CN116478625A - Liming liquid for preparing bone gelatin and preparation method of bone gelatin - Google Patents
Liming liquid for preparing bone gelatin and preparation method of bone gelatin Download PDFInfo
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- CN116478625A CN116478625A CN202310386721.XA CN202310386721A CN116478625A CN 116478625 A CN116478625 A CN 116478625A CN 202310386721 A CN202310386721 A CN 202310386721A CN 116478625 A CN116478625 A CN 116478625A
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- liming
- gelatin
- bone
- ossein
- acid
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- 108010010803 Gelatin Proteins 0.000 title claims abstract description 219
- 239000008273 gelatin Substances 0.000 title claims abstract description 219
- 229920000159 gelatin Polymers 0.000 title claims abstract description 219
- 235000019322 gelatine Nutrition 0.000 title claims abstract description 219
- 235000011852 gelatine desserts Nutrition 0.000 title claims abstract description 219
- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 141
- 239000007788 liquid Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 71
- 238000005406 washing Methods 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 50
- 238000000605 extraction Methods 0.000 claims abstract description 43
- 239000003513 alkali Substances 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 84
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000003292 glue Substances 0.000 claims description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 238000005554 pickling Methods 0.000 claims description 11
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- 229910001510 metal chloride Inorganic materials 0.000 claims description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 4
- 150000004692 metal hydroxides Chemical class 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 238000010088 rubber extraction Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- -1 tetramethyl hydroxide salt Chemical class 0.000 claims description 2
- 238000007710 freezing Methods 0.000 abstract description 39
- 230000008014 freezing Effects 0.000 abstract description 39
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 24
- 238000002834 transmittance Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 19
- 239000000499 gel Substances 0.000 description 13
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 12
- 235000011941 Tilia x europaea Nutrition 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 12
- 239000004571 lime Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 230000001954 sterilising effect Effects 0.000 description 11
- 238000004659 sterilization and disinfection Methods 0.000 description 11
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000008267 milk Substances 0.000 description 9
- 210000004080 milk Anatomy 0.000 description 9
- 235000013336 milk Nutrition 0.000 description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000009471 action Effects 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000003456 ion exchange resin Substances 0.000 description 8
- 229920003303 ion-exchange polymer Polymers 0.000 description 8
- 238000012805 post-processing Methods 0.000 description 8
- 238000000108 ultra-filtration Methods 0.000 description 8
- 102000008186 Collagen Human genes 0.000 description 7
- 108010035532 Collagen Proteins 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920001436 collagen Polymers 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 239000011087 paperboard Substances 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229910017053 inorganic salt Inorganic materials 0.000 description 5
- 239000005708 Sodium hypochlorite Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 230000002328 demineralizing effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 210000000845 cartilage Anatomy 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 210000003041 ligament Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 210000003491 skin Anatomy 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09H—PREPARATION OF GLUE OR GELATINE
- C09H1/00—Pretreatment of collagen-containing raw materials for the manufacture of glue
- C09H1/02—Pretreatment of collagen-containing raw materials for the manufacture of glue of bones
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09H—PREPARATION OF GLUE OR GELATINE
- C09H3/00—Isolation of glue or gelatine from raw materials, e.g. by extracting, by heating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09H—PREPARATION OF GLUE OR GELATINE
- C09H3/00—Isolation of glue or gelatine from raw materials, e.g. by extracting, by heating
- C09H3/02—Purification of solutions of gelatine
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Peptides Or Proteins (AREA)
Abstract
The invention discloses a liming liquid for preparing bone gelatin and a preparation method of the bone gelatin, and belongs to the technical field of gelatin processing. The preparation method of the bone gelatin comprises the following steps: washing bone particles with acid, performing solid-liquid separation to obtain decalcified bone element, washing the decalcified bone element with alkali liquor and clear water, mixing the washed deacidified bone element with homogeneous liming liquid, liming to obtain limed bone element, washing the limed bone element with acid and clear water to obtain limed bone element, and performing gum extraction and post treatment to obtain bone gelatin. The bone gelatin prepared by the method has overall freezing force and yield which are obviously higher than those of gelatin products obtained by the prior conventional alkaline technology.
Description
Technical Field
The invention belongs to the technical field of gelatin processing, and particularly relates to a liming liquid for preparing bone gelatin and a preparation method of high-freezing-force and high-yield bone gelatin.
Background
Gelatin is a polymer of high molecular polypeptide obtained by purifying and processing collagen contained in animal skin, bone, cartilage, ligament, myomembrane, etc. after primary hydrolysis. The gelatin product contains protein of 82% or more except small amount of water and inorganic salt, and can be widely used in the fields of food, medicine, cosmetics, biological materials, etc. Bone gelatin is used as one of the main sources of commercial high-quality gelatin, and has wide sources of raw materials and high product quality.
The preparation method of the bone gelatin mainly comprises an alkaline method, an acid method and an enzyme method, wherein the most traditional and widely applied method is the alkaline method, the alkaline method gelatin can be used for preparing gelatin products with different requirements and high viscosity and high freezing force, and the process is stable and is the main process of the bone gelatin. However, the conventional alkali method gelatin also has a plurality of problems, such as large wastewater amount, and about 500-600 tons of water consumption per ton of gelatin; the production period is long, because bone particles with the diameter of 3-20 mm are adopted for production, the countercurrent extraction decalcification and the lime emulsion liming with the concentration of 3-4% are carried out, the reaction is slow, the reaction time is long, and the production period is often 40-60 days; the extraction rate of the gelatin is low, compared with the extraction rate of bone particles, the gelatin is generally 13-15%, and meanwhile, 20-30% of low freezing force (lower than 170Bloom g) gelatin or other low-quality gelatin with seriously unqualified viscosity and transparency can be produced as by-products, and the low-quality gelatin can only be used as food-grade or even industrial-grade gelatin for sale, and has low price and profit of compression manufacturers.
