CN104430787A - Fish skin collagen casing and preparation method thereof - Google Patents
Fish skin collagen casing and preparation method thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A22—BUTCHERING; MEAT TREATMENT; PROCESSING POULTRY OR FISH
- A22C—PROCESSING MEAT, POULTRY, OR FISH
- A22C13/00—Sausage casings
- A22C13/0013—Chemical composition of synthetic sausage casings
- A22C13/0016—Chemical composition of synthetic sausage casings based on proteins, e.g. collagen
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Abstract
The invention discloses a fish skin collagen casing and a preparation method thereof. The preparation method specifically comprises the following step: after carrying out liming, deliming, acid-swelling, removing a film on the surface of the fish skin, adding auxiliaries, mixing, kneading, and aging, carrying out extrusion forming, carrying out crosslinking modification and drying to obtain a casing product. The method disclosed by the invention is simple in process and the quality is easy to control. The casing processed by adopting the method has the good processing adaptability, particularly high tensile strength and heat-processing resistance, and meanwhile, the casing is high in safety and meets the request of various enema foods.
Description
Technical field
The present invention relates to casing processing technique field, especially relate to a kind of collagen casing and preparation method thereof.
Background technology
Casing be a class in order to prepare the shaped packaging material of the meat products such as sausage, ham, natural casing and artificial casing two class can be divided into by raw material, artificial casing can be divided into again edibility with the casing two kinds of non-edibility.In edibility casing, usually with mammal skin corium (double-layer fur) for raw material, adopt physics or chemical method to obtain insoluble collagen fiber, then by adding additive, through the casing product that machinery or chemical modification obtain, be referred to as Collagent casing for sausages.Collagent casing for sausages have thickness evenly, bore adjustable, intensity is high, without natural casing unfavorable bending, can the advantages such as continuous seepage be realized, be the based packaging material that domestic and international bowel lavage based article is most popular at present.
Current whole world Collagent casing for sausages all main with the corium of pig, ox animal for Raw material processing forms.But the food that the rabid ox disease occurred in recent years and some religious beliefs are raw material as Islam, Hinduism etc. oppose/resist with ox or pig, the substitute of mammalian source collagen is urgently found in countries in the world particularly European countries.In addition, because leather industry is also be organized as raw material with the skin of the animal such as pig, ox, leather rub leather leftover bits and pieces also often easily by unlawfully for the production of casing, cause potential potential safety hazard.
Along with developing rapidly of aquatic products processing industry, can produce the leftover bits and pieces that quality accounts for 40% ~ 50% of fish body weight in fish division processing process, wherein about 10% is fish-skin.In fish-skin, collagen content is up to 60%, is a kind of good collagen sources.Therefore, derive from the skin tissue of aquatic livestock of ocean, rivers, from security, resource are ready availability, all possess alternative mammiferous potentiality.
The collagens such as current aquatic livestock fish-skin, fish scale are often used to produce the food such as gelatin, collagen polypeptide, amino acids oral-liquor and protein beverage.Collagen has good filming performance and degradable, resistance oxygen, the performance such as anti-oxidant, also the technical scheme utilizing collagen to prepare edible film is disclosed in Chinese patent literature CN101942204B, CN102504302B, but edible film all has larger difference with casing from the form of material, preparation, purposes and function: edible film form is mainly sheet material, purposes mostly is parcel or the covering of food surface, as candy wrapping, the purposes such as fresh-keeping, in its performance, the choke resistance of more reinforced film is wet or controlled atmosphere function, and part considers mechanical performance; And casing needs to have stronger toughness and intensity, the processing such as thermophilic digestion, fried baking can be stood, no matter therefore the two also or in concrete technology parameter all will inevitably there is significant difference in preparation technology's thinking.Specific in preparation method, edible film can be produced by simple liquid spreading or the tape casting, and casing must be prepared into specific jelly, then extruded by jacketed equipment.Thus, the difficulty of processing preparing edible film with collagen well below the difficulty of processing preparing casing with fish-skin, cannot use for reference simply, apply mechanically prepare edible film technique for the preparation of collagen casing.
