CN113333034A - Regeneration method and application of chloro-nitro-aromatic selective hydrogenation catalyst - Google Patents

Regeneration method and application of chloro-nitro-aromatic selective hydrogenation catalyst Download PDF

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CN113333034A
CN113333034A CN202110392296.6A CN202110392296A CN113333034A CN 113333034 A CN113333034 A CN 113333034A CN 202110392296 A CN202110392296 A CN 202110392296A CN 113333034 A CN113333034 A CN 113333034A
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丁军委
葛树文
于文龙
徐广文
单玉领
刘福胜
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Qingdao University of Science and Technology
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Abstract

The invention relates to the technical field of catalysts, and particularly discloses a regeneration method of a chloronitroaromatic selective hydrogenation catalyst. The regeneration method comprises the steps of impregnating a part of deactivated catalyst with a titanium oxide precursor and a stabilizing solution, carbonizing, mixing the carbonized catalyst and the deactivated catalyst, adding the mixture into a regeneration kettle containing a treatment solution, and decomposing organic impurities under the action of ultraviolet irradiation and microwaves; the treated catalyst is washed by microwave under the interaction of organic acid and organic solvent, so as to realize the dredging of the pore canal and the recovery of the active metal site. The treatment method can effectively remove the organic impurities adsorbed in the catalyst and recover the catalytic performance. The method has the advantages of simplicity, high efficiency, environmental friendliness and the like, can keep the structure and the active metal loading state of the catalyst while ensuring the removal of organic impurities, effectively recovers the activity of the catalyst, and reduces the use cost of the catalyst.

Description

Regeneration method and application of chloro-nitro-aromatic selective hydrogenation catalyst
(I) technical field
The invention relates to the technical field of catalysts, and particularly relates to a regeneration method and application of a chloronitroaromatic selective hydrogenation catalyst.
(II) background of the invention
The product produced by the selective hydrogenation reaction of the chloronitroaromatic is widely applied to 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 the chloronitroarene is subjected to hydrogenation reduction, and the chloronitroarene mainly comprises nitroso compounds, hydroxylamine, azobenzene and primary arylamine. The hydrogenation pathway is mainly divided into the direct pathway (nitroarene-nitrosobenzene-hydroxylamine-aniline) and the condensation pathway (nitrobenzene-nitrosobenzene-azoxybenzene-hydroazobenzene-aniline).
At present, the chloronitroaromatic selective hydrogenation catalyst is mainly researched for a supported noble metal catalyst. Noble metals (platinum, palladium, rhodium) exhibit a relatively strong activity in redox reactions because they have a relatively strong adsorption property because the d-electron orbitals of their outer atomic layers are not filled, and can form covalent bonds with hydrogen atoms or oxygen atoms. Because the cost of the noble metal catalyst is relatively high, and the catalytic performance of the noble metal catalyst is gradually reduced along with the increase of the reuse times of the catalyst, the shortening of the service life of the catalyst in the actual production process directly leads to the increase of the production cost of the product.
According to a great deal of research results of the inventor, the main performance deterioration reasons of the carbon-supported noble metal catalyst in the selective hydrogenation reduction reaction of chloronitroarene are as follows: the organic impurities block the catalyst pore channels and cover the hydrogenation active sites to cause the reduction of the hydrogenation activity. Extensive studies carried out earlier by the inventors have also found that washing with a single organic solvent has a very limited effect on the recovery of the specific surface area and pore volume of the deactivated catalyst. And the non-mild regeneration methods such as strong acid cleaning and the like can accelerate the damage of the catalyst carrier structure and the falling and loss of the noble metal component, thereby further causing the irreversible performance damage of the catalyst. Therefore, how to reasonably and effectively regenerate the deactivated catalyst for the selective hydrogenation of the chloronitroaromatic without damaging the original structural properties of the catalyst to recover the catalytic activity and prolong the service life is the key for developing a new process for the selective hydrogenation production of the chloronitroaromatic.
Disclosure of the invention
In order to make up for the defects of the prior art, the invention provides a regeneration method and application of a chloronitroaromatic selective hydrogenation catalyst, which are suitable for reaction characteristics, mild and friendly to the original structural property of the catalyst and can greatly prolong the service life.
The invention is realized by the following technical scheme:
a regeneration method of a chloronitroaromatic selective hydrogenation catalyst takes chloronitroaromatic as a raw material and takes a catalyst with reduced catalytic performance generated in the process of preparing chlorinated aromatic amine by selective hydrogenation as a treatment object, and comprises the following steps:
(1) adding part of the deactivated catalyst into the mixed alcohol solution of the precursor A and the stabilizer B, heating, stirring and dipping, filtering the catalyst after dipping, transferring the catalyst into a tubular atmosphere furnace, heating and carbonizing the catalyst according to a program in an inert atmosphere, and cooling and storing a product obtained by carbonization for later use;
(2) adding the carbonized catalyst and the deactivated catalyst obtained in the step (C) into a regeneration kettle provided with an ultraviolet light generating device and a microwave generating device according to a certain dry basis mass ratio, adding a treatment liquid C, starting stirring under the ultraviolet light irradiation condition for regeneration treatment, and pressing the treated feed liquid into a precision filter by nitrogen for filtering;
(3) a solvent D is adopted to back flush the catalyst in the filter into a regeneration kettle, stirring is started under the microwave assistance effect for washing, feed liquid after washing is pressed into a precision filter by nitrogen for filtering, and filtrate is recovered for later use;
(4) and (3) backflushing the catalyst in the filter into a regeneration kettle by using deionized water, washing the catalyst clean, and filtering the catalyst to obtain the regenerated wet-based catalyst.
