EP3425069B1 - Entkälkungsverfahren - Google Patents
Entkälkungsverfahren Download PDFInfo
- Publication number
- EP3425069B1 EP3425069B1 EP18181645.5A EP18181645A EP3425069B1 EP 3425069 B1 EP3425069 B1 EP 3425069B1 EP 18181645 A EP18181645 A EP 18181645A EP 3425069 B1 EP3425069 B1 EP 3425069B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- deliming
- acid
- process according
- hair
- trimmings
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 238000009966 trimming Methods 0.000 claims description 53
- 150000007524 organic acids Chemical class 0.000 claims description 50
- -1 amino acid salt Chemical class 0.000 claims description 45
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- 230000000996 additive effect Effects 0.000 claims description 25
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- 239000000126 substance Substances 0.000 claims description 5
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 4
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004471 Glycine Substances 0.000 claims description 4
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 claims description 4
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- 239000004472 Lysine Substances 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
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- 235000015165 citric acid Nutrition 0.000 claims description 4
- 235000004554 glutamine Nutrition 0.000 claims description 4
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- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 2
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 2
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- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims description 2
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- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 2
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
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- 235000008521 threonine Nutrition 0.000 claims description 2
- 229960002898 threonine Drugs 0.000 claims description 2
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- 229960004441 tyrosine Drugs 0.000 claims description 2
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 2
- 229960004295 valine Drugs 0.000 claims description 2
- 239000004474 valine Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 64
- 239000010985 leather Substances 0.000 description 33
- 238000004519 manufacturing process Methods 0.000 description 27
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- 238000007796 conventional method Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 102000008186 Collagen Human genes 0.000 description 16
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- 229920001436 collagen Polymers 0.000 description 16
- 102000011782 Keratins Human genes 0.000 description 15
- 108010076876 Keratins Proteins 0.000 description 15
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 14
- 230000003139 buffering effect Effects 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 206010039509 Scab Diseases 0.000 description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 9
- 235000011941 Tilia x europaea Nutrition 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000004571 lime Substances 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 6
- 239000000920 calcium hydroxide Substances 0.000 description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 241000283690 Bos taurus Species 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- 229910021529 ammonia Inorganic materials 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
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- 235000008206 alpha-amino acids Nutrition 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 150000001370 alpha-amino acid derivatives Chemical class 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 231100000615 substance of very high concern Toxicity 0.000 description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000282994 Cervidae Species 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 206010074268 Reproductive toxicity Diseases 0.000 description 1
- 241000282898 Sus scrofa Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001371 alpha-amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000005619 boric acid group Chemical class 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 210000004919 hair shaft Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000007065 protein hydrolysis Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000007696 reproductive toxicity Effects 0.000 description 1
- 231100000372 reproductive toxicity Toxicity 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002425 soil liming agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
Definitions
- the present invention relates to a deliming process.
- One technical route for hair treatment is to extract valuable protein like keratin and keratin pieces and using them as surfactant or as functional additives in personal care products.
- Another method is isolating of single valuable amino acids from the hair hydrolysates for pharmaceutical and fine chemical industries. These routes technically allow for high value-added utilization of hair.
- the high demand on technical control of the hydrolysis process and purification requires additional investment, as well as the big consumption of water resource during purification steps (1 Ton pure amino acid consumes around 200 Tons of water) inhibits the utilization of limed hair.
- Most of the hair is dumped on the vacant site around the tanneries, leading to foul smell and environmental problems due to long time storage.
- Leather industry has been seeking an economic and ecological approach for recovering of products from the limed hair during the past one and half century.
- deliming is required to bring pH value of pelt to a proper state of alkalinity.
- Deliming is about removing calcium hydroxide from pelts including surfaces and inner parts thereof and lowering pH value of pelts until around 8. During the deliming, if pH value of the pelts decreases too fast, excessive deliming happens and leads to surface acid swelling. To prevent grain damage and acid swelling, mild deliming should be carried out by applying satisfactory deliming agents which have good buffering capacity and are sufficient in lime removal.
- ammonium salts such as ammonium sulfate, ammonium chloride, etc.
- US 2,318,454 which was granted on May 4, 1943 used ammonium salt as deliming component.
- Ammonium salts have been widely accepted in leather industry due to the following characteristics: 1) cheap raw material compared with organic compounds; 2) buffering effect, which provides a narrow pH range in deliming float and prevents the surface damage of the pelts and a mild removal of lime from the limed pelt.
- Ammonium salts are known as good buffering agents in deliming recipes, that generate leather with clean surface, even dying property and good handle feeling.
- ammonium salts When ammonium salts are used for deliming purposes, they react with calcium hydroxide which are physically and chemically bonded on the limed pelt. For instance, the reactions between ammonium sulfate or ammonium chloride and calcium hydroxide are illustrated as below: Ca(OH) 2 +NH 4 Cl ⁇ CaCl 2 +NH 3 +H 2 O Ca(OH) 2 +(NH 4 ) 2 SO 4 ⁇ CaSO 4 +NH 3 +H 2 O
- Ammonium based deliming agents have two shortcomings, which limit their applications in industry.
