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WO2025099628A1 - Procédé de production d'hydrolysats de protéines à partir de résidus de traitement de cuir tanné selon une technologie sans métal - Google Patents

Procédé de production d'hydrolysats de protéines à partir de résidus de traitement de cuir tanné selon une technologie sans métal Download PDF

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Publication number
WO2025099628A1
WO2025099628A1 PCT/IB2024/061038 IB2024061038W WO2025099628A1 WO 2025099628 A1 WO2025099628 A1 WO 2025099628A1 IB 2024061038 W IB2024061038 W IB 2024061038W WO 2025099628 A1 WO2025099628 A1 WO 2025099628A1
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Prior art keywords
broth
phase
obtaining
acid
filtration
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Alberto CATTAZZO
Gabriele Rocchio
Andrea DALLA BENETTA
Massimo Costantino Neresini
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Sicit Group SpA
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Sicit Group SpA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
    • C08L89/04—Products derived from waste materials, e.g. horn, hoof or hair
    • C08L89/06—Products derived from waste materials, e.g. horn, hoof or hair derived from leather or skin, e.g. gelatin

Definitions

  • the invention relates to a process for obtaining products deriving from animal waste, preferably protein hydrolysates obtained from residues of leather processing as a tanning waste.
  • WW Wet White
  • aldehydes for example, glutaraldehyde or glutaric aldehyde (GA) (CAS 111-30-8)
  • GA glutaric aldehyde
  • the raw material i.e. the waste of the tanning industry deriving from the manufacturing process of the leather tanned with aldehydes (for example, glutaraldehyde) and tannins
  • aldehydes for example, glutaraldehyde
  • tannins organic tanning agents which are very affine to collagen, such as aldehydes (for example, glutaraldehyde) and tannins, and, at the same time, intrinsically more difficult to be removed than the metal tannings.
  • the removal of the tanning GA from the product protein hydrolysate is fundamental since aldehydes are generally characterized by remarkable chemi cal -physical and toxicological dangers, both for humans and environment, for example, glutaraldehyde (CAS 111-30-8), is classified according to the regulation (EC) N.
  • H301 toxic if ingested
  • H314 may cause severe skin burns and severe eye injury
  • H317 may cause a skin allergic reaction
  • H330 lethal if inhaled
  • H335 may cause respiratory irritation
  • H334 may cause allergic or asthmatic symptoms or respiratory difficulty if inhaled
  • H400 very toxic for aquatic organisms
  • H411 toxic for the aquatic organisms with long-lasting effects
  • aldehydes such as glutaraldehyde
  • glutaraldehyde in some cases are inserted in the list of the Substances of Very High Concern (SVHC) and on April, 12 th 2023 glutaraldehyde, in particular, was recommended from ECHA (European Chemicals Agency) to be inserted in the list of the substances subjected to authorization.
  • ECHA European Chemicals Agency
  • tannins they can be natural or synthetic.
  • the natural tannins used in the tanning industry can be classified in three groups: (i) hydrolysable tannins, based on sugars, mainly glucose, wherein the aliphatic hydroxyls are esterified from pyrogallic acid derivatives; (ii) condensed tannins (more common in the tanning processes) characterized by a flavonoid ring structure and different from each other for a different hydroxyl pattern; (iii) complex tannins (less common in the tanning processes) consisting of a mixture of different kinds of tannins.
  • the condensed tannins can also covalently react with the lysine (Lys) side groups of collagen through quinoid species. For this reason, about 5-10% of tannins is not removable from the agents breaking the hydrogen bonds.
  • the tannin content in the final product can reach 30% by weight, and this greatly influences the processability and the physical properties of the leather.
  • the vegetable tanned leather is highly hydrophilic.
  • the synthetic tannins termed Syntans, are very often used in the tanning operation. Generally, they are obtained through phenol sulfonation and subsequent polymerization with formaldehyde.
  • the need for a removal of the residual tannins (both natural and synthetic) of the tanning process is mostly due to an ethic and commercial factor: the product without the tanning is chemically purer, thus appearing lighter and clearer and highly sustainable.
