CN105533691A - Novel micro-nanometer grade fish oil/algae oil microcapsule and preparation process thereof - Google Patents

Novel micro-nanometer grade fish oil/algae oil microcapsule and preparation process thereof Download PDF

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CN105533691A
CN105533691A CN201510928123.6A CN201510928123A CN105533691A CN 105533691 A CN105533691 A CN 105533691A CN 201510928123 A CN201510928123 A CN 201510928123A CN 105533691 A CN105533691 A CN 105533691A
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oil
microcapsule
magnetic agitation
fish oil
algae
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CN105533691B (en
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霍军生
王连艳
黄建
杨婷媛
张贵锋
刘辉
张博
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Nutrition And Health Institute Chinese Center For Disease Control And Prevention
Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
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Abstract

The present invention relates to a fish oil/algal oil microencapsulated product rich in polyunsaturated fatty acids (PUFA) essential to the human body and a production process thereof. The microcapsule is prepared by means of a premix membrane emulsification process and a complex coacervation method using sodium alginate and chitosan which are biodegradable, have health-care functions and are cheap and readily available as wall materials. The prepared fish oil/algal oil microcapsule is uniform in particle size, and the particle size can be controlled at hundreds of nanometers-tens of microns. The prepared fish oil/algal oil microcapsule has the advantages of good sustained release and enteric digestion effects, high absorption efficiency, low production cost, etc., and can be widely applied to food nutrition enhancement and health-care food.

Description

A kind of novel micro nanometer meter level fish oil/algae oil microcapsule and preparation technology thereof
Technical field
The present invention relates to the microencapsulation technology in food processing field, be specially a kind of fish oil/algae oil microcapsule product and preparation technology thereof.
Background technology
The necessary polyunsaturated fatty acid of human body (PUFA) is rich in deep sea fish oil/algae oil.In PUFA family, the DHA (DHA) of n-3 series and the arachidonic acid (ARA) of n-6 series are two kinds of very important PUFA, their concentration in nerve fiber is very high, such as in retinal photoreceptor cells and in cerebral gray matter, these two kinds of PUFA take part in growth and the function formation of brain.Wherein, DHA is to neural and visual development is most important, and ARA is then very crucial to the normal use of normal development and vascular system.In addition, prostaglandin (PG) also plays vital effect as a kind of metabolite of PUFA to the growth of brain.In neonatal brain, the expression of PG and acceptor thereof can be accelerated, thus regulates blood supply in brain and nitric oxide synthesis before manufacture with after production.The acceptor of PG is present in sternzellen and oligodendroglia, and PG is considered to take part in the generation of myelin and the differentiation of oligodendroglia, and this has very important effect for human life's early intelligence and cognitive growth.
Fish oil/algae oil is inherently a kind of makes us unhappy fishy smell, and its polyunsaturated fatty acid be rich in is also very easily oxidized, oxidation product not only causes the reduction of fish oil/nutritive value of algae oil own, even can produce some harmful materials, this also makes it be subject to certain restrictions in food applications.Microencapsulation technology is widely used in pharmacy and field of food industry.Liquid fish oil/algae oil can be transformed into solid dry powder by micro-encapsulation technology, this effectively can not only hide its intrinsic disagreeable taste, prevents polyunsaturated fatty acid oxidized to greatest extent, and can also extend the shelf life of relevant food to greatest extent.
Fish oil on existing market/algae oil microencapsulation product obtains mainly through traditional spray drying technology, microcapsules prepared by this technique mainly have the following disadvantages: first, capsule size is general larger, from tens microns even to micron up to a hundred, and particle size heterogeneity, this limits its effective absorption on intestinal mucosa to a certain extent; Secondly, high temperature link intrinsic in drying process with atomizing flow process can, by the polyunsaturated fatty acid Partial digestion in fish oil/algae oil, cause product nutritive value to reduce.In addition, in the wall material selected by microcapsules, existing microcapsule product does not possess the characteristics such as good slowly-releasing and enteric, after this series products water is reconstituted or in human stomach's environment, wall material disintegration also will discharge fish oil/algae oil of embedding rapidly too early, this also can have a strong impact on products taste, reduces acceptable.For the deficiency of above-mentioned fish oil/algae oil microcapsule product, the scholars of association area are always in unremitting effort and innovation.The patent No. is that CN1120933.A discloses a kind of fish oil micro-capsule and preparation technology and purposes, have employed sodium alginate and shitosan etc. as wall material, by fish oil micro-capsule prepared by the methods such as spraying dry, product not only particle diameter is large but also be rendered as the graininess of indefinite form.Number of patent application is 201310590455.9 preparation methods disclosing a kind of fish oil nano liposome, obtains the fish oil micro-capsule of uniform particle diameter, Nano grade, but the production cost of liposome technique own is very high, is not suitable for large-scale promotion and application.