The method adopts a proper precursor and a proper stabilizing solution to soak and carbonize a part of deactivated catalyst, utilizes the stabilizing solution to anchor organic amine impurities attached to the surface of the deactivated catalyst so as to form stable structural nitrogen species in the carbonization process, and utilizes the catalytic action of the nitrogen species on the carbon surface of the catalyst and the residual exposed metal active sites to catalyze persulfate to decompose and generate high-activity free radicals under the conditions of ultraviolet irradiation and microwaves; meanwhile, the precursor can generate a nano titanium dioxide optical active site in situ in the carbonization process, and the nano titanium dioxide optical active site is matched with ultraviolet irradiation to form a photocatalysis effect, so that the chain scission decomposition of organic macromolecular impurities on the surface of the deactivated catalyst is cooperatively realized under mild conditions, and the carrier structure and the metal active site of the catalyst are not damaged. And (3) carrying out microwave washing on the treated catalyst under the interaction of organic acid and an organic solvent, and removing organic micromolecular impurities formed by chain scission of organic macromolecular impurities and ammonia adsorbed on metal active sites. Thereby realizing the dredging of the inactive catalyst pore and the recovery of the metal active site. The treatment method has mild conditions, and can effectively remove indissolvable macromolecular organic impurities blocked in the pore channels and covered on the metal active sites and recover the catalytic performance under the condition of not damaging the pore channel structure of the catalyst and the noble metal load.
The more preferable technical scheme of the invention is as follows:
the inactivation catalyst is one of Pt, Pd and Ru loaded by active carbon, nano porous carbon, porous carbon spheres, carbon nano tubes or active carbon fibers.
In the step (1), the precursor A is one of n-propyl titanate, isopropyl titanate, n-butyl titanate and isobutyl titanate; the stabilizing solution B is one of terephthalaldehyde, m-phthalaldehyde or o-phthalaldehyde; the solvent is one of methanol, ethanol or isopropanol; the content of the precursor A in the alcoholic solution is 1-30%, and the content of the stabilizer B in the solution is 5-30%; the mass ratio of the dry-based deactivated catalyst to the alcoholic solution is 1:4-20, and the dipping temperature is 50-80 ℃.
The inert atmosphere is one of high-purity nitrogen, high-purity helium and high-purity argon; the temperature rise rate in the carbonization process is 0.5-10 ℃/min, the highest carbonization temperature is 500-1100 ℃, and the maintaining time of the highest carbonization temperature is 0.5-2 hr.
In the step (2), the dry-basis mass ratio of the carbonization catalyst to the deactivated catalyst is 1:25-80, the treatment solution C is one of aqueous solutions of sodium peroxydisulfate, potassium peroxydisulfate, sodium monopersulfate or potassium monopersulfate, the mass fraction of persulfate in the treatment solution C is 0.5-10%, and the mass ratio of the total dry-basis catalyst to the treatment solution B is 1: 10-50.
The catalyst treatment temperature is 30-80 ℃, the ultraviolet wavelength of the regeneration kettle is 180-300 nm, and the microwave treatment power is 200-2000W.
In the step (3), the solvent D is one of a mixed solution of formic acid and dipropylene glycol dimethyl ether, a mixed solution of acetic acid and dipropylene glycol dimethyl ether or a mixed solution of propionic acid and dipropylene glycol dimethyl ether, the mass ratio of the dry-based catalyst to the solvent D is 1:15-80, the microwave washing power is 500W-1500W, and the washing temperature is 50-100 ℃.
In the mixed liquid of the organic acid and the dipropylene glycol dimethyl ether, the mass fraction of the organic acid is 1-15%.
In the step (4), the mass ratio of the dry-based catalyst to the deionized water is 1: 15-80.
The regenerated catalyst is used for one of the reaction of preparing 2, 2' -dichlorohydrazobenzene by selectively hydrogenating o-chloronitrobenzene, the reaction of preparing 2-amino-4-methyl-5-chlorobenzenesulfonic acid by selectively hydrogenating 2-nitro-4-methyl-5-chlorobenzenesulfonic acid, the reaction of preparing p-chloroaniline by selectively hydrogenating p-nitrochlorobenzene or the reaction of preparing m-chloroaniline by selectively hydrogenating m-nitrochlorobenzene.
