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    • 专利摘要:
    Discoloration of industrial effluents. The present invention relates to a process for decolorizing solutions of organic dyes comprising contacting a solution comprising at least one organic dye with a catalyst comprising pd on a support; and a reducing agent. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2568829A1
    申请号:ES201431605
    申请日:2014-11-03
    公开日:2016-05-04
    发明作者:Alejandro HERRERO PIZARRO；Carmen Bélen MOLINA CABALLERO；Juan José RODRÍGUEZ JIMÉNEZ
    申请人:Universidad Autonoma de Madrid；
    IPC主号:
    专利说明:

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    Bleaching of industrial effluents DESCRIPTION
    The present invention relates to the bleaching of industrial effluents through the use of catalysts and reducing agents. Therefore, the present invention can be framed in the technical field of the treatment of contaminating substances, more specifically, in the treatment of organic dyes. STATE OF THE TECHNIQUE
    Organic dyes represent a very important sector of the chemical industry and its use is widespread for the production of substances that serve in the textile industry, which consumes two thirds of the world production of synthetic dyes, in the production of different plastic materials or inks as well as in stains or other techniques, among others.
    The triarylmethane group dyes are synthetic organic compounds that contain a central carbon atom attached to three aromatic rings, depending on the color and properties of the number and nature of the auxochromic effects. They are the most important arylmetine group and in this group there are red, green, violet, blue and green dyes, characterized by being very hyperchromic, with bright shades. Specifically they are used in tissue stains and have a very intense coloration. (Gilabert, Chapter 4.4 Triarylmethane dyes, Textile chemistry Volume II: coloring matter, Polytechnic University of Valencia, 2003).
    On the other hand, azo dyes represent 70% of the total dyes produced in the world 7x105 t / year in 2003 (Fernandez et al., Trends in Analytica l Chemistry 29, 1202-1211, 2010). The discharge of coloring substances is expressly prohibited by current legislation (Law 10/1993, of October 26, on industrial liquid discharges into the integral sanitation system) and can be considered, in some cases, as toxic and hazardous waste. For the elimination of this type of substances, different types of processes have been used, including catalytic oxidation (advanced oxidation processes, wet oxidation, etc ...) and adsorption.
    The elimination of these types of dyes in aqueous medium is a problem for the industry in their production and use since these compounds generate a very intense coloration in aqueous medium in very low concentrations, which leads to try to eliminate them completely from the medium as the only solution to trouble.
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    Numerous publications on the oxidation of this type of compounds in real wastewater from industries such as textiles can be found in the scientific literature. The main disadvantages of this type of treatment based on catalytic oxidation lies in the possible formation of much more toxic species than the initial ones (as it does not achieve complete oxidation), an important issue in nitrogen compounds, which can condense giving rise to formation of other substances even more toxic than the starting ones. In advanced oxidation processes this usually occurs when sub-stoichiometric concentrations of the oxidizing reagents (H2O2 or O3) are used, making the process more expensive by requiring large amounts of reagents to achieve acceptable biodegradability. Another aspect to take into account is that wet oxidation processes, which achieve a greater elimination of organic matter, require expensive equipment and severe reaction conditions with high temperature and / or pressure.
    On the other hand, adsorption processes require the use of materials with a large surface area such as active coals or clays, among others. The main disadvantage of the use of adsorbent materials is that the material must be managed as a hazardous waste after use or properly treated to remove the contaminant from its surface.
    Another possibility to eliminate this type of nitrogen compounds is the reduction processes. The technologies that employ these processes have been used in order to eliminate the color of solutions or effluents with azo dyes. Traditionally reducing agents such as sodium hydrosulfite, sulfoxylate formaldehyde have been used
    or hydroxyacetone as they can carry out the "dismantling" of these structures by breaking the azo bond (Barragan, Thesis: Degradation of textile dyes by bacterial cultures, University of Salamanca, 2004).
    No publications have been found in which the discoloration of triarylmethane compounds is treated by hydrotreating with heterogeneous catalysts based on supported Pd. Yes, work has been found in which it is treated by oxidation technologies (Fernandez et al., Trends in Analytical Chemistry 29, 1202-1211, 2010).
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    There are publications in which the discoloration of azo compounds is treated by reductive techniques such as hydrogenation of the azo bond. Specifically, this treatment has been used for the reduction of the Congo red (CAS: 573-58-0) and methyl orange (CAS: 547-58-0) dyes using TiO2 catalysts (Bejarano-Pérez et al., Ultrasonics Sonochemistry 14, 2007, 589-595); nickel nanoparticles (Kalwar et al., App. Cat. A: Gen. 453, 2013, 54-59) or gold and silver nanoparticles (Rajesh et al., New J. Ch em. 38, 2014, 1551-1558 ; Wang et al., Chem. Eng. J. 237, 2014, 336-343), obtaining amines as a product.
    In addition, jobs that use Pd-based catalysts can also be found to carry out these processes. For example in Jia et al. (J. Env. Sci. 26, 2014, 478-482) a hydrophobic polymeric membrane with Pd is used for the hydrogenation of congo red). However, this technique requires high percentages of Pd (> 20% by weight) to achieve dye removal.
