CN106622342A - Catalyst for alkylation reaction at methylbenzene methanol side and technical method thereof - Google Patents

Catalyst for alkylation reaction at methylbenzene methanol side and technical method thereof Download PDF

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Publication number
CN106622342A
CN106622342A CN201510731435.8A CN201510731435A CN106622342A CN 106622342 A CN106622342 A CN 106622342A CN 201510731435 A CN201510731435 A CN 201510731435A CN 106622342 A CN106622342 A CN 106622342A
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catalyst
molecular sieve
side chain
hours
alkylation reaction
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曾铁强
缪长喜
张新玉
张磊
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/163—X-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C07C2529/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium

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  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a catalyst for alkylation reaction at methylbenzene methanol side and a technical method thereof; the invention mainly solves the problem of low methanol utilization rate, low methylbenzene conversion rate and bad catalyst stability of the catalyst for preparing ethylbenzene and styrene by alkylation reaction at methylbenzene methanol side. Through the catalyst for alkylation reaction at methylbenzene methanol side and the technical method thereof, the catalyst takes modified X or Y molecular sieve as the active component, and adopts at least one of alkali metals and at least one of rare-earth elements as the modifying component; the mass content of V element in the catalyst is less than 900 ppm, the mass content of Ti element is less than 900 ppm, and the mass content of Os element is less than 900 ppm; the technical scheme well solves the problem, and the catalyst and the technical method can be applied to the industrial production of preparing ethylbenzene and styrene by alkylation reaction at methylbenzene methanol side.

Description

For the catalyst and its process of the reaction of methylbenzene methanol side chain alkylation
Technical field
The present invention relates to a kind of catalyst and its process for the reaction of methylbenzene methanol side chain alkylation.
Background technology
Styrene is a kind of important Organic Chemicals, mainly for the production of polystyrene, butadiene-styrene rubber, ABS resin, The products such as unsaturated-resin, it may also be used for the field such as pharmacy, agricultural chemicals and dyestuff, it is of many uses.At present, overwhelming majority industry Cinnamic production is carried out in two steps.First, the Jing Friedel-Craft alkylations under catalyst action of benzene and ethene are anti- Ethylbenzene should be generated, then ethylbenzene Jing catalytic dehydrogenations generate styrene.The route raw material high cost, technological process is long, and equipment is thrown Money is big, and energy consumption is higher.The reaction of methylbenzene methanol side chain alkylation is to produce styrene etc. one to have the road of potential application foreground X-type and Y type molecules that the reported firsts such as line, Sidorenko in 1967 toluene, methyl alcohol can be exchanged in alkali metal ion There is side chain alkylation on sieve catalyst and react step generation styrene.The technique due to raw material sources extensively, it is low cost, anti- Answer that mild condition, synthesis technique be simple, energy consumption is relatively low, possess good commercial development value and application prospect, cause pole Big concern.
The mechanism of methylbenzene methanol side chain alkylation reaction obtains formaldehyde as reaction intermediate, basic active for base catalysis Methanol Decomposition The methyl of activation Toluene is gone back in position becomes carbanion, and the Adol-type reactions that then carbanion PARA FORMALDEHYDE PRILLS(91,95) occurs, product takes off Styrene is obtained after water.Ethylbenzene generated and hydrogenation reaction with the hydrogen that reaction is produced in part styrene there is.Methylbenzene methanol side chain The catalyst of alkylated reaction belongs to solid base catalyst, needs the alkali center of sufficient intensity and quantity with catalysis methanol dehydrogenation life Into formaldehyde and activation Toluene methyl c h bond generate methyl carbanion.Meanwhile, methylbenzene methanol side chain alkylation course of reaction Or the soda acid concerted catalysis reaction based on the catalysis of basic active position.It is demonstrated experimentally that individually basic active position is catalyzed methylbenzene methanol The efficiency of side chain alkylation is very low.In course of reaction, toluene molecule needs by Lewis acid absorption and stablizes, and otherwise toluene turns Rate is relatively low.But if catalyst is alkaline too strong, methyl alcohol and intermediate product formaldehyde easily further decompose into CO and hydrogen Gas；If acidity of catalyst is too strong, the alkylated reaction that phenyl ring mainly occurs generates benzene and dimethylbenzene.Therefore, catalyst Need to be matched with suitable soda acid.In addition, the adsorption equilibrium of toluene and methyl alcohol is also to affect methylbenzene methanol side chain alkylation anti- One of factor answered, suitable pore passage structure and cage size are conducive to the adsorption equilibrium of toluene and methyl alcohol.