And compared with mammal dermal collagen casing, proline, hydroxyproline, valine in fish skin collagen, leucine content is all on the low side relative to mammal, the gel strength that result in fish skin collagen is on the low side, also easily there is the hydrolysis of collagen peptide chain simultaneously and cause its gel strength to decline, thus being difficult to ensure that casing prepared by fish-skin compares favourably with mammal dermal collagen casing in shape, intensity, purposes.In addition, the structure of fish-skin has very big-difference with composition and the skin tissue of pig, ox: fish-skin is thinner, cannot complete fractionation of fatty layer, and easily brings part meat into when peeling off, and causes fat increase; The pigmentation layer that fish-skin surface has one deck uneven, and mammal skin corium color and luster is more shallow and even, therefore, fish-skin needs to do desolventing technology; The intensity of collagen fiber is not so good as the strong of pig ox-hide, more easily degrade under acid-alkali salt and high temperature, if the method indiscriminately imitating pig ox-hide collagen casing carries out acid treatment, the kind of such as acid, concentration select bad or treatment temperature, selection of time improper, fish-skin can absorb the acid solution of surrounding rapidly and be expanded to the several times of own wt, very easily cause collagenous fibres to be destroyed, the requirement of strength required for collagen casing cannot be reached, be difficult to realize micelle shaping.Therefore, take fish-skin as the technical scheme that Collagent casing for sausages produced by raw material, also cannot sum up from the Collagent casing for sausages process technology of pig ox-hide directly or indirectly, use for reference and obtain.
Summary of the invention
The object of this invention is to provide a kind of is raw material with fish-skin, adopt that special process is produced, there is good flexibility (adaptability) of operation, especially strong, the resistance to hot-working of tensile strength, the Collagent casing for sausages that security is simultaneously high.
It take fish-skin as the preparation method that edible collagen sausage-casing prepared by raw material that another object of the present invention is to provide a kind of.
Object of the present invention can be realized by following technical proposals:
One, the preparation method of collagen casing, specifically to comprise the steps: fish-skin of scaling through comprising liming, deliming, expanded, the peeling fish skin surface colour film of acid, add auxiliary material mix rub, aging operation, again through extruded, cross-linking modified, dry, obtain casing product; Liming wherein, deliming, peeling fish skin surface colour film, aging, extruded and drying process can be selected according to affiliated art general knowledge in conjunction with material characteristic voluntarily by technical staff, but inventor finds, remaining acid is expanded, add that auxiliary material is mixedly rubbed, this few procedure cross-linking modified is due to closely related with material characteristic, and interrelated between this upstream and downstream, a few road working procedure parameter, influence each other and to product make and performance parameter plays a decisive role, thus must process according to following technological requirement:
Described acid is expanded, is to be pulled out by the fish-skin material through deliming process to drain, and puts into acid solution and soaks 2 ~ 3 times that are expanded to the front weight of material that expands; Described acid solution is concentration is 0.01 ~ 0.1mol/L phosphoric acid, and soaking temperature is not higher than 30 DEG C;
Described interpolation auxiliary material is mixed to be rubbed, and is to add auxiliary material in the fish-skin matrix obtained in previous step to stir mixed rubbing, and obtains even micelle; The supplementary product kind added and addition include the sodium carboxymethylcellulose of fish skin raw material weight 10 ~ 20%, the hydroxypropyl PASELLI EASYGEL of 1 ~ 5% and 1 ~ 7% sodium phosphate trimer;
Described cross-linking modified, be through the glycerine of extruded casing surface sprinkling casing weight of material 1 ~ 5% and 0.1 ~ 0.5% glutaraldehyde, and be incubated 1 ~ 5min.
After tested, the collagen casing mechanical strength adopting such scheme to prepare is greater than 40MPa, shows that product has good tensile strength, simultaneously, this product digestion resistant, baking and fried, maturation process after-drawing intensity is all greater than 10MPa, is suitable for carrying out industrialization processing.
In addition, although above point out, described liming, deliming, peeling fish skin surface colour film, aging, extruded and drying process can refer to prior art and select voluntarily, but, when these steps adopt following technological parameter respectively, each processing step has better technological effect:
Described liming, preferably drops into fish skin raw material in milk of lime and soaks 6 ~ 10 days; Milk of lime used is 3 ~ 7 times of fish skin raw material weight;
Described deliming, preferably the fish-skin material through liming process is dropped in hydrochloric acid or ammonium chloride solution and process, described hydrochloric acid and ammonium chloride solution are respectively 0.01 ~ 0.05mol/L and 0.005 ~ 0.05mol/L, and number of processes is 2 ~ 5 times, and each processing time is 10 ~ 30 minutes; Especially recommend the fish-skin material through liming process to drop in acid ammonium salt solution to wash 2 ~ 5 times, each 10 ~ 30 minutes, containing the hydrochloric acid of 0.01 ~ 0.05mol/L and the ammonium chloride of 0.005 ~ 0.05mol/L in described acid ammonium salt solution.The experiment of the present inventor finds, compared with the acid system deliming of routine, use hydrochloric acid solution and ammonium chloride solution to carry out deliming simultaneously, the working concentration of hydrochloric acid can be reduced, reduce the palliating degradation degree of collagen, the rate of release of insoluble calcium and the deliming efficiency of material are also improved simultaneously.
