CN106622336B - Catalyst for preparing styrene and ethylbenzene by toluene side-chain alkylation reaction and application thereof - Google Patents
Catalyst for preparing styrene and ethylbenzene by toluene side-chain alkylation reaction and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing styrene and ethylbenzene by a toluene side chain alkylation reaction and application thereof, and mainly solves the problems of low utilization rate of a C1 raw material, low toluene conversion rate and poor catalyst stability of the existing catalyst for preparing ethylbenzene and styrene by toluene side chain alkylation. The catalyst takes a modified X or Y molecular sieve as an active component, and takes at least one of IIIA group elements, at least one of VIIB group elements, at least one of alkali metal elements, at least one of alkaline earth metal elements and at least one of lanthanide as the modified component; the technical scheme that the toluene and the C1 raw material are contacted with the catalyst to react to generate the ethylbenzene and the styrene better solves the problem and can be used for industrial production for preparing the ethylbenzene and the styrene by the side chain alkylation reaction of the toluene and the methanol.
Description
Technical Field
The invention relates to a catalyst for preparing styrene and ethylbenzene by side-chain alkylation of toluene and application thereof.
Background
Styrene is an important organic chemical raw material, is mainly used for producing products such as polystyrene, styrene-butadiene rubber, ABS resin, unsaturated resin and the like, can also be used in the fields of pharmacy, pesticides, dyes and the like, and has wide application. Currently, the production of most commercial styrenes is carried out in two steps. Firstly, benzene and ethylene are subjected to Friedel-Craft alkylation reaction under the action of a catalyst to generate ethylbenzene, and then the ethylbenzene is subjected to catalytic dehydrogenation to generate styrene. The route has high raw material cost, long process flow, large equipment investment and higher energy consumption. The toluene side-chain alkylation reaction is a potential application prospect route for producing styrene and ethylbenzene, Sidorenko and the like report that toluene and methanol can generate side-chain alkylation reaction on X-type and Y-type molecular sieve catalysts exchanged by alkali metal ions to generate styrene in one step for the first time in 1967. The process has wide raw material source, low cost, mild reaction condition and low energy consumption, has good industrial development value and application prospect, and has attracted great attention of researchers.
The mechanism of preparing styrene and ethylbenzene by the toluene side chain alkylation reaction is that C1 raw materials such as methanol and the like are decomposed under the catalysis of alkali to obtain formaldehyde as a reaction intermediate, the methyl of the toluene is activated by an alkali active site to become carbanions, then the Adol-type reaction of the carbanions on the formaldehyde is carried out, and the styrene is obtained after the product is dehydrated. Part of the styrene and hydrogen generated in the reaction are subjected to hydrogenation reaction to generate ethylbenzene. The catalyst for the toluene side alkylation belongs to a solid base catalyst, and needs enough strength and quantity of base centers to catalyze dehydrogenation of C1 raw material such as methanol to generate formaldehyde and activate toluene methyl C-H bond to generate methyl carbanion. Meanwhile, the toluene methanol side-chain alkylation reaction process is also an acid-base concerted catalysis reaction mainly based on base active site catalysis. Experiments prove that the single alkali active site has low efficiency of catalyzing the toluene methanol side chain alkylation. During the reaction process, toluene molecules need to be adsorbed and stabilized by Lewis acid, otherwise, the toluene conversion rate is low. However, if the catalyst is too basic, methanol and the intermediate product formaldehyde are easily decomposed further into CO and hydrogen; if the catalyst is too acidic, alkylation of the benzene ring to produce benzene and xylene occurs primarily. Therefore, the catalyst needs to have a suitable acid-base match. In addition, the adsorption equilibrium of the toluene and the C1 raw material is also one of the factors influencing the toluene side alkylation reaction, and the proper pore channel structure and cage size are favorable for the adsorption equilibrium of the toluene and the C1 raw material.