Various catalysis materials are attempted for the reaction of methylbenzene methanol side chain alkylation.Different types of modified molecular screen such as X, Y, USY, L, β, ZSM-5 and basic anhydride such as MgO, CaO, MgO-TiO2、CaO-TiO2Etc. studied application In the catalyst of methylbenzene methanol side chain alkylation reaction, certain catalytic performance is all shown.As US 4463204 reports Jing The X or Y type molecular sieve of K, Cs ion-exchanged improves toluene conversion in the reaction of methylbenzene methanol side chain alkylation And concrete 90% ethylbenzene, styrene overall selectivity.CN 101623650A are entered using K, Cs to X or Y type molecular sieve Row ion exchange, and load the stability that the method for B, P and alkali metal or alkaline-earth metal improves catalyst.CN 101623649A, again at high temperature with ammonia process, improves catalyst to the X or Y type molecular sieve of Jing alkali metals modifieds Activity and stability.These modified X for having reported or Y type molecular sieve are achieved in the reaction of methylbenzene methanol side chain alkylation Certain catalytic effect.But, how to take into account toluene conversion and use ratio of methanol is in the reaction of methylbenzene methanol side chain alkylation An important technology difficult problem.Report that catalyst obtains at the same time high toluene conversion and high methanol utilization rate aspect is still not enough managed Want for industrial requirement still has larger gap, and there is that hydrothermal stability is not high.Therefore, develop Suitable toluene conversion and use ratio of methanol, ethylbenzene, benzene second can be simultaneously taken into account in the reaction of methylbenzene methanol side chain alkylation Alkene is selective high and the high catalyst of hydrothermal stability is to realize methylbenzene methanol side chain alkylation preparing ethylbenzene by reaction, styrene work One of key factor that industry metaplasia is produced.In catalytic component, or the trace element introduced in catalyst preparation process is to catalysis The impact of agent performance is also the important topic in industrial catalyst research, but yet there are no document and studied.
The content of the invention
The technical problem to be solved is currently used for methylbenzene methanol side chain alkylation ethylbenzene and styrene reaction Catalyst is low to the utilization rate of methyl alcohol, toluene conversion is low and poor catalyst stability problem, there is provided a kind of new is used for Methylbenzene methanol side chain alkylation ethylbenzene and the catalyst of styrene reaction, the method for preparing catalyst is easy, in methylbenzene methanol There is higher toluene conversion and higher use ratio of methanol simultaneously in side chain alkylation reaction, select with ethylbenzene, styrene Selecting property height and the high advantage of catalyst performance stabilised.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows：One kind is used for methylbenzene methanol side chain alkylation The catalyst of reaction, comprising following components：
A) at least one in X molecular sieve or Y molecular sieve；With load modified component thereon：
B) at least one in alkali metal, the element is (0.1～20) with the mass ratio of molecular sieve carrier：100；
C) at least one in rare earth element, the element is (0.05～10) with the mass ratio of molecular sieve carrier：100；
It is characterized in that the mass content of V element is less than 900ppm in catalyst；The mass content of Ti elements is less than 900ppm。
In above-mentioned technical proposal, the molecular sieve is selected from SiO2/Al2O3In X molecular sieve or Y molecular sieve for 2～5 extremely Few one kind, preferred version is X molecular sieve；At least one of the alkali metal in K, Rb or Cs, more preferably scheme For Cs, alkali metal is (0.1～20) with the mass ratio of molecular sieve carrier：100, preferred version is (0.5～10)：100； At least one of the rare earth element in La, Ce, rare earth element is (0.05～10) with the mass ratio of molecular sieve carrier：100, Preferred version is (0.1～2)：100.