  • the present invention relates to a process for obtaining a protein hydrolysate purified, or free from, aldehydes (for example, glutaraldehyde) and/or tannins from a raw material which is a waste (residue) of animal origin resulting from the manufacturing process comprising, or consisting of, shaving, and/or trimming of leather tanned with aldehydes (for example, glutaraldehyde) and tannins, comprising the steps of: al) optional storage and supply of the raw material; bl) acid hydrolysis of the raw material by the addition of water to obtain an initial suspension and further addition of an acid selected from sulphuric acid, hydrochloric acid, nitric acid, acetic acid, preferably sulphuric acid; cl) first separation by a technique selected from filtration, centrifugation, and decantation, preferably filtration, thus obtaining at least two phases: i) an aqueous phase (or acid broth), and ii) a
  • a further object of the present invention is a cake (ii) obtainable by step cl) of the process of the invention and its use as an energy source after combustion.
  • the invention further relates to the use of the cake (ii) obtainable by step cl) of the process of the invention alone or in combination with the cake (vii) obtainable by step hl) as a soil improver and agricultural fertilizer.
  • Figure 1 shows the figurative scheme of the process of the invention.
  • pre-treating according to the process as described below a substrate (raw material) which is a waste (residue) of animal origin resulting from the shaving and/or trimming process of leather tanned with aldehydes (for example, glutaraldehyde) and/or tannins, also called processing of leather tanned with aldehydes (for example, glutaraldehyde) and/or with tannins (or RG), it is possible to make the tanning process completely circular and environmentally friendly and, at the same time, obtaining both a protein hydrolysate to be used as a bio-stimulant and at least an intermedial substrate (cake) usable as a soil improver and agricultural fertilizer and/or as an energy source, since characterized by a high calorific power.
  • aldehydes for example, glutaraldehyde
  • tannins also called processing of leather tanned with aldehydes (for example, glutaraldehyde) and/or with tannins (or RG
  • - “waste” or “residue” of animal origin means the residue deriving from the processing comprising, or consisting of, shaving, and/or trimming of animal leather already subjected to a tanning process with aldehydes (for example, glutaraldehyde) and/or tannins “RG;”
  • GRAC process or “GRAC” process of removal of aldehydes (for example, glutaraldehyde) and tannins by condensation/acid hydrolysis;
  • UF ultrafiltration
  • MWCO molecular weight cut-off
  • Object of the invention is a process for obtaining a protein hydrolysate purified, or free from aldehydes (for example, glutaraldehyde) and/or tannins from a raw material which is a waste (residue) of animal origin resulting from the manufacturing process comprising, or consisting of, shaving, and/or trimming of leather tanned with aldehydes (for example, glutaraldehyde) and/or tannins (RG), comprising the steps of: al) optional storage and supply of the raw material; bl) acid hydrolysis of the raw material by the addition of water to obtain an initial suspension and further addition of an acid selected from sulphuric acid, hydrochloric acid, nitric acid, acetic acid, preferably sulphuric acid; cl) first separation by a technique selected from filtration, centrifugation, and decantation, preferably filtration, thus obtaining at least two phases: i) an aqueous phase (or acid broth), and ii
  • aldehydes for example, glutaraldehyde
  • the inventors have surprisingly found that the use of a pre-treatment of the waste (residue) of animal origin resulting from the tanning industry, and specifically a waste resulting from the manufacturing process comprising, or consisting of, shaving and/or trimming of leather tanned with aldehydes (for example, glutaraldehyde) and/or tannins, comprising a first acid hydrolysis, followed by filtration and neutralization steps, allows to obtain a neutralized purified broth, suitable to be subjected to the subsequent basic hydrolysis, filtration and calcium precipitation steps, to obtain a protein hydrolysate purified from impurities, such as tannins and aldehydes (for example, glutaraldehyde), normally difficult to be removed, since organic and having high affinity with the collagen present in the aforesaid waste (or residue) of animal origin.
  • aldehydes for example, glutaraldehyde
  • tannins for example, glutaraldehyde
  • the process of the invention through the specific pre-treatment steps, allows to obtain a cake (ii) comprising the tannins precipitated during the acid hydrolysis step, which can be used as an energy source after combustion, in a perspective of complete circularity of the process.
  • said cake can be used to produce energy feeding the process itself, making the latter self-sufficient, or it can be used externally to provide heat energy to other plants.
  • the process of the invention allows to obtain, following the basic hydrolysis step and subsequent filtration, a second cake (vii) rich in calcium sulfate (CaSC ) and lime (Ca(OH)2) which can be used alone, or after mixing with the first cake rich in tannins (ii), as a soil improver and agricultural fertilizer, i.e. as a neutralizer for agricultural soils acidified during the intensive agriculture cycles.
