CN109851469B - Method for preparing styrene through anaerobic dehydrogenation of methanol and alkylation coupling reaction of toluene side chain - Google Patents
Method for preparing styrene through anaerobic dehydrogenation of methanol and alkylation coupling reaction of toluene side chain Download PDFInfo
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Abstract
The invention discloses a method for preparing styrene by coupling reaction of anaerobic dehydrogenation of methanol and alkylation of a toluene side chain; in the method, raw material gas containing toluene and methanol is introduced into a reactor to contact with a bifunctional catalyst, the methanol is subjected to an anaerobic dehydrogenation reaction to generate formaldehyde, and the obtained formaldehyde and the toluene are subjected to a side alkylation reaction to generate styrene. The method can improve the conversion rate of toluene, the utilization rate of methanol and the yield of styrene by coupling two reactions.
Description
Technical Field
The invention relates to a method for preparing styrene by anaerobic dehydrogenation of methanol and alkylation coupling reaction of a toluene side chain, belonging to the field of catalysis.
Background
Styrene is used as an important monomer of polymers and is mainly used for producing chemical products such as Polystyrene (PS), acrylonitrile-butadiene resin (ABS), Expanded Polystyrene (EPS), styrene-butadiene rubber (SBR) and the like. The traditional styrene production technology is an ethylbenzene dehydrogenation method, and the target product styrene is mainly obtained through Friedel-Craft reaction and catalytic dehydrogenation reaction. Therefore, a new styrene production process has received much attention.
Japanese researchers Sidorenko et al (Dokl. Akad. NaukSSSR,1967,173(1): 132-. However, the process route still has the problems of low toluene conversion rate, low serious methanol decomposition utilization rate, low product styrene selectivity, high ethylbenzene content and the like, and further industrial application of the toluene-methanol side chain alkylation process is hindered.
Disclosure of Invention
According to one aspect of the invention, the method for preparing styrene through the coupling reaction of anaerobic dehydrogenation of methanol and alkylation of a toluene side chain is provided, the conversion rate of toluene and the utilization rate of methanol can be effectively improved, and the yield of styrene is improved; solves the problems of low conversion rate and low selectivity existing in the prior preparation of styrene by the side chain alkylation reaction of toluene and methanol.
The method for preparing styrene by the anaerobic dehydrogenation of methanol and the alkylation coupling reaction of a toluene side chain is characterized by at least comprising the following steps: introducing raw material gas containing methanol and toluene into a reactor, contacting with a catalyst, and reacting to prepare the styrene;
the catalyst comprises a dehydrogenation catalyst and a basic molecular sieve;
the molar ratio of toluene to methanol in the raw material gas is 0.1-10: 1; the reaction temperature is 300-600 ℃, and the reaction pressure is 0.1-10 MPa; the total mass airspeed of the toluene and methanol raw material gas is 0.1-6 h-1。
Alternatively, the upper limit of the molar ratio of toluene to methanol in the feed gas is selected from 0.2:1, 1:3, 1:1, 3:1, 6:1, 9:1, or 10: 1; the lower limit is selected from 0.1:1, 0.2:1, 1:3, 1:1, 3:1, 6:1 or 9: 1.
Optionally, the upper reaction temperature limit is selected from 350 ℃, 380 ℃, 420 ℃, 460 ℃, 500 ℃ or 600 ℃; the lower limit is selected from 300 deg.C, 350 deg.C, 380 deg.C, 420 deg.C, 460 deg.C or 500 deg.C.
Optionally, the upper reaction pressure limit is 0.1MPa, 0.5MPa, 1.0MPa, 2.0MPa, or 10 MPa; the lower limit is selected from 0.1MPa, 0.5MPa, 1.0MPa or 2.0 MPa.
Alternatively, the upper limit of the total mass space velocity of the toluene and methanol raw gas is selected from 0.2h-1、1h-1、3h-1、5h-1Or 6h-1(ii) a The lower limit is selected from 0.1h-1、0.2h-1、1h-1、3h-1Or 5h-1。
Optionally, the molar ratio of toluene to methanol in the raw material gas is 0.2-9: 1; the reaction temperature is 350-500 ℃, and the reaction pressure is 0.1-2 MPa; the total mass airspeed of the toluene and methanol raw material gas is 0.2-5 h-1。
Optionally, the reactor comprises at least one catalyst bed containing the catalyst.
