EP3494237A1 - Utilisation d'eaux usées de moulins à olives dans l'industrie du tannage du cuir - Google Patents

Utilisation d'eaux usées de moulins à olives dans l'industrie du tannage du cuir

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Publication number
EP3494237A1
EP3494237A1 EP17761132.4A EP17761132A EP3494237A1 EP 3494237 A1 EP3494237 A1 EP 3494237A1 EP 17761132 A EP17761132 A EP 17761132A EP 3494237 A1 EP3494237 A1 EP 3494237A1
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EP
European Patent Office
Prior art keywords
omw
tanning
waste waters
mill waste
olive mill
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Application number
EP17761132.4A
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German (de)
English (en)
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EP3494237B1 (fr
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 O2/L and 30 grams O2/L, respectively, for waters originating from the most modern centrifugal plants, and even 150 grams O2/L and 90 grams O2/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.
  • 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.
  • 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.
  • OW olive oil mill waste waters
  • Tanning agents are more preferably 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, methacrylic acid, methyl methacrylate ester, ethyl acrylate ester, acrylamide, preferably salified, such as sodium polyacrylate (PA).
  • a natural tannin such as tara, mimosa, chestnut, myrobalan
  • a synthetic tannin such as hydroxydiphenyl sulphone
  • 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.
  • Leather treatment water means the liquid to be used for hides treatment, to which the various treatment agents are added; its quantity is normally expressed as Kg of liquid compared to Kg of hides to be treated;
  • Network water means the water supplied by the normal industrial water system, and typically used as treatment water in the leather tanning process.
  • 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. Therefore, all the chemical agents traditionally used in the various steps of the tanning process should, at the same time, ensure obtainment of the properties pursued in the specific step in which the agent is used, without compromising or altering the delicate reaction balance of the subsequent steps, or compromising the performances obtained after the treatments of the previous steps.
  • 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 cross- linking 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, methyl methacrylate ester, ethyl acrylate ester, acrylamide, preferably salified, such as sodium polyacrylate (PA), and mixture thereof.
  • a natural tannin such as tara, mimosa, chestnut, myrobalan
  • 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) and suitable additives.
  • OMW olive oil mill waste waters
  • the invention relates to a tanning composition
  • a tanning composition comprising olive oil mill waste waters (OMW) and one or more 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, methacrylic acid, methyl methacrylate ester, ethyl acrylate ester, acrylamide, preferably salified, such as sodium polyacrylate (PA), and mixture thereof.
  • OMW olive oil mill
  • 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.
  • said 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, 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, 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 preferably in the range from 5
  • 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:
  • Test 1 Dry hides + 100% (kg hides/kg bath ratio) of network water, at 25°C, rotating in a jar mill for 2 hours (blank test);
  • Test 2 Dry hides + 100% (kg hides/kg bath ratio) of network water added with a commercially available dithiocarbamate antimicrobial agent, at 25°C, rotating in a jar mill for 2 hours;
  • Test 3 Dry hides + 75% (kg hides/kg bath ratio) of network water + 25% OMW, at 25°C, rotating in a jar mill for 2 hours;
  • Test 4 Dry hides + 50% (kg hides/kg bath ratio) of network water + 50% OMW, at 25°C, rotating in a jar mill for 2 hours;
  • Test 5 Dry hides + 25% (kg hides/kg bath ratio) of network water + 75% OMW, at 25°C, rotating in a jar mill for 2 hours;
  • Test 6 Dry hides + 100% (kg hides/kg bath ratio) di OMW, at 25°C, rotating in a jar mill for 2 hours.
  • 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.
  • the measurement of the tanning capacity is determined according to the formula:
  • Ci and Cf are the concentrations of the tanning product in the aqueous solution having a tanning effect, initially and after absorption by the standard hide, respectively.
  • the measurement of the tanning capacity is determined according to the formula:
  • Pi and Pf are the total phenols concentrations in the aqueous solution having tanning effect, initially and after absorption by the standard hide.
  • the determination of total phenols was performed also on commercial tannins solutions.
  • the measurement of the tanning power results from the determination of the amount of phenols absorbed by the hide. The higher the percentage of absorbed phenols, the greater the tanning power of the agent used.
  • 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).
  • 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%.
  • Example 3 Evaluation of OMW as a preservative and tanning adjuvant agent. 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.
  • Test 1 Microbiological stabilization
  • 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 (a) showed that the OMW treatment was effective in the microbiological stabilization of the hides.
  • Test (b) showed a contraction temperature of 60°C, meaning an interesting tanning activity by OMW.
  • 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. In parallel, a similar preparation was performed where water was used instead of OMW. After resting the hides on a horse for a few days, the following tests were performed:
  • OMW bath had no mold or malodorousness formation, and no sign of degradation (putrefaction) of the tissues. On the contrary, with the water bath the hides were observed to be not as stabilized from the microbiological point of view, with the appearance of molded areas.
  • Test 2 showed that, in addition to microbiological stabilization, OMW worked in synergy with the oxazolidine tanning agent, enhancing the tanning power of the bath, as evidenced by an increase of 5°C in Tg in the case of OMW bath (Test d).
  • the OMW presence allowed to obtain a Tg value fully comparable to that of conventional tanning baths with aldehydes or tannins.
  • 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. After resting the hides on a horse for a few days, the contraction temperature was determined, which resulted to be:
  • 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 82, 82, 83°C - Average value: 82°C;
  • Tg 78, 79, 77°C - Average value: 78°C;
  • 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.
  • Example 4 Evaluation of the tanning capacity of OMW compositions comprising various amounts of acrylic resins
  • 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).
  • Tanning Power (%) 1 1 .47 68.59 82.27 Tg (°C) 67 75 77
  • 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 were used, whose characteristics are listed in Table 9 below
  • Mixture 5 wherein the resin was obtained by direct polymerization in OMW1
  • Mixture 6 wherein the resin was obtained by direct polymerization in OMW2
  • Table 10 The results of treating the hides with these Mixtures 5 and 6 are shown in Table 10 below, always as a comparison with the results obtained by treatment with the PA resin alone.
  • 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 1 1 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.
  • sulphited fish oil was used during the fatliquoring step, which, given the high content of unsaturated molecular sites, is a strong promoter of radical ionization processes, triggered by environmental conditions such as temperature and humidity, which lead to mobilization of Chromium III, normally fixated into the collagen fibers of the leather, by oxidation into Chromium VI, which is released and can be determined by spectrophotometry, according to the international method UNI EN ISO 17075.
  • the leather is 2.0% Dermoclean
  • 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.
  • Conditioning 1 24 h under UV irradiation 30 cm away from the source (Iron halogenide UV lamp, JELOSIL HG200 L, emitting a 300 W/m 2 , power in the range 320 - 400 nm), T 30°C, relative humidity 55%; • Conditioning 2: 24 h in climatic chamber at 60°C, relative humidity 90% (more stressful condition).
  • %red the percentage of Cr(VI) content abatement

