CN109295264B - Ammonium and boric acid free deliming agent, deliming method and use thereof - Google Patents
Ammonium and boric acid free deliming agent, deliming method and use thereof Download PDFInfo
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- CN109295264B CN109295264B CN201810735871.6A CN201810735871A CN109295264B CN 109295264 B CN109295264 B CN 109295264B CN 201810735871 A CN201810735871 A CN 201810735871A CN 109295264 B CN109295264 B CN 109295264B
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- amino acid
- deashing
- agent
- deliming
- acid
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 49
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000004327 boric acid Substances 0.000 title claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims abstract description 11
- 150000001413 amino acids Chemical class 0.000 claims abstract description 100
- -1 amino acid salts Chemical class 0.000 claims abstract description 60
- 108010009736 Protein Hydrolysates Proteins 0.000 claims abstract description 16
- 239000003531 protein hydrolysate Substances 0.000 claims abstract description 14
- 150000003868 ammonium compounds Chemical class 0.000 claims abstract description 3
- 229940024606 amino acid Drugs 0.000 claims description 146
- 235000001014 amino acid Nutrition 0.000 claims description 146
- 150000007524 organic acids Chemical class 0.000 claims description 54
- 239000000654 additive Substances 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 26
- 239000000413 hydrolysate Substances 0.000 claims description 23
- 230000000996 additive effect Effects 0.000 claims description 18
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 15
- 102000008186 Collagen Human genes 0.000 claims description 14
- 108010035532 Collagen Proteins 0.000 claims description 14
- 229920001436 collagen Polymers 0.000 claims description 14
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 14
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- 102000011782 Keratins Human genes 0.000 claims description 12
- 108010076876 Keratins Proteins 0.000 claims description 12
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 12
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000004471 Glycine Substances 0.000 claims description 9
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 9
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 9
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- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 6
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 6
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
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- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 claims description 5
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 claims description 5
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 claims description 5
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- 239000004475 Arginine Substances 0.000 claims description 4
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 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
- 239000004280 Sodium formate Substances 0.000 claims description 4
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- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 claims description 3
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- FDKWRPBBCBCIGA-REOHCLBHSA-N (2r)-2-azaniumyl-3-$l^{1}-selanylpropanoate Chemical compound [Se]C[C@H](N)C(O)=O FDKWRPBBCBCIGA-REOHCLBHSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 claims description 2
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 claims description 2
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- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims description 2
- 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
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
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- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 claims description 2
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- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
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- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 2
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- 150000001412 amines Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000001166 ammonium sulphate Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000000126 substance Substances 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
- 150000008574 D-amino acids Chemical class 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 239000006173 Good's buffer Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 241000282887 Suidae Species 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229960004452 methionine Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000037361 pathway Effects 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
- 238000002203 pretreatment Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002425 soil liming agent Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229960004799 tryptophan Drugs 0.000 description 1
- 239000002351 wastewater 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The present invention discloses an ammonium and boric acid free deliming agent comprising an amino acid component and no ammonium compound; the amino acid component comprises amino acids, amino acid salts and/or protein hydrolysates containing amino acids and/or amino acid salts. The invention also discloses a deashing method by using the deashing agent and the use of amino acids, amino acid salts and/or protein hydrolysates as the deashing agent. The deashing agent containing no boric acid or ammonium salt is environment-friendly and has good deashing effect.
Description
Technical Field
The present invention relates to a deliming agent free of ammonium and boric acid, and to a leather deliming method by using the deliming agent. The invention also relates to the use of amino acids, amino acid salts and/or protein hydrolysates as deliming agents.
Background
It is known that in leather manufacturing processes, the raw pelts should be pretreated before tanning and semi-tanning (sizing). Liming is one of the pretreatments that usually remove hair and unwanted proteins by immersing the pelt in a lime bath. Then, the pelt needs to be deashed in order to be in a proper alkaline state. The deliming is used to remove calcium hydroxide from the pelt (including its surface and interior parts) and to reduce the pH of the pelt up to about 8. During the deliming, if the pH of the pelt decreases too rapidly, excessive deliming occurs and causes the surface acid to swell. In order to prevent texture damage and acid swelling, mild deliming should be performed by applying a satisfactory deliming agent which has good buffering capacity and is sufficient to remove lime.
Conventional deliming agents for the leather industry are mainly based on ammonium salts, such as ammonium sulphate, ammonium chloride and the like. US 2,318,454, 4, authorized in 1943 uses ammonium salts as deashing components. Ammonium salts have been widely accepted in the leather industry due to the following characteristics: i) Inexpensive raw material price compared to organic compounds; ii) a buffering effect which provides a narrow pH range in the deliming float (float) and prevents surface damage of pelts and gentle removal of lime from the limed pelts. Ammonium salts are considered to be good buffers in the deashing process, which results in leather with clean surface, even dry properties and good hand.
