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EP3425068B1 - Agent de déchaulage exempt d'ammonium et d'acide borique, ses utilisations, processus de détartrage - Google Patents

Agent de déchaulage exempt d'ammonium et d'acide borique, ses utilisations, processus de détartrage Download PDF

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Publication number
EP3425068B1
EP3425068B1 EP18181640.6A EP18181640A EP3425068B1 EP 3425068 B1 EP3425068 B1 EP 3425068B1 EP 18181640 A EP18181640 A EP 18181640A EP 3425068 B1 EP3425068 B1 EP 3425068B1
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Prior art keywords
deliming
acid
amino acid
ammonium
deliming agent
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German (de)
English (en)
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EP3425068A1 (fr
Inventor
Li Rong HE
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Stahl International BV
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Stahl International BV
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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 ammonium and boric acid free deliming agent, and to a leather deliming process by using the said deliming agent.
  • pretreatments for raw pelts should be done before tanning and crusting.
  • Liming is one of the pretreatments to remove hair and unwanted proteins usually by soaking the pelts in a lime bath. Then it is necessary to delime the pelts so as to bring them into a proper state of alkalinity. Deliming is about removing calcium hydroxide from pelts including surfaces and inner parts thereof and lowering pelts pH value 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 sufficient in lime removal.
  • ammonium salts such as ammonium sulfate, ammonium chloride, etc.
  • US 2,318,454 which was granted May 4, 1943 used ammonium salt as deliming component.
  • Ammonium salts have been widely accepted in leather industry due to the following characteristics: i) cheap raw material prices compared with organic compounds; ii) 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 purpose, 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 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 application in industry.
  • the disadvantages are: i) the ammonia released during deliming leads to the workers' exposure in unsafe environment; ii) the high NH 3 -N content in tannery effluent made it necessary to perform NH 3 -N removal, which increases the cost and duration in wastewater treatment.
  • inorganic acid like boric acid
  • small molecular organic acids including lactic acid, citric acid, succinic acid, or adipic acid
  • macromolecule 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).
  • SVHC substance of very high concern
  • REACH Registration, evaluation, authorization and restriction of chemicals
  • 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 liming float.
  • WO 2013/107233 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.
  • DE2113214A1 describes the treatment of limed pelts with proteolytic enzymes using in a first step aqueous solutions of amino acids or their salts and in a second step a proteolytic enzyme mixture of papain and pancreatin at 20°C to 50°C until the desired bating level is achieved.
  • the deliming step comprises also traditional deliming agents such as ammonium sulfate, sodium bisulfate or ammonium chloride besides aqueous amino acids or aqueous amino acid salts.
  • the deliming agent comprises amino acid component.
  • 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 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 to prevent acid swelling on the grain layer.
  • the carboxylic groups After 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.
  • Amino acids in the present invention can be individually used in the deliming agent or combined with some additives, and achieve good deliming effect with no help of ammonium salts, thus enabling the replacement of conventionally used boric acid and ammonium salts.
  • the invention also discloses a deliming process.
  • the present deliming agent has the following features: i) amino acids are utilized as deliming agent, which are safe compounds both to environment and workers; ii) amino acids will not introduce NH 3 -N burden into deliming effluent, therefore the reduction of NH 3 -N generated in deliming process can be achieved.
  • the present deliming agent 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.
  • the object of the present invention is therefore to provide an ammonium and boric acid free deliming agent, which comprises amino acid component and no ammonium compound; the amino acid component comprises amino acid, amino acid salt, and/or protein hydrolysate which contains amino acid and/or amino acid salt.
  • the amino acid component could mean any component so long as it comprises amino acid and/or amino acid ion and could react with Ca(OH) 2 without bringing any negative effect to deliming.
  • the amino acid component in the present invention could comprise amino acid, amino acid salt, and/or protein hydrolysate which contains amino acid and amino acid salt.
  • the amino acid 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 acid 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 amounts of experiments, it was found that glycine, serine, asparagine, leucine, glutamine and/or lysine are more preferably.
  • the amino acid 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 in the present invention is preferably water soluble amino acid salt.
  • the common amino acid salt which will not precipitate with calcium ion could be used in the present invention.