    Also described are nanoparticles of Pd on hydroxyapatite and magnetite for the removal of methyl orange (Safavi and Momeni, J. Hazard. Mat. 201-202, 2012, 125-131) and nanoparticles of Pd using sodium borohydride as a reducing agent ( Amornkitbamrung et al., Spectrochim. Acta. A. Mol. Biomol. Spectrosc. 122, 2014, 182-192). Other studies describe the hydrogenation of methyl orange using zero-valent iron or zinc (Shih et al., J. Enviro n. Eng. Manage 20 (03) 137-143, 2010; Guo et al., J. Hazard. Mat. 195 , 2011, 290-296., Rahman et al., J. Env. Sci. 10 (2), 2014, 157-163.). However, these studies include soluble complexes or nanoparticles that, being unsupported, are not suitable for practical applications. DESCRIPTION OF THE INVENTION
    The main advantages obtained with this process are the following:
    -  This process allows to achieve a high degree of discoloration under environmental conditions of temperature and pressure due to the great capacity of the same to carry out the hydrogenation or substitution of chromophores groups;
    -  The catalyst has great stability in this process for the treatment of this type of compounds;
    -  it has been observed that during the treatment of congo red at acidic pH, in addition to effluent decolorization, the elimination of organic matter is formed when a precipitate forms
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    which can be removed as a solid residue, which is an advantage over adsorption processes in which the adsorbent material must also be treated; - Another additional advantage of the process of the present invention is the ability to reuse the reducing agent in the case of using hydrogen gas since it can be recirculated to the reactor and can be treated by continuous operation.
    In a first aspect, the present invention relates to a process for decolorizing organic dye solutions comprising contacting a solution comprising at least one organic dye with:
    a) a catalyst comprising Pd in a support; Y
    b) a reducing agent.
    By organic dye is meant an organic compound that is capable of absorbing certain wavelengths in the visible spectrum. These compounds comprise in their structure chromophores groups, which are the groups that make said absorption in the visible occur.
    In an embodiment of the first aspect of the present invention, the organic dyes are selected from azo dyes, triarylmethane dyes and any of their mixtures.
    An azo dye is a dye that comprises an azo group conjugated with aromatic groups, that is, they are compounds that have the general formula R-N = N-R ’, where R and R’ have aromaticity.
    A triarylmethane dye is a compound that has the general formula I:
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    (I)
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    Where each ring is independently optionally substituted by one or more substituents R ', R' ', R' '', where each R ', R' 'or R' 'are independently, -R –NR2, = NR2 +, -SO3- halogen -OR
    where R is -H or C1-C4 alkyl.
    In another embodiment of the first aspect of the present invention, the azo dye is selected from orange I, orange II, black amido 10B, acid blue 193, acid brown 425, acid orange 8, acid orange 10, acid orange 61, acid red 66 , acid red 14, acid red 33, acid red 73, acid red 88, acid red 97, red for, alizarin yellow R, allura AC red, acid red 27, 4-aminoazobenzene, azoviolet, brown Bismarck, gloss black BN, blue direct 1, direct blue 6, direct blue 15, direct blue 71, direct orange 61, direct red 23, direct violet 51, scattered orange 1, scattered red 1, Evans blue, fast yellow AB, litolubine BK, yellow methanyl, yellow pigment 10, methyl red, methyl yellow, mordant brown 33, oil red O, oil red EGN, Ponceau S, prontosil, black reagent 5, black reagent 39, blue reagent 49, orange reagent 16, red reagent 45, red reagent 120 , red reagent 141, red reagent 180, red reagent 239, re active red 272, reagent yellow 15, red 2G, solvent yellow 124, sweat black, sunset yellow, tartrazine, trypan blue, 2G yellow, congo red, methyl orange and any of their mixtures.
    A table with the azo dyes and their synonyms, as well as their CAS number, is added below.
    Name  Other namesCAS
    Orange II Acid Orange 7, Acid Orange A633-96-5
    Black Amido 10 B Naphthalene black 12B, acid black 10B, acid black 11064-48-8
    Acid Blue 193 Palatine Fast Blue BN12392-64-2
    Acid Brown 425 Sandoderm Brown G, Everacid Brown EG119509-49-8
    Acid Orange 8 5850-86-2
    Acid Orange 61 6408-33-9
    Acid red 14 Acid red 2B, crystalline red acid A, azorubin3567-69-9
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    Acid Red 33 Red 333567-66-6
    Acid Red 73 Crocein Scarlet, Croceine Acid red, brilliant crocein5413-75-2
    Acid red 88 Solid Red A, 2-naphthol red, Toyo roccelline, Fast Red A1658-56-6
    Acid Red 97 10169-02-5
    Alizarin Yellow R Mordant orange I, alizarin orange R2243-76-7 (acid), 171834-9 (sodium salt)
    AC Allura Red Red allura, Food red 1725956-17-6
    Acid red 27 Amaranth, azorubin S915-67-3
    4-aminoazobenzene Aniline yellow, Brasilazina oil Yellow G, Ceres Yellow, Fast spirit Yellow, Induline R, Oil Yellow AAB, Oil Yellow AN, Oil Yellow B, Oil Yellow 2G, Oil Yellow R, Organol Yellow, Organol Yellow 2A, Solvent Yellow, Somalia Yellow 2G, Stearix Brown 4R, Sudan Yellow R, Sudan Yellow RA60-09-3
