CN112547064A - Method for removing halogen in halogenated aromatic compound by using catalyst loaded with copper or copper oxide nanoparticles - Google Patents

Method for removing halogen in halogenated aromatic compound by using catalyst loaded with copper or copper oxide nanoparticles Download PDF

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CN112547064A
CN112547064A CN202011403596.1A CN202011403596A CN112547064A CN 112547064 A CN112547064 A CN 112547064A CN 202011403596 A CN202011403596 A CN 202011403596A CN 112547064 A CN112547064 A CN 112547064A
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copper
halogenated aromatic
aromatic hydrocarbon
cuo
catalyst
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丁玉强
江杰
杜立永
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Jiangnan University
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Abstract

The invention discloses a method for removing halogen in halogenated aromatic compounds by using a catalyst loaded with copper or copper oxide nanoparticles, belonging to the technical field of catalytic synthesis. The invention contacts the halogenated aromatic hydrocarbon substrate with selected alcohols and alkali in the presence of a catalyst loaded by copper or copper oxide nanoparticles, and heats and stirs the substrate. Attacking polyhalogenated aromatic hydrocarbon by utilizing active hydrogen formed on the surface of copper nanoparticles by using alcohol, so as to realize rapid deep dehalogenation of the halogenated aromatic hydrocarbon, wherein the alcohol is primary alcohol or secondary alcohol capable of being used as a solvent; the halogenated aromatic hydrocarbon compound comprises any one or more of chlorophenyl compound, bromophenyl compound and iodophenyl compound. The method is simple to operate, economic and low in cost, and halogenated aromatic hydrocarbon can be completely converted within 10-15 hours under optimized conditions.

Description

Method for removing halogen in halogenated aromatic compound by using catalyst loaded with copper or copper oxide nanoparticles
Technical Field
The invention relates to a method for removing halogen in halogenated aromatic compounds by using a catalyst loaded with copper or copper oxide nanoparticles, belonging to the technical field of catalytic synthesis.
Background
Halogen groups are typical protecting and directing groups, so halogenated aromatic compounds are widely used as starting materials for many chemical transformations in the chemical industry, agrochemistry. Polybrominated diphenyl ethers are the most widely used flame retardant materials, but the environmental pollution caused by the polybrominated diphenyl ethers is increasingly severe, so that a method for efficiently removing halogen in halogenated aromatic compounds needs to be found. Hydrodehalogenation is an important organic conversion reaction in synthesis and plays an important role in the degradation of halogenated aromatic compounds. Research shows that zero-valent iron dehalogenation is the most effective technology for hydrodehalogenation of halogenated aromatic hydrocarbon through Fenton-like reaction under aerobic condition. However, this process is slow and results in the release of iron ions, which in turn prevents efficient halogen removal.
The search for more efficient and environmentally friendly catalysts has been the focus of attention of researchers. The prior art has investigated the use of homogeneous catalytic systems of transition metal complexes for converting CArThe conversion of the-X bond to a C-H bond to effect the removal of the halogen from the halogenated aliphatic hydrocarbon compound. However, these transition metal complexes are generally unstable and unrecoverable, and certain ligands in the complexes are toxic, air-sensitive and difficult to synthesize. Among the various hydrodehalogenation catalysts, heterogeneous catalysts are therefore a powerful and efficient choice for cleaving the C-X bond in aryl halides under mild conditions. Currently, noble metal nanoparticles (MNP, M ═ Pd, Au, Ag, Pt) are widely used in hydrodehalogenation catalysis, and the cost is high. Not only does the catalyst play an important role in dehalogenation, but the choice of hydrogen source is another important direction of research. The prior art has disclosed the use of molecule H2Sodium borohydride, ammonium borohydride, hydrazine, ammonia borane, alcohols and aldehydes as hydrogen sources. However, for the dehalogenation processIn general, since the activity of the non-noble metal heterogeneous catalyst is low under mild reaction conditions, some toxic hydrogen source or high-pressure hydrogen is needed to match it to realize the dehalogenation process.