Among the current patents for preparing bone gelatin, the patent publication No. CN103333939A discloses a method for preparing gelatin by degrading bone collagen fibers with alkaline enzyme, which takes bone gelatin obtained by demineralizing large bone grains (2-5 cm) as a raw material, wherein the demineralizing of the large bone grains is carried out by using high-concentration hydrochloric acid, so that the damage to peptide chains in the collagen fibers is serious, the subsequent enzymolysis process is difficult to control, and the viscosity of a gelatin product is too low (2-4 mPa.s).
Chinese patent CN112608686A discloses a preparation method for improving traditional alkali method bone gelatin, which uses saturated clarified lime water to replace traditional 3-5% lime milk to carry out liming on 5-20mm bone grains, can greatly reduce solid waste of waste lime milk, can shorten liming period, improves gelatin extraction rate to 13-15% (bone consumption 6.6-7 tons/ton gelatin), but does not solve the problem of low freezing force gelatin existing in traditional alkali method gelatin, and according to the embodiment, the bright gelatin freezing force is 200-210 bloom mg obtained by the embodiment and the comparative example, which is a detection value combined by multiple passes, and the problem of low freezing force gelatin is not solved yet. In the theoretical and practical experiments, the hydrolysis capability of saturated clarified lime water to ossein is not stronger than that of the traditional 3-5% lime milk, so that the effect of shortening the liming period is difficult to realize. In addition, the existing alkali gelatin technology has the problems that the quality of gelatin gradually decreases along with the increase of gelatin extraction passes, and the final product contains low-quality gelatin products with unqualified indexes such as 20-30% freezing force, viscosity, transmittance and the like, and meanwhile, the existing bone gelatin has low gelatin extraction rate relative to bone grains, and has high bone consumption and high cost, and the gelatin extraction rate is 13-15%.
Therefore, development of a production process capable of improving the gelatin extraction rate and the freezing force of bone gelatin is highly demanded.
Disclosure of Invention
The invention aims to provide a liming liquid for preparing bone gelatin and a preparation method of the bone gelatin, which solve the problems of low freezing force and low quality gelatin in a certain proportion in the production process of alkali bone gelatin, reduce waste water as much as possible, shorten the production period and improve the gelatin extraction rate of the whole product.
In order to solve the technical problems, the inventor finds that the basic reason why the conventional alkali-process bone gelatin has low quality pass gelatin is that the inside of the bone grains with large particle diameter of 5-20mm is difficult to fully and properly obtain reaction, and the full reaction cannot be further realized through the concentration of lime and milk due to low solubility of calcium hydroxide, while the hydrolysis temperature of gelatin is higher than 20 ℃, the loss is obviously increased and bacteria are easy to grow, so that the full reaction cannot be realized through the conventional improvement of the reaction temperature. When the particle size of bone particles is larger than 10mm, the bone particles are difficult to diffuse into the bone particles for full reaction, and particularly when the difference of soft swelling and hard swelling of the bone particles exists (such as spongy bone and heavy bone) due to different source animals and parts, inconsistent over-liming and insufficient liming can occur, the over-liming can cause rotten dissolution and low gelatin loss extraction rate, insufficient liming can cause difficult dissolution and extraction of gelatin, the temperature and the extension time are required to be increased, and the low-freezing-force low-quality gelatin with poor quality is obtained through high-temperature extraction. And similarly, the reduction of the particle size of the bone particles is difficult to achieve, when the particle size is lower than 5mm and a large amount of solids exist as a suspension in lime milk with the concentration of 3-5%, the separation of the bone particles and the lime milk is extremely problematic, the too small bone particles can be discharged along with each ash liquid replacement and cleaning, the ash leaching process involves tens of ash replacement and cleaning, the loss of the bone particles is extremely large, and many bone particles cannot even completely carry out the ash leaching process.
For this reason, the inventors propose the following technical scheme through trial and error study:
in a first aspect, the present invention provides a liming solution for preparing bone gelatin, wherein the liming solution comprises 0.05-1.0% of alkali and 0.2-3% of salt by mass; the alkali is selected from one or more of metal hydroxide, metal carbonate and metal bicarbonate, and the salt is selected from at least one of metal chloride and ammonium chloride.
In a specific embodiment of the present invention, the metal in the metal hydroxide, metal carbonate, metal bicarbonate is selected from one of calcium, potassium, and sodium.
In a specific embodiment of the present invention, the metal in the metal chloride and the metal sulfide is selected from one of calcium, sodium and potassium.
In a specific embodiment of the present invention, the mass fraction of the alkali is 0.2 to 0.4%, and the mass fraction of the salt is 0.5 to 1%.
In the specific embodiment of the invention, the liming liquid component also comprises 0.5-5% of auxiliary agent by mass percent, wherein the auxiliary agent is selected from one or more of hydrogen peroxide, hypochlorite and tetramethyl hydroxide salt.
Compared with the traditional lime cream liming liquid with concentration of 3-5%, the homogeneous liming solution provided by the invention is more efficient and clean. In the homogeneous liming liquid, alkaline components such as calcium hydroxide, sodium hydroxide and the like which are completely dissolved mainly provide proper alkaline conditions necessary for hydrolyzing collagen; inorganic salts such as sodium chloride and calcium chloride which have swelling effect on the collagen fibers are used as swelling components, and the swollen collagen fibers are helpful for more fully and uniformly hydrolyzing; the homogeneous liming solution can be added with additives such as hydrogen peroxide, sodium hypochlorite and tetramethyl ammonium hydroxide, can play roles in oxidative decolorization and sterilization, further promotes collagen hydrolysis and/or chelation of heavy metal ions, and the three components are synergistic, so that liming efficiency is improved relative to single lime cream, and the homogeneous liming solution is free from cleaning during liming, does not generate a large amount of solid waste alkali, reduces waste water and solid waste, and is cleaner.
In a second aspect, the present invention also provides a method for preparing bone gelatin, comprising the steps of:
(1) Washing bone particles with acid, and then carrying out solid-liquid separation to obtain decalcified bone extract;
(2) Washing decalcified ossein with alkali liquor and clear water to obtain deacidified ossein, mixing the deacidified ossein with the liming liquid according to any one of claims 1-4 for liming, and separating to obtain limed ossein after liming is completed;
(3) Washing the liming ossein with acid and clear water to obtain the liming ossein, and then carrying out gum extraction and post-treatment to obtain the bone gelatin.
