WO2017147796A1 - 一种蛋壳回收方法及其用途 - Google Patents
一种蛋壳回收方法及其用途 Download PDFInfo
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- WO2017147796A1 WO2017147796A1 PCT/CN2016/075275 CN2016075275W WO2017147796A1 WO 2017147796 A1 WO2017147796 A1 WO 2017147796A1 CN 2016075275 W CN2016075275 W CN 2016075275W WO 2017147796 A1 WO2017147796 A1 WO 2017147796A1
- Authority
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- WIPO (PCT)
- Prior art keywords
- eggshell
- drying
- substances
- hydrolysis
- powder
- Prior art date
Links
- 210000003278 egg shell Anatomy 0.000 title claims abstract description 72
- 108010000912 Egg Proteins Proteins 0.000 title claims abstract description 68
- 102000002322 Egg Proteins Human genes 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000004064 recycling Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 21
- 229940012466 egg shell membrane Drugs 0.000 claims abstract description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 9
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 7
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 5
- 230000001954 sterilising effect Effects 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims description 18
- 239000004365 Protease Substances 0.000 claims description 15
- 102000004190 Enzymes Human genes 0.000 claims description 9
- 108090000790 Enzymes Proteins 0.000 claims description 9
- 229940088598 enzyme Drugs 0.000 claims description 9
- -1 ficinase Proteins 0.000 claims description 9
- 108091005804 Peptidases Proteins 0.000 claims description 8
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims description 7
- 235000019419 proteases Nutrition 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 229920002385 Sodium hyaluronate Polymers 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229940010747 sodium hyaluronate Drugs 0.000 claims description 4
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 235000009434 Actinidia chinensis Nutrition 0.000 claims description 3
- 244000298697 Actinidia deliciosa Species 0.000 claims description 3
- 235000009436 Actinidia deliciosa Nutrition 0.000 claims description 3
- 108010004032 Bromelains Proteins 0.000 claims description 3
- 108090000526 Papain Proteins 0.000 claims description 3
- 108090000284 Pepsin A Proteins 0.000 claims description 3
- 102000057297 Pepsin A Human genes 0.000 claims description 3
- 235000006886 Zingiber officinale Nutrition 0.000 claims description 3
- 235000019835 bromelain Nutrition 0.000 claims description 3
- 235000008397 ginger Nutrition 0.000 claims description 3
- 244000005700 microbiome Species 0.000 claims description 3
- 235000019834 papain Nutrition 0.000 claims description 3
- 229940055729 papain Drugs 0.000 claims description 3
- 229940111202 pepsin Drugs 0.000 claims description 3
- 238000011085 pressure filtration Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 102000035195 Peptidases Human genes 0.000 claims 1
- 244000273928 Zingiber officinale Species 0.000 claims 1
- 238000005202 decontamination Methods 0.000 claims 1
- 230000003588 decontaminative effect Effects 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 235000019833 protease Nutrition 0.000 claims 1
- 238000004659 sterilization and disinfection Methods 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 14
- 239000012528 membrane Substances 0.000 abstract description 13
- 230000007071 enzymatic hydrolysis Effects 0.000 abstract description 11
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 abstract description 11
- 230000007062 hydrolysis Effects 0.000 abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000005191 phase separation Methods 0.000 abstract description 3
- 241000894006 Bacteria Species 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 5
- 235000013601 eggs Nutrition 0.000 description 5
- 229920002674 hyaluronan Polymers 0.000 description 5
- 229960003160 hyaluronic acid Drugs 0.000 description 5
- 102000008186 Collagen Human genes 0.000 description 4
- 108010035532 Collagen Proteins 0.000 description 4
- 101710097834 Thiol protease Proteins 0.000 description 4
- 229920001436 collagen Polymers 0.000 description 4
- 108010014258 Elastin Proteins 0.000 description 3
- 102000016942 Elastin Human genes 0.000 description 3
- 229920002683 Glycosaminoglycan Polymers 0.000 description 3
