CN109365006B - M-Ce-TiO2-USY molecular sieve catalyst and method for generating o-cresol - Google Patents
M-Ce-TiO2-USY molecular sieve catalyst and method for generating o-cresol Download PDFInfo
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Abstract
The invention provides M-Ce-TiO2The catalyst has simple components, is especially suitable for catalyzing phenol and dimethyl carbonate to synthesize o-cresol, and has the features of high activity, high o-cresol selectivity, etc. The M-Ce-TiO2-a method for preparing a USY molecular sieve catalyst comprising the steps of: 1) TiO loaded on USY molecular sieve2And CeO2(ii) a 2) Loading a surfactant M on the molecular sieve obtained in the step 1) to obtain the catalyst, and marking as M-Ce-TiO2-a USY molecular sieve catalyst; wherein the surfactant M is preferably octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and/or hexadecyl pyridine.
Description
Technical Field
The invention relates to a method for synthesizing o-cresol, in particular to a catalyst for synthesizing o-cresol, a preparation method thereof and a method for synthesizing o-cresol by using the catalyst.
Background
O-cresol is an important chemical intermediate and is widely applied to the fields of pesticides, medicines, antioxidants, spices, epoxy phenolic resins and the like. O-cresol was first isolated from coal tar, the process was complex, the product purity was low, and the demand was far from being met. The o-cresol is then produced by a chemical synthesis method, and the o-cresol is synthesized by adopting an o-toluidine diazotization hydrolysis method and an o-chlorotoluene hydrolysis method, and the process has the defects of environmental pollution, equipment corrosion and high cost. The prior process adopts a phenol-methanol alkylation method to synthesize o-cresol, which is divided into a liquid phase method and a gas phase method, wherein the liquid phase method has harsh process conditions and more impurities at high temperature and high pressure, and the method is not adopted at present. The gas phase alkylation has high selectivity and simple process, and the earliest U.S. general electric uses MgO as a catalyst to synthesize the o-cresol, but the method has the defects of high temperature (about 550 ℃) and short service life of the catalyst. Japan Asahi Chemicals corporation developed V2O5-Fe2O3The catalyst is used for synthesizing o-cresol and creates Fe2O3The catalyst is used for synthesizing o-cresol. CN201310355671 adopts a novel catalyst to synthesize o-cresol, and the catalyst is complex in synthesis, high in reaction temperature, low in reaction activity of methanol, toxic and not in accordance with the concept of green chemistry.
Disclosure of Invention
In view of the above, the present invention provides a M-Ce-TiO compound2The catalyst has simple components and easy preparation, is particularly suitable for catalyzing phenol and dimethyl carbonate to synthesize o-cresol, and has the characteristics of high activity, high o-cresol selectivity and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides M-Ce-TiO2-a method for preparing a USY molecular sieve catalyst comprising the steps of:
1) TiO loaded on USY molecular sieve2And CeO2；
2) Loading a surfactant M on the molecular sieve obtained in the step 1) to obtain the catalyst, and marking as M-Ce-TiO2-a USY molecular sieve catalyst; wherein, the surfactant M is preferably one or the combination of more than two of octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and hexadecyl pyridine.
The invention is prepared by mixing TiO2The catalyst is loaded on the USY molecular sieve, the L acid center on the surface of the catalyst can be optimized, meanwhile, the Ce modified USY molecular sieve can be used for remarkably improving the B acid center on the surface of the catalyst, promoting the conversion of phenol, and the Ti and Ce double-metal modification can be used for synergistically modulating the acid type of the catalyst and improving the content of the L acid center, so that the selectivity of o-cresol is improved; in addition, the loading of the surfactant promotes the molecular sieve to better adsorb phenol, and the introduction of Ce element can also better promote TiO2Dispersion on the USY surface; the inventor of the application finds that the USY molecular sieve is used as a carrier, Ti, Ce bimetal and a surfactant are introduced for modification, and the combination of the Ti, Ce bimetal and the surfactant is adopted, so that the obtained catalyst can replace the traditional alkylating reagent methanol with a high-activity green chemical reagent dimethyl carbonate to synthesize o-cresol with phenol, and the dimethyl carbonate has higher activity and is non-toxic compared with methanol.
