EP3494237B2 - Verwendung von olivenmühlenabfallwasser in der ledergerbindustrie - Google Patents

Verwendung von olivenmühlenabfallwasser in der ledergerbindustrie

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Publication number
EP3494237B2
EP3494237B2 EP17761132.4A EP17761132A EP3494237B2 EP 3494237 B2 EP3494237 B2 EP 3494237B2 EP 17761132 A EP17761132 A EP 17761132A EP 3494237 B2 EP3494237 B2 EP 3494237B2
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EP
European Patent Office
Prior art keywords
tanning
omw
waste waters
mill waste
use according
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EP17761132.4A
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English (en)
French (fr)
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EP3494237A1 (de
EP3494237B1 (de
Inventor
Massimiliano Franceschi
Giacomo PACCHI
Maurizio MARAVIGLIA
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Tannow Srl
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Tannow Srl
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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
    • C14C1/02—Curing raw hides
    • 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
    • C14C1/04—Soaking
    • 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
    • C14C1/06—Facilitating unhairing, e.g. by painting, by liming
    • 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
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/10—Vegetable tanning
    • 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
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/22—Chemical tanning by organic agents using polymerisation products

Definitions

  • the invention relates to a process for the requalification of olive oil mill waste waters in the tanning industry.
  • Olive oil mill waste waters are aqueous solutions of organic substances and minerals, further containing suspended vegetal solid material, resulting from the separation of oily must step. Their composition is extremely variable and depends on several factors, including the type of olive cultivar and their degree of ripening, soil, extraction process, and conservation methodology.
  • Olive oil mill waste waters comprise a variety of ingredients, such as organic substances, nitrogenous substances, sugars, tannins, phenolic compounds, polyalcohols, pectins, lipids, minerals, and polyphenols.
  • Sugars are the predominant organic substances, especially fermentable sugars, such as glucose (70%), mannitol (14%), fructose (10%), sucrose (5%), galactose (1%), and cellulose.
  • the pH value typically comprised between 4 and 6, is determined by the content of organic acids, such as malic, citric, tartaric, succinic, and oxalic. These pH oscillations are attributable to olive variety, maturation period, and storage life.
  • the organic fraction of olive oil mill waste waters determines their high polluting power, normally characterized by very high chemical oxygen demand (COD) and biological oxygen demand (BOD5), ranging between 90 grams O 2 /L and 30 grams O 2 /L, respectively, for waters originating from the most modern centrifugal plants, and even 150 grams O 2 /L and 90 grams O 2 /L for waters originating from traditional plants.
  • COD chemical oxygen demand
  • BOD5 biological oxygen demand
  • the concentration of some easily fermentable organic components may be also significantly reduced by the action of aerobic and anaerobic microorganisms present therein, which are able to decompose them.
  • OMW are in fact a very complex matrix, being therein present a plurality of microorganisms, molds and yeasts reaching even concentration values of 10 5 -10 6 .
  • the production and characteristics of olive oil mill waste waters are, therefore, directly related both to the production of olives for olive oil production and to their characteristics, as well as to the extraction process used, and to the subsequent storage conditions and times.
  • GR20020100071A describes the obtaining of substances with cytotoxic and antioxidant activity from extraction processes starting from olive leaves, olives, olive oil and olive processing waste.
  • Ahmed Tafesh et al ( Ahmed Tafesh et al: "Synergistic antibacterial effects of polyphenolic compounds from olive mill wastewater”, EVIDENCE-BASED COMPLEMENTARY AND ALTERNATIVE MEDICINES: ECAM, HINDAWI PUBLISHING CORPORATION, UNITED STATES, vol.
  • Obied et al "Bioscreening of Australian olive mill waste extracts: Biophenol content, antioxidant, antimicrobial and molluscicidal activities", FOOD AND CHEMICAL TOXICOLOGY, PERGAMON GB, vol.45, no.7, 19 April 2007, pages 1238-1248 ) describe the antibacterial properties of compounds extracted from the waters of olive vegetation.
  • the cited documents propose long and laborious procedures of extraction, purification and concentration in order to be able to recover reusable components normally present in the waters of olive vegetation, so as to be able to plan their valuable and alternative use for disposal.
  • the primary aim of the present invention is, therefore, to requalify olive oil mill waste waters resulting from the process of olive processing.
