CN106466618A - A kind of method of modifying of Y type molecular sieve - Google Patents

A kind of method of modifying of Y type molecular sieve Download PDF

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CN106466618A
CN106466618A CN201510520373.6A CN201510520373A CN106466618A CN 106466618 A CN106466618 A CN 106466618A CN 201510520373 A CN201510520373 A CN 201510520373A CN 106466618 A CN106466618 A CN 106466618A
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molecular sieve
silicon source
serosity
method
mass ratio
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CN106466618B (en
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郑金玉
王成强
罗斌
罗一斌
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中国石油化工股份有限公司
中国石油化工股份有限公司石油化工科学研究院
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Abstract

A kind of method of modifying of Y type molecular sieve is it is characterised in that include:NaY molecular sieve adds water after making beating, by 1~20:1 alcohol sieve mass ratio adds polyhydroxy-alcohol, and processes at 80~200 DEG C of temperature and obtain serosity A;By 0.1~1:1 alkali sieve mass ratio, serosity A and organic base are mixed to get serosity B, then order adds silicon source and silicon source and is aged and obtains serosity C, and described silicon source presses Al2O3Meter is 0.1~1 with the mass ratio of NaY molecular sieve:1, silicon source is with SiO2Meter and silicon source are with Al2O3The mass ratio of meter is 0.1~0.5:1, described silicon source is to add after silicon source is sufficiently mixed uniformly with serosity B;By serosity C in closed reactor hydrothermal crystallizing recovery product.The method can improve the framework si-al ratio of molecular sieve, improves acid distribution, ensure that molecular sieve has more preferable hydrothermal structural stability and excellent heavy oil conversion performance simultaneously.

Description

A kind of method of modifying of Y type molecular sieve

Technical field

The present invention relates to a kind of method of modifying of Y type molecular sieve.

Background technology

After being synthesized from the Y type molecular sieve sixties in last century, due to its have uniform pore passage structure, The features such as excellent heat and hydrothermal stability, stronger acid and higher catalysis activity, it is widely used in In modern industry.As the important micropore catalysis material of a class, Y type molecular sieve petroleum refining with processed Also be used widely in journey, such as catalytic cracking, be hydrocracked etc. in course of reaction, Y type molecular sieve is to urge Of paramount importance cracking activity constituent element in agent.

The NaY molecular sieve being directly synthesized out has a higher sodium oxide content, in the case of high-temperature water heat Na from Son can be had an effect thus saboteur's sieve structure with framework aluminum, and the NaY molecular sieve therefore synthesizing can not be straight Scoop out for refining process such as catalytic cracking, by the ion exchange such as method such as ammonium exchange, sodium oxide need to be washed till Reduced levels, or sodium oxide both can be eluted to simultaneously also by reduced levels using the method for rare earth ion exchanged Structural stability and the cracking activity of molecular sieve can be improved.

The operating condition of catalytic cracking process is more harsh, the stability particularly hydrothermal stability to molecular sieve Propose very high requirement.For the Y type molecular sieve of non-rare-earth type, the raising of framework si-al ratio is to molecule The hydrothermal stability of sieve has obvious facilitation.For conventional NaY molecular sieve, its silica alumina ratio is about 5.0 about, aluminium content is of a relatively high, goes out through numerous studies work summary to improve stability scientific research personnel Several improve the method for stability, main inclusion:High temperature hydro-thermal method, Coordinative Chemistry method, gas phase and liquid phase are taken out Aluminum silicon reinsertion method etc..High temperature hydro-thermal method refers to remove framework aluminum by hydrothermal calcine process at high temperature, improves bone Frame silica alumina ratio is thus improve stability, but due to not additional silicon source, only leans on the silicon in molecular sieve to go to fill up dealuminzation Hole, easily causes the destruction of molecular sieve structure, affects degree of crystallinity, is also easy to produce a large amount of non-framework aluminums simultaneously, Blocking molecular sieve pore passage, the selectivity of impact molecular sieve.Coordinative Chemistry method is based on organic compound and aluminum shape Become the principle of stable complex, chelated with framework aluminum by adding the organic compound such as EDTA, reach removing The purpose of framework aluminum, this method dealuminzation effect is obvious, but reaction condition is wayward, results even in molecular sieve The destruction completely of structure.Gas phase and liquid phase aluminium-eliminating and silicon-replenishing rule are the mechanism based on isomorphous substitution, in removing aluminum While by silicon be inserted into dealuminzation generation hole in, effectively improve the silica alumina ratio of molecular sieve, dealumination agent used It is active silicon source, while dealuminzation, active silicon source fills into and reaches aluminium-eliminating and silicon-replenishing in tetrahedral holes simultaneously again Purpose.Larger using the impact to molecular sieve for hot conditionss during vapor phase method, particularly to degree of crystallinity impact, And the by-product of generation is unfriendly to environment during being somebody's turn to do.Although liquid phase method dealuminzation effect is preferably, due to F is contained in dealumination agent-, on the one hand easily cause emission problem, the partially fluorinated thing dissolubility being additionally formed is poor, It is difficult to eluting, the stability on molecular sieve and activity cause necessarily to affect on the contrary.