The use of Cu (0) -NP for the process of removing halogen from aliphatic hydrocarbon halogenated materials has been disclosed, and the removal of halogen from aliphatic hydrocarbon halogenated materials can be realized in the environment of high-pressure hydrogen. Due to CArThe bond energy of the-Cl bond reaches 97.1 kcal/mol, CArThe energy of the-Br bond reaches 84.0 kcal/mol, so that the structure of the catalyst is more stable than that of the aliphatic hydrocarbon halide. Such a high bond energy makes removal of halogen on the aromatic ring more difficult, and simple use of hydrogen or sodium borohydride as a hydrogen source in a system in which copper nanoparticles are used as a catalyst has not been able to achieve the effect of removing halogen on the aromatic ring.
Therefore, a method for removing halogen in halogenated aromatic compounds with low cost, no toxicity, mildness and high efficiency is needed.
Disclosure of Invention
In order to achieve the purpose, the invention provides a method for removing halogen in halogenated aromatic compounds by using a catalyst loaded with copper or copper oxide nanoparticles, the method takes the loaded copper or copper oxide nanoparticles as the catalyst and alcohols as a hydrogen source, the raw materials are non-toxic and do not need a high-pressure environment, and the reaction selectivity and the conversion rate can reach 100%.
Specifically, the invention provides a method for dehalogenating halogen in aromatic hydrocarbon compounds by using a catalyst loaded with copper or copper oxide nanoparticles, which comprises the following steps:
(1) placing halogenated aromatic hydrocarbon compounds, alcohols, alkali and catalysts loaded with copper or copper oxide nano particles into a reaction device, and filling inert gas into the reaction device to remove air in the reaction device;
(2) heating to 120 ℃ and 300 ℃, stirring and reacting for 10-15 h;
(3) after the reaction is finished, the catalyst is removed by solid-liquid separation, and the aromatic hydrocarbon compound after halogen removal is obtained by distillation and crystallization.
In one embodiment of the invention, the haloaromatic compound is a halophenyl compound comprising one or more halogen atoms.
In one embodiment of the present invention, the halogenated aromatic hydrocarbon compound includes any one or more of a chlorophenyl compound, a bromophenyl compound and an iodophenyl compound.
In one embodiment of the invention, the alcohol is a primary or secondary alcohol capable of acting as a solvent.
In one embodiment of the invention, the alcohol comprises one or more of isopropanol, ethylene glycol, glycerol, 1-pentanol, 2-pentanol, 1-octanol, and cyclohexanol.
In one embodiment of the present invention, the alcohol is added in an amount equal to or greater than the amount of the halogenated aromatic hydrocarbon, preferably 2 times the molar amount of the halogenated aromatic hydrocarbon
In one embodiment of the invention, the base comprises any one or more of an organic base, an inorganic base or a basic salt.
In one embodiment of the present invention, the organic base comprises one or more of potassium tert-butoxide, sodium ethoxide and sodium methoxide.
In one embodiment of the present invention, the inorganic base comprises one or more of potassium hydroxide, sodium hydroxide and calcium hydroxide.
In one embodiment of the present invention, the basic salt comprises one or more of cesium carbonate, potassium carbonate, sodium carbonate, potassium phosphate, and sodium phosphate.
In one embodiment of the present invention, the molar ratio of the halogenated aromatic hydrocarbon to the base is (1 to 5):1, preferably 1: 1.
In one embodiment of the present invention, the carrier of the catalyst loaded with copper or copper oxide nanoparticles is an alkali-resistant material, preferably, includes any one or more of activated carbon, hydrotalcite, ZSM-5, molecular sieve, titanium dioxide, zirconium dioxide, aluminum oxide, and magnesium oxide.