  • the invention therefore relates to the use of olive oil mill waste waters (OMW) as a bactericide in any stage of the tanning process requiring a bactericidal action, preferably in the soaking step.
  • OMW olive oil mill waste waters
  • the invention relates to the use of olive oil mill waste waters (OMW) as a tanning agent or tanning adjuvant agent, in particular in the tanning step.
  • OMW olive oil mill waste waters
  • OW olive oil mill waste waters
  • the invention relates to the use of olive oil mill waste waters (OMW) as an antioxidant agent to prevent the formation of Chromium (VI) in the retanning step.
  • OMW olive oil mill waste waters
  • OMW may be used in at least one step of the leather tanning industry, thus enabling the valorization of a product until now only destined to disposal.
  • the invention therefore relates to the use of olive oil mill waste waters in the leather tanning process in the tanning industry.
  • Olive oil mill waste waters are waste waters resulting from olive oil processing, and they are obtained during the separation of water from oily must and from plant washing operations.
  • OMW used in the present invention have a pH comprised between 2 and 8, more preferably between 3 and 5, a suspended solids content comprised between 10,000 and 100,000 mg/L, more preferably between 20,000 and 70,000 mg/L, a dry residue comprised between 1 and 12% by weight, more preferably between 2 and 8%, a total phenols content (as determined according to Folin Ciocalteau method, expressed as gallic acid mg equivalents/L of OMW) comprised between 100 and 15,000, more preferably between 500 and 10,000, a hydroxytyrosol content (as determined by HPLC-UV DAD) comprised between 25 and 5,000 mg/L, more preferably between 500 and 3,000 mg/L.
  • a pH comprised between 2 and 8, more preferably between 3 and 5
  • a suspended solids content comprised between 10,000 and 100,000 mg/L, more preferably between 20,000 and 70,000 mg/L
  • a dry residue comprised between 1 and 12% by weight, more preferably between 2 and 8%
  • a total phenols content
  • olive oil mill waste waters used in the tanning process according to the invention are olive oil mill waste waters previously subjected to stabilization methods by treatment with nitrogen.
  • said olive oil mill waste waters are enriched in one or more polyphenols, such as hydroxytyrosol, by treatment with nitrogen in the form of a liquid or a gas, preferably a gas.
  • said olive oil mill waste waters previously subjected to stabilization methods by treatment with nitrogen optionally provide for an earlier step of enrichment with lactic bacteria.
  • the tanning process is generally carried out in various ways, depending on the type of raw hides and the type of product to be made.
  • the treatment water comprises network water and a given percentage of olive oil mill waste waters (OMW), expressed as a percentage by weight based on the total weight of the treatment water.
  • OMW olive oil mill waste waters
  • the whole tanning process is very complex due to the nature and plurality of chemical-biological reactions occurring in the various steps of treatment.
  • the aim of the tanning process is to provide tanned leather having, at the same time, high hydrothermal stability, good chemical resistance, high resistance to bacterial and enzymatic agents, as well as a number of properties associated with their commercialization, such as softness, flexibility, fullness, firmness, compactness, dyeability, and good physical-mechanical characteristics.
  • the soaking step allows to bring the hides back to the original conditions of when just skinned, removing the salt used during storage, cleaning the dirt away and making them adsorb the water lost following the preservation treatment.
  • OMW as such, i.e. which did not undergo any purification and/or extraction of components thereof, could be added as bactericides at any stage of the tanning process, particularly during the hides soaking or tanning step, preferably in the soaking step.
  • the invention therefore relates to the use of olive oil mill waste waters (OMW) as a bactericide in at least one step of the tanning process requiring a bactericidal action, preferably in the soaking step.
  • OMW olive oil mill waste waters
  • hides soaking is performed in a treatment water bath consisting of network water at 25°C, wherein detergents for removing dirt, globular proteins and blood, and biocides are added to prevent bacterial charge formation, which generates malodorous substances and degrades the leather.
  • OMW have proved to be excellent bactericides in the environment of use, and have therefore advantageously allowed to significantly reduce, or even replace, the amounts of biocides typically used during the soaking step, such as chlorophenols (chlorocresols, trichlorophenols, etc.), dithiocarbamates (sodium salts), and thiocyanomethylthiobenzothiazoles.
