CN109721463B - Process for preparing halogenated aromatic compounds - Google Patents
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- CN109721463B CN109721463B CN201711023809.6A CN201711023809A CN109721463B CN 109721463 B CN109721463 B CN 109721463B CN 201711023809 A CN201711023809 A CN 201711023809A CN 109721463 B CN109721463 B CN 109721463B
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Abstract
The present disclosure relates to a process for preparing halogenated aromatic compounds, characterized in that it comprises: the method comprises the following steps of contacting a liquid material containing an aromatic compound, an oxidant and halogen acid with a catalyst for reaction, wherein the catalyst is a titanium silicalite catalyst and/or a zirconium silicalite catalyst. The method has the advantages of simple operation process, mild reaction conditions and high raw material conversion rate.
Description
Technical Field
The present disclosure relates to a process for preparing halogenated aromatic compounds.
Background
Halogenated organic compounds are important compounds as starting materials or intermediates of organic synthesis, and are widely applied to the fields of material synthesis, preparation of industrial chemicals, preparation of bioactive compounds and the like.
Chlorine is used as a chlorinating agent, and is a main method for industrially producing chlorinated compounds. In the preparation of chlorinated aromatic compounds, catalysts such as Lewis acid catalysts, iron trichloride, tin tetrachloride, aluminum trichloride, etc., are usually added because of the low activity of the aromatic compounds. In order to solve the problem that the catalyst is difficult to separate in the homogeneous chlorination reaction, a silicon-aluminum molecular sieve is introduced as the catalyst, such as a Y-type molecular sieve, an X-type molecular sieve, an L-type molecular sieve (patent US 4794201), mordenite and the like, and has good catalytic activity. However, after the reaction is completed, chlorine gas is used as a chlorinating agent, hydrogen chloride is produced as a byproduct, and the structure of the silicon-aluminum molecular sieve is seriously damaged under a high-concentration hydrogen chloride system, so that the reutilization of the silicon-aluminum molecular sieve is influenced. In addition, chlorine gas is a toxic gas and requires special equipment for its transportation, storage and use. When chlorine is used as a chlorinating agent, hydrogen chloride is generated by reaction, the utilization rate of chlorine atoms is only 50%, and hydrochloric acid obtained by the generated byproduct hydrogen chloride through water absorption is difficult to treat due to organic impurities, so that the further utilization of the hydrochloric acid is influenced.
The hydrogen chloride or hydrogen bromide and hydrogen peroxide system can be used for in-situ chlorination of aromatic hydrocarbon, toxic halogen simple substances are not needed, strong acid byproducts are not generated, and the atom economy of halogen atoms is obviously improved, so that the oxychlorination reaction utilizing the system is a halogenated compound preparation route with great potential and environmental friendliness.
The literature (Angew. chem. int. Ed.2009,48,8424-8450) uses a hydrogen chloride and hydrogen peroxide system to chlorinate an active aromatic ring, and uses anisole to prepare 2, 4-dichloroanisole, uses p-nitroaniline to chlorinate 2, 6-dichloro-p-nitroaniline, and uses naphthalene to chlorinate monochloronaphthalene to obtain better results. Less active alkylaromatics require an excess of hydrogen chloride to increase the conversion of alkylaromatics over such more active aromatic substrates (Tetrahedron,1999,55, 11127-. In these prior arts, since no catalyst is used, a large amount of hydrogen peroxide is required to achieve a good reaction effect, and thus the catalytic reaction effect is limited and still needs to be further improved; or a homogeneous catalyst containing active sites such as molybdenum and vanadium is used, but this brings about a problem that the catalyst is difficult to recover.
The literature (J.Am.chem.Soc.2003,125,12116-12117) reports that the use of a polyfluoro alcohol as a solvent to catalyze hydrogen peroxide and promote a cyclochlorination reaction can significantly increase the reaction rate, for example, when trifluoroethanol is used as a solvent to catalyze toluene chlorination, the yield of monochlorobenzene reaches 99%. However, the use of a polyfluoro alcohol as a solvent is expensive and not suitable for large-scale industrial production.
The document (J.Am.chem.Soc.1997,119,6921-6922) obtains better effect and solves the problem of catalyst separation by grafting titanium on mesoporous MCM-48 or MCM-41 molecular sieve and brominating reactants by hydrogen peroxide and bromide ions under neutral condition, but the material is not suitable for long-term use under strong acid condition.
Disclosure of Invention
The purpose of the present disclosure is to provide a method for preparing halogenated aromatic compounds, which has simple operation process, mild reaction conditions and high conversion rate of raw materials.
In order to achieve the above objects, the present disclosure provides a method of preparing a halogenated aromatic compound, the method comprising: the method comprises the following steps of contacting a liquid material containing an aromatic compound, an oxidant and halogen acid with a catalyst for reaction, wherein the catalyst is a titanium silicalite catalyst and/or a zirconium silicalite catalyst.
Optionally, the titanium silicalite molecular sieve is at least one selected from the group consisting of an MFI-type titanium silicalite molecular sieve, an MEL-type titanium silicalite molecular sieve, a BEA-type titanium silicalite molecular sieve and an MWW-type titanium silicalite molecular sieve;
the zirconium silicate molecular sieve is at least one selected from MFI type zirconium silicate molecular sieve, MEL type zirconium silicate molecular sieve, BEA type zirconium silicate molecular sieve and MWW type zirconium silicate molecular sieve.
