CN105218698A - A kind of take shrimp and crab shells as the method that raw material prepares hydroxyapatite and chitosan - Google Patents
A kind of take shrimp and crab shells as the method that raw material prepares hydroxyapatite and chitosan Download PDFInfo
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Abstract
The invention provides a kind of is the method that raw material prepares hydroxyapatite and chitosan with shrimp and crab shells, solves the difficult problem that can not make full use of shrimp and crab shells at present.The present invention simplifies shrimp and crab shells pre-treating technology and active substance---calcium carbonate and the chitin that can make full use of in shrimp and crab shells simultaneously, only need to carry out simple and easy pre-treatment to starting material, the method of a step alkalization microwave is adopted to react, the alkali added during microwave reaction can by the protein that remains in shrimp and crab shells and lipid solubilization, and without the need to carrying out the complicated pre-treatment of such as soda boiling deproteinated, acidleach decalcification, effective Reaction time shorten (tapering to 2 ~ 12h by 10 days), and effectively can reduce reaction energy barrier.And the liquid after microwave reaction is reclaimed again, protein residual in shrimp and crab shells and grease can be made full use of, thus can production cost be reduced, high-efficiency environment friendly.
Description
Technical field
The invention belongs to chemical technology field, particularly a kind of method preparing hydroxyapatite and chitosan using shrimp and crab shells as raw material.
Background technology
Hydroxyapatite is a kind of weakly alkaline (pH=7 ~ 9) calcium phosphate salt being slightly soluble in water.Having many uses of hydroxy apatite powder, by being heated to 800 ~ 1200 DEG C of obtained hydroxylapatite ceramics, or the complex phase ceramic based on hydroxyapatite, for the hard tissue repair of human body; Also can with macromolecular material compound, as poly(lactic acid), collagen, poly-phthalein amine etc., thus improve the biocompatibility of material; Can also as the raw material of the metallic implant surface such as joint prosthesis, tooth implant spraying hydroxyapatite coating.Hydroxyapatite is more and more subject to people's attention as a kind of important biological active materials.
Chitosan is the general name of formed soluble chitin after taking off a certain amount of acetyl degree by chitin, chitosan is a kind of biodegradable positively charged alkaline polysaccharide of nature, the premium propertiess such as the biological functionality of this natural polymer and consistency, blood compatibility, security, microbic resolvability, are applied to the numerous areas such as medicine, food, chemical industry, makeup, water treatment, METAL EXTRACTION and recovery, biochemistry and biomedical engineering.Chitin is extensively present in the shell of the crustaceans such as shrimp, crab, insect.General and the protein of chitin or calcium carbonate or both be closely linked simultaneously, become complex compound, can remove the impurity such as calcium salt and protein by acid-alkali treatment, shrimp, crab shell also have pigment, can be removed by redox.Chitin is poly-2-acetamido-2-deoxidation-D-pyranoglucose, is a kind of linear neutral macromolecule polysaccharide, removes ethanoyl and obtain chitosan, be i.e. chitosan through concentrated base process.
Shrimp and crab shells is all the byproduct of ocean aquatic products, and its main inorganic composition is calcium carbonate and chitin, and has unique organic evolution microstructure.But utilizing of current shrimp and crab shells is limited, and majority is used as rubbish to process, and has potential harm in the course of time to environment, and produces the serious waste of resource; Part also only utilizes the calcium carbonate in crab shell to transform hydroxyapatite to the method that crab shell is recycled, or is only that effective constituent transforms chitosan with chitin, cannot make full use of the effective constituent in crab shell.If can be used to the calcium carbonate in crab shell and chitin by simple and effective transform mode simultaneously, and the protein remained in energy effective recycling shrimp and crab shells and grease, both can reduce the pollution to environment, and effective utilization of resource can have been realized again, realize environmental protection.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of is the method that raw material prepares hydroxyapatite and chitosan with shrimp and crab shells, solves the difficult problem that can not make full use of shrimp and crab shells at present.
