CN106145133A - A kind of H beta molecular sieve and preparation method thereof - Google Patents
A kind of H beta molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of H beta molecular sieve and preparation method thereof.Described H beta molecular sieve character is as follows: SiO2/Al2O3Mol ratio is 40～100, and specific surface area is 502～850m2/ g, pore volume is 0.35～0.60mL/g, and relative crystallinity is 100%～148%；This H beta molecular sieve relative crystallinity after water vapour hydrothermal treatment consists is more than 95%.The preparation method of the present invention not only can reduce the usage amount of organic formwork agent, it is also possible to synthesizes the H beta molecular sieve of high-crystallinity, high silica alumina ratio, and has more preferable heat stability and hydrothermal stability.
Description
Technical field
The present invention relates to the preparation method of a kind of molecular sieve, specifically, it is provided that a kind of H beta molecular sieve and preparation method thereof.
Background technology
1967, the wadlinger of Mobile company was combined to beta-molecular sieve first by sodium aluminate, silica gel, tetraethyl ammonium hydroxide (TEAOH) and water mix-crystal.Beta-molecular sieve has twelve-ring intersection pore passage structure, 12 yuan of annular apertures of the one-dimensional channels being parallel to (001) crystal face are 0.57～0.75nm, 12 yuan of annular apertures of another two-dimensional channel parallel with (100) crystal face are 0.56～0.65nm, particularity because of its structure, have acid catalysis characteristic and structure selectivity concurrently, may be used for being hydrocracked through the beta-molecular sieve that various methods are modified, hydrofinishing, light aliphatic hydrocarbon are converted in many petrochemical industry catalytic fields such as aromatic hydrocarbons, benzene alkylation, cracking, isomerization.
United States Patent (USP) US
The 3308069 whole preparation process that describe in detail beta-molecular sieve.Typical case's composition of its product can be represented by the formula:
XNa ［ (1.0 ± 0.1X)-X ］ TEA Al2O3·Y
SiO2·WH2O
Generally X < 0.75, TEA represents tetraethyl amine ion, and it introduces as template, and Y value scope is that 5 < Y < 100, W values may be up to 60, and its preparation method is as follows: according to molar ratio: SiO2/Al2O3=10～200, TEAOH/SiO2=0.1～1.0, Na2O/TEAOH=0～0.1, H2O/TEAOH=20～75, by each raw material mix homogeneously, 75～200 DEG C of crystallizations 3～60 days in autoclave, obtain beta-molecular sieve.
US4847055 discloses the method for the synthesis beta-molecular sieve of a kind of improvement, wherein uses a kind of special silicon source, with TEABr as template, prepares beta-molecular sieve under conditions of crystal seed exists.This silicon source is to be added precipitant under certain condition by soluble silicon solution to prepare.The large usage quantity of the method template, and easily produce modenite and ZSM-5 stray crystal.Only as (TEA)2O/SiO2> 0.14, i.e. TEA+/SiO2> 0.28 time, the growing amount of stray crystal could be reduced.
Above-mentioned water heat transfer beta-molecular sieve needs a large amount of expensive organic formwork agent tetraethyl ammonium hydroxide, the cost major part of beta-molecular sieve synthesis to come from template, typically constitute from about 70%.Reduce template consumption, thus reduce beta-molecular sieve synthesis cost, the always focus of this area research.
Furthermore, the organic formwork agent being blocked in zeolite cavity removing must be fallen just can make it have before beta-molecular sieve uses as catalyst catalysis activity.The method of conventional removing organic formwork agent is high-temperature roasting, and owing to high-temperature roasting will destroy the structure of beta-molecular sieve so that it is degree of crystallinity declines, heat stability and hydrothermal stability are deteriorated, and consumption of template agent is the biggest, and this destructiveness is the most serious.And using the beta-molecular sieve adding a small amount of template synthesizing high-silicon aluminum ratio, the degree of crystallinity of products obtained therefrom can be the lowest, and heat stability and hydrothermal stability are poor.
CN1351959A relates to the synthetic method of a kind of molecular sieve.First Al is pressed2O3: (30-150) SiO2: (5-20) (TEA)2O:(1-8.5) Na2O:(650-1200) H2The mol ratio of O prepares Alusil A, by Al2O3: (20-80) SiO2: (5-15) Na2O:(350-1000) H2The mol ratio of O prepares Alusil B, then Alusil A and Alusil B is pressed the weight ratio mixing of 1:10, proceed to after stirring in autoclave pressure, after sealing at a temperature of 100-200 DEG C, stir crystallization 15-150 hour under static or 10-150rpm rotating speed, end product through sucking filtration, wash and be dried to obtain beta-molecular sieve.Although the consumption of organic formwork can be reduced to TEAOH/SiO by this synthetic method2=0.05, but beta-molecular sieve silica alumina ratio prepared by the method is relatively low, and also the characteristic peak of beta-molecular sieve has a small amount of miscellaneous peak, has stray crystal to generate.