In a specific embodiment of the present invention, the bone particles in step (1) have a particle diameter of 0.01 to 3mm.
On the basis of using a homogeneous liming solution, the invention replaces bone particles with the particle size of 5-20mm in the traditional alkali method with bone particles with the particle size of 0.01-3 mm, so that the liming reaction of the bone particles is more complete, the 1-3-pass gelatin extraction rate can reach 15-17%, the gelatin extraction rate of all passes is higher than 180bloom (the common freezing force of the gelatin of the traditional alkali method gelatin powder passes is 120-170 bloom), the problems of low gelatin extraction rate of the gelatin of the alkali method gelatin powder passes and poor quality are solved, and the total gelatin extraction rate is greatly improved compared with the prior art.
Further, the particle diameter of the bone particles is preferably 0.25 to 1mm.
Further, the acid in the step (1) is selected from one or more of hydrochloric acid, phosphoric acid and organic acid;
further, the mass fraction of the acid is 1-5 wt%;
further, the pickling time is 2-5 hours.
In a specific embodiment of the invention, the alkali of the alkaline solution in step (2) is selected from one or more of calcium hydroxide, sodium hydroxide and potassium hydroxide;
further, the mass fraction of the alkali is 0.1-10%;
further, washing decalcified ossein with alkali liquor and clear water until the pH value is=5-8 to obtain deacidified ossein;
further, the mass ratio of the liming liquid to the deacidified bone mineral is 4-8: 1.
in a specific embodiment of the invention, the liming conditions are: liming for 15-45 d at 8-27 ℃; further, ash is soaked for 20-40 d at the temperature of 10-20 ℃;
further, the liming system is subjected to liming liquid circulation and/or stirring for 5-10 min at intervals of 4-8 h, wherein the rate of the liming liquid circulation is not higher than 80 r/min;
further, the liming liquid is replaced every 2-7 d and/or when the COD of the liming liquid is more than 3000 mg/L.
Further, when the liming liquid is replaced, a centrifugal or filtering device is used for separating the liming liquid from the bone element, the bone element after separation is transferred back to the liming device, and a new homogeneous liming liquid is filled; the centrifugal or filtering device is at least one selected from a decanter centrifuge, a bag centrifuge, a plate and frame filter press and a vacuum suction filter.
In a specific embodiment of the present invention, the acid in step (3) is selected from one or more of hydrochloric acid, phosphoric acid, organic acid; further, the organic acid is selected from one or more of formic acid, acetic acid, propionic acid and oxalic acid;
further, the liming ossein is washed with acid and clean water until the pH=4 to 6 to obtain the liming ossein.
In the specific embodiment of the invention, the step of extracting the adhesive is as follows: extracting the rubber for 1-3 times at 55-90 ℃, extracting the rubber for 2-3 hours in each time, adding clear water after the rubber extraction of each time is finished, and entering the next time of rubber extraction;
further, the clear water: the mass ratio of the ash removing ossein is 1-10: 1, a step of; further, the ratio is 1-5:1.
Further, the temperature of the glue extracted in each pass is gradually increased.
In a specific embodiment of the present invention, the step of post-treatment in step (3) includes, but is not limited to, filtration, ion exchange, sterilization, concentration, shaping, drying, and the like.
The beneficial effects of the invention are as follows: the invention uses the technology of small-grain-diameter bone grain acid washing decalcification, homogeneous liming and 1-3 times of gum extraction of 0.01-3 mm, thus greatly shortening the production period of alkali gelatin, the traditional alkali gelatin adopts 5-20mm bone grain, acid leaching decalcification adopts countercurrent extraction, the period is about 7-15 d, and the invention adopts small-grain-diameter bone grain acid washing, decalcification only needs 2-5 h; the traditional alkaline method has a liming period of 40-60 d, and the small-particle-size homogeneous liming period of about 20-40 d, so that the liming period is greatly shortened; the traditional alkali gelatin is subjected to multiple times of gelatin extraction for 4-6 times, the gelatin extraction of the invention is not more than 3 times, and the gelatin extraction rate and the freezing force are integrally improved while the operation time is shortened.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
It should be noted that the experimental methods used in the following examples are conventional methods unless otherwise specified, and the materials, reagents, etc. used in the following examples are commercially available unless otherwise specified.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, or article of manufacture that comprises a list of elements is not necessarily limited to only those elements, but may include other elements not expressly listed or inherent to such composition, step, method, or article of manufacture.
In the embodiment of the invention, the implementation conditions which are not mentioned are kept the same as the operation conditions, methods or requirements of the existing conventional alkaline method industrial production, for example, the bone particles are defatted bone particles with the residual fat lower than 2% after degreasing, the gelatin extraction water is industrial pure water, and the methods for analyzing indexes such as gelatin freezing force, viscosity, transmittance and the like are well known to the person skilled in the art.
The detection data in the embodiment of the invention are all average values.
Example 1
S1, acid washing decalcification: stirring, pickling and decalcification 10kg of bone particles with the particle size of 0.01-0.25 mm under the action of 3w% dilute hydrochloric acid for 2h, and separating by using a decanter centrifuge to obtain decalcified bone extract;
s2, washing and deacidifying: washing the decalcified ossein obtained in S1 with 0.1% calcium hydroxide solution and clear water to ph=5 to obtain deacidified ossein;
s3, homogeneous liming: the deacidified ossein obtained in S2 is treated with homogeneous liming liquid (alkali: 10 ℃ C. Saturated calcium hydroxide solution+0.2% NaOH; salt: 0.5% CaCl) 2 Auxiliary agent: 5% hydrogen peroxide) is mixed and limed, and the mass ratio of liming liquid to deacidified ossein is 4:1, liming at 10-12 ℃ for 20d, circulating the liming system for 5min at intervals of 4h, and homogenizing the liming liquid COD at intervals of 2d>Changing the homogeneous liming liquid at 3000mg/L, and separating to obtain limed bone extract after liming;
s4, washing and deashing: washing the ash-impregnated bone extract obtained in S3 with 5% diluted hydrochloric acid and clear water to ph=4 to obtain ash-impregnated bone extract;
s5, extracting glue and post-processing: adding clear water (water: ossein mass ratio=5:1) into the ossein obtained in the step S4, extracting the gelatin for 1 pass at 70 ℃, extracting the gelatin for 3 hours, placing the gelatin, and filtering the large-particle suspended matters from the gelatin solution through cotton cakes to obtain a dilute gelatin solution. The diluted glue solution is further treated by diatomite, a paperboard filter and ultrafiltration to remove fine impurities to obtain a refined glue solution, the refined glue solution is treated by ion exchange resin to remove inorganic salt to obtain a purified glue solution, the purified glue solution is subjected to 5S sterilization at 138-146 ℃, the glue solution is concentrated to 25-35% after sterilization, the glue solution is sent to a glue extruder for molding and extrusion, the extruded glue strip is dried and crushed in a fourdrinier to obtain 1531.66g of gelatin, the extraction rate of relative bone grains is 15.32%, the freezing force of sampling test is 229Blommg, and the viscosity of the sample test is 4.83 mPa.s.