Because treatment conditions are different in above several method, the silicon source for filling up hole is also different, therefore reaches To effect be also not quite similar.Divide after being replaced by the shorter Si-O key of bond distance due to the longer Al-O key of bond distance Son sieve structure cell reduces, and framework si-al ratio improves, but molecular sieve acid site can be affected simultaneously, acid Amount decreases, and has certain impact to cracking activity and selectivity.In addition, in addition to hydro-thermal method other several sides Fado is to lose molecular sieve yield as cost, even if the filling into of active silicon source, the product of overall molecule sieve Rate is to reduce, and has therefore both caused the waste of silicon source to be likely to cause the pollution to environment;Although and hydro-thermal method There is no the loss of yield, but the loss of the presence of non-framework aluminum and degree of crystallinity is equally unfavorable factor.

Content of the invention

The purpose of the present invention is for the deficiencies in the prior art, provides one kind both to improve framework of molecular sieve silica alumina ratio Also improve acid distribution, and ensure that molecular sieve has the Y of excellent water heat structure stability and heavy oil conversion performance The method of modifying of type molecular sieve.

The purpose of the present invention is achieved through the following technical solutions, a kind of method of modifying of Y type molecular sieve, After the making beating it is characterized in that NaY molecular sieve adds water, by 1~20:1 alcohol sieve mass ratio adds polyhydroxy-alcohol, And process at 80~200 DEG C of temperature and obtain serosity A;By 0.1~1:1 alkali sieve mass ratio, by serosity A It is mixed to get serosity B with organic base, then order adds silicon source and silicon source and is aged and obtains serosity C, described aluminum Al is pressed in source2O3Meter is 0.1~1 with the mass ratio of NaY molecular sieve:1, silicon source is with SiO2Meter and silicon source are with Al2O3 The mass ratio of meter is 0.1~0.5:1, described silicon source be after silicon source and serosity B are sufficiently mixed uniformly again Add;By serosity C in closed reactor hydrothermal crystallizing recovery product.

In the method for the present invention, described NaY molecular sieve can be the NaY molecule of various conventional method preparations Sieve, to sial, when grain size etc. is not particularly limited, degree of crystallinity typically more than 80%, lattice constant About 2.464-2.466nm.For example, US3639099, US4482530, US4576807, CN1621349A, Y type molecular sieve disclosed in the documents such as CN1840475A is used equally to the present invention.NaY molecular sieve adds water making beating In step, the weight of NaY molecular sieve and deionized water is than for 1:5~20, preferably 1:8~15.

In the method for the present invention, the purpose of polyhydroxy-alcohol is added to be to activate NaY molecular sieve, described polyhydroxy Base alcohol is preferably one or more of glycerol, propylene glycol and Isopropanediol.Described alcohol sieve mass ratio is excellent Elect 3~15 as:1.Described temperature is 80~200 DEG C, preferably 100~180 DEG C, and the time is 1~10 Hour, preferably 2~8 hours.