In the preparation method, the step 1) can be carried out according to the following scheme one or scheme two; the first scheme specifically comprises the following steps:
1.1a) mixing and stirring the USY molecular sieve and the organic titanium solution, soaking, preferably for 12-36 hours (for example, 12, 15, 20, 25, 30 and 35 hours), and then removing the solvent; in a specific embodiment, the USY molecular sieve can be subjected to grinding and drying treatment in advance;
1.2a) reaction of the product obtained in step 1.1a) with Ce (NO)3)3·6H2Mixing the O aqueous solution, stirring, and soaking for 12-36 hr (for example, 12, 15, 20, 25, 30, etc.),35h) Then removing the solvent and roasting;
the second scheme specifically comprises the following steps:
1.1b) mixing USY molecular sieves with Ce (NO)3)3·6H2Mixing and stirring the O aqueous solution, soaking for 12-36h (for example, 12, 15, 20, 25, 30 and 35h), and removing the solvent; in a specific embodiment, the USY molecular sieve can be subjected to grinding and drying treatment in advance;
1.2b) the product obtained in step 1.1b) is mixed with an organotitanium solution, stirred, impregnated, preferably for a period of 12 to 36 hours (for example 12, 15, 20, 25, 30, 35 hours), after which the solvent is removed and calcined.
Wherein, in the step 1), the organic titanium is preferably selected from one or more of butyl titanate, isopropyl titanate and ethyl titanate; the solvent in the organic titanium solution used is preferably one or a combination of two or more of benzene, toluene, cyclohexane and n-hexane.
In some preferred embodiments, CeO2The loading in the catalyst is preferably 2 to 5 wt%. In some embodiments, the Ce (NO) is3)3·6H2O is used in an amount of 5-12% by mass of the USY molecular sieve, e.g., 5%, 7%, 9%, 10%, 12%, etc. In some preferred embodiments, the catalyst is made of TiO2In an amount of 5 to 15 wt.% (based on the total mass of the catalyst), e.g. 5%, 7%, 9%, 13%, 15%, etc., the amount of organotitanium used in step 1) is based on the amount of TiO in the catalyst2The amount of the load of (c) is determined. With the preferred Ce (NO)3)3·6H2Amount of O and TiO2The load capacity of the catalyst is that Ce and Ti are combined according to a specific proportion in the obtained catalyst, so that the catalyst can achieve better synergistic effect, the activity of the catalyst is high, the conversion rate of the prepared catalyst phenol is high, and the selectivity of a target product is high.
In some embodiments, the impregnation involved in each particular operating step of step 1) is a closed impregnation at room temperature (e.g., 20-30 ℃); the solvent removal in each specific operation step of the step 1) can be carried out by evaporating the solvent in a water bath drying mode; the roasting involved in each specific operation step of step 1) is roasting at 450-540 ℃.
In some preferred embodiments, the step 2) comprises: mixing the molecular sieve obtained in step 1) with the surfactant aqueous solution at 50 to 70 ℃ (e.g., 50 ℃, 60 ℃, 70 ℃) for stirring, preferably for 20 to 50min, and then washing, drying, and molding, wherein the specific molding manner of the molding is not particularly limited, and for example, the molding is performed by mixing with a binder (e.g., inert alumina, silica, etc.), for example, into 20 to 40 mesh particles.
By introducing a surfactant, particularly octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and/or hexadecyl pyridine, into the catalyst, the molecular sieve can better adsorb phenol, the conversion rate of the phenol in the reaction is improved, and the catalytic effect is improved; in preferred embodiments, the aqueous surfactant solution has a concentration of 1-5 wt% (e.g., 1 wt%, 2 wt%, 4 wt%, 5 wt%, etc.), the amount of the surfactant is 10-50 wt% (e.g., 10%, 20%, 30%, 40%, 50%) of the mass of the USY molecular sieve, and the resulting molecular sieve has a better phenol adsorption effect with the preferred amount of surfactant.
The invention also provides M-Ce-TiO2The catalyst takes the USY molecular sieve as a carrier, and a surfactant and TiO are loaded on the carrier2And CeO2Wherein the TiO of the catalyst2Is preferably 5 to 15 wt% (e.g., 5 wt%, 8 wt%, 10 wt%, 13 wt%, 15 wt%, etc.), and the CeO2The loading amount of (b) is preferably 2 to 5 wt% (e.g., 2 wt%, 3 wt%, 4 wt%, 5 wt%, etc.); the loading amount of the surfactant M is preferably 0.1 to 0.5 wt% (e.g., 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, etc.); the surfactant M is preferably one or a combination of two or more selected from among octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and hexadecyl pyridine. The catalyst can be prepared by the preparation method described above.