Example 2
S1, acid washing decalcification: stirring, pickling and decalcification for 3 hours by using 78.6 kg of bone particles with the particle size of 0.25-1mm under the action of 4w% dilute hydrochloric acid, and centrifuging to obtain decalcified bone extract;
s2, washing and deacidifying: washing the decalcified ossein obtained in S1 with 1% sodium hydroxide solution and clear water to ph=6 to obtain deacidified ossein;
s3, homogeneous liming: mixing the deacidified bone extract obtained in S2 with homogeneous liming liquid (alkali: 0.3% NaOH+0.05% calcium hydroxide solution; salt: 0.9% NaCl) for liming, wherein the mass ratio of the liming liquid to the deacidified bone extract is 4:1, liming for 30d at 10-12 ℃, wherein the homogeneous liming liquid is 20cm higher than ossein in the liming process, stirring the liming system for 5min at intervals of 5h, and simultaneously replacing the homogeneous liming liquid at intervals of 2d or when the COD of the homogeneous liming liquid is more than 3000mg/L, and separating to obtain the liming ossein after liming is completed;
s4, washing and deashing: washing the ash-impregnated bone extract obtained in S3 with 10% dilute phosphoric acid and clear water to ph=5 to obtain ash-impregnated bone extract;
s5, extracting glue and post-processing: adding clear water (clear water: mass ratio of ossein=2:1) into the ossein obtained in the step S4, respectively extracting the gelatin at 65 ℃ and 75 ℃ for 2 times, extracting the gelatin for 3 hours each time, filtering large-particle suspended matters from each time of gelatin solution through cotton cakes to obtain thin gelatin solution, removing fine impurities from the thin gelatin solution through diatomite, a paperboard filter and ultrafiltration to obtain fine filtrate solution, removing inorganic salt from the fine filtrate solution through ion exchange resin to obtain purified gelatin solution, standing the purified gelatin solution at 138-146 ℃ for 5S for sterilization, concentrating the sterilized gelatin solution to 25-35%, conveying the concentrated gelatin solution into a gelatin extruder for molding, drying and crushing the extruded gelatin strips in a long-mesh dryer to obtain one-and two-pass gelatin products respectively.
8.60kg of primary gelatin is obtained, and the test freezing force is 242 bloom; 4.63kg of second-pass gelatin, and the test freezing force is 219 bloom; the total gel extraction rate of the relative bone particles is 16.84%, and indexes such as viscosity, transmittance and the like are tested on the final-pass gel (namely the 2 nd-pass gel): viscosity 3.75 mPas, transmittance 450 nm: 75%; transmittance at 620 nm: 85% meets the requirements of relevant indexes of the medical gelatin standard QB 2354-2005.
Example 3
S1, acid washing decalcification: stirring, pickling and decalcification for 3 hours under the action of 4w% dilute hydrochloric acid on 78.6 kg of bone particles with the particle size of 0.25-1mm, and centrifuging to obtain decalcified bone extract;
s2, washing and deacidifying: washing the decalcified ossein obtained in S1 with 1% sodium hydroxide solution and clear water to ph=7 to obtain deacidified ossein;
s3, homogeneous liming: mixing the deacidified bone extract obtained in S2 with homogeneous liming liquid (alkali: 0.3% NaOH; salt: 0.9% NaCl, auxiliary agent: 2% hydrogen peroxide+0.5% calcium hypochlorite) for liming, wherein the mass ratio of the liming liquid to the deacidified bone extract is 4:1, liming for 30d at 15-18 ℃, wherein the homogeneous liming liquid is 20cm higher than ossein in the liming process, stirring the liming system for 5min at intervals of 4h, and simultaneously replacing the homogeneous liming liquid at intervals of 2d or when the COD of the homogeneous liming liquid is more than 3000mg/L, and separating to obtain the liming ossein after liming is completed;
s4, washing and deashing: washing the ash-impregnated bone extract obtained in S3 with 10% dilute phosphoric acid and clear water to ph=6 to obtain ash-impregnated bone extract;
s5, extracting glue and post-processing: adding clear water (clear water: mass ratio of ossein=2:1) into the ossein obtained in the step S4, respectively extracting the gelatin at 65 ℃ and 75 ℃ for 2 times, extracting the gelatin for 3 hours each time, filtering large-particle suspended matters from each time of gelatin solution through cotton cakes to obtain thin gelatin solution, removing fine impurities from the thin gelatin solution through further diatomite, a paperboard filter and ultrafiltration to obtain fine filtrate, removing inorganic salts from the fine filtrate through ion exchange resin exchange to obtain purified gelatin solution, standing the purified gelatin solution at 138-146 ℃ for 5S for sterilization, concentrating the sterilized gelatin solution to 25-35%, conveying the concentrated gelatin solution into a gelatin extruder for molding, drying and crushing the extruded gelatin strips in a long-mesh dryer to obtain one-pass gelatin product and two-pass gelatin product respectively.