The method has the advantages of simplicity, high efficiency, environmental friendliness, mild conditions and the like, can keep the pore structure of the catalyst and the loading state of the noble metal nanoparticles while ensuring the removal of organic macromolecules, highly conforms to the characteristic of the selective hydrogenation reaction of the chloronitroaromatic, effectively recovers the activity of the catalyst, increases the application frequency of the catalyst, and obviously reduces the use cost of the catalyst.
(IV) description of the drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is a TEM micrograph of fresh 5 w% Pt/C catalyst Cat1-F of example 1;
FIG. 2 is a TEM photograph of Cat1-U-R as a catalyst after regeneration in example 1.
(V) detailed description of the preferred embodiments
The present invention will be further described with reference to the following examples.
Example 1: the method for regenerating the inactivated 5w percent Pt/C catalyst in the reaction of preparing the 2, 2' -dichlorohydrazobenzene by selectively hydrogenating the o-chloronitrobenzene comprises the following steps:
(1) dispersing 10g of deactivated catalyst (Cat 1-U) into 50g of methanol solution containing 5% of N-butyl titanate and 5% of terephthalaldehyde, stirring and dipping at 50 ℃, filtering the catalyst after dipping, transferring the catalyst into a tubular atmosphere furnace, and adding N2Under the protection of (2 ℃/min), heating to 500 ℃ at a heating rate of 2 ℃/min, maintaining for 2h for carbonization, and obtaining a product (marked as N)&Ti @ Cat1-U) was cooled and stored for further use.
(2) 10g N & Ti @ Cat1-U and 250g Cat1-U were put into a 10L regeneration vessel equipped with an ultraviolet irradiation device and a microwave generation device, 2.5kg of an aqueous solution containing 5% sodium peroxodisulfate was added, and regeneration treatment was carried out under the irradiation of ultraviolet light at a wavelength of 200nm at a treatment temperature of 50 ℃ and a microwave power of 1000W, and the treated feed liquid was filtered by being pressed into a precision filter by nitrogen.
(3) The catalyst in the filter is backflushed into a regeneration kettle by adopting 5kg of dipropylene glycol dimethyl ether mixed solution containing 10% formic acid, stirring is started under the assistance of 1000W of microwave for washing, feed liquid after washing is pressed into a precision filter by nitrogen for filtering, and filtrate is recovered for later use.
(4) And (3) backflushing the catalyst in the filter into a regeneration kettle by using 5kg of deionized water, washing the catalyst clean, and filtering the catalyst to obtain the regenerated wet-based catalyst (recorded as Cat 1-U-R).
The performance of the regenerated catalyst was evaluated: 54g of o-chloronitrobenzene, 28g of toluene, 0.216g of regenerated catalyst Cat1-U-R (calculated by dry basis), 27.5g of 17% sodium hydroxide solution, 0.216g of 2, 3-dichloro-1, 4-naphthoquinone and 0.432g of sodium dodecyl benzene sulfonate are added into a 500ml high-pressure reaction kettle, hydrogen is filled after nitrogen replacement, the temperature is raised to 65 ℃, the hydrogen pressure is maintained at 2.0MPa until the reaction system does not absorb hydrogen, and the reaction is judged to be finished. The reaction solution mixed with the catalyst was filtered to recover the catalyst. The catalyst was used continuously for 5 times without additional addition. And (3) carrying out quantitative analysis on the 5 batches of reaction liquid by adopting a high performance liquid chromatograph, and calculating the conversion rate of o-chloronitrobenzene and the purity of the product 2, 2' -dichlorohydrazobenzene. The results are as follows:
Figure BDA0003017193410000041
the experimental results in the table show that the regenerated catalyst Cat1-U-R can be continuously used for 5 times without being supplemented, the conversion rate of o-chloronitrobenzene can reach 100%, the purity of the product 2, 2' -dichlorohydrazobenzene is higher than 99%, the reaction time is basically unchanged along with the increase of the application times, the catalyst stability is excellent, and compared with the catalyst before regeneration, the catalyst performance is obviously improved.
By using N2The fresh, deactivated and regenerated catalysts are contrastively analyzed by low-temperature physical adsorption and desorption and ICP and CO chemical adsorption, and the results are as follows:
sample (I) Specific surface area/m2g-1 Pore volume/cm3g-1 Specific surface area of metal/m2g-1
Cat1-F 1632.43 1.65 158
Cat1-U 712.58 0.54 70
Cat1-U-R 1616.20 1.62 155
From the characterization results in the table above, it can be seen that the specific surface area of the deactivated catalyst Cat1-U is reduced by 56.3%, the pore volume is reduced by 67.3%, and the metal specific surface area is reduced by 55.7% compared with that of the fresh catalyst Cat 1-F. The specific surface area of the regenerated catalyst Cat1-U-R can be recovered to 99% of that of the fresh catalyst, the pore volume can be recovered to 98% of that of the fresh catalyst, and the specific surface area of the metal can be recovered to 98% of that of the fresh catalyst. The regeneration method can effectively remove the organic impurities attached to the catalyst, realize the cleaning of the pore channel and release the active sites of the catalyst.