Various catalytic materials have been tried for the toluene side-alkylation reaction to produce styrene and ethylbenzene, various types of modified molecular sieves such as X, Y, USY, L, β, ZSM-5, and basic oxides such as MgO, CaO, MgO-TiO2、CaO-TiO2And the like, all show certain catalytic performance when being applied to catalysts for toluene side alkylation reaction. Modified by K, Cs ion exchange as reported in US 4463204The X or Y type molecular sieve improves the conversion rate of toluene in the side-chain alkylation reaction of toluene and has the total selectivity of ethylbenzene and styrene of 90 percent. U.S. Pat. No. 4, 4140726 reports that K, Rb, Cs and B, P modified X or Y type molecular sieve catalysts have higher toluene conversion, but the total selectivity of ethylbenzene and styrene is not ideal. US 8318999B2 reports an X-type molecular sieve catalyst modified with Cs and one of Ga, B, Co, which method improves styrene selectivity. CN101623650A adopts K, Cs to carry out ion exchange on X or Y type molecular sieve, and the method of loading B, P and alkali metal or alkaline earth metal improves the stability of the catalyst. CN 101623649A is used for treating the X or Y type molecular sieve modified by alkali metal with ammonia gas at high temperature, thus improving the activity and stability of the catalyst. The reported modified X or Y type molecular sieves have certain catalytic effect in the reaction of preparing styrene and ethylbenzene by alkylating toluene side chains. However, how to achieve both toluene conversion and C1 feedstock utilization is an important technical challenge in toluene side alkylation reactions. The reported catalyst is not ideal enough in the aspect of simultaneously achieving high toluene conversion rate and high material utilization rate, has a large gap for the requirement of industrial production, and has the defect of low hydrothermal stability. Therefore, the development of a catalyst which can simultaneously achieve proper toluene conversion rate and C1 raw material utilization rate in the toluene side alkylation reaction, has high ethylbenzene and styrene selectivity and high hydrothermal stability is one of the key factors for realizing the route industrial production of ethylbenzene and styrene by the toluene side alkylation reaction. In addition, higher styrene selectivity is also beneficial to improving economic benefits.
Disclosure of Invention
The invention aims to solve the technical problems that the existing catalyst for preparing styrene and ethylbenzene by toluene side chain alkylation has low utilization rate of C1 raw materials, low toluene conversion rate and poor catalyst stability, and provides a novel catalyst for preparing ethylbenzene and styrene by toluene side chain alkylation.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a catalyst for preparing styrene and ethylbenzene by the side-chain alkylation reaction of toluene comprises the following components:
a) at least one of an X molecular sieve or a Y molecular sieve; and a modifying component supported thereon:
b) at least one element in IIIA group, wherein the mass ratio of the element to the molecular sieve carrier is (0.05-10): 100, respectively;
c) at least one element in the VIIB group, wherein the mass ratio of the element to the molecular sieve carrier is (0.05-10): 100, respectively;
d) at least one alkali metal element, wherein the mass ratio of the element to the molecular sieve carrier is (0.1-20): 100, respectively;
e) at least one alkaline earth metal element, wherein the mass ratio of the element to the molecular sieve carrier is (0.05-10): 100, respectively;
f) at least one lanthanide element, wherein the mass ratio of the element to the molecular sieve carrier is (0.05-10): 100.
in the above technical solution, the raw material C1 is at least one of methanol, formaldehyde, paraformaldehyde and methylal, and preferably at least one of methanol and formaldehyde; the molecular sieve is selected from SiO2/Al2O3At least one of an X molecular sieve and a Y molecular sieve of 2-5, wherein the preferred scheme is the X molecular sieve; in the IIIA group elements, at least one of B, Al, Ga and In is preferably selected, and at least one of B or Al is more preferably selected, and the mass ratio of the element to the molecular sieve carrier is (0.05-10): 100, and the preferable scheme is (0.1-2): 100, respectively; in the VIIB group element, the preferable scheme is that at least one of Mn and Re and the mass ratio of the molecular sieve carrier is (0.05-10): 100, and the preferable scheme is (0.1-2): 100, respectively; the alkali metal element is selected from K, Rb or at least one of Cs, more preferably Cs, and the mass ratio of the alkali metal element to the molecular sieve carrier is (0.1-20): 100, preferably (0.5-10): 100, respectively; the alkaline earth metal element is selected from at least one of Mg, Ca, Sr and Ba, and the mass ratio of the alkaline earth metal element to the molecular sieve carrier is (0.05-10): 100,the preferable scheme is (0.1-2): 100, respectively; the lanthanide is selected from at least one of La, Ce, Pr and Nd, preferably one of La and Ce, more preferably Ce, and the mass ratio of the lanthanide to the molecular sieve carrier is (0.05-10): 100, and the preferable scheme is (0.1-2): 100, respectively;
the invention relates to a catalyst for preparing styrene and ethylbenzene by side-chain alkylation of toluene, which comprises the following steps: carrying out ion exchange or impregnation on the molecular sieve and the solution containing the modified element; and drying, roasting and forming the modified molecular sieve.