In one embodiment of the invention, the carrier particle size is typically between 10nm and 100 μm.
In one embodiment of the invention, the copper oxide comprises cupric oxide or cuprous oxide.
In one embodiment of the present invention, the copper or copper oxide nanoparticle-supported catalyst preferably comprises CuO/TiO2,Cu2O/TiO2,Cu/TiO2,Cu2O/Al2O3,Cu2O/Al2O3，Cu2O/Al2O3，CuO/MgO,Cu2O/MgO，Cu/MgO，CuO/ZrO2,Cu2O/ZrO2,Cu/ZrO2CuO/hydrotalcite, Cu2O/hydrotalcite, Cu/hydrotalcite, CuO/activated carbon, Cu2O/activated carbon, Cu/activated carbon, CuO/ZSM-5, Cu2One or more of O/ZSM-5 and Cu/ZSM-5.
In one embodiment of the present invention, the amount of the catalyst loaded with copper or copper oxide nanoparticles is 0.1 to 100% of the molar amount of the halogenated aromatic hydrocarbon.
In one embodiment of the present invention, the loading amount of the copper element in the catalyst loaded with copper or copper oxide nanoparticles is 0.005 to 0.5, preferably 0.05.
In one embodiment of the present invention, the catalyst loaded with copper or copper oxide nanoparticles is prepared by an impregnation method, a coprecipitation method, a hydrothermal method, a chemical vapor deposition method, or an atomic layer deposition method, and mainly loads a copper species on a carrier.
In one embodiment of the present invention, hydrothermal synthesis is exemplified as follows: 38g of copper nitrate trihydrate is dissolved in 1L of deionized water, 1kg of hydrotalcite is added, the mixture is stirred for 2 hours after ultrasonic oscillation is carried out for 30 minutes, then all water is evaporated at the temperature of 80 ℃, and after grinding, the mixture is calcined for 2 hours at the temperature of 300 ℃ and 500 ℃. So as to obtain the corresponding catalyst CuO/hydrotalcite.
In one embodiment of the invention, the inert gas is nitrogen or argon.
In one embodiment of the invention, the solid-liquid separation comprises filtration or centrifugation.
In one embodiment of the invention, the dehalogenation hydrogenation reaction may be carried out under liquid phase conditions or gas phase conditions or mixed liquor/gas phase conditions.
In one embodiment of the present invention, the dehalogenation reaction is carried out mainly at the temperature of reflux using alcohols, if necessary with the addition of a reflux apparatus.
The invention also provides the application of the method in the fields of chemical engineering, environment and the like.
Compared with the prior art, the invention has the advantages that:
(1) in the method, a copper-loaded catalyst can be used, so that the catalyst is cheaper and easily obtained, and copper oxide nanoparticles can be used for loading, so that the preparation of the catalyst is simplified; the alcohol substance is used as the hydrogen source, so that the reaction is more green and safe.
(2) The dehalogenation effect can completely debrominate the bromobenzene within 10 hours, and the requirements of production or environment are completely met.
Detailed Description
To further illustrate the present invention, the method for mild dehalogenation of halogenated aromatic hydrocarbons using alcohol as hydrogen source using a catalyst loaded with copper or copper oxide nanoparticles is described in detail below with reference to the following examples.
Example 1
CuO/ZrO2The method for dehalogenating and hydrogenating the bromotoluene by adding KOH into a catalyst (wherein Cu accounts for 5 percent of the mass of the catalyst) and taking 1-octanol as a hydrogen source comprises the following steps:
weighing 100mgZrO2Supported nano CuO catalyst (CuO/ZrO)2) 5ml of 1-octanol and 1mmol of p-bromotoluene were sequentially added thereto in a pressure resistant tube. Under stirring, 1.1mmol KOH in the solution is reacted at 140 ℃ for 10h, after the reaction is finished, a certain amount of reaction solution is sucked up by a syringe and centrifuged at 6000 rpm for 5min, and the obtained supernatants are subjected to the following tests.