- 229920002549 elastin Polymers 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 2
- 108090000270 Ficain Proteins 0.000 description 2
- 241000234314 Zingiber Species 0.000 description 2
- 230000001153 anti-wrinkle effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000014103 egg white Nutrition 0.000 description 2
- 210000000969 egg white Anatomy 0.000 description 2
- 210000002969 egg yolk Anatomy 0.000 description 2
- 235000013345 egg yolk Nutrition 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 235000019836 ficin Nutrition 0.000 description 2
- POTUGHMKJGOKRI-UHFFFAOYSA-N ficin Chemical compound FI=CI=N POTUGHMKJGOKRI-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- SQDAZGGFXASXDW-UHFFFAOYSA-N 5-bromo-2-(trifluoromethoxy)pyridine Chemical compound FC(F)(F)OC1=CC=C(Br)C=N1 SQDAZGGFXASXDW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920001287 Chondroitin sulfate Polymers 0.000 description 1
- 108010026206 Conalbumin Proteins 0.000 description 1
- 108060003393 Granulin Proteins 0.000 description 1
- 229920002971 Heparan sulfate Polymers 0.000 description 1
- 229920000288 Keratan sulfate Polymers 0.000 description 1
- 102000016943 Muramidase Human genes 0.000 description 1
- 108010014251 Muramidase Proteins 0.000 description 1
- 108010062010 N-Acetylmuramoyl-L-alanine Amidase Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001384 anti-glaucoma Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 206010003246 arthritis Diseases 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229940059329 chondroitin sulfate Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- KXCLCNHUUKTANI-RBIYJLQWSA-N keratan Chemical compound CC(=O)N[C@@H]1[C@@H](O)C[C@@H](COS(O)(=O)=O)O[C@H]1O[C@@H]1[C@@H](O)[C@H](O[C@@H]2[C@H](O[C@@H](O[C@H]3[C@H]([C@@H](COS(O)(=O)=O)O[C@@H](O)[C@@H]3O)O)[C@H](NC(C)=O)[C@H]2O)COS(O)(=O)=O)O[C@H](COS(O)(=O)=O)[C@@H]1O KXCLCNHUUKTANI-RBIYJLQWSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229960000274 lysozyme Drugs 0.000 description 1
- 239000004325 lysozyme Substances 0.000 description 1
- 235000010335 lysozyme Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 238000002054 transplantation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
Definitions
- the present invention is in the field of waste recycling, and in particular, relates to the recovery of an eggshell and the use of the recovered material.
- the egg is composed of egg yolk, egg white, two-layer eggshell membrane and eggshell. Eggs are frequent visitors on each table. The consumption is very large. After cooking egg yolk and egg white, the rest is generally treated as waste and will not be recycled, but In fact, the value of eggshells is underestimated as waste materials. Osuoji et al. reported the presence of acidic glycosaminoglycans in eggshell membranes, and glycosaminoglycans (ie, hyaluronic acid) may be used for moisture retention and resistance to bacterial attack.
- eggshell membranes contain many valuable compounds, such as cross-linked collagen (1, V and X), glycosaminoglycans (ie hyaluronic acid, chondroitin sulfate, heparan sulfate). And keratan sulfate), egg white proteins (such as ovotransferrin, lysozyme) and eggshell matrix proteins (such as egg calcium)
- cross-linked collagen (1, V and X) glycosaminoglycans (ie hyaluronic acid, chondroitin sulfate, heparan sulfate). And keratan sulfate
- egg white proteins such as ovotransferrin, lysozyme
- eggshell matrix proteins such as egg calcium
- eggshell membrane may still be firmly attached to the eggshell, not It can be completely recycled, and the eggshell is still discarded as waste.
- useful components such as calcium carbonate, eggshell membrane powder (containing protein, collagen, elastin, hyaluronic acid)
- recycle the most abundant useful calcified eggshell powder containing calcium carbonate and can increase The amount of valuable organic content, such as protein, collagen, elastin, and hyaluronic acid, extracted from the eggshell and eggshell membranes and then dried into egg
- the method provided by the present invention is as follows:
- An eggshell waste recycling method comprising the following steps:
- the recovery method further comprises the steps of: dissolving the eggshell membrane powder, separating, purifying, and drying to obtain sodium hyaluronate, the purity of which is up to 90% or more.