Optionally, the aromatic compound is at least one selected from the group consisting of substituted or unsubstituted monocyclic aromatic hydrocarbon, substituted or unsubstituted condensed-ring aromatic hydrocarbon, and substituted or unsubstituted heterocyclic compound, and in the substituted monocyclic aromatic hydrocarbon, substituted condensed-ring aromatic hydrocarbon, and substituted heterocyclic compound, the substituent is at least one selected from the group consisting of alkyl group, hydroxyl group, ketone group, carboxyl group, ether group, ester group, phenyl group, sulfonic group, nitro group, amine group, and halogen.
Optionally, the aromatic compound is at least one selected from the group consisting of benzene, toluene, ethylbenzene, cumene, xylene, trimethylbenzene, phenol, chlorobenzene, bromobenzene, iodobenzene, nitrobenzene, benzoic acid, benzenesulfonic acid, anisole, benzyl chloride, acetophenone, biphenyl, naphthalene, anthracene, furan, pyrrole, thiophene, pyridine, 2-methylpyridine, 3-pyridinesulfonic acid, 1,3, 5-trimethylpyridine, 2-hydroxypyridine, pyridine N-oxide, indole, quinoline, isoquinoline, and imidazole.
Optionally, the oxidizing agent is at least one selected from the group consisting of inorganic peroxides, organic peroxides and ozone, the inorganic peroxides are at least one selected from the group consisting of hydrogen peroxide, potassium monopersulfate, potassium persulfate, sodium percarbonate, percarbamide and sodium perborate, and the organic peroxides are at least one selected from the group consisting of t-butyl hydroperoxide, cyclohexyl hydroperoxide, cumene peroxide, ethylbenzene hydroperoxide, benzoic acid peroxide, methyl ethyl ketone peroxide, t-butyl peroxypivalate, isopropyl hydroperoxide, t-amyl hydroperoxide and di-t-butyl peroxide.
Optionally, the hydrohalic acid is at least one selected from the group consisting of hydrochloric acid, hydrobromic acid, and hydroiodic acid.
Alternatively, the catalyst is used in an amount of 0.01 to 1.5 parts by weight relative to 1 part by weight of the aromatic compound;
with H+The molar ratio of the hydrohalic acid to the aromatic compound is (0.2-8): 1;
the oxidizing agent and H+The molar ratio of the halogen acid is (0.1-3): 1.
alternatively, the catalyst is used in an amount of 0.2 to 1.2 parts by weight relative to 1 part by weight of the aromatic compound;
with H+The molar ratio of the hydrohalic acid to the aromatic compound is (1-5): 1;
the oxidizing agent and H+The molar ratio of the halogen acid is (1-2.5): 1.
optionally, the liquid material further contains a compound capable of ionizing an acid ion, the acid ion being at least one selected from the group consisting of a sulfate ion, a hydrogen sulfate ion, a phosphate ion, a monohydrogen phosphate ion and a dihydrogen phosphate ion, the molar ratio of the acid ion to the aromatic compound being (0.01 to 0.2) in terms of the ion in a completely ionized state: 1.
optionally, the method further comprises: the reaction is carried out in the presence of a solvent, the molar ratio of the solvent to the aromatic compound being (5-100): 1.
optionally, the solvent is water and/or an organic solvent, and the organic solvent is at least one selected from the group consisting of diethyl ether, C1-C6 alcohols, C3-C8 ketones, C2-C6 nitriles, tetrahydrofuran, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, acetic anhydride, and 1, 4-dioxane.
Optionally, the reaction conditions are: the reaction temperature is 0-80 ℃, and the reaction time is 0.1-48 h.
According to the technical scheme, the method adopts a titanium silicalite molecular sieve catalyst and/or a zirconium silicalite molecular sieve catalyst to catalyze halogen ions to react with an oxidant under an acidic condition to generate active halogen, and performs a halogenation reaction on an aromatic compound to prepare the halogenated aromatic compound. Compared with the prior art, the method provided by the disclosure does not need to use toxic halogen elementary substances such as chlorine and the like in the reaction process, is simple in operation process, mild in reaction condition, high in raw material conversion rate, stable in catalyst performance, easy to separate, low in product subsequent separation energy consumption, safer and more efficient in process, and is suitable for large-scale industrial production and application.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The present disclosure provides a method of preparing a halogenated aromatic compound, the method comprising: the method comprises the following steps of contacting a liquid material containing an aromatic compound, an oxidant and halogen acid with a catalyst for reaction, wherein the catalyst is a titanium silicalite catalyst and/or a zirconium silicalite catalyst.
The method provided by the disclosure can react halogen ions and an oxidant to generate active halogen under the action of a catalyst and under an acidic condition, and performs a halogenation reaction on an aromatic compound to prepare a halogenated aromatic compound. Compared with the prior art, the method has the characteristics of no use of toxic halogen simple substance, simple operation process, mild reaction condition, high raw material conversion rate, good catalyst stability, easy separation, safe and efficient reaction process and the like.