For achieving the above object and other relevant objects, the present invention is by the following technical solutions:
Take shrimp and crab shells as the method that raw material prepares hydroxyapatite and chitosan, comprise the following steps:
(1) simple and easy pre-treatment: directly dried by shrimp and crab shells, pulverizes, obtains shrimp and crab shells raw material powder;
(2) reacting by heating: take step (1) gained shrimp and crab shells raw material powder, add a certain amount of Secondary ammonium phosphate and primary ammonium phosphate, add deionized water and stirring even, with diluted alkaline adjust ph to 10.0 ~ 13.0, be heated to 80-150 DEG C of reaction 2 ~ 12 hours, by the cleaning of gained reaction product, drying, obtain hydroxyapatite-chitosan composite granule;
(3) product separation: hydroxyapatite-chitosan composite granule that step (2) is obtained, add deionized water, with diluted acid adjust ph to 3.5 ~ 6.5, stir 30min ~ 24h, solid-liquid separation, the solid deionized water wash obtained obtains pure ha powder to neutral, drying, and the liquid after obtained solid-liquid separation is added diluted alkaline adjust ph to 8.0 ~ 11.0, the solid of precipitation is carried out collect, dry, namely obtain chitosan powder.
Preferably, in step (2), the mass ratio of described shrimp and crab shells powder, Secondary ammonium phosphate, primary ammonium phosphate is 20:1.6-3.6:1.4-3.1, is more preferred from 20:2.4-3.2:2.1-2.8.
Preferably, in step (2), the NaOH aqueous solution or the mass percent of described diluted alkaline to be mass percent be 5 ~ 20wt% are the ammonia soln of 5 ~ 20wt%.
Preferably, in step (2), be microwave heating reaction, described heating can be carried out in microwave reaction kettle, better, and the microwave reaction power of microwave reaction kettle is 200 ~ 800W.
Preferably, in step (3), described diluted acid to be volume percent be 5 ~ 15% aqueous hydrochloric acid or volume percent be the aqueous acetic acid of 5 ~ 15%.
Preferably, in step (3), the NaOH aqueous solution mass percent of described diluted alkaline to be mass percent be 5 ~ 20wt% is 5 ~ 20wt% or ammonia soln.
Beneficial effect of the present invention is:
(1) the present invention adopts the marine biomass waste shrimp and crab shells of rich reserves to be material, produce hydroxyapatite and chitosan simultaneously, and hydroxyapatite and the total yield of chitosan up to 92.37%, can adequately achieve raw-material effective comprehensive utilization.
(2) the present invention simplifies shrimp and crab shells pre-treating technology and active substance---calcium carbonate and the chitin that can make full use of in shrimp and crab shells simultaneously, only need to carry out simple and easy pre-treatment to starting material, the method of a step alkalization microwave is adopted to react, the alkali added during microwave reaction can by the protein that remains in shrimp and crab shells and lipid solubilization, and without the need to carrying out the complicated pre-treatment of such as soda boiling deproteinated, acidleach decalcification, effective Reaction time shorten (tapering to 2 ~ 12h by 10 days), and effectively can reduce reaction energy barrier.Thus can production cost be reduced, high-efficiency environment friendly.
(3) calcium carbonate in shrimp and crab shells that only utilizes in the present invention and prior art transforms hydroxyapatite, or be only that effective constituent conversion chitosan is compared with chitin, advantage is the various active substances (calcium carbonate and chitin) taken full advantage of in shrimp and crab shells, simultaneous reactions generates hydroxyapatite and chitosan, and realize effective separation of nanometer hydroxyapatite-chitosan powder, technique is simple and utilization ratio is high.
(4) method of the present invention is simple to operate, process stabilization, is applicable to large-scale batch production.
(5) another advantage is that shrimp and crab shells generally all contains grease and albumen, and process not in time all can be smelly.In the process of traditional chitin extraction, alkali cleaning is adopted to remove protein and grease.In our method, can these waste materials of fast processing, and adopt saponification reaction etc. of saltouing to reclaim to the liquid after microwave reaction, utilize these greases and protein completely.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum that embodiment 1 prepares the hydroxyapatite of gained.
Fig. 2 is the infrared spectrogram that embodiment 1 prepares the chitosan of gained.
Fig. 3 is the X ray diffracting spectrum that embodiment 1 prepares the chitosan of gained.
Embodiment
Below by way of specific specific examples, embodiments of the present invention are described, those skilled in the art the content disclosed by this specification sheets can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this specification sheets also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
In addition should be understood that the one or more method stepss mentioned in the present invention do not repel and can also to there is additive method step or can also insert additive method step before and after described combination step between these steps clearly mentioned, except as otherwise noted.