- the disadvantages are: 1) the ammonia released during deliming leads to the workers' exposure in unsafe environment; 2) the high NH 3 -N content in tannery effluent makes it necessary to perform NH 3 -N removal, which increases the cost and duration of wastewater treatment.
- inorganic acid like boric acid
- small molecular organic acids including lactic acid, citric acid, succinic acid, or adipic acid
- macromolecules such as polyimides, polysuccinimide and hydroxy polysuccinimide.
- Boric acid has very good buffering effect in deliming float and was used as the alternative deliming agent, which enables even deliming across the thick pelts and generates leather with good quality.
- boric acid has reproductive toxicity and is listed in SVHC (substance of very high concern) according to REACH (Registration, evaluation, authorization and restriction of chemicals). Buffering system which has low impact on workers' health and environment are lacking.
- CN 102010917A mentions an ammonia free deliming agent, which is the combination of two organic acids.
- One organic acid is a small molecular organic acid, such as citric acid, or succinic acid; the other organic acid is gluconic acid or sulfosalicylic acid.
- the above used small molecular organic acids have very limited buffering effect in limed pelt.
- WO 2013/107233A also discloses an ammonia free deliming agent.
- the deliming agent comprises polysuccinimide or hydroxy polysuccinimide.
- Polyimides, polysuccinimides are polymers, which are slow in penetrating into thick limed pelts.
- DE 2113214 describes the deliming of lime-soaked unhaired hides with an aqueous solution of aminoacid(s) or aminoacid salt(s) followed by treating at 20-50 °C with a mixed enzyme of papaine and pancreatine until desired drenching effect is reached.
- the deliming process comprises a deliming step: deliming the limed pelt with a deliming agent which is free of ammonium salts and boric acid, the deliming agent comprising protein hydrolysate, the protein hydrolysate being produced according to a method comprising the following steps: (A) hydrolyzing hair, shavings, trimmings and/or feathers to generate amino acid and/or amino acid salt, then obtaining protein hydrolysate.
- the deliming agent has high lime dissolving value and good buffering capacity during deliming process, and ensures zero add-on NH 3 -N load originating from liming agents, resulting in low NH 3 -N load in deliming effluent.
- the final NH 3 -N value in effluent is around 100 ppm.
- the active component of the protein hydrolysate is amino acids and/or amino acid salts. Deliming with amino acids or amino acid salt is implemented via the below route:
- the protonated amine groups After reacting with hydroxide ion, the protonated amine groups generate amine compounds, which are weak bases and provide buffering capacity for the system. Good buffering capacity allows the pH value to decline gradually and prevent acid swelling on the grain layer.
- the carboxylic groups While reacting with calcium ion, the carboxylic groups form soluble calcium salts, enabling the effective removal of lime and produce wet blue/ wet white with clean surface.
- Protein hydrolysate of the present invention could be individually used in the deliming agent or combined with some additives, and achieve good deliming effect with no help of ammonium salts, which enables the replacement of conventional boric acid and ammonium salts.
- the deliming agent of the present invention has the following features: 1) protein hydrolysates are utilized as deliming agent; they are safe compounds both to environment and workers; 2) amino acids in protein hydrolysate will not introduce NH 3 -N burden into deliming effluent, therefore the reduction of NH 3 -N generated in deliming process can be achieved; 3) compared with the known ammonium free deliming agents, the present deliming agent has good deliming effect which is almost equal to ammonium salts and will not cause acid swelling; 4) the deliming agent can be obtained by hydrolyzing limed hair or chrome contaminated shavings or trimmings from leather manufacturing process. This decreases the cost of the deliming agent and solves the issue of waste of limed hair, shavings and trimmings, and prevents the environmental pollution caused by disposal of contaminated keratin and collagen based solid waste.
- the objective of the present invention is therefore to provide a deliming process comprising a deliming step: deliming the limed pelt with a deliming agent which is free of ammonium and boric acid, the deliming agent comprising protein hydrolysate, the protein hydrolysate being produced according to a method comprising the following steps: (A) hydrolyzing hair, shavings, trimmings and/or feathers to generate amino acid and/or amino acid salt, then obtaining the protein hydrolysate.
- the hair refers to all kinds of animal hair and/or human hair so long as the hair comprises keratin.
- the feathers in step (A) refer to all kinds of bird feathers so long as the feathers comprise keratin.
- step (A) the shavings or trimmings are solid waste from leather manufacturing process.
- the shavings or trimmings in step (A) refer to all kinds of hair or leather shavings or trimmings so long as the shavings or trimmings comprise collagen.
- hydrolyzing can be done via conventional protein hydrolysis method so long as amino acids can be generated by hydrolyzing.
- the hydrolyzing method can be acid, alkali and/or enzyme hydrolysis, preferably acid hydrolysis.
- the acid hydrolysis comprises the following steps: (a-1) hydrolyzing hair, shavings, trimmings and/or feathers in inorganic acid solution I at 80-130 °C, (a-2) removing the insoluble substances by pressure filtration, (a-3) neutralizing the filtrate with ammonium free alkaline compounds to pH value of 4-7 and obtaining protein hydrolysate solution, and optionally (a-4) spraying dry the protein hydrolysate solution and obtaining the protein hydrolysate.