According to the present disclosure, the titanium silicalite molecular sieves and/or the zirconium silicalite molecular sieves are common titanium silicalite molecular sieves and/or zirconium silicalite molecular sieves with various structures. In particular, to ensure stable catalytic performance of the molecular sieve in a strongly acidic environment, the heteroatoms (i.e., titanium or zirconium) in the molecular sieve used in the present disclosure need to be present at least in part as framework heteroatoms, and the molecular sieve precursor needs to have a stable crystal structure. The supported heteroatom molecular sieve, such as titanium-supported all-silicon molecular sieve, or the heteroatom molecular sieve whose parent body is amorphous mesoporous, such as Ti-MCM-22, Ti-SBA-15, Ti-MCM-41, etc., because the bond between the active center atom and the parent body of the molecular sieve is not as stable as the bond between the active center atom and the heteroatom molecular sieve on the framework, it is difficult to bear the use under the harsh conditions.
Therefore, the titanium silicalite molecular sieve is preferably at least one selected from the group consisting of an MFI-type titanium silicalite molecular sieve (e.g., TS-1 molecular sieve), an MEL-type titanium silicalite molecular sieve (e.g., TS-2 molecular sieve), a BEA-type titanium silicalite molecular sieve (e.g., Ti-beta molecular sieve), and an MWW-type titanium silicalite molecular sieve (e.g., Ti-MCM-22 molecular sieve); further preferred are MFI-type titanium silicalite molecular sieves; more preferably, the MFI type titanium silicalite molecular sieve has a hollow structure, the radial length of a cavity part of the hollow structure is 5-300 nanometers, and the titanium silicalite molecular sieve has the P/P ratio at 25 DEG C0The benzene adsorption capacity measured under the condition of 0.10 and the adsorption time of 1 hour is at least 70 mg/g molecular sieve, and a hysteresis loop exists between the adsorption isotherm and the desorption isotherm of the low-temperature nitrogen adsorption.
According to the present disclosure, the catalyst is preferably a zirconium silicalite catalyst. The zirconium silicate molecular sieve may be at least one selected from an MFI-type zirconium silicate molecular sieve (e.g., Zr-MFI molecular sieve), an MEL-type zirconium silicate molecular sieve (e.g., Zr-MEL molecular sieve), a BEA-type zirconium silicate molecular sieve (e.g., Zr-beta molecular sieve), and an MWW-type zirconium silicate molecular sieve (e.g., Zr-MCM-22 molecular sieve), and is more preferably an MFI-type zirconium silicate molecular sieve.
The method of the present disclosure is applicable to any aromatic compound conforming to the houcker 4n +2 rule, for example, the aromatic compound may be at least one selected from the group consisting of substituted or unsubstituted monocyclic aromatic hydrocarbons, substituted or unsubstituted condensed-ring aromatic hydrocarbons, and substituted or unsubstituted heterocyclic compounds in which the substituent may be at least one selected from the group consisting of alkyl groups, hydroxyl groups, ketone groups, carboxyl groups, ether groups, ester groups, phenyl groups, sulfonic acid groups, nitro groups, amine groups, and halogens. Specifically, the aromatic compound may include, but is not limited to, benzene, toluene, ethylbenzene, cumene, xylene, trimethylbenzene, phenol, chlorobenzene, bromobenzene, iodobenzene, nitrobenzene, benzoic acid, benzenesulfonic acid, anisole, benzyl chloride, acetophenone, biphenyl, naphthalene, anthracene, furan, pyrrole, thiophene, pyridine, 2-methylpyridine, 3-pyridinesulfonic acid, 1,3, 5-trimethylpyridine, 2-hydroxypyridine, pyridine N-oxide, indole, quinoline, isoquinoline, imidazole, and the like.
According to the present disclosure, the oxidizing agent may be at least one selected from the group consisting of inorganic peroxides, organic peroxides, and ozone. The inorganic peroxide may be at least one selected from the group consisting of hydrogen peroxide, potassium hydrogen peroxymonosulfate, potassium persulfate, sodium percarbonate, percarbamide, and sodium perborate; the organic peroxide may be at least one selected from the group consisting of t-butyl hydroperoxide, cyclohexyl hydroperoxide, cumene peroxide, ethylbenzene hydroperoxide, benzoic acid peroxide, methyl ethyl ketone peroxide, t-butyl peroxypivalate, isopropyl hydroperoxide, t-amyl hydroperoxide and di-t-butyl peroxide. The oxidizing agent is most preferably hydrogen peroxide.
According to the present disclosure, the hydrohalic acid may be at least one selected from the group consisting of hydrochloric acid, hydrobromic acid, and hydroiodic acid. The halogen acid may be an aqueous solution containing a halogen acid, and when the halogen acid is an aqueous solution containing an acid, the present disclosure does not particularly limit the amount of water used in the reaction system.