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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)

Abstract

L'invention concerne l'utilisation d'eaux usées de moulins à olives (olive mill waste waters - OMW) dans au moins une étape du procédé de tannage du cuir dans l'industrie du tannage. De préférence, lesdites eaux usées de moulins à olives sont utilisées comme bactéricides, agents de tannage ou agent adjuvant de tannage et/ou agents antioxydants pour empêcher la formation de chrome (VI) pendant l'étape de retannage. De manière avantageuse, l'invention concerne une composition de tannage comprenant lesdites eaux usées de moulins à olives (OMW) et des additifs appropriés.
EP17761132.4A 2016-08-03 2017-08-03 Utilisation des eaux usées des moulins de l'huile d'olive dans l'industrie de tannage de cuir Active EP3494237B1 (fr)

Priority Applications (1)

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PL17761132T PL3494237T3 (pl) 2016-08-03 2017-08-03 Zastosowanie ścieków z tłoczni oleju oliwkowego w przemyśle garbowania skór

Applications Claiming Priority (2)

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IT102016000081688A IT201600081688A1 (it) 2016-08-03 2016-08-03 Impiego di acque di vegetazione olearia nell'industria conciaria
PCT/IB2017/054743 WO2018025210A1 (fr) 2016-08-03 2017-08-03 Utilisation d'eaux usées de moulins à olives dans l'industrie du tannage du cuir

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EP3494237B1 EP3494237B1 (fr) 2021-04-14

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CN (1) CN109952384A (fr)
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WO (1) WO2018025210A1 (fr)

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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
EP4180541B1 (fr) 2021-11-15 2024-05-15 Cyclica S.r.l. Procédé de préparation d'un produit tanné
EP4379067A1 (fr) * 2022-12-01 2024-06-05 Institut National Des Sciences Appliquées De Rouen Dérivés iridoïdes et leur utilisation dans un procédé de tannage
EP4379068A1 (fr) * 2022-12-01 2024-06-05 Institut National Des Sciences Appliquées De Rouen Dérivés iridoïdes ou séco-iridoïdes et leur utilisation dans un procédé de tannage

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GR1004402B (el) * 2002-02-08 2003-12-19 Lavipharm S.A. Αξιολογηση της αντιοξειδωτικης και κυτταροπροστατευτικης ικανοτητας του 5-(αιθυλιδενο-2-οξο-τετραυδρο-πυρανυλ-4) οξικου οξεως και εκχυλισματων απο ελιες, ελαιολαδο, αποβλητα ελαιοτριβειων και φυλλα ελαιοδενδρων, και οι εφαρμογες τους
JP5172228B2 (ja) * 2007-06-28 2013-03-27 ミドリホクヨー株式会社 革
EP2062985A1 (fr) 2007-11-23 2009-05-27 N-Zyme BioTec GmbH Agent et procédé de tannage de peaux et de pelages
RU2603139C2 (ru) * 2011-06-02 2016-11-20 ЛЕНКСЕСС Дойчланд ГмбХ Привитые полимеры на основе полисахаридов и/или полипептидов в качестве синтетических танинов
CN104413076A (zh) * 2013-08-28 2015-03-18 青岛医防消毒专业技术中心 一种含睡莲提取物的皮革防霉剂
EP3157540A1 (fr) * 2014-05-15 2017-04-26 Pesle, Livio Décoction de feuilles d'olivier
IT201600081688A1 (it) 2016-08-03 2018-02-03 Tannow S R L Impiego di acque di vegetazione olearia nell'industria conciaria

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Publication number Publication date
EP3494237B1 (fr) 2021-04-14
ES2880083T3 (es) 2021-11-23
IT201600081688A1 (it) 2018-02-03
WO2018025210A1 (fr) 2018-02-08
PT3494237T (pt) 2021-07-14
PL3494237T3 (pl) 2021-12-13
CN109952384A (zh) 2019-06-28

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