In sum, in view of the current situation of fish oil/algae oil microcapsule technology, develop the homogeneous controlled nanometer of particle size and cover good and the slowly-releasing that absorptivity is high, enteric, low cost fish oil/algae oil microcapsule have very important significance to micron order, smell.
Summary of the invention
For the deficiency of prior art and product, the invention provides a kind of novel micro nanometer meter level fish oil/algae oil microcapsule and production technology thereof:
A kind of novel micro nanometer meter level fish oil/algae oil microcapsule, comprises by the oily active layer formed of fish oil/algae and the wall sheet material layers be made up of Ah-ACMS, it is characterized in that: described active layer and wall sheet material layers account for 25-35%, 65-75% of gross weight respectively; The particle size range of described microcapsules is 500 ~ 800nm, and the efficient loading rate of fish oil/algae oil is 25%-35%.
Further, in described microcapsules also containing accounting for the fat-soluble antioxidant of gross weight 0.05-1.5%, the hydrophilic emulsifier of 1-10%.
Further, one or both in described fat-soluble antioxidant preferred vitamin E or fat soluble ascorbic acid.
Further, described hydrophilic emulsifier is selected from one or both in sucrose fatty ester (SE-15) or Tween-20.
Further, one or both in the preferred polyglyceryl fatty acid ester of described lipophilic emulsifier (PO-5S) or Span-80.
The preparation technology of novel micro nanometer meter level fish oil/algae oil microcapsule of the present invention, carries out according to following steps:
(1) interior oil phase preparation: take appropriate fat-soluble antioxidant, add in a fish oil/algae oil by it according to mass percent 0.1 ~ 5.0%, magnetic agitation is to mixing;
(2) aqueous phase preparation: take one or more appropriate hydrophilic emulsifiers, it added to according to mass percent 0.2 ~ 2.0% in the sodium alginate aqueous solution of a 0.5 ~ 3.0%, magnetic agitation is to mixing;
(3) outer oil phase preparation: take one or more appropriate lipophilic emulsifiers, add in a edible oil by it according to mass percent 1 ~ 4%, magnetic agitation is to mixing;
(4) preparation of calcium chloride curing agent: first prepare the calcium chloride water that a certain amount of weight ratio is 1 ~ 10%, then adds in the outer oil phase of a certain amount of step (3) according to the ratio of volume 1:5 ~ 1:10 by calcium chloride water, for subsequent use after ultrasonic mixing;
(5) preparation of chitosan solution: according to weight ratio be 1 ~ 3% ratio a certain amount of shitosan to be dissolved into pH value be in the acid solutions such as the acetic acid/citric acid of 3 ~ 4, magnetic agitation evenly after for subsequent use;
(6) first time fast film emulsification: the interior oil phase of step (1) added in advance to magnetic agitation in the aqueous phase of step (2) according to the ratio of volume 1:3 ~ 1:10 even, first the SPG film of hole between 0.10 ~ 0.28 μm is chosen as small as possible, then premixed liquid is put in device and carry out first time fast film emulsification, after emulsification 1 ~ 3 time, form colostrum;
(7) second time fast film emulsification: it is even according to the ratio of volume 1:5 ~ 1:20 the colostrum of step (6) to be added in advance to magnetic agitation in the outer oil phase of step (3), first 0.28 ~ 18.00 μm of SPG film do not waited is chosen respectively according to the desired microcapsule diameter size that will reach, then premixed liquid is put in device and carry out the emulsification of second time fast film, after emulsification 1 ~ 3 time, form emulsion;
(8) calcium chloride solidification: according to the quantity of guluronic units contained in the large molecule of sodium alginate, calcium chloride prepared by step (4) added in emulsion prepared by step (7) according to the mol ratio of 1:1 ~ 1:4, under 30 ~ 60 DEG C of temperature-controlled conditions, solidify 2 ~ 6h;
(9) complex coacervation: first sodium alginate microcapsule prepared by step (8) is washed away outer oil phase, then suspend by a certain amount of deionized water, according to isopyknic ratio, chitosan solution prepared by step (5) is added in this solution again, solidify 1 ~ 3h under magnetic agitation, after washing away unnecessary shitosan, a small amount of deionized water of micro-capsule is suspended;
(10) freeze drying: by step (9) microcapsule suspensions freeze drying 24 ~ 72h, obtains the Ah-ACMS solid microcapsules of described fish oil/algae oil.
