WO2009000962A1 - Procédé de récupération de chrome et de bioproduits à partir de résidus de fourrures, installation à cet effet et produits obtenus - Google Patents

Procédé de récupération de chrome et de bioproduits à partir de résidus de fourrures, installation à cet effet et produits obtenus Download PDF

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Publication number
WO2009000962A1
WO2009000962A1 PCT/ES2008/070123 ES2008070123W WO2009000962A1 WO 2009000962 A1 WO2009000962 A1 WO 2009000962A1 ES 2008070123 W ES2008070123 W ES 2008070123W WO 2009000962 A1 WO2009000962 A1 WO 2009000962A1
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WO
WIPO (PCT)
Prior art keywords
chromium
iii
collagen
hydrogen peroxide
stage
Prior art date
Application number
PCT/ES2008/070123
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English (en)
Spanish (es)
Inventor
Jaime Cot Cosp
Agustín MARSAL MONGE
Albert Manich Bou
Pere Celma Serra
Jaume Cot Gores
Fernando FERNÁNDEZ HERVÁS
Original Assignee
Consejo Superior De Investigaciones Científicas
Instituto Químico De Sarrià
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Consejo Superior De Investigaciones Científicas, Instituto Químico De Sarrià filed Critical Consejo Superior De Investigaciones Científicas
Publication of WO2009000962A1 publication Critical patent/WO2009000962A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23J—PROTEIN COMPOSITIONS FOR FOODSTUFFS; WORKING-UP PROTEINS FOR FOODSTUFFS; PHOSPHATIDE COMPOSITIONS FOR FOODSTUFFS
    • A23J1/00—Obtaining protein compositions for foodstuffs; Bulk opening of eggs and separation of yolks from whites
    • A23J1/10—Obtaining protein compositions for foodstuffs; Bulk opening of eggs and separation of yolks from whites from hair, feathers, horn, skins, leather, bones, or the like
    • 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
    • C14C3/32—Recovering tanning agents from leather

