CN108706607B - Zeolite molecular sieve, preparation method and application thereof - Google Patents
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Abstract
本发明公开了一种沸石分子筛及其制备方法以及应用，属于化学技术领域。本发明利用离子液体干胶法合成不同钒含量(0‑25％)的V‑Si‑ZSM‑22沸石分子筛，其中钒物种主要以链式聚VO3 ‑形式存在并通过钒氧键与沸石骨架相连，应用于芳烃的快速羟基化反应，在底物与双氧水等摩尔比的理想条件下，30s反应时间内得到高的酚类产物收率。本发明所用的催化剂制备简单；反应时间极短，高效节能；酚类产物收率高，较低的副产物生成；以双氧水作为氧化剂，经济和环境成本低；产物和催化剂易分离，后处理简单；催化剂易于重复使用，绿色环保，具有十分重要的应用前景。
The invention discloses a zeolite molecular sieve, a preparation method and application thereof, and belongs to the technical field of chemistry. The present invention utilizes the ionic liquid dry glue method to synthesize V-Si-ZSM-22 zeolite molecular sieves with different vanadium contents (0-25%), wherein the vanadium species mainly exist in the form of chain poly VO 3 and pass through the vanadium-oxygen bond and the zeolite framework. It is applied to the rapid hydroxylation of aromatic hydrocarbons. Under the ideal conditions of equimolar ratio of substrate and hydrogen peroxide, a high yield of phenolic products can be obtained within 30s reaction time. The catalyst used in the invention is simple to prepare; the reaction time is extremely short, high efficiency and energy saving; the yield of phenolic products is high, and the generation of by-products is relatively low; the hydrogen peroxide is used as the oxidant, and the economic and environmental costs are low; the product and the catalyst are easy to separate, and the post-processing is simple ; The catalyst is easy to reuse, green and environmentally friendly, and has a very important application prospect.
Description
Technical Field
The invention relates to the technical field of chemistry, in particular to a zeolite catalyst, a preparation method and application thereof.
Background
Aromatic compounds having hydroxyl groups on the benzene ring (such as phenol and cresol) are important organic intermediates, and they are widely used as precursors of dyes, polymers, plastics, drugs, and pesticides. However, for the preparation of phenolic compounds, the industrial production process has the defects of large energy consumption, environmental pollution and peroxidation, and the yield of the phenolic products generated by the reaction is low. The direct hydroxylation reaction of benzene ring oxidized by hydrogen peroxide is always the focus of attention, however, to design an effective catalytic system in the reaction, the following challenges are mainly faced: (1) inert sp to the benzene ring (especially to benzene)2Activation of the C-H bond is very difficult; (2) over-oxidation of a portion of the phenolic product results in reduced yield and selectivity; (3) in oxidation of aromatic compounds, sp on the side chain3C-H bond to sp on aromatic ring2The C-H bond is more easily oxidized because the former has much lower bond dissociation energy than the latter and is therefore more easily oxidized, making the reaction difficult to produce phenolic products.
When the molar ratio of the hydrogen peroxide to the aromatic hydrocarbon substrate is 1, the yield is low, the selectivity is low, and the reaction generally requires tens of hours of reaction time to complete the reaction.
Disclosure of Invention
The invention discloses a vanadium-based zeolite molecular sieve and a synthesis method thereof, and the vanadium-based zeolite molecular sieve is applied to hydroxylation reaction of aromatic hydrocarbon, and can realize rapid (30s) hydroxylation reaction of the aromatic hydrocarbon.
The invention relates to a catalyst, a preparation method of the catalyst and application of the catalyst, and mainly relates to a catalyst prepared by ionic liquidSynthesizing vanadium-based zeolite catalyst with vanadium content (0-25%) by dry glue method, wherein vanadium species in zeolite are mainly polymerized VO in chain mode3 -The catalyst exists in a form and is connected with a zeolite framework through a vanadium-oxygen bond, and the rapid (30s) hydroxylation reaction of aromatic hydrocarbon is realized under a catalytic reaction system of vanadium-based zeolite, acetonitrile and sulfuric acid. The catalytic performance of the vanadium-based zeolite catalyst is improved, and the vanadium-based zeolite catalyst has the characteristics of high selectivity, high stability and good reusability.
A zeolite molecular sieve, in which the vanadium species is polymerized VO in chain mode3 -Exist and are attached to the zeolite framework by vanadium-oxygen bonds.
The zeolite molecular sieve has a structure of V-Si-ZSM-22.
The zeolite molecular sieve has a structure of 0.05V-Si-ZSM-22, and n represents the molar ratio of V/Si.