  • the amino acid salt preferably comprises alkali metal salt and/or hydrochloride salt.
  • the alkali metal is preferably sodium and/or potassium.
  • the protein hydrolysate is a mixture of amino acids and/or amino acid salts, which could be prepared according to the conventional method, for example by splitting proteins with acid, alkali, and/or enzyme. All proteins that could be hydrolyzed into amino acid and/or amino acid salt can be used in the present invention.
  • the protein hydrolysate comprises collagen hydrolysate and/or keratin hydrolysate.
  • the degree of hydrolysis is not limited in the present invention, so long as there is amino acid in the protein hydrolysate.
  • the hydrolyzation into high content of amino acids level is preferred.
  • the deliming agent in the present invention could further comprise organic acid and/or carbon dioxide, the organic acid herein excluding amino acid.
  • the organic acids for use in the present invention are those that are commonly used in leather manufacturing processes.
  • 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 succinic acid and adipic acid.
  • the combination of the amino acid component and the organic acid could realize better deliming efficiency.
  • the deliming agent in the present invention could further comprise additives.
  • the additives which come into consideration in the present invention are the conventional additives in leather manufacturing industry.
  • the preferable additive is 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 content of 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 is used to calculate the content of the total amino acids and the amino acid salts.
  • the content of the total amino acids and the amino acid salts in the deliming agent could be chosen according to the conventional methods in leather process industry.
  • the content of the total amino acids and the amino acid salts in the deliming agent is 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 total amino acids, the amino acid salts, the organic acid and the additives.
  • the content of the organic acid in the deliming agent could be chosen according to conventional methods in leather process industry, preferably is 25 wt% or less; more preferably 5-20 wt%; most preferably 5-10 wt%, wt% is based on the total weight of the total amino acids, the amino acid salts, the organic acid and the additives.
  • the content of the additives in the deliming agent could be chosen according to conventional method in leather process industry, preferably is 25 wt% or less, more preferably 20 wt% or less, most preferably 10 wt% or less, wt% is based on the total weight of the total amino acids, the amino acid salts, the organic acid and the additive.
  • the deliming agent comprises the amino acid component in which the content of the total amino acids and the amino acid salts is 55-100 wt%, 0-20 wt% of the organic acid and 0-25 wt% of the additive, wt% is all based on the total weight of the total amino acids, the amino acid salts, the organic acid and the additives; and the amino acid component is glycine, asparagine, glutamine, lysine, leucine, serine, collagen hydrolysate and/or keratin hydrolysate.
  • the deliming agent comprises the amino acid component in which the content of the total amino acids and the amino acid salts is 80-100 wt%, 0-10 wt% of the organic acid and 0-10 wt% of the additives, wt% is all based on the total weight of the total amino acids, the amino acid salts, the organic acid and the additive; the amino acid component is glycine, lysine, serine, leucine, collagen hydrolysate and/or keratin hydrolysate.
  • Another object of the present invention is to provide a deliming process, comprising deliming step: deliming limed pelt with the deliming agent of the present invention.
  • the pelt in the present invention could be also referred to 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, deer, or from common birds.
  • the deliming process comprises: (A) a pre-deliming step: pre-deliming the limed pelt with the additive, the organic acid and/or the carbon dioxide; and (B) the deliming step: deliming the limed pelt with the deliming agent.
  • the step (A) preferably comprises (i) washing the limed pelt with water, removing the float; (ii) pre-deliming the limed pelt with the additive, and the organic acid and/or carbon dioxide; and (iii) when the pH value of float is about 8, draining the float.
  • the deliming step (B) shall be conducted as deliming the limed pelt in an aqueous solution of the deliming agent.
  • the additive in step (A) is the same additive mentioned above in the deliming agent.
  • the organic acid in step (A) is the same organic acid mentioned above in the deliming agent.
  • the amount of the additive could be chosen according to conventional methods in the leather manufacturing process, preferably is 0.05-0.3 wt% of the limed pelt.
  • the amount of the organic acid could be chosen according to conventional methods in the leather manufacturing process, preferably is 0.1-0.5 wt% of the limed pelt.
