CN103462018A - Production process for fish scale collagen peptide calcium - Google Patents
Production process for fish scale collagen peptide calcium Download PDFInfo
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- CN103462018A CN103462018A CN2013104161934A CN201310416193A CN103462018A CN 103462018 A CN103462018 A CN 103462018A CN 2013104161934 A CN2013104161934 A CN 2013104161934A CN 201310416193 A CN201310416193 A CN 201310416193A CN 103462018 A CN103462018 A CN 103462018A
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Abstract
The invention discloses a production process for fish scale collagen peptide calcium, and belongs to the technical field of biology. The production process comprises the following steps: (1) pretreating fish scale; (2) extracting fish scale collagen peptide and a calcium solution by an acid heat extraction technology; (3) preparing crude finished fish scale collagen peptide calcium by a peptide calcium chelating technology; (4) removing solid impurities by a centrifuge separation technology; (5) concentrating the fish scale collagen peptide calcium; (6) purifying the fish scale collagen peptide calcium by an anion exchange resin column chromatography technology to obtain a fish scale collagen peptide calcium solution; (7) drying the solution to obtain finished fish scale collagen peptide powder with the calcium content of greater than 1 percent and the protein content of greater than 85 percent. According to the process, fish scrap, namely fish scale, serves as a raw material; an exogenous calcium salt is not added; a separation and purification technology system integrated with the centrifuge separation technology and the anion exchange resin column chromatography technology is established, an organic solvent is not required to be used, the produced fish scale collagen peptide calcium product has high calcium content, high bioavailability and high safety; both the peptide and the calcium can be supplemented, so that the fish scale collagen peptide calcium has a great market prospect.
Description
Technical field
The present invention relates to a kind of production technology of scale collagen peptide calcium, belong to biological technical field.
Background technology
Calcium constituent is one of nutrient of needed by human, has many important physiological functions.Calcium deficiency easily causes the generation of the diseases such as osteoporosis, osteoproliferation, children rachitis, tetany disease, kidney stone, colon cancer, senile dementia, hypertension and coronary heart disease.In China's 1,300,000,000 populations, ubiquity calcium deficiency in various degree, and so a large amount of calcium supplementing products has been expedited the emergence of in huge market, and constantly has new brand to add.Along with improving constantly that the aggravation of competing and consumers in general are familiar with health product, the collagen peptide calcium chelate with high-absorbility, the giving young employees remedial-courses in general knowledge and vocational skills of peptide calcium becomes the preferred standard of calcium product.Aquatic Product Process Industry is one of main pillar industry of China, produces a large amount of fish scale discarded objects, serious environment pollution in the processing of aquatic products production process.The fish scale main component is collagen and calcium salt, is the important raw material sources of producing collagen peptide calcium.
At present, the research and development of China's collagen peptide calcium reap rich fruits, but also have following problem:
1, in existing collagen peptide calcium production technology, need to add a large amount of organic solvents, organic solvent is difficult to recycle, production cost is high, simultaneously, due to volatile, inflammable, the explosive characteristic that organic solvent has, determined that there are larger potential safety hazard in production workshop, production equipment and producers.
2,, in collagen peptide calcium production process, need to add exogenous calcium to produce collagen peptide calcium as calcium chloride, calcium carbonate and collagen peptide chelatropic reaction.The type production technology adds exogenous calcium, increases cost, and the Product Safety of production is low, and added value is low.
Summary of the invention
The production cost existed in research and development for existing collagen peptide calcium is high, production operation is complicated, the production Product Safety is hanged down and the problems such as added value is low, technical problem to be solved by this invention is to provide that a kind of production cost is low, the production technology of the simple a kind of scale collagen peptide calcium of production operation, produces the scale collagen peptide calcium product with high added value and high security.