When ammonium salts are used for deliming purposes, they react with calcium hydroxide which is physically and chemically bound to the pelt being treated. For example, the reaction between ammonium sulfate or ammonium chloride and calcium hydroxide is exemplified as follows:
Ca(OH)2+NH4Cl→CaCl2+NH3+H2O
Ca(OH)2+(NH4)2SO4→CaSO4+NH3+H2O
Ammonium-based deliming agents have two drawbacks that limit their use in industry. The defects are as follows: i) Ammonia released during deashing results in worker exposure to unsafe conditions; ii) the high NH 3 -N content in the tannery effluent necessitates NH 3 -N removal, which increases the cost and duration of wastewater treatment.
Due to the high NH 3 -N contamination by ammonium salts, three types of acids have been developed in the literature and patents as deliming agents: i) Mineral acids such as boric acid; ii) small molecule organic acids including lactic acid, citric acid, succinic acid or adipic acid; iii) Macromolecules such as polyimide, polysuccinimide and hydroxysuccinimide.
Boric acid has a very good cushioning effect in the deliming float and is used as an alternative deliming agent, which is even capable of deliming through thick pelts and gives leather of good quality. However, boric acid is reproduction toxic and is listed in SVHC (very interesting substances) according to REACH (registration, assessment, authorization and limitation of chemicals). There is currently a lack of cushioning systems that have low impact on worker health and the environment.
CN 102010917a mentions ammonia-free deliming agents, which are combinations of two organic acids. An organic acid is a small molecule organic acid such as citric acid or succinic acid; another organic acid is gluconic acid or sulfosalicylic acid. However, the small molecular organic acids used above have a very limited buffering effect in the limed float.
WO 2013/107233 also discloses ammonia-free deliming agents. The deliming agent comprises polysuccinimide or hydroxysuccinimide. Polyimide, polysuccinimide, is a polymer that is slow when penetrating into thick, limed pelts.
Due to the use of ammonium salts, many experiments have been completed to find safe, sufficient and mild deliming agents. However, for many years, there has been a need to develop an environmentally friendly deliming agent having a deliming ability comparable to that of ammonium salts and a high permeation rate.
Disclosure of Invention
An ammonium and boric acid free deliming agent is disclosed. The deliming agent comprises an amino acid component. The deliming agent has a high lime dissolution value and good buffering capacity during the deliming process and ensures zero increase in NH 3 -N loading from the deliming agent, resulting in a low NH 3 -N loading in the deliming effluent. According to the invention, the final NH 3 -N value in the effluent is about 100ppm.
Deliming with amino acids is carried out via the following pathway:
Upon reaction with hydroxide ions, the protonated amine groups produce amine compounds, which are weak bases and provide buffer capacity to the system. Good buffering capacity allows the pH to gradually decrease and prevents acid swelling on the texture layer.
After reaction with calcium ions, the carboxyl groups form soluble calcium salts that are effective in lime removal and produce blue/white wet skins with clean surfaces.
The amino acids of the present invention can be used alone or in combination with some additives and achieve good deashing without the aid of ammonium salts, thus being able to replace conventionally used boric acid and ammonium salts. The invention also discloses a deashing method and application of the amino acid in a deashing agent.
The present invention provides an environmentally friendly deliming agent compared to ammonium-based deliming agents. The deashing agent of the invention has the following characteristics: i) Amino acids are used as deliming agents, which are environmentally and worker safe compounds; ii) the amino acid does not introduce a load of NH 3 -N (burden) into the deashing wastewater, so that a reduction of NH 3 -N generated during the deashing can be achieved.
The present deliming agent has a good deliming effect almost equivalent to that of ammonium salts, and does not cause acid swelling, compared with the known deliming agent containing no ammonium.
Detailed Description
It is therefore an object of the present invention to provide an ammonium and boric acid free deliming agent comprising an amino acid component and being free of ammonium compounds; the amino acid component comprises amino acids, amino acid salts and/or protein hydrolysates containing amino acids and/or amino acid salts.
The amino acid component may mean any component as long as it contains an amino acid and/or an amino acid ion and can react with Ca (OH) 2 without any negative effect on deliming. The amino acid component of the present invention may comprise amino acids, amino acid salts and/or protein hydrolysates containing amino acids and amino acid salts.
The amino acids of the present invention are generally known amino acids that contain amine and carboxyl functional groups and side chains (R groups) specific to the respective amino acid. Amino acids with good buffering capacity and lime dissolving capacity are preferred for use in the present invention. Preferably, the amino acid is an alpha-amino acid having amine and carboxyl functionalities attached to an alpha-carbon atom. The general formula of the alpha-amino acid is in most cases H 2 NCH (R) COOH.