The catalyst provided by the invention is particularly suitable for catalyzing phenol and dimethyl carbonate to alkylate and synthesize o-cresol, and has higher o-cresol selectivity and stability. Based on the above, the invention also provides a method for generating o-cresol, wherein phenol and dimethyl carbonate react under the catalysis of a catalyst to generate the o-cresol, wherein the catalyst is prepared by the preparation method or the catalyst. When the catalyst is used for synthesizing o-cresol, dimethyl carbonate can be used as an alkylating reagent to replace the traditional methanol, and the dimethyl carbonate is a high-activity green chemical reagent containing methyl, methoxy and carbonyl, has the activity obviously higher than that of the methanol and is non-toxic.
In some preferred embodiments, the reaction is carried out in a fixed bed at a reaction temperature of 250-500 deg.C (e.g., 250 deg.C, 300 deg.C, 350 deg.C, 400 deg.C, 500 deg.C, etc.), preferably 300-400 deg.C, a gauge pressure of 0.05-0.5MPa (e.g., 0.05MPa, 0.1MPa, 0.3MPa, 0.5MPa, etc.), and a mass space velocity of 1-5h-1The molar ratio of phenol to dimethyl carbonate is 1: (0.5-2). The catalyst of the invention is used for catalyzing the reaction of synthesizing o-cresol from phenol and dimethyl carbonate to be preferably carried out in a fixed bed, the adopted fixed bed process does not generate three wastes, and the molecular sieve can be regenerated and recycled, thereby meeting the requirements of modern green chemical industry. The fixed bed is specifically, for example, a tubular electrothermal reactor.
The technical scheme provided by the invention has the following beneficial effects:
the novel catalyst provided by the invention has high activity and high o-cresol selectivity, in some embodiments, the o-cresol selectivity can reach more than 70%, the prior art can only reach about 50%, and the catalyst is renewable and environment-friendly.
When the catalyst is used for synthesizing o-cresol, the adopted raw materials are phenol and dimethyl carbonate, and the alkylating reagent is safe, environment-friendly and low in toxicity, and accords with the concept of green chemistry.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The following examples used test instruments including: the gas phase was analyzed by using Shimadzu Angilent model 7820A gas chromatograph (hydrogen flame detector, nitrogen as carrier gas) and DB-5 capillary column (5% Phenyl Methyl Siloxan, 30 m.times.0.32 mm.times.0.25 μm), hydrogen flame detector (FID). The sample injector and detector temperatures were both 280 ℃; column temperature is controlled by adopting programmed temperature rise: the column temperature is initially kept at 100 ℃ for 0.5 minute, and the temperature is raised to 260 ℃ at 15 ℃/min and kept for 5 minutes. Column pressure 8.5868psi, flow rate 1.5 mL/min. Sample introduction amount: 0.2. mu.L. Conversion and selectivity were calculated using area normalization.
Chemical composition of the catalyst the test instrument used was an Agilent ICP-OES 720.
The raw materials used in the following experiments are all commercially available raw materials, and some of the raw materials are described below:
example 1
Respectively weighing 42.5g, 85g and 127.5g of butyl titanate, respectively dissolving in 200g of toluene, respectively dissolving 20g of USY in the solution, fully stirring, hermetically soaking at room temperature for 24h, finally evaporating the toluene through water bath and drying, and marking the product as TiO2-a USY molecular sieve, wherein,
then 1.0g Ce (NO)3)3·6H2O was dissolved in 50ml of distilled water, and 10g, 12.5g and 16g of TiO were added thereto, respectively2Stirring at room temperature for 3h, soaking at room temperature for 24h, stirring in 80 deg.C water bath, evaporating to dryness, drying at 110 deg.C for 12h, and roasting at 450 deg.C in muffle furnace for 5h to obtain loaded CeO2Ce-TiO of2-USY molecular sieves.
Weighing 2g of octadecyl trimethyl ammonium bromide, stirring and dissolving in 200g of distilled water, and taking 4g of Ce-TiO2Putting the-USY molecular sieve in the solution, stirring for 30min at 60 ℃, washing with distilled water after finishing, and drying for 6h at 100 ℃ to obtain M-Ce-TiO2-USY molecular sieves. The loading capacity of the three molecular sieve surfactants is 0.2 percent and is respectively marked asCatalysts A1, A2, A3, TiO2The loading amounts of (A) and (B) are respectively 5%, 10% and 15%, and CeO2The loading amounts of the components are respectively 3.0%, 2.5% and 2.0% in sequence.
Respectively forming the catalysts A1, A2 and A3 into 20-mesh particles, filling the particles into a vertically placed tubular electrothermal reactor, wherein the filling mass is 2g, the temperature is 350 ℃, the pressure is 0.5MPa, and the mass space velocity is 2h-1The molar ratio of phenol to dimethyl carbonate is 1: 1, the conversion rate of phenol is 45%, 75% and 85%, and the selectivity of o-cresol is 72.1%, 70.2% and 68.6%.