CN 1198404A proposes a kind of method synthesizing beta-molecular sieve, uses the composite mould plate agent formed in the basic conditions by halogenide, tetraethyl ammonium hydroxide and the fluoride of tetraethyl ammonium, makes silicon source, aluminum source and crystal seed reaction crystallization produce beta-molecular sieve.Although the method reduces template consumption, adding the productivity of beta-molecular sieve, however it is necessary that addition composite mould plate agent and crystal seed, and after silica alumina ratio is more than 30, degree of crystallinity is relatively low, heat stability and hydrothermal stability are poor.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of heat stability and the high silica alumina ratio H beta molecular sieve that hydrothermal stability is good, degree of crystallinity is higher and preparation method thereof.
A kind of H beta molecular sieve that the present invention provides, described H beta molecular sieve character is as follows: SiO2/Al2O3Mol ratio is 40～100, and specific surface area is 502～850m2/ g, pore volume is 0.35～0.60mL/g, and relative crystallinity is 100%～148%；This H beta molecular sieve relative crystallinity after water vapour hydrothermal treatment consists is more than 95%.
Preferably, described H beta molecular sieve character is as follows: SiO2/Al2O3Mol ratio is 60～100, and specific surface area is 505～800m2/ g, pore volume 0.40～0.60mL/g, relative crystallinity is 110%～140%；This H beta molecular sieve relative crystallinity after water vapour hydrothermal treatment consists is 95%～130%.
Preferably, described H beta molecular sieve character is as follows: SiO2/Al2O3Mol ratio is 60～100, and specific surface area is 600～750 m2/ g, pore volume 0.45～0.55mL/g, relative crystallinity is 115%～140%；This H beta molecular sieve relative crystallinity after water vapour hydrothermal treatment consists is 108%～130%.
In the present invention, this H beta molecular sieve was as follows through the condition of water vapour hydrothermal treatment consists: through 750 DEG C of water vapour hydrothermal treatment consists 2 hours.
Present invention also offers the preparation method of a kind of H beta molecular sieve, this preparation method includes:
(1), using preparing amorphous silicon alumnium using carbonization predecessor, described amorphous silica-alumina predecessor is on the basis of the gross weight of silicon dioxide and aluminium oxide, and the content that silicon is counted with silicon dioxide is as 40wt%～75wt%, preferably 55wt%～70wt%；Its preparation process includes:
Preparation sodium aluminate solution and silicon-containing compound solution respectively；Sodium aluminate solution is mixed with part silicon-containing compound solution, then passes to CO2Gas, as the CO being passed through2 When gas flow accounts for the 60% ~ 100% of total intake, preferably 85% ~ 100%, add described remainder silicon-containing compound solution；
(2), the said mixture in step (1) stablizes 10 ~ 30 minutes in ventilated environment；
(3), by Al2O3: SiO2: Na2O:H2O=1:(42 ~ 110): (0.5～3.0): (100～500), TEAOH/SiO2Total molar ratio of=0.010 ~ 0.095, preferably SiO2/Al2O3Be 62 ~ 110, TEAOH/SiO2=0.020 ~ 0.080, in the amorphous silica-alumina predecessor of step (2) gained, add water, silicon source and template, stir, obtain silica-alumina gel, TEA represents the quaternary amine alkali cation in template；
(4), the silica-alumina gel of step (3) gained through two step dynamic crystallizations, then through filtering, washing, prepare Na beta-molecular sieve；
(5), described Na beta molecular sieve carries out ammonium salt exchange and Template removal processes, and prepares H beta molecular sieve.
Preferably, in step (1), described remainder silicon-containing compound solution accounts for addition silicon-containing compound solution total amount 5wt% ~ 85wt% in terms of silicon dioxide, preferably 30wt% ~ 70wt% in terms of silicon dioxide.
Preferably, in step (1), the reaction temperature of described plastic is 10～40 DEG C, preferably 15～35 DEG C, and controlling the pH value after cemented into bundles is 8～11.
Preferably, in step (1), described silicon-containing compound solution is waterglass and/or sodium silicate solution.
Preferably, in step (1), with A12O3Quality meter, the concentration of described sodium aluminate solution is 15～55g Al2O3/
L, with SiO2Quality meter, the concentration of described silicon-containing compound solution is 50～150
gSiO2/ L, described CO2The concentration of gas is 30v% ~ 60v%.
Preferably, in step (3), generating the reaction temperature 0 of described silica-alumina gel～40 DEG C, pH value is 9.5～12.0；Being preferably, the reaction temperature generating described silica-alumina gel is 10～30 DEG C, and pH value is 10～11.