Definitions

  • the present invention falls within the area of disposal and recovery of industrial wastes from the fur industry, and more specifically in a method for processing chromium collagen residues and their recovery.
  • Group V waste represents the highest percentage of the total volume of waste being also the most complex.
  • the group includes the unusable cut pieces of the leather products manufacturing industry such as shoes, clothing and upholstery.
  • Chromed collagen residues are those that are stabilized or bound with chromium salts type (III) which block any subsequent treatment to obtain collagen using conventional methods.
  • chromed waste cuts, recesses, serrajes, etc.
  • a large part of this type of waste is used for the production of agglomerates of regenerated leather or reusable products by the tanning industry:
  • An aspect of the invention constitutes a procedure for recovering chromium and bioproducts from a fur residue, hereinafter the method of the invention, characterized in that it is based on the oxidation of chromium (III) to chromium (Vl) using peroxides in an alkaline medium and because it comprises the following steps: i) a decromate stage, initially consisting of the process of oxidation of chromium (III) to chromium (Vl) using peroxides, generally hydrogen peroxide (H2O2), in an alkaline medium obtained, for example with sodium hydroxide or sodium carbonate, at room temperature, according to the following reaction:
  • a runoff stage preferably by means of a hydro-extractive centrifuge ( Figure 10, S-130) that produces a filtrate with chromium (Vl) and a solid phase with the decromated collagen fibers, iv) storage of the filtrate with chromium ( Vl) with stirring to which the chromium (III) reduction stage is subjected, with H2O2 in acidic medium, subsequently adjusting its pH for subsequent mixtures with chromium (III) solutions, preferably with reducing agents such as those belonging to the following group: hydrogen peroxide, sodium disulfite and glucose, and v) a stage of purification or isolation of the collagen in which the treated decromated collagen residues undergo a second highly controlled topochemical hydrolysis process.
  • reducing agents such as those belonging to the following group: hydrogen peroxide, sodium disulfite and glucose
  • Another aspect of the invention constitutes a necessary installation to carry out the process of the invention comprising the different elements to execute the aforementioned steps: a machine for the treatment of fibers, a hydro-extractive centrifuge, two reactors (decromation and another for obtain the biopolymers), a tank for storage and reduction of chromium (Vl), an atomizer (optional), an equipment to heat the concentrated solution of biopolymers and a transport system (see Figure 10).
  • Another aspect of the invention constitutes chromium (III) as well as the biopolymers or collagen obtained by the process of the invention.
  • the process of the present invention is based on the oxidation of chromium (III) to chromium (Vl) using peroxides, generally hydrogen peroxide (H2O2), in an alkaline medium. Thanks to the following process, the chromed collagen fibers are extracted at an early stage of the tanning phase, before doing anything or introducing it into the first liquid, non-stabilized or bound stage (1), (2), (3) , (4), (5), (6).
  • peroxides generally hydrogen peroxide (H2O2)
  • the advantages of the process of the present invention are the total elimination of chromium III (100%) by oxidation with H2O2 in alkaline medium to chromium Vl, at room temperature, in less than 1 hour, without alteration of the original physical-mechanical properties of the fiber, with a yield of 97% (recovery of solid collagen residue).
  • Said chromium-free residue is subjected to gentle hydrolysis to obtain biopolymers for application in the tanning industry itself. This procedure is also a shorter procedure than the existing ones (2, 3 and 4).
  • the chromium Vl obtained is reduced to chromium III with H2O2 in acidic medium and, once its alkalinity is adjusted, its concentration is increased with the addition of commercial chromium III and it is ready for reuse in the industry itself in the tanning stage .
  • the excess peroxide is completely removed from chromium (Vl), being acidified to the dichromate anion.
  • dichromate is strongly bound to an ion exchange resin column.
  • the chromium is reduced to form (III) using an acidic medium in the presence of the same peroxide. Since chromium has the same positive charge as that of the matrix of the resin, it can be easily collected, thus obtaining a solution with a high concentration.
  • peroxchromate is generated in situ, which is very active and that has a high oxidation capacity and accelerates the pre-hydrolysis (maceration of the fibers in the stage of obtaining the gelatin).
  • These compounds contain 2,5-peroxo groups for each chromium atom, which are strongly linked to the ionic groups of the collagen structure.
  • the presence of these peroxchromates during the second hydrolysis process carried out at 60 ° C-70 ° C, accelerates the kinetics of the reaction, favoring the production of the bioproduct, "gelatin", with excellent characteristics and in a minimum time. In two hours a yield of 98% or greater is obtained.
  • the treated chromium collagen residues undergo a second highly controlled topochemical hydrolysis process.
  • the control method depends on the degree of interaction of the following variables: - macerators - alkaline, acidic, liotropic. - activators - peroxides - hydrogen peroxide, sodium percarbonate, sodium perborate, etc.
  • the biopolymer obtained can be used in the tanning industry as: 1) protein retanning; 2) biodegradable film (film) in the finishing stage; 3) triggering agent and 4) basifying agent.
  • the biopolymer can also be used in the tanning industry as: 1) protein retanning; 2) biodegradable film (film) in the finishing stage; 3) triggering agent and 4) basifying agent.
  • the biopolymer can also be used in the tanning industry as: 1) protein retanning; 2) biodegradable film (film) in the finishing stage; 3) triggering agent and 4) basifying agent.
  • the biopolymer can also be used in the tanning industry as: 1) protein retanning; 2) biodegradable film (film) in the finishing stage; 3) triggering agent and 4) basifying agent.
  • the biopolymer can also be used in
  • a pilot plant has been designed to carry out all types of waste; capable of processing quantities in a range of 25-50 kg (Figure 10).
  • This plant includes the following equipment: fiber treatment machine, a hydro-extractive centrifuge, two reactors (decromation and another to obtain biopolymers), a tank for storage and reduction of chromium (Vl), an atomizer (optional), an equipment to heat the concentrated solution of biopolymers, transport truck ( Figure 10).
  • Pielcolor SA as partial and / or total substitution of casein in glossy finish.
  • Tabercolor SA as partial and / or total substitution of casein for the production of inks and printing of decorating paper for furniture
  • Virmit SA as binder for the process of engraving and textile printing Incusa as pretanning, retanning resin; as a filling agent and as an intensifier for dyeing.
  • the bioproduct is copolymerized with acrylic or polyurethane monomers (14), (15), (16), (17).