The beneficial effect of patent of the present invention is:
(1) according to actual product needs, by choosing the SPG film of different aperture, 500 ~ 800nm size can not prepared not etc., and fish oil/algae oil microcapsule that particle size is homogeneous;
(2) relative to traditional as the emulsion preparation technology such as high-pressure homogeneous, ultrasonic, fast film emulsification possesses the technical advantage such as low energy consumption, low-shearing force, and the protection for the polyunsaturated fatty acid in the stability of colostrum and the fish oil/algae oil of embedding is most important;
(3) what adopt in the whole microencapsulation technological process of production is food grade materials, do not introduce any food processing aid and poisonous and hazardous chemical substance, this is for follow-up the applying of microcapsules, and especially the strengthening of infant food will be more safe and reliable;
(4) raw material sodium alginate and shitosan are natural biodegradable polysaccharose substance, cheap and easy to get and have health-care efficacy concurrently, because production cost is low, are suitable for promotion and application widely;
(5) Ah-ACMS microcapsules have the insoluble and characteristic of enteric, slowly-releasing of stomach, and the covering effect for fish oil/algae oil fishy smell is fine, so can improve consumer to this series products can acceptance.
Accompanying drawing explanation
Fig. 1 is preparation technology's flow chart of fish oil/algae oil microcapsule;
Fig. 2 is the fish oil described in embodiment 1/algae oil microcapsule scanning electron microscopic picture.
Fig. 3 is the fish oil described in embodiment 2/algae oil microcapsule scanning electron microscopic picture.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described, but be not limited to the content on description.
Embodiment 1:
(1) interior oil phase preparation: take 0.5g vitamin E, added in 100mL deep sea fish oil/algae oil, magnetic agitation 1h;
(2) aqueous phase preparation: take 0.2g sucrose fatty ester (SE-15), being added to 100mL mass ratio is in the sodium alginate aqueous solution of 1.5%, magnetic agitation 2h;
(3) outer oil phase preparation: take appropriate 1g polyglyceryl fatty acid ester (PO-5S), added in 100mL sunflower oil, magnetic agitation 1h;
(4) preparation of calcium chloride curing agent: by 5mL mass ratio be 5% calcium chloride water add in the outer oil phase of 15mL step (3), setting power is ultrasonic emulsification 2min under 30% condition;
(5) preparation of chitosan solution: 1.5g shitosan is added in the acetum of 100mLpH4.0, after magnetic agitation 2h, centrifuging and taking supernatant is for subsequent use;
(6) first time fast film emulsification: add the interior oil phase of 2ml step (1) in the aqueous phase of 10mL step (2) magnetic agitation 1h in advance according to 1:5 volume ratio, choose the SPG film that hole is 0.1 μm, then premixed liquid is put in device after carrying out first time fast film emulsification 3 times and form colostrum;
(7) second time fast film emulsification: according to 1:10 volume ratio the colostrum of 10mL step (6) added in advance to magnetic agitation 1h in the outer oil phase of 100mL step (3), choose the SPG film that hole is 9.2 μm, then premixed liquid is put in device after carrying out second time fast film emulsification 3 times and form emulsion;
(8) calcium chloride solidification: measure calcium chloride prepared by 20mL step (4) and add in emulsion prepared by step (7), solidify 5h under 40 DEG C of temperature-controlled conditions;
(9) complex coacervation: suspend by 10mL deionized water after first sodium alginate microcapsule prepared by step (8) being washed away outer oil phase, then chitosan solution prepared by 10mL step (5) is slowly dripped, 1.5h is solidified, conventional freezing 12h after micro-capsule 3mL deionized water being suspended after washing away unnecessary shitosan under magnetic agitation;
(10) freeze drying: the freezing sample of step (9) microcapsules is carried out 72h freeze drying, obtains the Ah-ACMS solid microcapsules of described fish oil/algae oil.