Wherein 6.80kg of primary gelatin is obtained, and the test freezing force is 312 bloom; 5.86kg of second-pass gelatin, and the test freezing force is 202 bloom; the total gel extraction rate of the relative bone particles is 16.11 percent.
Indexes such as viscosity, transmittance and the like are tested on the final glue (namely glue of the 2 nd step): viscosity 4.20 mPas, transmittance at 450 nm: 85%; transmittance at 620 nm: 95% meets the relevant index requirements of the medical gelatin standard QB 2354-2005.
From the analysis of the products in example 2 and example 3, it is known that the homogeneous liming solutions containing the components A and B can obtain high-yield bone gelatin, but the product obtained in the presence of the auxiliary agent C (such as 2% hydrogen peroxide and 0.5% calcium hypochlorite) has better indexes such as viscosity, transmittance and the like, and the product quality is higher.
Example 4
S1, acid washing decalcification: stirring, pickling and decalcification 58.7 kg of bone particles with the particle size of 0.5-1mm under the action of 4w% dilute hydrochloric acid for 3h, and centrifuging to obtain decalcified bone extract;
s2, washing and deacidifying: washing the decalcified ossein obtained in S1 with 1% sodium hydroxide solution and clear water to ph=8 to obtain deacidified ossein;
s3, homogeneous liming: the deacidified bone extract obtained in S2 is treated with homogeneous liming liquid (alkali: 0.3% NaOH+0.1NaHCO) 3 The method comprises the steps of carrying out a first treatment on the surface of the Salt 0.5% CaCl 2 Auxiliary agent 1% sodium hypochlorite and 0.5% tetramethyl ammonium hydroxide) and liming, wherein the mass ratio of liming liquid to deacidified bone extract is 4:1, liming at 18-20 ℃ for 40d, wherein the homogeneous liming liquid is 20cm higher than ossein in the liming process, stirring the liming system for 5min at intervals of 4h with the stirring speed of not higher than 60r/min, and simultaneously, carrying out COD (chemical oxygen demand) treatment on the liming liquid at intervals of 2d or homogeneous liming liquid>Changing the homogeneous liming liquid at 3000mg/L, and separating to obtain limed bone extract after liming;
s4, washing and deashing: washing the ash-impregnated bone extract obtained in S3 with 10% dilute phosphoric acid and clear water to ph=5 to obtain ash-impregnated bone extract;
s5, extracting glue and post-processing: adding clear water (clear water: mass ratio of ossein=2:1) into the ossein obtained in the step S4, respectively extracting the gelatin at 60 ℃, 70 ℃ and 80 ℃ for 3 times, extracting the gelatin for 2 hours each time, filtering large-particle suspended matters from each time of gelatin solution through cotton cakes to obtain thin gelatin solution, removing fine impurities from the thin gelatin solution through further diatomite, a cardboard filter and ultrafiltration to obtain fine filtrate, removing inorganic salts from the fine filtrate through ion exchange resin to obtain purified gelatin solution, standing the purified gelatin solution at 138-146 ℃ for 5S for sterilization, concentrating the sterilized gelatin solution to 25-35%, feeding the concentrated gelatin solution into a gelatin extruder for molding, drying and crushing the extruded gelatin strips in a long-mesh dryer to obtain 1-3 times gelatin products respectively.
Wherein 4.17kg of 1-pass gelatin is obtained, and the test freezing force is 252 bloom; 2-pass gelatin 2.70kg, test freezing force 211Blommg; 3-pass gelatin 1.95kg, test freezing force of 198bloom mg and total gelatin extraction rate of 15.07% relative to bone grains; and the indexes such as viscosity, transmittance and the like are tested on the final glue (the glue of the 3 rd way in the embodiment): viscosity 4.25 mPas, transmittance at 450 nm: 80%; transmittance at 620 nm: 90 percent meets the relevant index requirements of the medical gelatin standard QB 2354-2005.
Example 5
S1, acid washing decalcification: stirring, pickling and decalcification for 5h under the action of 3.5w% dilute hydrochloric acid on 66.56 kg of bone particles with the particle size of 1-3mm, and centrifuging to obtain decalcified bone extract;
s2, washing and deacidifying: washing the decalcified ossein obtained in S1 with 10% sodium hydroxide solution and clear water to ph=6 to obtain deacidified ossein;
s3, homogeneous liming: the deacidified ossein obtained in S2 is treated with homogeneous liming liquid (alkali: 0.4% KOH+1% K) 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the Salt 1% CaCl 2 Auxiliary agent is 4% hydrogen peroxide and 0.5% tetramethyl ammonium hydroxide) and the mass ratio of the liming liquid to the deacidified bone extract is 4:1, liming at 25-27 ℃ for 40d, wherein the homogeneous liming liquid is 20cm higher than ossein in the liming process, stirring the liming system for 5min at intervals of 8h with the stirring speed of not higher than 80r/min, and simultaneously, carrying out COD (chemical oxygen demand) treatment on the liming liquid at intervals of 2d or homogeneous liming liquid>Changing the homogeneous liming liquid at 3000mg/L, and separating to obtain limed bone extract after liming;
s4, washing and deashing: washing the ash-impregnated bone extract obtained in S3 with 10% dilute phosphoric acid and clear water to ph=6 to obtain ash-impregnated bone extract;
s5, extracting glue and post-processing: adding clear water (clear water: mass ratio of ossein=3:1) into the ossein obtained in the step S4, respectively extracting the gelatin at 65 ℃ and 75 ℃ and 85 ℃ for 3 times, extracting the gelatin for 2 hours each time, filtering large-particle suspended matters from each time of gelatin solution through cotton cakes to obtain thin gelatin solution, further removing fine impurities from the thin gelatin solution through diatomite, a paperboard filter and ultrafiltration to obtain fine filtrate solution, removing inorganic salts from the fine filtrate solution through ion exchange resin to obtain purified gelatin solution, standing the purified gelatin solution at 138-146 ℃ for 5S for sterilization, concentrating the sterilized gelatin solution to 25-35%, feeding the concentrated gelatin solution into a gelatin extruder for molding, and respectively obtaining 1-3 times of gelatin products after the extruded gelatin strips are dried and crushed by a long-mesh dryer.