Preferably, in step (3), described silicon source is one or more in White Carbon black, silica gel, Ludox and waterglass, and described template is tetraethyl ammonium hydroxide.
Preferably, in step (4), the silica-alumina gel of step (3) gained includes through the concrete steps of two step dynamic crystallizations: the condition of first step dynamic crystallization is: carry out crystallization under agitation, and temperature is 50～90 DEG C, and the time is 0.5～18.0 hour；The condition of second step dynamic crystallization is: carry out crystallization under agitation, and temperature is 100～200 DEG C, and the time is 40～120 hours.
Preferably, in step (4), the condition of described first step dynamic crystallization is: carry out crystallization under agitation, and temperature is 60～80 DEG C, and the time is 1～10 hour；The condition of described second step dynamic crystallization is: carry out crystallization under agitation, and temperature is 120～170 DEG C, and the time is 50～100 hours.
Preferably, in step (5), ammonium salt exchange uses conventional method to carry out, as one or many ammonium salt exchanges, and Na in the beta-molecular sieve after ammonium salt exchange2O weight content is less than 0.3%；Can be through washing and the step being dried after ammonium salt exchange, the condition being wherein dried is as follows: be dried 3～6 hours at 80 DEG C ~ 150 DEG C.
Preferably, in step (5), described Template removal processes and uses aerobic high-temperature process, and treatment temperature is 400～800 DEG C, and the process time is 5～20 hours, is preferably, and treatment temperature is 500～700 DEG C, and the process time is 10～15 hours.
Compared with prior art, advantages of the present invention is as follows:
The preparation method of the Na beta molecular sieve of the present invention, in the preparation process of amorphous silica-alumina predecessor, first mixes part silicon-containing compound solution with sodium aluminate solution, then passes to CO2Gas, thus form stable colloidal state and sial integrated structure.Owing to this colloid surface has a lot of hydroxyl structures, can be combined with the remainder silicon-containing compound added below well, so that amorphous silica-alumina predecessor has more stable structure.Afterwards, amorphous silica-alumina predecessor, template are mixed and made into silica-alumina gel with another part silicon source etc., so can form more nucleus in synthetic system, it is evenly dispersed in synthetic system, there is good crystallization guide effect, again through two step dynamic crystallizations, easily form complete framing structure, the Na beta molecular sieve that degree of crystallinity is high.The preparation method of the present invention not only can reduce the usage amount of organic formwork agent, the Na beta molecular sieve of high-crystallinity, high silica alumina ratio can also be synthesized, and have more preferable heat stability and hydrothermal stability, and the Na beta molecular sieve purity of the present invention is high, does not has stray crystal.
By the Na beta molecular sieve of the present invention through the exchange of simple ammonium salt and Template removal, just the H beta-molecular sieve of high silica alumina ratio, high-crystallinity, good stability can be obtained, without carrying out the dual-spectrum process such as dealuminzation or dealumination complement silicon again, and the H beta molecular sieve purity of the present invention is high, does not has stray crystal.
The H beta molecular sieve of the present invention, has suitable splitting action and good isomerization to the long side chain n-alkyl of long chain alkane and aromatic hydrocarbons, cycloalkane, makes hydrogenation catalyst prepared therefrom show good cracking activity and product property.
Detailed description of the invention
The present invention analyzes method: specific surface area and pore volume use low temperature liquid nitrogen physisorphtion, and silica alumina ratio uses chemical method, and relative crystallinity and the purity of molecular sieve are measured by X ray powder diffraction method (XRD).In the present invention, wt% is mass fraction, and v% is volume fraction.
In order to the present invention is better described, further illustrate the present invention below in conjunction with embodiment and comparative example.But the scope of the present invention is not limited solely to the scope of these embodiments.
Embodiment 1
(1) preparation of amorphous silica-alumina predecessor
Compound concentration is 40gAl2O3/ L sodium aluminate working solution, takes containing SiO2The sodium silicate solution of 28wt%, then to be diluted to concentration be 100g SiO2/ L sodium silicate working solution.Take 150mL sodium aluminate working solution to be placed in plastic cans, be subsequently adding 45mL sodium silicate working solution, control reaction temperature 20 DEG C, be passed through the CO that concentration is 50v%2Gas, stops logical CO when pH value reaches 10.02, add 95mL sodium silicate working solution, then ventilate and stablize 20 minutes, obtain amorphous silica-alumina predecessor.Amorphous silica-alumina predecessor is on the basis of silicon dioxide and aluminium oxide gross weight, and the content counted with silicon dioxide is as 70wt%.