In a preferred embodiment, the amino acid comprises at least one selected from 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 extensive experimentation, glycine, serine, asparagine, leucine, glutamine and/or lysine were found to be more preferred.
The amino acids of the present invention may be natural or synthetic amino acids. All stereoisomers of amino acids may be used in the present invention, for example D-amino acids, L-amino acids or D, L-amino acids.
The amino acid salt of the present invention is preferably a water-soluble amino acid salt. Common amino acid salts that do not precipitate with calcium ions can be used in the present invention. The amino acid salt preferably comprises an alkali metal salt and/or a hydrochloride salt. The alkali metal is preferably sodium and/or potassium.
Protein hydrolysates are mixtures of amino acids and/or amino acid salts, which can be prepared according to conventional methods, for example by decomposing proteins using acids, bases and/or enzymes. All proteins which can be hydrolysed to amino acids and/or amino acid salts can be used in the present invention. Preferably, the protein hydrolysate comprises collagen hydrolysate and/or keratin hydrolysate. The degree of hydrolysis is not limited in the present invention as long as amino acids are present in the protein hydrolysate. Hydrolysis to high levels of amino acids is preferred.
The deliming agent of the present invention may further comprise an organic acid and/or carbon dioxide, the organic acid herein excluding amino acids. The organic acid used in the present invention is an organic acid commonly used in leather manufacturing processes. Preferably, the organic acid comprises at least one selected from lactic acid, citric acid, adipic acid, malonic acid, succinic acid, glutaric acid and gluconic acid; more preferably, succinic acid and adipic acid are included. The combination of the amino acid component and the organic acid may achieve better de-ashing efficiency.
The deliming agent of the present invention may further comprise additives. The additives contemplated by the present invention are conventional additives in the leather manufacturing industry. Preferred additives are oxidizing agents and/or catalysts. Preferred additives comprise at least one selected from the group consisting of manganese sulfate, manganese chloride, manganese acetate, sodium formate, potassium formate, sodium bisulfate, sodium metabisulfite, potassium metabisulfite, sodium acetate, potassium acetate, sodium sulfate, potassium sulfate, sodium bisulfate, potassium bisulfate, sodium percarbonate and potassium percarbonate.
The content of the amino acid component in the deliming agent is calculated from the total amino acid and amino acid salt content in the deliming agent. For protein hydrolysates, the amino acids and amino acid salts in the protein hydrolysates are used to calculate the total amino acid and amino acid salt content. The total amino acid and amino acid salt content of the deliming agent may be selected according to conventional methods in the leather processing industry. It is particularly advantageous if the total amino acids and amino acid salts in the deliming agent are present in an amount of 40 to 100 wt.%, more preferably 55 to 100 wt.%, even more preferably 70 to 100 wt.%, most preferably 80 to 100 wt.%, wt.% based on the total weight of total amino acids, amino acid salts, organic acids and additives.
The organic acid content of the deliming agent may be selected according to conventional methods in the leather processing industry, preferably 25wt% or less; more preferably from 5wt% to 20wt%; most preferably from 5wt% to 10wt%, based on the total weight of total amino acids, amino acid salts, organic acids and additives.
The amount of additive in the deliming agent may be selected according to conventional methods in the leather processing industry, preferably 25wt% or less, more preferably 20wt% or less, most preferably 10wt% or less, the wt% being based on the total weight of total amino acids, amino acid salts, organic acids and additives.
In a preferred embodiment, the deashing agent comprises an amino acid component, 0 to 20wt% of an organic acid and 0 to 25wt% of an additive, wherein the total amino acid and amino acid salt content is 55wt% to 100wt%, the wt% being based on the total weight of the total amino acid, amino acid salt, organic acid and additive; and the amino acid component is glycine, asparagine, glutamine, lysine, leucine, serine, collagen hydrolysate and/or keratin hydrolysate.
In a more preferred embodiment, the deashing agent comprises an amino acid component, 0 to 10wt% of an organic acid and 0 to 10wt% of an additive, wherein the total amino acid and amino acid salt content is 80 to 100wt%, the wt% being based on the total weight of the total amino acid, amino acid salt, organic acid and additive; the amino acid component is glycine, lysine, serine, leucine, collagen hydrolysate and/or keratin hydrolysate.
It is another object of the present invention to provide a deashing method comprising the deashing step: the liming agent of the invention is used for liming limed fur.
The pelts according to the invention can also be referred to as pelts (hide) in the field of leather manufacture. The fur may be from common animals used in the leather manufacturing field (e.g., cattle, sheep, pigs, deer) or from common birds.