    azoviolet Magneson, pnitrophenylazoresorcinol74-39-5
    Acid red 66 Biebrich Scarlet, Ponceau BS4196-99-0
    Bismarck Brown Marron Manchester, Phenylene brown, basic brown 18005-77-4
    BN gloss black Brilliant Black PN, Brilliant Black A, Black PN, Food Black 1, Naphthol Black, Certicol Black PNW, Cilefa Black B, E 151, Edicol Supra Black BN, Hexacol Black PN; L Black 8000, Melan Black; Xylene Black F2519-30-4
    Black 7984 Food black 22118-39-0
    Congo red 573-58-0
    Direct Blue 1 Airedale Blue FFD, Amanil Sky2610-05-1
    Blue 6B, Amanil Sky Blue FF, Atlantic Resin Fast Blue, Chicago Sky Blue 6B
    Direct Blue 6 Airedale Blue 2BD Aizen Direct Blue 2BH Amanil Blue 2BX Atlantic Blue 2B Atul Direct Blue 2B Azocard Blue 2B, direct blue 2b, direct blue A2602-46-2
    Direct Blue 15 direct blue 5B, blue 5B, blue 5BN, direct blue FFN,2429-74-5
    Direct Blue 71 4399-55-7
    Direct Orange 61 1325-53-7
    Direct Red 23 Direct Scarlet 4BS, Direct Red B, Direct Fast Scarlet 4BS, Solophenyl Scarlet RS3441-14-3
    Direct Violet 51 Direct Fast Violet BB, Direct Violet BB, Diazol Violet B, Direct Brilliant Fast Violet BB, Direct Fast Violet 2B5489-77-0
    Scattered Orange 1 4- (4-Nitrophenylazo) diphenylamine2581-69-3
    Scattered red 1 N-ethyl-N- (2-hydroxyethyl) -4- (4nitrophenylazo) aniline2872-52-8
    Evans blue 314-13-6
    AB yellow fast Fast yellow, fast yellow, Food yellow 2, E-105, Solid yellow79873-36-2
    Litol-Rubina BK Ruby Pigment, Carmine 6b, E-180, Brilliant Carmine 6B, Permanent Rubin L6B, Litholrubine, Latolrubine, Pigment Red 575281-04-9
    Yellow Methanil Acid yellow 36, acid yellow 36587-98-4
    Methyl orange 547-58-0
    Methyl red Acid red 2493-52-7, 63451-28-5 (hydrochloric salt)
    Methyl yellow dimethylazobenzene,60-11-7
    Brown mordant 33 3618-62-0
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    Oil red O Solvent red 27, oil red O, solvent red 27, Sudan Red 5B1320-06-5
    orange I Į-Naphthol Orange, acid orange 20, Tropaeolin OOO-1, orange I523-44-4
    Acid Orange 10 Orange G, Wool orange 2G1936-15-8
    Red for paranitraniline red, Pigment Red 16410-10-2
    Pigment Yellow 10 Benzidine Yellow 10G, Sanyo Pigment Yellow 81056407-75-6
    Ponceau S Red Acid 1126226-79-5
    prompt Rubi azol 1, parazol103-12-8
    Black reagent 5 Remazol Black B17095-24-8
    Reagent black 39 68259-02-9
    Blue reagent 49 Reactive Blue K-3R, Reactive brilliant Blue P-3R Reactive Blue K-3R, Reactive brilliant Blue P3R, Cibacron Blue P-3R12236-92-9
    Orange reagent 16 Remazol Brilliant Orange 3R12225-83-1
    Red reagent 2 Reactive brilliant Red X-3B, Red MX-5B12226-03-8, 17804-49-8 (salt)
    Red reagent 45 Reactive Red P-3B, Cibacron Brilliant Red 3B-P, Reactive brilliant red 6B12226-22-1, 70210-46-7
    Red reagent 120 Reactive Brilliant Red KE4B, Reactive Red KE-3B, Reactive Brilliant Red KE-3B61951-82-4
    Red reagent 141 Reactive Red KE-7B, Reactive Red 2KE-7B61931-52-0
    Red reagent 180 Reactive Red F3B, Reactive Red KN-3B72828-03-6
    Red reagent 239 Reactive Red 3BS, Reactive brilliant Red 3BS89157-03-9
    Red reagent 272
    Yellow Reagent 15 Reactive Yellow GR, Reactive12226-47-0
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    Yellow KN-GR
    Red 2G Red acid 1, E-1283734-67-6
    EGN oil red Solvent Red 264477-79-6
    Solvent yellow 124 SY124; Sudan 455; Somalia Yellow; T10 Yellow LBN;4432-92-3
    Black sweat sudan black B, fat black HB, solvent black 3, Ceres black BN, Fat Black HB4197-25-5
    Sunset yellow Orange Yellow S, Sunset Yellow FCF2783-94-0
    Tartracin Acid Yellow 23, Food Yellow 4 1934-21-0
    2G yellow Food Yellow5, Acid Yellow 176359-98-4
    Trypan blue Blue 3B Blue EMB Direct Blue 14, Direct Blue 3B72-57-1
    Another embodiment of the first aspect of the present invention relates to a process for decolorizing organic dye solutions comprising contacting a solution comprising at least one organic dye with:
    a) a catalyst comprising Pd in a support; Y
    b) a reducing agent;
    where the organic dye is an azo dye selected from orange I, orange II, black amido 10B, acid blue 193, acid brown 425, acid orange 8, acid orange 10, acid orange 61, acid red 66, acid red 14, acid red 33, acid red 73, acid red 88, acid red 97, red for, yellow alizarin R, allura AC red, acid red 27, 4-aminoazobenzene, azoviolet, Bismarck brown, bright black BN, direct blue 1, direct blue 6, Direct Blue 15, Direct Blue 71, Direct Orange 61, Direct Red 23, Direct Violet 51, Disperse Orange 1, Disperse Red 1, Evans Blue, Quick Yellow AB, Litol Rubin BK, Yellow Metanyl, Yellow Pigment 10, Methyl Red , methyl yellow, mordant brown 33, oil red O, oil red EGN, Ponceau S, prontosil, black reagent 5, black reagent 39, blue reagent 49, orange reagent 16, red reagent 45, red reagent 120, red reagent 141, reagent red 180, reagent red 239, reagent red 272, reagent yellow 15, 2G red, solvent yellow 124, sweat black, sunset yellow, tartrazine, trypan blue, 2G yellow, Congo red, methyl orange and any of their mixtures, preferably the azo dye is selected from Congo red, methyl orange, Oil red O and any of its mixtures.