  • an amount of treatment water usually network water, comprised between 0.5 kg and 2.5 kg, preferably between 0.7 kg and 1.5 kg, even more preferably of about 1 kg per kg of hides to be treated is used.
  • OMW are used in an amount from 50 to 100% by weight based on the treatment water, preferably in an amount from 75% to 100%, even more preferably in an amount of 100%, i.e. they totally replace the network water.
  • the invention relates to the use of olive oil mill waste waters (OMW) as a tanning agent, or a tanning adjuvant agent, in the leather tanning step.
  • OMW olive oil mill waste waters
  • tanning is a set of operations that allow to obtain a stable crosslinking of the collagen fibers within the dermis of the skin.
  • stable cross-links among collagen polypeptide chains are formed, with a consequent consolidation that preserves the dermal substance from the degradation processes, and provides tanned leather with mechanical strength and resistance to humidity, temperature, and chemical agents.
  • OMW Olive oil mill waste waters
  • the invention relates to the use of olive oil mill waste waters (OMW) as tanning agents, or tanning adjuvating agents, in the tanning step of the leather tanning process.
  • OMW olive oil mill waste waters
  • an amount of treatment water expressed as kg of water per kg of dry hides, comprised between 0.5 kg and 2 kg, preferably between 0.8 kg and 1.5 kg, is used.
  • OMW are used in an amount from 50 to 100% by weight based on the treatment water, preferably in an amount from 75% to 100%, even more preferably in an amount of 100%, i.e. they totally replace the network water.
  • OMW olive oil mill waste waters
  • other tanning agents selected from the group consisting of a natural tannin, such as tara, mimosa, chestnut, myrobalan, a synthetic tannin, such as hydroxydiphenyl sulphone, a compound belonging to the family of phenolic resins, a compound belonging to the family of naphthalene resins, an aldehyde or a precursor thereof, such as glutaraldehyde, isoxazolidine, oxazolidine, a metal salt, such as a chromium, zirconium, or titanium salt, and an acrylic resin, such as a resin obtained by homopolymerization or radical copolymerization of acrylic acid, such as sodium polyacrylate, methacrylic acid,
  • a natural tannin such as tara
  • olive oil mill waste waters are used in combination with an acrylic resin, such as the resin obtained by homopolymerization or radical copolymerization of acrylic acid, methacrylic acid, methyl methacrylate ester, ethyl acrylate ester, acrylamide, optionally preferably salified, such as sodium polyacrylate (PA).
  • an acrylic resin such as the resin obtained by homopolymerization or radical copolymerization of acrylic acid, methacrylic acid, methyl methacrylate ester, ethyl acrylate ester, acrylamide, optionally preferably salified, such as sodium polyacrylate (PA).
  • PA sodium polyacrylate
  • olive oil mill waste waters are used in combination with sodium polyacrylate resin (PA), obtained by homopolymerization or radical copolymerization carried out in the same OMW, as a reaction medium.
  • PA sodium polyacrylate resin
  • Advantageously OMW may also be used as adjuvating agents of tanning agents in tanning processes, preferably in tanning processes not employing chromium (the so-called chromium-free tanning processes).
  • OMW may be used in a composition with other tanning agents in a chromium-free tanning process, such as for example oxazolidine, glutaraldehyde o dihydroxydiphenyl sulphone (DIDS), acting as synergistic compounds of known tanning compounds, as it will be apparent from the experimental part.
  • DIDS glutaraldehyde o dihydroxydiphenyl sulphone
  • the invention relates to a tanning composition
  • a tanning composition comprising olive oil mill waste waters(OMW), one or more tanning agents selected from the group consisting of a natural tannin selected from the group consisting of:tara, mimosa, chestnut and myrobalan, a synthetic tannin, such as hydroxydiphenyl sulphone, a compound belonging to the family of phenolic resins, a compound belonging to the family of naphthalene resins, an aldehyde or a precursor thereof, such as glutaraldehyde, isoxazolidine, oxazolidine, a metal salt, such as a chromium, zirconium, or titanium salt, and an acrylic resin, such as a resin obtained by homopolymerization or radical copolymerization of acrylic acid, methacrylic acid, methyl methacrylate ester, ethyl acrylate ester, acrylamide, preferably salified, such as sodium polyacrylate (PA), and mixture thereof, and suitable
  • the invention relates to a tanning composition
  • a tanning composition comprising olive oil mill waste waters (OMW) and at least one acrylic resin obtained by homopolymerization or radical copolymerization of acrylic acid, methacrylic acid, methyl methacrylate ester, ethyl acrylate ester, acrylamide, preferably salified.