In the above technical scheme, the precursor of the modified metal component of the catalyst can be selected from one of chloride, hydroxide or nitrate; the B element component precursor may be selected from boric acid or an alkali metal salt of boric acid; the drying temperature is 90-150 ℃, the drying time is 1-24 hours, the roasting temperature is 400-650 ℃, and the roasting time is 1-24 hours.
The application of the catalyst in the reaction of preparing ethylbenzene and styrene by alkylating the side chain of toluene can adopt the following process steps:
toluene and a C1 source are used as raw materials, the molar ratio of the toluene to the C1 source in the raw materials is (0.1-10): 1, the reaction temperature is 300-500 ℃, and the mass space velocity of the raw materials is 0.1-5.0 h-1Under the condition of (1), the raw material and the catalyst are contacted and reacted to generate ethylbenzene and styrene.
In the above technical solution, the C1 source is a C1 raw material, which is a generic name of raw materials containing one carbon, and is preferably at least one of methanol, formaldehyde, paraformaldehyde, and methylal; more preferably, it is at least one of methanol and formaldehyde.
Compared with the prior art, the invention has obvious advantages and outstanding effects. Methanol, formaldehyde, paraformaldehyde or methylal are used as C1 raw materials, so that the raw materials for the toluene side-chain alkylation reaction are wide in source, and the methanol and the formaldehyde or formaldehyde polymer are mixed for use, so that the utilization rate of the C1 raw materials and the conversion rate of toluene in the toluene side-chain alkylation reaction are improved, and the reaction performance is improved. The toluene side alkylation reaction requires concerted catalysis of acid-base sites on the catalyst, where the basic site plays a major role in the toluene side alkylation reaction. The alkali metal modified X-type molecular sieve can obviously improve the toluene side chain alkylation reaction activity, after the alkali metal is subjected to ion exchange, the molecular sieve framework oxygen with partial negative charges can be used as a Lewis alkali center through electron transfer, and simultaneously, the metal oxide which is immersed in the molecular sieve pore channel is used as a new basic center with proper strength to become a new active site of the toluene side chain alkylation reaction, so that the catalytic reaction has higher toluene conversion rate. The addition of the modifying element can enable the molecular sieve to have proper acid-base matching, and improve the performance of the catalyst. The lanthanide has strong acting force with O atoms of the molecular sieve framework, so that the positive charge of Al atoms of the molecular sieve framework can be obviously increased, the acting force between Al and adjacent O atoms is increased, the framework Al of the molecular sieve is effectively stabilized, the framework Al is prevented from being removed, the framework structure of the molecular sieve is favorably stabilized, and the hydrothermal stability of the catalyst is improved. The catalyst has simple preparation method, simultaneously has higher toluene conversion rate and higher utilization rate of C1 raw materials in the side-chain alkylation reaction of toluene, and has the advantages of high selectivity of ethylbenzene and styrene, higher resource utilization rate and good performance stability of the catalyst.
The toluene side alkylation reaction was carried out in a micro catalytic reactor unit of a continuous flow quartz tube reactor. And the product analysis adopts an Agilent 7890A gas chromatograph to detect the compositions of reactants and products on line and calculate the conversion rate and the product selectivity of the reaction. The catalyst prepared by the method is used for the reaction of preparing ethylbenzene and styrene by toluene side chain alkylation, the toluene conversion rate reaches 10-15%, the utilization rate of C1 raw materials reaches 50-60%, and the total selectivity of ethylbenzene and styrene is more than 95%. The catalyst has good performance and high stability, and obtains good technical effect.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Weigh 100g of Si/Al to SiO2/Al2O3NaX type molecular sieve of 2.1, ion exchanged for 2 hours at 60 ℃ in 500mL of an aqueous solution of potassium nitrateThen ion-exchanged 2 times at 60 ℃ for 2 hours in 500mL of an aqueous solution of cesium nitrate, 2 times, filtered after exchange, and dried in an oven at 110 ℃ for 4 hours. 100mL of aqueous solution containing a proper amount of sodium metaaluminate, rhenium chloride, calcium nitrate and cerium nitrate is prepared, the molecular sieve after ion exchange is stirred for 4 hours at the temperature of 60 ℃ for impregnation, and then the water is evaporated to dryness. Drying the mixture in an oven at 110 ℃ for 4 hours, roasting the dried mixture in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst A, and grinding the catalyst A into particles of 40-60 meshes for catalyst evaluation. The mass ratio of the modified elements contained in the catalyst A to the molecular sieve carrier is as follows: al 1%, Re 0.6%, K2%, Cs 8%, Ca 0.8%, Ce 1%.