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    In another embodiment of the first aspect of the present invention, the azo dye is selected from Congo red, methyl orange, oil red O and any of its mixtures.
    In another embodiment of the first aspect of the present invention, the triarylmethane dye is selected from patented blue V, Victoria BO blue, fuchsin, acid fuchsin, pararosaniline, new fuchsin, methyl violet 2B, methyl violet 6B, methyl violet 10B, malachite green, bright green, ethyl green and any of its mixtures.
    A table with the triarylmethane dyes and their synonyms, as well as their CAS number, is added below.
    Name  Other namesCAS
    Patented Blue V Food blue 5, Sulphan blue, Acid blue 33536-49-0
    Victoria Blue BO Basic blue 72390-60-5
    Fuchsina Rosaniline hydrochloride, fuchsin hydrochloride, paramagenta hydrochloride632-99-5
    Acid fuchsin Acid Violet 19, Rubina S3244-88-0
    Pararosaniline Basic network 9569-61-9
    New fuchsina Magenta III, basic violet 23248-91-7
    2B methyl violet Basic violet 18004-87-3
    6B methyl violet 67339-79-1
    10B methyl violet Basic violet 3, gentian violet, crystal violet548-62-9
    Malachite green Aniline green; Basic green 4; Diamond green B; Victoria green B569-64-2
    Shining green Malachite green G, Emerald green, Solid green JJO, Diamond green G, Aniline green, Benzaldehyde green, Fast green J633-03-4
    Ethyl green Ethyl green7114-03-6
    Another embodiment of the first aspect of the present invention relates to a process for decolorizing organic dye solutions comprising contacting a solution comprising at least one organic dye with:
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    a) a catalyst comprising Pd in a support;
    b) a reducing agent;
    where the organic dye is a triaryl methane dye selected from patented blue V, Victoria BO blue, fuchsin, acid fuchsin, pararosaniline, new fuchsin, 2B methyl violet, 6B methyl violet, 10B methyl violet, malachite green, bright green, green of ethyl and any of its mixtures, preferably the triarylmethane dye is selected from methyl violet 10B, fuchsin and any of its mixtures.
    In another embodiment of the first aspect of the present invention, the organic dye has a concentration greater than 0.1 mg / l, preferably the organic dye has a concentration between 1 mg / l and 500 mg / l, more preferably the organic dye has a concentration between 10 mg / l and 100 mg / l.
    In another embodiment of the first aspect of the present invention the solution comprising at least one organic dye is a solution comprising water, methanol and any mixture thereof.
    In another embodiment of the first aspect of the present invention, the pH of the solution comprising at least one organic dye is less than 7, preferably between 1 and 6, more preferably between 2.5 and 5, even more preferably at pH 3.
    Another embodiment of the first aspect of the present invention relates to a process for decolorizing organic dye solutions comprising contacting a solution comprising at least one organic dye with:
    a) a catalyst comprising Pd in a support;
    b) a reducing agent;
    where the organic dye is an azo dye selected from orange I, orange II, black amido 10B, acid blue 193, acid brown 425, acid orange 8, acid orange 10, acid orange 61, acid red 66, acid red 14, acid red 33, acid red 73, acid red 88, acid red 97, red for, yellow alizarin R, allura AC red, acid red 27, 4-aminoazobenzene, azoviolet, Bismarck brown, bright black BN, direct blue 1, direct blue 6, Direct Blue 15, Direct Blue 71, Direct Orange 61, Direct Red 23, Direct Violet 51, Disperse Orange 1, Disperse Red 1, Evans Blue, Quick Yellow AB, Litol Rubin BK, Yellow Metanyl, Yellow Pigment 10, Methyl Red , methyl yellow, mordant brown 33, oil red O, oil red EGN, Ponceau S, prontosil, black reagent 5, black reagent 39, blue reagent 49, orange reagent 16, red reagent 45, red reagent 120, red reagent 141, reagent red 180, reagent red 239, reagent red 272, reagent yellow 15, 2G red, solvent yellow 124, sweat black, sunset yellow, tartrazine, trypan blue, 2G yellow, Congo red, methyl orange and any of their mixtures, preferably the azo dye is selected from Congo red, methyl orange, oil red O and any of its mixtures; and where the pH of the solution comprising at least one organic dye is less than 7, preferably between 1 and 6, more preferably between 2.5 and 5, even more preferably at pH 3.
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    In another embodiment of the first aspect of the present invention, the process is carried out at a temperature of 5 ° C to 90 ° C, preferably at a temperature of 20 ° C to 60 ° C.
    In another embodiment of the first aspect of the present invention, where the process is carried out at a pressure of 1 to 5 bar.