  • OMW olive oil mill waste waters
  • acrylic resin obtained by homopolymerization or radical copolymerization of acrylic acid, methacrylic acid, methyl methacrylate ester, ethyl acrylate ester, acrylamide, preferably salified.
  • acrylic resin is sodium polyacrylate resin (PA).
  • said acrylic resin is obtained by homopolymerization or radical copolymerization, carried out in the same OMW as a reaction medium, of acrylic acid, methacrylic acid, methyl methacrylate ester, ethyl acrylate ester, acrylamide, preferably salified, such as sodium polyacrylate.
  • said acrylic resin obtained by polymerization, carried out in the same OMW as a reaction medium is sodium polyacrylate resin (PA).
  • PA sodium polyacrylate resin
  • the tanning composition of the invention preferably comprises a ratio, by weight, between OMW and one or more tanning agents selected from the group consisting of a natural tannin selected from the group consisting of:tara, mimosa, chestnut and myrobalan, a synthetic tannin, such as hydroxydiphenyl sulphone, a compound belonging to the family of phenolic resins, a compound belonging to the family of naphthalene resins, an aldehyde or a precursor thereof, such as glutaraldehyde, isoxazolidine, oxazolidine, a metal salt, such as a chromium, zirconium, or titanium salt, and an acrylic resin, such as a resin obtained by homopolymerization or radical copolymerization of acrylic acid, methacrylic acid, methyl methacrylate ester, ethyl acrylate ester, acrylamide, preferably salified, such as sodium polyacrylate (PA), and mixture thereof, in the range from 2 to 20, more
  • OMW organic light-emitting compound
  • they also advantageously act as microbiological stabilizers of the leather itself, i.e. as leather preservatives in the tanning step.
  • the invention relates to the use of olive oil mill waste waters (OMW) as an antioxidant agent to prevent the formation of Chromium (VI) in the retanning step.
  • OMW olive oil mill waste waters
  • retanning is another step of the leather tanning process, and it consist in a chemical treatment that allow to improve some leather characteristics.
  • the leather adsorbs further tanning or filling substance, such that it provides the final product with the desired grade of fullness, softness, sweat resistance, and more.
  • tannins, chromium salts or other salts are used as retanning agents, and temperature and humidity conditions can convert Chromium (III) into Chromium (VI), a known toxic and carcinogenic agent, highly aggressive towards biological systems, hence having a high environmental pollution impact.
  • olive oil mill waste waters resulted to be advantageous antioxidant agents that prevent the formation of Chromium (VI) in the retanning step, as it is apparent from the experimental part reported below.
  • an amount of treatment water expressed as kg of water per kg of dry leather, comprised between 0.5 kg and 2 kg, preferably between 0.8 kg and 1.5 kg is used.
  • OMW are used in an amount from 50 to 100% by weight based on the treatment water, preferably in an amount from 75% to 100%, even more preferably in an amount of 100%, i.e. they totally replace the network water.
  • Example 1 Evaluation of OMW in the process of soaking hides as a bactericide
  • OMW used in the example had the characteristic shown in the Table 1 below: Table 1 pH 4.82 Suspended Solids (mg/L) 63815 Dry Weight (%) 8.38 Total Phenols (mg AG eq/L) 1 2791.7 Hydroxytyrosol (mg/L) 2 811.59 Antioxidant Power (mg AG eq/L) 3 1315.32
  • the jars were opened and samples of the hides so soaked were left to rest, wet, in a hermetic container (plastic bag) for 24 hours, then they were inspected the following day.
  • Olfactory evaluations of hides bacterial degradation assessed based on a numerical index comprised between 0 and 3 (specifically: 0-no smell; 1-mild smell; 2-moderate smell; 3-intense smell) are summarized in Table 2 below: Table 2 Test no. Olfactory Evaluation Index 1 3 2 0 3 3 4 2 5 1 6 0
  • OMW in the process allowed a significant reduction of malodorousness, significant at high OMW concentrations, especially for ratios between network water and OMW of 1:3 or more (Tests 5 and 6), i.e. for OMW concentrations in treatment water ranging from 75% to 100%.