[ example 2 ]
Weigh 100g of Si/Al to SiO2/Al2O3NaX type molecular sieves, 2, were ion-exchanged in 500mL of an aqueous solution of potassium nitrate at 60 ℃ for 2 hours and 2 times, and then in 500mL of an aqueous solution of cesium nitrate at 60 ℃ for 2 hours and 2 times, filtered after the exchange, and dried in an oven at 90 ℃ for 24 hours. 100mL of aqueous solution containing a proper amount of sodium metaaluminate, rhenium chloride, calcium nitrate and cerium nitrate is prepared, the molecular sieve after ion exchange is stirred for 4 hours at the temperature of 60 ℃ for impregnation, and then the water is evaporated to dryness. Drying the mixture in an oven at 90 ℃ for 24 hours, roasting the dried mixture in a muffle furnace at 400 ℃ for 24 hours to obtain a catalyst B, and grinding the catalyst B into particles of 40-60 meshes for catalyst evaluation. The mass ratio of the modified elements contained in the catalyst B to the molecular sieve carrier is as follows: al 1%, Re 0.6%, K0.5%, Cs 0.5%, Ca 0.1%, Ce 0.1%.
[ example 3 ]
Weigh 100g of Si/Al to SiO2/Al2O3A NaX type molecular sieve of 2.9, ion-exchanged 2 times in 500mL of an aqueous solution of potassium nitrate at 60 ℃ for 2 hours, and then ion-exchanged 2 times in 500mL of an aqueous solution of cesium nitrate at 60 ℃ for 2 hours, after exchange, filtered, and dried in an oven at 150 ℃ for 1 hour. Preparing 100mL of aqueous solution containing proper amount of sodium metaaluminate, rhenium chloride, calcium nitrate and cerium nitrate, and performing ion exchange on the prepared molecular sieveThe solution was immersed in the solution at 60 ℃ for 4 hours with stirring, and then the water was evaporated. Drying the mixture in an oven at 150 ℃ for 1 hour, roasting the dried mixture in a muffle furnace at 650 ℃ for 1 hour to obtain a catalyst C, and grinding the catalyst C into particles of 40-60 meshes for catalyst evaluation. The mass ratio of the modified elements contained in the catalyst C to the molecular sieve carrier is as follows: al 1%, Re 0.6%, K10%, Cs 10%, Ca 2%, Ce 2%.
[ example 4 ]
Weigh 100g of Si/Al to SiO2/Al2O3NaX type molecular sieve, 2, was ion-exchanged in 500mL of an aqueous solution of potassium nitrate at 60 ℃ for 2 hours and 2 times, and then in 500mL of an aqueous solution of cesium nitrate at 60 ℃ for 2 hours and 2 times, after exchange, filtered, and dried in an oven at 110 ℃ for 4 hours. 100mL of aqueous solution containing a proper amount of sodium metaaluminate, rhenium chloride, calcium nitrate and cerium nitrate is prepared, the molecular sieve after ion exchange is stirred for 4 hours at the temperature of 60 ℃ for impregnation, and then the water is evaporated to dryness. Drying the mixture in an oven at 110 ℃ for 4 hours, roasting the dried mixture in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst D, and grinding the catalyst D into particles of 40-60 meshes for catalyst evaluation. The mass ratio of the modified elements contained in the catalyst D to the molecular sieve carrier is as follows: al 1%, Re 0.6%, K0.1%, Cs 0.3%, Ca 0.05%, Ce 0.05%.