  • the amount of the water in step (i) or in the aqueous solution of the deliming agent could be chosen according to conventional methods in leather manufacturing process, preferably is 300 wt% of the limed pelt or less, more preferably 200 wt% of the limed pelt or less, based on the total weight of the limed pelt.
  • the step (B) preferably comprises: (iv) deliming the limed pelt with the deliming agent; and (v) ending the deliming step.
  • 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 1-10 wt% of the limed pelt, more preferably 1-5 wt% of the limed pelt, most preferably 1-2.5 wt% of the limed pelt.
  • the deliming process in the present invention could be conducted in the conventional temperature range, preferred is 5°C-35°C, more preferred is 25°C-35°C.
  • the end of the deliming step could be decided according to conventional methods in leather process industry.
  • the deliming step could 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 invention refers to 8 ⁇ 0.8.
  • pH value of the float is preferably monitored.
  • the limed pelt could be limed according to conventional liming methods in leather process industry.
  • the present invention has the following benefits: (1) raw material does not contain boric acid, and is compliant with safe operation; (2) without using ammonium salts and hence greatly reduces the ammonia-nitrogen values in the effluent; (3) no ammonia releasing during deliming process, which facilitates safe operation; (4) amino acids have good buffering capacity during deliming pH range, which enables the successful lime removal from the limed pelts without inducing acid swelling especially on the grain layer; (5) amino acids have high solubility in water and small molecules which enables fast penetration into limed pelts; (6) the formation of soluble calcium salts between amino acids compounds and lime resulting in high lime removal efficiency, which enables a clean pelt surface and soft handle feeling of the crust.
  • the deliming process comprises the following steps:
  • crust was obtained after bating, pickling, chrome tanning, retanning, neutralization, dying and fat-liquoring.
  • the deliming process comprises the following steps:
  • crust was obtained after bating, pickling, chrome tanning, retanning, neutralization, dying and fat-liquoring.
  • the deliming process comprises the following steps:
  • crust was obtained after bating, pickling, chrome tanning, retanning, neutralization, dying and fat-liquoring.
  • the deliming process comprises the following steps:
  • crust was obtained after bating, pickling, chrome tanning, retanning, neutralization, dying and fat-liquoring.
  • the content of the amino acids in the collagen hydrolysate is 40 wt%.
  • the deliming process comprises the following steps:
  • crust was obtained after bating, pickling, chrome tanning, retanning, neutralization, dying and fat-liquoring.
  • the content of the amino acids in the keratin hydrolysate is 43 wt%.
  • the deliming process comprises the following steps:
  • crust was obtained after bating, pickling, chrome tanning, retanning, neutralization, dying and fat-liquoring.
  • the deliming process comprises the following steps:
  • crust was obtained after bating, pickling, chrome tanning, retanning, neutralization, dying and fat-liquoring.
  • the content of the amino acids in the collagen hydrolysate is 70 wt%.
  • the deliming process comprises the following steps:
  • crust was obtained after bating, pickling, chrome tanning, retanning, neutralization, dying and fat-liquoring.
  • the content of the amino acids in the collagen hydrolysate is 70 wt%.
  • the deliming process comprises the following steps:
  • crust was obtained after bating, pickling, chrome tanning, retanning, neutralization, dying and fat-liquoring.
  • the content of the amino acids in the keratin hydrolysate is 43 wt%.
  • the deliming process comprises the following steps:
  • crust was obtained after bating, pickling, chrome tanning, retanning, neutralization, dying and fat-liquoring.
  • the content of the amino acids in the keratin hydrolysate is 28 wt%.
  • the deliming process comprises the following steps:
  • crust was obtained after bating, pickling, chrome tanning, retanning, neutralization, dying and fat-liquoring.
  • the content of the amino acids in the collagen hydrolysate is 40 wt%.
  • the deliming process comprises the following steps:
  • crust was obtained after bating, pickling, chrome tanning, retanning, neutralization, dying and fat-liquoring.