In a preferred embodiment, the deashing process comprises: (A) a pre-deashing step: pre-deliming the limed pelts with additives, organic acids and/or carbon dioxide; and (B) a deashing step: the ashed fur is deashed by a deashing agent.
Step (a) preferably comprises (i) washing the ashed pelt with water to remove the floats; (ii) Pre-deliming the limed pelts with additives and organic acids and/or carbon dioxide; and (iii) draining the float when the pH of the float is about 8.
In a preferred embodiment, if the deashing process does not comprise a pre-deashing step (a), the deashing step (B) should be carried out in order to deashing the limed pelt in an aqueous solution of the deashing agent.
The additives in step (a) are the same additives mentioned above in the deashing agent.
The organic acid in step (a) is the same organic acid as mentioned above in the deliming agent.
In step (A), the amount of additive may be selected according to conventional methods in leather manufacturing processes, preferably from 0.05 to 0.3% by weight of the limed pelt.
In step (A), the amount of organic acid may be selected according to conventional methods in leather manufacturing processes, preferably from 0.1 to 0.5% by weight of the limed pelt.
The amount of water in step (i) or in the aqueous solution of the deliming agent may be selected according to conventional methods in leather manufacturing processes, based on the total weight of the limed pelt, preferably 300wt% or less of the pelt, more preferably 200wt% or less of the pelt.
Step (B) preferably comprises: (iv) deashing the limed pelt with a deashing agent; and (v) ending the deashing step.
In the deashing step, the amount of the deashing agent is calculated based on the total amino acids and amino acid salts in the deashing agent. The total amino acids and amino acid salts in the deliming agent are preferably present in an amount of from 1 to 10% by weight of the pelt to be pelt which is pelt-dressed, more preferably from 1 to 5% by weight of the pelt to be pelt which is pelt-dressed, most preferably from 1 to 2.5% by weight of the pelt which is pelt-dressed.
The deashing process of the present invention can be carried out in a conventional temperature range, preferably from 5 ℃ to 35 ℃, more preferably from 25 ℃ to 35 ℃.
The end of the deashing step can be determined according to conventional methods in the leather processing industry. Preferably, the deashing step can be ended when the cross section of the pelt slit becomes colorless after the addition of phenolphthalein and the float of the deashing step is 6 to 8.8, more preferably about 8. The time of the deashing step is preferably 1 to 6 hours, more preferably 1 to 3 hours.
"About 8" in the present invention means 8.+ -. 0.8.
During the deashing step, the pH of the float is preferably monitored.
The limed pelts can be limed according to the usual liming methods in the leather processing industry.
It is a further object of the present invention to provide the use of an amino acid, an amino acid salt or a protein hydrolysate containing an amino acid and/or an amino acid salt as a deliming agent.
It is a further object of the present invention to provide the use of an amino acid, an amino acid salt or a protein hydrolysate containing an amino acid and/or an amino acid salt as a buffer in a deliming agent.
In the present invention, the technical features mentioned above can be freely combined to form a preferred embodiment.
The invention has the following benefits: (1) The raw materials do not contain boric acid and are in line with safe operation; (2) No ammonium salts are used and thus the ammonia-nitrogen value in the emissions is greatly reduced; (3) No ammonia is released during the deashing process, which contributes to safe operation; (4) The amino acids have a good buffering capacity in the deliming pH range, which enables successful lime removal from the delimed pelt without causing acid swelling, in particular on the grain layer; (5) Amino acids have high solubility in water and small molecules that can rapidly penetrate into the limed pelt; (6) The formation of soluble calcium salts between amino acid compounds and lime results in high lime removal efficiency, which enables clean fur surfaces and soft hand feel of crust leather (crust).
Examples
The following examples are illustrative of the invention but are not intended to limit the invention:
raw materials: organic acid mixture: 50% by weight of succinic acid and 50% by weight of adipic acid.
Example 1
Cowhide (CATTLE HIDE) that had been soaked and ash-impregnated in a conventional manner was used for the application test. The deashing method comprises the following steps:
(A) Pre-deashing:
(i) The limed pelts (weight 16kg, thickness 7 mm) were washed in a rotating drum (drum) at 30℃with 150 wt.% (wt.% based on the weight of the limed pelts) of water; the floats were discharged after 10 minutes;
(ii) Pre-deliming the limed pelt with a mixture of 100 wt.% water, 0.15 wt.% sodium metabisulfite and 0.3 wt.% organic acid mixture at 30 ℃ for 30 minutes, the wt.% being based on the weight of the limed pelt; and
(Iii) Measuring the pH value of the float (8.2) and discharging the float again; and
(B) And (3) deashing:
(iv) Deliming the greyed pelts with a deliming agent comprising 0.2% by weight of an organic acid mixture, 0.15% by weight of sodium metabisulfite, 2.0% by weight of glycine (table 1), the% by weight being based on the weight of the greyed pelts; and
(V) After 120 minutes, the deashing step is ended and the degree of deashing is 100% when the cross section of the pelt incision is not developed with the addition of phenolphthalein and the pH of the float is 8.4.