For solving the problems of the technologies described above, technical solution of the present invention is:
A kind of production technology of scale collagen peptide calcium, comprise the steps:
(1) pretreatment
Fish scale drops in reactor after cleaning and removing granule foreign, adds aqueous slkali to stir, and after stirring, washes;
(2) extract
To be placed in reactor through pretreatment clean fish scale, and add water, and add the acid for adjusting pH value, and the pH that controls reaction is 0.5-2, reaction temperature is 40-100 ℃, and reaction 4-8 hour, finish reaction, obtains the extract of scale collagen peptide and free calcium;
(3) chelating
The described solution temperature of step (2) is dropped to normal temperature, and chelating 4-24 hour, obtain scale collagen peptide calcium solution;
(4) separate
Utilize centrifuge isolation technics separation and purification scale collagen peptide calcium solution, remove particulate contamination;
(5) concentrated
The described solution of concentration step (4), the mass percentage concentration of concentrated rear solution is 10%-40%;
(6) purifying
Get the concentrate of step (5), utilize the anion-exchange resin column chromatography to remove impurity;
(7) drying
Utilize spray-drying rapid draing scale collagen peptide calcium solution, obtain scale collagen peptide calcium powder finished product.
The alkali that described step (1) pretreatment is used is sodium acid carbonate or NaOH.
The mass percentage concentration of the alkali that described step (1) pretreatment is used is 1-5%, and mixing time is 4-12 hour;
The water added in described step (2) is equivalent to 5-20 times of fish scale weight, and regulating pH acid is sulfuric acid or hydrochloric acid.
The centrifuge that the centrifuge used in described step (4) is 4000-14000rpm for rotating speed.
In described step (5) solution concentrated concentrated by NF membrane, evaporimeter is concentrated or vacuum concentration pot is concentrated.
Institute's ion exchange resin column chromatography that uses is removed impurity in described step (6), and concentrate adsorbs wash-out afterwards, and eluent is pure water, and flow velocity is 0.1-10 liter/min.
In described step (7), spray-dired leaving air temp is that 70-90 ℃, EAT are 140-180 ℃.
After adopting such scheme, compared with the prior art the present invention has the following advantages:
1, to take main component collagen and the calcium salt of fish scale be raw material in the present invention, utilize acid heat extractive technique and peptide calcium chelating technology to produce collagen peptide calcium, do not add the external source calcium salt, break through the key technology of low value living marine resources higher value application, reduce production costs, improve the comprehensive higher value application technical merit of fish scale, the collagen peptide calcium product of production is safe, added value is high.
2, the present invention utilizes the centrifuge isolation technics to work in coordination with anion-exchange resin column chromatographic technique separation and purification scale collagen peptide calcium, sample protein content after purifying>85%, calcium content>1%, and resin extender is renewable repeatedly to be used, production cost is low, production technology is simple, solves collagen peptide calcium tradition ethanol precipitation production technology and has the shortcomings such as cost is high, complicated operation.
3,, without with an organic solvent, avoid, due to environment and the safety problem of using a large amount of organic solvents to cause, significantly having reduced safety in production cost and environmental protection cost.
In a word, the present invention adopts above-mentioned technique, cost is low, yield is high, simple to operate, the scale collagen peptide calcium sample calcium content of producing is high, protein content is high, safe, bioavilability is high and can the giving young employees remedial-courses in general knowledge and vocational skills of peptide calcium, take full advantage of aquatic products leftover bits and pieces fish scale, turn waste into wealth, be applicable to large-scale industrial production.
The accompanying drawing explanation
Fig. 1 is process chart of the present invention.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Disclosed is a kind of production technology of scale collagen peptide calcium, as shown in Figure 1,---solid impurity of fish scale is removed in washing, and---alkaline process is removed the surface impurity of fish scale, and---the acid heat extractive technique is extracted scale collagen peptide and calcium solution, and---peptide calcium chelating technology prepares the thick finished product of scale collagen peptide calcium, and---centrifuge isolation technics collagen purification peptide calcium---concentrates collagen peptide calcium---anion-exchange resin column chromatographic technique collagen purification peptide calcium---dry scale collagen peptide calcium solution---scale collagen peptide calcium powder finished product to the present invention includes following steps: fish scale.
Below by specific embodiment, illustrate.
embodiment mono-:
1, using the high-quality fish scale as raw material, selected fish scale can be that the marine fishes fish scale can be also the freshwater fish fish scale.Get fish scale 10kg and drop in the stirring and washing machine, add water clean to fish scale without granule foreign after.Fish scale is dropped in reactor, and adding mass percentage concentration is 3% sodium bicarbonate solution, stirs 4 hours, washes, and removes stickum, fat and other impurity on fish scale surface.