(2) preparation of gel
By Al2O3: SiO2: Na2O:H2O=1:60:1.3: 200, TEAOH/SiO2=
Total molar ratio of 0.072, adds water, sodium silicate solution and tetraethyl ammonium hydroxide in the amorphous silica-alumina predecessor of step (1) gained, and control ph is 10.5, reaction temperature 20 DEG C, and uniform stirring 30 minutes obtains silica-alumina gel.
(3) crystallization
Gel obtained by step (2) is poured in stainless steel cauldron, stirs crystallization 5 hours at 75 DEG C, then heat to 140 DEG C, stirring crystallization 30 hours, then filters, washs, and washs and is dried at 120 DEG C to neutrality, obtain Na beta-molecular sieve product N β-1, record relative crystallinity；N β-1, after roasting in 550 DEG C of air 3 hours, records the relative crystallinity after roasting；N β-1, after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, records the relative crystallinity after hydrothermal treatment consists, and concrete N β-1 character is shown in Table 1.
(4) ammonium salt exchange and Template removal
Adding appropriate water purification in Na beta-molecular sieve N β-1, and add a certain amount of ammonium nitrate, making liquid-solid ratio (weight) is 10:1, the concentration of ammonium nitrate is 2mol/L, stirring, is warmed up to 95～100 DEG C, and constant temperature stirs 2 hours, then filter, filter cake secondary again carries out ammonium salt exchange, and the condition of exchange is identical with first time, till finally washing molecule is sieved to pH value neutrality, put in dry zone and be dried, be dried 8 hours at 100～120 DEG C.Taking dried beta-molecular sieve to carry out deviating from template process, use open kiln to process, 570 DEG C of constant temperature process 15 hours, make H beta molecular sieve S β-1, XRD determining S β-1 relative crystallinity；S β-1 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, the results are shown in Table 2.
Embodiment 2
(1) preparation of amorphous silica-alumina predecessor
Compound concentration is 40gAl2O3/ L sodium aluminate working solution, takes containing SiO2The sodium silicate solution of 28wt%, then to be diluted to concentration be 120g SiO2/ L sodium silicate working solution.Take 200mL sodium aluminate working solution to be placed in plastic cans, be subsequently adding 50mL sodium silicate working solution, control reaction temperature 18 DEG C, be passed through the CO that concentration is 50v%2Gas, stops logical CO when pH value reaches 10.22, adding 50mL sodium silicate working solution, then ventilate and stablize 20 minutes, obtain amorphous silica-alumina predecessor, amorphous silica-alumina predecessor is on the basis of silicon dioxide and aluminium oxide gross weight, and the content counted with silicon dioxide is as 60wt%.
(2) preparation of gel
By Al2O3: SiO2: Na2O:H2O=1:80: 1.5: 240, TEAOH/SiO2=0.070
Total molar ratio, adds water, sodium silicate solution and tetraethyl ammonium hydroxide in the amorphous silica-alumina predecessor of step (1) gained, and control ph is 11, reaction temperature 25 DEG C, and uniform stirring 30 minutes obtains silica-alumina gel.
(3) crystallization
Gel obtained by step (2) is poured in stainless steel cauldron, stirs crystallization 5 hours at 80 DEG C, then heat to 150 DEG C, stirring crystallization 30 hours, then filters, washs, and washs and is dried at 120 DEG C to neutrality, obtain Na beta-molecular sieve product N β-2, record relative crystallinity；N β-2, after roasting in 550 DEG C of air 3 hours, records the relative crystallinity after roasting；N β-2 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, and concrete N β-2 character is shown in Table 1.
(4) ammonium salt exchange and Template removal
Adding appropriate water purification in Na beta-molecular sieve N β-2, and add a certain amount of ammonium nitrate, making liquid-solid ratio (weight) is 10:1, the concentration of ammonium nitrate is 2mol/L, stirring, is warmed up to 95～100 DEG C, and constant temperature stirs 2 hours, then filter, filter cake secondary again carries out ammonium salt exchange, and the condition of exchange is identical with first time, till finally washing molecule is sieved to pH value neutrality, put in dry zone and be dried, be dried 8 hours at 100～120 DEG C.Taking dried beta-molecular sieve to carry out deviating from template process, use open kiln to process, 570 DEG C of constant temperature process 15 hours, make H beta molecular sieve S β-2, XRD determining S β-2 relative crystallinity；S β-2 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, the results are shown in Table 2.
Embodiment 3
(1) preparation of amorphous silica-alumina predecessor
Compound concentration is 50gAl2O3/ L sodium aluminate working solution, takes containing SiO2The sodium silicate solution of 28wt%, then to be diluted to concentration be 100g SiO2/ L sodium silicate working solution.Take 200mL sodium aluminate working solution to be placed in plastic cans, be subsequently adding 60mL sodium silicate working solution, control reaction temperature 20 DEG C, be passed through the CO that concentration is 50v%2Gas, stops logical CO when pH value reaches 10.02, adding 40mL sodium silicate working solution, then ventilate and stablize 20 minutes, obtain amorphous silica-alumina predecessor, amorphous silica-alumina predecessor is on the basis of silicon dioxide and aluminium oxide gross weight, and the content counted with silicon dioxide is as 50wt%.