Embodiment 1
(1) shrimp shell pre-treatment: direct for shrimp shell ovendry power is broken into powder stand-by.
(2) microwave reaction: take 40g shrimp husk as raw material powder and put into microwave reaction kettle, add 4.67g Secondary ammonium phosphate and 4.07g primary ammonium phosphate and 2.5L deionized water, stir, with the aqueous sodium hydroxide solution adjust ph of 10wt% 10.0, temperature of reaction is controlled at 90 DEG C by regulating microwave reaction power 400w, reaction times is 4h, and the product after microwave reaction is to obtain nanometer hydroxyapatite-chitosan powder 16.8520g after washed with de-ionized water, drying.
(3) product separation: 16.8520g nanometer hydroxyapatite-chitosan powder step (2) obtained adds deionized water, the dilute hydrochloric acid adjust ph slowly adding 10wt% under room temperature is while stirring 4.0, solid-liquid separation after stirring 2h at normal temperatures, the solid deionized water wash obtained is to neutral, and drying obtains 10.2713g pure ha powder; By the liquid that solid-liquid separation is collected, the sodium hydroxide adjust ph slowly adding 10wt% under room temperature is while stirring 11.0, the solid of precipitation is carried out collection dry, namely obtains chitosan powder 5.2174g.
X-ray diffractometer (XRD) is adopted to carry out phase structure test to gained hydroxy apatite powder, result as shown in Figure 1, consistent with the standard diagram of hydroxyapatite (JCPDS standard card 09-0432), there is no the diffraction peak of other impurity phases, high purity pure ha powder is obtained, the space hexagonal crystallographic texture of its crystalline structure conformance with standard hydroxyapatite after showing to adopt this method to be separated.The characteristic peak of hydroxyapatite is all there is at crystal faces such as (002) (300) (222), and (002) crystal face characteristic peak is very sharp-pointed, illustrates that hydroxyapatite crystal has had the trend along c-axis direction preferential growth.
Infrared spectrometer (IR) is adopted to carry out structural characterization as shown in Figure 2 to chitosan powder, 3428.45cm
-1left and right forms hydrogen bond association-OH stretching vibration absorption peak multi-absorption peak overlapping and broadening with the stretching vibration absorption peak of-NH.Also exist in a large amount of chains in chitosan molecule, interchain hydrogen bond, because of the length of hydrogen bond and power not etc., make its flexible peak in a wider range of frequency.At 2922.62cm
-1and 2857.41cm
-1place is respectively two stretching vibration absorption peaks of C-H.1637.48cm
-1there is stronger acid amides I absorption peak, 1597.18cm
-1place is acid amides II absorption peak.=CH
2bend and-CH
3distortion absorption peak is at 1423.12cm
-1place, C-H bends and-CH
3symmetrical deformation vibration absorption peak is at 1381.66cm
-1place.At 1320.87cm
-1locate to be out of shape coupling absorption peak for acid amides C-N is flexible with N-H.At 1157.43cm
-1place is the vibration peak of β-glycosidic link.From the analysis of above vibration peak, can determine that product is chitosan.X-ray diffractometer (XRD) is adopted to carry out phase structure test to gained chitosan powder, result as shown in Figure 3, the sharp-pointed diffraction peak belonging to chitosan is all there is near 2 θ=11 ° and 20 °, illustrate that it all has very high degree of crystallinity, this is the result of molecular memory at hydrogen bond.Near 2 θ=11 °, occur that diffraction peak judges, the chitosan obtained belongs to α-type chitosan.
Embodiment 2
(1) shrimp shell pre-treatment: direct for shrimp shell ovendry power is broken into powder stand-by.
(2) microwave reaction: take 40g shrimp husk as raw material powder and put into microwave reaction kettle, add 4.67g Secondary ammonium phosphate and 4.07g primary ammonium phosphate and 2.5L deionized water, stir, with the sodium hydroxide solution adjust ph of 15wt% 12.0, controlling temperature of reaction by regulating microwave reaction power 500w controls at 100 DEG C, reaction times is 2h, and the product after microwave reaction is to obtain nanometer hydroxyapatite-chitosan powder 15.9876g after washed with de-ionized water, drying.