- the protein hydrolysate used in the deliming agent can be in the form of protein hydrolysate solution obtained in step (a-3), as well as in the form of dried protein hydrolysate obtained in step (a-4).
- the inorganic acid of the inorganic acid solution I is conventional inorganic acid used in the leather manufacturing process, preferably comprising at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
- the content of the inorganic acid in the inorganic acid solution I can be chosen according to the conventional method, preferably is 5-40 wt%.
- the time of hydrolyzing can be chosen according to the conventional method, preferably is 1-10 hours.
- the pH value is preferably 5-6.5.
- the amount of hair is preferably 10-50 wt%, more preferably 20-50 wt%, most preferably 30-50 wt%, based on the total weight of the inorganic acid solution I and the hair.
- the content of the inorganic acid in the inorganic solution I is preferably 10-38 wt%.
- the hydrolysis of hair is preferably conducted at 80-130 °C.
- the time of hydrolyzing hair is preferably 2-8 hours.
- the amount of the shavings and the trimmings is preferably 40-80 wt%, more preferably 50-75 wt%, based on the total weight of the inorganic acid solution I, the shavings and the trimmings.
- the content of the inorganic acid in the inorganic acid solution I is preferably 10-40 wt%.
- the hydrolysis of the shavings and/or the trimmings is preferably conducted at 80-130 °C.
- the time of hydrolyzing the shavings and/or the trimmings is preferably 2-7 hours.
- the basic compound is conventional basic compound used in the leather manufacturing process, preferably comprising at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
- the hair when hydrolyzing the hair in step (A), can be limed hair.
- the limed hair is preferably pretreated before hydrolyzing.
- the pretreatment for the limed hair could be done according to the conventional method to remove grease, dirt and contaminated chemicals, preferably comprising the steps: (i) washing the limed hair with inorganic acid solution II, (ii) neutralizing the inorganic acid solution II to pH value of 5-8, and (iii) removing the effluent, drying and obtaining the pretreated hair.
- the content of the inorganic acid in the inorganic acid solution II is preferably 0.3-2 mol/L.
- the amount of the inorganic acid solution II is preferably 3-20 times, more preferably is 3-10 times the weight of the limed hair.
- the inorganic acid of the inorganic acid solution II is conventional inorganic acid used in the leather manufacturing process, preferably comprising at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
- the time of washing is preferably 1-5 hours. The washing is preferably conducted under stirring.
- alkaline can be used to neutralize the inorganic acid solution II
- the alkaline can be conventional alkaline used in the leather manufacturing process, preferably comprising at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
- the amount of the alkaline can be chosen according to conventional method used in the leather manufacturing process to adjust the pH value to 5-8.
- step (iii) the drying is preferably conducted at 30-60 °C.
- the shavings and/or the trimmings when hydrolyzing the shavings and/or the trimmings in step (A), can be chrome containing shavings and/or trimmings.
- the chrome containing shavings and/or trimmings are preferably pretreated before hydrolyzing.
- the pretreatment for the chrome containing shavings and/or trimmings can be done according to the conventional method to remove dirt, preferably comprising the steps: (iv) washing the chrome containing shavings and/or trimmings with water, removing the dirt, soaking in the solution of calcium oxide, glucose and water; (v) removing water, (vi) acid dechroming with inorganic acid solution III to dissociate the chromium from the shavings and trimmings, and (vii) sufficient washing to remove chromium and obtaining the pretreated shavings and/or trimmings.
- the amount of the water is preferably 3-20 times of the weight of the chrome containing shavings and trimmings, more preferably 3-10 times.
- the time of washing is preferably 1-5 hours.
- the washing is preferably conducted under stirring.
- step (iv) soaking is to open the fiber structure in the chrome containing shavings and/or trimmings.
- the content of calcium oxide in the solution is preferably 1- 3 wt%, based on the weight of water.
- the content of glucose in the solution is preferably 0.1-0.3 wt%, based on the weight of water.
- the time of soaking is preferably 2-4 days.
- the content of the inorganic acid in the inorganic acid solution III is preferably 4-15 wt%.
- the inorganic acid of the inorganic acid solution III is conventional inorganic acid used in the leather manufacturing process, preferably comprising at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
- the time for acid dechroming depends on the dissociation of chromium, preferably is 0.5-2 hours.
- the deliming agent can further comprise organic acid and/or carbon dioxide, the organic acid herein excluding amino acid.
- the organic acid which comes into consideration in the present invention is the one that is commonly used in leather manufacturing process.
- the organic acid comprises at least one selected from the group consisting of lactic acid, citric acid, adipic acid, malonic acid, succinic acid, glutaric acid, and gluconic acid; more preferably is succinic acid and/or adipic acid.
- the combination of the protein hydrolysate and the organic acid can realize better deliming efficiency.
- the deliming agent can further comprise additives.
- the additives which come into consideration for use in the present invention is any of the conventional additives used in leather manufacturing process.
- the preferable additive is y oxidizing agent and/or catalyst.