According to the present disclosure, the catalyst may be used in an amount of 0.01 to 1.5 parts by weight, preferably 0.2 to 1.2 parts by weight, relative to 1 part by weight of the aromatic compound, in order to achieve a desired reaction effect. With H+The molar ratio of the hydrohalic acid to the aromatic compound may be (0.2-8): 1, preferably (1-5): 1. the oxidizing agent and H+The molar ratio of the hydrohalic acid may be (0.1-3): 1, preferably (1-2.5): 1.
according to the present disclosure, in order to further increase the conversion rate of the raw material, the liquid material may further contain a compound capable of ionizing an acid radical ion, wherein the acid radical ion may be selected from sulfate radical ion (SO)4 2-) Hydrogen sulfate ion (HSO)4 -) Phosphate radical ion (PO)4 3-) Monohydrogen phosphate ion (HPO)4 2-) And dihydrogen phosphate ion (H)2PO4 -) At least one of (1). The acid radical being present in the fully ionized state of the ionThe molar ratio of the seed to the aromatic compound may be (0.01-0.2): 1, preferably (0.05-0.15): 1.
according to the present disclosure, the liquid material may include a salt or an acid containing the above-mentioned ions. Furthermore, the liquid material is introduced with an appropriate amount of metal cations of the first main group and/or the second main group, or ammonium ions do not cause significant adverse effects on the reaction, and therefore, the cation in the salt capable of ionizing the above-mentioned acid ions is preferably at least one cation selected from the group consisting of the first main group cation, the second main group metal cation, and the ammonium ion.
According to the present disclosure, in order to achieve good mass transfer of each reaction raw material in the reactant containing the catalyst, the reaction may be performed in the presence of a solvent, and the molar ratio of the solvent to the aromatic compound may be (5-100): 1, preferably (15-70): 1. the solvent may be water and/or an organic solvent, and the organic solvent may be at least one selected from the group consisting of diethyl ether, C1-C10 alcohol, C3-C8 ketone, C2-C6 nitrile, tetrahydrofuran, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, acetic anhydride and 1, 4-dioxane.
According to the present disclosure, the conditions of the reaction may be: the reaction temperature is 0-80 deg.C, preferably 20-50 deg.C, and the reaction time is 0.1-48 h.
The reaction described in the present disclosure may be carried out in a conventional catalytic reactor, and the present disclosure is not particularly limited, for example, the reaction of the present disclosure may be carried out in a batch tank reactor or a three-necked flask, or in a suitable other reactor such as a fixed bed, a moving bed, a suspended bed, and the like.
It will be understood by those skilled in the art that, depending on the reactor used, the titanium silicalite and/or zirconium silicalite catalyst of the present disclosure may be a molecular sieve raw powder, or a molded catalyst formed by mixing a molecular sieve and a carrier. The separation of the product from the catalyst can be achieved in various ways, for example, when the original powdery molecular sieve is used as the catalyst, the separation of the product and the recovery and reuse of the catalyst can be achieved by settling, filtering, centrifuging, evaporating, membrane separation, or the like, or the catalyst can be molded and then loaded into a fixed bed reactor, and the catalyst can be recovered after the reaction is completed.
The present disclosure is further illustrated by the following examples, but is not limited thereto.
The preparation method of the TS-1 molecular sieve adopted in the embodiment comprises the following steps: an amount of about 3/4 tetrapropylammonium hydroxide (TPAOH, 20%, available from Aldrich, USA) solution was added to the Tetraethylorthosilicate (TEOS) solution to obtain a liquid mixture with a pH of about 13, and then the desired amount of n-butyl titanate [ Ti (OBu) ] was added dropwise to the resulting liquid mixture under vigorous stirring4]Stirring the anhydrous isopropanol solution for 15 minutes to obtain a clear liquid, and finally slowly adding the rest TPAOH into the clear liquid, and stirring the mixture for about 3 hours at 348-2：SiO2：0.36TPA：35H2And O sol, then crystallizing for 3 days at the temperature of 443K, filtering the obtained solid, washing with distilled water, drying for 5 hours at the temperature of 373K, and then roasting for 10 hours at the condition of 823K to obtain a molecular sieve sample. Wherein TEOS is 42g, TPAOH is 73g, Ti (OBu)4The amount of (A) was 2g, the amount of anhydrous isopropyl alcohol was 10g, and the amount of water was 68 g.
The hollow titanium silicalite molecular sieve HTS is prepared according to the method described in the specification example 1 of Chinese patent CN1301599A, the HTS molecular sieve has a hollow structure with the radial length of 5-100 nanometers, and the benzene adsorption capacity measured by adopting a static adsorption method under the conditions of 25 ℃, P/P0 of 0.10 and the adsorption time of 1 hour is 85 mg/g molecular sieve; there is a hysteresis loop between the adsorption and desorption isotherms for low temperature nitrogen adsorption as determined by the standard method of ASTM D4222-98.
The preparation method of the TS-2 molecular sieve used in the examples comprises the following steps: a certain amount of tetrabutylammonium hydroxide solution (TBAOH, 20%) was mixed with tetraethyl orthosilicate (TEOS), and then to the resulting clear liquid mixture was added dropwise the desired amount of n-butyl titanate [ Ti (OBu) ]with vigorous stirring4]In anhydrous isopropanol solutionStirring for 30 minutes to obtain a clear liquid after hydrolysis. Finally, 2 times the required amount of distilled water was added and the resulting sol was stirred at 348-. The resulting sol had a chemical composition of 0.20TBAOH SiO2:0.03TiO2:20H2And O. And (3) placing the sol at 443K for crystallization for 3 days, filtering and washing the obtained crystallized product, drying for 6h under 373K, and roasting for 16h under 823K to obtain a molecular sieve sample. Wherein TEOS is 42g, TBAOH is 52g, Ti (OBu)4The amount of (A) was 2g, the amount of anhydrous isopropyl alcohol was 10g, and the amount of water was 30 g.