  • a second cake (vii) rich in calcium sulfate (CaSC ) and lime (Ca(OH)2) which can be used alone, or after mixing with the first cake rich in tannins (ii), as a soil improver and agricultural fertilizer, i.e. as a neutralizer for agricultural soils acidified during the intensive agriculture cycles.
  • such raw material is withdrawn from tanneries and optionally placed in a suitable accumulation tank in an optional storage step al).
  • the process of the invention comprises in step bl) an acid hydrolysis of the raw material by the addition of water to obtain an initial suspension and a further addition of an acid preferably selected from sulphuric acid, hydrochloric acid, nitric acid, acetic acid, more preferably sulphuric acid.
  • step bl) the acid, preferably sulphuric acid, can be added until a pH from 0 to 4, preferably a pH comprised from 1 to 2, more preferably equal to 1, is reached.
  • a pH from 0 to 4 preferably a pH comprised from 1 to 2, more preferably equal to 1
  • said step bl) can occur at a temperature comprised in a range from 50 to 160 °C, preferably from 80 to 140 °C, more preferably equal to 110 °C, and for a time from 1 to 15 hours, preferably from 1 to 10 hours, more preferably equal to 1.5 or 5 hours or 8 hours.
  • the sulphuric acid preferably in an aqueous solution 40% by weight on the total weight of the solution is added in a concentration ranging from 0.5% to 5 by weight, preferably 1 or 4% by weight with respect to the total weight of the initial suspension.
  • step bl) occurs at atmospheric pressure, i.e. 101325 Pa.
  • step bl) can be carried out at a pressure comprised from 101325 Pa (1 atm) to 506625 Pa (5 atm).
  • a step bl’) can be carried out consisting of cooling the resulting slurry from step bl) at a temperature comprised from 5 °C to 20° C, preferably 10 °C.
  • the process of the invention comprises a step cl) of first separation, wherein the raw material resulting from step bl), is subjected to a first separation by means of a technique selected from filtration, centrifugation, and decantation, preferably filtration, thus obtaining at least two phases: i) an aqueous phase (or acid broth), and ii) a first solid phase (or cake).
  • Step cl) of first separation occurs preferably by filtration.
  • step cl) the phase ii), i.e. the first solid phase (or cake), contains the tannins precipitated during the acid hydrolysis step bl) and it is separated from the aqueous phase i) (acid broth) and only the phase i) is subjected to the subsequent steps, while the solid phase ii) (or cake) can be used as an energy source after combustion, in a perspective of complete circularity of the process.
  • said cake ii) can be used to produce energy, after combustion, which feeds the process itself, making the latter self-sufficient, or it can be used externally to provide heat energy to other plants.
  • the cake ii) has a %DM preferably equal to 74%, and a lower calorific power, determined by the UNI CEN/TS 16023:2004 regulation, preferably equal to 24000 kJ/Kg.
  • Step cl) can be optionally followed by a step cl’) preferably of filtration, preferably on diatomaceous earth, more preferably by means of the technique of microfiltration of the aqueous phase i) (or acid broth) before subjecting it to the subsequent treatment of step dl).
  • the process of the invention comprises a subsequent step dl) of pH adjustment of the phase i) (or acid broth) with the addition of a pH regulator which is a base selected from the group comprising, or consisting of, Ca(OH>2, NaOH, Mg(0H)2, KOH, NH3, preferably NH3, until a pH comprised from 6.0 to 8.0, preferably equal to 7.0, is reached thus obtaining a phase iii) (clear broth).
  • the pH regulator is added until a pH of the phase iii) (clear broth) ranging from 6 to 8, preferably equal to 7, is reached at 15 °C.
  • an ammonia aqueous solution is added, more preferably having a concentration ranging from 20% to 33%, even more preferably equal to 30% by weight with respect to the total weight of the ammonia solution, or ammonia-enriched air (2 atm, NH3 5-10 g/NMC) is bubbled, to raise the pH of phase iii) (clear broth) to a pH comprised from 6 to 8, preferably equal to 7, thus facilitating the subsequent separation.
  • Said step dl) can occur at a temperature from 5 °C to 20 °C, preferably 15 °C.
  • Step dl) can be optionally followed by a step dl’) preferably of filtration, preferably on diatomaceous earth, more preferably by means of the technique of microfiltration, of the aqueous phase iii) (or clear broth), before subjecting it to the subsequent treatment of step el).