By many experiments, the present inventor obtains the technical scheme of that two kinds of Suitable commercial are produced, preferred peeling fish skin surface colour film, specifically can adopt filter press technique or heating and filtering method; Described filter press technique be by material under 100 ~ 500Pa pressure by 50 ~ 80 order screens; Described heating and filtering method is by heating material to 35 ~ 45 DEG C, then by 200 ~ 300 order screens.Adopt this two kinds of technical schemes, both can get rid of the hidden danger of traditional chemical routes (oxidation-reduction method) decolouring to casing edible safety, and also ensure that color and luster and the transparency of final products.
Described aging, preferably the mixed material rubbed is put into 4 ~ 10 DEG C of freezer storages 4 ~ 8 hours.
Described extruded can be by the extrusion molding of ring-type grinding tool, obtain tubular film casing.
Described drying, preferably by material 35 ~ 45 DEG C of hot-air seasonings.
Two, collagen casing
Namely collagen casing of the present invention is adopt above-mentioned collagen casing preparation method preparation and obtain.
As from the foregoing, the present invention utilizes aquatic products processing leftover bits and pieces fish-skin to be raw material, can prepare to have that good flexibility (adaptability) of operation, especially tensile strength are strong, heat resistance processability, the Collagent casing for sausages that security is simultaneously high.Technical solution of the present invention also has following characteristics and advantage:
1, with fish processing fent fish-skin for primary raw material, both can make up the mammalian collagen such as pig, ox casing be subject to the factor such as Animal diseases, religious belief impact defect, the added value of fish processing fent can be improved again;
2, the preparation method of collagen casing provided by the invention is by the precise and appropriate selection to bulking process (containing using acid, expanding volume and technological temperature), realize the uncoiling of collagen appropriateness, keep the integrality of tropocollagen molecule chain to greatest extent simultaneously, make material after auxiliary material adds mixed rubbing, easily form micelle (otherwise, very easily because the reason of fish-skin material itself is modulated into paste); The selected auxiliary material being simultaneously equipped with interpolation not only improves color and luster and the viscosity of micelle, and the ductility of micelle and intensity are further strengthened, thus obtain the micelle that plasticity is better, be more conducive to extrusion molding, after cross-linking modified, final obtained strong, the resistance to hot-working of Collagent casing for sausages tensile strength, can meet daily bowel lavage requirement.
Detailed description of the invention
Below in conjunction with detailed description of the invention and test data of experiment, the present invention is described in detail.
One, embodiment
1, the first embodiment
Key step: first by scale through pre-treatment, clean fish-skin liming, deliming, acid expanded, peeling fish skin surface colour film, obtain thick collagenous fibres; Then add auxiliary material mixed to rub, aging, make material shape uniformly micelle; Express material is shaping, cross-linking modified, dry again, namely obtain casing product.Liming wherein, deliming, peeling fish skin surface colour film, aging, extruded and drying process can be selected with reference to routine techniques in conjunction with material characteristic by one of ordinary skill in the art, and acid expanded, add that auxiliary material is mixedly rubbed, cross-linking modified technique needs to process according to following technological requirement:
Described acid is expanded, specifically drains after pulling out through the fish-skin material of deliming process, put into concentration be the phosphoric acid solution of 0.01 ~ 0.1mol/L soak be expanded to expand before 2 ~ 3 times of weight of material, soaking temperature is not higher than 30 DEG C;
Described interpolation auxiliary material is mixed to be rubbed, and is to add auxiliary material in the fish-skin matrix obtained in previous step to stir mixed rubbing, and makes it to form even micelle; The supplementary product kind added and addition are respectively: the sodium carboxymethylcellulose of fish skin raw material weight 10 ~ 20%, the hydroxypropyl PASELLI EASYGEL of 1 ~ 5% and 1 ~ 7% sodium phosphate trimer;
Described cross-linking modified, be through the glycerine of extruded casing surface sprinkling casing weight of material 1 ~ 5% and 0.1 ~ 0.5% glutaraldehyde, and be incubated 1 ~ 5min.