- Sodium hyaluronate is a biochemical drug with high clinical value and is widely used in various ophthalmic operations such as crystal implantation, corneal transplantation and anti-glaucoma surgery, and can also be used for treating arthritis and accelerating wound healing. It is used in cosmetics to provide a unique protective effect on the skin. It keeps the skin moist and smooth, delicate and tender, and has elasticity. It has anti-wrinkle, anti-wrinkle, beauty care and restores skin's physiological functions.
- the eggshell is pulverized to have a particle diameter of 0.1 to 99 ⁇ m in order to shorten the hydrolysis of the enzyme.
- the enzyme used in the step (3) is a protease having at least one thiol group, such as kiwi egg A combination of more than one enzyme of white enzyme, bromelain, ficin, papain, pepsin or ginger protease, single thiol protease or thiol protease for specific enzymatic hydrolysis to increase extraction from eggshell waste (egg shells and eggshells)
- a protease having at least one thiol group such as kiwi egg A combination of more than one enzyme of white enzyme, bromelain, ficin, papain, pepsin or ginger protease, single thiol protease or thiol protease for specific enzymatic hydrolysis to increase extraction from eggshell waste (egg shells and eggshells)
- the solubility of the organic content of both membranes does not digest valuable organic content in large quantities.
- the method used in the separation in the step (4) is suction filtration separation, pressure filtration separation or centrifugal separation.
- the drying method in the steps (5) and (6) is spray drying or freeze drying.
- the use of the eggshell powder prepared by the above method is characterized in that it is used for preparing a thermoplastic instead of the existing calcium carbonate polymer filler, and the eggshell powder obtained by the method has a particle diameter of 0.1 to 99 micrometers. Also having a calcium carbonate content of from 90% to 99%, with little or no organic content, can be used in place of existing calcium carbonate polymer fillers and blended into thermoplastic products using single or twin screw extruders.
- thermoplastic is made of polyethylene, polylactic acid, polypropylene, poly(ethylene vinyl acetate) or polyvinyl chloride.
- the composition of the thermoplastic material is composed of 20% to 60% eggshell powder, and may also contain other additive components such as an antimicrobial agent, an antistatic agent, a coupling agent, a dye and a pigment, a filler, and a flame retardant.
- Agent, foaming agent, heat stabilizer, nucleating agent, odor releasing agent, ultraviolet light or light stabilizer, thermoplastic polymer composite can be further processed by extrusion, injection molding, blow molding and fused deposition molding to make thermoplastic product.
- the beneficial effects of the present invention are: 1. Maximum waste recycling and utilization; 2. It is not necessary to separate the eggshell and the eggshell membrane and then recover, hydrolyzed by enzymatic hydrolysis but does not destroy the same. The organic matter, and then the organic portion and the inorganic portion are separately dried to obtain a substance different in use.
