CN106622338A - Catalyst for side chain alkylation reaction of toluene and methanol and application thereof - Google Patents
Catalyst for side chain alkylation reaction of toluene and methanol and application thereof Download PDFInfo
- Publication number
- CN106622338A CN106622338A CN201510731130.7A CN201510731130A CN106622338A CN 106622338 A CN106622338 A CN 106622338A CN 201510731130 A CN201510731130 A CN 201510731130A CN 106622338 A CN106622338 A CN 106622338A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- molecular sieve
- side chain
- hours
- chain alkylation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a catalyst for a side chain alkylation reaction of toluene and methanol and application thereof, and mainly solves the problems of low utilization rate of methanol, low conversion rate of toluene and poor stability of a current catalyst used for the side chain alkylation reaction of toluene and methanol to produce ethylbenzene and styrene. The catalyst uses a modified X or Y molecular sieve as an active component, and at least one of Al, P and B, at least one of rare earth elements, at least one of alkali metal elements and at least one of platinum elements as modified components. A preparation method of the catalyst include the steps of ion exchange or impregnation, and molecular sieve surface modification by using an oxide of silicon. A technical scheme for application of the catalyst includes: the steps that raw materials of toluene and methanol contact with the catalyst to be subjected to a reaction to produce ethylbenzene and styrene, and well solves the problems, and the catalyst can be used in the industrial production of preparation of ethylbenzene and styrene by the side chain alkylation reaction of toluene and methanol.
Description
Technical field
The present invention relates to a kind of catalyst for the reaction of methylbenzene methanol side chain alkylation and application thereof.
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.It is that cinnamic one of production has potential answering by methylbenzene methanol side chain alkylation synthesizing styrene
With the route of prospect, the X-type that the reported first such as Sidorenko in 1967 toluene, methyl alcohol can be exchanged in alkali metal ion
Step generation styrene is reacted with there is side chain alkylation in Y zeolite catalyst.Compare traditional styrene synthesis road
Line, the technique adopts Coal Chemical Industry Route, due to raw material sources extensively, low cost, reaction condition be gentle, energy consumption is relatively low, tool
Standby good commercial development value and application prospect, cause greatly concern.
Methylbenzene methanol side chain alkylation is completed by soda acid synergy.The mechanism of reaction obtains formaldehyde for base catalysis Methanol Decomposition
Used as reaction intermediate, the methyl of activation Toluene is gone back in basic active position becomes carbanion, and then carbanion PARA FORMALDEHYDE PRILLS(91,95) occurs
Adol-type reacts, and after product dehydration styrene is obtained.There is hydrogenation reaction life with the hydrogen that reaction is produced in part styrene
Into ethylbenzene.The catalyst of methylbenzene methanol side chain alkylation reaction belongs to solid base catalyst, needs the alkali of sufficient intensity and quantity
Center generates formaldehyde with catalysis methanol dehydrogenation and activation Toluene methyl c h bond generates methyl carbanion.Meanwhile, toluene first
The soda acid concerted catalysis reaction still based on the catalysis of basic active position of alcohol side chain alkylation course of reaction.It is demonstrated experimentally that individually
The efficiency of basic active position catalysis methylbenzene methanol side chain alkylation is very low.In course of reaction, toluene molecule needs to be inhaled by Lewis acid
Echo stable, otherwise toluene conversion is relatively low.But if catalyst is alkaline too strong, methyl alcohol and intermediate product formaldehyde are easy
Further decompose into CO and hydrogen；If acidity of catalyst is too strong, mainly occur phenyl ring alkylated reaction generate benzene and
Dimethylbenzene.Therefore, catalyst needs to be matched with suitable soda acid.In addition, the adsorption equilibrium of toluene and methyl alcohol is also to affect
One of factor of methylbenzene methanol side chain alkylation reaction, suitable pore passage structure and cage size are conducive to the absorption of toluene and methyl alcohol
Balance.
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.US 4140726 reports Jing K, Rb, Cs and B, P and is modified
X or Y zeolite catalyst, with higher toluene conversion, but ethylbenzene, styrene overall selectivity are not ideal enough.
US 8318999B2 report Jing Cs and a kind of element modified X-type molecular sieve catalyst in Ga, B, Co, should
Method improves selectivity of styrene.CN 101623650A carry out ion exchange using K, Cs to X or Y type molecular sieve,
And load the stability that the method for B, P and alkali metal or alkaline-earth metal improves catalyst.CN 101623649A are to Jing
The X or Y type molecular sieve of alkali metals modified uses at high temperature again ammonia treatment, improves the activity and stability of catalyst.This
A little modified X for having reported or Y type molecular sieve achieve certain catalytic effect in the reaction of methylbenzene methanol side chain alkylation.