In above-mentioned technical proposal, it is preferable that Bi elements, Bi elements mass content in the catalyst are also included in catalyst For 0.05～10%, preferred version is 0.1～5%.
In above-mentioned technical proposal, the preferred version of the mass content of V element is less than 800ppm, more preferably just in catalyst Case is that most preferably scheme is less than 400ppm less than 600ppm.
In above-mentioned technical proposal, the preferred version of the mass content of Ti elements is less than 800ppm, more preferably just in catalyst Case is that most preferably scheme is less than 400ppm less than 600ppm.
In above-mentioned technical proposal, in catalyst the mass content of Os elements be less than 900ppm, preferred version be less than 800ppm, More preferably scheme is that most preferably scheme is less than 400ppm less than 600ppm.
A kind of catalyst reacted for methylbenzene methanol side chain alkylation ethylbenzene and styrene involved in the present invention, can adopt It is prepared by following steps：
A) molecular sieve is carried out into ion exchange or dipping with the solution containing the modifying element；
B) modified molecular sieve is dried, roasting, shaping.
In above-mentioned technical proposal, the baking temperature of catalyst is 90 DEG C～150 DEG C, and drying time is 1～24 hour, roasting Temperature is 400 DEG C～650 DEG C, and roasting time is 1～24 hour.
The application of catalyst involved in the present invention in methylbenzene methanol side chain alkylation ethylbenzene and styrene reaction, can adopt Comprising following processing step：
With toluene and methyl alcohol as raw material, toluene and methanol molar ratio are (0.1～10) in raw material:1, reaction temperature be 300 DEG C～ 500 DEG C, material quality air speed is 0.1～5.0h-1Under conditions of, raw material is with generating ethylbenzene and benzene second after catalyst haptoreaction Alkene.
Compared with prior art, the present invention has significant advantage and high-lighting effect.The reaction of methylbenzene methanol side chain alkylation is needed Acid and basic sites on catalyst are wanted to carry out concerted catalysis, wherein basic sites play Main Function in Benzyl Side-Chain alkylated reaction. The X-type molecular sieve of alkali metals modified can make methylbenzene methanol side chain alkylation reactivity be significantly improved, alkali metal carry out from After son is exchanged, through electro transfer, the framework of molecular sieve oxygen with partial negative charge can be used as Lewis alkali center.Rare earth element The positive charge that there is stronger active force between framework of molecular sieve O atom, framework of molecular sieve Al atoms can be dramatically increased, Increase the active force between Al and adjacent O atom, effectively stabilize the skeleton Al of molecular sieve, it is to avoid skeleton Al's Removing, is conducive to molecular sieves stabilized skeleton structure, improves the hydrothermal stability of catalyst.Applicants have discovered that, catalyst Some micro (or a small amount of) elements are introduced in preparation process can significantly change the property such as electronic property and surface acidic-basic property of catalyst Matter, so as to significantly affect catalyst performance is affected.A small amount of presence of the elements such as V, Ti, Os can make catalyst inactivation serious. Understand fully which micro or oligo-element has catalyst performance to significantly affect that obviously there is weight to the industrial applications of catalyst Want meaning.Still further, it was discovered that the oxide of some metal oxides, such as Bi, by the electronic property of regulating catalyst, Be conducive to further improving the activity of catalyst.The method for preparing catalyst is easy, in the reaction of methylbenzene methanol side chain alkylation There is higher toluene conversion and higher use ratio of methanol simultaneously, the utilization of resources high with ethylbenzene, selectivity of styrene The advantage that rate is higher and catalyst performance stabilised is good.