Wherein 5.28kg of 1-pass gelatin is obtained, and the test freezing force is 246 bloom; 2-pass gelatin 3.08kg, test freezing force 211Blommg; 2.64kg of 3-pass gelatin, and the test freezing force is 185 bloom; the total gel extraction rate of the relative bone particles is 16.53 percent.
Example 6
S1, acid washing decalcification: stirring, pickling and decalcification for 3 hours under the action of 4w% dilute hydrochloric acid on 5.22 kg of bone particles with the particle size of 0.25-1mm, and centrifuging to obtain decalcified bone extract;
s2, washing and deacidifying: washing the decalcified ossein obtained in S1 with 1% sodium hydroxide solution and clear water to ph=7 to obtain deacidified ossein;
s3, homogeneous liming: mixing the deacidified ossein obtained in S2 with homogeneous liming liquid (alkali: 0.5% sodium carbonate+0.2% NaOH; salt: 0.9% NaCl, auxiliary agent: 2% hydrogen peroxide+1% calcium hypochlorite) for liming, wherein the mass ratio of the liming liquid to the deacidified ossein is 4:1, liming for 30d at 10-15 ℃, wherein the homogeneous liming liquid is 20cm higher than ossein in the liming process, stirring the liming system for 5min at intervals of 4h, and simultaneously replacing the homogeneous liming liquid at intervals of 2d or when the COD of the homogeneous liming liquid is more than 3000mg/L, and separating to obtain the liming ossein after liming is completed;
s4, washing and deashing: washing the ash-impregnated bone extract obtained in S3 with 10% dilute phosphoric acid and clear water to ph=5 to obtain ash-impregnated bone extract;
s5, extracting glue and post-processing: adding clear water (clear water: mass ratio of ossein=2:1) into the ossein obtained in the step S4, respectively extracting the gelatin at 65 ℃ and 75 ℃ for 2 times, extracting the gelatin for 3 hours each time, filtering large-particle suspended matters from each time of gelatin solution through cotton cakes to obtain thin gelatin solution, removing fine impurities from the thin gelatin solution through further diatomite, a paperboard filter and ultrafiltration to obtain fine filtrate, removing inorganic salts from the fine filtrate through ion exchange resin exchange to obtain purified gelatin solution, standing the purified gelatin solution at 138-146 ℃ for 5S for sterilization, concentrating the sterilized gelatin solution to 25-35%, conveying the concentrated gelatin solution into a gelatin extruder for molding, drying and crushing the extruded gelatin strips in a long-mesh dryer to obtain one-pass gelatin product and two-pass gelatin product respectively.
Wherein, obtaining 550.23g of 1-pass gelatin and testing the freezing force to be 234 bloom; 395.48g of 2-pass gelatin, 222Blommg of test freezing force; the total gel extraction rate of the relative bone particles is 16.47 percent.
Example 7
S1, acid washing decalcification: stirring, pickling and decalcification 10kg of bone particles with the particle size of 0.01-0.25 mm under the action of 1w% dilute hydrochloric acid for 2h, and separating by using a decanter centrifuge to obtain decalcified bone extract;
s2, washing and deacidifying: washing the decalcified ossein obtained in S1 with 10% potassium hydroxide solution and clear water to ph=8 to obtain deacidified ossein;
s3, homogeneous liming: the deacidified ossein obtained in S2 is treated by homogeneous liming liquid (alkali: 1% potassium hydroxide +0.05% NaOH; salt: 3% CaCl) 2 Auxiliary agent: 5% sodium hypochlorite) is mixed and limed, and the mass ratio of liming liquid to deacidified ossein is 8:1, liming at 8-12 ℃ for 45d, stirring the liming system for 10min at intervals of 4-8 h under the condition of not higher than 80r/min, and carrying out uniform liming liquid COD at intervals of 7d>Changing the homogeneous liming liquid at 3000mg/L, and separating to obtain limed bone extract after liming;
s4, washing and deashing: washing the ash-impregnated bone extract obtained in S3 with 5% diluted hydrochloric acid and clear water until the pH value is=5 to obtain ash-impregnated bone extract,
s5, extracting glue and post-processing: adding clear water (water: ossein mass ratio=10:1) into the ossein obtained in the step S4, extracting the gelatin for 1 pass at 90 ℃, extracting the gelatin for 3 hours, placing the gelatin, and filtering the large-particle suspended matters from the gelatin solution through cotton cakes to obtain a dilute gelatin solution. Further removing fine impurities from the diluted glue solution by diatomite, a paperboard filter and ultrafiltration to obtain a refined glue solution, removing inorganic salt from the refined glue solution by ion exchange resin to obtain a purified glue solution, standing the purified glue solution at 138-146 ℃ for 5S for sterilization, concentrating the sterilized glue solution to 25-35%, feeding the concentrated glue solution into a glue extruder for forming and extruding, drying and crushing the extruded glue strip in a fourdrinier to obtain 1505.35g of gelatin, wherein the extraction rate of relative bone particles is 15.05%, the freezing force of the sample is 199Blommg, and the viscosity of the sample is 4.31 mPa.s.