Through repeatedly testing, the collagen casing mechanical strength adopting said method to prepare all is greater than 40MPa, further, through 90 DEG C of boilings after 10 minutes product still can keep original form and tensile strength is greater than 10MPa, and 70 DEG C of bakings after 2 hours tensile strength be greater than 15MPa.
2, the second embodiment
Grass carp skin 100kg through scaling, cleaning is put into 300kg milk of lime to soak 10 days, take out clear water and rinse well, put into the ammonium chloride solution cleaning 3 times that concentration is 0.05mol/L, each 20 minutes not occasional agitation; Taking-up drains, and adding concentration is soak (soaking temperature is not higher than 30 DEG C) in the phosphoric acid solution of 0.1mol/L, treats that cladding expands and becomes 2 ~ 3 times of the front weight of material that expands, take out; By 40 DEG C of water-baths by heating material to semifluid shape, with 200 order screens filter to remove fish-skin surface colour film, obtain fish-skin matrix; In fish-skin matrix, add 15kg sodium carboxymethylcellulose, 3kg hydroxypropyl PASELLI EASYGEL and 3kg sodium phosphate trimer, stir mixed rubbing and to put into Cool Room 4 DEG C evenly and deposit 8h and carry out aging; Then take out micelle and be preheated to 30 DEG C, putting into screw extruder, obtain tubular film casing by the extrusion molding of ring-type grinding tool; Toward the glycerine of tubular film casing surface spraying casing weight of material 3% and the glutaraldehyde of 0.3%, and be incubated 3min; Finally dry 3h with 40 DEG C of hot blasts and carry out drying, after folding, packaging gets product.
After tested, the collagen casing mechanical strength adopting this programme to prepare is greater than 40MPa, further, through 90 DEG C of boilings after 10 minutes product still can keep original form and tensile strength is greater than 10MPa, and 70 DEG C of bakings after 2 hours tensile strength be greater than 15MPa.
3, the 3rd embodiment:
Java tilapia skin 100kg through scaling, cleaning is put into 680kg milk of lime to soak 6 days, take out and put into the hydrochloric acid solution cleaning 3 times that concentration is 0.03mol/L, each 10 minutes not occasional agitation; Taking-up drains, and adding concentration is soak (soaking temperature is not higher than 30 DEG C) in the phosphoric acid solution of 0.02mol/L, treats that cladding expands and becomes 2 ~ 3 times of the front weight of material that expands, take out; Under 200Pa pressure, adopted by material 60 order screens to filter to remove fish-skin surface colour film, obtain fish-skin matrix; Add in fish-skin matrix and be pre-mixed uniform 10kg sodium carboxymethylcellulose, 3.5kg hydroxypropyl PASELLI EASYGEL and 4.5kg sodium phosphate trimer, stir mixed rubbing and put into Cool Room 4 DEG C evenly and deposit 6h; Then take out micelle and be preheated to 35 DEG C, putting into screw extruder, obtain tubular film casing by the extrusion molding of ring-type grinding tool; Toward the glycerine of tubular film casing surface spraying casing weight of material 1.5% and the glutaraldehyde of 0.25%, and be incubated 3min; Finally use 35 DEG C of hot-air seasonings, packed products after folding.
After tested, the collagen casing mechanical strength adopting this programme to prepare is greater than 40MPa, further, through 90 DEG C of boilings after 10 minutes product still can keep original form and tensile strength is greater than 10MPa, and 70 DEG C of bakings after 2 hours tensile strength be greater than 15MPa.