(2) preparation of gel
By Al2O3: SiO2: Na2O:H2O=1:90: 1.7: 260, TEAOH/SiO2=
0.060 total molar ratio, adds water, sodium silicate solution and tetraethyl ammonium hydroxide in the amorphous silica-alumina predecessor of step (1) gained, and control ph is 11, reaction temperature 25 DEG C, and uniform stirring 30 minutes obtains silica-alumina gel.
(3) crystallization
Gel obtained by step (2) is poured in stainless steel cauldron, stirs crystallization 5 hours at 90 DEG C, then heat to 160 DEG C, stirring crystallization 30 hours, then filters, washs, and washs and is dried at 120 DEG C to neutrality, obtain Na beta-molecular sieve product N β-3, record relative crystallinity；N β-3, after roasting in 550 DEG C of air 3 hours, records the relative crystallinity after roasting；N β-3 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, and concrete N β-3 character is shown in Table 1.
(4) ammonium salt exchange and Template removal
Adding appropriate water purification in Na beta-molecular sieve N β-3, and add a certain amount of ammonium nitrate, making liquid-solid ratio (weight) is 10:1, the concentration of ammonium nitrate is 2mol/L, stirring, is warmed up to 95～100 DEG C, and constant temperature stirs 2 hours, then filter, filter cake secondary again carries out ammonium salt exchange, and the condition of exchange is identical with first time, till finally washing molecule is sieved to pH value neutrality, put in dry zone and be dried, be dried 8 hours at 100～120 DEG C.Taking dried beta-molecular sieve to carry out deviating from template process, use open kiln to process, 570 DEG C of constant temperature process 15 hours, make H beta molecular sieve S β-3, XRD determining S β-3 relative crystallinity；S β-3 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, the results are shown in Table 2.
Embodiment 4
(1) preparation of amorphous silica-alumina predecessor
Compound concentration is 50gAl2O3/ L sodium aluminate working solution, takes containing SiO2The sodium silicate solution of 28wt%, then to be diluted to concentration be 100g SiO2/ L sodium silicate working solution.Take 160mL sodium aluminate working solution to be placed in plastic cans, be subsequently adding 45mL sodium silicate working solution, control reaction temperature 20 DEG C, be passed through the CO that concentration is 50v%2Gas, stops logical CO when pH value reaches 10.02, adding 35mL sodium silicate working solution, then ventilate and stablize 20 minutes, obtain amorphous silica-alumina predecessor, amorphous silica-alumina predecessor is on the basis of silicon dioxide and aluminium oxide gross weight, and the content counted with silicon dioxide is as 50wt%.
(2) preparation of gel is with embodiment 2, and difference is: according to Al2O3: SiO2: Na2O:H2O=1:70: 1.4: 250, TEAOH/SiO2Each material is mixed by total molar ratio of=0.062.
(3) crystallization is with embodiment 2, records relative crystallinity after obtaining Na beta-molecular sieve product N β-4；N β-4, after roasting in 550 DEG C of air 3 hours, records the relative crystallinity after roasting；N β-4 is again after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, and concrete N β-4 character is shown in Table 1.
(4) ammonium salt exchange and Template removal
Na beta-molecular sieve N β-4, with embodiment 2, is made H beta molecular sieve S β-4, XRD determining S β-4 relative crystallinity by the method for ammonium salt exchange and Template removal；S β-4 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, the results are shown in Table 2.
Comparative example 1 (with reference to CN1351959A)
By 20.5g White Carbon black, 2mL sodium aluminate solution, 59g tetraethyl ammonium hydroxide and 0.9g sodium hydroxide, mix under room temperature and mechanical agitation, and continue stirring to raw material mix homogeneously: mixture is proceeded in autoclave pressure, after static state is aged 5 hours at a temperature of 130 DEG C after sealing, takes out and quick cooling pressure still, obtain Alusil A.120g Ludox, 6.3mL sodium metaaluminate, 6g sodium hydroxide and 17mL distilled water are mixed under room temperature and mechanical agitation, and stirs to raw material mix homogeneously, obtain Alusil B.5g Alusil A and 50g Alusil B is mixed under room temperature and mechanical agitation, and stirs and proceed in autoclave pressure to raw material mix homogeneously, after sealing at a temperature of 130 DEG C, to stir crystallization 48 hours under 60rpm rotating speed, take out and quick cooling pressure still.Product, through sucking filtration, washing, washs and is dried at 120 DEG C to neutrality, obtain Na beta-molecular sieve products C N β-1, and characterization result shows, product is the characteristic peak possessing beta-molecular sieve, but has a small amount of miscellaneous peak, i.e. has a small amount of stray crystal.And record the relative crystallinity of CN β-1；CN β-1, after roasting in 550 DEG C of air 3 hours, records the relative crystallinity after roasting；CN β-1 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, and concrete CN β-1 character is shown in Table 1.