- an eggshell waste recycling method includes the following steps
- the enzyme is a protease having at least one thiol group, such as kiwi protease, bromelain, ficin, papain, pepsin or ginger protease, and a combination of a single thiol protease or thiol protease for specific enzymatic hydrolysis to increase extraction
- a protease having at least one thiol group such as kiwi protease, bromelain, ficin, papain, pepsin or ginger protease, and a combination of a single thiol protease or thiol protease for specific enzymatic hydrolysis to increase extraction
- the eggshell membrane powder is obtained, and the obtained eggshell membrane powder is dissolved, further separated, purified, and dried to obtain sodium hyaluronate, and the purity can be more than 90%.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Cosmetics (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
一种蛋壳回收方法及其用途，所述的方法包括如下步骤：(1)选取回收带膜蛋壳，洗涤、灭菌，以除去污垢和微生物；(2)粉碎蛋壳以增加比表面积；(3)酶水解，粉碎后的蛋壳接触面积增大，能加快水解过程，以便缩短酶水解的时间；水解后得到类似液相的有机物和没有被水解的无机物；(4)将水解后的物质进行固液相分离；(5)取液相，干燥后得蛋壳膜粉；(6)取固相，干燥后得蛋壳粉。该方法制备的蛋壳粉可用于代替碳酸钙聚合物填料制备热塑性塑料。该方法的有益效果在于：1.能最大程度的废物再回收和利用；2.无需将蛋壳和蛋壳膜分离后再回收，通过酶水解的方法水解但是并不会破坏其中的有机物，然后分别干燥的有机部分和无机部分后，得到用处不同的物质。
Description
一种蛋壳回收方法及其用
技术领域
[0001] 本发明属于废料回收领域， 具体来讲， 是涉及一种蛋壳的回收以及回收物的用 途。
背景技术
蛋由蛋黄、 蛋清、 两层蛋壳膜和蛋壳组成， 鸡蛋作为每家餐桌上的常客， 消耗 量非常庞大， 在烹饪完蛋黄和蛋清后， 其余的一般作为废物处理， 不会回收， 但是实际上， 蛋壳的价值被低估为废弃材料， Osuoji等报道蛋壳膜中存在酸性糖 胺聚糖， 并且糖胺聚糖 （即， 透明质酸） 有可能用于水份保持及抵抗细菌侵袭 ， 此后， 更多的研究报道称， 蛋壳膜含有许多有价值的化合物， 如交联胶原蛋 白 （1、 V和 X) 、 糖胺聚糖 （即透明质酸、 硫酸软骨素、 硫酸乙酰肝素和硫酸角 质素） 、 蛋清蛋白质 （例如卵转铁蛋白、 溶菌酶） 和蛋壳基质蛋白 （例如卵钙
[0003] 根据 2013年香港进口商品贸易统计数据的报道， 约 2,243,000,000个单位的带壳 禽蛋进口到香港， 这表示存在着蛋壳的巨大废物量 （每只鸡蛋壳约 6克） ， 因为 在香港和中国有大量的蛋糕和面包制造商， 所以收集质量稳定的蛋壳废料比其 它食物废料也相对容易得多。 因此， 这种蛋壳废料应被充分利用并转化成不同 种类和能被广泛应用的循环再造产品。