The mass ratio of the basic molecular sieve to the dehydrogenation catalyst is 0.1-10: 1.
Optionally, the upper limit of the mass ratio of the basic molecular sieve to the dehydrogenation catalyst is selected from 1:2, 2:1, 4:1, 6:1, 8:1, or 10: 1; the lower limit is selected from 0.1:1, 1:2, 2:1, 4:1, 6:1 or 8: 1.
Optionally, the mass ratio of the basic molecular sieve to the dehydrogenation catalyst is 0.5-5: 1.
Optionally, the dehydrogenation catalyst is selected from at least one of an alkali metal refractory salt, a supported metal oxide, a metal ion exchanged molecular sieve.
The basic molecular sieve is selected from at least one of basic molecular sieves.
Optionally, the catalyst comprises a dehydrogenation catalyst, a basic molecular sieve;
the dehydrogenation catalyst is selected from at least two of alkali metal refractory salt, supported metal oxide, metal ion exchanged molecular sieve, supported metal oxide or metal ion exchanged molecular sieve;
the basic molecular sieve is selected from at least one of basic molecular sieves;
the mass ratio of the basic molecular sieve to the dehydrogenation catalyst is 0.1-10: 1.
Optionally, the mass loading of the metal oxide in the loaded metal oxide is 10-30%.
Optionally, the upper limit of the mass loading of the metal oxide in the supported metal oxide is selected from 15%, 20%, 25% or 30%; the lower limit is selected from 10%, 15%, 20% or 25%.
Optionally, the alkali metal refractory salt is obtained by grinding, drying and roasting an alkali metal refractory salt compound;
the alkali metal refractory salt compound is selected from at least one of sodium carbonate, sodium borate and sodium molybdate;
the carrier of the supported metal oxide is SiO2The metal oxide is at least one of copper oxide, silver oxide, zinc oxide and zirconium oxide;
the metal ions in the metal ion exchanged molecular sieve are selected from at least one of sodium ions, copper ions, cerium ions, manganese ions and magnesium ions; the molecular sieve is a ZSM-5 molecular sieve.
Optionally, the basic molecular sieve is selected from at least one of alkali metal ion exchange modified FAU structure molecular sieves; in the FAU-structured molecular sieve modified by alkali metal ion exchange, the exchange degree of alkali metal ions is 20-90%.
Alternatively, the upper limit of the degree of exchange of alkali metal ions is selected from 23.1%, 29.8%, 51.3%, 56.1%, 58.8%, 60.9%, 62.3%, 63.2%, 63.3%, 68.7%, or 90%; the lower limit is selected from 20%, 23.1%, 29.8%, 51.3%, 56.1%, 58.8%, 60.9%, 62.3%, 63.2%, 63.3%, or 68.7%.
Optionally, the alkali metal ions are selected from at least one of potassium ions, rubidium ions and cesium ions; the FAU structure molecular sieve is selected from at least one of X-type molecular sieve and Y-type molecular sieve.
Optionally, the alkali metal refractory salt is prepared by drying an alkali metal refractory salt compound at 110-130 ℃ and roasting at 500-650 ℃ for 1-6 h.
Optionally, the molar ratio of silicon atoms to aluminum atoms of the FAU-structure molecular sieve is 1-10.
Alternatively, the FAU structure molecular sieve has an upper limit on the molar ratio of silicon to aluminum atoms selected from 1.17, 2.89, 4.53, 5.54, 8.98, 9.79, or 10; the lower limit is selected from 1, 1.17, 2.89, 4.53, 5.54, 8.98 or 9.79.
Optionally, the basic molecular sieve is an alkali metal type X molecular sieve and/or a alkali metal type Y molecular sieve, and the alkali metal element is at least one selected from K, Rb, and Cs.
Optionally, the method for preparing the bifunctional catalyst is characterized by at least comprising the following steps:
(a) obtaining a dehydrogenation catalyst;
(b) obtaining an alkaline molecular sieve;
(c) ball-milling the dehydrogenation catalyst and the alkaline molecular sieve on a ball mill for 2-20 hours respectively, and then mixing uniformly to perform catalyst molding; or
And (3) ball-milling the mixture containing the dehydrogenation catalyst and the alkaline molecular sieve for 2-20 hours on a ball mill, and then carrying out catalyst molding.