In the method for the present invention, described serosity A is product after polyhydroxy-alcohol activation for the NaY molecular sieve, Organic base is added after being preferably cooled to room temperature.Described organic base be preferably TPAOH, four One or more of ethyl ammonium hydroxide or Tetramethylammonium hydroxide.Described alkali sieve mass ratio is 0.1~ 1:1st, it is preferably 0.2~0.8:1.

In the method for the present invention, described silicon source is selected from aluminum sulfate, aluminum nitrate, sodium metaaluminate or aluminium oxide One or more.Described silicon source presses Al2O3Meter is 0.1~1 with the mass ratio of molecular sieve:1st, preferred 0.2~0.8:1.

In the method for the present invention, the described silicon source mixing with serosity B be preferably waterglass, sodium silicate, four One or more of ethyoxyl silicon, tetramethoxy-silicane and silicon oxide.Difference due to cost and response speed Different, more preferably waterglass and sodium silicate are as silicon source.Described silicon source is with SiO2Meter and silicon source are with Al2O3Meter Weight is than for 0.1~0.5:1st, preferably 0.15~0.45:1.Described ageing is preferably entered at 50~80 DEG C 1~10 hour, more preferably 2-5 hour of row.

The method of modifying of the present invention, with NaY molecular sieve as raw material, by add polyhydroxy-alcohol, organic base and Add the collective effect of silicon source, silicon source and secondary hydrothermal crystallization process, improve framework of molecular sieve sial Acid distribution is improved ratio, and hydrothermal structural stability and heavy oil conversion performance increase, and molecular sieve produces Rate increases.

Specific embodiment

The present invention is further illustrated for the following examples, but not thereby limiting the invention.

In each embodiment and comparative example, the framework silicon-aluminum atomic ratio (Si/Al) of molecular sieve adopts solid core Magnetic NMR method measures.Acid data adopts infrared pyridine adsorption in site measurement method to measure.

Embodiment 1

By 20g (butt) industry NaY molecular sieve (Na2O 13.1%, degree of crystallinity 85%, framework silicon-aluminum atom Ratio 2.62, Sinopec Chang Ling catalyst plant) mix with 160g glycerol and 200g deionized water, stirring It is warming up to 150 DEG C of depolymerization 4h after uniformly;Then the serosity standing after depolymerization is cooled to after room temperature, acutely stirs Mix lower addition 24g TPAOH solution (mass fraction 25wt%), by 20mL at 40 DEG C after stirring 30 minutes Sodium metaaluminate (Al2O3Content 190g/L) it is added thereto, add 3mL waterglass after continuing stirring 30 minutes Solution (SiO2Content 250g/L, modulus 3.3), under stirring, it is warming up to 70 DEG C of ageing 2h.Subsequently will be above-mentioned Serosity is transferred in rustless steel crystallizing kettle in 110 DEG C of crystallization 10h, the product obtaining is filtered, wash, does After dry, roasting 2h at 550 DEG C, gained molecular sieve is designated as GYSA-1.Powder diffraction XRD spectra shows it There is the feature of typical Y type molecular sieve.

Embodiment 2

20g (butt) industry NaY molecular sieve (ibid) is mixed with 60g glycerol and 160g deionized water Close, after stirring, be warming up to 180 DEG C of depolymerization 2h;Then the serosity standing after depolymerization is cooled to after room temperature, It is stirred vigorously lower addition 32g TEAOH solution (mass fraction 25wt%), after stirring 30 minutes at room temperature By 80mL aluminum sulfate (Al2O3Content 90g/L) it is added thereto, add 8.5mL after continuing stirring 30 minutes Water glass solution, is warming up to 60 DEG C of ageing 2h under stirring.Subsequently above-mentioned serosity is transferred to rustless steel crystallization In 100 DEG C of crystallization 20h in kettle, after the product obtaining filtration, washing, being dried, roasting at 600 DEG C 2h, gained molecular sieve is designated as GYSA-2.Powder diffraction XRD spectra shows that it has typical Y type molecular sieve Feature.