Thereafter, crust leather was obtained after softening, pickling, chrome tanning, retanning, neutralization, drying and fatliquoring using conventional methods.
Example 2
Cowhide that had been soaked and limed in a conventional manner was used for the application test. The deashing method comprises the following steps:
(A) The pre-deashing step was the same as in example 1;
(B) And (3) deashing:
(iv) Deliming the greyed pelts with a deliming agent comprising 0.2% by weight of an organic acid mixture, 0.15% by weight of sodium metabisulfite, 2.5% by weight of lysine (table 1), the% by weight being based on the weight of the greyed pelts; and
(V) After 120 minutes, the deashing step is ended and the degree of deashing is 100% when the cross section of the pelt incision is not developed with the addition of phenolphthalein and the pH of the float is 8.4.
Thereafter, crust leather was obtained after softening, pickling, chrome tanning, retanning, neutralization, drying and fatliquoring using conventional methods.
Example 3
Cowhide that had been soaked and limed in a conventional manner was used for the application test. The deashing method comprises the following steps:
(A) The pre-deashing step was the same as in example 1;
(B) And (3) deashing:
(iv) Deliming the greyed pelts with a deliming agent comprising 0.2% by weight of an organic acid mixture, 0.15% by weight of sodium metabisulfite, 4% by weight of leucine (table 1), the% by weight being based on the weight of the greyed pelts; and
(V) After 120 minutes, the deashing step is ended and the degree of deashing is 100% when the cross section of the pelt incision is not developed with the addition of phenolphthalein and the pH of the float is 8.5.
Thereafter, crust leather was obtained after softening, pickling, chrome tanning, retanning, neutralization, drying and fatliquoring using conventional methods.
Example 4
Cowhide that had been soaked and limed in a conventional manner was used for the application test. The deashing method comprises the following steps:
(A) The pre-deashing step was the same as in example 1;
(B) And (3) deashing:
(iv) Deliming the greyed pelts with a deliming agent comprising 0.8% by weight of an organic acid mixture, 1% by weight of sodium formate, 4% by weight of arginine (Table 1), the% by weight being based on the weight of the greyed pelts; and
(V) After 120 minutes, the deashing step is ended and the degree of deashing is 100% when the cross section of the pelt slit is not developed in the case of the addition of phenolphthalein and the pH of the float is 7.6.
Thereafter, crust leather was obtained after softening, pickling, chrome tanning, retanning, neutralization, drying and fatliquoring using conventional methods.
Example 5
Cowhide that had been soaked and limed in a conventional manner was used for the application test.
The amino acid content of the collagen hydrolysate was 40wt%.
The deashing method comprises the following steps:
(A) The pre-deashing step was the same as in example 1;
(B) And (3) deashing:
(iv) Deliming the greyed pelts with a deliming agent comprising 0.2wt% of an organic acid mixture, 0.15wt% sodium metabisulfite, 6wt% of collagen hydrolysate (table 1), the wt% being based on the weight of the greyed pelts; and
(V) After 120 minutes, the deashing step is ended and the degree of deashing is 100% when the cross section of the pelt incision is not developed with the addition of phenolphthalein and the pH of the float is 8.5.
Thereafter, crust leather was obtained after softening, pickling, chrome tanning, retanning, neutralization, drying and fatliquoring using conventional methods.
Example 6
Cowhide that had been soaked and limed in a conventional manner was used for the application test.
The amino acid content in the keratin hydrolysate was 43wt%.
The deashing method comprises the following steps:
(A) The pre-deashing step was the same as in example 1;
(B) And (3) deashing:
(iv) Deliming the greyed pelts with a deliming agent comprising 0.2% by weight of an organic acid mixture, 0.15% by weight of sodium metabisulfite, 5% by weight of keratin hydrolysate (table 1), the% by weight being based on the weight of the greyed pelts; and
(V) After 120 minutes, the deashing step is ended and the degree of deashing is 100% when the cross section of the pelt incision is not developed with the addition of phenolphthalein and the pH of the float is 8.5.
Thereafter, crust leather was obtained after softening, pickling, chrome tanning, retanning, neutralization, drying and fatliquoring using conventional methods.