The preparation method of the Ti-beta molecular sieve used in the examples comprises the following steps: a certain amount of tetraethyl orthosilicate (TEOS) was added to a solution of metered tetraethylammonium hydroxide solution (TEAOH, 20%) and hydrogen peroxide and hydrolyzed under stirring for 2 h. Then weighed n-butyl titanate [ Ti (OBu) ]4]Adding the anhydrous isopropanol solution into hydrolysate of ethyl orthosilicate, continuously stirring for 3h to remove alcohol, and finally obtaining the chemical composition of TiO2:60SiO2:33TEAOH:400H2O:20H2O2The sol of (4). Finally, adding dealuminized P-type molecular sieve seed crystals and stirring vigorously (the seed crystal adding amount is that the sol is calculated by silica, and 4g of seed crystals are added into 100g of silica). After the mixture is crystallized under 413K for 14 days, the obtained slurry is filtered, washed by water, dried under 373K for 6h, and then calcined under 823K for 12h to obtain a molecular sieve sample. Wherein TEOS is used in an amount of 42g, TEAOH is used in an amount of 81g, Ti (OBu)4The dosage of the compound is 1.16g, the dosage of the anhydrous isopropanol is 10g, and the dosage of the hydrogen peroxide is 7.5 g.
The preparation method of the Zr-MFI molecular sieve adopted in the embodiment comprises the following steps: an amount of about 3/4 tetrapropylammonium hydroxide (TPAOH, 20%, available from Aldrich, USA) solution was added to Tetraethylorthosilicate (TEOS) solution to obtain a liquid mixture with a pH of about 13, then a desired amount of zirconium n-propanol solution (70%) was added dropwise to the obtained liquid mixture under vigorous stirring to obtain a clear liquid after stirring for 30 minutes, and finally, the remaining TPAOH was slowly added to the clear liquid and stirred at 348 and 353KAbout 3 hours, a chemical composition of 0.01ZrO was obtained2：SiO2：0.3TPA：30H2And O sol, then crystallizing for 3 days at the temperature of 443K, filtering the obtained solid, washing with distilled water, drying for 5 hours at the temperature of 373K, and then roasting for 10 hours at the condition of 823K to obtain a molecular sieve sample. Wherein, the dosage of TEOS is 42g, the dosage of TPAOH is 61g, the dosage of the zirconium n-propoxide solution is 1g, and the dosage of water is 60 g.
The preparation method of the Ti-SBA-15 molecular sieve adopted in the embodiment comprises the following steps: tetraethyl orthosilicate (TEOS) is used as a silicon source, tetra-n-butyl titanate (TBOT) is used as a titanium source, P123 is used as a surfactant, 2g P123 is dissolved in a solution of HCl (60g, 2mol/L) and 15g of water at a constant temperature of 40 ℃, then 2.08g of tetraethyl orthosilicate is added, and simultaneously reaction liquid of tetra-n-butyl titanate and acetylacetone (the mol ratio of the tetra-n-butyl titanate to the acetylacetone is 1: 0.6) is added according to a certain proportion. After reacting for 30min, precipitate appears, stirring is continued for 24h, and then the mixed solution is transferred to a polytetrafluoroethylene bottle and aged for 24h at 100 ℃. And after the aging is finished, taking out the product, filtering, drying at 120 ℃ for 6h, and finally roasting the dried product at 550 ℃ for 6h to obtain the Ti-SBA-15.
The starting materials used in the examples were, unless otherwise specified, analytical reagents.
The composition of the reaction product is analyzed by gas chromatography, and the analysis result is quantified by an external standard method. Wherein, the chromatographic analysis conditions are as follows: agilent-6890 type chromatograph, HP-5 capillary chromatographic column, sample amount of 0.5 μ L, and sample inlet temperature of 280 deg.C. The column temperature was maintained at 100 ℃ for 3min, then ramped up to 260 ℃ at a rate of 10 ℃/min and maintained for 20 min. FID detector, detector temperature 300 ℃.
The XRF was used to measure the titanium content of the active sites in the molecular sieves using a model 3013X-ray fluorescence spectrometer manufactured by Nippon Denshi electric motors.
In each of the examples and comparative examples:
(ii) aromatic compound conversion (%) - (number of moles of aromatic compound in the raw material-number of moles of aromatic compound in the product)/number of moles of aromatic compound in the raw material X100%
Example 1
Toluene, 30 wt% aqueous hydrogen peroxide, 37 wt% aqueous hydrochloric acid, and a required amount of water were put into a reaction vessel to obtain a mixture containing toluene and H2O2A liquid feed of HCl and water, wherein H2O2HCl, water and toluene in a molar ratio of 3: 6: 10: 1. putting the TS-1 molecular sieve as a catalyst into a reaction kettle, wherein the weight ratio of the TS-1 molecular sieve to toluene is 0.1: 1. the reaction mixture in the autoclave was then allowed to react at a temperature of 20 ℃ for 6 hours, and after completion of the reaction, samples were taken for analysis, the analysis results being shown in Table 1.