[ example 5 ]
Weigh 100g of Si/Al to SiO2/Al2O3NaY type molecular sieve, 5, was ion exchanged 2 times at 60 ℃ for 2 hours in 500mL of cesium nitrate in water, filtered after exchange, and dried in an oven at 110 ℃ for 4 hours. 100mL of aqueous solution containing a proper amount of sodium metaaluminate, rhenium chloride, calcium nitrate and cerium nitrate is prepared, the molecular sieve after ion exchange is stirred for 4 hours at the temperature of 60 ℃ for impregnation, and then the water is evaporated to dryness. Drying the mixture in an oven at 110 ℃ for 4 hours, roasting the dried mixture in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst E, and grinding the catalyst E into particles of 40-60 meshes for catalyst evaluation. The mass ratio of the modified elements contained in the catalyst E to the molecular sieve carrier is as follows: al 1%, Re 0.6%, Cs 20%, Ca 10%, Ce 10%.
[ example 6 ]
Weigh 100g of Si/Al to SiO2/Al2O3NaY type molecular sieve 5, ion exchanged 2 times in 500mL of an aqueous solution of rubidium nitrate at 60 ℃ for 2 hours, then ion exchanged 2 times in 500mL of an aqueous solution of cesium nitrate at 60 ℃ for 2 hours, then filtered after exchange, and dried in an oven at 110 ℃ for 4 hours. 100mL of aqueous solution containing a proper amount of rhenium chloride, boric acid, magnesium nitrate and lanthanum nitrate is prepared, the molecular sieve after ion exchange is stirred for 4 hours at the temperature of 60 ℃ for impregnation, and then the water is evaporated to dryness. Drying the catalyst F in an oven at 110 ℃ for 4 hours, roasting the dried catalyst F in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst F, and grinding the catalyst F into particles of 40-60 meshes for catalyst evaluation. The mass ratio of the modified elements contained in the catalyst F to the molecular sieve carrier is as follows: b1%, Re 0.6%, Rb 2%, Cs 8%, Mg 0.8%, La 1%.
[ example 7 ]
Weigh 100g of Si/Al to SiO2/Al2O3NaX type molecular sieves, 2.1, were ion exchanged in 500mL cesium hydroxide in water for 2 hours at 60 deg.C, 2 times, filtered after exchange, and dried in an oven at 110 deg.C for 4 hours. 100mL of aqueous solution containing a proper amount of rhenium chloride, boric acid, strontium hydroxide and praseodymium nitrate is prepared, the molecular sieve after ion exchange is stirred for 4 hours at the temperature of 60 ℃ for impregnation, and then the water is evaporated to dryness. Drying the mixture in an oven at 110 ℃ for 4 hours, roasting the dried mixture in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst G, and grinding the catalyst G into particles of 40-60 meshes for catalyst evaluation. The mass ratio of the modified elements contained in the catalyst G to the molecular sieve carrier is as follows: b1%, Re 0.6%, Cs 8%, Sr 0.8%, and Pr 1%.
[ example 8 ]
Weigh 100g of Si/Al to SiO2/Al2O3NaX type molecular sieves, 2.1, were ion exchanged in 500mL cesium chloride in water for 2 hours at 60 deg.C, 2 times, filtered after exchange, and dried in an oven at 110 deg.C for 4 hours. Preparing 100mL of aqueous solution containing proper amounts of manganese nitrate, gallium nitrate, barium nitrate and neodymium nitrate, and ionizing ionsThe exchanged molecular sieve was immersed in the above solution at 60 ℃ for 4 hours under stirring, and then the water was evaporated. Drying the sample in an oven at 110 ℃ for 4 hours, roasting the dried sample in a muffle furnace at 600 ℃ for 4 hours, refluxing the obtained sample and methyl silicone oil in 500mL of diethyl ether for 4 hours, filtering the obtained product, drying the dried sample in the oven at 110 ℃ for 4 hours, roasting the dried sample in the muffle furnace at 600 ℃ for 4 hours to obtain a catalyst H, and grinding the catalyst H into particles of 40-60 meshes for catalyst evaluation. The mass ratio of the modified elements contained in the catalyst H to the molecular sieve carrier is as follows: ga 1%, Mn 0.6%, Cs 8%, Ba 0.8%, Nd 1%.
[ example 9 ]
Weigh 100g of Si/Al to SiO2/Al2O3NaX type molecular sieves, 2.1, were ion exchanged in 500mL cesium nitrate in water at 60 ℃ for 2 hours, 4 times, filtered after exchange, and dried in an oven at 110 ℃ for 4 hours. Preparing 100mL of aqueous solution containing proper amounts of manganese nitrate, indium nitrate, calcium nitrate and cerium nitrate, soaking the ion-exchanged molecular sieve in the aqueous solution at 60 ℃ for 4 hours under stirring, and then evaporating the water to dryness. Drying the mixture in an oven at 110 ℃ for 4 hours, roasting the dried mixture in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst I, and grinding the catalyst I into particles of 40-60 meshes for catalyst evaluation. The mass ratio of the modified elements contained in the catalyst I to the molecular sieve carrier is as follows: in 1%, Mn 0.6%, Cs 8%, Ca 0.8%, Ce 1%.