Completely hydrolyzing a silicon source and vanadium ions in an acidic aqueous solution, completing condensation in the environment of a template agent and an alkali liquor, preparing dry glue, and crystallizing the dry glue in an oven to synthesize a target material, wherein the silicon source is tetramethyl orthosilicate, tetraethyl orthosilicate, tetrabutyl orthosilicate, tetramethoxysilane, silicic acid, silica sol or silicon oxide, the vanadium ions are ammonium metavanadate, sodium metavanadate, vanadyl sulfate or vanadium acetylacetonate, the acidic aqueous solution is sulfuric acid, nitric acid, hydrochloric acid or perchloric acid, and the template agent is 1-butyl-3-methylimidazole bromide, 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole iodide or 1-butyl-3-methylimidazole tetrafluoroborate.
The hydrolysis process takes place in an aqueous acidic solution mixed with tetraethyl orthosilicate and ammonium metavanadate, with a molar ratio of V/Si of 0 to 0.25. In the actual operation, the molar ratio of tetraethyl orthosilicate to ammonium metavanadate is calculated.
The condensation process comprises the steps of adding template agent 1-butyl-3-methylimidazolium bromide into the mixed solution, stirring uniformly, adding NaOH solution until the pH value of the gel is 11 after the template agent is dissolved, placing the gel at room temperature, stirring, drying, and removing water in the gel to prepare the dry gel.
The crystallization process is to put dry glue on a polytetrafluoroethylene support, put the support into a reaction kettle with a polytetrafluoroethylene lining containing water, put the reaction kettle into a drying oven for crystallization for a period of time, take out a solid product, wash, pump-filter, dry and roast to obtain the target catalyst nV-Si-ZSM-22 zeolite molecular sieve, wherein n represents the molar ratio of V/Si, and finally obtain the V-Si-ZSM-22 zeolite molecular sieve with different vanadium contents, which is expressed as nV-Si-ZSM-22.
The zeolite molecular sieve catalyzes an aromatic hydrocarbon hydroxylation reaction.
The aromatic hydrocarbon hydroxylation reaction is carried out under a catalytic reaction system with the vanadium-based zeolite molecular sieve as a catalyst, acetonitrile as a solvent, sulfuric acid as an additive and hydrogen peroxide as an oxidant.
The aromatic hydrocarbon in the aromatic hydrocarbon hydroxylation reaction comprises benzene, toluene, ethylbenzene, isopropylbenzene, trimethylbenzene, tetramethylbenzene, tert-butyl benzene, o-xylene, p-xylene, m-xylene, chlorobenzene, bromobenzene, iodobenzene, benzaldehyde and naphthalene.
ZSM is a molecular sieve with TON type topology, orthorhombic center crystal type, pore size 4.5 times 5.5 angstroms. Non-cross one-dimensional 10-membered ring channels, adjustable acidity and channel shape selectivity.
Has the advantages that:
the invention introduces vanadium species into the zeolite molecular sieve by an ionic liquid dry glue method, and the vanadium species in the target material is mainly polymerized VO in a chain manner3 -In the form of (a) and attached to the zeolite framework by vanadium-oxygen bonds, in which system the solution of acetonitrile sulphate reduces the vanadium species to the 4-valent state, the 4-valent vanadium species being the main active centre for carrying out the catalytic reaction.
The traditional vanadium-impregnated species have the problems of difficult control of vanadium state, poor vanadium species stability and the like, and the vanadium-based zeolite molecular sieve (V-Si-ZSM-22) synthesized by the ionic liquid dry glue method has good stability and reusability. Vanadium in the V-Si-ZSM-22 subjected to high-temperature roasting presents a valence state of 5, the vanadium is different from the traditional vanadium species with the valence of 5, the vanadium species is reduced by adopting an acetonitrile sulfate solution, and the vanadium species with the valence of 4 has a very good catalytic effect in the rapid hydroxylation reaction of aromatic hydrocarbon.
The yield of aromatic hydrocarbon hydroxylation product phenolic compound is 20-31%, the selectivity is 90-100%, the conversion frequency is ultrahigh, and vanadium species in zeolite are polymerized VO in a chain manner3 -The method is characterized in that the rapid (30s) hydroxylation reaction of aromatic hydrocarbon is realized under a catalytic reaction system of vanadium-based zeolite-acetonitrile-sulfuric acid.
After the reaction is finished, washing is carried out by acetonitrile, and the catalyst is recovered, so that good stability and reusability are maintained.
The catalyst used in the invention is simple to prepare; the reaction time is extremely short, and the efficiency and the energy are high; the yield of the phenol product is high, and the generation of a lower byproduct is realized; hydrogen peroxide is used as an oxidant, so that the economic and environmental cost is low; the product and the catalyst are easy to separate, and the post-treatment is simple; the catalyst is easy to reuse, is green and environment-friendly, and has very important application prospect.
