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Regeneration method and application of chloronitro aromatic hydrocarbon selective hydrogenation catalyst

A technology for hydrogenation catalysts and nitroaromatic hydrocarbons, applied in catalyst regeneration/reactivation, chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, etc. Loss, recovery of deactivated catalyst specific surface area and pore volume are limited

Pending Publication Date: 2021-09-03
QINGDAO UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Due to the relatively high cost of noble metal catalysts, and the catalytic performance of noble metal catalysts gradually decreases with the increase in the number of times the catalyst is applied, so in the actual production process, the shortened service life of the catalyst will directly lead to an increase in the production cost of the product
[0006] According to a large number of previous research results of the inventors, the main reason for the performance degradation of carbon-supported noble metal catalysts in the selective hydrogenation reduction reaction of chlorinated nitroaromatics is that organic impurities block the pores of the catalyst and cover the hydrogenation active sites, resulting in hydrogenation activity. reduction of
A large number of studies done by the inventor in the early stage also found that the effect of single organic solvent washing on restoring the specific surface area and pore volume of the deactivated catalyst is extremely limited
However, non-mild regeneration methods such as strong acid cleaning will accelerate the destruction of the catalyst support structure and the loss of precious metal components, which will further cause irreversible performance damage to the catalyst.

Method used

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  • Regeneration method and application of chloronitro aromatic hydrocarbon selective hydrogenation catalyst
  • Regeneration method and application of chloronitro aromatic hydrocarbon selective hydrogenation catalyst
  • Regeneration method and application of chloronitro aromatic hydrocarbon selective hydrogenation catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Embodiment 1: The 5w% Pt / C catalyst deactivated in the selective hydrogenation of o-chloronitrobenzene to prepare 2,2'-dichlorohydroazobenzene is regenerated, comprising the following steps:

[0034] (1) Take 10g of deactivated catalyst (referred to as Cat1-U) and disperse it into 50g of methanol solution containing 5% n-butyl titanate and 5% terephthalaldehyde, stir and impregnate at 50°C, and the impregnation is completed Afterwards, the catalyst was filtered and transferred to a tube atmosphere furnace under N 2 Under the protection of 2°C / min, the heating rate was increased to 500°C and then maintained for 2h for carbonization treatment. The product obtained after carbonization (denoted as N&Ti@Cat1-U) was cooled and stored for later use.

[0035] (2) Add 10g of N&Ti@Cat1-U and 250g of Cat1-U to a 10L regenerating kettle equipped with an ultraviolet light irradiation device and a microwave generating device, add 2.5kg of an aqueous solution containing 5% sodium pero...

Embodiment 2

[0049] Embodiment 2: The 3w% Pd / C catalyst deactivated in the selective hydrogenation of o-chloronitrobenzene to prepare 2,2'-dichlorohydroazobenzene is regenerated, comprising the following steps:

[0050] (1) Take 10g of deactivated catalyst (Cat2-U) and disperse it into 50g of methanol solution containing 15% n-butyl p-titanate and 15% terephthalaldehyde, and stir and impregnate it at 80°C. The catalyst was filtered and transferred to a tube atmosphere furnace under N 2 Under the protection of the temperature rising rate of 5 ℃ / min to 800 ℃ and then maintained for 2 hours for carbonization treatment, the product obtained after carbonization (denoted as N&Ti@Cat2-U) was cooled and stored for later use.

[0051] (2) Add 10g of N&Ti@Cat2-U and 300g of Cat2-U to a 10L regenerating kettle equipped with an ultraviolet light irradiation device and a microwave generating device, and add 3kg of an aqueous solution containing 5% potassium peroxodisulfate. The regeneration treatmen...

Embodiment 3

[0057] Embodiment 3: comparative experiment of regeneration method

[0058] (1) Add 250g of Cat1-U directly to a 10L regeneration kettle equipped with a UV irradiation device and a microwave generator, add 2.5kg of an aqueous solution containing 5% sodium peroxodisulfate, and irradiate it with ultraviolet light with a wavelength of 200nm Regeneration treatment is carried out under the action, the treatment temperature is 50°C, and the microwave power is 1000W. The processed material liquid is filtered by nitrogen pressure into the precision filter.

[0059] (2) Carry out subsequent regeneration experiments according to steps (3) and (4) of Example 1. Catalyst performance evaluation is carried out to the regenerated catalyst (referred to as Cat1-U-R1): evaluation method and analysis method are the same as embodiment 1. The result is as follows:

[0060]

[0061] As can be seen from the experimental results in the above table, compared with the catalyst regenerated in Examp...

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Abstract

The invention relates to the technical field of catalysts, and particularly discloses a regeneration method of a chloronitro aromatic hydrocarbon selective hydrogenation catalyst. The regeneration method comprises the following steps: impregnating a part of the deactivated catalyst by adopting a titanium oxide precursor and a stabilizing solution, carbonizing, mixing the carbonized catalyst and the deactivated catalyst, adding the mixture into a regeneration kettle filled with a treatment solution, and decomposing organic impurities under the action of ultraviolet irradiation and microwaves; and carrying out microwave washing on the treated catalyst under the interaction effect of the organic acid and the organic solvent, so as to realize dredging of pore channels and recovery of active metal sites. According to the treatment method, organic impurities adsorbed in the catalyst can be effectively removed, and the catalytic performance is recovered. The method has the advantages of being simple, efficient, environmentally friendly and the like, the structure of the catalyst and the active metal loading state can be kept while it is guaranteed that organic impurities are removed, the activity of the catalyst is effectively recovered, and the use cost of the catalyst is reduced.

Description

[0001] (1) Technical field [0002] The invention relates to the technical field of catalysts, in particular to a regeneration method and application of a chlorinated nitroaromatic selective hydrogenation catalyst. [0003] (2) Background technology [0004] The products produced by the selective hydrogenation reaction of chloronitroaromatics are widely used in the production process of organic dyes, pesticides, synthetic fibers, plasticizers and printing and dyeing auxiliaries. According to different reaction conditions, different products can be obtained after hydrogenation reduction of chloronitroaromatics, mainly including nitroso compounds, hydroxylamine, azobenzenes and primary aramides. The hydrogenation pathway is mainly divided into direct pathway (nitroaromatics-nitrosobenzene-hydroxylamine-aniline) and condensation pathway (nitrobenzene-nitrosobenzene-azobenzene oxide-hydroazobenzene-aniline). [0005] At present, the selective hydrogenation catalysts of chloronitro...

Claims

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Application Information

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IPC IPC(8): B01J38/52B01J38/02B01J38/00B01J23/42B01J23/44B01J23/46C07C211/52C07C209/36
CPCB01J38/52B01J38/02B01J38/00B01J23/42B01J23/44B01J23/462C07C209/36C07C211/52Y02P20/584
Inventor 丁军委葛树文于文龙徐广文单玉领刘福胜
Owner QINGDAO UNIV OF SCI & TECH
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