Optionally, the dehydrogenation catalyst in step (a) is selected from at least one of an alkali metal refractory salt, a supported metal oxide, a metal ion exchanged molecular sieve;
the method for obtaining the supported metal oxide comprises a deposition precipitation method or an equivalent-volume impregnation method;
the method for obtaining the metal ion exchanged molecular sieve in the dehydrogenation catalyst comprises the following steps: carrying out ion exchange on the molecular sieve by using a metal salt precursor solution, carrying out suction filtration, washing, drying and roasting to obtain the metal ion exchanged molecular sieve;
the method for obtaining the basic molecular sieve in the step (b) comprises the following steps: and (3) carrying out ion exchange on the molecular sieve by adopting an alkali metal salt precursor solution, carrying out suction filtration, washing, drying and roasting to obtain the alkaline molecular sieve.
Optionally, the metal ion salt precursor is one of nitrate and/or acetate of the corresponding metal.
Optionally, the upper concentration limit of the metal salt precursor solution is selected from 0.3mol/L, 0.4mol/L or 0.6 mol/L; the lower limit is selected from 0.2mol/L, 0.3mol/L or 0.4 mol/L.
Optionally, the concentration of the metal salt precursor solution is 0.2-0.6 mol/L.
Optionally, the upper concentration limit of the alkali metal salt precursor solution is selected from 0.3mol/L, 0.4mol/L or 0.6 mol/L; the lower limit is selected from 0.2mol/L, 0.3mol/L or 0.4 mol/L.
Optionally, the concentration of the alkali metal salt precursor solution is 0.2-0.6 mol/L.
Alternatively, the precipitation method is prepared by precipitating soluble salts of corresponding metals on a carrier under the action of a precipitating agent. The soluble salt is preferably nitrate or acetate, and the precipitant is at least one selected from sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonia water and potassium carbonate.
As a specific embodiment, the preparation steps of the deposition precipitation method are as follows:
(a) adding a precipitator into a suspension containing metal soluble salt and a carrier under the stirring condition of 55-90 ℃;
(b) aging at 75-85 ℃ for at least 5h, separating to obtain a solid, drying at 110-130 ℃ and roasting at 500-650 ℃ for 1-6 h to obtain the supported metal oxide.
As a specific embodiment, the isometric impregnation method comprises the following steps:
and (3) carrying out isometric impregnation on the carrier by using impregnation liquid containing metal ions, drying at 110-130 ℃, and roasting at 500-650 ℃ for 1-6 h to obtain the supported metal oxide.
As a specific embodiment, the preparation steps of the metal ion-exchanged ZSM-5 molecular sieve are as follows: respectively carrying out ion exchange on a ZSM-5 molecular sieve with a certain mass by using 0.2-0.6 mol/L of metal nitrate or/and acetate precursor solution, carrying out ion exchange at 80 ℃ for 4h when the solid-liquid ratio is 10:1, carrying out suction filtration, washing and drying, roasting the obtained solid in a muffle furnace at 550 ℃ for 6h, and repeating the process for 2 times to obtain the metal ion exchanged ZSM-5 molecular sieve.
As a specific embodiment, the alkali metal type X type molecular sieve or Y type molecular sieve is prepared by the following steps: respectively adopting 0.2-0.6 mol/L alkali metal nitrate precursor solution to carry out ion exchange on a NaX or NaY molecular sieve with certain mass, carrying out ion exchange for 4 hours at 80 ℃ when the solid-liquid ratio is 10:1, carrying out suction filtration, washing and drying, roasting the obtained solid for 6 hours at 550 ℃ in a muffle furnace, and repeating the process for 2 times to obtain the alkali metal X or Y molecular sieve.
As a specific embodiment, the method for preparing styrene by the anaerobic dehydrogenation of methanol and the side chain alkylation coupling reaction of toluene is carried out in a fixed bed reactor, and the steps are briefly as follows: putting a required amount of catalyst in a constant temperature area of a reactor, filling quartz sand at two ends of the reactor, and activating the catalyst for 1-2 hours at the temperature of 400-650 ℃ in a helium atmosphere. And then cooling to the reaction temperature and setting the reaction pressure, injecting the mixture of the toluene and the methanol which are prepared in proportion into a preheater by a micro pump, mixing with carrier gas, introducing into a reactor, carrying out contact reaction with the bifunctional catalyst, and analyzing the reaction product by a gas chromatograph.
