CN109746037A - Compound pore zeolite catalyst of side chain alkylation and application thereof - Google Patents
Compound pore zeolite catalyst of side chain alkylation and application thereof Download PDFInfo
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Abstract
Compound pore zeolite catalyst of side chain alkylation and application thereof.The invention mainly relates to a kind of compound pore zeolite catalysts for toluene and methanol side chain alkylation ethylbenzene and styrene, and there are catalyst easy in inactivation is low with use ratio of methanol when mainly solving the problems, such as catalyst used in the prior art for the reaction of methylbenzene methanol side chain alkylation.It is catalyst material that the present invention introduces mesoporous directed agents synthetic microporous composite mesoporous hole X molecular sieve during hydrothermal synthesis method；The catalyst is solving the problems, such as with alkali metal ion exchange and preferably this with the technical solution of supported rare earth and aluminon to composite holes X molecular sieve using preceding, can be used for methylbenzene methanol side chain alkylation reaction and prepares in the industrial production of ethylbenzene and styrene.
Description
Technical field
The present invention relates to a kind of compound pore zeolite catalysts for being used to prepare ethylbenzene and styrene, especially methylbenzene methanol
Side chain alkylation prepares the compound pore zeolite catalyst of ethylbenzene styrene.
Background technique
Styrene monomer is a kind of important Organic Chemicals, is mainly used for polystyrene, (ABS) resin, butylbenzene rubber
The production of the products such as glue, unsaturated-resin.Furthermore, it may also be used for pharmacy, dyestuff produce farm chemical emulgent and dressing agent etc.,
Purposes is very extensive.The yield of styrene series resin is only second to PE, PVC in synthetic resin and comes in third.Current big portion
Division of labor industry styrene is to be reacted to generate ethylbenzene through Friedel-Craft by benzene and ethylene, then get through catalytic dehydrogenation.The method process
Compared with long, side reaction is more, energy consumption is high, cost of material accounts for the 85% of production variable cost, and production cost is higher.Toluene and methanol alkyl
Change, which is one of production styrene, the route of potential application foreground, and Sidorenko in 1967 etc. is handed over alkali metal ion for the first time
The X-type and y-type zeolite changed is that catalyst successfully uses toluene and methanol-fueled CLC ethylbenzene and styrene.Compared with traditional handicraft,
The method has many advantages, such as that raw material sources are wide, at low cost, low energy consumption, pollution is few.Thus the reaction just receives people once report
Attention, the research in relation to this respect also starts to increase.
The catalyst of methylbenzene methanol side chain alkylation preparation of styrene belongs to solid base catalyst, but catalytic process is a soda acid
Concerted catalysis reaction, and be leading with the catalysis of basic active position.The acidic site of catalyst can play the role of stable toluene phenyl ring,
And the methyl group of basic sites energy activation Toluene and methanol.Methanol is decomposed into formaldehyde on alkali center first, and toluene is adsorbed on acid
On center, pendant methyl is activated by alkali center, then formaldehyde and the methyl activated reaction production styrene, part styrene
It is reacted with the hydrogen of generation and generates ethylbenzene.If catalyst alkalinity is too strong, formaldehyde can be made further to decompose, while generate more hydrogen
Gas and ethylbenzene；If acidity of catalyst is too strong, the alkylation and toluene disproportionation of phenyl ring can occur, generate benzene and dimethylbenzene, institute
To require catalyst to match with suitable soda acid, while the presence of phenyl ring requires catalyst to have certain space pore structure.
The reaction of methylbenzene methanol side chain alkylation once conducted extensive research on multiple catalysts.Many molecular sieves such as X,
Y, L, β, ZSM-5 and some basic anhydride such as MgO, MgO-TiO2And CaO-TiO2The research that is all reported is applied to catalysis
In the reaction of methylbenzene methanol side chain alkylation, such as JOURNAL OF CATALYSIS 173,490-500 (1998) and
CN101623649A,CN101623650A.Result of study discovery, to reach preferable side chain alkylation catalytic effect, catalysis
Agent must satisfy following 4 points requirement: it is methylating reagent first that catalyst, which must have enough basic center activation methanol conversions,
Aldehyde；There is the weak acid site Lewis to stablize toluene and its methyl that polarizes；Toluene and methanol to have on a catalyst one very well
Stoichiometry adsorption equilibrium；Catalyst must have micropore canals structure.Therefore, research knot active to some zeolite catalysises
Fruit shows that the X-type zeolite of alkali metal cation-exchanged is the catalyst of relative efficiency.The reactivity of y-type zeolite is boiled inferior to X-type
Stone.And the reactivity of other such as L, β, ZSM-5 type zeolites is all undesirable, and some not microcellular structures is alkaline oxygenated
Object, such as MgO, MgO-TiO2And CaO-TiO2Deng only very low activity.Currently, most of reported in the literature for methylbenzene methanol
Side chain alkylation Fau type molecular sieve catalyst is all conventional X and Y zeolite catalyst, and molecular sieve contains only micropore, is not situated between
Hole duct.
It is not used for the report of side chain alkylation reaction using composite holes molecular sieve catalytic agent material favorably in the prior art.
Summary of the invention
The first technical problem to be solved by the present invention is that catalyst used in the prior art is anti-for side chain alkylation
At once there are problems that raw material availability is low and catalyst is easy inactivation, provide a kind of new side chain alkylation catalyst, this is urged
Agent has use ratio of methanol high, catalyst not easy in inactivation the characteristics of.The second technical problem to be solved by the present invention is new
The preparation method of side chain alkylation catalyst when this method is used to prepare side chain alkylation catalyst, has preparation process simple
The advantages that.