  • a step dl’ preferably of filtration, preferably on diatomaceous earth, more preferably by means of the technique of microfiltration, of the aqueous phase iii) (or clear broth), before subjecting it to the subsequent treatment of step el).
  • Step el) allows to further purify the collagen from the residual tannins of phase iii) of step bl).
  • the soluble (not precipitable) tannins can stay as residues after the hydrolysis of step bl) and are separated in this membrane filtration step.
  • step el The ultrafiltration of step el) is therefore carried out preferably on a membrane, more preferably with a membrane having a molecular weight cut-off (MWCO) ranging from 50 kDa to 10 kDa, preferably of 30 kDa.
  • MWCO molecular weight cut-off
  • step el From the filtration of step el) at least two fractions result: iv) an unpurified homogeneous phase (unpurified liquid retentate); and v) a homogeneous phase substantially or completely free from tannings (purified permeate or purified broth).
  • the unpurified homogeneous phase (unpurified liquid retentate iv)) can instead undergo an optional mixing in a step fl) with the raw material (the waste (residue)) of step al), and therefore being re-introduced at the head of the present process of the invention, to be subsequently subjected to the hydrolysis step bl) for its complete recycle.
  • the homogeneous phase v) (purified permeate or purified broth) is therefore substantially or completely free from tannings.
  • a step el’) of washing of the unpurified homogeneous phase iv) (unpurified liquid retentate) with water and subsequent step el”) of further optional separation by ultrafiltration with a polymeric membrane having MWCO of 10 KDa can be optionally present, thus obtaining at least two fractions: v’) an unpurified homogeneous phase (liquid retentate) to be added to phase iv); and v”) a homogeneous phase substantially or completely free from tannings (or purified broth or purified permeate) to be added to phase v).
  • phase v) (with or without the addition of phase v’)) can be further treated to reach the required analytical standards and in particular to reach a percentage of free amino acids (AA F ree) of 10%.
  • the process comprises a further step gl) of basic hydrolysis, only for phase v) thus obtaining a phase vi) basic suspension (or basic slurry).
  • phase gl) of basic treatment occurs by basic hydrolysis of phase v) (purified permeate or purified broth).
  • the basic hydrolysis occurs at atmospheric pressure, preferably in a reactor under stirring, with the addition of a basifying agent selected from the group comprising, or consisting of, Ca(OH)2, NaOH, Mg(0H)2, KOH, preferably (Ca(OH)2).
  • a basifying agent selected from the group comprising, or consisting of, Ca(OH)2, NaOH, Mg(0H)2, KOH, preferably (Ca(OH)2).
  • said basic hydrolysis can be carried out at a pH comprised form 10 to 13, for a time comprised from 1 to 10 hours, preferably 2 or 5 hours, and at a temperature comprised from 90 to 145 °C, preferably at 95 °C.
  • ammonia vapors develop, which can be optionally reintroduced in a step gl’), in step cl) of pH adjustment and then stripped and recycled.
  • step gl) of basification of phase v) occurs by basification of phase v) and ammonia stripping.
  • the basification step gl) allows to obtain a phase vi) basic suspension (or basic slurry).
  • the process comprises a further step hl) of third separation, only of phase vi) basic suspension (or basic slurry), by a technique selected from filtration, centrifugation, and decantation, preferably filtration, even more preferably filtration on filter cloth, thus separating the residues and obtaining at least two fractions: vii) a second solid phase (or cake); viii) a clear basic broth.
  • phase vi) is then separated yielding a phase vii) (clear basic broth), for example yellow-orange colored, and a second solid phase vii) (or cake), mainly consisting of undissolved lime (CaOH)2) and precipitated calcium sulphate (CaSC ).
  • a phase vii) (clear basic broth), for example yellow-orange colored
  • a second solid phase vii) (or cake), mainly consisting of undissolved lime (CaOH)2) and precipitated calcium sulphate (CaSC ).
  • Said cake vii) can be mixed with the first solid phase of step cl), i.e. the cake ii).
  • said cake vii) is rich in calcium sulphate (CaSC ) and lime (Ca(OH)2) and can be used alone, or after mixing with the first cake rich in tannins ii), as a soil improver and agricultural fertilizer, i.e. as a neutralizer for agricultural soils acidified during the intensive agriculture cycles.