In the present invention, the particle size unit "mesh" refers to the number of holes per inch of distance on a screen used to screen different particle sizes. For example, 20 mesh means a sieve having 20 holes per inch, and 20 to 40 mesh means a particle size that can pass through the 20 mesh sieve and be retained by the 40 mesh sieve.
The catalyst is a bifunctional catalyst, and is compounded with the basic molecular sieve catalyst through the dehydrogenation catalyst, so that on one hand, the reaction rate of the methanol dehydrogenation process for generating the formaldehyde can be improved, the occurrence of methanol decomposition side reaction is inhibited, the utilization rate of the methanol is improved, the obtained formaldehyde is used as a real alkylating reagent to react with the toluene, the toluene conversion rate can be further improved, the side chain alkylation rate is increased, and the styrene yield is improved; on the other hand, the addition of the dehydrogenation catalyst effectively inhibits the benzene naphthenation reaction of the toluene and the methanol, and reduces the generation of byproducts such as xylene, toluene and the like.
The invention can produce the beneficial effects that:
(1) the method for preparing styrene by adopting the coupling reaction of anaerobic dehydrogenation of methanol and alkylation of the side chain of toluene can improve the conversion rate of toluene, the utilization rate of methanol and the selectivity of styrene as a product;
(2) the bifunctional catalyst provided by the invention has better stability, and has no obvious inactivation phenomenon after continuous operation for 500 hours on a fixed bed reactor;
(3) the method for preparing styrene through the coupling reaction of anaerobic dehydrogenation of methanol and alkylation of the side chain of toluene has simple and convenient operation, meets the requirements of industrial application, and is convenient for large-scale industrial production.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present invention were all purchased from commercial sources.
In the embodiment of the invention, the toluene conversion rate, the methanol utilization rate and the styrene yield are calculated according to the following formulas:
example 1: preparation of basic molecular sieves
The molecular sieves employed in the examples were all from commercial sources.
Preparing the alkali metal ion modified X-type and Y-type molecular sieves:
taking 20g of NaX or NaY molecular sieve, respectively adopting 0.2-0.6 mol/L of precursor solution of potassium nitrate, rubidium nitrate, cesium nitrate and the like to carry out ion exchange on the molecular sieve, wherein the solid-liquid ratio is 10:1, the exchange is carried out for 4H at 80 ℃, the solid obtained after suction filtration, washing and drying is roasted for 6H at 550 ℃ in a muffle furnace, then the process is repeated for 2 times to obtain the alkali metal type X-type and Y-type molecular sieves, and the samples are respectively numbered as H-1#～H-6#。
The obtained sample numbers, the types and concentrations of the precursor solutions, and the ion exchange degrees are shown in Table 1. The obtained sample was subjected to elemental analysis using an XRF elemental analyzer (panabalytic Axios model 2.4 KW), the ion exchange degree was calculated from the sodium content of the sample before and after the exchange, and the calculation formula was:
the ion exchange degree is 100% × (mole percent of Na element in the molecular sieve before exchange-mole percent of Na element in the molecular sieve after exchange)/mole percent of Na element in the molecular sieve before exchange.