- the preferable additive comprises at least one selected from the group consisting of manganese sulfate, manganese chloride, manganese acetate, sodium formate, potassium formate, sodium hydrogen sulfite, sodium metabisulfite, potassium metabisulfite, sodium acetate, potassium acetate, sodium sulfate, potassium sulfate, sodium hydrosulfate, potassium hydrosulfate, sodium percarbonate and potassium percarbonate.
- the deliming agent preferably further comprises amino acid component.
- the amino acid component means any component so long as it comprises amino acid and/or amino acid ion and can react with Ca(OH) 2 without bringing any negative effect to deliming.
- the amino acid component for use in the present invention preferably comprises amino acid, amino acid salt, and/or other protein hydrolysate which contains amino acid and/or amino acid salt.
- the other protein hydrolysate means the one that is not obtained according to the step (A).
- the amino acid for use in the present invention is the commonly known amino acid which contains amine and carboxyl functional group, along with a side-chain (R group) specific to each amino acid.
- Amino acid having good buffering capacity and lime dissolving ability is preferably used in the present invention.
- the amino acid is ⁇ -amino acid, which has both the amine and the carboxyl functional group attached to the ⁇ -carbon atom.
- the generic formula of the ⁇ -amino acids is H 2 NCH(R)COOH in most cases.
- the ⁇ -amino acid comprises at least one selected from the group consisting of glycine, alanine, valine, leucine, isoleucine, phenylalanine, tryptophan, tyrosine, histidine, serine, threonine, cysteine, aspartic acid, glutamic acid, asparagine, glutamine, lysine, arginine, proline, methionine and selenocysteine. Based on experiments, it was found that glycine, serine, asparagine, leucine, glutamine and/or lysine is more preferable.
- the amino acid for use in the present invention can be natural or synthetized amino acid. All the stereoisomers of amino acid can be used in the present invention, such as D-, L-, or D,L- amino acid.
- the amino acid salt for use in the present invention is preferably water soluble amino acid salt.
- the common amino acid salt which will not precipitate with calcium ion can be used in the present invention.
- the amino acid salt is preferably alkali metal salt and/or hydrochloride salt.
- the alkali metal is preferably sodium and/or potassium.
- the other protein hydrolysate is preferably collagen hydrolysate and/or keratin hydrolysate.
- the degree of hydrolysis is not limited in the present invention, so long as there is amino acid or salt thereof in the other protein hydrolysate.
- the hydrolyzation into high content of amino acids level is preferred.
- the total content of the protein hydrolysate and the amino acid component in the deliming agent is calculated according to the content of the total amino acids and amino acid salts in the deliming agent.
- the amino acid and amino acid salt in the protein hydrolysate are used to calculated the content of the total amino acids and amino acid salts.
- the content of the total amino acids and the amino acid salts in the deliming agent can be chosen according to conventional methods in leather manufacturing industry.
- the content of the total amino acids and amino acids salts in the deliming agent is preferably 40-100 wt%, more preferably 55-100 wt%, further more preferably 70-100 wt%, most preferably 80-100 wt%, wt% is based on the total weight of the amino acids, the amino acid salts, the organic acid and the additives.
- the content of the organic acid in the deliming agent can be chosen according to conventional methods in leather manufacturing process, preferably is 40 wt% or less; more preferably 5-20 wt%; most preferably 5-10 wt%, wt% is based on the total weight of the amino acids, the amino acid salts, the organic acid and the additive.
- the content of the additive in the deliming agent can be chosen according to conventional methods used in leather manufacturing process, preferably is 25 wt% or less, more preferably 1-10 wt%, wt% is based on the total weight of the amino acids, the amino acid salts, the organic acid and the additives.
- the deliming agent comprises the protein hydrolysate in which the content of the total amino acids and the amino acid salts is 55-94 wt%, 5-20 wt% of the organic acid and 1-25 wt% of the additives, wt% is all based on the total weight of the amino acids, the amino acid salts, the organic acid and the additives.
- the preferred protein hydrolysate, the preferred organic acid and the preferred additive all can be respectively or together chosen according to the above preferred solutions.
- the deliming agent comprises the protein hydrolysate in which the content of the total amino acids and the amino acid salts is 80-90 wt%, 5-10 wt% of the organic acid and 5-10 wt% of the additive, wt% is all based on the total weight of the amino acids, the amino acid salts, the organic acid and the additive.
- the amount of the deliming agent is calculated based on the amount of the total amino acids and the amino acid salts in the deliming agent.
- the amount of the total amino acids and the amino acid salts in the deliming agent is preferably 1-5 wt% of the limed pelt, more preferably 1-2.5 wt% of the limed pelt.
- the deliming step includes the following steps: (b-1) a pre-deliming step: pre-liming the limed pelt with the additive, and the organic acid and/or the carbon dioxide; and (b-2) deliming the limed pelt with the deliming agent.
- the step (b-1) preferably comprises: (viii) washing the limed pelt with water, removing the float; (ix) pre-deliming the limed pelt with the additive, and the organic acid and/or carbon dioxide; and (x) when the pH value of float is about 8, draining the float.