The particle diameter of the Ah-ACMS solid microcapsules of the fish oil/algae oil of the present embodiment is 648 ± 75nm, and polydispersity index (PDI) is 0.147, and surface charge is+7.9mV, and the efficient loading rate of fish oil/algae oil is 32%, and awkward silence at a meeting surface sweeping electron microscopic picture is shown in accompanying drawing 2.
Embodiment 2:
(1) interior oil phase preparation: take 0.1g fat soluble ascorbic acid, added in 100mL deep sea fish oil/algae oil, magnetic agitation 1h;
(2) aqueous phase preparation: take 0.1g Tween-20, being added to 100mL mass ratio is in the sodium alginate aqueous solution of 1.0%, magnetic agitation 2h;
(3) outer oil phase preparation: take appropriate 2g Span-80, added in 100mL sunflower oil, magnetic agitation 1h;
(4) preparation of calcium chloride curing agent: by 5ml mass ratio be 6% calcium chloride water add in the outer oil phase of 40mL step (3), setting power is ultrasonic emulsification 2min under 30% condition;
(5) preparation of chitosan solution: 1.0g shitosan is added in the acetum of 100mLpH4.0, after magnetic agitation 2h, centrifuging and taking supernatant is for subsequent use;
(6) first time fast film emulsification: add the interior oil phase of 1mL step (1) in the aqueous phase of 10mL step (2) magnetic agitation 1h in advance according to 1:10 volume ratio, choose the SPG film that hole is 0.1 μm, then premixed liquid is put in device after carrying out first time fast film emulsification 3 times and form colostrum;
(7) second time fast film emulsification: according to 1:20 volume ratio the colostrum of 5mL step (6) added in advance to magnetic agitation 1h in the outer oil phase of 100mL step (3), choose the SPG film that hole is 7.2 μm, then premixed liquid is put in device after carrying out second time fast film emulsification 3 times and form emulsion;
(8) calcium chloride solidification: measure calcium chloride prepared by 10mL step (4) and add in emulsion prepared by step (7), solidify 6h under 40 DEG C of temperature-controlled conditions;
(9) complex coacervation: suspend by 10mL deionized water after first sodium alginate microcapsule prepared by step (8) being washed away outer oil phase, then chitosan solution prepared by 10mL step (5) is slowly dripped, 1.0h is solidified, conventional freezing 12h after micro-capsule 3mL deionized water being suspended after washing away unnecessary shitosan under magnetic agitation;
(10) freeze drying: the freezing sample of step (9) microcapsules is carried out 72h freeze drying, obtains the Ah-ACMS solid microcapsules of described fish oil/algae oil.
The particle diameter of the Ah-ACMS solid microcapsules of the fish oil/algae oil of the present embodiment is 573 ± 75nm, polydispersity index (PDI) is 0.212, surface charge is+8.0mV, and the efficient loading rate of fish oil/algae oil is 27%, and its awkward silence at a meeting surface sweeping electron microscopic picture is shown in accompanying drawing 3.

Claims (8)

1. micro/nano level fish oil/algae oil microcapsule, comprises by the oily active layer formed of fish oil/algae and the wall sheet material layers be made up of Ah-ACMS, it is characterized in that: described active layer and wall sheet material layers account for 25-35%, 65-75% of gross weight respectively; The particle size range of described microcapsules is 500 ~ 800nm, and the efficient loading rate of fish oil/algae oil is 25%-35%.
