WO2017181380A1 - Catalyseur supporté par un tissu composite à base de nanoparticules d'argent et utilisation associée - Google Patents

Catalyseur supporté par un tissu composite à base de nanoparticules d'argent et utilisation associée Download PDF

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Publication number
WO2017181380A1
WO2017181380A1 PCT/CN2016/079853 CN2016079853W WO2017181380A1 WO 2017181380 A1 WO2017181380 A1 WO 2017181380A1 CN 2016079853 W CN2016079853 W CN 2016079853W WO 2017181380 A1 WO2017181380 A1 WO 2017181380A1
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Prior art keywords
reaction
catalyst
nano
reduction
composite textile
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PCT/CN2016/079853
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English (en)
Chinese (zh)
Inventor
刘洪均
冯伟
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河南大学
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Priority to PCT/CN2016/079853 priority Critical patent/WO2017181380A1/fr
Publication of WO2017181380A1 publication Critical patent/WO2017181380A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/45—Monoamines
    • C07C211/46—Aniline
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention discloses a nano silver composite textile catalyst and an application thereof.
  • Nanoparticle materials have begun to be used in catalytic reactions due to their ultra-high surface area to volume ratio and unique catalytically active sites.
  • the nanocatalyst has very good catalytic performance, the dispersed nanomaterial is very easy to agglomerate in the reaction solution, so that it cannot be effectively used; at the same time, after the end of the chemical, the recovery of the catalyst is a great challenge.
  • centrifugation is often used, which causes agglomeration of the nanoparticles, so that the secondary catalytic efficiency of the nanoparticles is rapidly reduced.
  • Aromatic amino compounds are an extremely important organic raw material widely used in the production of dyes, pharmaceuticals, agrochemicals, additives, surfactants, textile auxiliaries, chelating agents, polymers, and flame retardants.
  • the preparation of aromatic amines mainly includes condensation preparation of amino group-containing compounds, reduction of nitro compounds, and the like.
  • the reduction of aromatic nitro compounds to the corresponding amino compounds is a common method for the preparation of aromatic amines in fine chemical production.
  • the preparation of aromatic amines by nitro reduction is widely used because of its simple operation and easy availability of raw materials.
  • the main methods for achieving this process include: (1) catalytic hydrogenation; (2) metal reduction; (3) hydrazine hydrate reduction; and (4) electrochemical reduction.
  • the above methods require relatively cumbersome and demanding reaction conditions.
  • the ester reduction reaction to prepare alcohol compounds is quite important in chemical synthesis.
  • the current common method is to use lithium tetrahydrogen aluminum to reduce esters in an anhydrous high temperature environment. However, this method is harsh and post-processing is dangerous, and is not suitable for large-scale applications.
  • the object of the present invention is to overcome the deficiencies of the prior art and to provide a nano-silver composite textile catalyst and its application.
  • a nanocatalyst consisting of nano silver supported on the surface of a textile material.
  • the method for preparing the above nanocatalyst comprises the steps of: washing and drying the textile material in deionized water, then placing it in a mixed aqueous solution of silver nitrate and 3-aminopropyltriethoxysilane, dipping; taking out the textile material and using The deionized water is washed, and the textile material is placed in a 5 mM sodium borohydride aqueous solution at room temperature, immersed, washed, and dried to obtain a nanosilver composite textile catalyst.
  • the concentration of the silver nitrate is 2.72 mM, and the temperature of the first immersion is 60 °C.
  • the above nanocatalyst is used as a catalyst for a reduction reaction.
  • the reduction reaction refers to a reduction reaction of a nitro compound or an ester compound.
  • the present invention has the following beneficial effects: the nano silver composite textile catalyst of the present invention, the nano silver particles are supported on the surface of the textile fiber by in-situ growth method, and the nano silver particles are between 1-50 nm;
  • the nano-silver composite textile material exhibits good catalytic performance, and can rapidly reduce the nitro compound and the ester compound at room temperature, thereby effectively solving the severe conditions for the reduction reaction of the current ester compound;
  • the nano-silver composite textile catalyst is easy It is a new type of catalytic technology because it is prepared, recyclable, cheap, and can be used for large-scale production.
  • the nano silver composite textile catalyst of the invention can rapidly reduce the aromatic nitro compound to an aromatic amine at room temperature, and can reduce the ester compound to alcohol at room temperature with an aqueous solvent as a reaction medium. Scale and industrial production. In addition, the nanosilver composite textile catalyst of the present invention can also be recycled.
  • Figure 1 Electron micrograph of nano-silver composite textile catalyst; A and B: natural cotton textile; C and D: nano-silver composite textile.
  • FIG. 1 Recycling of nanosilver composite textile catalysts.
  • the nano silver composite textile catalyst is prepared by a one-step in-situ growth synthesis method.
  • White cotton textiles are first washed and dried in a deionized water environment.
  • 43 g of water-washed cotton was placed in a mixed aqueous solution of silver nitrate and 3-aminopropyltriethoxysilane (water temperature: 60 ° C, AgNO 3 concentration: 2.72 mM), and immersed for 10 minutes; the sample was taken out and washed with deionized water.
  • the sample was placed in a 5 mM aqueous sodium borohydride solution at room temperature and immersed for 10 minutes. It was observed that the cotton cloth gradually changed from white to yellow, indicating the formation of nano silver particles on the textile, followed by subsequent washing and baking.
  • a nanosilver composite textile catalyst can be obtained by a dry process.
  • the nano silver particles are about 10 nm, which are uniformly distributed on the surface of the textile fiber.
  • Example 2 Nanosilver composite textile catalyzed reduction of nitro compounds
  • Example 1 Taking the nano-silver composite textile of Example 1 as a catalyst, we first tried to catalyze the reduction reaction of nitrophenol. Specifically, 0.2 mmol of 4-nitrophenol, 1 mmol of NaBH 4 and 2 cm 2 of a nanosilver composite textile catalyst were mixed in a solution of THF/H 2 O (1 ml/1 ml) at room temperature, and it was found by tracking the reaction. The 4-nitrophenol can be reduced to 4-aminophenol in 3 hours; at the same time, our negative control test showed that no reaction was carried out without adding a nanosilver composite textile catalyst in the reaction system (other reaction conditions were the same).
  • Reaction conditions 0.2 mmol of substrate, 1 mmol of NaBH 4 and 2 cm 2 of nanosilver composite textile catalyst were stirred in a mixture of THF/H 2 O (1 ml / 1 ml) at room temperature, and the progress of the reaction was followed by TLC.
  • a TLC was traced to the end of the reaction;
  • b purified yield.
  • c The reaction was carried out at 100 °C.
  • d The reaction did not end after 12 hours, and the purification of the product was stopped.
  • Example 3 Recycling of a nitro compound by a nano-silver composite textile catalyst
  • nano-silver composite textile catalysts are recycled.
  • 2-methyl-5-nitro-1H-indole as substrate (due to its reduction products and substrates). It is easy to separate and purify on the chromatogram).
  • ICP-MS inductively coupled plasma analysis
  • Example 4 Nanosilver composite textile catalyzed reduction of a large amount of nitro compounds
  • ester compounds As we mentioned in the background introduction, the reduction reaction of ester compounds is a huge challenge. We have tried the reduction reaction of multiple ester compounds as shown in Table 3 using nano silver composite textile catalyst. These ester compounds can be rapidly reduced to the corresponding alcohol products, and are a novel preparation method of an alcohol compound.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un catalyseur supporté par un tissu composite à base de nanoparticules d'argent et utilisation associée. Des nanoparticules d'argent sont portées sur la surface de fibres de tissu au moyen d'un procédé de croissance in situ et sont comprises dans une plage de 1 à 50 nm. Le catalyseur supporté par un tissu composite à base de nanoparticules d'argent permet la réduction d'un composé nitro aromatique en une amine aromatique et permet, dans un état d'un solvant aqueux qui est un milieu de réaction, la réduction d'un ester en un alcool. Le catalyseur supporté par un tissu composite à base de nanoparticules d'argent peut être recyclé et réutilisé.
PCT/CN2016/079853 2016-04-21 2016-04-21 Catalyseur supporté par un tissu composite à base de nanoparticules d'argent et utilisation associée WO2017181380A1 (fr)