Embodiment 3

By 20g (butt) industry NaY molecular sieve (ibid) and 110g glycerol and 200g deionized water Mixing, is warming up to 100 DEG C of depolymerization 8h after stirring;Then the serosity standing after depolymerization is cooled to room temperature Afterwards, it is stirred vigorously lower addition 30g TPAOH solution and 18g TEAOH solution, in room after stirring 30 minutes Under temperature, 80mL sodium metaaluminate is added thereto, after continuing stirring 30 minutes, adds 5.5g tetraethoxy-silicane, It is warming up to 80 DEG C of ageing 2h under stirring.Subsequently above-mentioned serosity is transferred in rustless steel crystallizing kettle in 100 DEG C of crystalline substances Change 8h, after the product obtaining filtration, washing, being dried, roasting 2h at 700 DEG C, gained molecular sieve is remembered For GYSA-3.Powder diffraction XRD spectra shows that it has the feature of typical Y type molecular sieve.

Embodiment 4

20g (butt) industry NaY molecular sieve (ibid) is mixed with 80g propylene glycol and 240g deionized water Close, after stirring, be warming up to 140 DEG C of depolymerization 6h;Then the serosity standing after depolymerization is cooled to after room temperature, It is stirred vigorously lower addition 64g TPAOH solution, will be molten for 110mL aluminum sulfate at 60 DEG C after stirring 30 minutes Liquid is added thereto, continue stirring 30 minutes after add 13g tetraethoxy-silicane, be warming up under stirring 70 DEG C old Change 2h.Subsequently above-mentioned serosity is transferred in 120 DEG C of crystallization 8h in rustless steel crystallizing kettle, by the product obtaining Filter, washing, be dried after, roasting 4h at 550 DEG C, gained molecular sieve is designated as GYSA-4.Powder diffraction XRD spectra shows that it has the feature of typical Y type molecular sieve.

Embodiment 5

By 20g (butt) industry NaY molecular sieve (ibid) and 140g glycerol and 300g deionized water Mixing, is warming up to 160 DEG C of depolymerization 3h after stirring;Then the serosity standing after depolymerization is cooled to room temperature Afterwards, it is stirred vigorously lower addition 56g TMAOH solution (mass fraction 25wt%), in room after stirring 30 minutes Under temperature, 42mL sodium metaaluminate is added thereto, adds 5mL water glass solution after continuing stirring 30 minutes, stir Mix down and be warming up to 60 DEG C of ageing 2h.Subsequently above-mentioned serosity is transferred in rustless steel crystallizing kettle in 110 DEG C of crystallization 15h, after the product obtaining filtration, washing, being dried, roasting 6h at 600 DEG C, gained molecular sieve is remembered For GYSA-5.Powder diffraction XRD spectra shows that it has the feature of typical Y type molecular sieve.

Embodiment 6

By 20g (butt) industry NaY molecular sieve (ibid) and 200g glycerol and 100g deionized water Mixing, is warming up to 80 DEG C of depolymerization 10h after stirring;Then the serosity standing after depolymerization is cooled to room temperature Afterwards, it is stirred vigorously lower addition 12g TPAOH solution, by 16mL meta-aluminic acid at 50 DEG C after stirring 30 minutes Sodium is added thereto, and adds 5.5mL water glass solution, be warming up to 60 DEG C under stirring after continuing stirring 30 minutes Ageing 2h.Subsequently above-mentioned serosity is transferred in 120 DEG C of crystallization 10h in rustless steel crystallizing kettle, by obtain Product filter, washing, be dried after, roasting 2h at 650 DEG C, gained molecular sieve is designated as GYSA-6.Powder Diffraction XRD spectra shows that it has the feature of typical Y type molecular sieve.

Embodiment 7

By 20g (butt) industry NaY molecular sieve (ibid) and 260g propylene glycol and 160g deionized water Mixing, is warming up to 150 DEG C of depolymerization 5h after stirring;Then the serosity standing after depolymerization is cooled to room temperature Afterwards, it is stirred vigorously lower addition 48g TMAOH solution, by 130mL sulphuric acid at 60 DEG C after stirring 30 minutes Aluminum is added thereto, continue stirring 30 minutes after add 12mL water glass solution, be warming up under stirring 70 DEG C old Change 2h.Subsequently above-mentioned serosity is transferred in 110 DEG C of crystallization 20h in rustless steel crystallizing kettle, by the product obtaining Thing filter, washing, be dried after, roasting 4h at 700 DEG C, gained molecular sieve is designated as GYSA-7.Powder spreads out Penetrate XRD spectra and show that it has the feature of typical Y type molecular sieve.