[ example 10 ]
Weigh 100g of Si/Al to SiO2/Al2O3NaX type molecular sieves, 2.1, were ion exchanged in 500mL of an aqueous solution of rubidium nitrate at 60 ℃ for 2 hours and 2 times, then in 500mL of an aqueous solution of cesium nitrate at 60 ℃ for 2 hours and 2 times, filtered after the exchange, and dried in an oven at 110 ℃ for 4 hours. 100mL of aqueous solution containing a proper amount of boric acid, sodium metaaluminate, manganese nitrate, strontium nitrate and cerium nitrate is prepared, the molecular sieve after ion exchange is stirred for 4 hours at the temperature of 60 ℃ for impregnation, and then the water is evaporated. Drying at 110 ℃ for 4 hours in an oven, roasting at 600 ℃ for 4 hours in a muffle furnace after drying to obtain a catalyst J, and grinding the catalyst J into particles of 40-60 meshesEvaluation was carried out on the catalyst. The mass ratio of the modified elements contained in the catalyst J to the molecular sieve carrier is as follows: b1%, Al 1%, Mn 0.6%, Rb 2%, Cs 8%, Sr 0.8%, Ce 1%.
[ example 11 ]
Weigh 100g of Si/Al to SiO2/Al2O3A NaX type molecular sieve (2.1) was ion-exchanged at 60 ℃ for 2 hours in 500mL of an aqueous solution of potassium nitrate and 2 times, then ion-exchanged at 500mL of an aqueous solution of rubidium nitrate for 2 hours and 2 times, and then ion-exchanged at 60 ℃ for 2 hours in 500mL of an aqueous solution of cesium nitrate and 2 times, then filtered after the exchange, and dried in an oven at 110 ℃ for 4 hours. 100mL of aqueous solution containing a proper amount of boric acid, sodium metaaluminate, indium nitrate, manganese chloride, rhenium chloride, cesium nitrate, magnesium nitrate, strontium nitrate, cerium nitrate and lanthanum nitrate is prepared, the molecular sieve after ion exchange is stirred for 4 hours at 60 ℃ in the solution for impregnation, and then the water is evaporated to dryness. Drying the mixture in an oven at 110 ℃ for 4 hours, roasting the dried mixture in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst K, and grinding the catalyst K into particles of 40-60 meshes for catalyst evaluation. The mass ratio of the modified elements contained in the catalyst K to the molecular sieve carrier is as follows: b1%, Al 1%, In 1%, Mn 0.6%, Re 0.6%, K1%, Rb 1%, Cs 8%, Mg 0.8%, Sr 0.8%, Ce 0.5%, and La 0.5%.
[ example 12 ]
Weigh 100g of Si/Al to SiO2/Al2O3NaX type molecular sieves, 2.1, were ion-exchanged in 500mL of an aqueous solution of potassium nitrate at 60 ℃ for 2 hours and 2 times, then in 500mL of an aqueous solution of cesium nitrate at 60 ℃ for 2 hours and 2 times, filtered after the exchange, and dried in an oven at 110 ℃ for 4 hours. 100mL of aqueous solution containing a proper amount of sodium metaaluminate, rhenium chloride, calcium nitrate, ammonium metavanadate and cerium nitrate is prepared, the molecular sieve after ion exchange is stirred for 4 hours at the temperature of 60 ℃ for impregnation, and then the water is evaporated to dryness. Drying the mixture in an oven at 110 ℃ for 4 hours, roasting the dried mixture in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst L, and grinding the catalyst L into particles of 40-60 meshes for catalyst evaluation. Modification of the content of catalyst LThe mass ratio of the elements to the molecular sieve carrier is as follows: al 1%, Re 0.6%, K2%, Cs 8%, Ca 0.8%, Ce 1%, V0.5%.