[0004] 为了更好的利用废弃的蛋壳， 许多研究人员和多家公司幵发出不同的蛋壳和蛋 壳膜分离方法， 旨在通过分离获得更好的回收产品。 如 MacNil幵发了一种用于 清除蛋壳颗粒的膜部分的方法和装置， 基于优先浮选可以将膜与蛋壳分离。 DeJ ong和 Vlad为在装有流体的分离罐中加工未分离的蛋壳并向流体中的蛋壳施加气 蚀作用而将蛋壳膜与蛋壳分离申请专利。 Snyder为通过调节蛋壳的含水量， 接着 施加气流而将蛋壳膜与蛋壳分离。 但是， 分离后再回收， 即使干燥、 压碎、 研 磨和翻倒 （带膜的） 蛋壳， 蛋壳膜上具有有价值的有机内容物， 如蛋白质、 胶 原蛋白、 弹性蛋白和透明质酸的蛋壳膜也可能仍旧牢固地附着于蛋壳上， 并不
能完全的回收， 而且， 蛋壳仍旧是作为废料丢弃。
技术问题
问题的解决方案
技术解决方案
[0005] 本发明的目的在于提供一种同吋能完全地回收蛋壳和蛋壳膜的方法， 而且， 本 发明提供的方法无需将蛋壳和蛋壳膜分离， 从蛋壳废料 （蛋壳和蛋壳膜） 提取 有用组分， 如碳酸钙、 蛋壳膜粉 （含有蛋白质、 胶原蛋白、 弹性蛋白、 透明质 酸） ， 回收最丰富的含有碳酸钙的有用钙化蛋壳粉， 并且能增加提取自蛋壳和 蛋壳膜然后干燥成蛋壳膜粉的有价值的有机内容物， 如蛋白质、 胶原蛋白、 弹 性蛋白、 透明质酸的量。
[0006] 本发明提供的方法如下：
[0007] 一种蛋壳废料回收方法， 所述的回收方法包括如下步骤：
[0008] (1) 选取回收带膜蛋壳， 洗涤、 灭菌， 以除去污垢和微生物；
[0009] (2) 粉碎蛋壳以增加比表面积；
[0010] (3) 酶水解， 粉碎后的蛋壳接触面积增大， 能加快水解过程， 以便缩短酶 水解的吋间； 水解后得到类似液相的有机物和没有被水解的无机物；
[0011] (4) 将水解后的物质进行固液相分离；
[0012] (5) 取液相， 干燥后得蛋壳膜粉；
[0013] (6) 取固相， 干燥后得蛋壳粉。
[0014] 进一步的， 所述的回收方法还包括如下步骤： 溶解所述的蛋壳膜粉， 分离、 纯 化、 干燥后得透明质酸钠， 其纯度可达 90%以上。
[0015] 透明质酸钠为具有较高临床价值的生化药物,广泛应用于各类眼科手术,如晶体 植入、 角膜移植和抗青光眼手术等， 还可用于治疗关节炎和加速伤口愈合。 将 其用于化妆品中,能起到独特的保护皮肤作用,可保持皮肤滋润光滑，细腻柔嫩,富 有弹性，具有防皱、 抗皱、 美容保健和恢复皮肤生理功能的作用。
[0016] 进一步的， 步骤 （2) 中蛋壳粉碎后粒径为 0.1至 99微米， 以便缩短酶水解的吋 间。
[0017] 进一步的， 步骤 （3) 中采用的酶为具有至少一个巯基的蛋白酶， 如猕猴桃蛋
白酶、 菠萝蛋白酶、 无花果蛋白酶、 木瓜蛋白酶、 胃蛋白酶或生姜蛋白酶的一 种以上酶， 单一巯基蛋白酶或巯基蛋白酶的组合用于特异性酶水解以增加提取 自蛋壳废料 （蛋壳和蛋壳膜两者） 的有机内容物的溶解性， 而不会大量地消化 有价值的有机内容物。
[0018] 进一步的， 步骤 （4) 中分离采用的方法有吸滤分离、 压滤分离或离心分离。
[0019] 进一步的， 步骤 （5) 和 （6) 中干燥的方法有喷雾干燥或冷冻干燥。
[0020] 采用上述的方法制备的蛋壳粉的用途， 其特征在于， 用于代替现有的碳酸钙聚 合物填料制备热塑性塑料， 本方法制得的蛋壳粉， 粒径为 0.1至 99微米且碳酸钙 含量为 90%至 99%， 含有极少或不含有机内容物， 可以用于代替现有的碳酸钙聚 合物填料并且使用单或双螺杆挤出机混入热塑性产品中。