Drawings
FIG. 1 is an XRD pattern of nV-Si-ZSM-22. n is 0, 0.01, 0.03, 0.05, 0.1, 0.15, 0.2, 0.25 is a, b, c, d, e, f, g, h respectively
FIG. 2 is a TEM image of (a) 0.05V-Si-ZSM-22 with SEM (b-d) 0.05V-Si-ZSM-2
FIG. 3(a) (b) (c) EXAFS plots of 5% V-Si-ZSM-22.
Figure 4 is a schematic diagram of the structure of the vanadium species in the zeolite.
FIG. 5 is a schematic representation of 5% V-Si-ZSM-22 catalyzing different aromatic substrates.
FIG. 6 is a graph of 5% V-Si-ZSM-22 catalytic reaction stability and reusability.
Detailed Description
Example 1
Firstly, 4g of concentrated sulfuric acid is weighed to prepare 1L of dilute acid solution (the pH value is about 1-2), then 25.2g of the dilute acid solution and 7.39g of TEOS are weighed, and 0, 0.04g, 0.124g, 0.207g, 0.414g, 0.621g, 0.828g and 1.035g of ammonium metavanadate (NH)4VO3) Mixing, and magnetically stirring at 25 deg.C for 24 hr to promote TEOS and ammonium metavanadate (NH)4VO3) Complete co-hydrolysis. After completion of the hydrolysis, 2.72g of [ Bmim ] was added to the mixed solution]Br, stirring uniformly untilAfter the dissolution, 1.7g of NaOH solution (12.5mol/L) was added dropwise. The proportion of the respectively synthesized gel is 1SiO2∶n NH4VO3∶0.35[Bmim]Br∶0.2Na2O∶40H2O (n is 0, 0.01, 0.03, 0.05, 0.1, 0.15, 0.2, 0.25), aging the gel in a water bath at 25 ℃ for 24 hours, and drying the aged gel in an oven at 100 ℃ for 4-5 hours to prepare a dry gel.
0.5g of dry glue was weighed onto a teflon holder, which was then placed in a teflon lined reactor containing 0.5g of water. And (3) crystallizing the reaction kettle in an oven at 170 ℃ for a period of time, taking out a solid product, washing and filtering the solid product by using ethanol and deionized water, and drying the solid product in the oven at 100 ℃ for 12 hours to obtain the molecular sieve raw powder which is not roasted. And roasting the sample in a muffle furnace at 550 ℃ for 5 hours to remove the template agent, thereby obtaining the roasted V-Si-ZSM-22 zeolite molecular sieve. (wherein n represents the molar ratio b of V/Si, and n is 0, 0.01, 0.03, 0.05, 0.1, 0.15, 0.2, 0.25. finally, the zeolite molecular sieve V-Si-ZSM-22 with different vanadium contents is expressed as nV-Si-ZSM-22.) is shown in FIGS. 1, 2, 3, 4. From the EXAFS spectrum of FIG. 3, the state of the vanadium species in 0.05V-Si-ZSM-22 is similar to that of ammonium metavanadate, and poly VO is in chain form3 -The structure of (1).
Example 2
In order to detect the capability of the V-Si-ZSM-22 of the invention for rapidly hydroxylating the aromatic hydrocarbon, the V-Si-ZSM-22 is applied to the hydroxylation reaction of benzene series aromatic hydrocarbon, and the aromatic hydrocarbon compound is rapidly and highly selectively produced into the phenol product within 30 s. The yields of the product phenolic compounds in the examples were analyzed by gas chromatography as shown in FIGS. 5 and 6.
Hydroxylation reaction of benzene series aromatic compounds is carried out in a 25mL quartz glass tube reactor, and is heated and stirred in a water bath kettle with a magnetic stirring device.
The reaction conditions of the hydroxylation of the toluene and the chlorobenzene are as follows: 5mmol of toluene, chlorobenzene, 0.1g of a catalyst (5% V-Si-ZSM-22), and 12mL of acetonitrile were sequentially added to a reaction tube, followed by dropwise addition of 0.15g of concentrated sulfuric acid. Then preheating and stirring for a period of time under the heating condition of 80 ℃, dropwise adding 5mmol of hydrogen peroxide, reacting for 30s after dropwise adding, and stopping reaction.
The hydroxylation reaction conditions of benzene, ethylbenzene, tertiary butyl benzene, o-xylene and m-xylene are as follows: 5mmol of benzene, ethylbenzene, tert-butyl benzene, o-xylene, m-xylene, 0.1g of catalyst (5% V-Si-ZSM-22), and 14mL of acetonitrile were sequentially added to the reaction tube, followed by dropwise addition of 0.15g of concentrated sulfuric acid. Then preheating and stirring for a period of time under the heating condition of 80 ℃, dropwise adding 5mmol of hydrogen peroxide, reacting for 30s after dropwise adding, and stopping reaction.