2. micro-sodium meter level fish oil/algae oil microcapsule as claimed in claim 1, is characterized in that: also containing accounting for the fat-soluble antioxidant of gross weight 0.05-1.5%, the hydrophilic emulsifier of 1-10% in described microcapsules.
3. micro-sodium meter level fish oil/algae oil microcapsule as claimed in claim 2, is characterized in that: described fat-soluble antioxidant be selected from vitamin E or fat soluble ascorbic acid one or both.
4. micro-sodium meter level fish oil/algae oil microcapsule as claimed in claim 2, is characterized in that: described hydrophilic emulsifier be selected from sucrose fatty ester or Tween-20 one or both.
5. micro-sodium meter level fish oil/algae oil microcapsule as claimed in claim 2, is characterized in that: one or both in the preferred polyglyceryl fatty acid ester of described lipophilic emulsifier or Span-80.
6. prepare a method for micro-sodium meter level fish oil/algae oil microcapsule as claimed in claim 1, it is characterized in that, the method comprises the steps:
(1) interior oil phase preparation: take appropriate fat-soluble antioxidant, add in a fish oil/algae oil by it according to mass percent 0.1 ~ 5.0%, magnetic agitation is to mixing;
(2) aqueous phase preparation: take one or more appropriate hydrophilic emulsifiers, it added to according to mass percent 0.2 ~ 2.0% in the sodium alginate aqueous solution of a 0.5 ~ 3.0%, magnetic agitation is to mixing;
(3) outer oil phase preparation: take one or more appropriate lipophilic emulsifiers, add in a edible oil by it according to mass percent 1 ~ 4%, magnetic agitation is to mixing;
(4) preparation of calcium chloride curing agent: first prepare the calcium chloride water that a certain amount of weight ratio is 1 ~ 10%, then adds in the outer oil phase of a certain amount of step (3) according to the ratio of volume 1:5 ~ 1:10 by calcium chloride water, for subsequent use after ultrasonic mixing;
(5) preparation of chitosan solution: according to weight ratio be 1 ~ 3% ratio a certain amount of shitosan to be dissolved into pH value be in the acid solutions such as the acetic acid/citric acid of 3 ~ 4, magnetic agitation evenly after for subsequent use;
(6) first time fast film emulsification: the interior oil phase of step (1) added in advance to magnetic agitation in the aqueous phase of step (2) according to the ratio of volume 1:3 ~ 1:10 even, first the SPG film of hole between 0.10 ~ 0.28 μm is chosen as small as possible, then premixed liquid is put in device and carry out first time fast film emulsification, after emulsification 1 ~ 3 time, form colostrum;
(7) second time fast film emulsification: it is even according to the ratio of volume 1:5 ~ 1:20 the colostrum of step (6) to be added in advance to magnetic agitation in the outer oil phase of step (3), first 0.28 ~ 18.00 μm of SPG film do not waited is chosen respectively according to the desired microcapsule diameter size that will reach, then premixed liquid is put in device and carry out the emulsification of second time fast film, after emulsification 1 ~ 3 time, form emulsion;
(8) calcium chloride solidification: according to the quantity of guluronic units contained in the large molecule of sodium alginate, calcium chloride prepared by step (4) added in emulsion prepared by step (7) according to the mol ratio of 1:1 ~ 1:4, under 30 ~ 60 DEG C of temperature-controlled conditions, solidify 2 ~ 6h;
(9) complex coacervation: first sodium alginate microcapsule prepared by step (8) is washed away outer oil phase, then suspend by a certain amount of deionized water, according to isopyknic ratio, chitosan solution prepared by step (5) is added in this solution again, solidify 1 ~ 3h under magnetic agitation, after washing away unnecessary shitosan, a small amount of deionized water of micro-capsule is suspended;
(10) freeze drying: by step (9) microcapsule suspensions freeze drying 24 ~ 72h, obtains the Ah-ACMS solid microcapsules of described fish oil/algae oil.
7. method according to claim 6, is characterized in that: can prepare 500nm ~ 800nm size by the SPG film choosing corresponding hole and not wait and the homogeneous micro-sodium meter level fish oil/algae oil microcapsule of particle size.