  • an advantage of the procedure is of an environmental and economic nature, by solving the need imposed by waste disposal regulations in such a way as to prevent the contamination of the environment by chromium III, capable of passing naturally to chromium Vl , highly toxic. This currently involves high costs for tanners.
  • one aspect of the invention constitutes a procedure for the recovery of chromium and bioproducts from a leather waste, hereinafter the method of the invention, characterized in that it is based on the oxidation of chromium (III) to chromium (Vl ) using peroxides in an alkaline medium and because it comprises the following steps: i) a decromate stage, initially consisting of the oxidation process of chromium (III) to chromium (Vl) using peroxides, generally hydrogen peroxide (H2O2), in a alkaline medium obtained, for example with sodium hydroxide or sodium carbonate, at room temperature, according to the following reaction:
  • a runoff stage preferably by means of a hydro-extractive centrifuge ( Figure 10, S-130) that produces a filtrate with chromium (Vl) and a solid phase with the decromated collagen fibers, iv) storage of the filtrate with chromium ( Vl) with stirring to which it is subjected to chromium (III) reduction stage, with H2O2 in acidic medium, subsequently adjusting its pH for subsequent mixtures with solutions with chromium (III), preferably with reducing agents such as those belonging to the following group: hydrogen peroxide, sodium disulfite and glucose, and v) a stage of purification or isolation of the collagen in which the treated decromated collagen residues suffer a second highly controlled topochemical hydrolysis process.
  • Another aspect of the invention constitutes a necessary installation to carry out the process of the invention comprising the different elements to execute the aforementioned steps: a machine for the treatment of fibers, a hydro-extractive centrifuge, two reactors (decromation and another for obtain the biopolymers), a tank for storage and reduction of chromium (Vl), an atomizer (optional), an equipment to heat the concentrated solution of biopolymers and a transport system (see Figure 10).
  • Another aspect of the invention constitutes chromium (III) as well as the biopolymers or collagen obtained by the process of the invention.
  • Another aspect of the invention constitutes the use of chromium (III) obtained by the process of the invention in new industrial processes where its presence is required, for example, in the leather industry.
  • Figure 1 Effects of formaldehyde, sodium carbonate, hydrogen peroxide and time on the residual chromium content in ppm.
  • Figure 2. Interaction: Hydrogen peroxide x formaldehyde.
  • Figure 3. Evolution of residual chromium as a function of the concentration of hydrogen peroxide and formaldehyde at 2% Na2CO3 and 69 minutes of treatment corresponding to the conditions of minimum residual chromium.
  • Figure 4. Effect of the concentration of formaldehyde, sodium carbonate and hydrogen peroxide on the performance Figure 5.- Interaction formaldehyde x hydrogen peroxide and sodium carbonate x hydrogen peroxide.
  • Figure 9. Evolution of the desirability as a function of the concentration of sodium carbonate and hydrogen peroxide.
  • Figure 10. Scheme of the transformation plant. J-110, container to defibrate; R-120, oxidation reactor; S-130, hydro-extractive centrifuge; R-140, reactor for the isolation of the collagen biopolymer; T-150; heating equipment; D-160; spray dryer
  • Example 1 Procedure of purification of chromium and waste value electorates
  • thermodynamic equation indicates the possibility of spontaneous oxidation in a wide range of pHs.
  • the component that acts as an oxidative agent is the oxygen that comes from the decomposition of hydrogen peroxide:
  • the blue complex is presented with a neutral medium and a brown complex with an alkaline medium.
  • This alkaline medium is favored by the excess of hydrogen peroxide and by the basic level of the sample.
  • this reaction is influenced by the diffusion of oxygen in the reaction medium.
  • the method for obtaining the "liquor" chromium with disulfite is very similar to that used with sulphite.
  • the disulfite reacts with the acid forming sulphite that acts as a reducer and provides large amounts of sulfates.
  • the following equation presents the global reaction that governs the process.
  • glucose is not completely oxidized to carbon dioxide, but some intermediate compounds are formed, generally organic acids that play an interesting role due to their influence to decrease alkalinity and hide the effect of chromium.
  • the following equation presents the reaction when the glucose undergoes a complete oxidation.
  • the masking effect increases with the increase in glucose, favoring the formation of organic acids.
  • the reduction temperature produces an effect on the desired basic pH.
  • a problem that arises when using this method is doubt whether it is better to add glucose to the glucose-dichromate mixture or to add acid to the glucose-dichromate mixture.
  • the decolorized collagen fibers are pushed by a conventional pump until the next stage.
  • biopolymers can be marketed in two forms; first, as a 30% solution which can be stored in a covered stainless steel tank; however, care should be taken when the temperature drops below 14 0 C, therefore it is necessary to heat about 4O 0 C with special equipment. In this way, it becomes a manageable viscous liquid when needed. (Figure 10, T-150); or in a solid powder using a spray dryer ( Figure 10, D-160).
  • This procedure can be adjusted to treat other types of INI chromium residues from tanneries, produced during different stages of the tanning process; such as: chrome of the complete tanning process, fatliquoring, retanning, dyeing, finishing and, in addition, residues of the double-sided process, hair and wool separation process with a suitable filtration machine.
  • Residual Cr 2970.34 + 277.458 * HCHO + 36.3611 * Na 2 CO 3 - 593.763 * H 2 O 2
  • the evolution of the desirability parameter is presented as a function of the variables formaldehyde and hydrogen peroxide for the optimum levels of the other two factors ( Figure 8) and the variables sodium carbonate and hydrogen peroxide ( Figure 9) for the optimal levels of formaldehyde and weather. It is observed that the optimum zone is obtained for a formaldehyde concentration around 1.92% s / b, a sodium carbonate concentration of 6.36% s / b, a hydrogen peroxide concentration 110 vol of 9.77% s / b and high time (90 minutes).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Zoology (AREA)
  • Biochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention se rapporte à un procédé de récupération de chrome et de bioproduits à partir d'un résidu de fourrure, lequel procédé repose sur l'oxydation du chrome (III) en chrome (IV) au moyen de peroxydes dans un milieu alcalin; et à une installation destinée à la mise en oeuvre dudit procédé. Etant donné que le chrome et les bioproduits peuvent être réutilisés, l'invention permet de résoudre le problème de la pollution du milieu ambiant et de valoriser les rebuts.
PCT/ES2008/070123 2007-06-25 2008-06-25 Procédé de récupération de chrome et de bioproduits à partir de résidus de fourrures, installation à cet effet et produits obtenus WO2009000962A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES200701770A ES2310483B1 (es) 2007-06-25 2007-06-25 Procedimiento para la recuperacion de cromo y bioproductos a partir de residuos peleteros, instalacion para llevarlo a cabo y los productos asi obtenidos.
ESP200701770 2007-06-25