  • CaSC calcium sulphate
  • Ca(OH)2 lime
  • said cake vii) is rich in calcium sulphate (CaSC ) and lime (Ca(OH)2) and can be used alone, or after mixing with the first cake rich in tannins ii), as a soil improver and agricultural fertilizer, i.e. as a neutralizer for agricultural soils acidified during the intensive agriculture cycles.
  • the phase v) can be subjected to a basic hydrolysis under pressure, preferably in a range comprised from 6 to 5 bars, more preferably 5.8 bars.
  • the process comprises a subsequent further step 11) of calcium precipitation from phase viii) clear basic broth of step hl), to obtain a phase ix) (neutral broth).
  • said step 11) can occur by the addition to the hydrolyzed broth of CO2, ammonium bicarbonate, potassium bicarbonate, sodium bicarbonate, ammonium carbonate, potassium carbonate, sodium carbonate, preferably by the addition of ammonium bicarbonate.
  • the process comprises a subsequent step of fourth separation ml) of phase ix) (neutral broth) by a technique selected from filtration, centrifugation, and decantation, preferably filtration, even more preferably filtration on filter cloth, thus separating the residues and obtaining at least two fractions: x) a filtered clear neutral broth; and xi) a third solid phase (or cake).
  • a technique selected from filtration, centrifugation, and decantation preferably filtration, even more preferably filtration on filter cloth, thus separating the residues and obtaining at least two fractions: x) a filtered clear neutral broth; and xi) a third solid phase (or cake).
  • the third solid phase (or cake) xi) mainly consists of calcium carbonate (CaCO 3 ).
  • the process of the invention comprises a subsequent step nl) of purification and concentration x) filtered clear neutral broth to obtain a concentrated protein hydrolysate purified from aldehydes (for example, glutaraldehyde) and/or tannins.
  • aldehydes for example, glutaraldehyde
  • step nl) of purification and concentration occurs by a technique selected from the group comprising, or consisting of, purification by activated carbons, purification by decol orating earths, such as aluminum hydro-silicates containing Mg, Ca, Fe, which adsorb colored impurities from liquids, and purification by polyvinylpolypyrrolidone (PVPP).
  • PVPP polyvinylpolypyrrolidone
  • step nl occurs preferably by evaporator.
  • a further object of the present invention is a cake ii) obtainable by step cl) of the process of the invention and its use as an energy source after combustion.
  • a further object of the present invention is a cake vii) obtainable by step hl) of the process of the invention and its use alone or in combination with cake ii) as a soil improver and agricultural fertilizer.
  • a parameter can be the %AATotai on the total dry matter (%DM) or the ratio between the total elemental carbon over the percentage by weight of elemental nitrogen of organic origin (C/N).
  • the best parameter is the ratio between the percentage by weight of total elemental carbon over the percentage by weight of elemental nitrogen of organic origin (C/N) since specific for each type of protein and free from mistakes due to inorganic material.
  • the bovine leather from which RG derives from is mainly consisting of Type 1 collagen (85%) and, in a lower amount, from Type III collagen (15%).
  • Type I and Type III collagen From the crystallographic structure of Type I and Type III collagen it is possible to obtain the amino acid sequence and therefore the C/N ratio which is equal to 2.67 in the first case and 2.52 in the second case. Carrying out an acid and/or basic hydrolysis, the side groups of some amino acids, such as arginine and glutamine, decompose, freeing ammonia and forming the relative carboxylic acids. The C/N ratio has therefore to be re-calculated keeping into consideration the decomposition of such amino acids for both the collagen types. Considering the relative abundance of Type I and Type III collagen in the bovineleather, the averaged C/N ratio is equal to 2.83. This value is therefore a reference purity index: if the protein hydrolysate has a C/N ratio higher than 2.83, it has impurities with high carbon content and in particular the tannings, such as aldehydes and tannins, are not efficiently removed.
  • the tannings such as aldehydes and tannins
  • the determination was performed by drying in an oven at the temperature of 105 °C until reaching a constant weight.
  • the method is based on the complete combustion of the sample in the presence of oxygen.
  • the sample is carried by a helium flow through a column filled with a catalyst, chromium oxide.
  • the nitrogen oxides formed in the column are then reduced in a copper column withholding oxygen as well.
  • the formed substances, N2, CO2 and H2O, pass through a filter withholding water.
  • CO2 and N2 are separated by column chromatography and the analysis of the combustion products is carried out by gaschromatography (elemental analysis).