TABLE 1
| Sample numbering | Molecular sieves | Precursor solution and concentration | Degree of ion exchange/%) |
| H-1# | NaX(Si/Al＝1.17) | 0.4mol/L potassium nitrate | 62.3 |
| H-2# | NaX(Si/Al＝1.17) | 0.4mol/L rubidium nitrate | 56.1 |
| H-3# | NaX(Si/Al＝1.17) | 0.4mol/L cesium nitrate | 51.3 |
| H-4# | NaY(Si/Al＝2.89) | 0.4mol/L potassium nitrate | 68.7 |
| H-5# | NaY(Si/Al＝2.89) | 0.4mol/L rubidium nitrate | 63.2 |
| H-6# | NaY(Si/Al＝2.89) | 0.4mol/L cesium nitrate | 58.8 |
| H-7# | NaX(Si/Al＝4.53) | 0.2mol/L rubidium nitrate | 23.1 |
| H-8# | NaX(Si/Al＝8.98) | 0.6mol/L cesium nitrate | 60.9 |
| H-9# | NaY(Si/Al＝5.54) | 0.2mol/L rubidium nitrate | 29.8 |
| H-10# | NaY(Si/Al＝9.79) | 0.6mol/L cesium nitrate | 63.3 |
Example 2: preparation of dehydrogenation catalyst
Alkali metal refractory salt preparation: the alkali metal refractory salt is selected from sodium carbonate and boronAt least one of sodium, sodium molybdate and sodium metaaluminate. Firstly, grinding the alkali metal refractory salt, and then drying at 110 ℃ and roasting at 550 ℃ for 6 h. Obtaining alkali metal refractory salt with the sample number of DE-1#～DE-6#。
The obtained sample numbers, the types of the alkali metal refractory salts, and the mixing ratios are shown in Table 2. Wherein the mixing proportion is calculated according to the mass of the alkali metal refractory salt.
| Sample numbering | Alkali metal refractory salt species | Mixing ratio |
| DE-1# | Sodium carbonate | -- |
| DE-2# | Sodium borate | -- |
| DE-3# | Sodium molybdate | -- |
| DE-4# | Sodium carbonate + sodium borate | 1:2 |
| DE-5# | Sodium carbonate + sodium molybdate | 1:1 |
| DE-6# | Sodium carbonate + sodium borate | 2:1 |
The load type metal oxide carrier is SiO2The metal oxide is at least one selected from the group consisting of copper oxide, silver oxide, zinc oxide, and zirconium oxide. The preparation method of the load type metal oxide is a deposition precipitation method or an isometric immersion method.
The preparation method of the supported metal oxide by the deposition precipitation method comprises the following steps:
(a) adding a precipitant into a suspension containing metal soluble salt and a carrier under the condition of stirring at 80 ℃;
(b) aging at 80 deg.C for at least 5h, separating to obtain solid, oven drying at 130 deg.C, and baking at 550 deg.C for 6h to obtain supported metal oxide with sample number of DE-7#～DE-13#。
The method for preparing the supported metal oxide by the isometric impregnation method comprises the following steps: impregnating the carrier with an impregnating solution containing metal ions in an equal volume, drying at 110 ℃, and roasting at 550 ℃ for 6 hours to obtain the supported metal oxide, wherein the sample number is DE-14#～DE-16#。
The obtained sample numbers, types of supported metal oxides, preparation methods, and mixing ratios are shown in table 3, for example. Wherein the mixing ratio is calculated according to the mass of the supported metal oxide.
TABLE 3
In the ZSM-5 molecular sieve exchanged by metal ions, the metal ions are selected from at least one of sodium ions, copper ions, cerium ions, manganese ions and magnesium ions, and the preparation steps are as follows:
taking 5g of ZSM-5 molecular sieve, respectively carrying out ion exchange on the molecular sieve by using 0.2-0.6 mol/L of metal nitrate precursor solution, carrying out ion exchange at 80 ℃ for 4h when the solid-liquid ratio is 10:1, carrying out suction filtration, washing and drying, roasting the obtained solid in a muffle furnace at 550 ℃ for 6h, then repeating the process for 2 times to obtain the metal ion exchanged ZSM-5 molecular sieve, wherein the obtained sample is numbered DE-17#～DE-24#。
The sample numbers, the types of molecular sieves, and the mixing ratios are shown in Table 4. Wherein the mixing proportion is calculated according to the concentration of the ion exchange liquid.