One of in order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of side chain alkylation is compound
Pore zeolite catalyst, it is characterised in that catalyst uses rare earth modified compound porous molecular sieve.
In above-mentioned technical proposal, it is preferred that compound porous molecular sieve contains micropore and mesoporous two kinds of cellular structures.
In above-mentioned technical proposal, it is preferred that composite holes microporous molecular sieve and mesoporous volume ratio 0.5~15, more preferably 3
~8.
In above-mentioned technical proposal, it is preferred that the compound mesoporous pore size range of porous molecular sieve is in 2~20nm；More preferably 5~
15nm。
In above-mentioned technical proposal, it is preferred that compound porous molecular sieve is modified through alkali metal ion；It is furthermore preferred that alkali metal from
Son exchange modification is completed before rare earth modified, and the load capacity of rare earth element is between 0.3~5%, and preferably 0.5~3%.
In above-mentioned technical proposal, it is preferred that compound porous molecular sieve is modified by aluminium；It is furthermore preferred that aluminium is modified to use inclined aluminium
Sour sodium is modified；Preferably, in terms of catalyst weight percent, the content for modified sodium metaaluminate is 2~5%.
In above-mentioned technical proposal, it is preferred that compound porous molecular sieve is modified through bismuth element；Preferably, with catalyst weight hundred
Dividing the content than meter, for modified bismuth element is 0.1~1.5%；More preferably, the content for modified bismuth element is
0.2~1.2%.
In order to solve the above-mentioned technical problem two, The technical solution adopted by the invention is as follows: a kind of side chain alkylation is catalyzed
The preparation method of agent, preparation step are as follows: with sodium aluminate, sodium metasilicate, sodium hydroxide, potassium hydroxide, mesoporous directed agents hexadecane
Base trimethyl ammonium chloride (or the mesoporous directed agents such as cetyl trimethylammonium bromide, polydimethyl diallyl ammonium chloride) with
And water is that raw material mixes according to a certain percentage, crystallization certain time under conditions of 60~150 DEG C, then roasting synthesis contains
Micropore and mesoporous composite holes X or Y molecular sieve material.
In order to solve the above-mentioned technical problem two, the present invention is also the technical solution adopted is as follows: a kind of side chain alkylation is urged
Agent, preparation method are as follows: with aluminium hydroxide, silica solution, sodium hydroxide, potassium hydroxide, mesoporous directed agents cetyl three
Ammonio methacrylate (or the mesoporous directed agents such as cetyl trimethylammonium bromide, polydimethyl diallyl ammonium chloride) and water
It is mixed according to a certain percentage for raw material, crystallization certain time under conditions of 60~150 DEG C, then roasting synthesis contains micropore
With mesoporous composite holes X or Y molecular sieve material.
The composite holes microporous molecular sieve size of synthesis between 0.6~0.8nm, mesopore size range between 2~20nm,
Micropore and mesoporous volume ratio 0.5~15, silica alumina ratio SiO2/Al2O3Range is between 1~7.In above-mentioned technical proposal, preferably
, the composite holes molecular screen material silica alumina ratio SiO2/Al2O3Range is between 2~3, preferred composite holes molecular screen material
Silica alumina ratio SiO2/Al2O3X molecular sieve material of the range 2~2.5；
In above-mentioned technical proposal, it is preferred that the composite holes molecular screen material mesopore size is between 5~15nm；
In above-mentioned technical proposal, it is preferred that the composite holes molecular screen material micropore and mesoporous volume ratio are 3~8.
It can be seen from the figure that hysteresis loop occur in the molecular sieve Adsorption and desorption isotherms of composite holes, show containing mesoporous, and
It obviously can be seen that from pore-size distribution.
The method of the present invention can carry out in continuous flow reactor of fixed bed, and process is summarized as follows: take the desired amount of
Catalyst is put into the flat-temperature zone of reactor, and catalyst lower part is filled with quartz sand.At the temperature, pressure of setting, by toluene and
Methanol mixing is pumped into after preheater and nitrogen mixture into reactor upper end with micro, flows through catalyst bed progress
Catalysis reaction, reaction product directly enter gas-chromatography with valve injection and are analyzed.
The activity and selectivity of catalyst is calculated according to following formula:
Compared to selectivity, this index of use ratio of methanol is even more important.
It is catalyst material that the method for the present invention, which selects the composite holes X-type molecular sieve of synthesis, is conducive to reaction molecular in molecule
Diffusion in sieve catalyst duct, reduces the decomposition of methanol, to effectively increase use ratio of methanol.It is carried out simultaneously dilute
Earth elements and aluminon modification reduce the decomposition of methanol in the reaction of methylbenzene methanol side chain alkylation, effectively solution methylbenzene methanol
The problem of use ratio of methanol is low in side chain alkylation reaction, catalyst is easy inactivation.Especially when modified using Al, further
Improve the catalytic activity of alkylation catalyst；It is greatly improved using rare earth modification rear catalyst stability.Using present invention side
Method is 6: 1 in toluene and methanol molar ratio, and reaction temperature is 425 DEG C, reaction pressure 0MPa, and raw material weight air speed is 2.5 small
When-1Under conditions of, use ratio of methanol can be up to 54%, and up to 96%, catalyst stability reaches ethylbenzene styrene overall selectivity
By 200 hours, preferable technical effect is achieved.
Detailed description of the invention
Fig. 1 is the adsorption/desorption isotherms and graph of pore diameter distribution of common X molecular sieve catalyst described in comparative example 1.