The reaction of methylbenzene methanol side chain alkylation is carried out on the miniature catalyst reaction device of continuous flowing quartz tube reactor.Product point Analysis constitutes and calculates the conversion ratio and product of reaction using Agilent 7890A gas chromatograph on-line checking reactants and product Thing selectivity.Catalyst prepared by the method provided using the present invention is used for methylbenzene methanol side chain alkylation ethylbenzene and styrene Reaction, toluene conversion reaches 10～15%, use ratio of methanol up to more than 50%, ethylbenzene, styrene overall selectivity>92%. Catalyst performance is preferable and stability is high, achieves preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieves, at 60 DEG C, in 500mL potassium nitrate The aqueous solution in carry out ion exchange 2 hours, exchange 2 times, then at 60 DEG C, in the water-soluble of 500mL cesium nitrates Ion exchange is carried out in liquid 2 hours, exchanged 2 times, filtered after exchange, in an oven 110 DEG C of dryings 4 hours.Prepare Aqueous solution 100mL containing appropriate cerous nitrate, by the molecular sieve after ion exchange, stirring 4 is little at 60 DEG C in above-mentioned solution Shi Jinhang impregnates, then evaporating water.110 DEG C of dryings 4 hours in an oven, after being dried again in Muffle furnace in 600 DEG C Lower roasting 4 hours, obtains catalyst A, grinds to form 40～60 mesh particles for evaluating catalyst.Change contained by catalyst A Property element is with the mass ratio of molecular sieve carrier：K 2%, Cs 6%, Ce 1%.Reagent used in preparation process is height Purity, the 40ppm containing V in terms of mass fraction, Ti 20ppm, Os 10ppm in catalyst.
【Embodiment 2】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2 NaX type molecular sieves, at 60 DEG C, in 500mL potassium nitrate The aqueous solution in carry out ion exchange 2 hours, exchange 2 times, then at 60 DEG C, in the water-soluble of 500mL cesium nitrates Ion exchange is carried out in liquid 2 hours, exchanged 2 times, filtered after exchange, in an oven 90 DEG C of dryings 24 hours.Prepare Aqueous solution 100mL containing appropriate cerous nitrate, by the molecular sieve after ion exchange, stirring 4 is little at 60 DEG C in above-mentioned solution Shi Jinhang impregnates, then evaporating water.90 DEG C of dryings 24 hours in an oven, after being dried again in Muffle furnace in 400 DEG C Lower roasting 24 hours, obtains catalyst B, grinds to form 40～60 mesh particles for evaluating catalyst.Contained by catalyst B Modifying element is with the mass ratio of molecular sieve carrier：K 0.5%, Cs 0.5%, Ce 0.1%.Examination used in preparation process Agent is high-purity, the 180ppm containing V in terms of mass fraction, Ti 150ppm, Os 50ppm in catalyst.
【Embodiment 3】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.9 NaX type molecular sieves, at 60 DEG C, in 500mL potassium nitrate The aqueous solution in carry out ion exchange 2 hours, exchange 2 times, then at 60 DEG C, in the water-soluble of 500mL cesium nitrates Ion exchange is carried out in liquid 2 hours, exchanged 2 times, filtered after exchange, in an oven 150 DEG C of dryings 1 hour.Prepare Aqueous solution 100mL containing appropriate cerous nitrate, by the molecular sieve after ion exchange, stirring 4 is little at 60 DEG C in above-mentioned solution Shi Jinhang impregnates, then evaporating water.150 DEG C of dryings 1 hour in an oven, after being dried again in Muffle furnace in 650 DEG C Lower roasting 1 hour, obtains catalyst C, grinds to form 40～60 mesh particles for evaluating catalyst.Change contained by catalyst C Property element is with the mass ratio of molecular sieve carrier：K 5%, Cs 10%, Ce 2%.Reagent used in preparation process is High-purity, the 240ppm containing V in terms of mass fraction, Ti 260ppm, Os 60ppm in catalyst.
【Embodiment 4】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2 NaX type molecular sieves, at 60 DEG C, in 500mL potassium nitrate The aqueous solution in carry out ion exchange 2 hours, exchange 2 times, then at 60 DEG C, in the water-soluble of 500mL cesium nitrates Ion exchange is carried out in liquid 2 hours, exchanged 2 times, filtered after exchange, in an oven 110 DEG C of dryings 4 hours.Prepare Aqueous solution 100mL containing appropriate cerous nitrate, by the molecular sieve after ion exchange, stirring 4 is little at 60 DEG C in above-mentioned solution Shi Jinhang impregnates, then evaporating water.110 DEG C of dryings 4 hours in an oven, after being dried again in Muffle furnace in 600 DEG C Lower roasting 4 hours, obtains catalyst D, grinds to form 40～60 mesh particles for evaluating catalyst.Change contained by catalyst D Property element is with the mass ratio of molecular sieve carrier：K 0.1%, Cs 0.4%, Ce 0.05%.Reagent used in preparation process High-purity is, the 320ppm containing V in terms of mass fraction, Ti 280ppm, Os 200ppm in catalyst.