Comparative example 1

According to embodiment 1, difference is the process no adding polyhydroxy-alcohol to process to this comparative example.

20g (butt) industry NaY molecular sieve (ibid) is mixed with 200g deionized water, is stirred vigorously Lower addition 24g TPAOH solution, 20mL sodium metaaluminate is added thereto after 30 minutes at 40 DEG C by stirring, Add 3mL water glass solution after continuing stirring 30 minutes, under stirring, be warming up to 70 DEG C of ageing 2h.Subsequently will Above-mentioned serosity is transferred in rustless steel crystallizing kettle in 110 DEG C of crystallization 10h, the product obtaining is filtered, washs, After drying, at 550 DEG C, roasting 2h obtains contrasting molecular sieve, and powder diffraction XRD spectra shows that it has The feature of typical Y type molecular sieve, is designated as DB-1.

Comparative example 2

This comparative example is no to add the process of organic base according to embodiment 1, difference.

By 20g (butt) industry NaY molecular sieve (ibid) and 160g glycerol and 200g deionized water Mixing, is warming up to 150 DEG C of depolymerization 4h after stirring;Standing is cooled to 20mL sodium metaaluminate when 40 DEG C It is added thereto, add 3mL water glass solution after continuing stirring 30 minutes, under stirring, be warming up to 70 DEG C of ageings 2h.Subsequently above-mentioned serosity is transferred in 110 DEG C of crystallization 10h in rustless steel crystallizing kettle, by the product obtaining Filter, washing, be dried after, at 550 DEG C roasting 2h i.e. obtain contrast molecular sieve, powder diffraction XRD Spectrogram shows that it has the feature of typical Y type molecular sieve, is designated as DB-2.

Comparative example 3

According to embodiment 1, difference is no to add the process of silicon source and silicon source this comparative example.

By 20g (butt) industry NaY molecular sieve (ibid) and 160g glycerol and 200g deionized water Mixing, is warming up to 150 DEG C of depolymerization 4h after stirring;Then the serosity standing after depolymerization is cooled to room temperature Afterwards, it is stirred vigorously lower addition 24g TPAOH solution, then heat to 70 DEG C of ageing 2h.Subsequently will be above-mentioned Serosity is transferred in rustless steel crystallizing kettle in 110 DEG C of crystallization 10h, the product obtaining is filtered, wash, does After dry, at 550 DEG C, roasting 2h obtains contrasting molecular sieve, and powder diffraction XRD spectra shows that it has allusion quotation The feature of type Y type molecular sieve, is designated as DB-3.

Comparative example 4

According to embodiment 1, difference is no to add the process of silicon source this comparative example.

By 20g (butt) industry NaY molecular sieve (ibid) and 160g glycerol and 200g deionized water Mixing, is warming up to 150 DEG C of depolymerization 4h after stirring;Then the serosity standing after depolymerization is cooled to room temperature Afterwards, it is stirred vigorously lower addition 24g TPAOH solution, by 20mL meta-aluminic acid at 40 DEG C after stirring 30 minutes Sodium is added thereto, and then heats to 70 DEG C of ageing 2h.Subsequently above-mentioned serosity is transferred to rustless steel crystallizing kettle In in 110 DEG C of crystallization 10h, the product obtaining is filtered, washing, be dried after, roasting 2h at 550 DEG C Obtain contrasting molecular sieve, powder diffraction XRD spectra shows that it has the feature of typical Y type molecular sieve.Note For DB-4.

Comparative example 5

According to embodiment 1, difference is no to add the process of silicon source this comparative example.