Carry out ammonium salt exchange and Template removal according to the method for embodiment 2, Na beta-molecular sieve CN β-1 is made H beta molecular sieve products C S β-1, XRD determining CS β-1 relative crystallinity；CS β-1 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, the results are shown in Table 2.
Comparative example 2(is with reference to CN1198404A)
16g tetraethylammonium bromide and 1.6g sodium fluoride D are dissolved in 30g deionized water, it is sequentially added under stirring and is dissolved in 20g deionized water gained solution, 53.7g Ludox and 0.72g crystal seed by 1.67g sodium aluminate B, continue stirring 60 minutes, proceed in stainless steel cauldron, crystallization 4 days at 160 DEG C.Then filter, wash, be dried to obtain Na beta-molecular sieve products C N β-2, record relative crystallinity；CN β-2, after roasting in 550 DEG C of air 3 hours, records the relative crystallinity after roasting；CN β-2 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, and concrete CN β-2 character is shown in Table 1.
Carry out ammonium salt exchange and Template removal according to the method for embodiment 2, Na beta-molecular sieve CN β-2 is made H beta molecular sieve products C S β-2, XRD determining CS β-2 relative crystallinity；CS β-2 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, the results are shown in Table 2.
Comparative example 3
(1) preparation of amorphous silica-alumina predecessor
Compound concentration is 40gAl2O3/ L sodium aluminate working solution, takes containing SiO2The sodium silicate solution of 28wt%, then to be diluted to concentration be 120g SiO2/ L sodium silicate working solution.Take 200mL sodium aluminate working solution to be placed in plastic cans, be subsequently adding 100mL sodium silicate working solution, control reaction temperature 18 DEG C, be passed through the CO that concentration is 50v%2Gas, stops logical CO when pH value reaches 10.22, then ventilating and stablize 20 minutes, obtain amorphous silica-alumina predecessor, amorphous silica-alumina predecessor is on the basis of silicon dioxide and aluminium oxide gross weight, and the content counted with silicon dioxide is as 60wt%.
(2) preparation of gel is with embodiment 2；
(3) crystallization is with embodiment 2, records relative crystallinity after obtaining Na beta-molecular sieve products C N β-3；CN β-3, after roasting in 550 DEG C of air 3 hours, records the relative crystallinity after roasting；CN β-3 is again after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, and concrete CN β-3 character is shown in Table 1.
(4) ammonium salt exchange and Template removal
Na beta-molecular sieve CN β-3, with embodiment 2, is made H beta molecular sieve products C S β-3, XRD determining CS β-3 relative crystallinity by the method for ammonium salt exchange and Template removal；CS β-3 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, the results are shown in Table 2.
Comparative example 4
(1) preparation of amorphous silica-alumina predecessor
Compound concentration is 40gAl2O3/ L sodium aluminate working solution, takes containing SiO2The sodium silicate solution of 28wt%, then to be diluted to concentration be 120g SiO2/ L sodium silicate working solution.Take 200mL sodium aluminate working solution to be placed in plastic cans, control reaction temperature 18 DEG C, be passed through the CO that concentration is 50v%2Gas, stops logical CO when pH value reaches 10.22, adding 100mL sodium silicate working solution, then ventilate and stablize 20 minutes, obtain amorphous silica-alumina predecessor, amorphous silica-alumina predecessor is on the basis of silicon dioxide and aluminium oxide gross weight, and the content counted with silicon dioxide is as 60wt%.
(2) preparation of gel is with embodiment 2；
(3) crystallization is with embodiment 2, records relative crystallinity after obtaining Na beta-molecular sieve products C N β-4；CN β-4, after roasting in 550 DEG C of air 3 hours, records the relative crystallinity after roasting；CN β-4 is again after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, and concrete CN β-4 character is shown in Table 1.
(4) ammonium salt exchange and Template removal
Na beta-molecular sieve CN β-4, with embodiment 2, is made and obtains H beta molecular sieve products C S β-4, XRD determining CS β-4 relative crystallinity by the method for ammonium salt exchange and Template removal；CS β-4 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, the results are shown in Table 2.