  • the method provides for the ammonia distillation in boric acid solutions.
  • the concentration is determined by acid-base titration.
  • the content is determined by ionic chromatography after dissolution in water.
  • the organic nitrogen content is calculated subtracting the ammonium content from the total nitrogen content expressed in the same unit of measurement.
  • the amino acid and peptide total content is calculated as organic nitrogen x 6.25.
  • the content is determined by ionic chromatography after dissolution in water.
  • the content is determined by ionic chromatography after dissolution in water.
  • Example 1 Preparation and analysis of a protein hydrolysate from a tanning industry waste resulting from the manufacturing process of leather tanned with aldehydes and tannins without pre-treatment with acid
  • the protein hydrolysate was prepared as below described according to a process comprising the steps of: al) providing 2 kg of a tanning industry waste resulting from the manufacturing process, comprising shaving, of leather tanned with aldehydes (for example, glutaraldehyde) and tannins (RG) and mixing with 8 Kg of water; gl) basic hydrolysis at atmospheric pressure in a reactor under stirring with the addition of 260 g of Ca(OH)2 until a pH comprised from 10 to 13 is reached, for a time of 24 hours and at a temperature of 92 °C; hl) separation by filtration on paper thus separating the residues and obtaining at least two fractions: vii) a solid phase (or cake); and viii) a clear basic broth.
  • aldehydes for example, glutaraldehyde
  • tannins RG
  • gl basic hydrolysis at atmospheric pressure in a reactor under stirring with the addition of 260 g of Ca(OH)2 until a pH comprised from
  • phase viii) calcium abatement of phase viii) by the addition of 234.11 g of ammonium bicarbonate to obtain a neutral broth ix); ml) separation of the neutral broth ix) by filtration, thus separating the residues and obtaining at least two fractions: x) a filtered clear neutral broth; and xi) a third solid phase (or cake) consisting of 301.9 g of calcium carbonate having %DM equal to 83.60%; and nl) purification and concentration of the filtered clear neutral broth x) under vacuum, to obtain a concentrated protein hydrolysate purified from aldehydes (for example, glutaraldehyde) and tannins.
  • aldehydes for example, glutaraldehyde
  • the obtained product has a very dark appearance and is markedly opalescent.
  • the C/N ratio is 3.00, therefore far from the reference (2.83). This because the used tannings are not removed by the carried out treatment but remain present in the final concentrate.
  • Example 2 Preparation and analysis of a protein hydrolysate from a tanning industry waste resulting from the manufacturing process of leather tanned with aldehydes (for example, glutaraldehyde) and tannins (RG), without pre-treatment with acid hydrolysis bl) and with a double step of basic hydrolysis gl) and hl’) - Comparative
  • aldehydes for example, glutaraldehyde
  • RG tannins
  • the protein hydrolysate was prepared as below described according to a process comprising the steps of: al) providing 2 kg of a tanning industry waste resulting from the manufacturing process, comprising shaving, of leather tanned with aldehydes (for example, glutaraldehyde) and tannins (RG); gl) basic hydrolysis at atmospheric pressure in a reactor under stirring with the addition of 260 g of Ca(OH)2 until a pH comprised from 10 to 13 is reached and 8 kg of water, for a time of 5 hours and at a temperature of 95 °C; hl) separation by filtration on paper thus separating the residues and obtaining at least two fractions: vii) a solid phase (or cake); and viii) a clear basic broth.
  • aldehydes for example, glutaraldehyde
  • tannins RG
  • gl basic hydrolysis at atmospheric pressure in a reactor under stirring with the addition of 260 g of Ca(OH)2 until a pH comprised from 10 to 13 is reached
  • phase viii) (clear basic broth) by the addition of 91.35 g of ammonium bicarbonate to obtain a neutral broth ix); ml) separation of the neutral broth ix) by filtration, thus separating the residues and obtaining at least two fractions: x) a filtered clear neutral broth; and xi) a third solid phase (or cake) consisting of 981 g of calcium carbonate having %DM equal to 65%; and nl) purification and concentration of the filtered clear neutral broth x) under vacuum, to obtain a concentrated protein hydrolysate purified from aldehydes (for example, glutaraldehyde) and tannins.
  • aldehydes for example, glutaraldehyde
  • the obtained concentrated product is a very viscous fluid with a black-brown color and green-yellow reflexes observable on the container walls.