Fig. 2 is the adsorption/desorption isotherms and graph of pore diameter distribution of composite holes X molecular sieve catalyst described in embodiment 1.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
With sodium aluminate, sodium metasilicate, sodium hydroxide, potassium hydroxide, mesoporous directed agents hexadecyltrimethylammonium chloride and
Water be raw material mix according to a certain percentage, the certain 16h of crystallization under conditions of 100 DEG C, synthetic product through filtration washing then
Roasting obtains composite holes X molecular sieve material.Synthesize the SiO of composite holes X molecular sieve2/Al2O3Than being 2.0, mesopore size is on the left side 7nm
It is right.
It takes at 10 grams, 80 DEG C of above-mentioned molecular sieve, it is small that ion exchange 2 is carried out in the KNO3 solution of 100 milliliter of 1 mol/L
When, it exchanges 2 times；Then in the RbNO of 50 milliliter of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；Finally at 50 milliliters
Ion exchange is carried out in the CsNO3 solution of 1 mol/L, is exchanged 2 times；100 DEG C drying 10 hours after filtering.After exchange, catalyst
The ion-exchange degree of sodium ion is 82.3% in middle alkali metal ion exchange molecular sieve.
10 grams of molecular sieve obtained above are taken, using cerous nitrate and sodium metaaluminate as presoma, using step impregnation method by cerium
It is loaded on catalyst with aluminium, the content of cerium is 2% after load, and the content of sodium metaaluminate is 4%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 200 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[embodiment 2]
With sodium aluminate, sodium metasilicate, sodium hydroxide, potassium hydroxide, mesoporous directed agents cetyl trimethylammonium bromide and
Water be raw material mix according to a certain percentage, the certain 16h of crystallization under conditions of 100 DEG C, synthetic product through filtration washing then
Roasting obtains composite holes X molecular sieve material.Synthesize the SiO of composite holes X molecular sieve2/Al2O3Than being 2.0, mesopore size is on the left side 8nm
It is right.
It takes at 10 grams, 80 DEG C of above-mentioned molecular sieve, it is small that ion exchange 2 is carried out in the KNO3 solution of 100 milliliter of 1 mol/L
When, it exchanges 2 times；Then ion exchange is carried out in the RbNO3 solution of 50 milliliter of 1 mol/L, is exchanged 2 times；Finally at 50 milliliters
Ion exchange is carried out in the CsNO3 solution of 1 mol/L, is exchanged 2 times；100 DEG C drying 10 hours after filtering.After exchange, catalyst
The ion-exchange degree of sodium ion is 86.7%. in middle alkali metal ion exchange molecular sieve
10 grams of molecular sieve obtained above are taken, using cerous nitrate and sodium metaaluminate as presoma, using step impregnation method by cerium
It is loaded on catalyst with aluminium, the content of cerium is 2% after load, and the content of sodium metaaluminate is 4%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 200 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[embodiment 3]
With sodium aluminate, sodium metasilicate, sodium hydroxide, potassium hydroxide, mesoporous directed agents polydimethyl diallyl ammonium chloride with
And water is that raw material mixes according to a certain percentage, the certain 16h of crystallization, synthetic product are right through filtration washing under conditions of 100 DEG C
Roasting obtains composite holes X molecular sieve material afterwards.Synthesize the SiO of composite holes X molecular sieve2/Al2O3Than being 2.0, mesopore size is in 5nm
Left and right.
It takes at 10 grams, 80 DEG C of above-mentioned molecular sieve, it is small that ion exchange 2 is carried out in the KNO3 solution of 100 milliliter of 1 mol/L
When, it exchanges 2 times；Then ion exchange is carried out in the RbNO3 solution of 50 milliliter of 1 mol/L, is exchanged 2 times；Finally at 50 milliliters
Ion exchange is carried out in the CsNO3 solution of 1 mol/L, is exchanged 2 times；100 DEG C drying 10 hours after filtering.After exchange, catalyst
The ion-exchange degree of sodium ion is 83.7% in middle alkali metal ion exchange molecular sieve.
10 grams of molecular sieve obtained above are taken, using cerous nitrate and sodium metaaluminate as presoma, using step impregnation method by cerium
It is loaded on catalyst with aluminium, the content of cerium is 2% after load, and the content of sodium metaaluminate is 4%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 200 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[embodiment 4]
It is pressed using sodium aluminate, sodium metasilicate, sodium hydroxide, mesoporous directed agents hexadecyltrimethylammonium chloride and water as raw material
It is mixed according to certain ratio, the certain 16h of crystallization under conditions of 100 DEG C, then synthetic product is roasted through filtration washing and answered
Close hole X molecular sieve material.Synthesize the SiO of composite holes X molecular sieve2/Al2O3Than being 2.3, mesopore size is in 12nm or so.
It takes at 10 grams, 80 DEG C of above-mentioned molecular sieve, in the KNO of 100 milliliter of 1 mol/L3It is small that ion exchange 2 is carried out in solution
When, it exchanges 2 times；Then in the RbNO of 50 milliliter of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；Finally at 50 milliliters
The CsNO of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；100 DEG C drying 10 hours after filtering.After exchange, catalyst
The ion-exchange degree of sodium ion is 83.1% in middle alkali metal ion exchange molecular sieve.
10 grams of molecular sieve obtained above are taken, using cerous nitrate and sodium metaaluminate as presoma, using step impregnation method by cerium
It is loaded on catalyst with aluminium, the content of cerium is 2% after load, and the content of sodium metaaluminate is 4%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, Activity Results are listed in Table 1 below.
[embodiment 5]
It is pressed using sodium aluminate, sodium metasilicate, sodium hydroxide, mesoporous directed agents cetyl trimethylammonium bromide and water as raw material
It is mixed according to certain ratio, the certain 16h of crystallization under conditions of 100 DEG C, then synthetic product is roasted through filtration washing and answered
Close hole X molecular sieve material.Synthesize the SiO of composite holes X molecular sieve2/Al2O3Than being 2.3, mesopore size is in 14nm or so.