Example 8
S1, acid washing decalcification: stirring, pickling and decalcification for 3 hours by using 78.6 kg of bone particles with the particle size of 0.25-1mm under the action of 5w% dilute hydrochloric acid, and centrifuging to obtain decalcified bone extract;
s2, washing and deacidifying: washing the decalcified ossein obtained in S1 with 5% sodium hydroxide solution and clear water to ph=6 to obtain deacidified ossein;
s3, homogeneous liming: mixing the deacidified ossein obtained in the step S2 with a homogeneous liming liquid (alkali: 1.0% NaOH; salt: 0.2% NaCl) for liming, wherein the mass ratio of the liming liquid to the deacidified ossein is 4:1, liming for 15 days at 20-27 ℃, wherein the homogeneous liming liquid is 20cm higher than ossein in the liming process, stirring the liming system for 5min at intervals of 4h, and simultaneously replacing the homogeneous liming liquid at intervals of 2d or when the COD of the homogeneous liming liquid is more than 3000mg/L, and separating to obtain the liming ossein after liming is completed;
s4, washing and deashing: washing the ash-impregnated bone extract obtained in S3 with 10% dilute phosphoric acid and clear water to ph=4 to obtain ash-impregnated bone extract;
s5, extracting glue and post-processing: adding clear water (clear water: mass ratio of ossein=1:1) into the ossein obtained in the step S4, respectively extracting the gelatin at 60 ℃ and 80 ℃ for 2 times, extracting the gelatin for 3 hours each time, filtering large-particle suspended matters from each time of gelatin solution through cotton cakes to obtain thin gelatin solution, removing fine impurities from the thin gelatin solution through diatomite, a paperboard filter and ultrafiltration to obtain fine filtrate solution, removing inorganic salt from the fine filtrate solution through ion exchange resin to obtain purified gelatin solution, standing the purified gelatin solution at 138-146 ℃ for 5S for sterilization, concentrating the sterilized gelatin solution to 25-35%, conveying the concentrated gelatin solution into a gelatin extruder for molding, drying and crushing the extruded gelatin strips in a long-mesh dryer to obtain one-and two-pass gelatin products respectively.
Wherein 8.10kg of primary gelatin is obtained, and the test freezing force is 212 bloom; 4.15kg of two-pass gelatin, and the test freezing force is 199 bloom; the total gel extraction rate of the relative bone particles is 15.58%, and indexes such as viscosity, transmittance and the like are tested on the final-pass gel (namely the 2 nd-pass gel): viscosity 3.34 mPas, transmittance at 450 nm: 74%; transmittance at 620 nm: 83% meets the relevant index requirements of the medical gelatin standard QB 2354-2005.
Comparative example 1
Under the same conditions as in example 5, only the S3-stage homogeneous liming liquor (alkali: 0.4% KOH+1% K) 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the Salt 1% CaCl 2 Auxiliary agent of 4% hydrogen peroxide and 0.5% tetramethyl ammonium hydroxide) The solution was changed to saturated clear lime water at 10℃and the amount of the solution was changed to 5Kg.
Finally, obtaining 177.41g of 1-pass gelatin, wherein the test freezing force is 248 bloom; 110.86g of 2-pass gelatin, 205Blommg of test freezing force; 155.23g of 3-pass gelatin, 185bloom tested; the total gel extraction rate of the relative bone particles is 8.87 percent.
As is apparent from the experimental results of example 5 and comparative example 1, although the freezing force of the gelatin is not greatly changed in 3 passes compared with the homogeneous liming liquid liming using the present invention, the gelatin extraction rate is greatly reduced, the gelatin extraction rate of example 5 is 16.53%, the gelatin extraction rate of comparative example 1 is 8.87%, and it is apparent that the homogeneous liming liquid of example 5 is more sufficient for the hydrolysis of bone particulate ossein than the clarified liming liquid alone.
Comparative example 2 bone gelatin was prepared using conventional alkaline process with a bone grain size of 10mm
The gelatin is prepared by using 10mm particle size defatted bone particles and 3% lime milk according to a traditional alkaline method, and comprises the following specific steps:
(1) Countercurrent extraction, pickling and decalcification are carried out on 5Kg of defatted bone particles with the particle size of 10mm for 72 hours at the temperature of 10-20 ℃ to obtain decalcified bone extract;
(2) Neutralizing decalcified ossein with dilute alkali, and cleaning with clear water until the pH value of the ossein is=5-8;
(3) Mixing the ossein and 3% lime milk in the step (2), liming at 10-20 ℃, blowing compressed air every 8h, fully stirring, replacing the lime milk when the liming liquid turns yellow according to 1, 3, 5, 7, 9 and … … days (every two days), and carrying out clear water washing for 1-3 times in the ash replacing process until the ossein turns white, soft and flexible and slightly ammonia-flavored.
(4) The dilute hydrochloric acid and clear water are used for neutralizing and washing the ossein until the pH=5-8, and the pH of the system is stable after the acid washing of the ossein is kept for 8-24 hours because the ossein is larger.
(5) The pH value of ossein is regulated to be 4-5 by dilute phosphoric acid, clear water (2 times of the volume of the ossein is added for comparison) is added, 1-4 times of gelatin extraction is carried out at 60, 70, 80 and 90 ℃ for 3 hours respectively, and the extracted gelatin solution is treated in the same way as the post-treatment method of the embodiment to obtain 1-4 times of gelatin.
Finally, obtaining 222.01g of 1-pass gelatin, wherein the test freezing force is 246 bloom; 134.26g of 2-pass gelatin, the test freezing force is 210Blomg; 143.21g of 3-pass gelatin, 185bloom tested; 187.65g of 4-pass gelatin, the test freezing force is 165bloom mg, and the total gelatin extraction rate of 1-4-pass gelatin relative to bone particles is 13.74%.
Likewise, other key indicators of its last pass gelatin (as glue 4) were also tested: viscosity 3.2 mPa.s, transmittance at 450 nm: 65%,620nm transmittance 80%.
As is clear from the comparison of the results of the embodiment of example 4 and the comparative example 2, the embodiment of 4 uses bone particles with the particle size of 0.5-1mm as the raw material, and the bone particles are immersed in the homogeneous ash liquid (alkali: 0.3% NaOH+0.1NaHCO) 3 The method comprises the steps of carrying out a first treatment on the surface of the Salt 0.5% CaCl 2 The auxiliary agent is 1% sodium hypochlorite and 0.5% tetramethyl ammonium hydroxide), wherein the obtained 1-3-pass gelatin is respectively:
5.17kg of 1-pass gelatin, and the test freezing force is 252 bloom; 3.10kg of 2-pass gelatin, and the test freezing force is 211Blommg; 2.07kg of 3-pass gelatin, wherein the test freezing force is 198bloom mg, and indexes such as viscosity, transmittance and the like are tested on the final-pass gelatin: viscosity 4.25 mPas, transmittance at 450 nm: 80%; transmittance at 620 nm: 90%; the total gel extraction rate of the relative bone particles is 17.61 percent.