  • the chemi cal -physical properties are summarized in Table 2.
  • the C/N ratio is 3.12 far from the reference (2.83).
  • Example 3 Preparation and analysis of a protein hydrolysate from a tanning industry waste resulting from the manufacturing process of leather tanned with aldehydes (for example, glutaraldehyde) and tannins , with pre-treatment with an acid hydrolysis bl) without ultrafiltration step el) - Comparative Example
  • the protein hydrolysate was prepared as below described according to a process comprising the steps of: al) providing 1 kg of a tanning industry waste resulting from the manufacturing process, shaving, and trimming, of leather tanned with aldehydes (for example, glutaraldehyde) and tannins (RG); bl) acid hydrolysis by addition of 102.3 g of 96% by weight sulphuric acid and 4 Kg of water, at 95 °C under stirring for 5 hours at atmospheric pressure; cl) separation by filtration on paper, thus obtaining at least two phases: i) 4576.8 g of an aqueous phase (or acid broth), and ii) 130.1 g of a solid phase (or cake), having %DM equal to 35.0%; gl) basic hydrolysis at atmospheric pressure in a stirred reactor with the addition of 160 g di Ca(OH)2 until a pH comprised from 10 to 13 is reached, for a time of 5 hours and at a temperature of 95 °C.
  • step bl The pre-treatment with acid hydrolysis (step bl)) produces the desired effect of the removal of part of tannins and aldehydes (for example, glutaraldehyde).
  • Example 4 Preparation and analysis of a protein hydrolysate from a tanning industry waste resulting from the manufacturing process of leather tanned with aldehydes (for example, glutaraldehyde) and tannins (RG), with pre-treatment with an acid hydrolysis bl) with an ultrafiltration step el) according to the invention
  • aldehydes for example, glutaraldehyde
  • tannins RG
  • the protein hydrolysate was prepared as below described according to a process comprising the steps of: al) providing 400 g of a tanning industry waste resulting from the manufacturing process, comprising shaving, of leather tanned with aldehydes (for example, glutaraldehyde) and tannins (RG); bl) acid hydrolysis by the addition of 72.3 g of 40% by weight sulphuric acid and 1.530 Kg of water, at 95 °C under stirring for 3.5 hours at atmospheric pressure and subsequent cooling until room temperature; cl) separation by decantation for 24 hours, thus obtaining at least two phases: i) 1893.6 g of an aqueous phase (or acid broth), and ii) 75.4 of a solid phase (or cake), having %DM equal to 35.1%; cl’) filtration on diatomaceous earth of the aqueous phase i) (or acid broth); dl) treatment of phase i) (or acid broth), with the addition of 45.7 g of 30% by weight NH
  • the clear broth has a dark red-brown color.
  • second separation by ultrafiltration through a polymeric membrane with MWCO of 30 KDa, thus separating the residues of phase iii) (or clear broth) and obtaining at least two fractions: iv) 297 g of an unpurified homogeneous phase (unpurified liquid retentate); and v) 1596 g of a homogeneous phase substantially purified from tannings (purified permeate or purified broth); gl) basic hydrolysis of phase v) (purified permeate or purified broth) with the addition of 100 g of Ca(OH)2 at atmospheric pressure at 95 °C in a stirred reactor for 2 hours, thus obtaining a phase vi) basic suspension (or basic slurry); hl) separation by filtration on paper, thus separating the residues and obtaining at least two fractions: vii) 147.2 g of a solid phase (or cake), having %DM equal to 45.7%; viii) 15
  • phase viii) (clear basic broth) by the addition of 10.4 g of ammonium bicarbonate to obtain a neutral broth ix); ml) separation of phase ix) by filtration, thus separating the residues and obtaining at least two fractions: x) a filtered clear neutral broth; and xi) a third solid phase (or cake); and nl) purification and concentration of the filtered clear neutral broth x) on rotavapor under vacuum, to obtain 114.0 g of a concentrated protein hydrolysate purified from aldehydes (for example, glutaraldehyde) and tannins.
  • aldehydes for example, glutaraldehyde
  • the obtained concentrated product is a very viscous fluid with a red-brown color free from green-yellow reflexes.
  • the chemi cal -physical properties are summarized in Table 4.
  • the concentrated protein hydrolysate obtained from Example 4 has a C/N ratio of 2.84; a value that, compared to the concentrated protein hydrolysate obtained from Example 3, is superimposable to the reference (2.83).