  • the hides soaked with 50% OMW in the treatment water showed a higher hair pull resistance, more consistent for higher concentrations, and even comparable to that achieved with traditional soaking methods, for 100% OMW concentrations, i.e. when network water was completely replaced by OMW.
  • the test was performed by preparing samples having the same initial concentration of total phenols (determined by Folin Ciocalteau method) of about 2 g/L, and submitting said samples to tanning treatment with OMW, or with traditional tannins (Tara, Myrobalan, Chestnut, and Mimosa).
  • Table 4 Tanning Agent Phenols absorbed (%) OMW 82.94 TARA 91.71 MYROBALAN 86.75 CHESTNUT 90.20 MIMOSA 91.32
  • OMW exhibited a very high tanning power, of about 83%, i.e. fully comparable to that of vegetable tannins used as a comparison, and traditionally used in vegetal tanning, exhibiting a tanning power ranging between about 87% and 92%.
  • Some leather tanning tests were carried out in order to evaluate the use of OMW as a microbiological stabilizer for hides (to eliminate putrescibility), and as an adjuvant in Chromium-free tanning processes.
  • Tests were conducted either by using OMW alone, or OMW in combination with several Chrome-free tanners.
  • the evaluated parameters were the control of formation of malodorousness and molds, for the evaluation of the antimicrobial capacity of the baths, and the determination of the contraction temperature Tg, for the evaluation of the tanning activity. It should be considered that this second parameter normally ranges from 70°C to 80°C in the case of tanning processes carried out with tannins or aldehydes.
  • the hides were picked from the wet work drum and drained from Pickle's bath, and then transferred to the drum containing the tanning bath, made of 100% OMW, based on hides weight, and heated to 30°C. 5% of washed sea salt was added to OMW in order to bring the bath density to about 6°Be.
  • the hides were then made to rotate in the drum for 2 hours, then their thickness was checked, and it resulted to be completely permeated by OMW. As a confirmation of complete permeation across the skin thickness, the bath color was lighter, indicating that the hides had absorbed a certain amount of bath components. Since the fixation process for these types of tanning procedures requires a long time, the hides were rested on a horse for a few days.
  • Test 2 Microbiological stabilization and synergistic adjuvant of known tanning agents
  • the hides were picked from the wet work drum and drained from Pickle's bath, and then transferred to the drum containing the tanning bath, made of 100% OMW and 5% oxazolidine, previously mixed with OMW and homogenized for 10 minutes. The hides were then made to rotate in the drum for 2 hours, then their thickness was checked, and it resulted to be completely permeated by OMW.
  • the hides were picked from the wet work drum, and drained from Pickle's bath, and then transferred into two drums containing the tanning baths, made of 100% OMW and 5% oxazolidine, previously mixed with OMW and homogenized for 10 minutes.
  • the hides were made to rotate in the drum for 2 hours, then their thickness was checked, and it resulted to be completely permeated by OMW.
  • DIDS dihydroxydiphenyl sulphone
  • the pH of the bath was 3.7, an indication that tannins and other tanning compounds had been, at least in part, fixed by the hide.
  • Test 3 also showed that OMW work synergically with oxazolidine and DIDS tanning agents, as evidenced by the high Tg values obtained, broadly comparable to those obtainable in conventional tanning processes, that increase as the OMW concentration in the tanning bath increases.
  • Test 4 Chromium-free vegetal-like tanning tests with OMW adjuvant in tanning
  • Tanning tests were carried out on pickled hides, i.e. acidified until the pH of the tanning bath was at 2.8-2.9.
  • Acidification in bath is mandatory for any type of tanning because the alkaline substances used in the previous dehairing phase have to be removed from the hide fibers to modify the hide isoelectric point, in order to aid the entry of the tanning molecules (natural tannins, chromium), which are then reacted with the hide by modifying the isoelectric point again, de facto raising the pH of the bath (and hence of the hides themselves) to about 3.8-4.0.