It takes at 10 grams, 80 DEG C of above-mentioned molecular sieve, it is small that ion exchange 2 is carried out in the KNO3 solution of 100 milliliter of 1 mol/L
When, it exchanges 2 times；Then ion exchange is carried out in the RbNO3 solution of 50 milliliter of 1 mol/L, is exchanged 2 times；Finally at 50 milliliters
Ion exchange is carried out in the CsNO3 solution of 1 mol/L, is exchanged 2 times；100 DEG C drying 10 hours after filtering.After exchange, catalyst
The ion-exchange degree of sodium ion is 85.7% in middle alkali metal ion exchange molecular sieve.
10 grams of molecular sieve obtained above are taken, using cerous nitrate and sodium metaaluminate as presoma, using step impregnation method by cerium
It is loaded on catalyst with aluminium, the content of cerium is 2% after load, and the content of sodium metaaluminate is 4%.By catalyst obtained above
The beaded catalyst of 40~60 mesh of compression molding is packed into reactor, is 5:1, at 2.5 hours in normal pressure, methylbenzene methanol molar ratio-1
Liquid air speed, 425 DEG C, N2Flow velocity is to carry out activity rating under conditions of 10 ml/mins, 200 hours non-inactivations of catalyst,
Its Activity Results is listed in Table 1 below.
[embodiment 6]
Using sodium aluminate, sodium metasilicate, sodium hydroxide, mesoporous directed agents polydimethyl diallyl ammonium chloride and water as raw material
It mixes according to a certain percentage, the certain 16h of crystallization under conditions of 100 DEG C, then synthetic product is roasted through filtration washing and obtained
Composite holes X molecular sieve material.Synthesize the SiO of composite holes X molecular sieve2/Al2O3Than being 2.3, mesopore size is in 10nm or so.
It takes at 10 grams, 80 DEG C of above-mentioned molecular sieve, it is small that ion exchange 2 is carried out in the KNO3 solution of 100 milliliter of 1 mol/L
When, it exchanges 2 times；Then ion exchange is carried out in the RbNO3 solution of 50 milliliter of 1 mol/L, is exchanged 2 times；Finally at 50 milliliters
Ion exchange is carried out in the CsNO3 solution of 1 mol/L, is exchanged 2 times；100 DEG C drying 10 hours after filtering.After exchange, catalyst
The ion-exchange degree of sodium ion is 86.7% in middle alkali metal ion exchange molecular sieve.
10 grams of molecular sieve obtained above are taken, using cerous nitrate and sodium metaaluminate as presoma, using step impregnation method by cerium
It is loaded on catalyst with aluminium, the content of cerium is 2% after load, and the content of sodium metaaluminate is 4%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 200 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[embodiment 7]
With sodium aluminate, sodium metasilicate, sodium hydroxide, potassium hydroxide, mesoporous directed agents cetyl trimethylammonium bromide and
Water be raw material mix according to a certain percentage, the certain 16h of crystallization under conditions of 100 DEG C, synthetic product through filtration washing then
Roasting obtains composite holes Y molecular sieve material.Synthesize the SiO of composite holes Y molecular sieve2/Al2O3Than being 5.0, mesopore size is on the left side 8nm
It is right.
It takes at 10 grams, 80 DEG C of above-mentioned molecular sieve, it is small that ion exchange 2 is carried out in the KNO3 solution of 100 milliliter of 1 mol/L
When, it exchanges 2 times；Then ion exchange is carried out in the RbNO3 solution of 50 milliliter of 1 mol/L, is exchanged 2 times；Finally at 50 milliliters
Ion exchange is carried out in the CsNO3 solution of 1 mol/L, is exchanged 2 times；100 DEG C drying 10 hours after filtering.After exchange, catalyst
The ion-exchange degree of sodium ion is 85.8%. in middle alkali metal ion exchange molecular sieve
10 grams of molecular sieve obtained above are taken, using cerous nitrate and sodium metaaluminate as presoma, using step impregnation method by cerium
It is loaded on catalyst with aluminium, the content of cerium is 2% after load, and the content of sodium metaaluminate is 4%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 200 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[embodiment 8]
With aluminium hydroxide, silica solution, sodium hydroxide, potassium hydroxide, mesoporous directed agents hexadecyltrimethylammonium chloride with
And water is that raw material mixes according to a certain percentage, the certain 16h of crystallization, synthetic product are right through filtration washing under conditions of 100 DEG C
Roasting obtains composite holes X molecular sieve material afterwards.Synthesize the SiO of composite holes X molecular sieve2/Al2O3Than being 2.0, mesopore size is in 7nm
Left and right.
It takes at 10 grams, 80 DEG C of above-mentioned molecular sieve, it is small that ion exchange 2 is carried out in the KNO3 solution of 100 milliliter of 1 mol/L
When, it exchanges 2 times；Then in the RbNO of 50 milliliter of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；Finally at 50 milliliters
Ion exchange is carried out in the CsNO3 solution of 1 mol/L, is exchanged 2 times；100 DEG C drying 10 hours after filtering.After exchange, catalyst
The ion-exchange degree of sodium ion is 82.3%. in middle alkali metal ion exchange molecular sieve
10 grams of molecular sieve obtained above are taken, using cerous nitrate and sodium metaaluminate as presoma, using step impregnation method by cerium
It is loaded on catalyst with aluminium, the content of cerium is 2% after load, and the content of sodium metaaluminate is 4%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 200 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[embodiment 9]
It is pressed using sodium aluminate, sodium metasilicate, sodium hydroxide, mesoporous directed agents hexadecyltrimethylammonium chloride and water as raw material
It is mixed according to certain ratio, the certain 16h of crystallization under conditions of 100 DEG C, then synthetic product is roasted through filtration washing and answered
Close hole X molecular sieve material.Synthesize the SiO of composite holes X molecular sieve2/Al2O3Than being 2.3, mesopore size is in 12nm or so.