Example 2
The reaction was carried out in the same manner as in example 1, except that the TS-1 molecular sieve was separated after the completion of the reaction and then the reaction was repeated 3 times for the same conditions. After the end of sampling analysis, TS-1 molecular sieve is taken to analyze the titanium content, and the analysis results are shown in tables 1 and 2.
Example 3
The reaction was carried out as in example 1, except that Ti-SBA-15 molecular sieve was used as the catalyst and the weight ratio of Ti-SBA-15 molecular sieve to toluene was 0.1: 1. After the reaction, a sample was taken and analyzed, and the analysis results are shown in Table 1.
Example 4
The reaction was carried out in the same manner as in example 3, except that the Ti-SBA-15 molecular sieve was separated and used in the reaction under the same conditions 3 times after the completion of the reaction. After the end of sampling and analyzing, Ti-SBA-15 molecular sieve is taken to analyze the titanium content, and the analysis results are shown in tables 1 and 2.
Example 5
Benzene, 30 wt% aqueous hydrogen peroxide, 37 wt% aqueous hydrochloric acid, and acetone were put into a reaction vessel to obtain benzene and H2O2Liquid contents of HCl and acetone, where H2O2HCl, acetone and benzene in a molar ratio of 2.4: 0.8: 80: 1. putting the TS-1 molecular sieve as a catalyst into a reaction kettle, wherein the weight ratio of the TS-1 molecular sieve to benzene is 1.5: 1. then the reaction mixture in the reaction kettle is reacted for 12 hours at the temperature of 50 ℃, and after the reaction is finished, the mixture is sampled and analyzed and is divided intoThe analysis results are shown in Table 1.
Example 6
Toluene, 30 wt% aqueous hydrogen peroxide, 37 wt% aqueous hydrochloric acid, and a required amount of water were put into a reaction vessel to obtain a mixture containing toluene and H2O2A liquid feed of HCl and water, wherein H2O2HCl, water and toluene in a molar ratio of 1.6: 1: 50: 1. putting the TS-1 molecular sieve as a catalyst into a reaction kettle, wherein the weight ratio of the TS-1 molecular sieve to toluene is 0.8: 1. the reaction mixture in the autoclave was then allowed to react at a temperature of 30 ℃ for 6 hours, and after completion of the reaction, samples were taken for analysis, and the analysis results are shown in Table 1.
Example 7
Toluene, 30 wt% aqueous hydrogen peroxide, 37 wt% aqueous hydrochloric acid, phosphoric acid, and a required amount of water were put into a reaction vessel to obtain a mixture containing toluene and H2O2、HCl、PO4 3-And water, wherein H2O2、HCl、PO4 3-Water and toluene in a 1.6: 1: 0.05: 50: 1. putting the TS-1 molecular sieve as a catalyst into a reaction kettle, wherein the weight ratio of the TS-1 molecular sieve to toluene is 0.8: 1. the reaction mixture in the autoclave was then allowed to react at a temperature of 30 ℃ for 6 hours, and after completion of the reaction, samples were taken for analysis, and the analysis results are shown in Table 1.
Example 8
The reaction is carried out as in example 7, with the difference that a hollow titanium silicalite HTS is used as catalyst. After the reaction, a sample was taken and analyzed, and the analysis results are shown in Table 1.
Example 9
Ethylbenzene, 30 wt% aqueous hydrogen peroxide, 37 wt% aqueous hydrochloric acid, sodium dihydrogen phosphate and a required amount of water were put into a reaction vessel to obtain a mixture containing ethylbenzene and H2O2、HCl、H2PO4 -And water, wherein H2O2、HCl、H2PO4 -Water and ethylbenzene in a molar ratio of 11: 5: 0.18: 20: 1. putting a hollow titanium silicalite molecular sieve HTS as a catalyst into a reaction kettle,HTS to ethylbenzene weight ratio was 0.3: 1. the reaction mixture in the autoclave was then allowed to react at a temperature of 30 ℃ for 12 hours, and after completion of the reaction, samples were taken for analysis, and the analysis results are shown in Table 1.
Example 10
Nitrobenzene, 30 weight percent aqueous hydrogen peroxide, 48 weight percent aqueous hydrobromic acid, sodium dihydrogen phosphate and the required amount of water are put into a reaction kettle to obtain nitrobenzene and H2O2、HCl、H2PO4 -And water, wherein H2O2、HCl、H2PO4 -The molar ratio of water to nitrobenzene was 3.6: 3: 0.05: 60: 1. putting a hollow titanium silicalite molecular sieve HTS as a catalyst into a reaction kettle, wherein the weight ratio of HTS to nitrobenzene is 0.6: 1. the reaction mixture in the autoclave was then allowed to react at a temperature of 50 ℃ for 24 hours, and after completion of the reaction, samples were taken for analysis, and the results of the analysis are shown in Table 1.
Example 11
Putting anthracene, 30 wt% aqueous hydrogen peroxide solution, 37 wt% aqueous hydrochloric acid solution, sodium phosphate and trichloromethane into a reaction kettle to obtain anthracene and H2O2、HCl、PO4 3-Liquid materials of water and trichloromethane, wherein, H2O2、HCl、PO4 3-Water, chloroform and anthracene in a molar ratio of 2.25: 1.5: 0.1: 16: 50: 1. putting a hollow titanium silicalite molecular sieve HTS as a catalyst into a reaction kettle, wherein the weight ratio of HTS to anthracene is 1: 1. the reaction mixture in the autoclave was then allowed to react at a temperature of 20 ℃ for 36 hours, after completion of the reaction, a sample was taken for analysis, and the analysis results are shown in Table 1.