TABLE 4
| Sample numbering | Molecular sieve species | Precursor solution and concentration |
| DE-17# | Na-ZSM-5 | 0.2mol/LNaNO3 |
| DE-18# | Cu-ZSM-5 | 0.4mol/L Cu(NO3)2 |
| DE-19# | Ce-ZSM-5 | 0.4mol/L Ce(NO3)3 |
| DE-20# | Mn-ZSM-5 | 0.6mol/LMn(NO3)2 |
| DE-21# | Mg-ZSM-5 | 0.6mol/L Mg(NO3)2 |
| DE-22# | Mn,Mg-ZSM-5 | 0.2mol/LMn(NO3)2+0.4mol/L Mg(NO3)2 |
| DE-23# | Cu,Mn-ZSM-5 | 0.2mol/L Cu(NO3)2+0.2mol/L Mn(NO3)2 |
| DE-24# | Cu,Ce-ZSM-5 | 0.4mol/L Cu(NO3)2+0.2mol/L Ce(NO3)3 |
Example 3: preparation of a bifunctional catalyst
Basic molecular sieve H-1 prepared in example 1#～H-6#And practiceDehydrogenation catalyst DE-1 obtained in example 2#～DE-24#At least one of the two is mixed, molded, crushed and sieved to 20-40 meshes, and the serial number of the obtained bifunctional catalyst is CAT-1#～CAT-40#. Wherein CAT-1#～CAT-20#Respectively ball-milling the alkaline molecular sieve and the dehydrogenation catalyst on a ball mill for 10h (CAT-1)#～CAT-5#)、15h(CAT-6#～CAT-15#)、20h(CAT-16#～CAT-20#) After being mixed evenly, the mixture is molded; CAT-21#～CAT-40#Mixing the basic molecular sieve and the dehydrogenation catalyst uniformly, and ball-milling for 10h (CAT-21) on a ball mill#～CAT-25#)、15h(CAT-26#～CAT-35#)、20h(CAT-36#～CAT-40#) And then molding is carried out.
The relationship between the number of the obtained bifunctional catalyst and the types and mass ratios of the basic molecular sieve and the dehydrogenation catalyst contained in the bifunctional catalyst is shown in Table 5.
TABLE 5
| Numbering | Species and mass ratio of bifunctional catalyst | Numbering | Species and mass ratio of bifunctional catalyst |
| CAT-1# | H-1#:DE-7#＝2:1 | CAT-21# | H-3#:DE-11#＝6:1 |
| CAT-2# | H-2#:DE-7#＝2:1 | CAT-22# | H-3#:DE-12#＝6:1 |
| CAT-3# | H-3#:DE-7#＝2:1 | CAT-23# | H-8#:DE-13#＝8:1 |
| CAT-4# | H-4#:DE-7#＝2:1 | CAT-24# | H-8#:DE-14#＝8:1 |
| CAT-5# | H-5#:DE-7#＝2:1 | CAT-25# | H-8#:DE-15#＝8:1 |
| CAT-6# | H-6#:DE-7#＝2:1 | CAT-26# | H-8#:DE-16#＝8:1 |
| CAT-7# | H-7#:DE-7#＝2:1 | CAT-27# | H-8#:DE-17#＝8:1 |
| CAT-8# | H-8#:DE-7#＝2:1 | CAT-28# | H-8#:DE-18#＝8:1 |
| CAT-9# | H-9#:DE-7#＝2:1 | CAT-29# | H-8#:DE-19#＝8:1 |
| CAT-10# | H-10#:DE-7#＝2:1 | CAT-30# | H-8#:DE-20#＝10:1 |
| CAT-11# | H-3#:DE-1#＝4:1 | CAT-31# | H-8#:DE-21#＝10:1 |
| CAT-12# | H-3#:DE-2#＝4:1 | CAT-32# | H-8#:DE-22#＝10:1 |
| CAT-13# | H-3#:DE-3#＝4:1 | CAT-33# | H-8#:DE-23#＝10:1 |
| CAT-14# | H-3#:DE-4#＝4:1 | CAT-34# | H-8#:DE-24#＝10:1 |
| CAT-15# | H-3#:DE-5#＝4:1 | CAT-35# | H-3#:DE-7#＝1:2 |
| CAT-16# | H-3#:DE-6#＝6:1 | CAT-36# | H-8#:DE-7#＝1:2 |
| CAT-17# | H-3#:DE-7#＝6:1 | CAT-37# | H-3#:DE-1#:DE-7#＝8:1:1 |
| CAT-18# | H-3#:DE-8#＝6:1 | CAT-38# | H-3#:DE-7#:DE-17#＝8:1:1 |
| CAT-19# | H-3#:DE-9#＝6:1 | CAT-39# | H-3#:DE-7#＝4:1 |
| CAT-20# | H-3#:DE-10#＝6:1 | CAT-40# | H-3#:DE-7#＝4:1 |
Comparative example 1 catalyst preparation
H-3 from example 1#And H-6#The alkaline molecular sieve is directly used as a contrast catalyst, and is crushed and sieved into 20-40 meshes with the serial number of CAT-D1 after being molded#And CAT-D2#。
Example 4: catalyst evaluation
1g of the bifunctional catalyst prepared in example 3 and the catalyst prepared in comparative example 1 were charged into a small fixed-bed reactor, respectively, and both ends were packed with quartz sand. The catalyst is firstly activated for 1h at 550 ℃ under the He atmosphere with the flow rate of 40mL/min, then the temperature is reduced to the reaction temperature, raw materials of toluene and methanol are pumped in by a trace feed pump to react, and the feeding molar ratio, the space velocity, the reaction pressure and the reaction temperature of the toluene and the methanol are shown in a table 6. The product was analyzed by gas chromatography, and the reaction results are shown in Table 6.