It takes at 10 grams, 80 DEG C of above-mentioned molecular sieve, in the KNO of 100 milliliter of 1 mol/L3It is small that ion exchange 2 is carried out in solution
When, it exchanges 2 times；Then in the RbNO of 50 milliliter of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；Finally at 50 milliliters
The CsNO of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；100 DEG C drying 10 hours after filtering.After exchange, catalyst
The ion-exchange degree of sodium ion is 83.1% in middle alkali metal ion exchange molecular sieve.
10 grams of molecular sieve obtained above are taken, using cerous nitrate and sodium metaaluminate as presoma, using step impregnation method by cerium
It is loaded on catalyst with aluminium, the content of cerium is 2% after load, and the content of sodium metaaluminate is 0.5%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 200 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[embodiment 10]
It is pressed using sodium aluminate, sodium metasilicate, sodium hydroxide, mesoporous directed agents hexadecyltrimethylammonium chloride and water as raw material
It is mixed according to certain ratio, the certain 16h of crystallization under conditions of 100 DEG C, then synthetic product is roasted through filtration washing and answered
Close hole X molecular sieve material.Synthesize the SiO of composite holes X molecular sieve2/Al2O3Than being 2.3, mesopore size is in 12nm or so.
It takes at 10 grams, 80 DEG C of above-mentioned molecular sieve, in the KNO of 100 milliliter of 1 mol/L3It is small that ion exchange 2 is carried out in solution
When, it exchanges 2 times；Then in the RbNO of 50 milliliter of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；Finally at 50 milliliters
The CsNO of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；100 DEG C drying 10 hours after filtering.After exchange, catalyst
The ion-exchange degree of sodium ion is 83.1% in middle alkali metal ion exchange molecular sieve.
10 grams of molecular sieve obtained above are taken, using lanthanum nitrate and sodium metaaluminate as presoma, using step impregnation method by lanthanum
It is loaded on catalyst with aluminium, the content of lanthanum is 2% after load, and the content of sodium metaaluminate is 3%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 200 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[embodiment 11]
It is pressed using sodium aluminate, sodium metasilicate, sodium hydroxide, mesoporous directed agents hexadecyltrimethylammonium chloride and water as raw material
It is mixed according to certain ratio, the certain 16h of crystallization under conditions of 100 DEG C, then synthetic product is roasted through filtration washing and answered
Close hole X molecular sieve material.Synthesize the SiO of composite holes X molecular sieve2/Al2O3Than being 2.3, mesopore size is in 12nm or so.
It takes at 10 grams, 80 DEG C of above-mentioned molecular sieve, in the KNO of 100 milliliter of 1 mol/L3It is small that ion exchange 2 is carried out in solution
When, it exchanges 2 times；Then in the RbNO of 50 milliliter of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；Finally at 50 milliliters
The CsNO of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；100 DEG C drying 10 hours after filtering.After exchange, catalyst
The ion-exchange degree of sodium ion is 83.1% in middle alkali metal ion exchange molecular sieve.
10 grams of molecular sieve obtained above are taken, using lanthanum nitrate and sodium metaaluminate as presoma, using step impregnation method by lanthanum
It is loaded on catalyst with aluminium, the content of lanthanum is 2 after load, and the content of sodium metaaluminate is 5%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 200 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[embodiment 12]
It is pressed using sodium aluminate, sodium metasilicate, sodium hydroxide, mesoporous directed agents hexadecyltrimethylammonium chloride and water as raw material
It is mixed according to certain ratio, the certain 16h of crystallization under conditions of 100 DEG C, then synthetic product is roasted through filtration washing and answered
Close hole X molecular sieve material.Synthesize the SiO of composite holes X molecular sieve2/Al2O3Than being 2.3, mesopore size is in 12nm or so.
It takes at 10 grams, 80 DEG C of above-mentioned molecular sieve, in the KNO of 100 milliliter of 1 mol/L3It is small that ion exchange 2 is carried out in solution
When, it exchanges 2 times；Then in the RbNO of 50 milliliter of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；Finally at 50 milliliters
The CsNO of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；100 DEG C drying 10 hours after filtering.After exchange, catalyst
The ion-exchange degree of sodium ion is 83.1% in middle alkali metal ion exchange molecular sieve.
10 grams of molecular sieve obtained above are taken, using cerous nitrate and sodium metaaluminate as presoma, using step impregnation method by cerium
It is loaded on catalyst with aluminium, the content of cerium is 2% after load, and the content of sodium metaaluminate is 7%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 200 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[embodiment 13]
It is pressed using sodium aluminate, sodium metasilicate, sodium hydroxide, mesoporous directed agents hexadecyltrimethylammonium chloride and water as raw material
It is mixed according to certain ratio, the certain 16h of crystallization under conditions of 100 DEG C, then synthetic product is roasted through filtration washing and answered
Close hole X molecular sieve material.Synthesize the SiO of composite holes X molecular sieve2/Al2O3Than being 2.3, mesopore size is in 12nm or so.
It takes at 10 grams, 80 DEG C of above-mentioned molecular sieve, in the KNO of 100 milliliter of 1 mol/L3It is small that ion exchange 2 is carried out in solution
When, it exchanges 2 times；Then in the RbNO of 50 milliliter of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；Finally at 50 milliliters
The CsNO of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；100 DEG C drying 10 hours after filtering.After exchange, catalyst
The ion-exchange degree of sodium ion is 83.1% in middle alkali metal ion exchange molecular sieve.