But, how to take into account toluene conversion and use ratio of methanol be an important technology difficult problem in the reaction of methylbenzene methanol side chain alkylation.
Report that catalyst obtains at the same time high toluene conversion and high methanol utilization rate aspect is still not ideal enough, for industrial
Requirement still has larger gap, and haves the shortcomings that hydrothermal stability is not high.Therefore, exploitation is in methylbenzene methanol pendant alkyl group
Changing can simultaneously take into account suitable toluene conversion and use ratio of methanol in reaction, ethylbenzene, selectivity of styrene height and hydro-thermal
The high catalyst of stability is to realize methylbenzene methanol side chain alkylation preparing ethylbenzene by reaction, the key factor of styrene industrialized production
One of.In addition, higher selectivity of styrene also advantageously improves economic benefit.
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
Ethylbenzene processed and the catalyst of styrene 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 Al, P and B, the element is (0.05～10) with the mass ratio of molecular sieve carrier：100；
C) at least one in alkali metal, the element is (0.1～20) with the mass ratio of molecular sieve carrier：100；
D) at least one in platinum group, the element is (0.05～10) with the mass ratio of molecular sieve carrier：100；
E) at least one in rare earth element, the element is (0.05～10) with the mass ratio of molecular sieve carrier：100；
F) oxide of Si, the Si elements are (0.1～10) with the mass ratio of molecular sieve carrier：100.
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；In modified component Al, P, B, preferred version be Al, P, B at least
One kind, with the mass ratio of molecular sieve carrier (0.05～10) is preferably：100, more preferably scheme is (0.1～2)：100；Alkali gold
At least one of the category element in K, Rb or Cs, more preferably scheme are the matter of Cs, alkali metal and molecular sieve carrier
Amount is than being preferably (0.1～20)：100, more preferably scheme is (0.5～10)：100；Platinum group is in Ru, Rh or Pt
At least one, the mass ratio of platinum group and molecular sieve carrier is preferably (0.05～10)：100, more preferably scheme for (0.1～
2)：100；At least one of the rare earth element in La, Ce, Pr, Nd, preferred version is the one kind in La, Ce,
More preferably scheme is Ce, and rare earth element is preferably (0.05～10) with the mass ratio of molecular sieve carrier：100, more preferably scheme is
(0.1～2)：100；Si elements and the mass ratio of molecular sieve carrier are (0.1～10) in Si oxides：100, preferred version is
(0.5～5)：100.
In above-mentioned technical proposal, Si oxide sources are preferably methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, aminomethyl phenyl silicon
Oil, methylchlorophenyl silicone oil, MethylethoxylsiliconFluid Fluid, methyl vinyl silicon oil, methylhydroxy silicone oil, tetramethoxy-silicane,
The silicon-containing compounds such as tetraethoxysilane, tetrapropoxysilane, four butoxy silanes；Most preferably methyl-silicone oil, ethyl silicon
At least one in oil, phenyl silicone oil, tetraethoxysilane and four butoxy silanes.
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) surface modification is carried out to molecular sieve using silicon-containing compound, forms Si oxides in molecular sieve surface after roasting and cover
Layer；
C) modified molecular sieve is dried, roasting, shaping.
In above-mentioned technical proposal, the modified metal component precursor of catalyst may be selected from chloride, hydroxide or nitrate
It is a kind of；Al elemental constituent precursors may be selected from NaAlO2Or KAlO2；B, P element component precursor may be selected from boric acid, phosphoric acid
Or alkali metal salt；Baking temperature is 90 DEG C～150 DEG C, and drying time is 1～24 hour, and sintering temperature is 400 DEG C～650
DEG C, roasting time is 1～24 hour；Si oxide surface modifications process is using silicon-containing compound with molecular sieve in organic solvent
Middle heating is carried out, and organic solvent may be selected from toluene or the one kind in hexamethylene.