TABLE 6
The results of the above examples show that the bifunctional catalyst provided by the present invention can improve the conversion rate of toluene, the utilization rate of methanol, and the yield of styrene in the product when used in the reaction of preparing styrene from toluene and methanol.
Although the present invention has been described with reference to a few embodiments, it should be understood that the present invention is not limited to the above embodiments, but rather, the present invention is not limited to the above embodiments.
Claims (5)
1. A method for preparing styrene by methanol anaerobic dehydrogenation and toluene side chain alkylation coupling reaction is characterized by at least comprising the following steps: introducing raw material gas containing methanol and toluene into a reactor, contacting with a catalyst, and reacting to prepare the styrene; the molar ratio of toluene to methanol in the raw material gas is 0.1-10: 1, the reaction temperature is 300-600 ℃, the reaction pressure is 0.1-10 MPa, and the total mass space velocity of the toluene and methanol raw material gas is 0.1-6 h-1；
The reactor comprises at least one catalyst bed layer containing the catalyst;
the catalyst comprises a dehydrogenation catalyst and a basic molecular sieve;
the dehydrogenation catalyst is selected from alkali metal refractory salts;
the alkali metal salt difficult to melt is sodium borate;
the basic molecular sieve is selected from at least one of alkali metal ion exchange modified FAU structure molecular sieves;
the mass ratio of the basic molecular sieve to the dehydrogenation catalyst is 0.1-10: 1.
2. The method for preparing styrene through the oxygen-free dehydrogenation of methanol and the alkylation coupling reaction of a toluene side chain according to claim 1, wherein the alkali metal refractory salt is obtained by grinding, drying and roasting an alkali metal refractory salt compound.
3. The method for preparing styrene through the anaerobic dehydrogenation of methanol and the side chain alkylation coupling reaction of toluene according to claim 1, wherein in the alkali metal ion exchange modified FAU structure molecular sieve, the exchange degree of alkali metal ions is 20-90%;
the alkali metal ions are selected from at least one of potassium ions, rubidium ions and cesium ions, and the FAU structure molecular sieve is selected from at least one of X-type molecular sieve and Y-type molecular sieve.
4. The method for preparing styrene by the anaerobic dehydrogenation of methanol and the alkylation coupling reaction of toluene side chain according to claim 1, wherein the preparation method of the catalyst at least comprises the following steps:
(a) obtaining a dehydrogenation catalyst;
(b) obtaining an alkaline molecular sieve;
(c) respectively ball-milling the dehydrogenation catalyst and the alkaline molecular sieve on a ball mill for 2-20 hours, and then uniformly mixing to form the catalyst, or ball-milling a mixture containing the dehydrogenation catalyst and the alkaline molecular sieve on the ball mill for 2-20 hours and then forming the catalyst.
5. The method for preparing styrene by the anaerobic dehydrogenation of methanol and the side chain alkylation coupling reaction of toluene according to claim 4, wherein the dehydrogenation catalyst in step (a) is selected from alkali metal refractory salts; the method for obtaining the basic molecular sieve in the step (b) comprises the following steps: and (3) carrying out ion exchange on the molecular sieve by adopting an alkali metal salt precursor solution, and then carrying out solid-liquid separation, washing, drying and roasting to obtain the alkaline molecular sieve.
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