10 grams of molecular sieve obtained above are taken, using cerous nitrate and sodium metaaluminate as presoma, using step impregnation method by cerium
It is loaded on catalyst with aluminium, the content of cerium is 0.3% after load, and the content of sodium metaaluminate is 4%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 150 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[embodiment 14]
It is pressed using sodium aluminate, sodium metasilicate, sodium hydroxide, mesoporous directed agents hexadecyltrimethylammonium chloride and water as raw material
It is mixed according to certain ratio, the certain 16h of crystallization under conditions of 100 DEG C, then synthetic product is roasted through filtration washing and answered
Close hole X molecular sieve material.Synthesize the SiO of composite holes X molecular sieve2/Al2O3Than being 2.3, mesopore size is in 12nm or so.
It takes at 10 grams, 80 DEG C of above-mentioned molecular sieve, in the KNO of 100 milliliter of 1 mol/L3It is small that ion exchange 2 is carried out in solution
When, it exchanges 2 times；Then in the RbNO of 50 milliliter of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；Finally at 50 milliliters
The CsNO of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；100 DEG C drying 10 hours after filtering.After exchange, catalyst
The ion-exchange degree of sodium ion is 83.1% in middle alkali metal ion exchange molecular sieve.
10 grams of molecular sieve obtained above are taken, using lanthanum nitrate and sodium metaaluminate as presoma, using step impregnation method by lanthanum
It is loaded on catalyst with aluminium, the content of lanthanum is 1% after load, and the content of sodium metaaluminate is 4%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 180 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[embodiment 15]
It is pressed using sodium aluminate, sodium metasilicate, sodium hydroxide, mesoporous directed agents hexadecyltrimethylammonium chloride and water as raw material
It is mixed according to certain ratio, the certain 16h of crystallization under conditions of 100 DEG C, then synthetic product is roasted through filtration washing and answered
Close hole X molecular sieve material.Synthesize the SiO of composite holes X molecular sieve2/Al2O3Than being 2.3, mesopore size is in 12nm or so.
It takes at 10 grams, 80 DEG C of above-mentioned molecular sieve, in the KNO of 100 milliliter of 1 mol/L3It is small that ion exchange 2 is carried out in solution
When, it exchanges 2 times；Then in the RbNO of 50 milliliter of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；Finally at 50 milliliters
The CsNO of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；100 DEG C drying 10 hours after filtering.After exchange, catalyst
The ion-exchange degree of sodium ion is 83.1% in middle alkali metal ion exchange molecular sieve.
10 grams of molecular sieve obtained above are taken, using lanthanum nitrate and sodium metaaluminate as presoma, using step impregnation method lanthanum cerium
It is loaded on catalyst with aluminium, the content of lanthanum is 3% after load, and the content of sodium metaaluminate is 4%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 200 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[embodiment 16]
It is pressed using sodium aluminate, sodium metasilicate, sodium hydroxide, mesoporous directed agents hexadecyltrimethylammonium chloride and water as raw material
It is mixed according to certain ratio, the certain 16h of crystallization under conditions of 100 DEG C, then synthetic product is roasted through filtration washing and answered
Close hole X molecular sieve material.Synthesize the SiO of composite holes X molecular sieve2/Al2O3Than being 2.3, mesopore size is in 12nm or so.
It takes at 10 grams, 80 DEG C of above-mentioned molecular sieve, in the KNO of 100 milliliter of 1 mol/L3It is small that ion exchange 2 is carried out in solution
When, it exchanges 2 times；Then in the RbNO of 50 milliliter of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；Finally at 50 milliliters
The CsNO of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；100 DEG C drying 10 hours after filtering.After exchange, catalyst
The ion-exchange degree of sodium ion is 83.1% in middle alkali metal ion exchange molecular sieve.
10 grams of molecular sieve obtained above are taken, using cerous nitrate and sodium metaaluminate as presoma, using step impregnation method by cerium
It is loaded on catalyst with aluminium, the content of cerium is 5% after load, and the content of sodium metaaluminate is 4%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 200 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[embodiment 17]
It is pressed using sodium aluminate, sodium metasilicate, sodium hydroxide, mesoporous directed agents cetyl trimethylammonium bromide and water as raw material
It is mixed according to certain ratio, for 24 hours, then synthetic product roasts through filtration washing and obtains composite holes crystallization under conditions of 160 DEG C
Mordenite molecular sieve material.Composite holes mordenite molecular sieve mesopore size is synthesized in 8nm or so.
Take 3 grams of above-mentioned molecular sieve and 7 grams of mechanical mixtures of molecular sieve of [embodiment 4] synthesis uniform, at 80 DEG C, in 100 millis
Rise the KNO of 1 mol/L3It carries out ion exchange 2 hours, exchanges 2 times in solution；Then in the RbNO of 50 milliliter of 1 mol/L3It is molten
Ion exchange is carried out in liquid, is exchanged 2 times；Finally in the CsNO of 50 milliliter of 1 mol/L3Ion exchange, exchange 2 are carried out in solution
It is secondary；100 DEG C drying 10 hours after filtering.After exchange, the ion of sodium ion is handed in alkali metal ion exchange molecular sieve in catalyst
Degree of changing is 80.8%.