(3) product separation: 15.9876g nanometer hydroxyapatite-chitosan powder step (2) obtained adds deionized water, the dilute hydrochloric acid adjust ph slowly adding 15wt% under room temperature is while stirring 6.5, solid-liquid separation after stirring 24h at normal temperatures, the solid deionized water wash obtained is to neutral, and drying obtains 9.5702g pure ha powder; By the liquid that solid-liquid separation is collected, slowly adding 10wt% ammoniacal liquor adjust ph under room temperature is while stirring 10.0, the solid of precipitation is carried out collection dry, namely obtains chitosan powder 4.8220g.
X-ray diffractometer (XRD) and infrared spectrometer is adopted to test gained hydroxy apatite powder and chitosan powder, result shows that gained hydroxy apatite powder is high purity space hexagonal crystallographic texture, and chitosan powder is the α-type chitosan with higher degree of crystallinity.
Embodiment 3
(1) crab shell pre-treatment: direct for crab shell ovendry power is broken into powder stand-by.
(2) microwave reaction: take 40g crab husk as raw material powder and put into microwave reaction kettle, add 6.34g Secondary ammonium phosphate and 5.52g primary ammonium phosphate and 2.5L deionized water, stir, regulate pH value 8.0 with the sodium hydroxide solution of 5wt%, controlling temperature of reaction by regulating microwave reaction power 400w controls at 90 DEG C, reaction times is 8h, and the product after microwave reaction is to obtain nanometer hydroxyapatite-chitosan powder 18.9652g after washed with de-ionized water, drying.
(3) product separation: 18.9652g nanometer hydroxyapatite-chitosan powder step (2) obtained adds deionized water, the dilute hydrochloric acid adjust ph slowly adding 5wt% under room temperature is while stirring 4.0, solid-liquid separation after stirring 6h at normal temperatures, the solid deionized water wash obtained is to neutral, and drying obtains 13.4368g pure ha powder; By the liquid that solid-liquid separation is collected, the sodium hydroxide adjust ph slowly adding 5wt% under room temperature is while stirring 10.0, the solid of precipitation is carried out collection dry, namely obtains chitosan powder 3.8177g.
X-ray diffractometer (XRD) and infrared spectrometer is adopted to test gained hydroxy apatite powder and chitosan powder, result shows that gained hydroxy apatite powder is high purity space hexagonal crystallographic texture, and chitosan powder is the α-type chitosan with higher degree of crystallinity.
Embodiment 4
(1) crab shell pre-treatment: direct for crab shell ovendry power is broken into powder stand-by.
(2) microwave reaction: take 40g crab husk as raw material powder and put into microwave reaction kettle, add 6.34g Secondary ammonium phosphate and 5.52g primary ammonium phosphate and 2.5L deionized water, stir, with the ammoniacal liquor adjust ph of 10wt% 12.0, controlling temperature of reaction by regulating microwave reaction power 600w controls at 115 DEG C, reaction times is 6h, and the product after microwave reaction is to obtain nanometer hydroxyapatite-chitosan powder 19.4302g after washed with de-ionized water, drying.
(3) product separation: 19.4302g nanometer hydroxyapatite-chitosan powder step (2) obtained adds deionized water, the dilute hydrochloric acid adjust ph slowly adding 10wt% under room temperature is while stirring 4.0, solid-liquid separation after stirring 30min at normal temperatures, the solid deionized water wash obtained is to neutral, and drying obtains 12.0331g pure ha powder; By the liquid that solid-liquid separation is collected, the ammoniacal liquor adjust ph slowly adding 10wt% under room temperature is while stirring 10.0, the solid of precipitation is carried out collection dry, namely obtains chitosan powder 5.9146g.
X-ray diffractometer (XRD) and infrared spectrometer is adopted to test gained hydroxy apatite powder and chitosan powder, result shows that gained hydroxy apatite powder is high purity space hexagonal crystallographic texture, and chitosan powder is the α-type chitosan with higher degree of crystallinity.
Embodiment 5
(1) crab shell pre-treatment: direct for crab shell ovendry power is broken into powder stand-by.
(2) microwave reaction: take 40g crab husk as raw material powder and put into microwave reaction kettle, add 7.13g Secondary ammonium phosphate and 6.21g primary ammonium phosphate and 3.0L deionized water, stir, regulate pH value 13.0 with the sodium hydroxide solution of 20wt%, controlling temperature of reaction by regulating microwave reaction power 800w controls at 150 DEG C, reaction times is 12h, and the product after microwave reaction is to obtain nanometer hydroxyapatite-chitosan powder 20.3269g after washed with de-ionized water, drying.