The obtained supernatant was directly subjected to high performance liquid chromatography-diode array detector to measure the benzene concentration (detection conditions: detection wavelength 270nm, mobile phase of 80 v/v% methanol and 20 v/v% water solution, flow rate 1mL/min, column chromatography SB-C18). The detection result can calculate that the content of the toluene is 0.192mol/L, namely the invention realizes the debromination process of the p-bromotoluene, and the debromination rate of the bromine reaches 96 percent.
Example 2
100mg of ZSM-5 supported nano Cu catalyst (Cu/ZSM-5, wherein the mass fraction of Cu in the catalyst is 5%) is weighed in a pressure resistant tube, and 5ml of 1-octanol and 1mmol of bromobenzene are sequentially added into the pressure resistant tube. Under stirring, 1.1mmol KOH in the solution is reacted at 120 ℃ for 15h, after the reaction is finished, a certain amount of reaction solution is sucked up by a syringe and centrifuged at 6000 rpm for 5min, and the obtained supernatants are respectively subjected to the following tests.
The obtained supernatant was directly subjected to high performance liquid chromatography-diode array detector to measure the benzene concentration (detection conditions: detection wavelength 270nm, mobile phase of 80 v/v% methanol and 20 v/v% water solution, flow rate 1mL/min, column chromatography SB-C18). According to the detection result, the content of benzene is calculated to be 0.199mol/L, namely the invention realizes the debromination process of bromobenzene, and the debromination rate of bromine reaches up to 99.5%.
Example 3
Weighing 100mgAl2O3The supported nano CuO catalyst (CuO/hydrotalcite Cu accounts for 10 percent of the mass fraction of the catalyst) is put into a pressure-resistant pipe, and 5ml of 1-octanol and 1mmol of p-chlorotoluene are sequentially added into the pressure-resistant pipe. Under stirring, 1.1mmol of the above solutiontBuOK, reacting at 150 ℃ for 12h, sucking a certain reaction liquid by using a syringe after the reaction is finished, centrifuging for 5min at 6000 revolutions, and respectively carrying out the following tests on obtained supernate.
The obtained supernatant was directly subjected to high performance liquid chromatography-diode array detector to measure the benzene concentration (detection conditions: detection wavelength 270nm, mobile phase of 80 v/v% methanol and 20 v/v% water solution, flow rate 1mL/min, column chromatography SB-C18). According to the detection result, the content of the benzene can be calculated to be 0.199mol/L, namely, the dechlorination process of the p-chlorobenzene is realized, and the chlorine removal rate is up to 99.2%.
Example 4
Weighing 100 mgMgO-loaded nano Cu2O catalyst (CuO)MgO, Cu accounts for 3 percent of the mass of the catalyst) is put into a pressure-resistant tube, and 5ml of 1-pentanol and 1mmol of p-bromotoluene are added into the pressure-resistant tube in sequence. Under stirring, 1.1mmol of the above solutiontBuOK, reaction for 15h, after the reaction is finished, a certain amount of reaction liquid is sucked by a syringe and centrifuged for 5min at 6000 revolutions, and the obtained supernatant is subjected to the following tests respectively.
The obtained supernatant was directly subjected to high performance liquid chromatography-diode array detector to measure the benzene concentration (detection conditions: detection wavelength 270nm, mobile phase of 80 v/v% methanol and 20 v/v% water solution, flow rate 1mL/min, column chromatography SB-C18). The detection result can calculate that the invention realizes the debromination process of the p-bromotoluene, and the debromination rate is as high as 85.2 percent.