10 grams of molecular sieve obtained above are taken, using cerous nitrate and sodium metaaluminate as presoma, using step impregnation method by cerium
It is loaded on catalyst with aluminium, the content of cerium is 2% after load, and the content of sodium metaaluminate is 4%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 200 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[embodiment 18]
Take 7 grams of [embodiment 4] X molecular sieve it is uniform with 3 grams of mechanical mixtures of [embodiment 7] Y molecular sieve, at 80 DEG C, 100 milli
Rise the KNO of 1 mol/L3It carries out ion exchange 2 hours, exchanges 2 times in solution；Then in the RbNO of 50 milliliter of 1 mol/L3It is molten
Ion exchange is carried out in liquid, is exchanged 2 times；Finally in the CsNO of 50 milliliter of 1 mol/L3Ion exchange, exchange 2 are carried out in solution
It is secondary；100 DEG C drying 10 hours after filtering.After exchange, the ion of sodium ion is handed in alkali metal ion exchange molecular sieve in catalyst
Degree of changing is 80.8%.
10 grams of molecular sieve obtained above are taken, using cerous nitrate and sodium metaaluminate as presoma, using step impregnation method by cerium
It is loaded on catalyst with aluminium, the content of cerium is 2% after load, and the content of sodium metaaluminate is 4%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 200 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[embodiment 19]
Take 7 grams of [embodiment 4] X molecular sieve it is uniform with 3 grams of mechanical mixtures of [embodiment 7] Y molecular sieve, at 80 DEG C, 100 milli
Rise the KNO of 1 mol/L3It carries out ion exchange 2 hours, exchanges 2 times in solution；Then in the RbNO of 50 milliliter of 1 mol/L3It is molten
Ion exchange is carried out in liquid, is exchanged 2 times；Finally in the CsNO of 50 milliliter of 1 mol/L3Ion exchange, exchange 2 are carried out in solution
It is secondary；100 DEG C drying 10 hours after filtering.After exchange, the ion of sodium ion is handed in alkali metal ion exchange molecular sieve in catalyst
Degree of changing is 80.8%.
Take 10 grams of molecular sieve obtained above, using cerous nitrate as presoma, load to cerium and aluminium using step impregnation method
On catalyst, the content of cerium is 2% after load.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 200 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[embodiment 20]
With sodium aluminate, sodium metasilicate, sodium hydroxide, potassium hydroxide, mesoporous directed agents hexadecyltrimethylammonium chloride and
Water be raw material mix according to a certain percentage, the certain 16h of crystallization under conditions of 100 DEG C, synthetic product through filtration washing then
Roasting obtains composite holes X molecular sieve material.Synthesize the SiO of composite holes X molecular sieve2/Al2O3Than being 2.0, mesopore size is on the left side 7nm
It is right.
It takes at 10 grams, 80 DEG C of above-mentioned molecular sieve, it is small that ion exchange 2 is carried out in the KNO3 solution of 100 milliliter of 1 mol/L
When, it exchanges 2 times；Then in the RbNO of 50 milliliter of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；Finally at 50 milliliters
Ion exchange is carried out in the CsNO3 solution of 1 mol/L, is exchanged 2 times；100 DEG C drying 10 hours after filtering.After exchange, catalyst
The ion-exchange degree of sodium ion is 82.3% in middle alkali metal ion exchange molecular sieve.
10 grams of molecular sieve obtained above are taken, using cerous nitrate, bismuth nitrate and sodium metaaluminate as presoma, using step impregnation
Method loads to cerium and aluminium on catalyst, and the content of cerium is 2% after load, and the content of bismuth is 0.2%；The content of sodium metaaluminate is
4%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 200 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[embodiment 21]
With sodium aluminate, sodium metasilicate, sodium hydroxide, potassium hydroxide, mesoporous directed agents hexadecyltrimethylammonium chloride and
Water be raw material mix according to a certain percentage, the certain 16h of crystallization under conditions of 100 DEG C, synthetic product through filtration washing then
Roasting obtains composite holes X molecular sieve material.Synthesize the SiO of composite holes X molecular sieve2/Al2O3Than being 2.0, mesopore size is on the left side 7nm
It is right.
It takes at 10 grams, 80 DEG C of above-mentioned molecular sieve, it is small that ion exchange 2 is carried out in the KNO3 solution of 100 milliliter of 1 mol/L
When, it exchanges 2 times；Then in the RbNO of 50 milliliter of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；Finally at 50 milliliters
Ion exchange is carried out in the CsNO3 solution of 1 mol/L, is exchanged 2 times；100 DEG C drying 10 hours after filtering.After exchange, catalyst
The ion-exchange degree of sodium ion is 82.3% in middle alkali metal ion exchange molecular sieve.
10 grams of molecular sieve obtained above are taken, using cerous nitrate, bismuth nitrate and sodium metaaluminate as presoma, using step impregnation
Method loads to cerium and aluminium on catalyst, and the content of cerium is 2% after load, and the content of bismuth is 1%；The content of sodium metaaluminate is
4%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 200 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[comparative example 1]
Take the common X molecular sieve (SiO of purchase2/Al2O3Than being 2.0, not containing mesopore), at 10 grams, 80 DEG C, at 100 milliliter 1
The KNO of mol/L3It carries out ion exchange 2 hours, exchanges 2 times in solution；Then in the RbNO of 50 milliliter of 1 mol/L3In solution
Ion exchange is carried out, is exchanged 2 times；Finally in the CsNO of 50 milliliter of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；It crosses
100 DEG C drying 10 hours after filter.After exchange, the ion-exchange degree of sodium ion is in alkali metal ion exchange molecular sieve in catalyst
82.9%.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, use ratio of methanol decline 50% in catalyst 70 hours, Activity Results are listed in Table 1 below.