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 350 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 as Lewis alkali center, while dipping
Metal oxide in molecular sieve pore passage becomes Benzyl Side-Chain alkylation as the new basic center with appropriate intensity
The new active sites of reaction, the addition with more alkaline meta-aluminate enhances catalyst alkali centered active site, makes catalysis anti-
There should be higher toluene conversion.Modifying element can make molecular sieve that there is suitable soda acid to match.Rare earth element and molecule
There is stronger active force between sieve skeleton frame O atom, the positive charge of framework of molecular sieve Al atoms can be dramatically increased, increase Al
And the active force between adjacent O atom, effectively stabilize the skeleton Al of molecular sieve, it is to avoid the removing of skeleton Al, have
Beneficial to molecular sieves stabilized skeleton structure, the hydrothermal stability of catalyst is improved.Molecular sieve outer surface is because be difficult to toluene
CO and hydrogen are resolved into molecular sieve outer surface with the intermediate formaldehyde of the adsorption equilibrium of methyl alcohol, methyl alcohol and generation, is reduced
The utilization rate of methanol feedstock.The outer surface of molecular sieve is covered using the Si oxides of relative inertness, raw material first can be avoided
The decomposition of alcohol, improves raw material availability.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 15%, use ratio of methanol up to 60%, ethylbenzene, styrene overall selectivity>95%.Catalyst
Better performances and stability height, achieve 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, with methyl-silicone oil in 500mL hexamethylenes
Middle backflow 4 hours, 110 DEG C of dryings 4 hours in an oven after filtration, then roasting 4 is little at 600 DEG C in Muffle furnace
When.By gained sample at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL potassium nitrate 2 hours, exchange 2
It is secondary, then at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL cesium nitrates 2 hours, exchange 2 times, hand over
Filter after changing, in an oven 110 DEG C of dryings 4 hours.Prepare and contain appropriate potassium metaaluminate, boric acid, ruthenium trichloride, nitric acid
The aqueous solution 100mL of cerium, 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 A is obtained, 40～60 mesh particles are ground to form for evaluating catalyst.Modifying element contained by catalyst A with point
Son sieves the mass ratio of carrier：Al 1%, B 1%, K 2%, Cs 6%, Ru 0.8%, Ce 1%, Si 2%.
【Embodiment 2】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2 NaX type molecular sieves, with methyl-silicone oil in 500mL hexamethylenes
Backflow 4 hours, 90 DEG C of dryings 24 hours in an oven after filtration, then roasting 24 is little at 400 DEG C in Muffle furnace
When.By gained sample at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL potassium nitrate 2 hours, exchange 2
It is secondary, then at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL cesium nitrates 2 hours, exchange 2 times, hand over
Filter after changing, in an oven 90 DEG C of dryings 24 hours.Prepare and contain appropriate potassium metaaluminate, boric acid, ruthenium trichloride, nitric acid
The aqueous solution 100mL of cerium, 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.90 DEG C of dryings 24 hours in an oven, the roasting 24 at 400 DEG C in Muffle furnace again after being dried
Hour, catalyst B is obtained, 40～60 mesh particles are ground to form for evaluating catalyst.Modifying element contained by catalyst B with
The mass ratio of molecular sieve carrier is：Al 0.1%, B 0.1%, K 0.5%, Cs 0.5%, Ru 0.1%, Ce 0.1%, Si 0.5%.
【Embodiment 3】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.9 NaX type molecular sieves, with methyl-silicone oil in 500mL hexamethylenes
Middle backflow 4 hours, 150 DEG C of dryings 1 hour in an oven after filtration, then roasting 1 is little at 650 DEG C in Muffle furnace
When.By gained sample at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL potassium nitrate 2 hours, exchange 2
It is secondary, then at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL cesium nitrates 2 hours, exchange 2 times, hand over
Filter after changing, in an oven 150 DEG C of dryings 1 hour.Prepare and contain appropriate potassium metaaluminate, boric acid, ruthenium trichloride, nitric acid
The aqueous solution 100mL of cerium, 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.150 DEG C of dryings 1 hour in an oven, again roasting 1 is little at 650 DEG C in Muffle furnace after being dried
When, catalyst C is obtained, 40～60 mesh particles are ground to form for evaluating catalyst.Modifying element contained by catalyst C with point
Son sieves the mass ratio of carrier：Al 2%, B 2%, K 5%, Cs 10%, Ru 2%, Ce 2%, Si 5%.
【Embodiment 4】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2 NaX type molecular sieves, with methyl-silicone oil in 500mL hexamethylenes
Backflow 4 hours, 110 DEG C of dryings 4 hours in an oven after filtration, then in Muffle furnace at 600 DEG C roasting 4 hours.