Example 12
The reaction was carried out as in example 7, except that Zr-MFI molecular sieves were used as catalysts. After the reaction, a sample was taken and analyzed, and the analysis results are shown in Table 1.
Example 13
Naphthalene, 30 wt% aqueous hydrogen peroxide, 48 wt% aqueous hydrobromic acid, disodium hydrogen phosphate and a required amount of water were put into a reaction vessel to obtain a mixture containing naphthalene and H2O2、HBr、HPO4 2-And water, wherein H2O2、HBr、HPO4 2-The molar ratio of water to naphthalene was 5.4: 3: 0.09: 50: 1. putting the Zr-MFI molecular sieve as a catalyst into a reaction kettle, wherein the weight ratio of the Zr-MFI molecular sieve to naphthalene is 0.8: 1. the reaction mixture in the autoclave was then allowed to react at a temperature of 25 ℃ for 8 hours, and after completion of the reaction, samples were taken for analysis, the analysis results being shown in Table 1.
Example 14
Putting anthracene, 30 wt% aqueous hydrogen peroxide, 37 wt% aqueous hydrochloric acid, sulfuric acid and acetonitrile into a reaction kettle to obtain anthracene and H2O2、HCl、SO4 2-And acetonitrile, wherein H2O2、HCl、SO4 2-Acetonitrile and anthracene in a molar ratio of 3.25: 1.3: 0.15: 15: 1. putting the Zr-MFI molecular sieve as a catalyst into a reaction kettle, wherein the weight ratio of the Zr-MFI molecular sieve to anthracene is 1: 1. the reaction mixture in the autoclave was then allowed to react at a temperature of 30 ℃ for 24 hours, and after completion of the reaction, samples were taken for analysis, and the analysis results are shown in Table 1.
Example 15
Anisole, 30 wt% aqueous hydrogen peroxide, 37 wt% aqueous hydrochloric acid, disodium hydrogen phosphate and a required amount of water were put into a reaction vessel to obtain anisole and H2O2、HCl、HPO4 2-And water, wherein H2O2、HCl、HPO4 2-The molar ratio of water to anisole was 5.6: 4: 0.08: 40: 1. putting the Zr-MFI molecular sieve as a catalyst into a reaction kettle, wherein the weight ratio of the Zr-MFI molecular sieve to anisole is 1.2: 1. the reaction mixture in the autoclave was then allowed to react at 45 ℃ for 18h, after completion of the reaction, a sample was taken for analysis, and the results of the analysis are shown in Table 1.
Example 16
Pyridine, 80 wt% cumene hydroperoxide solution, 37 wt% hydrochloric acid aqueous solution and acetone are put into a reaction kettle to obtain a liquid material containing pyridine, cumene hydroperoxide, HCl and acetone, wherein the molar ratio of the cumene hydroperoxide, HCl, acetone and pyridine is 1.2: 8: 5: 1. putting the TS-2 molecular sieve as a catalyst into a reaction kettle, wherein the weight ratio of the TS-2 molecular sieve to pyridine is 0.05: 1. the reaction mixture in the autoclave was then allowed to react at a temperature of 5 ℃ for 36 hours, after completion of the reaction, a sample was taken for analysis, and the analysis results are shown in Table 1.
Example 17
Putting naphthalene, a 70 wt% aqueous solution of tert-butyl hydroperoxide, a 37 wt% aqueous solution of hydrochloric acid and tert-butyl alcohol into a reaction kettle to obtain a liquid material containing naphthalene, tert-butyl hydroperoxide, HCl and tert-butyl alcohol, wherein the molar ratio of tert-butyl hydroperoxide to HCl to tert-butyl alcohol to naphthalene is 2.4: 0.8: 90: 1. putting a Ti-beta molecular sieve serving as a catalyst into a reaction kettle, wherein the weight ratio of the Ti-beta molecular sieve to naphthalene is 1.3: 1. the reaction mixture in the autoclave was then allowed to react at a temperature of 70 ℃ for 48 hours, and after completion of the reaction, a sample was taken for analysis, and the analysis results are shown in Table 1.
Comparative example 1
The reaction was carried out as in example 1, except that this comparative example did not use a TS-1 molecular sieve as the catalyst. After the reaction, a sample was taken and analyzed, and the analysis results are shown in Table 1.
Comparative example 2
The reaction was carried out as in example 1, except that this comparative example was carried out with ferric chloride hexahydrate (FeCl)3·6H2O) is used as a catalyst, and the weight ratio of ferric trichloride hexahydrate to toluene is 0.1: 1. after the reaction, a sample was taken and analyzed, and the analysis results are shown in Table 1.