8. method according to claim 6, is characterized in that, the method comprises the steps:
(1) interior oil phase preparation: take 0.5g vitamin E, added in 100mL deep sea fish oil, magnetic agitation 1h;
(2) aqueous phase preparation: take 0.2g sucrose fatty ester (SE-15), being added to 100mL mass ratio is in the sodium alginate aqueous solution of 1.5%, magnetic agitation 2h;
(3) outer oil phase preparation: take appropriate 1g polyglyceryl fatty acid ester (PO-5S), added in 100mL sunflower oil, magnetic agitation 1h;
(4) preparation of calcium chloride curing agent: by 5mL mass ratio be 5% calcium chloride water add in the outer oil phase of 15mL step (3), setting power is ultrasonic emulsification 2min under 30% condition;
(5) preparation of chitosan solution: 1.5g shitosan is added in the acetum of 100mLpH4.0, after magnetic agitation 2h, centrifuging and taking supernatant is for subsequent use;
(6) first time fast film emulsification: add the interior oil phase of 2ml step (1) in the aqueous phase of 10ml step (2) magnetic agitation 1h in advance according to 1:5 volume ratio, choose the SPG film that hole is 0.1 μm, then premixed liquid is put in device after carrying out first time fast film emulsification 3 times and form colostrum;
(7) second time fast film emulsification: according to 1:10 volume ratio the colostrum of 10mL step (6) added in advance to magnetic agitation 1h in the outer oil phase of 100mL step (3), choose the SPG film that hole is 9.2 μm, then premixed liquid is put in device after carrying out second time fast film emulsification 3 times and form emulsion;
(8) calcium chloride solidification: measure calcium chloride prepared by 20mL step (4) and add in emulsion prepared by step (7), solidify 5 hours under 40 DEG C of temperature-controlled conditions;
(9) complex coacervation: suspend by 10ml deionized water after first sodium alginate microcapsule prepared by step (8) being washed away outer oil phase, then chitosan solution prepared by 10mL step (5) is slowly dripped, 1.5h is solidified, conventional freezing 12h after micro-capsule 3mL deionized water being suspended after washing away unnecessary shitosan under magnetic agitation;
(10) freeze drying: the freezing sample of step (9) microcapsules is carried out 72h freeze drying, obtains the Ah-ACMS solid microcapsules of described micro-sodium meter level fish oil/algae oil.
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CN106035739B (en) * 2016-05-23 2019-05-17 中国农业大学 A kind of method that LBL self-assembly solidifies linseed oil and its compounds grease
CN106036829A (en) * 2016-05-27 2016-10-26 天津科技大学 Compound mature vinegar micro-capsules as well as preparation method and application thereof
CN107723091A (en) * 2017-11-29 2018-02-23 武汉黄鹤楼新材料科技开发有限公司 A kind of cigarette preparation method of the quick-fried pearl of minty note essential oil
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CN110839873A (en) * 2019-09-30 2020-02-28 青岛农业大学 Method for preparing polyunsaturated fatty acid microcapsule by using chitosan and short straight chain starch
CN110839873B (en) * 2019-09-30 2023-07-04 青岛农业大学 Method for preparing polyunsaturated fatty acid microcapsule from chitosan and short amylose
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CN114073920B (en) * 2020-08-12 2024-01-30 财团法人食品工业发展研究所 Preparation method of microcapsule containing oily component
CN112106991A (en) * 2020-09-27 2020-12-22 中国疾病预防控制中心营养与健康所 Microcapsule carrying fish oil or algae oil and preparation method and application thereof
CN112675793A (en) * 2020-12-10 2021-04-20 广州中国科学院先进技术研究所 Preparation method of ganoderma lucidum spore oil nano microcapsule
CN113637188A (en) * 2021-08-27 2021-11-12 中国科学院长春应用化学研究所 Chitosan microsphere and preparation method thereof
CN115558330A (en) * 2022-09-20 2023-01-03 雄华(河源)光学科技有限公司 Glass deinking agent and preparation method thereof
CN115558330B (en) * 2022-09-20 2024-03-19 雄华(河源)光学科技有限公司 Glass deinking agent and preparation method thereof

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