By gained sample at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL potassium nitrate 2 hours, is exchanged 2 times,
Then at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL cesium nitrates 2 hours, is exchanged 2 times, after exchange
Filter, in an oven 110 DEG C of dryings 4 hours.Prepare containing appropriate potassium metaaluminate, boric acid, ruthenium trichloride, cerous nitrate
Aqueous solution 100mL, the molecular sieve after ion exchange is stirred in above-mentioned solution at 60 DEG C and is impregnated within 4 hours, so
Evaporating water afterwards.110 DEG C of dryings 4 hours in an oven, after being dried again in Muffle furnace at 600 DEG C roasting 4 hours,
Catalyst D is obtained, 40～60 mesh particles is ground to form for evaluating catalyst.Modifying element and molecular sieve contained by catalyst D
The mass ratio of carrier is：Al 0.05%, B 0.05%, K 0.1%, Cs 0.3%, Ru 0.05%, Ce 0.05%, Si 0.1%.
【Embodiment 5】
Weigh 100g silica alumina ratio SiO2/Al2O3For 5 NaY type molecular sieves, with methyl-silicone oil in 500mL hexamethylenes
Backflow 4 hours, 110 DEG C of dryings 4 hours in an oven after filtration, then in Muffle furnace at 600 DEG C roasting 4 hours.
By gained sample at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL cesium nitrates 2 hours, is exchanged 2 times,
Filter after exchange, in an oven 110 DEG C of dryings 4 hours.Prepare and contain appropriate potassium metaaluminate, boric acid, ruthenium trichloride, nitre
The aqueous solution 100mL of sour cerium, the molecular sieve after ion exchange is stirred in above-mentioned solution at 60 DEG C and is soaked within 4 hours
Stain, then evaporating water.110 DEG C of dryings 4 hours in an oven, the roasting at 600 DEG C in Muffle furnace again after being dried
4 hours, catalyst E is obtained, grind to form 40～60 mesh particles for evaluating catalyst.Modifying element contained by catalyst E
It is with the mass ratio of molecular sieve carrier：Al 10%, B 10%, Cs 20%, Ru 10%, Ce 10%, Si 10%.
【Embodiment 6】
Weigh 100g silica alumina ratio SiO2/Al2O3For 5 NaY type molecular sieves, with tetraethoxysilane in 500mL toluene
Middle backflow 4 hours, 110 DEG C of dryings 4 hours in an oven after filtration, then roasting 4 is little at 600 DEG C in Muffle furnace
When.By gained sample at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL rubidium nitrates 2 hours, exchange 2
It is secondary, then at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL cesium nitrates 2 hours, exchange 2 times, hand over
Filter after changing, in an oven 110 DEG C of dryings 4 hours.Prepare and contain appropriate boric acid, phosphoric acid, radium chloride, the water of lanthanum nitrate
Solution 100mL, 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, after being dried again in Muffle furnace at 600 DEG C roasting 4 hours,
Catalyst F is obtained, 40～60 mesh particles is ground to form for evaluating catalyst.Modifying element and molecular sieve contained by catalyst F
The mass ratio of carrier is：B 1%, P 1%, Rb 2%, Cs 6%, Rh 0.8%, La 1%, Si 2%.
【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.Prepare and contain appropriate phosphoric acid, chloroplatinic acid, the aqueous solution 100mL of cerous nitrate, by the molecular sieve after ion exchange above-mentioned
Stir at 60 DEG C in solution and impregnated for 4 hours, then evaporating water.110 DEG C of dryings 4 hours in an oven, do
After dry again in Muffle furnace at 600 DEG C roasting 4 hours, by gained sample and four butoxy silanes in 500mL hexamethylenes
Middle backflow 4 hours, 110 DEG C of dryings 4 hours in an oven after filtration, then roasting 4 is little at 600 DEG C in Muffle furnace
When, catalyst G is obtained, 40～60 mesh particles are ground to form for evaluating catalyst.Modifying element contained by catalyst G with point
Son sieves the mass ratio of carrier：P 1%, Cs 6%, Pt 0.8%, Ce 1%, Si 2%.
【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 and contain appropriate boric acid, palladium bichloride, the aqueous solution 100mL of lanthanum nitrate, 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, gained sample and methyl-silicone oil are flowed back in 500mL ether 4 little
When, 110 DEG C of dryings 4 hours in an oven after filtration, then in Muffle furnace at 600 DEG C roasting 4 hours, urged
Agent H, grinds to form 40～60 mesh particles for evaluating catalyst.Modifying element contained by catalyst H and molecular sieve carrier
Mass ratio is：B 1%, Cs 6%, Pd 0.8%, La 1%, Si 2%.