  • the deliming process comprises the following steps:
  • deliming with ammonium salts glycine, lysine, leucine, arginine, collagen hydrolysate, keratin hydrolysate achieved the end pH value of around 8, which means that amino acids have similar buffering capacity with 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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  • 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)

Claims (21)

  1. Agent de déchaulage sans ammonium et sans acide borique, qui comprend un composant acide aminé et aucun composé ammonium ; le composant acide aminé comprenant un acide aminé, un sel d'acide aminé et/ou un hydrolysat de protéine qui contient un acide aminé et/ou un sel d'acide aminé.
  2. Agent de déchaulage sans ammonium et sans acide borique selon la revendication 1, dans lequel l'acide aminé est un acide aminé-a.
  3. Agent de déchaulage sans ammonium et sans acide borique selon la revendication 1 ou 2, dans lequel l'acide aminé comprend au moins un acide aminé choisi dans le groupe constitué par la glycine, l'alanine, la valine, la leucine, l'isoleucine, la phénylalanine, le tryptophane, la tyrosine, l'histidine, la sérine, thréonine, cystéine, acide aspartique, acide glutamique, asparagine, glutamine, lysine, arginine, proline, méthionine et sélénocystéine.
  4. Agent de déchaulage exempt d'ammonium et d'acide borique selon l'une quelconque des revendications précédentes, dans lequel le sel d'acide aminé comprend un sel de métal alcalin et/ou un sel de chlorhydrate.
  5. Agent de déchaulage sans ammonium et sans acide borique selon la revendication 4, dans lequel le métal alcalin est le sodium et/ou le potassium.
  6. Agent de déchaulage sans ammonium et sans acide borique selon l'une quelconque des revendications précédentes, dans lequel l'hydrolysat de protéines comprend un hydrolysat de collagène et/ou un hydrolysat de kératine.
  7. Agent de déchaulage sans ammonium et sans acide borique selon l'une quelconque des revendications précédentes, dans lequel l'agent de déchaulage comprend en outre de l'acide organique et/ou du dioxyde de carbone.
  8. Agent de déchaulage sans ammonium et sans acide borique selon la revendication 7, dans lequel l'acide organique comprend au moins un acide choisi dans le groupe constitué par l'acide lactique, l'acide citrique, l'acide adipique, l'acide malonique, l'acide succinique, l'acide glutarique et l'acide gluconique ; de préférence est l'acide succinique et l'acide adipique.
  9. Agent de déchaulage sans ammonium et sans acide borique selon l'une quelconque des revendications précédentes, dans lequel l'agent de déchaulage comprend en outre un additif.
  10. Agent de déchaulage sans ammonium et sans acide borique selon la revendication 9, dans lequel
    l'additif comprend au moins un additif choisi dans le groupe consistant en sulfate de manganèse, chlorure de manganèse, acétate de manganèse, formiate de sodium, formiate de potassium, hydrogénosulfite de sodium, métabisulfite de sodium, métabisulfite de potassium, acétate de sodium, acétate de potassium, sulfate de sodium, sulfate de potassium, hydrosulfate de sodium, hydrosulfate de potassium, percarbonate de sodium et percarbonate de potassium.
  11. Agent de déchaulage sans ammonium et sans acide borique selon l'une quelconque des revendications précédentes, dans lequel la teneur en composant d'acide aminé dans l'agent de déchaulage est calculée en fonction de la teneur en acides aminés et en sels d'acides aminés totaux dans l'agent de déchaulage, la teneur en acides aminés et en sels d'acides aminés totaux dans l'agent de déchaulage étant de 40 à 100% en poids, de préférence de 55 à 100% en poids, plus préférablement 70 à 100% en poids, le plus préférablement de 80 à 100% en poids, le % en poids étant basé sur le poids total des acides aminés et des sels d'acides aminés totaux, de l'acide organique et de l'additif.
  12. Agent de déchaulage sans ammonium et sans acide borique selon la revendication 7 ou 8, dans lequel la teneur en acide organique dans l'agent de déchaulage est de 25% en poids ou moins, de préférence de 5 à 20% en poids, plus préférablement de 5 à 10% en poids, le % en poids étant basé sur le poids total des acides aminés et des sels d'acides aminés totaux, de l'acide organique et de l'additif.