- the additive in step (b-1) is the same additive mentioned above in the deliming agent.
- the organic acid in step (b-1) is the same organic acid mentioned above in the deliming agent.
- the amount of the additive can be chosen according to conventional methods used in the leather manufacturing process, preferably is 0.05-0.3 wt% of the limed pelt.
- the amount of the organic acid can be chosen according to conventional methods used in the leather manufacturing process, preferably is 0.1-0.5 wt% of the limed pelt.
- the deliming step is be conducted as deliming the limed pelt with an aqueous solution of the deliming agent.
- the amount of water in step (viii) or in the aqueous solution of the deliming agent can be chosen according to conventional methods used in leather manufacturing process, preferably is 300 wt% of the limed pelt or less, more preferably 200 wt% of the limed pelt or less.
- the step (b-2) preferably comprises: (xi) deliming the limed pelt with the deliming agent; and (xii) ending the deliming step.
- the step (b-1) or (b-2) can be conducted at conventional temperature, preferred is 5-35 °C, more preferred 25-35 °C.
- the end of the deliming step can be decided according to conventional methods used in leather manufacturing process.
- the deliming step can be ended.
- the time of the deliming step is preferably from 1 to 6 hours, more preferably from 1 to 3 hours.
- the "about 8" in the present invention refers to 8 ⁇ 0.8.
- pH value of the float is preferably monitored.
- the pelt in the present invention can be also explained as hide in the leather manufacturing field.
- the pelt could come from common mammals used in the leather manufacturing field, such as cattle, sheep, pig, or deer.
- the limed pelt could be limed according to conventional liming methods used in leather manufacturing process.
- the present invention has the following benefits: (1) The utilization of the waste (limed hair, chrome containing shavings and/or trimmings) from leather manufacture turns the tannery waste into raw material for deliming process, realizing the recycling and significantly enhancing the concept of "closed loop" process; (2) raw material for deliming process does not contain boric acid, which is compliant with safe operation; (3) without using ammonium salts, greatly reducing the ammonia-nitrogen values in the effluent; (4) no ammonia releasing during deliming process, which facilitates safe operation; (5) protein hydrolysate has good buffering capacity within deliming pH range, which enables the success lime removal from the limed pelts without inducing acid swelling especially on the grain layer; (6) protein hydrolysate has high solubility in water and small molecules which enables fast penetration into limed pelts; (7) the formation of soluble calcium salts from amino acids compounds and lime resulting in high lime removal efficiency, which enables a clean pelt surface and soft handle feeling of the
- the pretreatment of the limed hair was conducted by: (i) 1500g limed hair was added into 10 L, 0.3 mol/L hydrochloric acid solution (inorganic acid solution II), then the mixture was stirred for 2 hours; (ii) neutralization with sodium hydroxide solution to pH 6; and (iii) filtration was conducted to remove the effluent and hair was dried at 50 °C for 2 hours to obtain 1000g pretreated hair.
- the keratin hydrolysate solution used in the following deliming process was obtained according to the following steps:
- the pretreatment of the limed hair was conducted by: (i) 1500g limed hair was added into 10 L, 0.3 mol/L hydrochloric acid solution (inorganic acid solution II), then the mixture was stirred for 2 hours; (ii) neutralization with sodium hydroxide solution to pH 6; and (iii) filtration was conducted to remove the effluent and hair was dried at 50 °C for 2 hours to obtain 1000g pretreated hair.
- the keratin hydrolysate solution used in the following deliming process was obtained according to the following steps:
- the pretreated shavings and trimmings in step (a-1) were obtained by: (iv) 300g wet-blue chrome containing shavings and trimmings were cut into small pieces, 1L water was added and the mixture was stirred for 2 hours; filtering to remove the dirt; soaking in the aqueous solution of 30g CaO, 9g glucose and 3L water, the soaking was carried out for 4 days; (v) removing water via pressure filtration; (vi) soaking in 300mL, 4wt% hydrochloride solution (inorganic acid solution III) in a flask for 2 hours; (vii) sufficient washing to remove chromium, draining the float and obtaining the pretreated shavings and/or trimmings.
- the collagen hydrolysate solution used in the following deliming process was obtained according to the following steps:
- crust was obtained after bating, pickling, chrome tanning, retanning, neutralization, dying and fat-liquoring.
- the pretreated shavings and trimmings in step (a-1) were obtained by: (iv) 300g wet-blue chrome containing shavings and trimmings were cut into small pieces, 1L water was added and the mixture was stirred for 2 hours; filtering to remove the dirt; soaking in the aqueous solution of 60g CaO, 3g glucose and 3L water, the soaking was carried out for 2 days; (v) removing water via filter-press; (vi) soaking in 300mL, 15wt% hydrochloride solution (inorganic acid solution III) in a flask for 0.5 hours; (vii) sufficient washing to remove chromium, draining the float and obtaining the pretreated shavings and/or trimmings.
- the collagen hydrolysate solution used in the following deliming process was obtained according to the following steps:
- the deliming process comprises the following steps:
- the collagen hydrolysate solution obtained in example 4 (amino acid content 70%) was used in example 5.