【Embodiment 9】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieves, with methyl-silicone oil in 500mL hexamethylenes
Middle backflow 4 hours, 110 DEG C of dryings 4 hours in an oven after filtration, then roasting 4 is little at 600 DEG C in Muffle furnace
When.By gained sample at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL cesium nitrates 2 hours, exchange 2
It is secondary, filter after exchange, in an oven 110 DEG C of dryings 4 hours.Prepare containing appropriate sodium metaaluminate, boric acid, cesium hydroxide,
The aqueous solution 100mL of chloroplatinic acid, cerous nitrate, 4 are stirred by the molecular sieve after ion exchange in above-mentioned solution at 60 DEG C
Hour is impregnated, 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 I, grind to form 40～60 mesh particles for evaluating catalyst.Contained by catalyst I
Modifying element is with the mass ratio of molecular sieve carrier：Al 1%, B 1%, Cs 8%, Pt 0.8%, Ce 1%, Si 2%.
【Embodiment 10】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieves, with methyl-silicone oil in 500mL hexamethylenes
Backflow 4 hours, 110 DEG C of dryings 4 hours in an oven after filtration, then in Muffle furnace at 600 DEG C roasting 4 hours.
By gained sample at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL rubidium nitrates 2 hours, exchange 2 times, so
Afterwards at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL cesium nitrates 2 hours, is exchanged 2 times, filtered after exchange,
110 DEG C of dryings 4 hours in an oven.Prepare and contain appropriate potassium metaaluminate, phosphoric acid, ruthenium trichloride, the aqueous solution of lanthanum nitrate
100mL, the molecular sieve after ion exchange is stirred in above-mentioned solution at 60 DEG C and is impregnated within 4 hours, is then evaporated
Moisture.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 J, grinds to form 40～60 mesh particles for evaluating catalyst.Modifying element contained by catalyst J and molecular sieve carrier
Mass ratio is：Al 1%, P 1%, Rb 2%, Cs 6%, Ru 0.8%, La 1%, Si 2%.
【Embodiment 11】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieves, with methyl-silicone oil in 500mL hexamethylenes
Backflow 4 hours, 110 DEG C of dryings 4 hours in an oven after filtration, then in Muffle furnace at 600 DEG C roasting 4 hours.
By gained sample at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL potassium nitrate 2 hours, exchanged 2 times, then
Ion exchange is carried out in the aqueous solution of 500mL rubidium nitrates 2 hours, exchanged 2 times, then at 60 DEG C, in 500mL
Ion exchange is carried out in the aqueous solution of cesium nitrate 2 hours, exchanged 2 times, filtered after exchange, 110 DEG C of dryings 4 in an oven
Hour.Prepare containing appropriate potassium metaaluminate, boric acid, phosphoric acid, cesium nitrate, ruthenium trichloride, radium chloride, chloroplatinic acid, 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 to be carried out for 4 hours
Impregnate, then evaporating water.110 DEG C of dryings 4 hours in an oven, roast in Muffle furnace again after being dried at 600 DEG C
Burn 4 hours, obtain catalyst K, grind to form 40～60 mesh particles for evaluating catalyst.Be modified unit contained by catalyst K
Element is with the mass ratio of molecular sieve carrier：Al 1%, B 1%, P 1%, K 1%, Rb 1%, Cs 6%, Ru 0.8%,
Rh 0.8%, Pt 0.8%, Ce 1%, La 1%, Si 2%.
【Embodiment 12】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieves, with methyl-silicone oil in 500mL hexamethylenes
Backflow 4 hours, 110 DEG C of dryings 4 hours in an oven after filtration, then in Muffle furnace at 600 DEG C roasting 4 hours.
By gained sample at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL potassium nitrate 2 hours, exchange 2 times, so
Afterwards at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL cesium nitrates 2 hours, is exchanged 2 times, filtered after exchange,
110 DEG C of dryings 4 hours in an oven.Prepare containing appropriate potassium metaaluminate, boric acid, ruthenium trichloride, cerous nitrate, indium nitrate
Aqueous solution 100mL, the molecular sieve after ion exchange is stirred in above-mentioned solution at 60 DEG C and is impregnated within 4 hours, so
Evaporating water afterwards.110 DEG C of dryings 4 hours in an oven, after being dried again in Muffle furnace at 600 DEG C roasting 4 hours,
Catalyst L is obtained, 40～60 mesh particles is ground to form for evaluating catalyst.Modifying element and molecular sieve contained by catalyst L
The mass ratio of carrier is：Al 1%, B 1%, K 2%, Cs 6%, Ru 0.8%, Ce 1%, Si 2%, In 1%.