The Pt loading amounts of the fresh, deactivated and regenerated catalysts are compared and analyzed by adopting an inductively coupled plasma atomic emission spectrum, and the results are as follows:
Cat1-F Cat1-U Cat1-U-R
actual load/wt. -%) 4.97 4.96 4.96
The ICP characterization result shows that the actual loading of the regenerated catalyst is slightly different from the actual loading of the deactivated fresh catalyst, which indicates that the regeneration method does not influence the loading of the metal and the metal Pt does not run off in the regeneration process.
The morphology and microstructure of the fresh and regenerated catalysts were characterized by Transmission Electron Microscopy (TEM) and the results are shown in fig. 1 and 2. The TEM images show that there is little change in the particle size and dispersion of the regenerated catalyst from the fresh catalyst, indicating that the regeneration process does not grow or agglomerate the Pt particles.
By combining the above characterization analysis and reaction evaluation, the regeneration method can effectively recover the specific surface area, pore volume and active metal specific surface area of the catalyst, greatly improve the catalytic performance, and does not have adverse effects on the metal loading capacity of the catalyst and the dispersion state of the metal nanoparticles.
Example 2: the method for regenerating the deactivated 3w percent Pd/C catalyst in the reaction of preparing 2, 2' -dichlorohydrazobenzene by selectively hydrogenating o-chloronitrobenzene comprises the following steps:
(1) 10g of deactivated catalyst are taken(Cat2-U) was dispersed in 50g of a methanol solution containing 15% of N-butyl p-titanate and 15% of terephthalaldehyde, and the mixture was immersed in the methanol solution at 80 ℃ with stirring, and after completion of the immersion, the catalyst was filtered and transferred to a tubular atmosphere furnace where it was immersed in N2Under the protection of (2), the temperature is raised to 800 ℃ at the heating rate of 5 ℃/min, and then the temperature is maintained for 2h for carbonization treatment, and a product (marked as N) is obtained after carbonization&Ti @ Cat2-U) was cooled and stored for further use.
(2) 10g N & Ti @ Cat2-U and 300g Cat2-U are put into a 10L regeneration kettle equipped with an ultraviolet irradiation device and a microwave generation device, 3kg of aqueous solution containing 5% potassium peroxodisulfate is added, regeneration treatment is carried out under the action of ultraviolet radiation with the wavelength of 255nm, the treatment temperature is 50 ℃, the microwave power is 2000W, and the treated feed liquid is pressed into a precision filter by nitrogen and filtered.
(3) The catalyst in the filter is backflushed into a regeneration kettle by adopting 6kg of dipropylene glycol dimethyl ether mixed solution containing 10% acetic acid, stirring is started under the assistance of 1500W of microwave for washing, feed liquid after washing is pressed into a precision filter by nitrogen for filtering, and filtrate is recovered for later use.
(4) And (3) backflushing the catalyst in the filter into a regeneration kettle by adopting 6kg of deionized water, washing the catalyst clean, and filtering the catalyst to obtain the regenerated wet-based catalyst (marked as Cat 2-U-R).
And (3) evaluating the performance of the regenerated catalyst: 54g of o-chloronitrobenzene, 28g of toluene, 0.216g of regenerated catalyst Cat2-U-R (calculated by dry basis), 27.5g of 17% sodium hydroxide solution, 0.216g of 2, 3-dichloro-1, 4-naphthoquinone and 0.432g of sodium dodecyl benzene sulfonate are added into a 500ml high-pressure reaction kettle, hydrogen is filled after nitrogen replacement, the temperature is raised to 65 ℃, the hydrogen pressure is maintained at 2.0MPa until the reaction system does not absorb hydrogen, and the reaction is judged to be finished. The reaction solution mixed with the catalyst was filtered to recover the catalyst. The catalyst was used continuously for 5 times without additional addition. And (3) carrying out quantitative analysis on the 5 batches of reaction liquid by adopting a high performance liquid chromatograph, and calculating the conversion rate of o-chloronitrobenzene and the purity of the product 2, 2' -dichlorohydrazobenzene. The results are as follows:
Figure BDA0003017193410000061
the experimental results in the table show that the regenerated catalyst Cat2-U-R is continuously used for 5 times without being supplemented, the conversion rate of the o-nitrochlorobenzene is close to 100%, the purity of the product 2, 2' -dichlorohydrazobenzene is higher than 99%, the reaction time is basically unchanged along with the increase of the application times, the catalyst stability is excellent, and compared with the catalyst before regeneration, the catalyst performance is obviously improved.
Example 3: comparative experiment of regeneration method
(1) 250g of Cat1-U was directly charged into a 10L regeneration vessel equipped with an ultraviolet irradiation device and a microwave generation device, 2.5kg of an aqueous solution containing 5% sodium peroxodisulfate was added, and the regeneration treatment was carried out under the irradiation of ultraviolet light having a wavelength of 200nm at a treatment temperature of 50 ℃ under the action of a microwave power of 1000W, and the treated feed liquid was filtered by being pressed into a precision filter by nitrogen.