  13. Agent de déchaulage sans ammonium et sans acide borique selon les revendications 9 ou 10, dans lequel la teneur de l'additif dans l'agent de déchaulage est de 25% en poids ou moins, de préférence 20% en poids ou moins, plus préférablement 10% en poids ou moins, le % en poids étant basé sur le poids total des acides aminés et des sels d'acides aminés totaux, de l'acide organique et de l'additif.
  14. Agent de déchaulage sans ammonium et sans acide borique selon l'une quelconque des revendications précédentes, dans lequel l'agent de déchaulage comprend le composant acide aminé dans lequel la teneur en acides aminés et en sels d'acides aminés totaux est de 55 à 100% en poids, 0 -20% en poids de l'acide organique et 0-25% en poids de l'additif, le % en poids étant basé sur le poids total des acides aminés et des sels d'acides aminés totaux, de l'acide organique et de l'additif ; le composant acide aminé est la glycine, l'asparagine, la glutamine, la lysine, la leucine, la sérine, l'hydrolysat de collagène et/ou l'hydrolysat de kératine.
  15. Agent de déchaulage sans ammonium et sans acide borique selon la revendication 14, dans lequel l'agent de déchaulage comprend le composant acide aminé dans lequel la teneur en acides aminés et en sels d'acides aminés totaux est de 80 à 100% en poids, 0 à 10% en poids de l'acide organique et 0 à 10% en poids de l'additif, le % en poids étant basé sur le poids total des acides aminés et des sels d'acides aminés totaux, de l'acide organique et de l'additif.
  16. Procédé de déchaulage, comprenant l'étape de déchaulage consistant à déchauler la peau chaulée avec l'agent de déchaulage exempt d'ammonium et d'acide borique tel que défini dans l'une quelconque des revendications précédentes.
  17. Procédé de déchaulage selon la revendication 16, comprenant les étapes suivantes :
    (A) une étape de pré-déchaulage comprenant le pré-déchaulage de la peau chaulée avec l'additif, l'acide organique et/ou le dioxyde de carbone ; l'acide organique tel que défini dans la revendication 8, l'additif tel que défini dans la revendication 10 ; et
    (B) l'étape de déchaulage comprenant le déchaulage de la peau chaulée avec l'agent de déchaulage.
  18. Procédé de déchaulage selon la revendication 17, dans lequel l'étape (A) comprend (i) le lavage de la peau chaulée avec de l'eau, en enlevant le milieu d'application ; (ii) le pré-déchaulage de la peau chaulée avec l'additif et l'acide organique et/ou le dioxyde de carbone ; et (iii) lorsque la valeur de pH du milieu d'application est d'environ 8, le vidange du milieu d'application.
  19. Procédé de déchaulage selon la revendication 17 ou 18, dans lequel à l'étape (A), la quantité d'additif est de 0,05 à 0,3% en poids, de préférence de 0,1 à 0,5% en poids de la peau chaulée.
  20. Procédé de déchaulage selon au moins l'une des revendications 17 à 19, dans lequel l'étape (B) comprend : (iv) le déchaulage de la peau chaulée avec l'agent de déchaulage ; et (v) la terminaison de l'étape de déchaulage.
  21. Procédé de déchaulage selon au moins l'une des revendications 16 à 20, dans lequel la quantité d'agent de déchaulage est calculée sur la base de la quantité des acides aminés et des sels d'acides aminés totaux dans l'agent de déchaulage, la quantité des acides aminés et les sels d'acides aminés totaux dans l'agent de déchaulage étant de 1 à 10% en poids, de préférence de 1 à 5% en poids, plus préférablement de 1 à 2,5% en poids de la peau chaulée.
EP18181640.6A 2017-07-06 2018-07-04 Agent de déchaulage exempt d'ammonium et d'acide borique, ses utilisations, processus de détartrage Active EP3425068B1 (fr)

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EP3425068B1 true EP3425068B1 (fr) 2021-08-04

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CN109385494A (zh) * 2018-12-03 2019-02-26 四川大学 一种无铵盐无硼酸的皮革脱灰剂
NL2027083B1 (en) 2020-12-09 2022-07-07 Stahl Int B V Process for deliming of hides, skins or pelts
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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