  • the ultrafiltration brings an undeniable advantage in the removal of the impurities from the final product.
  • Example 5 Preparation of a protein hydrolysate depurated from o free from aldehydes (for example, glutaraldehyde) and/or tannins from a waste (residue) of animal origin, from shave tanned with aldehydes (for example, glutaraldehyde) (RG) by pretreatment with an acid hydrolysis at atmospheric pressure with ultrafiltration of step el) and further two steps el’) ed el”) according to the invention
  • aldehydes for example, glutaraldehyde
  • tannins from a waste (residue) of animal origin
  • the protein broth was prepared as below described according to a process comprising the steps of: al) providing 1.8 kg of a tanning industry waste resulting from the manufacturing process, comprising shaving, of leather tanned with aldehydes (for example, glutaraldehyde) and tannins (RG); bl) acid hydrolysis by the addition of 348 g of 40% by weight sulfuric acid and 6.88 Kg of water, at 95 °C under stirring for 12 hours at atmospheric pressure and subsequent cooling until room temperature; cl) separation by decantation for 24 hours, thus obtaining at least two phases: i) 9570 g of an aqueous phase (or acid broth), and ii) 176.4 g of a solid phase (or cake), having %DM equal to 56.9%; cl’) filtration on diatomaceous earth of the aqueous phase i) (or acid broth); dl) treatment of phase i) (or acid broth), with the addition of 202 g of 30% by weight NH3 (as a
  • el second separation by ultrafiltration through a polymeric membrane with MWCO of 10 KDa, thus separating the residues of phase iii) (or clear broth) and obtaining at least two fractions: iv) 1457 g of an unpurified homogeneous phase (unpurified liquid retentate); and v) 8113 g of a homogeneous phase substantially or completely free from suspended solids (purified permeate or purified broth); el’) washing of the unpurified homogeneous phase iv) (liquid retentate) with 1500 g of milliQ water; and el”) further separation by ultrafiltration by polymeric membrane with MWCO of 10 KDa, thus obtaining at least two fractions: iv’) 1199 g of an unpurified homogeneous phase (liquid retentate) to be added to phase iv); and v’) 1758 g of a homogeneous phase substantially or completely free from suspended solids (or purified broth or purified perme
  • phase viii) (clear basic broth) by the addition of 214.5 g of ammonium bicarbonate to obtain a neutral broth ix); ml) separation of phase ix) by filtration, thus separating the residues and obtaining at least two fractions: x) a filtered clear neutral broth; and xi) a third solid phase (or cake); and nl) purification and concentration of the filtered clear neutral broth x) on rotavapor under vacuum, to obtain 811.5 g of a concentrated protein hydrolysate purified from aldehydes (for example, glutaraldehyde) and tannins.
  • aldehydes for example, glutaraldehyde
  • tannins The chemi cal -physical properties are summarized in Table 5.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Dermatology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Peptides Or Proteins (AREA)

Abstract

L'invention concerne un procédé d'obtention d'un hydrolysat de protéines à partir d'un substrat qui est un déchet provenant de l'industrie du tannage, résultant spécifiquement du procédé de rasage et/ou de parage du cuir tanné avec des aldéhydes (tels que le glutaraldéhyde) et/ou des polyphénols (tels que des tanins).
PCT/IB2024/061038 2023-11-10 2024-11-07 Procédé de production d'hydrolysats de protéines à partir de résidus de traitement de cuir tanné selon une technologie sans métal Pending WO2025099628A1 (fr)

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IT102023000023838 2023-11-10
IT102023000023838A IT202300023838A1 (it) 2023-11-10 2023-11-10 Processo di produzione di idrolizzati proteici da residui di lavorazione delle pelli conciate con tecnologia metal free

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PCT/IB2024/061038 Pending WO2025099628A1 (fr) 2023-11-10 2024-11-07 Procédé de production d'hydrolysats de protéines à partir de résidus de traitement de cuir tanné selon une technologie sans métal

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WO (1) WO2025099628A1 (fr)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LESIA MAISTRENKO: "Collagen Obtained from Leather Production Waste Provides Suitable Gels for Biomedical Applications", POLYMERS, vol. 14, no. 21, 5 November 2022 (2022-11-05), CH, pages 4749, XP093156593, ISSN: 2073-4360, DOI: 10.3390/polym14214749 *

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