- the deliming process comprises the following steps:
- the deliming process comprises the following steps:
- deliming with ammonium salts, collagen hydrolysate, keratin hydrolysate achieved end pH value around 8, which means that amino acids have similar buffering capacity as ammonium salts.
- the deliming effluent of amino acids has NH 3 -N value around 100 ppm, which is less than 5% of ammonium salts deliming effluent. Low NH 3 -N value can significantly reduce effluent treatment time and cost.
- the crusts obtained from all the examples have even color, soft handle feeling and very fine grain, which is comparable with comparative example 1.
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Claims (25)
- Entkalkungsverfahren, umfassend einen Entkalkungsschritt:
Entkalken des gekalkten Fells mit einem Entkalkungsmittel, das frei von Ammonium und Borsäure ist, das Entkalkungsmittel umfassend Proteinhydrolysat, wobei das Proteinhydrolysat nach einem Verfahren hergestellt wird, umfassend die folgenden Schritte: (A) Hydrolysieren von Haaren, Rasierabfällen, Schneideabfällen und/oder Federn, um Aminosäure und/oder Aminosäuresalz zu erzeugen, dann Erhalten des Proteinhydrolysats. - Entkalkungsverfahren nach Anspruch 1, dadurch gekennzeichnet, dass in Schritt (A) das Hydrolysieren Säurehydrolyse ist, die die folgenden Schritte umfasst:(a-1) Hydrolysieren von Haaren, Rasierabfällen, Schneideabfällen und/oder Federn in anorganischer Säurelösung I bei 80 - 130 °C;(a-2) Entfernen der unlöslichen Substanzen durch Druckfiltration;(a-3) Neutralisieren des Filtrats mit Ammonium-freien basischen Verbindungen auf einen pH-Wert von 4 - 7 und Erhalten einer Proteinhydrolysatlösung;und optional (a-4) Trockensprühen der Proteinhydrolysatlösung und Erhalten des Proteinhydrolysats.
- Entkalkungsverfahren nach Anspruch 2, dadurch gekennzeichnet, dass in Schritt (a-1) die anorganische Säure der anorganischen Säurelösung I wenigstens eine , ausgewählt aus der Gruppe, bestehend aus Salzsäure, Schwefelsäure, Salpetersäure und Phosphorsäure, umfasst; wobei der Gehalt der anorganischen Säure in der anorganischen Säurelösung I 5 - 40 Gew.-% ist.
- Entkalkungsverfahren nach einem der Ansprüche 2 oder 3, dadurch gekennzeichnet, dass, wenn die Haare in Schritt (a-1) hydrolysiert werden, die Haarmenge 10 - 50 Gew.-%, vorzugsweise 20 - 50 Gew.-%, bevorzugter 30 - 50 Gew.-%, bezogen auf das Gesamtgewicht der anorganischen Säurelösung I und der Haare, ist; wenn die Rasierabfälle und/oder die Schneideabfälle in Schritt (a-1) hydrolysiert werden, die Menge der Rasierabfälle und Schneideabfälle 40 - 80 Gew.-%, vorzugsweise 50 - 75 Gew.-%, bezogen auf das Gesamtgewicht der anorganischen Säurelösung I, der Rasierabfälle und der Schneideabfälle, ist.
- Entkalkungsverfahren nach einem der Ansprüche 2 bis 4, dadurch gekennzeichnet, dass, wenn die Haare in Schritt (a-1) hydrolysiert werden, der Gehalt der anorganischen Säure in der anorganischen Lösung I 10 - 38 Gew.-% ist,; die Hydrolyse von Haaren bei 80 - 130 °C durchgeführt wird.
- Entkalkungsverfahren nach einem der Ansprüche 2 bis 5, dadurch gekennzeichnet, dass, wenn die Rasierabfälle und/oder die Schneideabfälle in Schritt (a-1) hydrolysiert werden, der Gehalt der anorganischen Säure in der anorganischen Säurelösung I 10 - 40 Gew.-% ist; die Hydrolyse der Rasierabfälle und/oder der Schneideabfälle bei 80 - 130°C durchgeführt wird.
- Entkalkungsverfahren nach einem der Ansprüche 2 bis 6, dadurch gekennzeichnet, dass in Schritt (a-3) die Ammonium-freie basische Verbindung wenigstens eine, ausgewählt aus der Gruppe bestehend aus Natriumhydroxid, Kaliumhydroxid, Natriumcarbonat, Kaliumcarbonat, Natriumbicarbonat und Kaliumbicarbonat, umfasst.
- Entkalkungsverfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass, wenn die Haare in Schritt (A) hydrolisiert werden, die Haare gekalkte Haare sind, die vor dem Hydrolysieren vorbehandelt werden, die Vorbehandlung für die gekalkten Haare umfassend die Schritte: (i) Waschen der gekalkten Haare mit anorganischer Säurelösung II, (ii) Neutralisieren der anorganischen Säurelösung II auf einen pH-Wert von 5 - 8, und (iii) Entfernen des Abwassers, Trocknen und Erhalten der vorbehandelten Haare.