(2) Subsequent regeneration experiments were carried out following steps (3), (4) of carrying out example 1. The regenerated catalyst (noted Cat1-U-R1) was evaluated for catalyst performance: the evaluation method and the analysis method were the same as in example 1. The results are as follows:
Figure BDA0003017193410000071
as can be seen from the experimental results in the above table, the catalyst Cat1-U-R1 after regeneration of the example has an ortho-chloronitrobenzene conversion of only 32.8% of that of Cat1-U-R, compared to the catalyst regenerated in the example 1. The structural properties of Cat1-U-R1 were characterized and analyzed by BET and CO chemisorption, and the results were as follows:
sample (I) Specific surface area/m2g-1 Pore volume/cm3g-1 Specific surface area of metal/m2g-1
Cat1-F 1632.43 1.65 158
Cat1-U 712.58 0.54 70
Cat1-U-R 1616.20 1.62 155
Cat1-U-R1 852.33 0.84 98
According to the BET and CO chemisorption characterization results, the specific surface area of the regenerated catalyst Cat1-U-R1 of the example is only 52.2 percent of that of the fresh catalyst, the pore volume is only 50.9 percent of that of the fresh catalyst, and the metal specific surface area is only 62 percent of that of the fresh catalyst. Therefore, the regenerated catalyst of this example does not completely recover the catalytic performance of the catalyst.
Example 4 of implementation: comparative experiment of regeneration method
(1) 10g of deactivated catalyst (Cat 1-U) was dispersed in 50g of 5% terephthalaldehyde in methanolStirring and dipping at 50 ℃, filtering the catalyst after dipping and transferring the catalyst into a tubular atmosphere furnace, and carrying out N2Under the protection of (1), heating to 500 ℃ at a heating rate of 2 ℃/min, maintaining for 2h for carbonization, cooling a product (marked as N @ Cat1-U) obtained after carbonization, and storing for later use.
The regenerated catalyst Cat1-U-R2 was obtained by the subsequent treatments according to the procedures (2), (3) and (4) in example 1, and the performance evaluation was carried out by the method in example 1, with the following results:
Figure BDA0003017193410000072
Figure BDA0003017193410000081
as can be seen from the above table, the conversion of o-chloronitrobenzene of catalyst Cat1-U-R2 was increased by 23% and the conversion of o-chloronitrobenzene of Cat1-U-R was increased by 44.7% compared to deactivated catalyst Cat 1-U-R. This indicates that the lack of a precursor involved in catalyst regeneration does not completely restore the catalytic performance of the catalyst.
Example 5 was carried out: comparative experiment of regeneration method
(1) 10g of the deactivated catalyst (designated as Cat1-U) were added to 50g of a methanol solution containing 5% N-butyl p-titanate, stirred and impregnated at 50 ℃ and after the impregnation the catalyst was filtered and transferred to a tube-type atmosphere furnace under N2Under the protection of (1), heating to 500 ℃ at a heating rate of 2 ℃/min, maintaining for 2h for carbonization, cooling a product (marked as Ti @ Cat1-U) obtained after carbonization, and storing for later use.
The regenerated catalyst Cat1-U-R3 was obtained by the subsequent treatments according to the procedures (2), (3) and (4) in example 1, and the performance evaluation was carried out by the method in example 1, with the following results:
Figure BDA0003017193410000082
as can be seen from the above table, the conversion of o-chloronitrobenzene of catalyst Cat1-U-R3 was increased by 26.1% and the conversion of o-chloronitrobenzene of Cat1-U-R was increased by 44.7% compared to deactivated catalyst Cat 1-U-R. This indicates that the lack of a stabilizing solution involved in the catalyst regeneration does not completely restore the catalytic performance of the catalyst.
Quantitative and qualitative analysis of N @ Cat1-U in examples 1 and 4 and Ti @ Cat1-U in example 5 by elemental analysis and XPS revealed that: the nitrogen content of N @ Cat1-U is 3.4%, nitrogen-containing species mainly comprise pyridine-state nitrogen, graphite-state nitrogen and oxide nitrogen atoms, and the nitrogen content of Ti @ Cat1-U is only 0.5%.
Example 6: comparative experiment of regeneration method
The same regeneration method as that used in the embodiment 1 is used for regenerating the deactivated catalyst Cat1-U, and the only difference from the technical scheme of the embodiment 1 is that in the step (3), the adopted washing solvent is pure dipropylene glycol dimethyl ether.
The regenerated catalyst was designated Cat 1-U-R4. The performance of the regenerated Cat1-U-R4 was evaluated: the evaluation method and the analysis method were the same as in example 1. The results are as follows:
Figure BDA0003017193410000083
Figure BDA0003017193410000091
as can be seen from the above table, the conversion of o-chloronitrobenzene of catalyst Cat1-U-R4 was increased by 17.2% and the conversion of o-chloronitrobenzene of Cat1-U-R was increased by 44.7% compared to deactivated catalyst Cat 1-U-R. The structural properties of Cat1-U-R4 were characterized and analyzed by BET and CO chemisorption, and the results were as follows:
sample (I) Specific surface area/m2g-1 Pore volume/cm3g-1 Specific surface area of metal/m2g-1
Cat1-F 1632.43 1.65 158
Cat1-U 712.58 0.54 70
Cat1-U-R 1616.20 1.62 155
Cat1-U-R4 1312.55 1.36 99
As can be seen from the experimental results in the above table, the specific surface area of Cat1-U-R4 is 80.4% of that of the fresh catalyst, and the pore volume is 82.4% of that of the fresh catalyst, but the metal specific surface area of Cat1-U-R4 is only 62.7% of that of the fresh catalyst.