Example 7
Cowhide that had been soaked and limed in a conventional manner was used for the application test. The deashing method comprises the following steps:
(A) The pre-deashing step was the same as in example 1;
(B) And (3) deashing:
(iv) Deashing the limed pelt with a deashing agent comprising 2.0wt% glycine and 2.0wt% lysine (table 1), the wt% being based on the weight of the limed pelt; and
(V) After 120 minutes, the deashing step is ended and the degree of deashing is 100% when the cross section of the pelt incision is not developed with the addition of phenolphthalein and the pH of the float is 8.2.
Thereafter, crust leather was obtained after softening, pickling, chrome tanning, retanning, neutralization, drying and fatliquoring using conventional methods.
Example 8
Cowhide that had been soaked and limed in a conventional manner was used for the application test.
The amino acid content of the collagen hydrolysate was 70wt%.
The deashing method comprises the following steps:
(A) The pre-deashing step was the same as in example 1;
(B) And (3) deashing:
(iv) Deliming the greyed pelts with a deliming agent comprising 0.8wt% of an organic acid mixture, 1wt% of sodium formate, 3.5wt% of collagen hydrolysate (table 1), the wt% being based on the weight of the greyed pelts; and
(V) After 120 minutes, the deashing step is ended and the degree of deashing is 100% when the cross section of the pelt slit is not developed with the addition of phenolphthalein and the pH of the float is 7.8.
Thereafter, crust leather was obtained after softening, pickling, chrome tanning, retanning, neutralization, drying and fatliquoring using conventional methods.
Example 9
Cowhide that had been soaked and limed in a conventional manner was used for the application test.
The amino acid content of the collagen hydrolysate was 70wt%.
The deashing method comprises the following steps:
(A) Pre-deashing:
(i) The limed pelts (weight 7kg, thickness 3.5 mm) were washed in a rotating drum at 30℃with 150 wt.% (wt.% based on the weight of the limed pelts) of water; the floats were discharged after 10 minutes;
(ii) Pre-deliming the limed pelt with a mixture of 100 wt.% water, 0.15 wt.% sodium metabisulfite and 0.3 wt.% organic acid mixture at 30 ℃ for 30 minutes, the wt.% being based on the weight of the limed pelt; and
(Iii) Measuring the pH value of the float (8.2) and discharging the float again; and
(B) And (3) deashing:
(iv) Deliming the greyed pelts with a deliming agent comprising 0.2wt% of an organic acid mixture, 0.2wt% sodium metabisulfite, 1.5wt% of a collagen hydrolysate (table 1), the wt% being based on the weight of the greyed pelts; and
(V) After 120 minutes, the deashing step is ended and the degree of deashing is 100% when the cross section of the pelt slit is not developed with the addition of phenolphthalein and the pH of the float is 7.6.
Thereafter, crust leather was obtained after softening, pickling, chrome tanning, retanning, neutralization, drying and fatliquoring using conventional methods.
Example 10
Cowhide that had been soaked and limed in a conventional manner was used for the application test.
The amino acid content in the keratin hydrolysate was 43wt%.
The deashing method comprises the following steps:
(A) The pre-deashing step was the same as in example 1;
(B) And (3) deashing:
(iv) Deliming the greyed pelts with a deliming agent comprising 0.2% by weight of an organic acid mixture, 0.15% by weight of sodium metabisulfite, 5% by weight of keratin hydrolysate (table 1), the% by weight being based on the weight of the greyed pelts;
(v) After 120 minutes, the deashing step is ended and the degree of deashing is 100% when the cross section of the pelt incision is not developed with the addition of phenolphthalein and the pH of the float is 8.5.
Thereafter, crust leather was obtained after softening, pickling, chrome tanning, retanning, neutralization, drying and fatliquoring using conventional methods.
Example 11
Cowhide that had been soaked and limed in a conventional manner was used for the application test.
The amino acid content in the keratin hydrolysate was 28wt%.
The deashing method comprises the following steps:
(A) The pre-deashing step was the same as in example 1;
(B) And (3) deashing:
(iv) Deashing the ashed pelts with a deashing agent (Table 1) comprising 0.2wt% of an organic acid mixture, 0.15wt% of sodium metabisulfite, 6.5wt% of keratin hydrolysates, all wt% based on the weight of the ashed pelts;
(v) After 120 minutes, the deashing step is ended and the degree of deashing is 100% when the cross section of the pelt incision is not developed with the addition of phenolphthalein and the pH of the float is 8.3.
Thereafter, crust leather was obtained after softening, pickling, chrome tanning, retanning, neutralization, drying and fatliquoring using conventional methods.
Example 12
Cowhide that had been soaked and limed in a conventional manner was used for the application test.
