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 PDFInfo
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- 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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- Prior art keywords
- chromium
- iii
- collagen
- hydrogen peroxide
- stage
- Prior art date
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000002699 waste material Substances 0.000 title claims abstract description 15
- 238000009434 installation Methods 0.000 title claims abstract description 6
- 238000004064 recycling Methods 0.000 title abstract 2
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- 150000002978 peroxides Chemical class 0.000 claims abstract description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 82
- 239000011651 chromium Substances 0.000 claims description 64
- 229910052804 chromium Inorganic materials 0.000 claims description 55
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 30
- 102000008186 Collagen Human genes 0.000 claims description 28
- 108010035532 Collagen Proteins 0.000 claims description 28
- 229920001436 collagen Polymers 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 28
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims description 27
- 229920001222 biopolymer Polymers 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- 239000000835 fiber Substances 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000011282 treatment Methods 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 239000010985 leather Substances 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 238000002955 isolation Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000011109 contamination Methods 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 62
- 229960002163 hydrogen peroxide Drugs 0.000 description 34
- 230000000694 effects Effects 0.000 description 18
- 235000017550 sodium carbonate Nutrition 0.000 description 14
- 230000003993 interaction Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- -1 dichromate anion Chemical class 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 108090000765 processed proteins & peptides Proteins 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical class NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- 229940045872 sodium percarbonate Drugs 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 102000005158 Subtilisins Human genes 0.000 description 1
- 108010056079 Subtilisins Proteins 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000000540 analysis of variance Methods 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000002610 basifying agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011173 biocomposite Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical class [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 239000003531 protein hydrolysate Substances 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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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- 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.
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 |
Publications (1)
Publication Number | Publication Date |
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WO2009000962A1 true WO2009000962A1 (fr) | 2008-12-31 |
Family
ID=40130667
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/ES2008/070123 WO2009000962A1 (fr) | 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 |
Country Status (2)
Country | Link |
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ES (1) | ES2310483B1 (fr) |
WO (1) | WO2009000962A1 (fr) |
Cited By (3)
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)
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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. |
-
2007
- 2007-06-25 ES ES200701770A patent/ES2310483B1/es not_active Expired - Fee Related
-
2008
- 2008-06-25 WO PCT/ES2008/070123 patent/WO2009000962A1/fr active Application Filing
Patent Citations (7)
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)
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 |
Also Published As
Publication number | Publication date |
---|---|
ES2310483B1 (es) | 2010-01-08 |
ES2310483A1 (es) | 2009-01-01 |
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