【Embodiment 5】
Weigh 100g silica alumina ratio SiO2/Al2O3For 5 NaY type molecular sieves, at 60 DEG C, in 500mL cesium nitrates The aqueous solution in carry out ion exchange 2 hours, exchange 2 times, filter after exchange, in an oven 110 DEG C of dryings 4 hours. The aqueous solution 100mL containing appropriate cerous nitrate is prepared, the molecular sieve after ion exchange is stirred in above-mentioned solution at 60 DEG C Impregnated within 4 hours, then evaporating water.110 DEG C of dryings 4 hours in an oven, after being dried again in Muffle furnace in Roasting 4 hours at 600 DEG C, obtain catalyst E, grind to form 40～60 mesh particles for evaluating catalyst.Catalyst E Contained modifying element is with the mass ratio of molecular sieve carrier：Cs 20%, Ce 10%.Reagent used in preparation process is High-purity, the 380ppm containing V in terms of mass fraction, Ti 350ppm, Os 160ppm in catalyst.
【Embodiment 6】
Weigh 100g silica alumina ratio SiO2/Al2O3For 5 NaY type molecular sieves, at 60 DEG C, in 500mL rubidium nitrates The aqueous solution in carry out ion exchange 2 hours, exchange 2 times, then at 60 DEG C, in the water-soluble of 500mL cesium nitrates Ion exchange is carried out in liquid 2 hours, exchanged 2 times, filtered after exchange, in an oven 110 DEG C of dryings 4 hours.Prepare Aqueous solution 100mL containing appropriate lanthanum nitrate, by the molecular sieve after ion exchange, stirring 4 is little at 60 DEG C in above-mentioned solution Shi Jinhang impregnates, then evaporating water.110 DEG C of dryings 4 hours in an oven, after being dried again in Muffle furnace in 600 DEG C Lower roasting 4 hours, obtains catalyst F, grinds to form 40～60 mesh particles for evaluating catalyst.Change contained by catalyst F Property element is with the mass ratio of molecular sieve carrier：Rb 2%, Cs 6%, La 1%.Reagent used in preparation process is High-purity, the 250ppm containing V in terms of mass fraction, Ti 200ppm, Os 60ppm in catalyst.
【Embodiment 7】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieves, at 60 DEG C, in 500mL hydroxides Ion exchange is carried out in the aqueous solution of caesium 2 hours, exchanged 2 times, filtered after exchange, in an oven 110 DEG C of dryings 4 are little When.The aqueous solution 100mL containing appropriate cerous nitrate and sodium metaaluminate is prepared, by the molecular sieve after ion exchange in above-mentioned solution In stir at 60 DEG C and impregnated for 4 hours, then evaporating water.110 DEG C of dryings 4 hours in an oven, after being dried Again in Muffle furnace at 600 DEG C roasting 4 hours, obtain catalyst G, grind to form 40～60 mesh particles for catalyst Evaluate.Modifying element contained by catalyst G is with the mass ratio of molecular sieve carrier：Cs 6%, Ce 1%, Bi 1%.Prepare During the reagent that uses be high-purity, the 160ppm containing V in terms of mass fraction, Ti 200ppm, Os in catalyst 40ppm。
【Embodiment 8】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieves, at 60 DEG C, in 500mL cesium chlorides The aqueous solution in carry out ion exchange 2 hours, exchange 2 times, filter after exchange, in an oven 110 DEG C of dryings 4 hours. Prepare the aqueous solution 100mL containing appropriate lanthanum nitrate and sodium metaaluminate, by the molecular sieve after ion exchange in above-mentioned solution Stirring at 60 DEG C is impregnated for 4 hours, then evaporating water.110 DEG C of dryings 4 hours in an oven, exist again after being dried In Muffle furnace at 600 DEG C roasting 4 hours, obtain catalyst H, grind to form 40～60 mesh particles for evaluating catalyst. Modifying element contained by catalyst H is with the mass ratio of molecular sieve carrier：Cs 6%, La 1%, Bi 0.1%.In preparation process The reagent for using is high-purity, the 200ppm containing V in terms of mass fraction, Ti 160ppm, Os 80ppm in catalyst.