- Entkalkungsverfahren nach Anspruch 8, dadurch gekennzeichnet, dass
in Schritt (i) der Gehalt der anorganischen Säure in der anorganischen Säurelösung II 0,3 - 2 mol/L ist; die Menge der anorganischen Säurelösung II das 3- bis 20-fache des Gewichts der gekalkten Haare ist; die anorganische Säure der anorganischen Säurelösung II wenigstens eine, ausgewählt aus der Gruppe bestehend aus Salzsäure, Schwefelsäure, Salpetersäure und Phosphorsäure, umfasst;
in Schritt (ii), Alkali verwendet wird, um die anorganische Säurelösung II zu neutralisieren, das Alkali wenigstens eines, ausgewählt aus der Gruppe bestehend aus Natriumhydroxid, Kaliumhydroxid, Natriumcarbonat, Kaliumcarbonat, Natriumbicarbonat und Kaliumbicarbonat, umfasst. - Entkalkungsverfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass, wenndie Rasierabfälle und/oder die Schneideabfälle in Schritt (A) hydrolisiert werden, die Rasierabfälle und/oder die Schneideabfälle chromhaltige Rasierabfälle und/oder Schneideabfälle sind, die vor dem Hydrolysieren vorbehandelt werden, die Vorbehandlung für die chromhaltigen Rasierabfälle und/oder Schneideabfälle umfassend die Schritte: (iv) Waschen der chromhaltigen Rasierabfälle und/oder Schneideabfälle mit Wasser, Entfernen des Schmutzes und Einweichen in der Lösung von Calciumoxid, Glucose und Wasser; (v) Entfernen von Wasser, (vi) Säure-Entchromen mit anorganischer Säurelösung III, und (vii) Waschen zum Entfernen von Chrom und Erhalten der vorbehandelten Rasierabfälle und/oder Schneideabfälle.
- Entkalkungsverfahren nach Anspruch 10, dadurch gekennzeichnet, dass in Schritt (iv) die Menge des Wassers das 3- bis 20-fache des Gewichts der chromhaltigen Rasierabfälle und Schneideabfälle ist; der Gehalt von Calciumoxid in der Lösung 1 - 3 Gew.-% , bezogen auf das Gewicht des Wassers, ist; der Gehalt an Glucose in der Lösung 0,1 - 0,3 Gew.-% , bezogen auf das Gewicht des Wassers, ist;
in Schritt (vi), der Gehalt der anorganischen Säure in der anorganischen Säurelösung III 4 - 15 Gew.-% ist; die anorganische Säure der anorganischen Säurelösung III wenigstens eines, ausgewählt aus der Gruppe bestehend aus Salzsäure, Schwefelsäure, Salpetersäure und Phosphorsäure, umfasst. - Entkalkungsverfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Entkalkungsmittel ferner organische Säure und/oder Kohlendioxid, und/oder Additiv umfasst.
- Entkalkungsverfahren nach Anspruch 12, dadurch gekennzeichnet, dass die organische Säure wenigstens eine, ausgewählt aus der Gruppe, bestehend aus Milchsäure, Zitronensäure, Adipinsäure, Malonsäure, Bernsteinsäure, Glutarsäure, und Gluconsäure, umfasst; vorzugsweise Bernsteinsäure oder Adipinsäure ist.
- Entkalkungsverfahren nach Anspruch 12, dadurch gekennzeichnet, dass das Additiv wenigstens eines, ausgewählt aus der Gruppe bestehend aus Mangansulfat, Manganchlorid, Manganacetat, Natriumformiat, Kaliumformiat, Natriumhydrogensulfit, Natriummetabisulfit, Kaliummetabisulfit, Natriumacetat, Kaliumacetat, Natriumsulfat, Kaliumsulfat, Natriumhydrosulfat, Kaliumhydrosulfat, Natriumpercarbonat und Kaliumpercarbonat, umfasst.
- Entkalkungsverfahren nach einem der Ansprüche 12 - 14, dadurch gekennzeichnet, dass das Entkalkungsmittel ferner eine Aminosäurekomponente umfasst, die Aminosäurekomponente eine Aminosäure, Aminosäuresalz, und/oder ein anderes Proteinhydrolysat umfasst, das eine Aminosäure und/oder Aminosäuresalz enthält.
- Entkalkungsverfahren nach Anspruch 15, dadurch gekennzeichnet, dass die Aminosäure wenigstens eine, ausgewählt aus der Gruppe, bestehend aus Glycin, Alanin, Valin, Leucin, Isoleucin, Phenylalanin, Tryptophan, Tyrosin, Histidin, Serin, Threonin, Cystein,Asparaginsäure, Glutaminsäure, Asparagin, Glutamin, Lysin, Arginin, Prolin, Methionin und Selenocystein, umfasst; vorzugsweise bestehend aus Glycin, Serin, Asparagin, Leucin, Glutamin und/oder Lysin; das Aminosäuresalz Alkalimetallsalz und/oder Hydrochloridsalz umfasst; das Alkalimetall vorzugsweise Natrium und/oder Kalium ist.