Example 5
CuO/ZrO2The method for dehalogenating and hydrogenating the bromotoluene by taking 1-octanol as a hydrogen source and adding NaOH as a catalyst (wherein Cu accounts for 2 percent of the mass of the catalyst), comprises the following steps of:
weighing 100mgZrO2Supported nano CuO catalyst (CuO/ZrO)2) 5ml of 1-octanol and 1mmol of p-2, 4-dibromobenzene were added sequentially to the mixture in a pressure resistant tube. Under stirring, 1.1mmol of K in the solution2CO3After the reaction was completed, a certain amount of the reaction solution was aspirated by a syringe and centrifuged at 6000 rpm for 5min, and the obtained supernatants were subjected to the following tests, respectively.
The obtained supernatant was directly subjected to high performance liquid chromatography-diode array detector to measure the benzene concentration (detection conditions: detection wavelength 270nm, mobile phase of 80 v/v% methanol and 20 v/v% water solution, flow rate 1mL/min, column chromatography SB-C18). According to the detection result, the content of the benzene is calculated to be 0.192mol/L, namely the invention realizes the debromination process of the 2,4 dibromobenzene, and the debromination rate of the bromine is up to 92.4 percent.
Example 6
Weighing nano Cu loaded with 100mg of hydrotalcite2O catalyst (Cu)2O/hydrotalcite, Cu accounting for 10 percent of the mass of the catalyst) is put into a pressure-resistant pipe, and 5ml of 1-pentanol and 1mmol of p-chloromethane are sequentially added into the pressure-resistant pipeBenzene. Under stirring, 1.1mmol NaOH in the solution was reacted at 150 ℃ for 12 hours, after the reaction was completed, a certain amount of the reaction solution was sucked up by a syringe and centrifuged at 6000 rpm for 5 minutes, and the obtained supernatants were subjected to the following tests, respectively.
The obtained supernatant was directly subjected to high performance liquid chromatography-diode array detector to measure the benzene concentration (detection conditions: detection wavelength 270nm, mobile phase of 80 v/v% methanol and 20 v/v% water solution, flow rate 1mL/min, column chromatography SB-C18). According to the detection result, the content of the toluene is calculated to be 0.193mol/L, namely, the invention realizes the dechlorination process of the p-chlorotoluene, and the chlorine removal rate is up to 96.2 percent.
Example 7
100mg of activated carbon-supported nano CuO catalyst (CuO/activated carbon, Cu accounting for 1% of the mass of the catalyst) is weighed into a pressure-resistant pipe, and 5ml of glycerol and 2mmol of p-iodotoluene are sequentially added into the pressure-resistant pipe. Under stirring, 1.1mmol of C in the solution2H5ONa, reacting at 120 ℃ for 15h, sucking a certain reaction solution by using an injector after the reaction is finished, centrifuging for 5min at 6000 revolutions, and respectively carrying out the following tests on obtained supernate.
The obtained supernatant was directly subjected to high performance liquid chromatography-diode array detector to measure the benzene concentration (detection conditions: detection wavelength 270nm, mobile phase of 80 v/v% methanol and 20 v/v% water solution, flow rate 1mL/min, column chromatography SB-C18). The content of the methylbenzene is calculated to be 0.382mol/L through a detection result, namely the method realizes the deiodination process of p-iodomethylbenzene, and the iodine removal rate is up to 95.5%.
Example 8
Weighing 100mgZrO2Supported nano CuO catalyst (CuO/ZrO)2And the mass fraction of Cu accounting for the catalyst is 5%) is put into a pressure-resistant pipe, and 5ml of ethylene glycol and 4mmol of p-bromoanisole are sequentially added into the pressure-resistant pipe. Under stirring, 1.1mmol of K in the solution3PO4After the reaction was completed, a certain amount of the reaction solution was aspirated by a syringe and centrifuged at 6000 rpm for 5min, and the obtained supernatants were subjected to the following tests, respectively.
The obtained supernatant was directly subjected to high performance liquid chromatography-diode array detector to measure the benzene concentration (detection conditions: detection wavelength 270nm, mobile phase of 80 v/v% methanol and 20 v/v% water solution, flow rate 1mL/min, column chromatography SB-C18). According to the detection result, the content of anisole is calculated to be 0.68mol/L, namely the invention realizes the debromination process of p-bromoanisole, and the debromination rate of bromine reaches 85.2 percent.