2, clean fish scale is placed in to reactor, adds the water of 200kg, adding the sulphur acid for adjusting pH value and controlling reaction system pH is 0.5, and reaction temperature is 60 ℃, reacts 5 hours, finishes reaction, obtains scale collagen peptide and free calcium solution.
3, scale collagen peptide and free calcium solution, under normal temperature, chelating is 4 hours, obtains scale collagen peptide calcium solution.
4, utilize the centrifuge that rotating speed is 14000rpm to separate the solid impurity in scale collagen peptide calcium solution.Supernatant utilizes NF membrane concentrated, and the relative molecular mass of holding back of NF membrane is 500Da, and the mass percentage concentration of concentrated rear liquid is 10%.
5, concentrate wash-out after the absorption of anion-exchange resin column chromatography, eluent is pure water, flow velocity is 0.1 liter/min.
6, utilize the dry scale collagen peptide of spray dryer calcium solution, EAT is 180 ℃, and leaving air temp is 90 ℃, and spray-drying finishes, and obtains scale collagen peptide solution powder finished product, and the protein content of powder finished product is 90%, and calcium content is 3%.
embodiment bis-:
1, using the high-quality fish scale as raw material, selected fish scale can be that the marine fishes fish scale can be also the freshwater fish fish scale.Get fish scale 100kg and drop in the stirring and washing machine, add water clean to fish scale without granule foreign after.Fish scale is dropped in reactor, and adding mass percentage concentration is 1% sodium hydroxide solution, stirs 8 hours, washes, and removes stickum, fat and other impurity on fish scale surface.
2, clean fish scale is placed in to reactor, adds the water of 1000kg, adding the sulphur acid for adjusting pH value and controlling reaction system pH is 2, and reaction temperature is 100 ℃, reacts 8 hours, finishes reaction, obtains scale collagen peptide and free calcium solution.
3, scale collagen peptide and free calcium solution, under normal temperature, chelating is 24 hours, obtains scale collagen peptide calcium solution.
4, utilize the centrifuge that rotating speed is 8000rpm to separate the solid impurity in scale collagen peptide calcium solution.Supernatant utilizes evaporimeter concentrated, and thickening temperature is 60 ℃, and the mass percentage concentration of concentrated rear liquid is 40%.
5, concentrate wash-out after the absorption of anion-exchange resin column chromatography, eluent is pure water, flow velocity is 1 liter/min.
6, utilize the dry scale collagen peptide of spray dryer calcium solution, EAT is 160 ℃, and leaving air temp is 80 ℃, and spray-drying finishes, and obtains scale collagen peptide solution powder finished product, and the protein content of powder finished product is 90%, and calcium content is 2%.
embodiment tri-:
1, using the high-quality fish scale as raw material, selected fish scale can be that the marine fishes fish scale can be also the freshwater fish fish scale.Get fish scale 1000kg and drop in the stirring and washing machine, add water clean to fish scale without granule foreign after.Fish scale is dropped in reactor, and adding mass percentage concentration is 5% sodium bicarbonate solution, stirs 6 hours, washes, and removes stickum, fat and other impurity on fish scale surface.
2, clean fish scale is placed in to reactor, adds the water of 5000kg, adding the sulphur acid for adjusting pH value and controlling reaction system pH is 1, and reaction temperature is 80 ℃, reacts 6 hours, finishes reaction, obtains scale collagen peptide and free calcium solution.
3, scale collagen peptide and free calcium solution, under normal temperature, chelating is 8 hours, obtains scale collagen peptide calcium solution.
4, utilize the centrifuge that rotating speed is 4000rpm to separate the solid impurity in scale collagen peptide calcium solution.Supernatant utilizes vacuum concentration pot concentrated, and thickening temperature is 50 ℃, and the mass percentage concentration of concentrated rear liquid is 30%.
5, concentrate wash-out after the absorption of anion-exchange resin column chromatography, eluent is pure water, flow velocity is 10 liter/mins.
6, utilize the dry scale collagen peptide of spray dryer calcium solution, EAT is 140 ℃, and leaving air temp is 70 ℃, and spray-drying finishes, and obtains scale collagen peptide solution powder finished product, and the protein content of powder finished product is 86%, and calcium content is 3%.
embodiment tetra-:
1, using the high-quality fish scale as raw material, selected fish scale can be that the marine fishes fish scale can be also the freshwater fish fish scale.Get fish scale 50kg and drop in the stirring and washing machine, add water clean to fish scale without granule foreign after.Fish scale is dropped in reactor, and adding mass percentage concentration is 3% sodium hydroxide solution, stirs 12 hours, washes, and removes stickum, fat and other impurity on fish scale surface.