    Another first aspect embodiment of the present invention relates to a process for decolorizing organic dye solutions comprising contacting a solution comprising at least one organic dye with:
    a) a catalyst comprising Pd in a support;
    b) a reducing agent;
    where the organic dyes are selected from azo dyes, triarylmethane dyes and any of their mixtures;
    where the process is carried out at a temperature of 5 ° C to 90 ° C, preferably at a temperature of 20 ° C to 60 ° C; Y
    where the procedure is carried out at a pressure of 1 to 5 bar.
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    Another embodiment of the first aspect of the present invention relates to a process for decolorizing organic dye solutions comprising contacting a solution comprising at least one organic dye with:
    a) a catalyst comprising Pd in a support;
    b) a reducing agent;
    where the organic dye is a triaryl methane dye selected from patented blue V, Victoria BO blue, fuchsin, acid fuchsin, pararosaniline, new fuchsin, 2B methyl violet, 6B methyl violet, 10B methyl violet, malachite green, bright green, green of ethyl and any of its mixtures, preferably the triarylmethane dye is selected from methyl violet 10B, fuchsin and any of its mixtures; Y
    where the pH of the solution comprising at least one organic dye is less than 7, preferably between 1 and 6, more preferably between 2.5 and 5, even more preferably at pH 3.
    In another embodiment of the first aspect of the present invention the support is a porous support selected from pilareated clay, alumina, silica gel, clays, zeolites and any of their mixtures.
    In another embodiment of the first aspect of the present invention the catalyst support is pilareada clay.
    In another embodiment of the first aspect of the present invention the catalyst support is alumina.
    In another embodiment of the first aspect of the present invention, the catalyst comprises 0.5% to 5% Pd.
    Another embodiment of the first aspect of the present invention relates to a process for decolorizing organic dye solutions comprising contacting a solution comprising at least one organic dye with:
    a) a catalyst comprising Pd in a support; b) a reducing agent;
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    where the organic dye is selected from azo dyes, triarylmethane dyes and any of their mixtures;
    wherein the support is a porous support selected from pilareated clay, alumina, silica gel, clays, zeolites and any of their mixtures, preferably the support is selected from pilareated clay, alumina and any of its mixtures; Y
    wherein the catalyst comprises 0.5% to 5% Pd, preferably 1% to 3% Pd.
    In another embodiment of the first aspect of the present invention the reducing agent is selected from hydrogen, formic acid, hydrazine and any of its mixtures, preferably the reducing agent is hydrogen.
    Another embodiment of the first aspect of the present invention relates to a process for decolorizing organic dye solutions comprising contacting a solution comprising at least one organic dye with:
    a) a catalyst comprising Pd in a support;
    b) a reducing agent;
    where the organic dye is selected from azo dyes, triarylmethane dyes and any of their mixtures;
    wherein the support is a porous support selected from pilareated clay, alumina, silica gel, clays, zeolites and any of their mixtures, preferably the support is selected from pilareated clay, alumina and any of its mixtures;
    wherein the catalyst comprises 0.5% to 5% Pd, preferably 1% to 3% Pd; Y
    where the reducing agent is selected from hydrogen, formic acid, hydrazine and any of its mixtures, preferably the reducing agent is hydrogen.
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    A second aspect of the present invention relates to the use of a catalyst comprising a porous support selected from pilareated clay, alumina, silica gel, clays, zeolites and any of its mixtures and between 0.5% and 5% of Pd to discolor organic dye solutions.
    In an embodiment of the second aspect of the present invention, the organic dyes are selected from azo dyes, triarylmethane dyes and any of their mixtures.
    In another embodiment of the second aspect of the present invention, the organic dye is an azo dye and where the azo dye is selected from orange I, orange II, black amido 10B, acid blue 193, acid brown 425, acid orange 8, acid orange 10, Acid Orange 61, Acid Red 66, Acid Red 14, Acid Red 33, Acid Red 73, Acid Red 88, Acid Red 97, Alizarin Yellow R Red, AC Allura Red, Acid Red 27, 4-Aminoazobenzene, Azoviolet, Bismarck brown, bright black BN, direct blue 1, direct blue 6, direct blue 15, direct blue 71, direct orange 61, direct red 23, direct violet 51, scattered orange 1, scattered red 1, Evans blue, fast yellow AB, litol-rubin BK, yellow methanyl, yellow pigment 10, methyl red, methyl yellow, mordant brown 33, oil red O, oil red EGN, Ponceau S, prontosil, black reagent 5, black reagent 39, blue reagent 49, reagent orange 16, reagent red 45, reagent red 120, reac tivo red 141, reagent red 180, reagent red 239, reagent red 272, reagent yellow 15, red 2G, solvent yellow 124, sweat black, sunset yellow, tartrazine, trypan blue, 2G yellow, congo red, methyl orange and any of its mixtures, preferably the azo dye is selected from Congo red, methyl orange, oil red O and any of its mixtures.
    In another embodiment of the second aspect of the present invention, the organic dye is a triarylmethane dye and where the triarylmethane dye is selected from patented blue V, Victoria BO blue, fuchsin, acid fuchsin, pararosaniline, new fuchsin, 2B methyl violet, violet of methyl 6B, methyl violet 10B, malachite green, bright green, ethyl green and any of their mixtures, preferably the triaryl methane dye is selected from methyl violet 10B, fuchsin and any of its mixtures.
    In an embodiment of the second aspect of the present invention the porous support is pilareada clay.
    In another embodiment of the second aspect of the present invention, the porous support is alumina.
