The Equivalent embodiments of invention；Meanwhile, all any equivalent variations made to above-described embodiment according to substantial technological of the invention
Variation, modification and evolution, still fall within the range of technical scheme.
Claims (7)
1. a kind of method for preparing hydroxyapatite and shitosan as raw material with shrimp and crab shells, comprises the following steps：
(1) simple pretreatment：Shrimp and crab shells are directly dried, is crushed, obtain shrimp and crab shells raw material powder；
(2) heating response：Step (1) gained shrimp and crab shells raw material powder is weighed, a certain amount of diammonium hydrogen phosphate and biphosphate is added
Ammonium, plus deionized water is stirred, and pH value is adjusted to 10.0~13.0 with diluted alkaline, is heated to small in 80-150 DEG C of reaction 2~12
When, by the cleaning of gained product, dry, obtain final product hydroxyapatite-shitosan composite granule；
(3) product is separated：The hydroxyapatite that step (2) is obtained-shitosan composite granule, adds deionized water, with diluted acid
Regulation pH value stirs 30min~24h, separation of solid and liquid to 3.5~6.5, resulting solid be washed with deionized to it is neutral,
Be dried to obtain pure ha powder, by the liquid after resulting separation of solid and liquid add diluted alkaline adjust pH value to 8.0~
11.0, the solid of precipitation is collected, is dried, that is, obtain chitosan powder body.
2. method according to claim 1, it is characterised in that in step (2), the shrimp and crab shells raw material powder, phosphoric acid hydrogen two
Ammonium, the mass ratio of ammonium dihydrogen phosphate are 20:1.6-3.6:1.4-3.1.
3. method according to claim 1, it is characterised in that in step (2), the diluted alkaline be mass percent be 5~
The NaOH aqueous solution or mass percent of 20wt% are the ammonia spirit of 5~20wt%.
4. method according to claim 1, it is characterised in that in step (2), is heating using microwave reaction, and the heating exists
Carried out in microwave reaction kettle.
5. method according to claim 4, it is characterised in that the microwave reaction power of microwave reaction kettle is 200~800W.
6. method according to claim 1, it is characterised in that in step (3), the diluted acid be percent by volume be 5~
15% aqueous hydrochloric acid solution or percent by volume are 5~15% aqueous acetic acid.
7. according to power require 1 described in method, it is characterised in that in step (3), the diluted alkaline be mass percent be 5~
The NaOH aqueous solution or mass percent of 20wt% are the ammonia spirit of 5~20wt%.
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| CN108079382B (en) * | 2017-12-29 | 2021-01-26 | 连云港碳谷材料科技有限公司 | Preparation method of porous hydroxyapatite |
| CN109225156A (en) * | 2018-10-26 | 2019-01-18 | 浙江海洋大学 | A kind of preparation method of the new and effective adsorbent for silver ion recycling |
| CN113085319A (en) * | 2021-03-16 | 2021-07-09 | 晋江市新迪新材料科技有限公司 | Full-biodegradable composite material for tableware and tableware using same |
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|---|---|---|---|---|
| CN1548461A (en) * | 2003-05-07 | 2004-11-24 | 吴汉民 | Production process and apparatus of high quality chitosan |
| CN101200505A (en) * | 2007-11-29 | 2008-06-18 | 湖北东方天琪生物工程股份有限公司 | Method for preparing high deacetylate degree and high viscosity chitosan by using shrimp shell |
| CN101983728A (en) * | 2010-11-09 | 2011-03-09 | 厦门大学 | Shell porous hydroxyapatite basal bone repair material and preparation method thereof |
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| JPH078226A (en) * | 1993-06-21 | 1995-01-13 | Morio Tokoro | Calcium-containing fine powder and its production |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1548461A (en) * | 2003-05-07 | 2004-11-24 | 吴汉民 | Production process and apparatus of high quality chitosan |
| CN101200505A (en) * | 2007-11-29 | 2008-06-18 | 湖北东方天琪生物工程股份有限公司 | Method for preparing high deacetylate degree and high viscosity chitosan by using shrimp shell |
| CN101983728A (en) * | 2010-11-09 | 2011-03-09 | 厦门大学 | Shell porous hydroxyapatite basal bone repair material and preparation method thereof |
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