(3) product separation: 20.3269g nanometer hydroxyapatite-chitosan powder step (2) obtained adds deionized water, the dilute hydrochloric acid adjust ph slowly adding 15wt% under room temperature is while stirring 4.0, solid-liquid separation after stirring 1h at normal temperatures, the solid deionized water wash obtained is to neutral, and drying obtains 11.8850g pure ha powder; By the liquid that solid-liquid separation is collected, slowly adding 10wt% ammoniacal liquor adjust ph under room temperature is while stirring 11.0, the solid of precipitation is carried out collection dry, namely obtains chitosan powder 6.4335g.
X-ray diffractometer (XRD) and infrared spectrometer is adopted to test gained hydroxy apatite powder and chitosan powder, result shows that gained hydroxy apatite powder is high purity space hexagonal crystallographic texture, and chitosan powder is the α-type chitosan with higher degree of crystallinity.
The above; be only preferred embodiment of the present invention; above-described embodiment is illustrative principle of the present invention and effect thereof only; and not to any formal and substantial restriction of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the inventive method; also can make some improvement and supplement, these improve and supplement and also should be considered as protection scope of the present invention.All those skilled in the art, without departing from the spirit and scope of the present invention, a little change made when utilizing disclosed above technology contents, the equivalent variations of modifying and developing, be Equivalent embodiments of the present invention; Meanwhile, all according to substantial technological of the present invention to the change of any equivalent variations that above-described embodiment is done, modify and differentiation, all still belong in the scope of technical scheme of the present invention.
Claims (7)
1. be the method that raw material prepares hydroxyapatite and chitosan with shrimp and crab shells, comprise the following steps:
(1) simple and easy pre-treatment: directly dried by shrimp and crab shells, pulverizes, obtains shrimp and crab shells raw material powder;
(2) reacting by heating: take step (1) gained shrimp and crab shells raw material powder, add a certain amount of Secondary ammonium phosphate and primary ammonium phosphate, add deionized water and stirring even, with diluted alkaline adjust ph to 10.0 ~ 13.0, be heated to 80-150 DEG C of reaction 2 ~ 12 hours, by the cleaning of gained reaction product, drying, obtain hydroxyapatite-chitosan composite granule;
(3) product separation: hydroxyapatite-chitosan composite granule that step (2) is obtained, add deionized water, with diluted acid adjust ph to 3.5 ~ 6.5, stir 30min ~ 24h, solid-liquid separation, the solid deionized water wash obtained obtains pure ha powder to neutral, drying, and the liquid after obtained solid-liquid separation is added diluted alkaline adjust ph to 8.0 ~ 11.0, the solid of precipitation is carried out collect, dry, namely obtain chitosan powder.
2. method according to claim 1, is characterized in that, in step (2), the mass ratio of described shrimp and crab shells raw material powder, Secondary ammonium phosphate, primary ammonium phosphate is 20:1.6-3.6:1.4-3.1.
3. method according to claim 1, is characterized in that, in step (2), the NaOH aqueous solution or the mass percent of described diluted alkaline to be mass percent be 5 ~ 20wt% are the ammonia soln of 5 ~ 20wt%.
4. method according to claim 1, is characterized in that, in step (2), be microwave heating reaction, described heating can be carried out in microwave reaction kettle.
5. method according to claim 4, is characterized in that, the microwave reaction power of microwave reaction kettle is 200 ~ 800W.
6. method according to claim 1, is characterized in that, in step (3), described diluted acid to be volume percent be 5 ~ 15% aqueous hydrochloric acid or volume percent be the aqueous acetic acid of 5 ~ 15%.
7. according to the method that power requires described in 1, it is characterized in that, in step (3), the NaOH aqueous solution mass percent of described diluted alkaline to be mass percent be 5 ~ 20wt% is 5 ~ 20wt% or ammonia soln.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108079382A (en) * | 2017-12-29 | 2018-05-29 | 连云港碳谷材料科技有限公司 | A kind of 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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| 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108079382A (en) * | 2017-12-29 | 2018-05-29 | 连云港碳谷材料科技有限公司 | A kind of 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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