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WO2009000962A1 true WO2009000962A1 (fr) 2008-12-31

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102719573A (zh) * 2012-06-27 2012-10-10 四川大学 单宁和维生素c协同作用降低皮革中六价铬含量的方法
CN103789463A (zh) * 2014-02-17 2014-05-14 湖南立得皮革有限公司 蓝湿牛皮脱铬软化处理方法
ES2777748A1 (es) * 2019-02-05 2020-08-05 Sotos Jose Manuel Sanchez Maquina modular y procedimiento para recuperacion de metales procedentes de restos de curtido de pieles

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4151161A (en) * 1976-06-14 1979-04-24 Canada Packers Limited Preparation of high-quality gelatine having low chromium content from chromed waste stock
US4483829A (en) * 1982-02-02 1984-11-20 Giuliano Guardini Process for recovering proteins and chromium from chrome-tanning waste
HUT55838A (en) * 1987-08-19 1991-06-28 Laszlo Hoffmann Working up chrome-tanned waste leather
WO1993014170A1 (fr) * 1992-01-15 1993-07-22 Invente S A Procede de recuperation de metaux contenus dans des produits de depart comprenant des substances proteiniques ainsi que materiau pouvant etre obtenu selon ce procede
EP0567671A1 (fr) * 1992-04-28 1993-11-03 Jozef Siska Elimination de chrome du cuir tanné au chrome
ES2042400A1 (es) * 1992-03-05 1993-12-01 Consejo Superior Investigacion Procedimiento para el tratamiento integral de subproductos de la industria de curtidos mediante el ataque controlado con peroxido de hidrogeno.
ES2299534T3 (es) * 2000-12-22 2008-06-01 ARTONI S.A.S. DI ARTONI GIANCARLO & C. Procedimiento para extraccion de gelatinas y recuperacion de sales de cromo a partir de raspaduras de cueros y pieles curtidas.

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4151161A (en) * 1976-06-14 1979-04-24 Canada Packers Limited Preparation of high-quality gelatine having low chromium content from chromed waste stock
US4483829A (en) * 1982-02-02 1984-11-20 Giuliano Guardini Process for recovering proteins and chromium from chrome-tanning waste
HUT55838A (en) * 1987-08-19 1991-06-28 Laszlo Hoffmann Working up chrome-tanned waste leather
WO1993014170A1 (fr) * 1992-01-15 1993-07-22 Invente S A Procede de recuperation de metaux contenus dans des produits de depart comprenant des substances proteiniques ainsi que materiau pouvant etre obtenu selon ce procede
ES2042400A1 (es) * 1992-03-05 1993-12-01 Consejo Superior Investigacion Procedimiento para el tratamiento integral de subproductos de la industria de curtidos mediante el ataque controlado con peroxido de hidrogeno.
EP0567671A1 (fr) * 1992-04-28 1993-11-03 Jozef Siska Elimination de chrome du cuir tanné au chrome
ES2299534T3 (es) * 2000-12-22 2008-06-01 ARTONI S.A.S. DI ARTONI GIANCARLO & C. Procedimiento para extraccion de gelatinas y recuperacion de sales de cromo a partir de raspaduras de cueros y pieles curtidas.

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102719573A (zh) * 2012-06-27 2012-10-10 四川大学 单宁和维生素c协同作用降低皮革中六价铬含量的方法
CN102719573B (zh) * 2012-06-27 2014-04-16 四川大学 单宁和维生素c协同作用降低皮革中六价铬含量的方法
CN103789463A (zh) * 2014-02-17 2014-05-14 湖南立得皮革有限公司 蓝湿牛皮脱铬软化处理方法
CN103789463B (zh) * 2014-02-17 2015-10-28 湖南立得皮革有限公司 蓝湿牛皮脱铬软化处理方法
ES2777748A1 (es) * 2019-02-05 2020-08-05 Sotos Jose Manuel Sanchez Maquina modular y procedimiento para recuperacion de metales procedentes de restos de curtido de pieles

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Publication number Publication date
ES2310483B1 (es) 2010-01-08
ES2310483A1 (es) 2009-01-01

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