【Embodiment 9】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieves, at 60 DEG C, in 500mL cesium nitrates The aqueous solution in carry out ion exchange 2 hours, exchange 2 times, filter after exchange, in an oven 110 DEG C of dryings 4 hours. Prepare the aqueous solution 100mL containing appropriate cerous nitrate and sodium metaaluminate, by the molecular sieve after ion exchange in above-mentioned solution Stirring at 60 DEG C is impregnated for 4 hours, then evaporating water.110 DEG C of dryings 4 hours in an oven, exist again after being dried In Muffle furnace at 600 DEG C roasting 4 hours, obtain catalyst I, grind to form 40～60 mesh particles for evaluating catalyst. Modifying element contained by catalyst I is with the mass ratio of molecular sieve carrier：Cs 8%, Ce 1%, Bi 6%.Make in preparation process Reagent is higher degree, the 300ppm containing V in terms of mass fraction, Ti 240ppm, Os 120ppm in catalyst.
【Embodiment 10】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieves, at 60 DEG C, in 500mL rubidium nitrates The aqueous solution in carry out ion exchange 2 hours, exchange 2 times, then at 60 DEG C, in the aqueous solution of 500mL cesium nitrates In carry out ion exchange 2 hours, exchange 2 times, filter after exchange, in an oven 110 DEG C of dryings 4 hours.Prepare containing suitable Amount cerous nitrate, the aqueous solution 100mL of lanthanum nitrate, the molecular sieve after ion exchange is stirred in above-mentioned solution at 60 DEG C Impregnated within 4 hours, then evaporating water.110 DEG C of dryings 4 hours in an oven, after being dried again in Muffle furnace in 600 Roasting 4 hours at DEG C, obtain catalyst J, grind to form 40～60 mesh particles for evaluating catalyst.Change contained by catalyst J Property element is with the mass ratio of molecular sieve carrier：Rb 2%, Cs 6%, Ce 1%, La 1%.Examination used in preparation process Agent is higher degree, the 650ppm containing V in terms of mass fraction, Ti 780ppm, Os 620ppm in catalyst.
【Embodiment 11】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieves, at 60 DEG C, in 500mL potassium nitrate The aqueous solution in carry out ion exchange 2 hours, exchange 2 times, then ion friendship is carried out in the aqueous solution of 500mL rubidium nitrates Change 2 hours, exchange 2 times, then at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL cesium nitrates 2 hours, Exchange 2 times, filter after exchange, in an oven 110 DEG C of dryings 4 hours.Prepare and contain appropriate cesium nitrate, cerous nitrate, nitric acid The aqueous solution 100mL of lanthanum, the molecular sieve after ion exchange is stirred in above-mentioned solution at 60 DEG C and is impregnated within 4 hours, Then evaporating water.110 DEG C of dryings 4 hours in an oven, again roasting 4 is little at 600 DEG C in Muffle furnace after being dried When, catalyst K is obtained, 40～60 mesh particles are ground to form for evaluating catalyst.Modifying element contained by catalyst K with point Son sieves the mass ratio of carrier：Rb 1%, Cs 6%, Ce 1%, La 1%.Reagent used in preparation process is more high-purity Degree, the 550ppm containing V in terms of mass fraction, Ti 500ppm, Os 450ppm in catalyst.