【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%.
【Comparative example 2】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieves, in the water of 500mL potassium nitrate at 60 DEG C
Ion exchange is carried out in solution 2 hours, exchanged 2 times, then at 60 DEG C, entered in the aqueous solution of 500mL cesium nitrates
Row ion exchange 2 hours, exchanges 2 times, filters after exchange, in an oven 110 DEG C of dryings 4 hours.Prepare and contain appropriate three
The aqueous solution 100mL of ruthenic chloride, the molecular sieve after ion exchange is stirred in above-mentioned solution at 60 DEG C to be carried out for 4 hours
Impregnate, then evaporating water.110 DEG C of dryings 4 hours in an oven, roast in Muffle furnace again after being dried at 600 DEG C
Burn 4 hours, obtain catalyst n, grind to form 40～60 mesh particles for evaluating catalyst.Be modified unit contained by catalyst n
Element is with the mass ratio of molecular sieve carrier：K 2%, Cs 6%, Ru 0.8%.
【Comparative example 3】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieves, in the water of 500mL potassium nitrate at 60 DEG C
Ion exchange is carried out in solution 2 hours, exchanged 2 times, then at 60 DEG C, entered in the aqueous solution of 500mL cesium nitrates
Row ion exchange 2 hours, exchanges 2 times, filters after exchange, in an oven 110 DEG C of dryings 4 hours.Prepare and contain appropriate boron
Acid, ruthenium trichloride, the aqueous solution 100mL of cerous nitrate, by the molecular sieve after ion exchange in above-mentioned solution at 60 DEG C
Stirring is impregnated for 4 hours, then evaporating water.110 DEG C of dryings 4 hours in an oven, after being dried again in Muffle furnace
Roasting 4 hours at 600 DEG C, obtain catalyst O, grind to form 40～60 mesh particles for evaluating catalyst.Catalyst
Modifying element contained by O is with the mass ratio of molecular sieve carrier：B 1%, K 2%, Cs 6%, Ru 0.8%, Ce 1%.
【Comparative example 4】
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieves, with methyl-silicone oil in 500mL hexamethylenes
Backflow 4 hours, 110 DEG C of dryings 4 hours in an oven after filtration, then in Muffle furnace at 600 DEG C roasting 4 hours.
By gained sample at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL potassium nitrate 2 hours, exchange 2 times, so
Afterwards at 60 DEG C, ion exchange is carried out in the aqueous solution of 500mL cesium nitrates 2 hours, is exchanged 2 times, filtered after exchange,
110 DEG C of dryings 4 hours in an oven.The aqueous solution 100mL containing appropriate ruthenium trichloride is prepared, by the molecule after ion exchange
Sieve is stirred at 60 DEG C in above-mentioned solution and impregnated for 4 hours, then evaporating water.110 DEG C of dryings 4 in an oven
Hour, be dried after again in Muffle furnace at 600 DEG C roasting 4 hours, obtain catalyst P, grind to form 40～60 mesh
Grain is used for evaluating catalyst.Modifying element contained by catalyst P is with the mass ratio of molecular sieve carrier：K 2%, Cs 6%, Ru
0.8%, Si 2%.
【Embodiment 13】
Taking 5g catalyst A～P carries out methylbenzene methanol side chain alkylation reaction evaluating.Reaction temperature is 415 DEG C；Reaction pressure
For normal pressure；Methylbenzene methanol mol ratio is 4：1；Toluene mass space velocity is 1.0h-1, carrier gas N2Flow velocity is 10mL/min.
Catalytic reaction is carried out under above-mentioned condition, product is analyzed with gas chromatography.After reaction, methanol conversion is 100%.
Reaction result is listed in table 1.