The comparison analysis of Temperature Programmed Desorption (TPD) is carried out on the fresh and regenerated catalyst by adopting a chemical adsorption instrument, and the result shows that: fresh catalyst Cat1-F showed no appearance of NH3The desorption peak of Cat1-U-R regenerated by the method of example 1 also showed no NH3While the regenerated Cat1-U-R4 showed a clear NH3Desorption peak of (2).
By combining the characteristics, most organic impurities can be removed by washing with dipropylene glycol dimethyl ether in the step (3), but the ammonia adsorbed on the metal active site cannot be removed due to the lack of organic acid participating in catalyst regeneration, so that the catalytic activity of the metal Pt cannot be recovered.
Example 7: comparative experiment of regeneration method
(1) 10g of catalyst Cat1-U is accurately weighed, 60ml of nitric acid solution with the concentration of 5% -20% is added, and the mixture is oscillated for 2 hours in a thermostatic water bath at the temperature of 25 ℃. Then filtering, washing and drying to constant weight. The treated catalyst was designated Cat1-U-R5 and evaluated and analyzed according to the evaluation and analysis methods of example 1.
(2) 10g of catalyst Cat1-U is accurately weighed, 60ml of hydrogen peroxide solution with the concentration of 10% -30% is added, and the mixture is oscillated for 2 hours in a thermostatic water bath at the temperature of 25 ℃. Then filtering, washing and drying to constant weight. The treated catalyst was designated Cat1-U-R6 and evaluated and analyzed according to the evaluation and analysis methods of example 1. The results are as follows:
Figure BDA0003017193410000092
the experimental results in the table above show that: compared with the deactivated catalyst Cat1-U-R, the conversion rate of o-chloronitrobenzene of the catalyst Cat1-U-R5 is increased by 30.8%, the conversion rate of o-chloronitrobenzene of the catalyst Cat1-U-R6 is increased by 31.2%, and the conversion rate of o-chloronitrobenzene of the catalyst Cat1-U-R is increased by 44.7%. Therefore, structural property characterization analysis including specific surface area, pore volume, metal specific surface area and Pt content measurement by ICP were carried out on Cat1-U-R5 and Cat1-U-R6, and the results are as follows:
sample (I) Specific surface area/m2g-1 Pore volume/cm3g-1 Specific surface area of metal/m2g-1
Cat1-U-R 1616.20 1.62 155
Cat1-U-R5 1342.31 1.39 122
Cat1-U-R6 1365.69 1.45 128
Cat1-U 712.58 0.54 70
Cat1-F 1632.43 1.65 158
Sample (I) Actual load/wt. -%)
Cat1-U-R 4.96
Cat1-U-R5 2.23
Cat1-U-R6 2.35
Cat1-U 4.96
Cat1-F 4.97
From the above table, the following conclusions can be drawn: the specific surface area and pore volume of the regenerated catalyst of the invention are close to those of a fresh catalyst, while the difference between the catalyst after the conventional oxidant oxidation treatment and the fresh catalyst is large. According to the analysis of the combined characterization result, the specific surface area, the pore volume and the specific surface area of the active metal of the catalyst after the oxidation treatment are recovered, but still cannot reach the level of a fresh catalyst, and the catalyst after the oxidation treatment has a serious Pt loss phenomenon, which is a main reason for poor catalyst activity. .
Example 8: comparative experiment of regeneration method
(1) 10g of catalyst Cat1-U was weighed out accurately, and 60ml of methanol was added thereto, followed by stirring and refluxing at 85 ℃ for 3 hours. Then filtering, washing and drying to constant weight. The treated catalyst was designated Cat1-U-R7 and evaluated and analyzed according to the evaluation and analysis methods of example 1.
(2) 10g of catalyst Cat1-U was weighed out accurately, and 60ml of acetone was added thereto, followed by stirring and refluxing at 85 ℃ for 3 hours. Then filtering, washing and drying to constant weight. The treated catalyst was designated Cat1-U-R8 and evaluated and analyzed according to the evaluation and analysis methods of example 1.
(3) 10g of catalyst Cat1-U was weighed out accurately, and 60ml of dipropylene glycol dimethyl ether was added thereto and stirred at 180 ℃ under reflux for 3 hours. Then filtering, washing and drying to constant weight. The treated catalyst was designated Cat1-U-R9 and evaluated and analyzed according to the evaluation and analysis methods of example 1.