The reaction conditions of the hydroxylation of bromobenzene, iodobenzene and p-xylene are as follows: 5mmol of bromobenzene, iodobenzene, p-xylene, 0.1g of catalyst (5% V-Si-ZSM-22) and 14mL of acetonitrile were sequentially added to the reaction tube, followed by dropwise addition of 0.15g of concentrated sulfuric acid. Then preheating and stirring for a period of time under the heating condition of 82 ℃, dropwise adding 5mmol hydrogen peroxide, reacting for 30s after dropwise adding, and stopping the reaction.
The reaction conditions of the hydroxylation of the isopropyl benzene, the trimethyl benzene and the tetramethyl benzene are as follows: 5mmol of cumene, trimethylbenzene, tetramethylbenzene, 0.1g of a catalyst (5% V-Si-ZSM-22) and 16mL of acetonitrile were sequentially added to a reaction tube, followed by dropwise addition of 0.15g of concentrated sulfuric acid. Then preheating and stirring for a period of time under the heating condition of 82 ℃, dropwise adding 5mmol hydrogen peroxide, reacting for 30s after dropwise adding, and stopping the reaction.
The reaction conditions for hydroxylation of naphthalene and anisole are as follows: 5mmol of naphthalene, anisole, 0.1g of catalyst (5% V-Si-ZSM-22), and 12mL of acetonitrile were sequentially added to the reaction tube, followed by dropwise addition of 0.15g of concentrated sulfuric acid. Then preheating and stirring for a period of time under the heating condition of 80 ℃, dropwise adding 2.5mmol hydrogen peroxide, reacting for 30s after dropwise adding, and stopping reaction.
After the reaction was completed, 30mg of 1, 4-dioxane was added to the reaction solution as an internal standard, and after mixing and stirring for 10min, centrifugal separation was performed, and the yield of cresol was 26.2% and the selectivity was 91.8% by gas chromatography.
In the examples, using toluene as an example, acetonitrile, water, methanol, ethanol, dimethylformamide, benzonitrile, acetone, and dimethylsulfoxide as solvents were used, and the effects of the solvents on the hydroxylation of toluene are shown in Table 1 below.
Table 1 effect of different solvents on the hydroxylation of toluene.
The results show that the phenolic product was detected only with acetonitrile as solvent and that the yield, selectivity and TOF values were high. Under the conditions, the yield of cresol is 26.2%, the selectivity is 91.8%, and the TOF value is 1969h-1。
In the catalytic reaction, the introduction of acid can change the catalytic reaction system to a certain extent and influence the valence state of vanadium in the catalyst, taking toluene hydroxylation as an example, we select the influence of different types of acid on the hydroxylation reaction of the aromatic compound. In the examples, sulfuric acid, ascorbic acid, acetic acid, perchloric acid, hydrochloric acid, and trifluoromethanesulfonic acid were used as acid assistants, and the effects of the acid assistants on the hydroxylation of toluene are shown in Table 2 below.
Table 2 effect of different acid promoters on the hydroxylation of toluene.
The results show that the yield, selectivity and TOF values of the phenolic product are highest only in the system with the addition of sulfuric acid, since the vanadium species having a valence of 5 are reduced to vanadium species having a valence of 4, which are the active centers that may be present, in the system with the addition of sulfuric acid as an auxiliary agent.
The content of vanadium, an active species, also affects the effectiveness of the reaction for the rapid hydroxylation of aromatic hydrocarbons, and for the example of the hydroxylation of toluene, we have chosen catalysts with different vanadium contents (0-25%), the effect of the catalysts with different vanadium contents on the hydroxylation of toluene being shown in table 3 below.
Table 3 effect of different vanadium content catalysts on toluene hydroxylation.
The results show that the yield and selectivity of the hydroxylation reaction in the system initially increase with increasing V content and then decrease sharply with increasing V content, with the result that, possibly, as the V content increases to a certain extent, the specific surface area of the catalyst decreases sharply to hinder the acquisition of part of the active sites.
In addition, we also designed several groups of comparative catalysts to influence the toluene hydroxylation reaction, including the presence or absence of acid auxiliary agent, vanadium pentoxide, ammonium metavanadate, V-A1Si-ZSM-22, V2O5The effect of @ Si-ZSM-22, the comparative catalyst, on the toluene hydroxylation reaction is set forth below in Table 4.
Table 4 compares the effect of the catalyst on the hydroxylation of toluene.
The results show that by carrying out parallel experiments with the control catalyst, yields in the range of 8.3-11.9% were obtained and the selectivity was also relatively low (70.8-83.9%).
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