Comparative example 1
Weigh 100g of Si/Al to SiO2/Al2O3The method comprises the following steps of carrying out ion exchange on a 2.1 NaX type molecular sieve in a 500mL cesium nitrate aqueous solution for 2 hours at 60 ℃, carrying out 2 times of ion exchange, filtering after the ion exchange, drying for 4 hours at 110 ℃ in an oven, roasting for 4 hours at 600 ℃ in a muffle furnace after the drying to obtain a catalyst M, and grinding the catalyst M into particles of 40-60 meshes for catalyst evaluation. The mass ratio of the modified elements contained in the catalyst M to the molecular sieve carrier is as follows: and (8) Cs.
Comparative example 2
Weigh 100g of Si/Al to SiO2/Al2O3NaX type molecular sieves, 2.1, were ion-exchanged in 500mL of an aqueous solution of potassium nitrate at 60 ℃ for 2 hours and 2 times, and then in 500mL of an aqueous solution of cesium nitrate at 60 ℃ for 2 hours and 2 times, filtered after the exchange, and dried in an oven at 110 ℃ for 4 hours. 100mL of aqueous solution containing a proper amount of sodium metaaluminate, rhenium chloride and calcium nitrate is prepared, the molecular sieve after ion exchange is stirred for 4 hours at the temperature of 60 ℃ for impregnation, and then the water is evaporated to dryness. Drying the mixture in an oven at 110 ℃ for 4 hours, roasting the dried mixture in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst N, and grinding the catalyst N into particles of 40-60 meshes for catalyst evaluation. The mass ratio of the modified elements contained in the catalyst N to the molecular sieve carrier is as follows: al 1%, Re 0.6%, K2%, Cs 8%, Ca 0.8%.
Comparative example 3
Weigh 100g of Si/Al to SiO2/Al2O3NaX type molecular sieves, 2.1, were ion-exchanged in 500mL of an aqueous solution of potassium nitrate at 60 ℃ for 2 hours and 2 times, and then in 500mL of an aqueous solution of cesium nitrate at 60 ℃ for 2 hours and 2 times, filtered after the exchange, and dried in an oven at 110 ℃ for 4 hours. 100mL of aqueous solution containing a proper amount of cerium nitrate is prepared, the molecular sieve after ion exchange is soaked in the solution at 60 ℃ for 4 hours under stirring, and then the water is evaporated. In an oven 110Drying for 4 hours, roasting at 600 ℃ for 4 hours in a muffle furnace after drying to obtain a catalyst O, and grinding into particles of 40-60 meshes for catalyst evaluation. The mass ratio of the modified elements contained in the catalyst O to the molecular sieve carrier is as follows: k2%, Cs 8%, Ce 1%.
[ example 13 ]
5g of the catalysts A to O were used for evaluation of the toluene side alkylation reaction. The C1 raw material is methanol solution of formaldehyde, and the molar ratio of the formaldehyde to the methanol in the solution is 1: 4, the reaction temperature is 420 ℃; the reaction pressure is normal pressure; the molar ratio of the toluene to the carbon element in the C1 raw material is 5: 1; the mass space velocity of the toluene is 1.5h-1Carrier gas N2The flow rate was 10 mL/min. The catalytic reaction was carried out under the above conditions and the reaction product was analyzed by gas chromatography. After the reaction, the conversion of the C1 starting material was 100%. The results are shown in Table 1(C1 raw material utilization is the ratio of carbon element entering the target product to carbon element consumed by the reaction).
TABLE 1
| Catalyst and process for preparing same | Toluene conversion (%) | Utilization ratio of C1 raw Material (%) | Ethylbenzene + styrene Selectivity (%) |
| A | 11.6 | 58 | 98.2 |
| B | 10.1 | 50.5 | 95.6 |
| C | 11.2 | 56 | 92.5 |
| D | 9.8 | 49 | 94.1 |
| E | 11.7 | 58.5 | 92.0 |
| F | 10.5 | 52.5 | 96.4 |
| G | 11.3 | 56.5 | 97.9 |
| H | 10.7 | 53.5 | 95.4 |
| I | 10.8 | 54 | 94.8 |
| J | 11.5 | 57.5 | 97.1 |
| K | 11.6 | 58 | 97.6 |
| L | 11.1 | 55.5 | 96.3 |
| Comparative example M | 5.1 | 25.5 | 89.8 |
| Comparative example N | 5.7 | 28.5 | 90.3 |
| Comparative example O | 4.5 | 22.5 | 91.1 |
10 hours of reaction averaging
[ example 14 ]
5g of catalyst A was taken for evaluation of the toluene side-alkylation reaction. The reaction temperature is 420 ℃; the reaction pressure is normal pressure; the molar ratio of the toluene to the carbon element in the C1 raw material is 5: 1; the mass space velocity of the toluene is 1.5h-1Carrier gas N2The flow rate was 10 mL/min. The catalytic reaction was carried out under the above conditions and the reaction product was analyzed by gas chromatography. After the reactionThe conversion of the C1 feedstock was 100%, and the results are shown in Table 2(C1 feedstock utilization is the proportion of carbon that enters the target product as carbon consumed by the reaction).