[0021] 进一步的， 热塑性塑料采用聚乙烯、 聚乳酸、 聚丙烯、 聚 (乙烯-酯酸乙烯酯)或 聚氯乙烯制备而成的材料。 所述的热塑性材料的组成成分由 20%至 60%的蛋壳粉 组成， 还可含有其他的添加剂组分， 如抗微生物剂、 抗静电剂、 偶联剂、 染料 和颜料、 填料、 阻燃剂、 起泡剂、 热稳定剂、 成核剂、 气味释放剂、 紫外线或 光稳定剂， 热塑性聚合物复合材料可以通过挤出、 注射成型、 吹塑成型和熔融 沉积成型进一步加工以制成热塑性产品。
发明的有益效果
有益效果
[0022] 本发明的有益效果在于， 1.能最大程度的废物再回收和利用； 2.无需将蛋壳和 蛋壳膜分离后再回收， 通过酶水解的方法水解但是并不会破坏其中的有机物， 然后分别干燥的有机部分和无机部分后， 得到用处不同的物质。
对附图的简要说明
附图说明
[0023] 图 1为本发明的工艺流程图。
本发明的实施方式
[0024] 实施例 1
[0025] 下面结合附图， 对本案进一步的说明。
[0026] 如附图工艺流程图， 一种蛋壳废料回收方法， 所述的回收方法包括如下步骤
[0027] (1) 选取回收带膜蛋壳， 洗涤、 灭菌， 以除去污垢和微生物；
[0028] (2) 粉碎蛋壳以增加比表面积， 蛋壳粉碎后粒径为 0.1至 99微米， 以便缩短 下一步骤中酶水解的吋间；
[0029] (3) 酶水解， 粉碎后的蛋壳接触面积增大， 能加快水解过程， 以便缩短酶 水解的吋间， 水解后得到类似液相的有机物和没有被水解的无机物， 采用的酶 为具有至少一个巯基的蛋白酶， 如猕猴桃蛋白酶、 菠萝蛋白酶、 无花果蛋白酶 、 木瓜蛋白酶、 胃蛋白酶或生姜蛋白酶的一种以上酶， 单一巯基蛋白酶或巯基 蛋白酶的组合用于特异性酶水解以增加提取自蛋壳废料 （蛋壳和蛋壳膜两者） 的有机内容物的溶解性， 而不会大量地消化有价值的有机内容物；
[0030] (4) 将水解后的物质进行固液相分离， 分离采用的方法有吸滤分离、 压滤 分离或离心分离；
[0031] (5) 取液相， 喷雾干燥或冷冻干燥后得蛋壳膜粉；
[0032] (6) 取固相， 喷雾干燥或冷冻干燥后得蛋壳粉。
[0033] 实施例 2
[0034] 经过实施例 1中的六个步骤后， 得到蛋壳膜粉， 将所得的蛋壳膜粉溶解， 进一 步分离、 纯化、 干燥后得透明质酸钠， 纯度可达 90%以上。
[0035]
Claims
[权利要求 1] 一种蛋壳回收方法， 其特征在于， 所述的回收方法包括如下步骤：
(1)选取回收蛋壳， 洗涤、 灭菌， 除去污垢和微生物；
(2)将灭菌除污后的蛋壳粉碎；
(3)将粉碎后的蛋壳酶水解；
(4)将水解后的物质固液相分离；
(5)取液相， 干燥后得蛋壳膜粉；
(6)取固相， 干燥后得蛋壳粉。
[权利要求 2] 如权利要求 1所述的回收方法， 其特征在于， 所述的回收方法还包括 如下步骤： 所述的蛋壳膜粉进一步分离、 纯化、 干燥后得透明质酸钠
[权利要求 3] 如权利要求 1所述的回收方法， 其特征在于， 步骤 （2) 中蛋壳粉碎后 粒径为 0.1至 99微米。
[权利要求 4] 如权利要求 1所述的回收方法， 其特征在于， 步骤 （3) 中采用的酶为 具有至少一个巯基的蛋白酶。
[权利要求 5] 如权利要求 4所述的回收方法， 其特征在于， 所述的酶为猕猴桃蛋白 酶、 菠萝蛋白酶、 无花果蛋白酶、 木瓜蛋白酶、 胃蛋白酶或生姜蛋白 酶的一种以上酶。
[权利要求 6] 如权利要求 1所述的回收方法， 其特征在于， 步骤 （4) 中分离采用的 方法有吸滤分离、 压滤分离或离心分离。
[权利要求 7] 如权利要求 1所述的回收方法， 其特征在于， 步骤 （5) 和 （6) 中干 燥的方法有喷雾干燥或冷冻干燥。
[权利要求 8] 根据权利要求 1-7任一权利要求所述的方法制备的蛋壳粉的用途， 其 特征在于， 用于代替碳酸钙聚合物填料制备热塑性塑料。
[权利要求 9] 如权利要求 8所述的蛋壳粉的用途， 其特征在于， 热塑性塑料采用聚 乙烯、 聚乳酸、 聚丙烯、 聚 (乙烯-酯酸乙烯酯)或聚氯乙烯制备而成的 材料。
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