Comparative example 5
(1) preparation of amorphous silica-alumina predecessor is with embodiment 2；
(2) preparation of gel is the most same as in Example 2, and difference is: amorphous silica-alumina predecessor, sodium silicate, tetraethyl ammonium hydroxide and water are according to Al2O3: SiO2: Na2O:H2O=1:80:1.5:240, TEAOH/SiO2Total molar ratio of=0.2.
(3) crystallization is with embodiment 2, prepares Na beta-molecular sieve CN β-5, records relative crystallinity；CN β-5, after roasting in 550 DEG C of air 3 hours, records the relative crystallinity after roasting；CN β-5 is again after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, and concrete CN β-5 character is shown in Table 1.
(4) ammonium salt exchange and Template removal
Na beta-molecular sieve CN β-5, with embodiment 2, is made H beta molecular sieve products C S β-5, XRD determining CS β-5 relative crystallinity by the method for ammonium salt exchange and Template removal；CS β-5 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, the results are shown in Table 2.
Table 1
| Feed intake SiO2/Al2O3Mol ratio | Specific surface area, m2/g | Pore volume, mL/g | SiO2/Al2O3Mol ratio | Relative crystallinity, % | Relative crystallinity *, % after roasting | The reservation degree of crystallization relatively after hydrothermal treatment consists, % | |
| Embodiment 1 | 60 | 610 | 0.50 | 56 | 136 | 130 | 116 |
| Embodiment 2 | 80 | 665 | 0.53 | 74 | 124 | 120 | 112 |
| Embodiment 3 | 90 | 680 | 0.55 | 83 | 122 | 112 | 107 |
| Embodiment 4 | 70 | 630 | 0.52 | 65 | 128 | 119 | 115 |
| Comparative example 1 | 86 | 581 | 0.46 | 28 | 102 | 93 | 80 |
| Comparative example 2 | 43 | 570 | 0.44 | 33 | 98 | 78 | 56 |
| Comparative example 3 | 80 | 610 | 0.47 | 52 | 102 | 93 | 82 |
| Comparative example 4 | 80 | 605 | 0.48 | 55 | 106 | 98 | 87 |
| Comparative example 5 | 80 | 603 | 0.49 | 65 | 104 | 96 | 84 |
Note: in the * present invention, Na beta molecular sieve is as follows through the condition of air roasting: roasting 3 hours in 550 DEG C of air.
Data from table 1: the preparation method of the embodiment of the present invention, not only can reduce the usage amount of organic formwork agent, it is also possible to synthesize the Na beta molecular sieve of high-crystallinity, high silica alumina ratio, and have more preferable heat stability and hydrothermal stability.
Table 2
| Specific surface area, m2/g | Pore volume, mL/g | SiO2/Al2O3Mol ratio | Relative crystallinity, % | The reservation degree of crystallization relatively after hydrothermal treatment consists, % | |
| Embodiment 1 | 615 | 0.51 | 56 | 132 | 119 |
| Embodiment 2 | 670 | 0.54 | 74 | 122 | 116 |
| Embodiment 3 | 685 | 0.56 | 83 | 117 | 109 |
| Embodiment 4 | 635 | 0.53 | 65 | 122 | 116 |
| Comparative example 1 | 578 | 0.46 | 28 | 95 | 83 |
| Comparative example 2 | 567 | 0.44 | 33 | 80 | 57 |
| Comparative example 3 | 611 | 0.48 | 52 | 94 | 84 |
| Comparative example 4 | 606 | 0.49 | 55 | 99 | 88 |
| Comparative example 5 | 605 | 0.50 | 65 | 97 | 86 |
Data from table 2: the preparation method of the embodiment of the present invention, not only can reduce the usage amount of organic formwork agent, it is also possible to synthesize the H beta molecular sieve of high-crystallinity, high silica alumina ratio, and have more preferable heat stability and hydrothermal stability.
Claims (15)
1. a H beta molecular sieve, it is characterised in that described H beta molecular sieve character is as follows: SiO2/Al2O3Mol ratio is 40～100, and specific surface area is 502～850m2/ g, pore volume is 0.35～0.60mL/g, and relative crystallinity is 100%～148%；This H beta molecular sieve relative crystallinity after water vapour hydrothermal treatment consists is more than 95%.
H beta molecular sieve the most according to claim 1, it is characterised in that: described H beta molecular sieve character is as follows: SiO2/Al2O3Mol ratio is 60～100, and specific surface area is 505～800m2/ g, pore volume 0.40～0.60mL/g, relative crystallinity is 110%～140%；This H beta molecular sieve relative crystallinity after water vapour hydrothermal treatment consists is 95%～130%.
H beta molecular sieve the most according to claim 1, it is characterised in that: described H beta molecular sieve character is as follows: SiO2/Al2O3Mol ratio is 60～100, and specific surface area is 600～750 m2/ g, pore volume 0.45～0.55mL/g, relative crystallinity be 115%～
140%；This H beta molecular sieve relative crystallinity after water vapour hydrothermal treatment consists is 108%～130%.