2, clean fish scale is placed in to reactor, adds the water of 750kg, adding the sulphur acid for adjusting pH value and controlling reaction system pH is 1.5, and reaction temperature is 90 ℃, reacts 4 hours, finishes reaction, obtains scale collagen peptide and free calcium solution.
3, scale collagen peptide and free calcium solution, under normal temperature, chelating is 12 hours, obtains scale collagen peptide calcium solution.
4, utilize the centrifuge that rotating speed is 14000rpm to separate the solid impurity in scale collagen peptide calcium solution.Supernatant utilizes evaporimeter concentrated, and thickening temperature is 65 ℃, and the mass percentage concentration of concentrated rear liquid is 20%.
5, concentrate wash-out after the absorption of anion-exchange resin column chromatography, eluent is pure water, flow velocity is 0.5 liter/min.
6, utilize the dry scale collagen peptide of spray dryer calcium solution, EAT is 140 ℃, and leaving air temp is 70 ℃, and spray-drying finishes, and obtains scale collagen peptide solution powder finished product, and the protein content of powder finished product is 89%, and calcium content is 2%.
embodiment five:
1, using the high-quality fish scale as raw material, selected fish scale can be that the marine fishes fish scale can be also the freshwater fish fish scale.Get fish scale 500kg and drop in the stirring and washing machine, add water clean to fish scale without granule foreign after.Fish scale is dropped in reactor, and adding mass percentage concentration is 5% sodium hydroxide solution, stirs 4 hours, washes, and removes stickum, fat and other impurity on fish scale surface.
2, clean fish scale is placed in to reactor, adds the water of 5000kg, adding the salt acid for adjusting pH value and controlling reaction system pH is 0.5, and reaction temperature is 40 ℃, reacts 6 hours, finishes reaction, obtains scale collagen peptide and free calcium solution.
3, scale collagen peptide and free calcium solution, under normal temperature, chelating is 6 hours, obtains scale collagen peptide calcium solution.
4, utilize the centrifuge that rotating speed is 4000rpm to separate the solid impurity in scale collagen peptide calcium solution.Supernatant utilizes evaporimeter concentrated, and thickening temperature is 55 ℃, and the mass percentage concentration of concentrated rear liquid is 30%.
5, concentrate wash-out after the absorption of anion-exchange resin column chromatography, eluent is pure water, flow velocity is 5 liter/mins.
6, utilize the dry scale collagen peptide of spray dryer calcium solution, EAT is 160 ℃, and leaving air temp is 80 ℃, and spray-drying finishes, and obtains scale collagen peptide solution powder finished product, and the protein content of powder finished product is 90%, and calcium content is 3%.
embodiment six:
1, using the high-quality fish scale as raw material, selected fish scale can be that the marine fishes fish scale can be also the freshwater fish fish scale.Get fish scale 100kg and drop in the stirring and washing machine, add water clean to fish scale without granule foreign after.Fish scale is dropped in reactor, and adding mass percentage concentration is 3% sodium bicarbonate solution, stirs 8 hours, washes, and removes stickum, fat and other impurity on fish scale surface.
2, clean fish scale is placed in to reactor, adds the water of 500kg, adding the salt acid for adjusting pH value and controlling reaction system pH is 0.8, and reaction temperature is 60 ℃, reacts 4 hours, finishes reaction, obtains scale collagen peptide and free calcium solution.
3, scale collagen peptide and free calcium solution, under normal temperature, chelating is 10 hours, obtains scale collagen peptide calcium solution.
4, utilize the centrifuge that rotating speed is 14000rpm to separate the solid impurity in scale collagen peptide calcium solution.Supernatant utilizes vacuum concentration pot concentrated, and thickening temperature is 50 ℃, and the mass percentage concentration of concentrated rear liquid is 30%.
5, concentrate wash-out after the absorption of anion-exchange resin column chromatography, eluent is pure water, flow velocity is 1 liter/min.