Table 1*
| Catalyst | Toluene conversion (%) | Use ratio of methanol (%) | Ethylbenzene+selectivity of styrene (%) |
| A | 15.4 | 61.6 | 98.1 |
| B | 10.7 | 42.8 | 95.8 |
| C | 12.9 | 51.6 | 91.4 |
| D | 10.1 | 40.4 | 94.7 |
| E | 15.6 | 62.4 | 88.1 |
| F | 12.3 | 49.2 | 96.4 |
| G | 11.5 | 46.0 | 95.2 |
| H | 11.9 | 47.6 | 97.5 |
| I | 14.7 | 58.8 | 94.5 |
| J | 13.6 | 54.4 | 96.3 |
| K | 13.8 | 55.2 | 97.0 |
| L | 15.2 | 60.8 | 95.9 |
| Comparative example M | 5.5 | 22.0 | 89.2 |
| Comparative example N | 6.1 | 24.4 | 88.6 |
| Comparative example O | 6.3 | 25.2 | 89.2 |
| Comparative example P | 6.7 | 26.8 | 91.4 |
* reaction is averaged for 10 hours
【Embodiment 14】
Taking 5g catalyst A, M 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 4：1；Toluene mass space velocity is 1.0h-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 Al, P and B, the element is (0.05～10) with the mass ratio of molecular sieve carrier：100；
C) at least one in alkali metal, the element is (0.1～20) with the mass ratio of molecular sieve carrier：100；
D) at least one in platinum group, the element is (0.05～10) with the mass ratio of molecular sieve carrier：100；
E) at least one in rare earth element, the element is (0.05～10) with the mass ratio of molecular sieve carrier：100；
F) oxide of Si, the Si elements are (0.1～10) with the mass ratio of molecular sieve carrier：100.
2. 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.
3. the catalyst of methylbenzene methanol side chain alkylation reaction is used for according to claim 1, it is characterised in that described point
Son sieve is X molecular sieve.
4. the catalyst of methylbenzene methanol side chain alkylation reaction is used for according to claim 1, it is characterised in that described to change
Property at least one of the component in the Al and B, the element is (0.1～2) with the mass ratio of molecular sieve carrier：100.
5. 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。
6. the catalyst of methylbenzene methanol side chain alkylation reaction is used for according to claim 1, it is characterised in that the platinum
At least one of the series elements in Ru, Rh or Pt, the element is (0.1～2) with the mass ratio of molecular sieve carrier：100.
7. 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 or Ce, the element is (0.1～2) 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 the Si
It is (0.5～5) 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
Preparation method comprise the steps of：
A) molecular sieve is carried out into ion exchange or dipping with the solution containing the modifying element；
B) surface modification is carried out to molecular sieve using silicon-containing compound, forms Si oxides in molecular sieve surface after roasting and cover
Layer；
C) modified molecular sieve is dried, roasting, shaping.
10. it is a kind of for methylbenzene methanol side chain alkylation reaction catalyst purposes, with toluene and methyl alcohol as raw material, raw material
Middle toluene is (0.1～10) with methanol molar ratio:1, reaction temperature be 350 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 1～8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510731130.7A CN106622338B (en) | 2015-11-02 | 2015-11-02 | Catalyst and application thereof for the reaction of methylbenzene methanol side chain alkylation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510731130.7A CN106622338B (en) | 2015-11-02 | 2015-11-02 | Catalyst and application thereof for the reaction of methylbenzene methanol side chain alkylation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106622338A true CN106622338A (en) | 2017-05-10 |
| CN106622338B CN106622338B (en) | 2019-10-11 |
Family
ID=58809946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510731130.7A Active CN106622338B (en) | 2015-11-02 | 2015-11-02 | Catalyst and application thereof for the reaction of methylbenzene methanol side chain alkylation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106622338B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107866264A (en) * | 2017-11-21 | 2018-04-03 | 万华化学集团股份有限公司 | A kind of synthesis DEMMA catalyst and preparation method thereof, application |
| CN109529910A (en) * | 2018-11-29 | 2019-03-29 | 中国科学院大连化学物理研究所 | Catalyst, styrene preparation method for the reaction of methylbenzene methanol side chain alkylation |
| CN109701592A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Side chain alkylation catalyst and its application method |
| CN109701593A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Side chain alkylation catalyst and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915512A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Catalyst for alkylation of toluene methanol |
| CN102740969A (en) * | 2010-02-05 | 2012-10-17 | 弗纳技术股份有限公司 | Styrene production processes and catalysts for use therein |
| CN104557374A (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 |