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    In another embodiment of the second aspect of the present invention, the catalyst comprises between 1% and 3% Pd.
    Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention. BRIEF DESCRIPTION OF THE FIGURES
    FIG. one . Discoloration of the Congo red with the Pd-PILC catalyst at pH = 6 shown in an absorbance spectrum at 498 nm. A: Absorbance; T (min): Time in minutes.
    FIG. 2. Photograph showing the Congo red solution at time 0 and after 10 minutes of the reaction at pH 3.
    FIG. 3rd. Discoloration of methyl orange with Pd-PILC at pH 6 shown in an absorbance spectrum at 464 nm. A: Absorbance; T (min): Time in minutes.
    FIG. 3b Discoloration of methyl orange with Pd-PILC at pH 3 shown in an absorbance spectrum at 468 nm. A: Absorbance; T (min): Time in minutes.
    FIG. 4th. Discoloration of the Congo red with the Pd-Al2O3 catalyst continuously at pH 3 shown in an absorbance spectrum at 575 nm. A: Absorbance; T (h): Time in hours. The measures of total organic carbon (TOC) in% are also shown.
    FIG. 4b Congo red influence of example 5 (concentration 10 mg / l).
    FIG. 4c. Photograph of the effluents of example 5 with precipitate at 4 h, 30 h, 48 h and 75
    h.
    FIG. 5. Discoloration of methyl orange with the Pd-PICL catalyst continuously at pH 3 shown in an absorbance spectrum at 468 nm. pH: pH solution; A: Absorbance; T (h): Time in hours.
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    FIG. 6a. Discoloration of Oil Red O with Pd-PILC catalyst shown in an absorbance spectrum at 515 nm pH solution; A: Absorbance; T (min): Time in minutes.
    FIG. 6b Photograph of the influent and the reaction samples at 15 min, 30 min, 1 h, 2 h, 3 h, and 4 h respectively.
    FIG. 7a. Violet crystal discoloration shown in an absorbance spectrum at 590 nm,
    A: Absorbance; T (min): Time in minutes.
    FIG. 7b Initial Violet Crystal Solution and reaction samples taken at 1 h, 2 h, 3 h, 4 h, 6 h and 8 h, respectively.
    FIG. 8a. Fuchsin discoloration shown in an absorbance spectrum at 550 nm. A: Absorbance; T (min): Time in minutes.
    FIG. 8b Initial fuchsin solution and samples taken at 1 h, 2 h, 3 h, 4 h, 6 h and 8 h, respectively. EXAMPLES
    The invention will now be illustrated by tests carried out by the inventors, which demonstrates the effectiveness of the product of the invention. EXAMPLE 1. Synthesis of a catalyst with clay support reada stack with aluminum (Pd-PILC)
    Pilareada clays were prepared with a ratio of 10 mmol of Al per gram of clay. These clays were synthesized by adding a pilareant solution at 25 ° C to a bentonite suspension.
    The pilareant solution was prepared by slowly adding a solution of NaOH to another of AlCl3 (molar ratio OH / Al = 2) and aged at 90 ° C for 3 hours. It was then allowed to stand at 25 ° C for 2 hours and a suspension was added under vigorous stirring of bentonite with 1% by weight clay for 17 hours. The resulting material was washed by centrifugation, dried for 18 hours at 110 ° C and calcined at 350 ° C for 2 hours. The resulting pilarea clay is a powder with a particle size of less than 100 µm.
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    Pd (1% by weight) was incorporated into the clay by wet impregnation using an acid solution of PdCl2 (0.1M HCl). After impregnation, the material was dried for 17 hours at 110 ° C and calcined at 500 ° C for 2 hours in an oxidizing atmosphere. The catalyst was reduced at 90 ° C under hydrogen flow for two hours before being used in the catalytic reactions. Example 2. Synthesis of a catalyst with alumina support (Pd-Al2O3)
    The alumina used was from Sigma-Aldrich, which is an alumina in the form of 3 mm spheres.
    Pd (1% by weight) was incorporated into the alumina by wet impregnation using an acid solution of PdCl2 (0.1M HCl). After impregnation, the material was dried for 17 hours at 110 ° C and calcined at 500 ° C for 2 hours in an oxidizing atmosphere. The catalyst was reduced at 90 ° C under hydrogen flow for two hours before being used in the catalytic reactions. Example 3. Procedure for removing Congo red (azoic) with the Pd-PILC catalyst in batch
    The catalytic process was carried out in a stirred tank reactor of 1 L capacity with magnetic stirring (400 rpm). 1 L of an aqueous dye solution (congo red or methyl orange, initial concentration 100 mg / l) was used as the reaction medium to which the Pd-PILC catalyst was added in an initial concentration of 1 g / l. The catalytic reaction began by adding H2 to the reactor (flow rate = 50 mLN / min, normal milliliters per minute, at 0 ° C and 1,013 bar).
    Two reactions were performed at 50 ° C and at pH 3 and 6.
    The samples were analyzed by means of a Shimadzu UV-visible spectophotometer, model UV-1603, using the wavelengths at which the maximum intensity for each dye and pH were presented. The effluents were analyzed by TXRF (X-ray Fluorescence by Total Reflection) with a TXRF EXTRA-II spectrophotometer, Rich & Seifert) to determine the possible leaching of the metal to the reaction medium.