Figure BDA0003017193410000111
The experimental results in the table above show that: compared with the deactivated catalyst Cat1-U-R, the conversion rate of o-chloronitrobenzene of the catalyst Cat1-U-R7 is increased by 4.9%, the conversion rate of o-chloronitrobenzene of the catalyst Cat1-U-R8 is increased by 4.1%, the conversion rate of o-chloronitrobenzene of the catalyst Cat1-U-R9 is increased by 14.9%, and the conversion rate of o-chloronitrobenzene of the catalyst Cat1-U-R is increased by 44.7%. Therefore, the structural feature characterization analysis including specific surface area, pore volume and metal specific surface area is carried out on Cat1-U-R7, Cat1-U-R8 and Cat1-U-R9, and the results are as follows:
sample (I) Specific surface area/m2g-1 Pore volume/cm3g-1 Specific surface area of metal/m2g-1
Cat1-U-R 1616.20 1.62 155
Cat1-U-R7 824.67 0.78 89
Cat1-U-R8 816.33 0.69 85
Cat1-U-R9 1130.52 1.33 117
Cat1-U 712.58 0.54 70
Cat1-F 1632.43 1.65 158
As can be seen from the above table, the specific surface area of the catalyst Cat1-U-R7 is only 50.5% of that of the fresh catalyst, the pore volume is only 47.3% of that of the fresh catalyst, and the specific surface area of the metal is only 56.3% of that of the fresh catalyst. The specific surface area of the catalyst Cat1-U-R8 was only 50.0% of that of the fresh catalyst, the pore volume was only 41.8% of that of the fresh catalyst, and the metal specific surface area was only 53.8% of that of the fresh catalyst. The specific surface area of the catalyst Cat1-U-R9 was only 69.3% of that of the fresh catalyst, the pore volume was only 80.6% of that of the fresh catalyst, and the metal specific surface area was only 74.1% of that of the fresh catalyst. Therefore, the impurities deposited on the surface of the catalyst cannot be effectively recovered only by the conventional organic solvent cleaning, and it is difficult to obtain a significant regeneration effect.

Claims (10)

1. A regeneration method of a chloronitroaromatic selective hydrogenation catalyst takes chloronitroaromatic as a raw material and takes a catalyst with reduced catalytic performance generated in the process of preparing chlorinated aromatic amine by selective hydrogenation as a treatment object, and is characterized by comprising the following steps: the method comprises the steps of adding a part of deactivated catalyst into a mixed alcohol solution of a precursor A and a stabilizer B, heating, stirring and dipping, filtering the catalyst after dipping, transferring the catalyst into a tubular atmosphere furnace, heating and carbonizing the catalyst according to a program in an inert atmosphere, and cooling and storing a product obtained through carbonization for later use; adding the carbonized catalyst and the deactivated catalyst obtained in the step into a regeneration kettle provided with an ultraviolet light generating device and a microwave generating device according to a certain dry basis mass ratio, adding a treatment liquid C, starting stirring under the ultraviolet light irradiation condition for regeneration treatment, and pressing the treated feed liquid into a precision filter by nitrogen for filtering; thirdly, a solvent D is adopted to back flush the catalyst in the filter into the regeneration kettle, stirring is started under the microwave assistance effect for washing, feed liquid after washing is pressed into the precision filter by nitrogen for filtering, and filtrate is recovered for later use; fourthly, the catalyst in the filter is backflushed into a regeneration kettle through deionization and is washed clean, and then the regeneration kettle is filtered to obtain the regenerated wet-based catalyst.
2. The process for regenerating a catalyst for the selective hydrogenation of chloronitroaromatics according to claim 1, characterized in that: the inactivation catalyst is one of Pt, Pd and Ru loaded by active carbon, nano porous carbon, porous carbon spheres, carbon nano tubes or active carbon fibers.
3. The process for regenerating a catalyst for the selective hydrogenation of chloronitroaromatics according to claim 1, characterized in that: in the step, a precursor A is one of n-propyl titanate, isopropyl titanate, n-butyl titanate and isobutyl titanate; the stabilizer B is one of terephthalaldehyde, m-phthalaldehyde or o-phthalaldehyde; the solvent alcohol is one of methanol, ethanol or isopropanol; the content of the precursor A in the alcoholic solution is 1-30%, and the content of the stabilizer B in the solution is 5-30%; the mass ratio of the dry-based deactivated catalyst to the alcoholic solution is 1:4-20, and the dipping temperature is 50-80 ℃.
4. The process for regenerating a catalyst for the selective hydrogenation of chloronitroaromatics according to claim 1, characterized in that: the method comprises the steps that an inert atmosphere is one of high-purity nitrogen, high-purity helium and high-purity argon; the temperature rise rate in the carbonization process is 0.5-10 ℃/min, the highest carbonization temperature is 500-1100 ℃, and the maintaining time of the highest carbonization temperature is 0.5-2 hr.
5. The process for regenerating a catalyst for the selective hydrogenation of chloronitroaromatics according to claim 1, characterized in that: in the step II, the mass ratio of the carbonization catalyst to the deactivated catalyst is 1:25-80, the treatment fluid C is one of aqueous solutions of sodium persulfate, potassium persulfate, sodium monopersulfate or potassium monopersulfate, the mass fraction of the persulfate in the treatment fluid C is 0.5-10%, and the mass ratio of the total dry-based catalyst to the treatment fluid C is 1: 10-50.