Example 2
Respectively weighing 71g of isopropyl titanate and 57g of ethyl titanate, respectively dissolving in 200g of toluene, respectively dissolving 20g of USY in the solution, fully stirring, hermetically soaking at room temperature for 24h, finally steaming out the toluene by water bath and drying, and marking the product as TiO2-USY molecular sieves. Then 1g of Ce (NO)3) 3·6H2O was dissolved in 50ml of distilled water, and 10g of TiO was added2Stirring at room temperature for 3h, soaking at room temperature for 24h, stirring in 80 deg.C water bath, evaporating to dryness, drying at 110 deg.C for 12h, and roasting at 450 deg.C in muffle furnace for 5h to obtain CeO-loaded molecular sieve2Ce-TiO of2-USY molecular sieves.
Weighing 2g of octadecyl trimethyl ammonium bromide, stirring and dissolving in 200g of distilled water, and taking 4g of Ce-TiO2Putting the USY molecular sieve in the solution, stirring for 30min at 60 ℃, washing by distilled water after the stirring, and drying for 6h at 100 ℃ to obtain the M-Ce-TiO with 0.2 percent of surfactant load2-USY molecular sieve, successively denoted as catalysts A4, A5, TiO respectively2The supported amount of (B) is 10% respectively, CeO2The supported amounts of (A) and (B) were 3.0%, respectively.
Respectively molding the catalysts A4 and A5 into 30-mesh particles, and filling the particles in a vertically placed tubular electrothermal reactor, wherein the filling mass is 2g, the temperature is 350 ℃, the pressure is 0.5MPa, and the mass space velocity is 2h-1The molar ratio of phenol to dimethyl carbonate is 1: 1, the conversion rate of phenol is 77.4 percent and 75.6 percent respectively, and the selectivity of o-cresol is 71.2 percent and 70.7 percent respectively.
Example 3
Weighing 71g of isopropyl titanate, dissolving the isopropyl titanate in 200g of toluene, dissolving 20g of USY in the solution, fully stirring, hermetically soaking at room temperature for 24h, and finally steaming out the toluene through water bath and drying to obtain a product, wherein the product is marked as TiO2-USY molecular sieves, then 1g Ce (NO)3)3·6H2O was dissolved in 50ml of distilled water, and 10g of TiO was added2Stirring at room temperature for 3h, soaking at room temperature for 24h, stirring in 80 deg.C water bath, evaporating to dryness, drying at 110 deg.C for 12h, and roasting at 450 deg.C in muffle furnace for 5h to obtain loaded CeO2Ce-TiO of2-USY molecular sieves.
Weighing 2g, 3g and 5g of octadecyl trimethyl ammonium bromide, stirring and dissolving in 200g of distilled water, and taking 4g of Ce-TiO2Stirring the USY molecular sieve in the solution at 60 ℃ for 30min, washing with distilled water, and drying at 100 ℃ for 6h to obtain the M-Ce-TiO with the surfactant loading amounts of 0.2%, 0.3% and 0.5% respectively2-USY molecular sieve, successively marked as catalysts A6, A7, A8, TiO respectively2The supported amount of (B) is 10% respectively, CeO2The supported amounts of (A) and (B) were 3.0%, respectively.
Respectively molding the catalysts A6, A7 and A8 into 30-mesh particles, and filling the particles into a vertically arranged tubular electrothermal reactor, wherein the filling mass is 2g, the temperature is 350 ℃, the pressure is 0.5MPa, and the mass space velocity is 2h-1The molar ratio of phenol to dimethyl carbonate is 1: 1, the conversion rate of phenol is 70.6%, 77.4% and 73.3%, and the selectivity of o-cresol is 67.7%, 71.2% and 68.3%.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (14)
1. M-Ce-TiO2-a method for preparing a USY molecular sieve catalyst, comprising the steps of:
1) TiO loaded on USY molecular sieve2And CeO2；
2) Loading a surfactant M on the molecular sieve obtained in the step 1) to obtain the catalyst; wherein, the surfactant M is one or the combination of more than two of octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and hexadecyl pyridine.