4. according to the H beta molecular sieve described in claim 1,2 or 3, it is characterised in that: this H beta molecular sieve was as follows through the condition of water vapour hydrothermal treatment consists: through 750 DEG C of water vapour hydrothermal treatment consists 2 hours.
5. a preparation method for H beta molecular sieve, including:
(1), using preparing amorphous silicon alumnium using carbonization predecessor, described amorphous silica-alumina predecessor is on the basis of the gross weight of silicon dioxide and aluminium oxide, and the content that silicon is counted with silicon dioxide is as 40wt%～75wt%, preferably 55wt%～70wt%；Its preparation process includes:
Preparation sodium aluminate solution and silicon-containing compound solution respectively；Sodium aluminate solution is mixed with part silicon-containing compound solution, then passes to CO2Gas, as the CO being passed through2When gas flow accounts for the 60% ~ 100% of total intake, preferably 85% ~ 100%, add described remainder silicon-containing compound solution；
(2), the said mixture in step (1) stablizes 10 ~ 30 minutes in ventilated environment；
(3), by Al2O3: SiO2: Na2O:H2O=1:(42 ~ 110): (0.5～3.0): (100～500), TEAOH/SiO2Total molar ratio of=0.010 ~ 0.095, preferably SiO2/Al2O3Be 62 ~ 110, TEAOH/SiO2=0.020 ~ 0.080, in the amorphous silica-alumina predecessor of step (2) gained, add water, silicon source and template, stir, obtain silica-alumina gel, TEA represents the quaternary amine alkali cation in template；
(4), the silica-alumina gel of step (3) gained through two step dynamic crystallizations, then through filtering, washing, prepare Na beta molecular sieve；
(5), described Na beta molecular sieve carries out ammonium salt exchange and Template removal processes, and prepares described H beta molecular sieve.
6. according to the preparation method described in claim 5, it is characterized in that, in step (1), described remainder silicon-containing compound solution accounts for addition silicon-containing compound solution total amount 5wt% ~ 85wt% in terms of silicon dioxide, preferably 30wt% ~ 70wt% in terms of silicon dioxide.
7. according to the preparation method described in claim 5, it is characterised in that in step (1), the reaction temperature of described plastic is 10～40 DEG C, preferably 15～35 DEG C, and controlling the pH value after cemented into bundles is 8～11.
8., according to the preparation method described in claim 5, it is characterised in that in step (1), described silicon-containing compound solution is waterglass and/or sodium silicate solution.
9. according to the preparation method described in claim 5 or 8, it is characterised in that in step (1), with A12O3Quality meter, the concentration of described sodium aluminate solution is 15～55g Al2O3/ L, with SiO2Quality meter, the concentration of described silicon-containing compound solution is 50～150gSiO2/ L, described CO2The concentration of gas is 30v% ~ 60v%.
Preparation method the most according to claim 5, it is characterised in that: in step (3), generating the reaction temperature 0 of described silica-alumina gel～40 DEG C, pH value is 9.5～12.0；Being preferably, the reaction temperature generating described silica-alumina gel is 10～30 DEG C, and pH value is 10～11.
11. preparation methoies according to claim 5, it is characterised in that: in step (3), described silicon source is one or more in White Carbon black, silica gel, Ludox and waterglass, and described template is tetraethyl ammonium hydroxide.
12. preparation methoies according to claim 5, it is characterized in that: in step (4), the silica-alumina gel of step (2) gained includes through the concrete steps of two step dynamic crystallizations: the condition of first step dynamic crystallization is: carry out crystallization under agitation, temperature is 50～90 DEG C, and the time is 0.5～18.0 hour；The condition of second step dynamic crystallization is: carry out crystallization under agitation, and temperature is 100～200 DEG C, and the time is 40～120 hours.
13. preparation methoies according to claim 12, it is characterised in that: in step (4), the condition of described first step dynamic crystallization is: carry out crystallization under agitation, and temperature is 60～80 DEG C, and the time is 1～10 hour；The condition of described second step dynamic crystallization is: carry out crystallization under agitation, and temperature is 120～170 DEG C, and the time is 50～100 hours.
14. according to the preparation method described in any one in claim 5, it is characterised in that Na in beta-molecular sieve after step (5) ammonium salt exchanges2O weight content is less than 0.3%.
15. according to the preparation method described in claim 5 or 14, it is characterized in that, in step (5), described Template removal processes and uses aerobic high-temperature process, treatment temperature is 400～800 DEG C, and the process time is 5～20 hours, is preferably, treatment temperature is 500～700 DEG C, and the process time is 10～15 hours.
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