| US20150225859A1 (en) * | 2014-02-07 | 2015-08-13 | Panasonic Intellectual Property Management Co., Ltd. | Dehydrogenation device |
| WO2014186207A3 (en) * | 2013-05-13 | 2015-10-29 | University Of Connecticut | Mesoporous materials and processes for preparation thereof |
-
2015
- 2015-11-02 CN CN201510731130.7A patent/CN106622338B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915512A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Catalyst for alkylation of toluene methanol |
| CN102740969A (en) * | 2010-02-05 | 2012-10-17 | 弗纳技术股份有限公司 | Styrene production processes and catalysts for use therein |
| WO2014186207A3 (en) * | 2013-05-13 | 2015-10-29 | University Of Connecticut | Mesoporous materials and processes for preparation thereof |
| CN104557374A (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 |
| US20150225859A1 (en) * | 2014-02-07 | 2015-08-13 | Panasonic Intellectual Property Management Co., Ltd. | Dehydrogenation device |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109701592A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Side chain alkylation catalyst and its application method |
| CN109701593A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Side chain alkylation catalyst and application thereof |
| CN109701592B (en) * | 2017-10-26 | 2021-12-28 | 中国石油化工股份有限公司 | Side chain alkylation catalyst and method of use |
| CN109701593B (en) * | 2017-10-26 | 2022-07-08 | 中国石油化工股份有限公司 | Side chain alkylation catalyst and use thereof |
| CN107866264A (en) * | 2017-11-21 | 2018-04-03 | 万华化学集团股份有限公司 | A kind of synthesis DEMMA catalyst and preparation method thereof, application |
| CN109529910A (en) * | 2018-11-29 | 2019-03-29 | 中国科学院大连化学物理研究所 | Catalyst, styrene preparation method for the reaction of methylbenzene methanol side chain alkylation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106622338B (en) | 2019-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106268923B (en) | A kind of preparation method and application of bifunctional catalyst | |
| CN111229303B (en) | Composite catalyst for directly preparing high-value aromatic hydrocarbon from carbon dioxide, preparation method and application | |
| CN106622338A (en) | Catalyst for side chain alkylation reaction of toluene and methanol and application thereof | |
| CN103007995B (en) | A kind of composite catalyst preparing trichlorosilane for catalytic hydrogenation of silicon tetrachloride | |
| CN104926580B (en) | Method for preparing ethylbenzene and styrene through toluene and methanol side chain alkylation | |
| CN101992082B (en) | Catalyst for toluene methanol side-chain alkylation reaction and preparation method thereof | |
| CN103418377B (en) | The thin-shell catalyst of low-carbon alkene is prepared for dehydrogenating low-carbon alkane | |
| CN101530813A (en) | Method for preparing molecular sieve catalyst used in carbon 4 liquid gas aromatization reaction | |
| CN106622334A (en) | Catalyst used in methylbenzene methanol side chain alkylation reaction and application thereof | |
| CN106622335B (en) | For Benzyl Side-Chain alkylated reaction preparation of styrene and the catalyst of ethylbenzene and application thereof | |
| CN103706391B (en) | A kind of preparation method of catalyst for producing propylene with methanol | |
| CN106622339B (en) | Catalyst and its application for the reaction of methylbenzene methanol side chain alkylation | |
| CN102039161B (en) | C8 arene isomerization catalyst and application thereof | |
| CN110280302A (en) | A kind of catalyst and its preparation method and application converting methane in aromatic hydrocarbons | |
| CN102091648A (en) | Method for preparing carclazyte olefin removing catalyst | |
| CN106622336A (en) | Catalyst for preparation of styrene and ethylbenzene by side chain alkylation reaction of toluene and application thereof | |
| CN106268925A (en) | A kind of alkylation of toluene methanol xylol catalyst, Preparation Method And The Use | |
| CN102039159B (en) | Xylene isomerization catalyst and application thereof | |
| CN111054384B (en) | Catalyst for organic liquid hydrogen storage material dehydrogenation and preparation method thereof | |
| CN100425343C (en) | Alkyl arene isomerizing catalyst and its usage | |
| CN104549444B (en) | The catalyst of oxygenatedchemicals aromatic hydrocarbons and its application | |
| CN102372537A (en) | Method for preparing propylene and aromatic hydrocarbon through methanol conversion | |
| CN100408167C (en) | Catalyst for ethylbenzene dehydrogenation-hydroxide reaction | |
| CN109529911B (en) | Platinum-tin-based mesoporous catalyst for propane anaerobic dehydrogenation and preparation and application thereof | |
| CN106540742A (en) | Multi-stage porous methane non oxidative aromatization and alkylating aromatic hydrocarbon coupled catalyst of a kind of high catalytic activity and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |