CN113244955A - Graphene-based sulfonic acid catalyst and application thereof in catalyzing alkylation reaction of cresol - Google Patents
Graphene-based sulfonic acid catalyst and application thereof in catalyzing alkylation reaction of cresol Download PDFInfo
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Abstract
The invention discloses a graphene-based sulfonic acid catalyst and application thereof in catalyzing an alkylation reaction of cresol, wherein the graphene-based sulfonic acid catalyst is obtained by grafting a covalent grafting on a benzene ring on graphene and then grafting a sulfonic acid group on the edge of the graphene or the covalently modified benzene ring through a sulfonation reaction. The graphene-based sulfonic acid catalyst can be used for catalyzing alkylation reaction of isobutene and mixed cresol in the separation process of the mixed cresol, and the research on the catalytic performance shows that the novel graphene-based solid acid catalyst has high-efficiency activity on the alkylation reaction of aromatic hydrocarbon and shows the similar catalytic efficiency of concentrated sulfuric acid.
Description
Technical Field
The invention belongs to the field of synthesis and application of catalysts, and particularly relates to a graphene-based sulfonic acid catalyst and application thereof in an alkylation reaction of catalytic cresol.
Background
Protonic acid represented by sulfuric acid and Lewis acid represented by aluminum trichloride are the most common traditional acidic catalysts in organic chemical production, and are widely applied. Although the traditional acid catalyst has the advantages of high catalytic activity and efficiency, low price and the like, the traditional acid catalyst has the inherent defects of large dosage, strong corrosivity, high equipment investment cost, certain influence on product quality and the like. More importantly, the traditional acid catalyst is often difficult to separate from other raw materials and products in a reaction system in the production process, a large amount of by-products and acidic wastewater are generated, the post-treatment process is complex, and the environmental pollution is serious. In recent decades, the use of solid acids to replace traditional protic acids and lewis acids has received widespread attention and application. The solid acid catalyzed organic reaction is usually a heterogeneous catalytic system, and after the catalytic reaction is completed, the catalyst can be easily separated and recovered. Therefore, the problems of large wastewater amount, corrosion to equipment and the like caused by the traditional acid catalyst can be effectively solved by selecting the solid acid catalyst to participate in the reaction. For inorganic solid acid catalysts such as metal oxides, metal sulfates, zeolite molecular sieves, heteropolyacids and the like, the defects of various structural types, various types of acidic active sites, complex control of catalytic performance, poor universal performance of the catalyst and the like exist. Although organic solid acid catalysts such as acidic ion exchange resins have many application examples, the base materials of the catalyst resins are easy to swell in organic compound production systems, so that the activity and stability of the catalyst are influenced, and the application range of the catalyst is limited.
The carbon-based nano material has great success in being used as a catalyst carrier due to various structural types and stable physicochemical properties. The introduction of functional groups containing O and N on the surface of the carbon material can change the acid-base property and the hydrophilicity of the surface of the carrier, and can form bonds with metal ions and nano-particles to obtain various types of supported catalysts, thereby facilitating the regulation and control of catalytic activity and recovery performance. The carbon-based solid acid is a novel solid acid catalyst which is developed rapidly in recent years, and is prepared by grafting-COOH and-SO on the surface of a carbon-based material3H, obtaining various heteropoly acid type carbon-based solid acid catalysts, such as activated carbon, carbon nano tubes, carbon fibers, graphene, carbon molecular sieves and other carbon-based solid acid catalysts, and a large number of preparation technologies and applications are reported. The preparation of the carbon-based solid acid catalyst mainly comprises two ways of sulfonating carbon-based carrier and carbonizing organic sulfonic acid compound, and SO in the catalyst exists3The method has the defects of small H load, low acid equivalent, poor catalyst structure controllability, large active site distribution randomness, low catalytic performance repeatability and the like, and influences the practical industrial application of the carbon-based solid acid.
Graphene (G) is applied to catalyst carriers as a carbon material which is most concerned in recent years, and various supported catalysts are prepared by means of direct adsorption, electrostatic interaction adsorption, covalent grafting loading and the like. In 2009, Rolf Mulhaupt et al used graphite oxide and functionalized graphene derivatives thereof to be doped with palladium nanoparticles and used for Suzuki-Miyaura coupling reactions. Reaction sites such as a benzene ring, a naphthalene ring and the like on the boundary of reduced graphene are utilized in the Junget 2010 to covalently graft through diazotization reaction of sulfanilic acid to form a C-C bond, so that the covalent supported carbon-based sulfonic acid catalyst can be obtained. However, the proportion of benzene ring and other aromatic rings at the boundary of graphene is relatively small, and the site for direct sulfonation reaction is limited, SO that-SO (sulfur oxide) grafted covalently is generated3The amount of H catalytic active sites is small, and the catalytic activity is low.
The three isomers of cresol can be used for synthesizing different perfume products and can also be used as different important fine chemical intermediates, for example, o-cresol can be used for preparing herbicide dimethyltetranitrogen, diluent for producing sebacic acid, disinfectant and medical intermediate, and also can be used for producing resin, plasticizer, perfume, dye and analytical reagent for detecting nitrate and arsenic acid. The metacresol is used as the dye intermediate of color film for producing fenitrothion, fenthion, metolcarb, permethrin and other pesticides, resin, plasticizer, etc. Para-cresol is a raw material for preparing antioxidant 2, 6-di-tert-butyl-para-cresol and rubber antioxidant, and is also an important basic raw material for producing medical TMP and dye kelitin sulfonic acid. The mixed cresol mainly comes from the recovery of by-products in petroleum products and the separation of coal gas wastewater, and also comes from chemical synthesis methods such as the alkylation of phenol and methanol, the sulfonation alkali dissolution of toluene and then diazotization hydrolysis. No matter mass cresol is prepared from petroleum or cresol is synthesized chemically, the obtained product is a mixture of two or three cresol isomers, and a large amount of byproducts are generated, so that the cresol monomer with high purity is difficult to obtain without a complicated separation process.
O-cresol differs greatly from m-cresol and p-cresol in boiling point, so o-cresol can be separated from mixed cresol by distillation. The close boiling points of m-cresol and p-cresol present a great challenge to the separation of the two. The boiling point difference of the tert-butyl product generated by the reaction of m-cresol and p-cresol with isobutene is utilized to separate the m-cresol and p-cresol, and the cresol monomer is obtained through dealkylation. The method is the main industrialized technology for separating m-cresol and p-cresol at home and abroad at present. At present, the cresol alkylation catalyst is usually concentrated sulfuric acid, phosphoric acid, aluminum trichloride, hydrochloric acid, organic sulfonic acid and the like. In particular, concentrated sulfuric acid is a relatively common acid catalyst in industrial production due to its abundant resource, low cost and easy availability. Although the sulfuric acid as the catalyst has good catalytic activity in the reaction, and the process is mature. But acid catalysts are severely corrosive to production equipment and instruments; after the reaction is completed, a large amount of alkali and water is required for washing to completely remove the sulfuric acid catalyst, and a large amount of heat is generated and waste water is polluted in the process. If the sulfuric acid has residues in the alkali neutralization process, the residual sulfuric acid can catalyze the dealkylation reaction of the tert-butylcresol in the subsequent rectification separation and mixing of the tert-butylcresol, and the rectification effect is seriously influenced. Meanwhile, in the alkylation reaction industrial production by using sulfuric acid as a catalyst, only a kettle type intermittent process can be applied, and the industrial production capacity is greatly limited.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a graphene-based sulfonic acid catalyst and application thereof in catalyzing an alkylation reaction of cresol, wherein the novel graphene sulfonic acid solid acid catalyst is prepared by sulfonating a graphene material modified by a benzene ring and is used for catalyzing the alkylation reaction of isobutene and mixed cresol in the separation process of mixed cresol.
According to the preparation method, a benzene ring (represented by G-Ph) is bonded on graphene through covalent grafting, then a sulfonate group is grafted on the edge of the graphene or the covalently modified benzene ring through a sulfonation reaction, and the graphene-based sulfonic acid catalyst (represented by G-Ph-SO) is obtained3H represents). According to the invention, the graphene-based sulfonic acid catalyst is used for replacing the traditional acid catalyst, because the reaction sites of the benzene ring grafted with the sulfonic acid groups are greatly increased, and the sulfonic acid groups and the graphene are linked through covalent bonds, the catalyst has a stable structure, so that active components are not easy to lose in the catalytic process, the catalytic activity equivalent to sulfuric acid is always kept, and the catalyst is favorable for recycling. In addition, the graphene-based sulfonic acid catalyst can also be used as a filling catalyst of a fixed bed reactor to realize the efficient continuous alkylation reaction of cresol, and has important significance for improving the separation efficiency of mixed cresol. Therefore, the graphene-based sulfonic acid catalyst provided by the invention is not easy to corrode equipment, good in reusability, high in reaction applicability, simple in post-reaction treatment and extremely high in industrial application value.
The graphene-based sulfonic acid catalyst is abbreviated as G-Ph-SO3H, the structure of which is schematically shown as follows:
the graphene-based sulfonic acid catalyst is prepared by the method comprising the following steps:
firstly, get throughBonding benzene rings on graphene through covalent grafting to synthesize G-Ph; then, sulfonating reaction is carried out, sulfonate is grafted on the edge of the graphene or a covalently modified benzene ring, and the graphene sulfonic acid catalyst G-Ph-SO is obtained3H。
The method specifically comprises the following steps:
step 1: preparation of G-Ph
Adding a proper amount of graphene, aniline, concentrated sulfuric acid (98% sulfuric acid) and deionized water into a flask, stirring to uniformly mix reaction liquid, placing the flask in an ice water bath, cooling to 0 ℃, dropwise adding a proper amount of sodium nitrite into the reaction liquid for 1.0-1.5h, and continuing to react at normal temperature for 2-24 h; after the reaction is finished, cooling the reaction mixed solution to room temperature, carrying out suction filtration to obtain a solid, washing with deionized water, ethanol and acetone in sequence, and carrying out vacuum drying to obtain G-Ph. And detecting and analyzing the composition and the structure of the material by methods such as element analysis, FT-IR, Raman spectroscopy and the like.
In step 1, the graphene includes Graphene Oxide (GO), Reduced Graphene (RG), Reduced Graphene Oxide (RGO), exfoliated graphene (SG), single-layer graphene, multi-layer graphene, and the like, and preferably is Reduced Graphene (RG), exfoliated graphene, or three-dimensional graphene.
In the step 1, the reaction time is 2-24h, preferably 8-12 h.
In the step 1, the reaction solvent is deionized water, methanol, ethanol or acetonitrile, preferably deionized water; the pH value range is as follows: 1-5, preferably pH 2-4. The pH value is regulated by the amount of sulfuric acid added.
In the step 1, the molar ratio of each reaction raw material is graphene: aniline: concentrated sulfuric acid: sodium nitrite 1: 1-2: 1.25: 2-1, preferably 1: 1.25-1.0: 1.25: 1.25-1.5.
The reaction of step 1 is carried out under normal pressure, and the reaction process is schematically shown as follows:
step 2: G-Ph-SO3Preparation of H
Adding a proper amount of G-Ph into a flask at the temperature of 80-200℃,Adding a sulfonation reagent under the stirring condition to carry out sulfonation reaction; after the reaction is finished, cooling the reaction mixed solution to room temperature, washing the product by deionized water and acetone in sequence, washing until the filtrate is neutral, and using Ba (OH)2Determining the washing end point, and vacuum drying the obtained solid to obtain G-Ph-SO3H. The acid value was determined by acid-base titration. Novel catalyst G-Ph-SO3The acid value of H is between 1.4 and 2.8mmol/g, and the highest value can reach 2.8mmol/g, and is influenced by the dropping speed of aniline, the addition amount of aniline and the reaction temperature. The acid value of the catalyst is positively correlated with the alkylation effect.
In step 2, the sulfonation reagent is concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid or sulfur trioxide.
In step 2, the mass ratio of the sulfonating agent to G-Ph is 1-20:1, preferably 2-5: 1.
In the step 2, the temperature of the sulfonation reaction is 80-200 ℃, preferably 120-140 ℃; the sulfonation reaction time is 8-24h, preferably 8-12 h.
The reaction process of step 2 is schematically as follows:
the application of the graphene-based sulfonic acid catalyst is to use the graphene-based sulfonic acid catalyst as a catalyst to catalyze the alkylation reaction of cresol, and comprises the following steps:
cresol and catalyst G-Ph-SO were added in sequence to a 250mL round bottom flask3H, starting stirring, controlling the reaction mixed solution to a proper temperature, and introducing isobutene gas into the reaction mixed solution at a determined flow rate; sampling at intervals, detecting the cresol content in the reaction mixture by using gas chromatography, monitoring the reaction process until the m-cresol raw material is completely reacted, and stopping introducing isobutene to finish the reaction; filtering the reaction mixed solution while the reaction is hot after the reaction is finished, separating and recovering G-Ph-SO3And H, a catalyst. And (3) selecting proper solvent to wash the catalyst according to different reactant raw materials, and drying the catalyst for recycling. Recovering the catalyst, vacuum distilling to separate and purify the unreacted cresol and monoalkyl of cresolAlkylated and double alkylated products. The composition was analyzed by gas chromatography.
The cresol is one or a mixture of more of o-cresol, m-cresol and p-cresol.
Catalyst G-Ph-SO3The mass ratio of H to cresol is 1: 10-1: 50, preferably 1: 30-1: 20.
the reaction temperature is 25-120 ℃, and preferably 45-100 ℃; the reaction time is 2-24h, preferably 8-12 h.
The flow rate of the isobutene gas is 20-500 mL/(min. mol cresol), preferably 150-300 mL/(min. mol cresol).
Recovered G-Ph-SO3The H catalyst can be directly used or circularly used after being washed.
The catalytic reaction process can also be continuously synthesized by adopting a fixed bed reactor.
The catalytic reaction scheme is schematically as follows:
G-Ph-SO3when H replaces liquid acid such as sulfuric acid and the like, a mixed system formed by H and reactants is generally a heterogeneous reaction system, and the H is easily separated from a product after the catalytic reaction is finished; G-Ph-SO3Active component sulfonate in H is connected with carrier graphene through covalent bonds, and the active component is not easy to lose from the carrier in the catalytic reaction process, so that the catalytic activity of the alkylation reaction of p-cresol is kept, the stability is high, the catalyst can be recycled for multiple times, and the industrial production requirement is met. The invention takes the alkylation reaction of m-cresol, p-cresol and tert-butylene as a model reaction to evaluate the catalytic activity of the alkylation reaction for synthesizing tert-butylcresol by replacing sulfuric acid.
The invention designs and prepares a graphene-based sulfonic acid solid catalyst with a novel structure, namely, benzene ring modified graphene (G-Ph for short) is prepared through phenyl diazotization reaction, and the modified benzene ring can be used as a new reaction site for covalent grafting-SO3H forms the target catalyst (G-Ph-SO for short)3H) In that respect The method is beneficial for improving activityThe loading of the active components realizes effective control of the structure, acidity and catalytic performance of the graphene-based solid acid. By optimizing conditions, the acid equivalent of the prepared catalyst can reach more than 2.8mmol/g at most. The research on the catalytic performance shows that the novel graphene-based solid acid catalyst has high-efficiency activity on the aromatic alkylation reaction and shows the similar catalytic efficiency of concentrated sulfuric acid. Meanwhile, the catalyst can be recycled by simple filtration. The graphene solid acid is used as a catalyst for filling the fixed bed reactor, and the continuous production process of various organic chemical products can be realized, so that the industrial application value is shown. The protonic acid catalyst is widely applied in the organic chemical industry, so that the application range of the graphene-based solid acid substituted catalyst is clear, the market demand is large, and the catalyst has great industrial application and development potential.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, phenyl diazonium salt reacts with graphene to obtain benzene ring modified graphite G-Ph, and then the benzene ring is grafted through sulfonation reaction and the graphene is connected with a sulfonate group to prepare the G-Ph-SO3And H, a catalyst. By grafting a benzene ring on graphene, the grafting site and the grafting amount of a sulfonic acid group on the graphene are increased, and G-Ph-SO is increased3H acid equivalent.
2. At G-Ph-SO3In the H, the carrier graphene and the active functional group sulfonate are connected in a covalent bond mode, and the catalyst has a stable structure, so that the active components are not easy to lose in the catalytic process and the catalytic activity is kept, and the industrial practical application is facilitated.
3. G-Ph-SO in the present invention3The H adopts graphene as a carrier, has the advantages of high stability and large specific surface area, and has good compatibility with organic compounds, SO that G-Ph-SO is ensured3H shows a catalytic activity comparable to sulfuric acid. The graphene is a two-dimensional structure substance, has a large specific surface area compared with other solid sulfonic acid catalysts, and can improve catalytic activity because reaction raw materials are fully contacted with the catalysts in the catalytic reaction process.
4、G-Ph-SO3The H solid acid catalyst is applied to organic reaction instead of the traditional sulfuric acid, and can avoid the reaction from passing through alkali after the reaction is finishedAnd a water washing step, namely removing sulfuric acid in the reaction mixed system, and greatly reducing the discharge of waste water. G-Ph-SO3The H solid acid catalyst is separated by simple filtration and is convenient to recover.
5. The solid phase catalyst can be recycled for many times, the catalytic activity is not obviously lost, the catalyst is used as the catalyst filler for the fixed bed reaction, the continuous reaction is realized, and the requirement of large-scale production is met.
6. Compared with the catalyst with toxicity such as sulfuric acid and the like, the catalyst is environment-friendly and harmless to human bodies, meets the requirement of industrial green production, and has wide development prospect.
Drawings
Fig. 1 is a raman characterization spectrum.
FIG. 2 is a gas chromatogram of a sulfuric acid catalyzed t-butylation reaction of m-cresol. Wherein, the No. 1 peak is solvent CH2Cl2The peak No. 2 is m-cresol, the peak No. 3 is 6-tert-butyl-m-cresol, and the peak No. 4 is 4, 6-di-tert-butyl-m-cresol.
FIG. 3 is a gas chromatogram of G-Ph-SO 3H-catalyzed tert-butylation of m-cresol. Wherein, the No. 1 peak is solvent CH2Cl2The peak No. 2 is m-cresol, the peak No. 3 is 6-tert-butyl-m-cresol, and the peak No. 4 is 4, 6-di-tert-butyl-m-cresol.
Figure 4 is an XRD characterization pattern.
FIG. 5 is an infrared characterization map. In FIG. 5, 3068cm-1And 1700cm-1Shows that there are benzene rings and hydrocarbon vibration absorption peaks of the benzene rings, and G-Ph-SO3The characteristic peak of H is obviously stronger than that of graphite, and a surface benzene ring is successfully modified on graphene. 1170cm-11075cm-1Has an absorption peak of-SO3The stretching vibration peak of O-S-O in H is almost zero, and the infrared absorption of the raw material of graphene is almost zero, which indicates that the sulfonic acid group is successfully grafted on the graphene carrier.
Detailed Description
Example 1: G-Ph-SO3Preparation of H
Preparation of G-Ph: to a 500mL single-neck flask, 1.26g of reduced graphene oxide, 200mL of deionized water, 10mL of aniline, and 5mL of sulfuric acid were sequentially added, and stirred so that graphene was uniformly dispersed in the aqueous solution. The temperature of the reaction mixture is reduced to 0-5 ℃ by ice bath cooling, and 7.23g of newly prepared sodium nitrite solution is slowly dripped into the system, and the dripping time is 1.5 h. After the dropwise addition, the temperature of the reaction mixed solution is raised to 25 ℃, and the reaction is continued for 12 hours to finish the reaction. And filtering the reaction mixed solution to obtain a solid product, sequentially washing the solid product with ethanol and acetone for three times, and then drying the product G-Ph 1.27G in vacuum. Elemental analysis for graphene G was C97.87%, H0.91%, N2.12% and S0.56%, C86.88%, H1.29%, N2.50% and S0.82% for G-Ph. The hydrogen content in G-Ph is obviously higher than that in G, which shows that the benzene ring is successfully grafted on the graphene.
G-Ph-SO3H, preparation: the 1.27g G-Ph prepared in the previous step is placed in a single-neck flask, 50ml of concentrated sulfuric acid is added, and the reaction is stirred at 140 ℃ for 12 hours. After the reaction is finished, 250ml of deionized water is added into the reaction system under cooling, the reaction mixed liquid is filtered and filtered to obtain a solid product, and the solid product is washed by the deionized water until Ba (OH)2Solution detection of washing solution without free SO4 2-. Vacuum drying to obtain solid 1.28G, i.e. G-Ph-SO3H。G-Ph-SO3Elemental analysis of H determined C71.88%, H2.32%, N1.32%, S4.69%. G-Ph-SO3The significant increase in S content of H indicates sulfonate groups on G-Ph grafting. Determination of G-Ph-SO by acid-base titration3The acid value of H was 2.28 mmol/mg.
Example 2: G-Ph-SO3Preparation of H
G-Ph-SO3H, preparation: 1.26g G-Ph obtained in example 1 was placed in a single-neck flask, and 40% SO was introduced3The fuming sulfuric acid is stirred and reacted for 12 hours at the temperature of 100 ℃. After the reaction is finished, adding 250ml of deionized water into the system under cooling, filtering the reaction mixed solution to obtain a solid product, washing the solid product with the deionized water until the Ba (OH)2 solution detects that the washing solution does not contain free SO4 2-. Vacuum drying to obtain solid 1.29G, i.e. G-Ph-SO3H, using acid-base dropsDetermination of prepared G-Ph-SO by assay3The acid value of H was 2.7 mmol/mg.
Example 3: G-Ph-SO3Preparation of H
Preparation of G-Ph: to a 500mL single-neck flask, 0.56g of reduced graphene oxide, 200mL of deionized water, 2.5mL of aniline, and 2.5mL of sulfuric acid were sequentially added, and the graphene was uniformly dispersed by sonication. Under the ice-bath condition, 3.00g of newly prepared sodium nitrite solution is slowly dripped into the system for 1h, the ice-bath device is removed after the dripping is finished, and the stirring reaction is continued for 12h at 25 ℃. And after the reaction is finished, cooling the mixed solution which is completely reacted to room temperature, carrying out suction filtration to obtain a solid, sequentially washing the solid with ethanol and acetone for three times, and carrying out vacuum drying on the product at a low temperature to obtain G-Ph, weighing the G-Ph and obtaining the product with the mass of 0.54G.
G-Ph-SO3H, preparation: G-PH-SO3The procedure for the preparation of H was the same as in example 1. The obtained product was detected by FT-IR, XPS, XRD, Raman, elemental analysis and its structure was confirmed. The weight of the product was 0.53 g. Determination of prepared G-PH-SO by acid-base titration3The acid value of H was 1.88 mmol/mg.
Example 4: G-Ph-SO3Preparation of H
Preparation of G-Ph: the preparation of G-Ph was carried out in the same manner as in example 1. The weight was 1.10 g.
G-Ph-SO3H, preparation: putting all the G-Ph prepared in the previous step into a single-neck flask, adding 50ml of concentrated sulfuric acid, and reacting for 12 hours under stirring at 80 ℃. After the reaction is finished, 250ml of deionized water is added into the system under cooling, the reaction mixed liquid is filtered and filtered to obtain a solid product, and the solid product is washed by the deionized water until Ba (OH)2Solution detection of washing solution without free SO4 2-. Vacuum drying to obtain solid 1.14G, detecting and determining the structure of the product by FT-IR, XPS, XRD, Raman, and element analysis, and determining the prepared G-Ph-SO by acid-base titration3The acid value of H was 1.35 mmol/mg.
Example 5: G-Ph-SO3Preparation of H
Preparation of G-Ph: to a 250mL single-neck flask, 0.56g of multilayer graphene, 100mL of deionized water, 5mL of aniline, and 2.5mL of sulfuric acid were sequentially added, and the graphene was uniformly dispersed by sonication. Under the ice-bath condition, 3.00g of newly prepared sodium nitrite solution is slowly dripped into the system for 1h, the ice-bath device is removed after the dripping is finished, and the stirring reaction is continued for 12h at 25 ℃. And after the reaction is finished, cooling the mixed solution which is completely reacted to room temperature, carrying out suction filtration to obtain a solid product, sequentially washing the solid product with ethanol and acetone for three times, and carrying out vacuum drying on the product at a low temperature to obtain the G-Ph. The weight was 0.58 g.
G-Ph-SO3H, preparation: G-Ph-SO3The procedure for preparation of H was the same as in example 1. 0.61G of the obtained product was analyzed and determined for structure by FT-IR, XPS, XRD, Raman, elemental analysis, and the prepared G-Ph-SO was measured by acid-base titration3The acid value of H was 1.20 mmol/mg.
Example 6:
to a 250mL round bottom flask equipped with a stirrer, reflux condenser, gas-line and thermometer was added, in order, 50mL of m-cresol and G-Ph-SO prepared in example 13And the H catalyst is connected with a tail gas absorption device on the reflux condenser. The temperature of the reaction mixture liquid is raised to 75 ℃ under stirring, isobutene gas is introduced at the speed of 200-240mL/min, and alkylation reaction is carried out. Sampling at intervals, detecting the content of cresol in the reaction mixture by using gas chromatography, monitoring the reaction process until the m-cresol raw material is completely reacted, and stopping the reaction. After the reaction is completed, the reaction mixed solution is filtered while the reaction mixed solution is hot, the catalyst is recovered, and the ethanol solvent can be directly recycled after being washed. The filtrate was subjected to rectification under reduced pressure to give 5.82g of 6-t-butyl-m-cresol with a yield of 7.38%. 93.82g of product 4, 6-di-tert-butyl-m-phenol, the yield is 88.7%.
Example 7:
to a 250mL round-bottom flask equipped with a stirrer, reflux condenser, gas-guide tube and thermometer were added in sequence 50mL of m-cresol and the G-Ph-SO recovered in example 63H catalyst, and a tail gas absorption device is connected to the reflux condenser. The temperature of the reaction mixture was raised to 75 ℃ with stirring, and isobutylene gas was introduced at 240mL/min to conduct alkylation. Sampling at intervals, using gas phaseAnd (4) detecting the content of cresol in the reaction mixture by a spectrum, monitoring the reaction process until the m-cresol raw material is basically reacted completely, and stopping the reaction. After the reaction is completed, the reaction mixed solution is filtered while the reaction mixed solution is hot, the catalyst is recovered, and the ethanol solvent can be directly recycled after being washed. The filtrate was subjected to rectification under reduced pressure to give 5.28g of 6-t-butyl-m-cresol with a yield of 6.69%. 95.93g of product 4, 6-di-tert-butyl-m-phenol, yield 90.7%.
Example 8:
to a 250mL round-bottom flask equipped with a stirrer, reflux condenser, gas-guide tube and thermometer were added in sequence 50mL of m-cresol and the G-Ph-SO recovered in example 73H catalyst, and a tail gas absorption device is connected to the reflux condenser. The temperature of the reaction mixture was raised to 75 ℃ with stirring, and isobutylene gas was introduced at 240mL/min to conduct alkylation. Sampling at intervals, detecting the content of cresol in the reaction mixture by using gas chromatography, monitoring the reaction process until the m-cresol raw material is completely reacted, and stopping the reaction. After the reaction is completed, the reaction mixed solution is filtered while the reaction mixed solution is hot, the catalyst is recovered, and the ethanol solvent can be directly recycled after being washed. After the filtrate was rectified under reduced pressure, 92.88g of 4, 6-di-tert-butyl-m-phenol was obtained in 87.81% yield.
Example 9:
50mL of m-cresol and 2.5g of concentrated sulfuric acid were added in this order to a 250mL round-bottomed flask equipped with a stirrer, reflux condenser, gas-guide tube and thermometer, and a tail gas absorption apparatus was connected to the reflux condenser. The temperature of the reaction mixture was raised to 75 ℃ with stirring, and isobutylene gas was introduced at 240mL/min to conduct alkylation. Samples were taken at intervals and, after the reaction was complete, 10ml of 10% strength Na was added2CO3The solution and 20ml of dichloromethane are stirred for 2 hours, kept stand, and the water layer is separated to obtain an oil layer of hydrocarbon compounds, and the content of cresol in the reaction mixture is detected by gas chromatography. After vacuum rectification is carried out on the filtrate, 10.64g of 6-tert-butyl m-cresol is obtained, and the yield is 13.50%; 90.96g of product 4, 6-di-tert-butyl-m-phenol, yield 86.0%.
Example 10:
to a 250mL round bottom flask equipped with a stirrer, reflux condenser, gas-line and thermometer, in that order, was added 50mL of m-cresol and G-Ph-SO synthesized according to the conditions of example 13H catalyst, and a tail gas absorption device is connected to the reflux condenser. The temperature of the reaction mixture was raised to 75 ℃ with stirring, and isobutylene gas was introduced at 240mL/min to conduct alkylation. Sampling at intervals, detecting the content of cresol in the reaction mixture by using gas chromatography, monitoring the reaction process until the content of the monoalkylated product of the m-cresol in the system reaches the maximum value, and stopping the reaction. After the reaction is completed, the reaction mixed solution is filtered while the reaction is hot, and the catalyst is recovered. The filtrate was subjected to rectification under reduced pressure to give 49.55g of 6-t-butyl-m-cresol in a yield of 62.85%, and 23.99g of 4, 6-di-t-butyl-m-phenol in a yield of 22.68%.
Example 11:
to a 250mL round bottom flask equipped with a stirrer, reflux condenser, gas-guide tube and thermometer, in order, was added 50mL of a 1:1 molar mixture of m-cresol and p-cresol, and G-Ph-SO synthesized according to the conditions in example 13H catalyst, and a tail gas absorption device is connected to the reflux condenser. The temperature of the reaction mixture was raised to 75 ℃ with stirring, and isobutylene gas was introduced at 240mL/min to conduct alkylation. Sampling at intervals, detecting the content of cresol in the reaction mixture by gas chromatography, monitoring the reaction process until the cresol raw material is completely reacted, and stopping the reaction. After the reaction is completed, the reaction mixed solution is filtered while the reaction mixed solution is hot, the catalyst is recovered, and the ethanol solvent can be directly recycled after being washed. After vacuum rectification, 47.07g of 4, 6-di-tert-butyl m-cresol is obtained from the filtrate, and the yield is 44.5%; 47.7g of 2, 6-di-tert-butyl-p-cresol was obtained, the yield was 45.1%.
Example 12:
to a 250mL round-bottomed flask equipped with a stirrer, a reflux condenser, a gas-guide tube and a thermometer, 50mL of a mixed solution of m-cresol and p-cresol in a molar ratio of 1:1 and G-Ph-SO synthesized from multilayer graphene in example 5 were added in this order3H catalyst, and a tail gas absorption device is connected to the reflux condenser. The temperature of the reaction mixture was raised to 75 ℃ with stirring, and isobutylene gas was introduced at 240mL/min to conduct alkylation. Sampling at intervals, detecting the content of cresol in the reaction mixture by gas chromatography, and monitoring the reactionThe reaction was carried out for the same period as in example 6, and the reaction was stopped. After the reaction is completed, the reaction mixed solution is filtered while the reaction mixed solution is hot, the catalyst is recovered, and the ethanol solvent can be directly recycled after being washed. The filtrate is rectified under reduced pressure to obtain 13.87g of 6-tert-butyl m-cresol, and the yield is 17.6 percent; 31.0g of 4, 6-di-tert-butyl-m-cresol with the yield of 29.3 percent; 13.09g of 6-tert-butyl m-cresol is obtained, and the yield is 16.1%; 33.10g of 2, 6-di-tert-butyl-p-cresol with a yield of 31.3%.
Claims (10)
1. A graphene-based sulfonic acid catalyst, characterized by:
the graphene-based sulfonic acid catalyst is obtained by firstly covalently grafting a benzene ring on graphene and then grafting a sulfonate group on the edge of the graphene or the covalently modified benzene ring through a sulfonation reaction3H；
The structure of the graphene-based sulfonic acid catalyst is schematically shown as follows:
2. the graphene-based sulfonic acid catalyst of claim 1, wherein:
the acid value of the graphene-based sulfonic acid catalyst is 1.4-2.8 mmol/g.
3. A method for preparing the graphene-based sulfonic acid catalyst according to claim 1 or 2, characterized by comprising the steps of:
step 1: preparation of G-Ph
Adding a proper amount of graphene, aniline, concentrated sulfuric acid and deionized water into a flask, stirring to uniformly mix reaction liquid, placing the flask in an ice water bath, cooling to 0 ℃, dropwise adding a proper amount of sodium nitrite into the reaction liquid, completing dropwise adding for 1.0-1.5h, and continuously reacting for 2-24h at normal temperature; after the reaction is finished, cooling the reaction mixed solution to room temperature, performing suction filtration to obtain a solid, washing the solid with deionized water, ethanol and acetone in sequence, and performing vacuum drying to obtain G-Ph;
step 2: G-Ph-SO3Preparation of H
Adding a proper amount of G-Ph into a flask, and adding a sulfonation reagent to perform sulfonation reaction at the temperature of 80-200 ℃ under the stirring condition; after the reaction is finished, cooling the reaction mixed solution to room temperature, washing the product by deionized water and acetone in sequence, washing until the filtrate is neutral, and using Ba (OH)2Determining the washing end point, and vacuum drying the obtained solid to obtain G-Ph-SO3H。
4. The production method according to claim 3, characterized in that:
in the step 1, the molar ratio of each reaction raw material is graphene: aniline: concentrated sulfuric acid: sodium nitrite 1: 1-2: 1.25: 2-1.
5. The production method according to claim 3, characterized in that:
in step 1, the graphene includes graphene oxide, reduced graphene oxide, exfoliated graphene, single-layer graphene, and multi-layer graphene.
6. The production method according to claim 3, characterized in that:
in step 2, the sulfonation reagent is concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid or sulfur trioxide.
7. The production method according to claim 3, characterized in that:
in the step 2, the mass ratio of the sulfonation reagent to G-Ph is 1-20: 1.
8. Use of the graphene-based sulfonic acid catalyst according to claim 1 or 2, wherein: it is used as catalyst to catalyze the alkylation reaction of cresol.
9. Use according to claim 8, characterized in that it comprises the following steps:
sequentially adding A into the reactorPhenol with catalyst G-Ph-SO3H, starting stirring, controlling the reaction mixed solution to a proper temperature, and introducing isobutene gas into the reaction mixed solution at a determined flow rate; sampling at intervals, detecting the cresol content in the reaction mixture by using gas chromatography, monitoring the reaction process until the m-cresol raw material is completely reacted, and stopping introducing isobutene to finish the reaction; filtering the reaction mixed solution while the reaction is hot after the reaction is finished, separating and recovering G-Ph-SO3H, catalyst, and separating and purifying unreacted raw material cresol and mono-alkylation and di-alkylation products of cresol by adopting reduced pressure distillation to the reaction solution after the catalyst is recovered.
10. Use according to claim 9, characterized in that:
the cresol is one or a mixture of more of o-cresol, m-cresol and p-cresol; catalyst G-Ph-SO3The mass ratio of H to cresol is 1: 10-1: 50.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106379893A (en) * | 2016-10-11 | 2017-02-08 | 南京信息工程大学 | Method for preparing sulfonated graphene material |
| CN106861722A (en) * | 2017-03-21 | 2017-06-20 | 广东工业大学 | A kind of solid acid catalyst, its preparation method and its application |
| WO2018024196A1 (en) * | 2016-08-02 | 2018-02-08 | 福建新峰二维材料科技有限公司 | Preparation method for graphene nanometer material |
| CN112500366A (en) * | 2020-11-18 | 2021-03-16 | 合肥工业大学 | Graphene covalent grafting thiazole salt catalyst and application thereof |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018024196A1 (en) * | 2016-08-02 | 2018-02-08 | 福建新峰二维材料科技有限公司 | Preparation method for graphene nanometer material |
| CN106379893A (en) * | 2016-10-11 | 2017-02-08 | 南京信息工程大学 | Method for preparing sulfonated graphene material |
| CN106861722A (en) * | 2017-03-21 | 2017-06-20 | 广东工业大学 | A kind of solid acid catalyst, its preparation method and its application |
| CN112500366A (en) * | 2020-11-18 | 2021-03-16 | 合肥工业大学 | Graphene covalent grafting thiazole salt catalyst and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 林菊香;董菁;陈丹青;陈国华;: "基于对氨基苯磺酸重氮盐功能化制备亲水性磺化石墨烯的研究", 中国科学:化学, no. 08, pages 791 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114772586A (en) * | 2022-04-22 | 2022-07-22 | 浙江南烯科技有限公司 | Method for preparing high-conductivity sulfonated graphene by graphite reduction |
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