4, the 4th embodiment:
Carp skin 100kg through scaling, cleaning is put into 500kg milk of lime to soak 8 days, take out the mixed solution putting into hydrochloric acid and ammonium chloride to clean 3 times, wherein the concentration of hydrochloric acid and ammonium chloride is respectively 0.01mol/L and 0.005mol/L, and each 20 minutes, period uninterruptedly stirred; Taking-up drains, and adding concentration is soak (soaking temperature is not higher than 30 DEG C) in the phosphoric acid solution of 0.05mol/L, treats that cladding expands and becomes 2 ~ 3 times of the front weight of material that expands, take out; With 45 DEG C of water-baths by heating material to semifluid shape, with 300 order screens filter, obtain fish-skin matrix; Add in fish-skin matrix and be pre-mixed uniform 20kg sodium carboxymethylcellulose, 1.5kg hydroxypropyl PASELLI EASYGEL and 2kg sodium phosphate trimer, put into 6 DEG C of freezers after stirring and deposit 6h; Micelle taken out and is preheated to 30 DEG C, putting into screw extruder, obtaining by the extrusion molding of ring-type grinding tool the tubular film casing that bore is 20 ~ 30mm, wall thickness is 0.5 ~ 1mm; Toward the glycerine of tubular film casing surface spraying casing weight of material 2.5% and the glutaraldehyde of 0.15%, and be incubated 5min, 45 DEG C of hot-air seasonings, packed products after folding.
An outstanding feature of this programme employs hydrochloric acid solution and ammonium chloride solution when being deliming simultaneously, and working concentration is all lower.After tested, the collagen casing mechanical strength adopting this programme to prepare still is greater than 40MPa, further, through 90 DEG C of boilings after 10 minutes product still can keep original form and tensile strength is greater than 10MPa, and 70 DEG C of bakings after 2 hours tensile strength be greater than 15MPa.
Two, test data of experiment
1, the expansion rate of expanded operation is on the impact (see table 1) of micelle compression properties
The expansion rate of table 1, expanded operation is on the impact of micelle compression properties
Wherein expansion rate=expanded rear weight/expanded front weight * 100%
2, the selection of expanded acid is on the impact of fish-skin expansion effect: adopt sensory evaluation method (Ranking)
Test stone: 1. plasticity is good, uniformity is good, and ductility is good, elasticity, toughness are low; 2. after the swelling is by heating material 30min, and plastic emitting is many, in sticky shape; Surplus skin is few, disperses by mechanical force.
Assay: from 1., D > E > C > A > B, from 2., A > D > C > E > B, wherein lactic acid (A), hydrochloric acid (B), acetic acid (C), phosphoric acid (D), citric acid (E).To sum up, phosphoric acid (D) is selected.
Inventor compares several variable concentrations acidulated condition by experiment, and result shows: under same concentrations, and the expansion effect of phosphoric acid is best.Therefore, the kind of acid is the key determining expansion effect and efficiency.
3, phosphoric acid concentration is on the impact (see table 2) of fish-skin expansion effect
Table 2, phosphoric acid concentration are on the impact of fish-skin expansion effect
Analyze: under the condition of expansion rate identical (300%), reduce with phosphoric acid concentration, acidificatoin time increases.The expanded fish-skin speed of high-concentration phosphoric acid is fast, and absorbent time is short, is unfavorable for production control, has partial white to fail expanded fish-skin particle in a heated condition, shows that fish-skin is expanded uneven, do not reach completely expanded; Low concentration phosphoric acid needs the expanded time long, expanded uneven, and plastic emitting phenomenon appears in part fish-skin in puffing process, and micelle fiber has portion fractures, and part is not expanded yet.When concentration is lower than 0.01mol/L, fish-skin expansion rate does not reach 300%.To sum up, when phosphoric acid concentration is 0.01-0.1mol/L, can reach expansion effect, the phosphoric acid concentration is preferably 0.025-0.075mol/L, and wherein when phosphoric acid is 0.05mol/L, expansion effect is best.
Above content is only some better embodiment exemplified for introducing technical solution of the present invention, should not be considered as limiting form of implementation of the present invention.The equivalent variations that all one of ordinary skill in the art can make according to technical solution of the present invention and improvement, within the covering scope that all should belong to technical solution of the present invention.