6, utilize the dry scale collagen peptide of spray dryer calcium solution, EAT is 140 ℃, and leaving air temp is 70 ℃, and spray-drying finishes, and obtains scale collagen peptide solution powder finished product, and the protein content of powder finished product is 87%, and calcium content is 2%.
embodiment seven:
1, using the high-quality fish scale as raw material, selected fish scale can be that the marine fishes fish scale can be also the freshwater fish fish scale.Get fish scale 50kg and drop in the stirring and washing machine, add water clean to fish scale without granule foreign after.Fish scale is dropped in reactor, and adding mass percentage concentration is 3% sodium hydroxide solution, stirs 10 hours, washes, and removes stickum, fat and other impurity on fish scale surface.
2, clean fish scale is placed in to reactor, adds the water of 750kg, adding the salt acid for adjusting pH value and controlling reaction system pH is 1.5, and reaction temperature is 60 ℃, reacts 8 hours, finishes reaction, obtains scale collagen peptide and free calcium solution.
3, scale collagen peptide and free calcium solution, under normal temperature, chelating is 24 hours, obtains scale collagen peptide calcium solution.
4, utilize the centrifuge that rotating speed is 8000rpm to separate the solid impurity in scale collagen peptide calcium solution.Supernatant utilizes evaporimeter concentrated, and thickening temperature is 55 ℃, and the mass percentage concentration of concentrated rear liquid is 20%.
5, concentrate wash-out after the absorption of anion-exchange resin column chromatography, eluent is pure water, flow velocity is 0.5 liter/min.
6, utilize the dry scale collagen peptide of spray dryer calcium solution, EAT is 140 ℃, and leaving air temp is 70 ℃, and spray-drying finishes, and obtains scale collagen peptide solution powder finished product, and the protein content of powder finished product is 86%, and calcium content is 2%.
embodiment eight:
1, using the high-quality fish scale as raw material, selected fish scale can be that the marine fishes fish scale can be also the freshwater fish fish scale.Get fish scale 1000kg and drop in the stirring and washing machine, add water clean to fish scale without granule foreign after.Fish scale is dropped in reactor, and adding mass percentage concentration is 5% sodium bicarbonate solution, stirs 12 hours, washes, and removes stickum, fat and other impurity on fish scale surface.
2, clean fish scale is placed in to reactor, adds the water of 10000kg, adding the salt acid for adjusting pH value and controlling reaction system pH is 1, and reaction temperature is 50 ℃, reacts 6 hours, finishes reaction, obtains scale collagen peptide and free calcium solution.
3, scale collagen peptide and free calcium solution, under normal temperature, chelating is 12 hours, obtains scale collagen peptide calcium solution.
4, utilize the centrifuge that rotating speed is 14000rpm to separate the solid impurity in scale collagen peptide calcium solution.Supernatant utilizes vacuum concentration pot concentrated, and thickening temperature is 60 ℃, and the mass percentage concentration of concentrated rear liquid is 40%.
5, concentrate wash-out after the absorption of anion-exchange resin column chromatography, eluent is pure water, flow velocity is 10 liter/mins.
6, utilize the dry scale collagen peptide of spray dryer calcium solution, EAT is 160 ℃, and leaving air temp is 80 ℃, and spray-drying finishes, and obtains scale collagen peptide solution powder finished product, and the protein content of powder finished product is 91%, and calcium content is 3%.
The above, be only preferred embodiment of the present invention, not technical scope of the present invention is imposed any restrictions, thus variation or the modification in every case according to claim of the present invention and specification, done, within all should belonging to the scope that patent of the present invention contains.
Claims (8)
1. the production technology of a scale collagen peptide calcium, it is characterized in that: it comprises the steps:
(1) pretreatment
Fish scale drops in reactor after cleaning and removing granule foreign, adds aqueous slkali to stir, and after stirring, washes;
(2) extract
To be placed in reactor through pretreatment clean fish scale, and add water, and add the acid for adjusting pH value, and the pH that controls reaction is 0.5-2, reaction temperature is 40-100 ℃, and reaction 4-8 hour, finish reaction, obtains the extract of scale collagen peptide and free calcium;
(3) chelating
The described solution temperature of step (2) is dropped to normal temperature, and chelating 4-24 hour, obtain scale collagen peptide calcium solution;
(4) separate
Utilize centrifuge isolation technics separation and purification scale collagen peptide calcium solution, remove particulate contamination;
(5) concentrated
The described solution of concentration step (4), the mass percentage concentration of concentrated rear solution is 10%-40%;
(6) purifying
Get the concentrate of step (5), utilize the anion-exchange resin column chromatography to remove impurity;
(7) drying
Utilize spray-drying rapid draing scale collagen peptide calcium solution, obtain scale collagen peptide calcium powder finished product.