By 20g (butt) industry NaY molecular sieve (ibid) and 160g glycerol and 200g deionized water Mixing, is warming up to 150 DEG C of depolymerization 4h after stirring;Then the serosity standing after depolymerization is cooled to room temperature Afterwards, it is stirred vigorously lower addition 24g TPAOH solution, stirring adds 3mL water glass after 30 minutes at 40 DEG C Glass solution, then heats to 70 DEG C of ageing 2h.Subsequently by above-mentioned serosity be transferred in rustless steel crystallizing kettle in 110 DEG C of crystallization 10h, after the product obtaining filtration, washing, being dried, at 550 DEG C, roasting 2h obtains final product To contrasting molecular sieve, powder diffraction XRD spectra shows that it has the feature of typical Y type molecular sieve, is designated as DB-5.

Comparative example 6

The process of high silica alumina ratio Y type molecular sieve is prepared in the explanation of this comparative example using the multiple roasting of high temperature hydro-thermal method.

Weigh 20g (butt) industry NaY molecular sieve (ibid) in beaker, according to ammonium salt:Molecular sieve: H2O=1:1:10 weight, than adding ammonium chloride and deionized water, is warming up to 70 DEG C and constant temperature 1 after stirring Hour, after filtering washing and drying, steam treatment 2h at 600 DEG C, by the molecule after High-temperature water heat treatment Sieve again with ammonium salt and deionized water hybrid switching, be dried after carry out secondary high-temperature hydrothermal treatment consists, that is, obtain two Hand over the super-stable Y molecular sieves of two roastings, be designated as DB-6.

Comparative example 7

The process of high silica alumina ratio Y type molecular sieve is prepared in the explanation of this comparative example using liquid phase aluminium-eliminating and silicon-replenishing method.

Weigh 20g (butt) industry NaY molecular sieve (ibid) in beaker, according to ammonium salt:Molecular sieve: H2O=1:1:10 weight, than adding ammonium chloride and deionized water, is warming up to 70 DEG C and constant temperature 1 after stirring Hour, after filtering washing and drying, steam treatment 2h at 600 DEG C, by the molecule after High-temperature water heat treatment Sieve is mixed in proportion with hexafluosilicic acid and hydrochloric acid, after filtering washing, that is, obtains the superstable gamma-type molecule of aluminium-eliminating and silicon-replenishing Sieve, is designated as DB-7.

Test case

The materialization of the molecular sieve fresh sample that this test case illustrates above-described embodiment and comparative example obtains characterizes number According to sample through the micro-activity evaluation knot after burin-in process under 800 DEG C, 100% water vapor conditions 12 hours Really.

The acid analysis of sample and micro-activity evaluation need to carry out under relatively low sodium oxide content, therefore will be upper State the comparative sample obtaining in sample GYSA-1~GYSA-7 that embodiment 1-7 obtains and comparative example 1-7 DB-1~DB-7 carries out ammonium and exchanges removing sodium process, makes sodium oxide content be less than below 0.3wt%, then using red Outer pyridine adsorption in site measurement method determination sample is acid.

The acid assay method of sample:By sample self-supporting tabletting, it is placed in sealing in the original position pond of infrared spectrometer, It is warming up to 350 DEG C and be evacuated to 10-3Pa, constant temperature removes the gas molecule of sample adsorption after 1 hour;Cold But import pyridine steam to room temperature and keep adsorption equilibrium 30 minutes, then heat to 200 DEG C, again take out true Empty to 10-3Pa is simultaneously desorbed 30 minutes under this vacuum, is down to room temperature and takes the photograph spectrum, and sweep limitss 1400~ 1700cm-1, you can obtain the Pyridine adsorption IR spectra figure through 200 DEG C of desorptions for the sample.Red according to pyridine adsorption External spectrum in figure 1540cm-1And 1450cm-1The intensity of characteristic absorption peak, calculates B-acid center and L acid center Relative quantity.

The mensure of light oil microactivity (MA):Sodium oxide content is less than the embodiment sample of 0.3wt% GYSA-1~GYSA-7 and comparative sample DB-1~DB-7 tabletting simultaneously grind to form 20~40 mesh granules, 800 DEG C, burin-in process 12 hours carry out light oil micro-reactor evaluation under 100% water vapor conditions.Light oil micro-reactor is evaluated Condition:Molecular sieve loading amount 2g, raw oil is huge port straight distillation light diesel oil, oil inlet quantity 1.56g, reaction temperature 460 ℃.

The determination data of materialization characterize data and light oil microactivity (MA) the results are shown in Table 1.