TABLE 2
10 hours of reaction averaging
[ example 15 ]
5g of catalyst A, M was taken for evaluation of the toluene side-alkylation reaction. The C1 raw material is methanol solution of formaldehyde, and the molar ratio of the formaldehyde to the methanol in the solution is 1: 4, the reaction temperature is 420 ℃; the reaction pressure is normal pressure; the molar ratio of the toluene to the carbon element in the C1 raw material is 5: 1; the mass space velocity of the toluene is 1.5h-1Carrier gas N2The flow rate was 10 mL/min. The catalytic reaction was carried out under the above conditions and the reaction product was analyzed by gas chromatography. After the reaction, the conversion rate of the C1 raw material is 100%, and the utilization rate of the C1 raw material is the proportion of carbon element entering a target product in the carbon element consumed by the reaction. The catalyst reacts for 200 hours in a single pass, and after the catalyst is burned and regenerated for 20 times, the reaction results are shown in Table 3.
TABLE 3
10 hours of reaction averaging
Claims (8)
1. The application of the catalyst for preparing styrene and ethylbenzene by the side-chain alkylation reaction of toluene uses toluene and a C1 source as raw materials, the molar ratio of the toluene to the C1 source is (0.1-10): 1, the reaction temperature is 300-500 ℃, and the mass space velocity of the raw materials is 0.1-5.0 h-1Under the condition of the catalyst, the raw material contacts and reacts with the catalyst for preparing the styrene and the ethylbenzene by the side chain alkylation reaction of the toluene to generate the ethylbenzene and the styrene,
wherein the catalyst comprises the following components:
a) at least one of an X molecular sieve or a Y molecular sieve; and a modifying component supported thereon:
b) at least one element in IIIA group, wherein the mass ratio of the element to the molecular sieve carrier is (0.05-10): 100, respectively;
c) at least one of VIIB group elements, wherein the mass ratio of the elements to the molecular sieve carrier is (0.05-10): 100, respectively;
d) at least one alkali metal element, wherein the mass ratio of the element to the molecular sieve carrier is (0.1-20): 100, respectively;
e) at least one alkaline earth metal element, wherein the mass ratio of the element to the molecular sieve carrier is (0.05-10): 100, respectively;
f) at least one lanthanide element, wherein the mass ratio of the element to the molecular sieve carrier is (0.05-10): 100,
the C1 source was a mixture of methanol and methylal.
2. Use according to claim 1, characterized in that the molecular sieve is selected from SiO2/Al2O3At least one of an X molecular sieve and a Y molecular sieve of 2-5.
3. Use according to claim 1, characterized in that the molecular sieve is an X molecular sieve.
4. The use according to claim 1, wherein the group IIIA element is selected from at least one of B, Al, Ga and In, and the mass ratio of the element to the molecular sieve carrier is (0.1-2): 100.
5. the use according to claim 1, wherein the VIIB group element is selected from at least one of Mn and Re, and the mass ratio of the element to the molecular sieve carrier is (0.1-2): 100.
6. the use according to claim 1, wherein the alkali metal element is selected from at least one of K, Rb or Cs, and the mass ratio of the element to the molecular sieve carrier is (0.5-10): 100.
7. the use according to claim 1, characterized in that the alkaline earth metal element is selected from at least one of Mg, Ca, Sr or Ba, and the mass ratio of the element to the molecular sieve support is (0.1-2): 100.
8. the use according to claim 1, characterized in that the lanthanide is selected from at least one of La, Ce, Pr, Nd, the mass ratio of said element to the molecular sieve support being (0.1-2): 100.
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| CN111054428A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for synthesizing ethylbenzene and styrene by toluene side chain alkylation and application thereof |
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