  • the recipe for the two tests I and II was the following: to pickled hides, OMW were added with the pickle bath (tanning bath); to said bath, 6% by weight of modified glutaraldehyde and 1.5% by weight of long chain alcohol sulfosuccinate were also added, then the jars were made to rotate for 180 minutes.
  • tanning acrylic resin specifically sodium polyacrylate resin
  • a rest under high humidity is needed by hides mainly to homogenize the absorbed chemicals, allowing them to evenly distribute throughout the hide thickness. In this period of time, the completion of chemical reactions, which actually exhaust any residual chemicals that are not yet fixated in the collagen, is allowed.
  • Tg values for chromium tanning are of 100°C, a maximum value of 80°C for vegetal tanning (natural tannins), and values typically ranging from 70 to 77°C for aldehydes tanning, whereby it is apparent that the Tg values ranging from 78°C to 82°C obtained with OMW, both containing and not containing acrylic resin, have shown to be broadly in line to those obtainable with other chromium-free tannings, sometimes even superior.
  • OMW as a tanning adjuvant
  • Tg values are obtained in Test I, wherein the acrylic resin polymerized in OMW is also present, showing, as in the previous cases, the OMW adjuvant power in the tanning step, when used with other traditional Chromium-free tanning agents.
  • the Chambort-Jamet standardized method as detailed in Example 2 above, was used for the evaluation of the tanning capacity of acrylic resins mixed with OMW. The measurement of the tanning power then results from the determination of the dry matter content of the tanning agent absorbed by the standard hide.
  • the test was performed by preparing tanning solutions having all the same initial concentration of dry matter of about 4 g/L.
  • the tanning tests were carried out on pickled hides in a jar mill, acidified until the pH of the tanning bath was at 2.8-2.9.
  • the tests were carried out by directly adding a 5% concentration of tanning agents to the pickle bath, and it was made to rotate overnight (8 hours).
  • OMW have largely demonstrated the ability to increase the tanning power of traditional tanning agents, thus enabling a drastic reduction in the quantities employed in the process, with a significant reduction in costs and environmental impact associated both with OMW disposal and production of chemicals.
  • OMW1 and OMW2 Two different OMW, referred to as OMW1 and OMW2, were used, whose characteristics are listed in Table 9 below Table 9 Characteristics OMW 1 OMW2 pH 4.68 4.71 Suspended Solids (mg/L) 69,025 5,893 Dry Residue (%) 9.09 3.13 Total Polyphenols (mg/L) 2,058.33 5,283.33 Hydroxytyrosol (mg/L) 514.46 1,834.70 Tanning Power (%) 79.03 47.73
  • Example 5 Evaluation of the antioxidant capacity of OMW to prevent the formation of Chromium VI in chromium tanned leather
  • This test was performed using chromium tanned wet-blue leather, and comparing the results obtained using a standard retanning recipe, employing as a vegetal tannin TARA tannin, and as a fatliquoring agent sulphited fish oil, with the results obtained by using a retanning step wherein the treatment water bath was replaced by OMW (150% based on the weight of the leather) and the vegetable tannin tara was eliminated, in the presence or not of the acrylic resin sodium polyacrylate (PA) obtained by a polymerization process carried out in the same OMW.
  • the whole process of treating the leather is described in Table 11 below.
  • the retanning step was carried out on chromium tanned leather (wet-blue), by developing a typical recipe to obtain a vegetalized-type product, where the leather aspect looks similar to vegetable-tanned leather.
  • the leather thus obtained were left to rest for one day, so as to allow uniform distribution of the products throughout the leather thickness; a number of drying operations were then carried out, involving the use of a vacuum machine, a hot roller machine, and then set out in overhead conveyor for further drying. In this case, however, given that for Chromium VI development the leather would have been subjected to severe humidity and heat conditions, the set out in overhead conveyor was carried out only for half a day, followed by the conditioning procedure for Chromium VI tests.
  • Example 6 Evaluation of the Cr (VI) abatement capacity in aqueous solution by means of tanning resins polymerized in OMW, with different antioxidant properties.