TABLE 1
TABLE 2
| New preservative TiO2Content/% by weight | TiO after repeated use2Content/% by weight | |
| Example 2 | 4.2 | 4.2 |
| Example 4 | 4.5 | 1.3 |
As can be seen from the results in tables 1 and 2, the method provided by the present disclosure has the advantages of simple operation process, mild reaction conditions, high conversion rate of raw materials, and stable catalyst performance. Specifically, as can be seen from the comparison between examples 1 to 17 and comparative examples 1 to 2, the use of a titanium silicalite molecular sieve and/or a zirconium silicalite molecular sieve as a catalyst can greatly improve the conversion rate of the raw material. As can be seen from the comparison between examples 1-2 and examples 3-4, compared with the supported heteroatom molecular sieve or the heteroatom molecular sieve whose parent is amorphous mesoporous, the molecular sieve using the framework heteroatom form with at least a part of the heteroatoms is more stable in catalytic performance, and can still maintain higher active center titanium content when being repeatedly used, and can further improve the conversion rate of raw materials. As can be seen from the comparison of examples 1, 5 and 6, the catalyst is used in an amount of 0.2 to 1.2 parts by weight, relative to 1 part by weight of the aromatic compound, and the molar ratio of the halogen acid to the aromatic compound is (1 to 5): 1, the molar ratio of the oxidant to the halogen acid is (1-2.5): 1, the conversion of the raw material can be further improved. As can be seen from a comparison of example 6 and example 7, when the liquid material contains acid ions, the conversion rate of the raw material can be further improved. Comparison of example 7 and example 12 shows that when zirconium silicalite is used as the catalyst, the conversion of the feedstock can be further improved.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (7)
1. A method of preparing a halogenated aromatic compound, comprising: contacting a liquid material containing an aromatic compound, an oxidant and halogen acid with a catalyst for reaction, wherein the catalyst is a titanium silicalite catalyst and/or a zirconium silicalite catalyst, and obtaining the halogenated aromatic compound;
wherein the titanium silicalite molecular sieve is at least one selected from the group consisting of an MFI type titanium silicalite molecular sieve, an MEL type titanium silicalite molecular sieve and a BEA type titanium silicalite molecular sieve; the zirconium silicate molecular sieve is at least one selected from MFI type zirconium silicate molecular sieve, MEL type zirconium silicate molecular sieve and BEA type zirconium silicate molecular sieve;
the aromatic compound is at least one selected from benzene, toluene, ethylbenzene, cumene, xylene, trimethylbenzene, phenol, chlorobenzene, bromobenzene, iodobenzene, nitrobenzene, benzoic acid, benzenesulfonic acid, anisole, benzyl chloride, acetophenone, biphenyl, naphthalene, anthracene, furan, pyrrole, thiophene, pyridine, 2-methylpyridine, 3-pyridinesulfonic acid, 1,3, 5-trimethylpyridine, 2-hydroxypyridine, pyridine N-oxide, indole, quinoline, isoquinoline and imidazole;
the oxidizing agent is at least one selected from the group consisting of inorganic peroxides, organic peroxides and ozone, the inorganic peroxides are at least one selected from the group consisting of hydrogen peroxide, potassium peroxymonosulfate, potassium persulfate, sodium percarbonate, percarbamide and sodium perborate, and the organic peroxides are at least one selected from the group consisting of tert-butyl hydroperoxide, cyclohexyl hydroperoxide, cumene peroxide, ethylbenzene hydroperoxide, benzoic acid peroxide, methyl ethyl ketone peroxide, tert-butyl peroxypivalate, isopropyl hydroperoxide, tert-amyl hydroperoxide and di-tert-butyl peroxide;
the hydrohalic acid is at least one selected from the group consisting of hydrochloric acid, hydrobromic acid, and hydroiodic acid.
2. The method according to claim 1, wherein the catalyst is used in an amount of 0.01 to 1.5 parts by weight relative to 1 part by weight of the aromatic compound;
with H+The molar ratio of the hydrohalic acid to the aromatic compound is (0.2-8): 1;
the oxidizing agent and H+The molar ratio of the halogen acid is (0.1-3): 1.
3. the method according to claim 2, wherein the catalyst is used in an amount of 0.2 to 1.2 parts by weight relative to 1 part by weight of the aromatic compound;
with H+The molar ratio of the hydrohalic acid to the aromatic compound is (1-5): 1;
the oxidizing agent and H+The molar ratio of the halogen acid is (1-2.5): 1.
4. the method according to claim 1, wherein the liquid material further contains a compound capable of ionizing an acid ion, the acid ion being at least one selected from the group consisting of a sulfate ion, a hydrogen sulfate ion, a phosphate ion, a monohydrogen phosphate ion and a dihydrogen phosphate ion, and the molar ratio of the acid ion to the aromatic compound based on the ion in a completely ionized state being (0.01 to 0.2): 1.
5. the method of claim 1, wherein the method further comprises: the reaction is carried out in the presence of a solvent, the molar ratio of the solvent to the aromatic compound being (5-100): 1.
6. the process according to claim 5, wherein the solvent is water and/or an organic solvent, and the organic solvent is at least one selected from the group consisting of diethyl ether, C1-C6 alcohol, C3-C8 ketone, C2-C6 nitrile, tetrahydrofuran, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, acetic anhydride and 1, 4-dioxane.
7. The process according to claim 1, wherein the reaction conditions are: the reaction temperature is 0-80 ℃, and the reaction time is 0.1-48 h.
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