[comparative example 2]
Take the common X molecular sieve (SiO of purchase2/Al2O3Than being 2.0, not containing mesopore), at 10 grams, 80 DEG C, at 100 milliliter 1
The KNO of mol/L3It carries out ion exchange 2 hours, exchanges 2 times in solution；Then in the RbNO of 50 milliliter of 1 mol/L3In solution
Ion exchange is carried out, is exchanged 2 times；Finally in the CsNO of 50 milliliter of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；It crosses
100 DEG C drying 10 hours after filter.After exchange, the ion-exchange degree of sodium ion is in alkali metal ion exchange molecular sieve in catalyst
82.9%.
Take 10 grams of molecular sieve obtained above, using cerous nitrate as presoma, load to cerium on catalyst using infusion process,
The content of cerium is 2% after load.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 200 hours non-inactivations of catalyst, Activity Results are listed in Table 1 below.
[comparative example 3]
Take the common X molecular sieve (SiO of purchase2/Al2O3Than being 2.0, not containing mesopore), at 10 grams, 80 DEG C, at 100 milliliter 1
The KNO of mol/L3It carries out ion exchange 2 hours, exchanges 2 times in solution；Then in the RbNO of 50 milliliter of 1 mol/L3In solution
Ion exchange is carried out, is exchanged 2 times；Finally in the CsNO of 50 milliliter of 1 mol/L3Ion exchange is carried out in solution, is exchanged 2 times；It crosses
100 DEG C drying 10 hours after filter.After exchange, the ion-exchange degree of sodium ion is in alkali metal ion exchange molecular sieve in catalyst
82.9%.
Take 10 grams of molecular sieve obtained above, using sodium metaaluminate as presoma, aluminium is loaded to catalyst using infusion process
On, the content of sodium metaaluminate is 4% after load.
By the beaded catalyst of 40~60 mesh of catalyst tablet forming obtained above, it is packed into reactor, in normal pressure, toluene
Methanol molar ratio is 5:1, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Flow velocity be 10 ml/mins under conditions of live
Property evaluation, 70 hours use ratio of methanol of catalyst reduce by 50%, and Activity Results are listed in Table 1 below.
Table 1
Claims (13)
1. a kind of compound pore zeolite catalyst of side chain alkylation, it is characterised in that catalyst is using rare earth modified composite holes point
Son sieve.
2. the compound pore zeolite catalyst of side chain alkylation according to claim 1, it is characterised in that the composite holes molecule
Sieve contains micropore and mesoporous two kinds of cellular structures.
3. the compound pore zeolite catalyst of side chain alkylation according to claim 1, it is characterised in that micropore and mesoporous
Volume ratio 0.5~15, preferably 3~8.
4. the compound pore zeolite catalyst of side chain alkylation according to claim 1, it is characterised in that mesoporous pore size model
It is trapped among 2~20nm；Preferably 2~15nm.
5. the compound pore zeolite catalyst of side chain alkylation according to claim 1, it is characterised in that molecular sieve is X molecule
One of sieve, Y molecular sieve, L molecular sieve, mercerising molecular sieve are at least one, and molecular sieve is using preceding carry out alkali metal ion
Exchange is modified.
6. the compound pore zeolite catalyst of side chain alkylation according to claim 1, it is characterised in that pass through rare earth and aluminium
It is modified that reagent carries out dip loading.
7. the compound pore zeolite catalyst of side chain alkylation according to claim 6, which is characterized in that rare earth element is born
Carrying capacity is between 0.3~5%, and preferably 0.5~3%.
8. the compound pore zeolite catalyst of side chain alkylation according to claim 6, which is characterized in that aluminon is using inclined
Aluminate, the load capacity of meta-aluminate is between 0.5~8%, and preferably 2~5%.
9. the compound pore zeolite catalyst of side chain alkylation according to claim 1, it is characterised in that catalyst passes through water
Mesoporous directed agents synthesis is introduced in thermal synthesis method.
10. the compound pore zeolite catalyst of side chain alkylation according to claim 1, it is characterised in that mesoporous directed agents choosing
From at least one in hexadecyltrimethylammonium chloride, cetyl trimethylammonium bromide, polydimethyl diallyl ammonium chloride
Kind.
11. the compound pore zeolite catalyst of side chain alkylation according to claim 1, it is characterised in that compound porous molecular sieve
Catalyst the preparation method is as follows: being raw material according to certain using sodium aluminate, sodium metasilicate, sodium hydroxide, mesoporous directed agents and water
Ratio mixing, crystallization, roasting synthesize compound pore zeolite catalyst under conditions of 60~150 DEG C.
12. a kind of method of side chain alkylation, using aromatic hydrocarbons and side chain alkylation reagent, described in any one of claim 1~8
Reaction obtains side chain alkylation product under the action of catalyst.
13. a kind of method of ethylbenzene processed and styrene, uses methanol and toluene for raw material, described in any one of claim 1~8
Reaction obtains ethylbenzene and styrene under the action of catalyst.
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| CN106032280A (en) * | 2015-03-17 | 2016-10-19 | 中国科学院大连化学物理研究所 | Synthesis method, product and applications of mordenite having mesopores and micropores |
| CN107262146A (en) * | 2016-12-04 | 2017-10-20 | 中国科学院大连化学物理研究所 | One kind prepares 2,6 dimethylnaphthalene catalyst and its preparation and application |
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| CN106032280A (en) * | 2015-03-17 | 2016-10-19 | 中国科学院大连化学物理研究所 | Synthesis method, product and applications of mordenite having mesopores and micropores |
| CN107262146A (en) * | 2016-12-04 | 2017-10-20 | 中国科学院大连化学物理研究所 | One kind prepares 2,6 dimethylnaphthalene catalyst and its preparation and application |
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| Title |
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| 付晓琴: "基于咪唑型离子液体微介孔Y分子筛的制备与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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