2. The method according to claim 1, wherein the step 1) is performed according to the following scheme one or scheme two;
wherein, the first scheme comprises the following steps:
1.1a) mixing and stirring the USY molecular sieve and an organic titanium solution, dipping, and then removing a solvent;
1.2a) reaction of the product obtained in step 1.1a) with Ce (NO)3)3·6H2Mixing and stirring the O aqueous solution, dipping, removing the solvent and roasting;
the second scheme comprises the following steps:
1.1b) mixing USY molecular sieves with Ce (NO)3)3·6H2Mixing and stirring the O aqueous solution, dipping, and then removing the solvent;
1.2b) mixing the product obtained in step 1.1b) with an organic titanium solution, stirring, impregnating, removing the solvent and roasting.
3. The method according to claim 2, wherein in step 1.1a) of the first embodiment, the immersion time is 12 to 36 hours; in the step 1.2a), the dipping time is 12-36 h;
in the step 1.1b) of the second scheme, the dipping time is 12-36 h; in step 1.2b), the immersion time is 12 to 36 hours.
4. The production method according to claim 2, wherein the organic titanium is one or a combination of two or more selected from butyl titanate, isopropyl titanate, and ethyl titanate;
the solvent in the organic titanium solution is one or the combination of more than two of benzene, toluene, cyclohexane and normal hexane.
5. Root of herbaceous plantThe production method according to claim 2 or 4, wherein the Ce (NO) is3)3·6H2The dosage of O is 5-12% of the mass of the USY molecular sieve.
6. The method according to claim 5, wherein the catalyst is prepared by adding TiO to the solution2The loading of (A) is 5-15 wt%.
7. The method according to any one of claims 2 to 4, wherein the impregnation in each step is closed impregnation at room temperature; the solvent removal in each step is carried out by evaporating the solvent through water bath drying;
the roasting in each step is carried out at the temperature of 450-540 ℃.
8. The production method according to any one of claims 1 to 4, wherein the step 2) includes: mixing and stirring the molecular sieve obtained in the step 1) and a surfactant aqueous solution at 50-70 ℃ for 20-50min, and then washing and drying.
9. The method according to claim 8, further comprising a step of molding after the washing and drying in the step 2).
10. The preparation method of claim 8, wherein the concentration of the aqueous surfactant solution is 1-5 wt%, and the amount of the surfactant M is 10-50% of the mass of the USY molecular sieve.
11. M-Ce-TiO2The USY molecular sieve catalyst is characterized in that the USY molecular sieve is used as a carrier, and a surfactant M, TiO is loaded on the carrier2And CeO2Said TiO being2The load amount in the catalyst is 5 to 15 weight percent, and the CeO2The loading in the catalyst is 2-5 wt%; the loading amount of the surfactant M is 0.1-0.5 wt%; the surface activity isThe agent M is one or the combination of more than two of octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and hexadecyl pyridine.
12. M-Ce-TiO according to claim 112-USY molecular sieve catalyst, characterized in that it is prepared according to the preparation process of any one of claims 1 to 10.
13. A process for the production of o-cresol, wherein phenol and dimethyl carbonate are reacted in the presence of a catalyst to produce said o-cresol, wherein said catalyst is a catalyst obtainable by the process according to any one of claims 1 to 10 or the catalyst according to claim 11.
14. The method as claimed in claim 13, wherein the reaction is carried out in a fixed bed at a reaction temperature of 250-500 ℃, a pressure of 0.05-0.5MPa and a mass space velocity of 1-5h-1The molar ratio of phenol to dimethyl carbonate is 1: (0.5-2).
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| US3857899A (en) * | 1968-10-05 | 1974-12-31 | Sumitomo Chemical Co | Process for selective methylation of phenols |
| CN101811938A (en) * | 2010-04-30 | 2010-08-25 | 常州大学 | Method for catalytically synthesizing p-methylphenol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3857899A (en) * | 1968-10-05 | 1974-12-31 | Sumitomo Chemical Co | Process for selective methylation of phenols |
| CN101811938A (en) * | 2010-04-30 | 2010-08-25 | 常州大学 | Method for catalytically synthesizing p-methylphenol |
| CN103254039A (en) * | 2013-06-08 | 2013-08-21 | 济南卡博唐生物科技有限公司 | Preparation method of orthocresol |
Non-Patent Citations (3)
| Title |
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| Ce/USY分子筛催化苯酚甲醇烷基化;李艳歌等;《精细石油化工》;20170331;第34卷(第2期);30-33 * |
| Mg/Ce-USY分子筛催化苯酚甲醇烷基化;明阳等;《分子催化》;20170228;第31卷(第1期);46-52 * |
| TiO2/MCM-41催化苯酚与碳酸二甲酯邻位烷基化研究;郑国才;《化学研究与应用》;20160131;第28卷(第1期);89-95 * |
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