  • %red the percentage of Cr(VI) content abatement
  • Table 14 Resin Resin Conc. (%) After 1h (%red) After 3h (%red) After 4 h (%red) 1 10 100 100 100 100 2 10 100 100 100 100 3 10 100 100 100 100 1 5 92.69 100 100 2 5 100 100 100 3 5 100 100 100 1 1 25.69 31.43 33.19 2 1 0 0 0 3 1 47.2 56.7 65.49

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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 (18)

  1. Verwendung von Olivenmühlenabwasser (OMW) in mindestens einem Schritt des Ledergerbverfahrens in der Gerbindustrie.
  2. Verwendung nach Anspruch 1, wobei das Olivenmühlenabwasser (OMW) einen pH-Wert im Bereich von 2 bis 8; einen Gehalt an suspendierten Feststoffen im Bereich von 10.000 bis 100.000 mg/l; einen trockenen Rückstand im Bereich von 1 bis 12 Gew.-%; einen Gesamtphenolgehalt (nach der Folin-Ciocalteau-Methode bestimmt, in mg Gallussäure-Äquivalenten/I OMW ausgedrückt) im Bereich von 100 bis 15.000 und einen Hydroxytyrosol-Gehalt (bestimmt durch HPLC-UV-DAD) im Bereich von 25 bis 5.000 mg/l aufweist.
  3. Verwendung nach Anspruch 1 oder 2, wobei das Olivenmühlenabwasser ein Olivenmühlenabwasser ist, das zuvor verschiedenen Stabilisierungsverfahren durch Behandlung mit Stickstoff unterzogen wurde.
  4. Verwendung nach irgendeinem der Ansprüche von 1 bis 3, wobei die Verwendung von Olivenmühlenabwasser als Bakterizid in mindestens einem Schritt des Ledergerbverfahrens in der Gerbindustrie eingesetzt wird.
  5. Verwendung nach Anspruch 4, wobei der Schritt des Ledergerbverfahrens der Einweichschritt ist.
  6. Verwendung nach Anspruch 5, wobei das Olivenmühlenabwasser (OMW) in einer Menge von 50 bis 100 Gew.-% bezogen auf das gesamte Lederbehandlungswasser, vorzugsweise in einer Menge von 75% bis 100%, noch bevorzugter in einer Menge von 100% verwendet wird.
  7. Verwendung nach Anspruch 4, wobei der Schritt des Ledergerbverfahrens der Gerbschritt ist.
  8. Verwendung nach irgendeinem der Ansprüche von 1 bis 3, wobei die Verwendung von Olivenmühlenabwasser als Gerbstoff oder Gerbstoffhilfsmittel im Gerbschritt des Ledergerbverfahrens in der Gerbindustrie eingesetzt wird.
  9. Verwendung nach Anspruch 8, wobei das Olivenmühlenabwasser (OMW) in einer Menge von 50 bis 100 Gew.-% bezogen auf das Lederbehandlungswasser, vorzugsweise in einer Menge von 75% bis 100%, noch bevorzugter in einer Menge von 100% verwendet wird.
  10. Verwendung nach Anspruch 8 oder 9, wobei das Olivenmühlenabwasser (OMW) in Kombination mit anderen Gerbstoffen verwendet wird, die ausgewählt sind aus der Gruppe bestehend aus einem natürlichen Tannin, wie Tara, Mimose, Kastanie, Myrobalan; einem synthetischen Tannin, wie Hydroxydiphenylsulfon; einer Verbindung, die der Familie der Phenolharze angehört; einer Verbindung, die der Familie der Naphthalinharze angehört; einem Aldehyd oder einem Vorläufer davon, wie Glutaraldehyd, Isoxazolidin, Oxazolidin; einem Metallsalz, wie ein Chrom-, Zirkonium- oder Titansalz; und einem Acrylharz, wie ein durch Homopolymerisation oder radikalische Copolymerisation von Acrylsäure erhaltenes Harz, wie Natriumpolyacrylat, Methacrylsäure, Methylmethacrylatester, Ethylacrylatester, Acrylamid, vorzugsweise versalzt, wie Natriumpolyacrylat (PA) und eine Mischung davon.
  11. Verwendung nach Anspruch 10, wobei das Olivenmühlenabwasser (OMW) in Kombination mit Natriumpolyacrylat (PA) verwendet wird.
  12. Verwendung nach den Ansprüchen von 10 bis 11, wobei das Acrylharz durch Homopolymerisation oder radikalische Copolymerisation, die im gleichen Olivenmühlenabwasser (OMW) durchgeführt wird, als Reaktionsmedium erhalten wird.