6. The process for regenerating a catalyst for the selective hydrogenation of chloronitroaromatics according to claim 1, characterized in that: in the step II, the catalyst treatment temperature is 30-80 ℃, the ultraviolet wavelength in the regeneration kettle is 180-300 nm, and the microwave treatment power is 200-2000W.
7. The process for regenerating a catalyst for the selective hydrogenation of chloronitroaromatics according to claim 1, characterized in that: in the third step, the solvent D is one of a mixed solution of formic acid and dipropylene glycol dimethyl ether, a mixed solution of acetic acid and dipropylene glycol dimethyl ether or a mixed solution of propionic acid and dipropylene glycol dimethyl ether, the mass ratio of the dry-based catalyst to the solvent D is 1:15-80, the microwave washing power is 500W-1500W, and the washing temperature is 50-100 ℃.
8. The process for regenerating a catalyst for the selective hydrogenation of chloronitroaromatics according to claim 1, characterized in that: in the fourth step, the mass ratio of the dry-based catalyst to the deionized water is 1: 15-80.
9. The process for regenerating a catalyst for the selective hydrogenation of chloronitroaromatics according to claim 7, characterized in that: in the mixed liquid of the organic acid and the dipropylene glycol dimethyl ether, the mass fraction of the organic acid is 1-15%.
10. The application of the regenerated catalyst obtained by the regeneration method according to claim 1 in the preparation of chlorinated aromatic amine by selective hydrogenation of chlorinated nitroaromatic hydrocarbon is characterized in that: the reaction is one of a reaction for preparing 2, 2' -dichlorohydrazobenzene by selectively hydrogenating o-chloronitrobenzene, a reaction for preparing 2-amino-4-methyl-5-chlorobenzenesulfonic acid by selectively hydrogenating 2-nitro-4-methyl-5-chlorobenzenesulfonic acid, and a reaction for preparing p-chloroaniline by selectively hydrogenating p-nitrochlorobenzene or a reaction for preparing m-chloroaniline by selectively hydrogenating m-nitrochlorobenzene.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1244789A (en) * 1984-08-16 1988-11-15 James E. Lewis Large pore catalysts for heavy hydrocarbon conversion
KR20050098826A (en) * 2005-02-22 2005-10-12 로디아 파마 솔루션즈 인코포레이티드 Kinetic resolution method
WO2015010994A1 (en) * 2013-07-24 2015-01-29 Basf Se Regeneration of a titanium containing zeolite
CN106732655A (en) * 2016-12-05 2017-05-31 江苏肯创催化剂再生技术有限公司 A kind of arsenic poisoning SCR denitration renovation process
CN109701669A (en) * 2019-02-27 2019-05-03 青岛科技大学 A kind of arylamine kind antioxidant prepares the regeneration method of spent hydroprocessing catalyst
CN110550815A (en) * 2019-07-29 2019-12-10 郑州大学 Device and method for advanced treatment of old landfill leachate

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1244789A (en) * 1984-08-16 1988-11-15 James E. Lewis Large pore catalysts for heavy hydrocarbon conversion
KR20050098826A (en) * 2005-02-22 2005-10-12 로디아 파마 솔루션즈 인코포레이티드 Kinetic resolution method
WO2015010994A1 (en) * 2013-07-24 2015-01-29 Basf Se Regeneration of a titanium containing zeolite
CN106732655A (en) * 2016-12-05 2017-05-31 江苏肯创催化剂再生技术有限公司 A kind of arsenic poisoning SCR denitration renovation process
CN109701669A (en) * 2019-02-27 2019-05-03 青岛科技大学 A kind of arylamine kind antioxidant prepares the regeneration method of spent hydroprocessing catalyst
CN110550815A (en) * 2019-07-29 2019-12-10 郑州大学 Device and method for advanced treatment of old landfill leachate

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
LIU MS等: "Squaramide functionalized ionic liquids with well-designed structures: Highly-active and recyclable catalyst platform for promoting cycloaddition of CO2 to epoxides", JOURNAL OF CO2 UTILIZATION, vol. 37, 30 April 2020 (2020-04-30), pages 39 - 44 *
WANG X等: "Recycling the Cathode Scrap of Spent Lithium-Ion Batteries as an Easily Recoverable Peroxymonosulfate Catalyst with Enhanced Catalytic Performance", ACS SUSTAINABLE CHEMISTRY & ENGINEERING, vol. 8, no. 30, 3 August 2020 (2020-08-03), pages 11337 - 11347 *
温继伟;王孝强;董长青;乔小康;: "失活SCR脱硝催化剂再生技术试验研究", 电力科技与环保, no. 03, 7 June 2018 (2018-06-07), pages 26 - 29 *
高文立等: "介质阻挡放电技术再生Pd/AC催化剂的机理探讨", 化工学报, vol. 64, no. 1, 15 January 2013 (2013-01-15), pages 297 - 302 *

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