【Embodiment 12】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieves, at 60 DEG C, in 500mL potassium nitrate The aqueous solution in carry out ion exchange 2 hours, exchange 2 times, then ion friendship is carried out in the aqueous solution of 500mL rubidium nitrates Change 2 hours, exchange 2 times, then at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL cesium nitrates 2 hours, Exchange 2 times, filter after exchange, in an oven 110 DEG C of dryings 4 hours.The aqueous solution 100mL containing appropriate cerous nitrate is prepared, Molecular sieve after ion exchange is stirred in above-mentioned solution at 60 DEG C and is impregnated within 4 hours, then evaporating water. 110 DEG C of dryings 4 hours in baking oven, after being dried again in Muffle furnace at 600 DEG C roasting 4 hours, obtain catalyst L, 40～60 mesh particles are ground to form for evaluating catalyst.Modifying element contained by catalyst L is with the mass ratio of molecular sieve carrier： K 1%, Rb 1%, Cs 6%, Ce 1%.Reagent used in preparation process is higher degree, with quality point in catalyst Number meter 820ppm containing V, Ti 850ppm, Os 810ppm.
【Comparative example 1】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieves, in the water of 500mL cesium nitrates at 60 DEG C Ion exchange is carried out in solution 2 hours, exchanged 2 times, filtered after exchange, in an oven 110 DEG C of dryings 4 hours, be dried Afterwards again in Muffle furnace at 600 DEG C roasting 4 hours, obtain catalyst M, grind to form 40～60 mesh particles for being catalyzed Agent is evaluated.Modifying element contained by catalyst M is with the mass ratio of molecular sieve carrier：Cs 6%.Examination used in preparation process Agent is the 1200ppm containing V in terms of mass fraction, Ti 1500ppm, Os 1000ppm in catalyst compared with low-purity.
【Comparative example 2】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieves, at 60 DEG C, in 500mL potassium nitrate The aqueous solution in carry out ion exchange 2 hours, exchange 2 times, then at 60 DEG C, in the aqueous solution of 500mL cesium nitrates In carry out ion exchange 2 hours, exchange 2 times, filter after exchange, in an oven 110 DEG C of dryings 4 hours.Prepare containing suitable The aqueous solution 100mL of amount cerous nitrate, the molecular sieve after ion exchange is stirred to enter for 4 hours in above-mentioned solution at 60 DEG C Row impregnates, then evaporating water.110 DEG C of dryings 4 hours in an oven, after being dried again in Muffle furnace at 600 DEG C Roasting 4 hours, obtains catalyst n, grinds to form 40～60 mesh particles for evaluating catalyst.It is modified contained by catalyst n Element is with the mass ratio of molecular sieve carrier：K 2%, Cs 6%, Ce 1%.Reagent used in preparation process is relatively low pure Degree, the 1500ppm containing V in terms of mass fraction, Ti 3000ppm, Os 1200ppm in catalyst.
【Comparative example 3】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieves, at 60 DEG C, in 500mL potassium nitrate The aqueous solution in carry out ion exchange 2 hours, exchange 2 times, then at 60 DEG C, in the aqueous solution of 500mL cesium nitrates In carry out ion exchange 2 hours, exchange 2 times, filter after exchange, in an oven 110 DEG C of dryings 4 hours.Prepare containing suitable The aqueous solution 100mL of amount cerous nitrate and sodium metaaluminate, the molecular sieve after ion exchange is stirred in above-mentioned solution at 60 DEG C Mix 4 hours and impregnated, then evaporating water.110 DEG C of dryings 4 hours in an oven, after being dried again in Muffle furnace in Roasting 4 hours at 600 DEG C, obtain catalyst O, grind to form 40～60 mesh particles for evaluating catalyst.Catalyst O Contained modifying element is with the mass ratio of molecular sieve carrier：K 2%, Cs 6%, Ce 1%, Bi 1%.Used in preparation process Reagent be the 1870ppm containing V in terms of mass fraction, Ti 3150ppm, Os 1100ppm in catalyst compared with low-purity.
【Embodiment 13】
Taking 5g catalyst A～O carries out methylbenzene methanol side chain alkylation reaction evaluating.Reaction temperature is 415 DEG C；Reaction pressure Power is normal pressure；Methylbenzene methanol mol ratio is 5：1；Toluene mass space velocity is 1.5h-1, carrier gas N2Flow velocity is 10mL/min. Catalytic reaction is carried out under these conditions, and product is analyzed with gas chromatography.After reaction, methanol conversion is 100%.Reaction result is listed in table 1.