  13. Verwendung nach irgendeinem der Ansprüche von 8 bis 12, wobei der Schritt des Ledergerbverfahrens in der Gerbindustrie ein chromfreier Gerbschritt ist.
  14. Verwendung nach irgendeinem der Ansprüche von 1 bis 3, wobei die Verwendung von Olivenmühlenabwasser als Antioxidationsmittel eingesetzt wird, um die Bildung von Chrom (VI) in dem Nachgerbungsschritt zu vermeiden.
  15. Verwendung nach Anspruch 14, wobei das Olivenmühlenabwasser (OMW) in einer Menge von 50 bis 100 Gew.-% bezogen auf das gesamte Lederbehandlungswasser, vorzugsweise in einer Menge von 75% bis 100%, noch bevorzugter in einer Menge von 100% verwendet wird.
  16. Gerbstoffzusammensetzung, umfassend Olivenmühlenabwasser (OMW), ein oder mehrere Gerbstoffe, ausgewählt aus der Gruppe bestehend aus einem natürlichen Tannin, ausgewählt aus der Gruppe bestehend aus: Tara, Mimose, Kastanie und Myrobalan; einem synthetischen Tannin, wie Hydroxydiphenylsulfon; einer Verbindung, die der Familie der Phenolharze angehört; einer Verbindung, die der Familie der Naphthalinharze angehört; einem Aldehyd oder einem Vorläufer davon, wie Glutaraldehyd, Isoxazolidin, Oxazolidin; einem Metallsalz, wie ein Chrom-, Zirkonium- oder Titansalz; und einem Acrylharz, wie ein durch Homopolymerisation oder radikalische Copolymerisation von Acrylsäure erhaltenes Harz, wie Natriumpolyacrylat, Methacrylsäure, Methylmethacrylatester, Ethylacrylatester, Acrylamid, vorzugsweise versalzt, wie Natriumpolyacrylat (PA) und eine Mischung davon; und geeigneten Zusatzstoffen.
  17. Zusammensetzung nach Anspruch 16, wobei das Olivenmühlenabwasser (OMW) in Kombination mit Natriumpolyacrylat (PA) verwendet wird.
  18. Zusammensetzung nach den Ansprüchen von 16 bis 17, wobei das Acrylharz als Reaktionsmedium durch Homopolymerisation oder radikalische Copolymerisation erhalten wird, die im gleichen Olivenmühlenabwasser (OMW) durchgeführt wird.
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PCT/IB2017/054743 WO2018025210A1 (en) 2016-08-03 2017-08-03 Use of olive mill waste waters in the leather tanning industry

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IT201600081688A1 (it) 2016-08-03 2018-02-03 Tannow S R L Impiego di acque di vegetazione olearia nell'industria conciaria
TR202008933A2 (tr) * 2020-06-09 2020-06-22 Biolive Biyolojik Ve Kimyasal Teknolojiler Sanayi Ve Ticaret Anonim Sirketi Senteti̇k deri̇ üreti̇mi̇ i̇çi̇n zeyti̇n ekstrakti esasli dolguya sahi̇p poli̇mer karişimi
IT202000019696A1 (it) 2020-08-07 2022-02-07 Unique S R L Composizioni riconcianti e ingrassanti comprendenti un derivato di olio di canapa
ES2987135T3 (es) 2021-11-15 2024-11-13 Cyclica S R L Procedimiento para obtener un producto curtido
ES3039342T3 (en) * 2022-12-01 2025-10-20 Institut Nat Des Sciences Appliquees De Rouen Iridoid or seco-iridoid derivatives and their use in a tanning process
EP4379067A1 (de) * 2022-12-01 2024-06-05 Institut National Des Sciences Appliquées De Rouen Iridoidderivate und ihre verwendung in einem gerbverfahren

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CN109952384A (zh) 2019-06-28
EP3494237A1 (de) 2019-06-12
PL3494237T5 (pl) 2025-11-03
EP3494237B1 (de) 2021-04-14
ES2880083T3 (es) 2021-11-23
ES2880083T5 (en) 2025-11-28
IT201600081688A1 (it) 2018-02-03
PL3494237T3 (pl) 2021-12-13
WO2018025210A1 (en) 2018-02-08

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