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    As shown in Figure 1, during the fading test of Congo red at pH 6, almost total color removal was achieved after 120 minutes of treatment (color measurements performed by spectrophotometry). When the reaction was carried out using a pH of the reaction medium of 3, a higher process speed was observed, with an almost total color removal after 15 minutes of reaction and being formed unlike the reaction at pH 6, precipitates (from blue color) as can be seen in Figure 2. The elementary analysis of this solid presented the following composition: C = 28.87%; H = 3.52%; N = 6.23%; S = 4.25%. Working at pH 3, the elimination of organic matter was achieved, in addition to the fading of the effluent. Example 4. Procedure of the imination of methyl orange (azoic) with the discontinuous Pd-PILC catalyst
    The procedure was carried out in the same manner as described in example 3.
    The reactions were carried out at 50 ° C and at pH 3 and 6, respectively.
    In figure 3a it can be seen that at pH 6 the total removal of the color is achieved after 1 h of reaction while at pH 3 (figure 3b) the almost total discoloration is achieved in the first 10 minutes of reaction. Example 5. Procedure for removing Congo red (azoic) with the Pd-Al2O3 catalyst in continuous.
    The stability of the catalysts was checked by long-term experiments (100 h), carried out in fixed-bed reactors (Pyrex glass, 30 cm long, 9 mm internal diameter).
    The catalyst (0.5 g of Pd-Al2O3 in the form of spherical particles 3mm in diameter) was placed in the central part of the reactor.
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    The aqueous Congo red solution (initial concentration of 10 mg / l) was fed with a volumetric flow rate of 0.42 ml / min. The H2 was passed with a flow rate of 1 mLN / min. Liquid samples were taken periodically at the outlet of the reactor.
    The reaction was carried out at 25 ° C and at pH 3.
    As can be seen in Figure 4a, the elimination of the color of the Congo red solution was almost total throughout the experiment (100 h) with reductions greater than 94% at all times. During the test, the formation of a blue precipitate was observed in the effluent obtained (Figure 4b). The measures of total organic carbon (TOC) reflected an elimination of organic matter greater than 45%.
    The presence of Pd in the reaction medium was not detected by TXRF analysis in the effluents obtained thereby confirming the stability of the catalyst without loss of active phase by leaching. Example 6. Procedure of the imination of methyl orange (azoic) with the Pd-PILC catalyst in continuous.
    The catalyst (0.1 g of Pd-PILC in powder form) was placed in the central part of the reactor. As the catalyst has a particle size of less than 100 µm, it was surrounded by glass wool to prevent the formation of preferential channels in the circulation of the liquid through the catalyst bed.
    The aqueous solution of methyl orange (initial concentration of 100 mg / l) was fed with a volumetric flow rate of 0.42 mL / min. The H2 was passed with a flow rate of 1 mLN / min. Liquid samples were taken periodically at the outlet of the reactor.
    The reaction was carried out at 25 ° C and at pH 3.
    As can be seen in Figure 5, the catalyst showed a high stability in the process of decolorization of this compound, obtaining a conversion of the same greater than 98% during almost the whole experiment (100h).
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    The presence of Pd in the reaction medium was not detected by TXRF analysis in the effluents obtained thereby confirming the stability of the catalyst without loss of active phase by leaching. Example 7. Discoloration procedure of Oil red O (azoic)
    A bleaching test was carried out under similar conditions with another disazoic dye such as Oil Red O. As can be seen in Figures 6a and 6b, a total discoloration of the reaction effluents was achieved in less than 4 hours of treatment at 25 ºC and 1 atm.
    The reaction was carried out with the Pd-PILC catalyst, with an initial dye concentration of 100 mg / L, an initial concentration of 1g / l of catalyst and a hydrogen flow rate of 50mLN / min. The solvent was a mixture of 5% H2O and 95% MeOH. Example 8. Method of decolorization of methyl violet 10B
    Figure 7a shows the evolution of the absorbance with the reaction time of an aqueous solution of violet crystal (100 mg / L), using the Pd-PILC catalyst, an initial concentration of 1g / l of catalyst at 25 ° C and using a flow rate of 50 mLN / min of hydrogen in an 8 hour test at pH 3. A total decolorization of the effluent was observed, as shown in Figure 7b. Example 9. Fuchsin (triarylmethane) fading procedure
    Another triarylmethane was chosen as fuchsin to carry out the process under the same conditions previously used in the discoloration of violet crystal. As can be seen in figure 8a, the discoloration is carried out at a higher speed, obtaining a transparent effluent after less than 5 hours of reaction (fig. 8b)
    权利要求:
    Claims (29)
    [1]
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    1. Process for decolorizing organic dye solutions comprising contacting a solution comprising at least one organic dye with:
    a) a catalyst comprising Pd in a support; Y
    b) a reducing agent.
    [2]
    2.  Process according to claim 1, wherein the organic dyes are selected from azo dyes, triarylmethane dyes and any of their mixtures.
    [3]
    3.  Method according to the preceding claim wherein the azo dye is selected from orange I, orange II, black amido 10B, acid blue 193, acid brown 425, acid orange 8, acid orange 10, acid orange 61, acid red 66, acid red 14, acid red 33, acid red 73, acid red 88, acid red 97, alizarin yellow R, red allura AC, acid red 27, 4 aminoazobenzene, azoviolet, Bismarck brown, bright black BN, direct blue 1, direct blue 6, blue Direct 15, Direct Blue 71, Direct Orange 61, Direct Red 23, Direct Violet 51, Disperse Orange 1, Disperse Red 1, Evans Blue, Quick Yellow AB, Litol-Rubina BK, Yellow Metanyl, Yellow Pigment 10, Methyl Red, methyl yellow, mordant brown 33, oil red O, oil red EGN, Ponceau S, prontosil, black reagent 5, black reagent 39, blue reagent 49, orange reagent 16, red reagent 45, red reagent 120, red reagent 141, reagent red 180, reagent red 239, reagent red 2 72, reagent yellow 15, red 2G, solvent yellow 124, sweat black, sunset yellow, tartrazine, trypan blue, yellow 2G, Congo red, methyl orange and any of their mixtures.