The amino acid content of the collagen hydrolysate was 40wt%.
The deashing method comprises the following steps:
(A) The pre-deashing step was the same as in example 1;
(B) And (3) deashing:
(iv) Deliming the greyed pelt with a deliming agent comprising 0.2wt% organic acid mixture, 0.15wt% sodium metabisulfite, 6wt% collagen hydrolysate solution (table 1), wt% based on the weight of the greyed pelt;
(v) After 120 minutes, the deashing process was ended with 100% deashing when the cross section of the pelt slit was not developed with the addition of phenolphthalein and the pH of the float was 8.5.
Thereafter, crust leather was obtained after softening, pickling, chrome tanning, retanning, neutralization, drying and fatliquoring using conventional methods.
Comparative example 1
Cowhide that had been soaked and limed in a conventional manner was used for the application test.
The deashing method comprises the following steps:
(A) The pre-deashing step was the same as in example 1;
(B) And (3) deashing: deliming the greyed pelts with 0.2wt% organic acid mixture, 0.15wt% sodium metabisulfite, 1.5wt% ammonium sulphate and 0.5wt% ammonium chloride; after 120 minutes, the deashing process was ended with 100% deashing when the cross section of the pelt incision was not developed with the addition of phenolphthalein and the pH of the float was 8.5.
Thereafter, crust leather was obtained after softening, pickling, chrome tanning, retanning, neutralization, drying and fatliquoring using conventional methods.
TABLE 1
All floats of examples 1 to 12 and comparative example 1 were taken to check the NH 3 -N value. The deliming results and crust leather effects of the various examples are shown in table 2.
TABLE 2
As shown in table 2, deliming with ammonium salts, glycine, lysine, leucine, arginine, collagen hydrolysates, keratin hydrolysates achieved a final pH of about 8, which means that the amino acids have a similar buffering capacity as the ammonium salts. In addition, the deashing emissions of amino acids have a NH 3 -N value of about 100ppm, which is less than 5% of the ammonium salt deashing emissions. Low NH 3 -N values can significantly reduce emissions treatment time and cost.
The crust leather obtained from all examples had a uniform colour, a soft hand and a very fine texture, which was comparable to comparative example 1.
Claims (21)
1. A deashing process comprising the steps of:
(A) Pre-deashing: pre-deliming the limed pelts with additives, organic acids and/or carbon dioxide, and
(B) And (3) deashing: the ashed pelts were deashed with an ammonium and boric acid free deashing agent,
Wherein the ammonium and boric acid free de-ashing agent comprises an amino acid component and does not comprise an ammonium compound; the amino acid component comprises amino acids, amino acid salts, and/or protein hydrolysates containing amino acids and/or amino acid salts, and
Wherein the amount of the deliming agent is calculated based on the total amino acids and amino acid salts in the deliming agent, which is 1 wt% to 10 wt% of the delimed pelt;
Wherein the organic acid comprises at least one selected from lactic acid, citric acid, adipic acid, malonic acid, succinic acid, glutaric acid and gluconic acid;
Wherein the additive comprises at least one selected from the group consisting of manganese sulfate, manganese chloride, manganese acetate, sodium formate, potassium formate, sodium bisulfate, sodium metabisulfite, potassium metabisulfite, sodium acetate, potassium acetate, sodium sulfate, potassium sulfate, sodium bisulfate, potassium bisulfate, sodium percarbonate and potassium percarbonate.
2. The deashing process of claim 1 wherein the amino acid is an α -amino acid.
3. The deashing method of claim 1, wherein 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.
4. The deashing process of claim 1 wherein the amino acid salt comprises an alkali metal salt and/or a hydrochloride salt.
5. The deashing process of claim 4 wherein the alkali metal is sodium and/or potassium.
6. The deashing process of claim 1 wherein the protein hydrolysate comprises collagen hydrolysate and/or keratin hydrolysate.
7. The deashing process of claim 1 wherein the organic acid is succinic acid and adipic acid.
8. The deashing process of any one of claims 1 to 7, wherein the content of the amino acid component in the deashing agent is calculated from the content of total amino acids and amino acid salts in the deashing agent, the content of total amino acids and amino acid salts in the deashing agent being 40 wt% to 100wt%, wt% based on the total weight of total amino acids, amino acid salts, organic acids and additives.
9. The deashing process of claim 8 wherein the content of the amino acid component in the deashing agent is calculated from the total amino acid and amino acid salt content in the deashing agent, the total amino acid and amino acid salt content in the deashing agent being 80 wt% to 100 wt%, wt% based on the total weight of total amino acid, amino acid salt, organic acid and additive.