Table 1

From table 1, the method for modifying that provided using the present invention, that is, by the depolymerisation of polyhydroxy-alcohol, Organic base, to the guide effect of additional silicon source and silicon source and secondary hydrothermal crystallization process, can make molecular sieve Framework silicon-aluminum atomic ratio appropriateness improve, afterwards plus silicon source and organic base induction, more conducively silicon enter molecular sieve Skeleton.

Using the method for the present invention, effectively can sieve the acid distribution of sample by Molecular regulator, increase total acid content.

After 800 DEG C, 12h burin-in process, in embodiment, the micro anti-active index MA of sieve sample reaches 53~56, higher than the 48~52 of comparative example, although showing the framework silicon-aluminum of molecular sieve after modified process Ratio varies slightly, but to acid promotor action substantially, molecular sieve shows more preferable cracking activity.

Claims (10)

1. after a kind of making beating it is characterised in that NaY molecular sieve adds water of method of modifying of Y type molecular sieve, by 1~ 20:1 alcohol sieve mass ratio adds polyhydroxy-alcohol, and processes at 80~200 DEG C of temperature and obtain serosity A;Press 0.1~1:1 alkali sieve mass ratio, serosity A is mixed to get serosity B with organic base, then order adds aluminum Source and silicon source are simultaneously aged and obtain serosity C, and described silicon source presses Al2O3Meter and the mass ratio of NaY molecular sieve be 0.1~ 1:1, silicon source is with SiO2Meter and silicon source are with Al2O3The mass ratio of meter is 0.1~0.5:1, described silicon source is Add after silicon source is sufficiently mixed uniformly with serosity B;By serosity C, in closed reactor, hydrothermal crystallizing is simultaneously Recovery product.
2., according to the method for claim 1 wherein, described alcohol sieve mass ratio is 3~15:1.
3., according to the method for claim 1 wherein, described polyhydroxy-alcohol is selected from glycerol, propylene glycol One or more of with Isopropanediol.
4., according to the method for claim 1 wherein, described alkali sieve mass ratio is 0.2~0.8:1.
5. according to the method for claim 1 wherein, described organic base be selected from TPAOH, One or more of tetraethyl ammonium hydroxide and Tetramethylammonium hydroxide.
6. according to the method for claim 1 wherein, described ageing, temperature is 50~80 DEG C.
7., according to the method for claim 1 wherein, described silicon source is selected from aluminum sulfate, aluminum nitrate, partially One or more of sodium aluminate and aluminium oxide.
8., according to the method for claim 1 wherein, silicon source presses Al2O3Meter and the mass ratio of NaY molecular sieve For 0.2~0.8:1.
9. according to the method for claim 1 wherein, described silicon source be selected from waterglass, sodium silicate, four One or more of ethyoxyl silicon, tetramethoxy-silicane and silicon oxide.
10., according to the method for claim 1 wherein, silicon source is with SiO2Meter and silicon source are with Al2O3The matter of meter Amount ratio is (0.15~0.45):1.
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN107720776A (en) * 2017-10-23 2018-02-23 中海油天津化工研究设计院有限公司 A kind of synthetic method of no sodium FAU type molecular sieves

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US20090155464A1 (en) * 2007-12-12 2009-06-18 Chunqing Liu Molecular Sieve/Polymer Mixed Matrix Membranes
WO2009076025A1 (en) * 2007-12-12 2009-06-18 Uop Llc Molecular sieve/polymer mixed matrix membranes

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CN1176848A (en) * 1996-09-19 1998-03-25 中国科学院山西煤炭化学研究所 Method for synthesis of small granular NaY molecular sieve
EP1883124A1 (en) * 2006-07-27 2008-01-30 IEE INTERNATIONAL ELECTRONICS & ENGINEERING S.A. Organic light emitting material formulation
US20090155464A1 (en) * 2007-12-12 2009-06-18 Chunqing Liu Molecular Sieve/Polymer Mixed Matrix Membranes
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107720776A (en) * 2017-10-23 2018-02-23 中海油天津化工研究设计院有限公司 A kind of synthetic method of no sodium FAU type molecular sieves

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