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PCT/CN2016/079853 WO2017181380A1 (fr) 2016-04-21 2016-04-21 Catalyseur supporté par un tissu composite à base de nanoparticules d'argent et utilisation associée

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101301608A (zh) * 2008-06-26 2008-11-12 南京大学 一种二氧化硅负载纳米银催化剂、其制备方法及其应用
JP2011036748A (ja) * 2009-08-07 2011-02-24 Ne Chemcat Corp 芳香族ニトロ化合物の選択的水素化触媒、その製造方法および再生方法並びにこれを用いた芳香族ニトロ化化合物の選択的水素化方法
CN102717094A (zh) * 2012-06-11 2012-10-10 无锡市顺业科技有限公司 原位合成纳米银的方法
CN104492429A (zh) * 2014-12-16 2015-04-08 上海华谊（集团）公司 草酸二甲酯加氢合成乙醇酸甲酯和乙二醇的催化剂和方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101301608A (zh) * 2008-06-26 2008-11-12 南京大学 一种二氧化硅负载纳米银催化剂、其制备方法及其应用
JP2011036748A (ja) * 2009-08-07 2011-02-24 Ne Chemcat Corp 芳香族ニトロ化合物の選択的水素化触媒、その製造方法および再生方法並びにこれを用いた芳香族ニトロ化化合物の選択的水素化方法
CN102717094A (zh) * 2012-06-11 2012-10-10 无锡市顺业科技有限公司 原位合成纳米银的方法
CN104492429A (zh) * 2014-12-16 2015-04-08 上海华谊（集团）公司 草酸二甲酯加氢合成乙醇酸甲酯和乙二醇的催化剂和方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HONGJUN LIU ET AL.: "A novel point-of-use water treatment method by antimicrobial nanosilver textile material", JOURNAL OF WATER AND HEALTH, vol. 4, no. 12, 31 December 2014 (2014-12-31), pages 671 *

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