Clearly, the total gelatin extraction rate of example 4 is 17.61% higher than the total gelatin extraction rate of the comparative example by 13.74%; meanwhile, the freezing force of the gel (final-stage gelatin) in the 3 rd stage of the example 3 is obviously higher than that of the gel (3 rd and 4 th stages) obtained in the comparative example 2, and is higher than 180bloom, and the viscosity and transmittance indexes are also higher than those of the final-stage gelatin obtained in the comparative example 2.
In conclusion, the freezing force and the yield of the bone gelatin obtained by using the method of the embodiment of the invention are obviously higher than those of the gelatin product obtained by the traditional alkaline method, which is beneficial to improving the product quality and the aggregate utilization rate, and meanwhile, the preparation process has shorter period, the decalcification period is only required to be 2-5 hours, and the liming period is about 20-40 days.
The foregoing examples are illustrative only and serve to explain some features of the method of the invention. The appended claims are intended to claim the broadest possible scope and the embodiments presented herein are merely illustrative of selected implementations based on combinations of all possible embodiments. It is, therefore, not the intention of the applicant that the appended claims be limited by the choice of examples illustrating the features of the invention. Some numerical ranges used in the claims also include sub-ranges within which variations in these ranges should also be construed as being covered by the appended claims where possible.
Claims (10)
1. The liming liquid for preparing bone gelatin is characterized by comprising 0.05-1.0% of alkali and 0.2-3% of salt by mass; the alkali is selected from one or more of metal hydroxide, metal carbonate and metal bicarbonate, and the salt is selected from at least one of metal chloride and ammonium chloride.
2. The liming solution according to claim 1, wherein the metal of the metal hydroxide, metal carbonate, metal bicarbonate is selected from one or more of calcium, potassium, sodium; the metal in the metal chloride is selected from one or more of calcium, sodium and potassium.
3. The liming liquid according to claim 1, wherein the mass fraction of the alkali is 0.2-0.4%, and the mass fraction of the salt is 0.5-1%.
4. The liming liquid according to claim 1, wherein the liming liquid component further comprises 0.5-5% by mass of an auxiliary agent selected from one or more of hydrogen peroxide, hypochlorite and tetramethyl hydroxide salt.
5. A method for preparing bone gelatin, comprising the steps of:
(1) Washing bone particles with acid, and then carrying out solid-liquid separation to obtain decalcified bone extract;
(2) Washing decalcified ossein with alkali liquor and clear water to obtain deacidified ossein, mixing the deacidified ossein with the liming liquid according to any one of claims 1-4 for liming, and separating to obtain limed ossein after liming is completed;
(3) Washing the liming ossein with acid and clear water to obtain the liming ossein, and then carrying out gum extraction and post-treatment to obtain the bone gelatin.
6. The method according to claim 5, wherein the bone particles in step (1) have a particle diameter of 0.01 to 3mm;
further, the acid in the step (1) is selected from one or more of hydrochloric acid, phosphoric acid and organic acid;
further, the mass fraction of the acid is 1-5 wt%;
further, the pickling time is 2-5 hours.
7. The process according to claim 5, wherein the alkali of the alkaline solution in the step (2) is one or more selected from the group consisting of calcium hydroxide, sodium hydroxide and potassium hydroxide;
further, the mass fraction of the alkali is 0.1-10%;
further, washing decalcified ossein with alkali liquor and clear water until the pH value is=5-8 to obtain deacidified ossein;
further, the mass ratio of the liming liquid to the deacidified bone mineral is 4-8: 1.
8. the method according to claim 5, wherein the liming conditions are: liming for 15-45 d at 8-27 ℃; further, ash is soaked for 20-40 d at the temperature of 10-20 ℃;
further, the liming system is subjected to liming liquid circulation and/or stirring for 5-10 min at intervals of 4-8 h, wherein the rate of the liming liquid circulation is not higher than 80 r/min;
further, the liming liquid is replaced every 2-7 d and/or when the COD of the liming liquid is more than 3000 mg/L.
9. The method according to claim 5, wherein the acid in the step (3) is one or more selected from the group consisting of hydrochloric acid, phosphoric acid, and organic acid; further, the organic acid is selected from one or more of formic acid, acetic acid, propionic acid and oxalic acid;
further, the liming ossein is washed with acid and clean water until the pH=4 to 6 to obtain the liming ossein.
10. The method according to claim 5, wherein the step of extracting the glue comprises: extracting the rubber for 1-3 times at 60-90 ℃, extracting the rubber for 2-3 hours in each time, adding clear water after the rubber extraction of each time is finished, and entering the next time of rubber extraction;
further, the clear water: the mass ratio of the ash removing ossein is 1-10: 1, a step of; further, the ratio is 1-5:1.
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| GB480712A (en) * | 1936-08-27 | 1938-02-28 | John Vernon Stuart Glass | Improvements in or relating to the manufacture of gelatine |
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| CN102827550A (en) * | 2012-09-07 | 2012-12-19 | 罗赛洛(大安)明胶有限公司 | Gelatin preparation process for acid process bone element gelatin |
| CN107083415A (en) * | 2017-05-27 | 2017-08-22 | 四川汇宇生物技术有限公司 | A kind of production method of gelatin |
| CN109181554A (en) * | 2018-10-23 | 2019-01-11 | 青海清华博众生物技术有限公司 | The preparation method of medicinal Islamic gelatin and medicinal Islamic gelatin |
| CN112608686A (en) * | 2020-12-04 | 2021-04-06 | 安徽丰原明胶有限公司 | Liming method for preparing bone gelatin and application |
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| GB480712A (en) * | 1936-08-27 | 1938-02-28 | John Vernon Stuart Glass | Improvements in or relating to the manufacture of gelatine |
| CN101176502A (en) * | 2007-12-12 | 2008-05-14 | 江南大学 | Method for preparing dope using fresh water fishbone |
| CN102827550A (en) * | 2012-09-07 | 2012-12-19 | 罗赛洛(大安)明胶有限公司 | Gelatin preparation process for acid process bone element gelatin |
| CN107083415A (en) * | 2017-05-27 | 2017-08-22 | 四川汇宇生物技术有限公司 | A kind of production method of gelatin |
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