Claims (10)
1. the preparation method of collagen casing, it is characterized in that comprising the steps: by fish-skin of scaling through comprising, liming, deliming, acid are expanded, peeling fish skin surface colour film, add auxiliary material mix rub, aging operation, again through extruded, cross-linking modified, dry, obtain casing product; Wherein,
Described acid is expanded, is to be pulled out by the fish-skin material through deliming process to drain, and puts into acid solution and soaks 2 ~ 3 times that are expanded to the front weight of material that expands; The phosphoric acid of described acid solution to be concentration be 0.01 ~ 0.1mol/L, soaking temperature is not higher than 30 DEG C;
Described interpolation auxiliary material is mixed to be rubbed, and is to add auxiliary material in the fish-skin matrix obtained in previous step to stir mixed rubbing, and obtains even micelle; The supplementary product kind added and addition include the sodium carboxymethylcellulose of fish skin raw material weight 10 ~ 20%, the hydroxypropyl PASELLI EASYGEL of 1 ~ 5% and 1 ~ 7% sodium phosphate trimer;
Described cross-linking modified, be through the extruded glycerine of casing surface sprinkling casing weight of material 1 ~ 5% and the glutaraldehyde of 0.1 ~ 0.5%, and be incubated 1 ~ 5min.
2. the preparation method of collagen casing according to claim 1, is characterized in that: described liming, is fish skin raw material to be dropped in milk of lime to soak 6 ~ 10 days; Milk of lime used is 3 ~ 7 times of fish skin raw material weight.
3. the preparation method of collagen casing according to claim 1, is characterized in that: what described peeling fish skin surface colour film adopted is filter press technique or heating and filtering method; Described filter press technique be by material under 100 ~ 500Pa pressure by 50 ~ 80 order screens; Described heating and filtering method is by heating material to 35 ~ 45 DEG C, then by 200 ~ 300 order screens.
4. the preparation method of collagen casing according to claim 1, is characterized in that: described aging be that the mixed material rubbed is put into 4 ~ 10 DEG C of freezers storages 4 ~ 8 hours.
5. according to the preparation method of the collagen casing one of Claims 1-4 Suo Shu, it is characterized in that described deliming is dropped in hydrochloric acid and/or ammonium chloride solution by the fish-skin material through liming process to process, concrete technology parameter is: described hydrochloric acid and ammonium chloride solution are respectively 0.01 ~ 0.05mol/L and 0.005 ~ 0.05mol/L, number of processes is 2 ~ 5 times, and each processing time is 10 ~ 30 minutes.
6. the preparation method of collagen casing according to claim 5, is characterized in that the phosphoric acid that the acid solution of the expanded middle use of described acid is 0.05mol/L for concentration.
7. the preparation method of collagen casing according to claim 5, it is characterized in that: described deliming is dropped in the mixed solution of hydrochloric acid and ammonium chloride by the fish-skin material through liming process to process, and the concentration of wherein said hydrochloric acid and ammonium chloride is respectively 0.01mol/L and 0.005mol/L.
8. collagen casing, it is characterized in that with the described collagen casing preparation method preparation of one of Claims 1-4 and obtains.
9. collagen casing according to claim 8, it is characterized in that described deliming is dropped in hydrochloric acid and/or ammonium chloride solution by the fish-skin material through liming process to process, concrete technology parameter is: described hydrochloric acid and ammonium chloride solution are respectively 0.01 ~ 0.05mol/L and 0.005 ~ 0.05mol/L, number of processes is 2 ~ 5 times, and each processing time is 10 ~ 30 minutes.
10. collagen casing according to claim 9, it is characterized in that described deliming is dropped in the mixed solution of hydrochloric acid and ammonium chloride by the fish-skin material through liming process to process, the concentration of wherein said hydrochloric acid and ammonium chloride is respectively 0.01mol/L and 0.005mol/L; Meanwhile, the acid solution of the expanded middle use of the described acid phosphoric acid that is 0.05mol/L for concentration.
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| CN105104493A (en) * | 2015-08-06 | 2015-12-02 | 梧州神冠蛋白肠衣有限公司 | Preparation method of collagen casings |
| CN105175533A (en) * | 2015-10-21 | 2015-12-23 | 淄博黄河龙生物工程有限公司 | Process for extracting collagen from thin cow skin |
| CN107014854A (en) * | 2017-03-29 | 2017-08-04 | 淄博黄河龙生物工程有限公司 | The durothermic detection method of collagen |
| CN107259413A (en) * | 2017-07-18 | 2017-10-20 | 诸城市和生食品有限公司 | A kind of sandwich fish-skin intestines of minced fillet and preparation method thereof |
| CN107897463A (en) * | 2017-11-06 | 2018-04-13 | 广东德福隆生物科技有限公司 | A kind of sugar-coat production technology |
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| CN113529410A (en) * | 2021-06-09 | 2021-10-22 | 山东海奥斯生物科技有限公司 | Production process and sealing method of collagen packaging film |
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