    [4]
    Four.  Process according to the preceding claim, wherein the azo dye is selected from Congo red, methyl orange, oil red O and any of its mixtures.
    [5]
    5.  Method according to claim 2, wherein the triarylmethane dye is selected from patented blue V, Victoria BO blue, fuchsin, acid fuchsin, pararosaniline, new fuchsin, methyl violet 2B, methyl violet 6B, methyl violet 10B, malachite green, green bright, ethyl green and any of its mixtures.
    [6]
    6.  Process according to the preceding claim, wherein the triarylmethane dye is selected from methyl violet 10B, fuchsin and any of its mixtures.
    [7]
    7.  Process according to any of the preceding claims wherein the organic dye has a concentration greater than 0.1 mg / l.
    [8]
    8.  Process according to any of the preceding claims wherein the organic dye has a concentration between 1 mg / l and 500 mg / l.
    [9]
    9.  Process according to any of the preceding claims, wherein the organic dye has a concentration between 10 mg / l and 100 mg / l.
    [10]
    10.  Process according to any of the preceding claims, wherein the solution comprising at least one organic dye is a solution comprising water, methanol and any of its mixtures.
    [11]
    eleven.  Process according to any of the preceding claims, wherein the pH of the solution comprising at least one organic dye is less than 7.
    [12]
    12.  Process according to the preceding claim, wherein the pH of the solution comprising at least one organic dye is between 1 and 6.
    [13]
    13.  Method according to the preceding claim, wherein the pH of the solution is between 2.5 and 5.
    [14]
    14. Process according to any of the preceding claims, wherein the process is carried out at a temperature of 5 ° C to 90 ° C.
    [15]
    fifteen. Method according to any of the preceding claims, wherein the process is carried out at a pressure of 1 to 5 bar.
    [16]
    16.  Process according to any of the preceding claims, wherein the support is a porous support selected from pilareada clay, alumina, silica gel, clays, zeolites and any of their mixtures.
    [17]
    17.  Process according to any of the preceding claims, wherein the catalyst support is pilareada clay.
    [18]
    18.  Process according to any one of claims 1 to 16, wherein the catalyst support is alumina.
    [19]
    19.  Process according to any of the preceding claims, wherein the catalyst comprises 0.5% to 5% Pd.
    [20]
    twenty.  Process according to any of the preceding claims, wherein the reducing agent is selected from hydrogen, formic acid, hydrazine and any of its mixtures.
    [21]
    twenty-one.  Process according to the preceding claim, wherein the reducing agent is hydrogen.
    [22]
    22  Use of a catalyst comprising a porous support selected from pilareated clay, alumina, silica gel, clays, zeolites and any of its mixtures and between 0.5% and 5% Pd to discolor organic dye solutions.
    [23]
    2. 3.  Use according to the preceding claim when the organic dyes are selected from azo dyes, triarylmethane dyes and any of their mixtures.
    [24]
    24.  Use according to the preceding claim wherein the organic dye is an azo dye and wherein the azo dye is selected from orange I, orange II, black amido 10B, acid blue 193, acid brown 425, acid orange 8, acid orange 10, acid orange 61 , acid red 66, acid red 14, acid red 33, acid red 73, acid red 88, acid red 97, red for alizarin yellow R, allura red AC, acid red 27, 4-aminoazobenzene, azoviolet, bismarck brown, gloss black BN, direct blue 1, direct blue 6, direct blue 15, direct blue 71, direct orange 61, direct red 23, direct violet 51, scattered orange 1, scattered red 1, Evans blue, fast yellow AB, litol-rubina BK, yellow methanyl, yellow pigment 10, methyl red, methyl yellow, mordant brown 33, oil red O, oil red EGN, Ponceau S, prontosil, black reagent 5, black reagent 39, blue reagent 49, orange reagent 16, red reagent 45, red reagent 120, red reagent 141, reagent red 180, reagent red 239, reagent red 272, reagent yellow 15, red 2G, solvent yellow 124, sweat black, sunset yellow, tartrazine, trypan blue, yellow 2G, congo red, methyl orange and any of their mixtures.
    [25]
    25.  Use according to the preceding claim wherein the azo dye is selected from Congo red, methyl orange, oil red O and any of its mixtures.
    [26]
    26.  Use according to claim 23, wherein the organic dye is a triarylmethane dye and wherein the triarylmethane dye is selected from patented blue V, Victoria BO blue, fuchsin, acid fuchsin, pararosaniline, new fuchsin, 2B methyl violet, 6B methyl violet, 10B methyl violet, malachite green, bright green, ethyl green and any of their mixtures.
    [27]
    27.  Use according to the preceding claim, wherein the triarylmethane dye is selected from 10B methyl violet, fuchsin and any of its mixtures.
    [28]
    28.  Use according to any of claims 22 to 27 wherein the porous support is pilareada clay.
    [29]
    29.  Use according to any of claims 22 to 27, wherein the porous support is alumina.
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