10. The deashing process of any one of claims 1 to 7, wherein the organic acid content in the deashing agent is 25 wt% or less, wt% based on the total weight of total amino acids, amino acid salts, organic acids, and additives.
11. The deashing process of claim 10 wherein the organic acid content of the deashing agent is from 5 wt% to 10 wt%, wt% based on the total weight of the total amino acid, amino acid salt, organic acid and additive.
12. The deashing process of any one of claims 1 to 7, wherein the additive is present in the deashing agent in an amount of 25 wt% or less, wt% based on the total weight of total amino acids, amino acid salts, organic acids, and additives.
13. The deashing process of claim 12 wherein the additive is present in the deashing agent in an amount of 10 wt% or less, wt% based on the total weight of the total amino acid, amino acid salt, organic acid, and additive.
14. The deashing process of any one of claims 1 to 7, wherein the deashing agent comprises the amino acid component, 0 to 20 wt% of the organic acid, and 0 to 25 wt% of the additive, the total amino acid and amino acid salt content in the amino acid component being 55 wt% to 100 wt%, wt% based on the total weight of the amino acid, amino acid salt, organic acid, and additive; the amino acid component is glycine, asparagine, glutamine, lysine, leucine, serine, collagen hydrolysate and/or keratin hydrolysate.
15. The deashing process of claim 14 wherein the deashing agent comprises the amino acid component, 0 to 10 wt% of the organic acid, and 0 to 10 wt% of the additive, the total amino acid and amino acid salt content in the amino acid component being 80 wt% to 100wt%, wt% based on the total weight of the total amino acid, amino acid salt, organic acid, and additive.
16. A deashing process according to claim 1 wherein step (a) comprises (i) washing the limed pelt with water to remove floats; (ii) Pre-deliming said limed pelt with said additives and said organic acids and/or carbon dioxide; and (iii) draining the float when the pH of the float is 8.
17. A deashing process according to claim 1 wherein in step (a) the amount of said additive is from 0.05 wt% to 0.3 wt% of the limed pelt.
18. A deashing process as claimed in claim 17 wherein in step (a) the amount of said additive is from 0.1 wt% to 0.5 wt% of the limed pelt.
19. The deashing process of claim 1 wherein step (B) comprises: (iv) deashing said limed pelt with said deashing agent; and (v) ending the deashing step.
20. The method of deliming according to claim 1, wherein the amount of the deliming agent is calculated based on the total amount of amino acids and amino acid salts in the deliming agent, which is from 1 wt% to 5 wt% of the delimed pelt.
21. A method of deliming according to claim 20, wherein the amount of deliming agent is calculated based on the total amount of amino acids and amino acid salts in the deliming agent, which is from 1 wt% to 2.5% wt% of the delimed pelt.
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| CN109385494A (en) * | 2018-12-03 | 2019-02-26 | 四川大学 | A kind of leather deliming agent of the no ammonium salt without boric acid |
| NL2027083B1 (en) | 2020-12-09 | 2022-07-07 | Stahl Int B V | Process for deliming of hides, skins or pelts |
| EP4032989B1 (en) | 2021-01-22 | 2023-10-11 | TFL Ledertechnik GmbH | Deliming composition and deliming method for deliming skins |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR502225A (en) * | 1919-08-05 | 1920-05-07 | Georges Lengrand | Process of deliming skins in tanneries |
| GB524788A (en) * | 1938-02-07 | 1940-08-14 | Ig Farbenindustrie Ag | Improvements in or relating to the deliming of limed pelts |
| DE2113214A1 (en) * | 1971-03-18 | 1972-09-28 | Diamalt Ag | Leather mfr - with amino acid deliming of hides and drenching with papaine andpancreatine mixt |
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| DE3108428A1 (en) * | 1981-03-06 | 1982-09-23 | Basf Ag, 6700 Ludwigshafen | METHOD FOR DE-SCALING SKIN |
| CN102010917A (en) * | 2010-11-22 | 2011-04-13 | 陕西科技大学 | Ammonia nitrogen-free leather-making deliming agent and preparation method thereof |
| EP2853605A1 (en) * | 2013-09-30 | 2015-04-01 | Rhodia Poliamida E Especialidades Ltda | Tanning process for obtaining leather |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR502225A (en) * | 1919-08-05 | 1920-05-07 | Georges Lengrand | Process of deliming skins in tanneries |
| GB524788A (en) * | 1938-02-07 | 1940-08-14 | Ig Farbenindustrie Ag | Improvements in or relating to the deliming of limed pelts |
| DE2113214A1 (en) * | 1971-03-18 | 1972-09-28 | Diamalt Ag | Leather mfr - with amino acid deliming of hides and drenching with papaine andpancreatine mixt |
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