Comparative example 1
When the alkali KOH was not added in example 1, the remaining steps were the same as in example 1.
After the reaction is finished, benzene is not detected through detection, namely, the debromination process is finished and cannot be carried out.
Comparative example 2
When no alcohol was added as a donor and hydrazine was selected as a hydrogen donor in example 1, the rest of the procedure was the same as in example 1. After the reaction is finished, the detection shows that the yield of the product benzene is only 25%, and the effect is poorer than that of the invention.
Comparative example 3
When a tertiary alcohol (e.g., t-butanol) is selected instead of 1-octanol as a donor without adding a primary or secondary alcohol as a donor in example 1, the remaining steps are the same as in example 1.
After the reaction is finished, benzene is not detected through detection, namely, the debromination process is finished and cannot be carried out.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. A method for dehalogenating halogen in aromatic compounds using a catalyst loaded with copper or copper oxide nanoparticles, the method comprising the steps of:
(1) placing halogenated aromatic hydrocarbon compounds, alcohols, alkali and catalysts loaded with copper or copper oxide nano particles into a reaction device, and filling inert gas into the reaction device to remove air in the reaction device;
(2) heating to 120 ℃ and 300 ℃, stirring and reacting for 10-15 h;
(3) after the reaction is finished, the catalyst is removed by solid-liquid separation, and the aromatic hydrocarbon compound after halogen removal is obtained by distillation and crystallization.
2. The process according to claim 1, characterized in that the haloaromatic compound is a halophenyl compound comprising one or more halogen atoms.
3. The method according to claim 1 or 2, characterized in that the alcohol is a primary or secondary alcohol capable of acting as a solvent.
4. The method of claim 3, wherein the alcohol comprises one or more of isopropanol, ethylene glycol, glycerol, 1-pentanol, 2-pentanol, 1-octanol, and cyclohexanol.
5. A process according to any one of claims 1 to 3, wherein the base comprises any one or more of an organic base, an inorganic base or a basic salt.
6. The process according to any one of claims 1 to 5, wherein the molar ratio of the halogenated aromatic hydrocarbon to the base is (1 to 5): 1.
7. The method according to any one of claims 1 to 6, wherein the carrier of the catalyst loaded with the copper or copper oxide nanoparticles is an alkali-resistant material, preferably comprises any one or more of activated carbon, hydrotalcite, ZSM-5, molecular sieve, titanium dioxide, zirconium dioxide, aluminum oxide and magnesium oxide.
8. The method of any one of claims 1 to 7, wherein the copper or copper oxide nanoparticle-supported catalyst comprises CuO/TiO2,Cu2O/TiO2,Cu/TiO2,Cu2O/Al2O3,Cu2O/Al2O3，Cu2O/Al2O3，CuO/MgO,Cu2O/MgO，Cu/MgO，CuO/ZrO2,Cu2O/ZrO2,Cu/ZrO2CuO/hydrotalcite, Cu2O/hydrotalcite, Cu/hydrotalcite, CuO/activated carbon, Cu2O/activated carbon, Cu/activated carbon, CuO/ZSM-5, Cu2One or more of O/ZSM-5 and Cu/ZSM-5.
9. The method according to any one of claims 1 to 8, wherein the amount of the catalyst loaded with the copper or copper oxide nanoparticles is 0.1 to 100 percent of the molar amount of the halogenated aromatic hydrocarbon.
10. Use of the method of any one of claims 1 to 9 in chemical or environmental fields.
CN202011403596.1A 2020-12-02 2020-12-02 Method for removing halogen in halogenated aromatic compound by using catalyst loaded with copper or copper oxide nanoparticles Pending CN112547064A (en)

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