Table 1*
* reaction is averaged for 10 hours
【Embodiment 14】
Taking 5g catalyst A, N carries out methylbenzene methanol side chain alkylation reaction evaluating.Reaction temperature is 415 DEG C；Reaction pressure Power is normal pressure；Methylbenzene methanol mol ratio is 5：1；Toluene mass space velocity is 1.5h-1, carrier gas N2Flow velocity is 10mL/min. Catalytic reaction is carried out under these conditions, and product is analyzed with gas chromatography.After reaction, methanol conversion is 100%.Catalyst one way is reacted 200 hours, and after Burning Coke on Catalyst regenerates 20 times, reaction result is listed in table 2.
Table 2*
* reaction is averaged for 10 hours

Claims (10)

1. it is a kind of for methylbenzene methanol side chain alkylation reaction catalyst, comprising following components：
A) at least one in X molecular sieve or Y molecular sieve；With load modified component thereon：
B) at least one in alkali metal, the element is (0.1～20) with the mass ratio of molecular sieve carrier：100；
C) at least one in rare earth element, the element is (0.05～10) with the mass ratio of molecular sieve carrier：100；
It is characterized in that the mass content of V element is less than 900ppm in catalyst；The mass content of Ti elements is less than 900ppm。
2. according to claim 1 for the catalyst of methylbenzene methanol side chain alkylation reaction, it is characterised in that institute The mass content for stating V element is less than 600ppm；The mass content of Ti elements is less than 600ppm.
3. the catalyst of methylbenzene methanol side chain alkylation reaction is used for according to claim 2, it is characterised in that the V The mass content of element is less than 400ppm；The mass content of Ti elements is less than 400ppm.
4. the catalyst of methylbenzene methanol side chain alkylation reaction is used for according to claim 1, it is characterised in that catalyst The mass content of middle Os elements is less than 900ppm.
5. the catalyst of methylbenzene methanol side chain alkylation reaction is used for according to claim 4, it is characterised in that catalyst The mass content of middle Os elements is less than 400ppm.
6. the catalyst of methylbenzene methanol side chain alkylation reaction is used for according to claim 1, it is characterised in that described point Son is screened from SiO2/Al2O3At least one in X molecular sieve or Y molecular sieve for 2～5.
7. the catalyst of methylbenzene methanol side chain alkylation reaction is used for according to claim 1, it is characterised in that the alkali At least one of the metallic element in K, Rb or Cs, the element is (0.5～10) with the mass ratio of molecular sieve carrier： 100。
8. the catalyst of methylbenzene methanol side chain alkylation reaction is used for according to claim 1, it is characterised in that described dilute At least one of the earth elements in La, Ce, the element is (0.1～2) with the mass ratio of molecular sieve carrier：100.
9. the catalyst of methylbenzene methanol side chain alkylation reaction is used for according to claim 1, it is characterised in that catalyst Bi elements are also included, the mass content of Bi elements is 0.05～10% in catalyst.
10. a kind of application of the catalyst for the reaction of methylbenzene methanol side chain alkylation, with toluene and methyl alcohol as raw material, raw material Middle toluene is (0.1～10) with methanol molar ratio:1, reaction temperature be 300 DEG C～500 DEG C, material quality air speed be 0.1～ 5.0h-1Under conditions of, ethylbenzene and styrene are generated after catalyst haptoreaction of the raw material with described in any one of claim 1～9.
CN201510731435.8A 2015-11-02 2015-11-02 Catalyst for alkylation reaction at methylbenzene methanol side and technical method thereof Pending CN106622342A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104557422A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Toluene/methanol side chain alkylation method
CN104926580A (en) * 2014-03-17 2015-09-23 中国石油化工股份有限公司 Method for preparing ethylbenzene and styrene through toluene and methanol side chain alkylation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104557422A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Toluene/methanol side chain alkylation method
CN104926580A (en) * 2014-03-17 2015-09-23 中国石油化工股份有限公司 Method for preparing ethylbenzene and styrene through toluene and methanol side chain alkylation

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