2. according to the production technology of the described a kind of scale collagen peptide calcium of claim 1, it is characterized in that: the alkali that described step (1) pretreatment is used is sodium acid carbonate or NaOH.
3. according to the production technology of the described a kind of scale collagen peptide calcium of claim 1, it is characterized in that: the mass percentage concentration of the alkali that described step (1) pretreatment is used is 1-5%, and mixing time is 4-12 hour.
4. according to the production technology of the described a kind of scale collagen peptide calcium of claim 1, it is characterized in that: the water added in described step (2) is equivalent to 5-20 times of fish scale weight, and regulating pH acid is sulfuric acid or hydrochloric acid.
5. according to the production technology of the described a kind of scale collagen peptide calcium of claim 1, it is characterized in that: the centrifuge that the centrifuge used in described step (4) is 4000-14000rpm for rotating speed.
6. the production technology of a kind of scale collagen peptide calcium according to claim 1 is characterized in that: in described step (5) solution concentrated concentrated by NF membrane, evaporimeter is concentrated or vacuum concentration pot is concentrated.
7. according to the production technology of the described a kind of scale collagen peptide calcium of claim 1, it is characterized in that: institute's ion exchange resin column chromatography that uses removal impurity in described step (6), wash-out after concentrate absorption, eluent is pure water, flow velocity is 0.1-10 liter/min.
8. according to the production technology of the described a kind of scale collagen peptide calcium of claim 1, it is characterized in that: in described step (7), spray-dired leaving air temp is that 70-90 ℃, EAT are 140-180 ℃.
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| CN104068121A (en) * | 2014-06-30 | 2014-10-01 | 广西南宁至简至凡科技咨询有限公司 | Vitis heyneana collagen polypeptide Ca yoghurt |
| CN104170975A (en) * | 2014-06-30 | 2014-12-03 | 广西南宁至简至凡科技咨询有限公司 | Acai berry collagen polypeptide Zn yogurt |
| CN104170974A (en) * | 2014-06-30 | 2014-12-03 | 广西南宁至简至凡科技咨询有限公司 | Acai berry collagen polypeptide Fe yoghurt |
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| CN104012651B (en) * | 2014-06-30 | 2016-10-19 | 广西南宁至简至凡科技咨询有限公司 | A kind of Fructus Pruni pseudocerasi collagen polypeptide Fe clabber |
| CN104012652A (en) * | 2014-06-30 | 2014-09-03 | 广西南宁至简至凡科技咨询有限公司 | Cranberry collagen polypeptide Mg yoghurt |
| CN104397162A (en) * | 2014-08-07 | 2015-03-11 | 广西南宁至简至凡科技咨询有限公司 | Mulberry collagen polypeptide Fe yoghurt |
| CN104397171A (en) * | 2014-08-07 | 2015-03-11 | 广西南宁至简至凡科技咨询有限公司 | Mulberry collagen polypeptide Ca yoghurt |
| CN104605363A (en) * | 2015-02-26 | 2015-05-13 | 哈尔滨工业大学 | Deep-sea fish collagen peptide chelate calcium capsule and preparation method thereof |
| CN109258916A (en) * | 2018-11-28 | 2019-01-25 | 潍坊医学院 | A kind of fish scale collagen peptide calcium and preparation method thereof, purposes |
| CN110897110A (en) * | 2019-12-11 | 2020-03-24 | 江西师范大学 | High-calcium fish gelatin cake and preparation method thereof |
| RU2787112C1 (en) * | 2022-02-21 | 2022-12-28 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Калининградский государственный технический университет" | Method for obtaining food dispersion |
| CN114920825A (en) * | 2022-05-09 | 2022-08-19 | 自然资源部第三海洋研究所 | Rapid preparation method of fish collagen small peptide chelated calcium |
| CN114920825B (en) * | 2022-05-09 | 2024-03-22 | 自然资源部第三海洋研究所 | Rapid preparation method of fish collagen small peptide chelated calcium |
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