- Entkalkungsverfahren nach einem der Ansprüche 12 - 16, dadurch gekennzeichnet, dass der Gehalt der gesamten Aminosäuren und der Aminosäuresalze in dem Entkalkungsmittel 40 - 100 Gew.-%, vorzugsweise 55 - 100 Gew.-%, bevorzugter 70 - 100 Gew.-%, am meisten bevorzugt 80 - 100 Gew.-% ist, Gew.-% sich auf das Gesamtgewicht der Aminosäuren, der Aminosäuresalze, der organischen Säure und des Additivs bezieht.
- Entkalkungsverfahren nach einem der Ansprüche 12 - 17, dadurch gekennzeichnet, dass der Gehalt der organischen Säure in dem Entkalkungsmittel 40 Gew.-% oder weniger ist; vorzugsweise 5 - 20 Gew.-%; bevorzugter 5 - 10 Gew.-%, Gew.-% sich auf das Gesamtgewicht der Aminosäuren, der Aminosäuresalze, der organischen Säure und des Additivs bezieht.
- Entkalkungsverfahren nach einem der Ansprüche 12 - 18, dadurch gekennzeichnet, dass der Gehalt des Additivs in dem Entkalkungsmittel 25 Gew.-% oder weniger, vorzugsweise 1 - 10 Gew.-% ist, Gew.-% sich auf das Gesamtgewicht der Aminosäuren, der Aminosäuresalze, der organischen Säure und des Additivs bezieht.
- Entkalkungsverfahren nach einem der Ansprüche 12 - 19, dadurch gekennzeichnet, dass das Entkalkungsmittel das Proteinhydrolysat umfasst, in dem der Gehalt der gesamten Aminosäuren und Aminosäuresalze 55 - 94 Gew.-%, 5 - 20 Gew.-% der organischen Säure und 1 - 25 Gew.-% des Additivs ist, Gew.-% sich ganz auf das Gesamtgewicht der Aminosäuren, der Aminosäuresalze, der organischen Säure und des Additivs bezieht.
- Entkalkungsverfahren nach Anspruch 20, dadurch gekennzeichnet, dass das Entkalkungsmittel das Proteinhydrolysat umfasst, in dem der Gehalt der gesamten Aminosäuren und Aminosäuresalze 80 - 90 Gew.-%, 5 - 10 Gew.-% der organischen Säure und 5 - 10 Gew.-% des Additivs ist, Gew.-% sich ganz auf das Gesamtgewicht der Aminosäuren, der Aminosäuresalze, der organischen Säure und des Additivs bezieht.
- Entkalkungsverfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Menge des Entkalkungsmittels bezogen auf die Menge der gesamten Aminosäuren und der Aminosäuresalze in dem Entkalkungsmittel berechnet ist, die Menge der gesamten Aminosäuren und der Aminosäuresalze in dem Entkalkungsmittel 1 - 5 Gew.-% des gekalkten Fells, vorzugsweise 1 - 2,5 Gew.-% des gekalkten Fells ist.
- Entkalkungsverfahren nach wenigstens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Entkalkungsschritt die folgenden Schritte einschließt: (b-1) einen Vorentkalkungsschritt:
Vorentkalken des gekalkten Fells mit dem Additiv und der organischen Säure und/oder dem Kohlendioxid; und (b-2) Entkalken des gekalkten Fells mit dem Entkalkungsmittel. - Entkalkungsverfahren nach Anspruch 23, dadurch gekennzeichnet, dass der Schritt (b-1) umfasst: (viii) Waschen des gekalkten Fells mit Wasser, Entfernen des Schwimmkörpers; (ix) Vorentkalken des gekalkten Fells mit dem Additiv, und der organischen Säure und/oder dem Kohlendioxid; und (x) wenn der pH-Wert des Schwimmkörpers 7,2 - 8,8 ist, Ablassen des Schwimmkörpers.
- Entkalkungsverfahren nach einem der Ansprüche 23 oder 24, dadurch gekennzeichnet, dass in Schritt (b-1) die Menge des Additivs 0,05 - 0,3 Gew.-% des gekalkten Fells ist; die Menge der organischen Säure 0,1 - 0,5 Gew.-% des gekalkten Fells ist.
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ES2964416T3 (es) | 2021-01-22 | 2024-04-05 | Tfl Ledertechnik Gmbh | Composición de desencalado y procedimiento de desencalado para desencalar pieles |
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FR502225A (fr) * | 1919-08-05 | 1920-05-07 | Georges Lengrand | Procédé de déchaulage des peaux en mégisserie |
US3652381A (en) * | 1969-08-14 | 1972-03-28 | Vyzk Ustav Kozedelny | Method of preparing collagen fibers |
DE2113214A1 (de) * | 1971-03-18 | 1972-09-28 | Diamalt Ag | Verfahren zum Behandeln geaescherter Bloessen |
DE3802640A1 (de) * | 1988-01-29 | 1989-08-03 | Roehm Gmbh | Haarerhaltendes aescherverfahren |
WO2003008650A1 (en) * | 2001-07-14 | 2003-01-30 | Insect Biotech Co., Ltd. | Method for preparing leather using protease and method for treating wastes derived from leather processing using the same |
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