CN105984879A

CN105984879A - MWW-structure molecular sieve and preparation method thereof

Info

Publication number: CN105984879A
Application number: CN201510046936.2A
Authority: CN
Inventors: 邢恩会; 石艳春; 谢文华; 张凤美; 慕旭宏; 刘强; 王卫东; 秦凤明; 舒兴田
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2015-01-29
Filing date: 2015-01-29
Publication date: 2016-10-05
Anticipated expiration: 2035-01-29
Also published as: CN105984879B

Abstract

The invention discloses a MWW-structure molecular sieve, wherein a BJH curve of nitrogen adsorption-desorption of the molecular sieve shows that nitrogen desorption quantity at 3.8 +/- 0.5 nm is 0.01-0.10 cm<3>/g; in addition, the molecular sieve is not less than 35 [mu]mol/g in adsorption quantity of 2,4,6-trimethylpyridine after adsorption at 20 DEG C and desorption at 200 DEG C.

Description

A kind of MWW structure molecular screen and preparation method thereof

Technical field

The present invention is about a kind of molecular sieve and preparation method thereof, more specifically about a kind of MWW knot Structure molecular sieve and preparation method thereof.

Background technology

MWW structure molecular screen include MCM-22, MCM-49, MCM-36, MCM-56, SSZ-25, ITQ-1, ITQ-2 and UZM-8 equimolecular sieves.Nineteen ninety, Mobil company is first with hexamethylene imine For template Hydrothermal Synthesis MCM-22 molecular sieve (US, 4954325,1990), and resolved first in 1994 Go out its structure, and with this named MWW structure molecular screen, therefore there is the layer of MWW topological structure Shape molecular sieve is also called MCM-22 family molecular sieves.

MWW structure molecular screen has the independent duct that two sets are non-cross: layer internal orifice dimension is 0.40 × 0.59 The oval 10MR two dimension sine duct of nm；Interlayer is the 12MR supercage of 0.71 × 0.71 × 1.82nm, And communicate with the external world with the 10MR opening of 0.40 × 0.54nm；Additionally also it is distributed some 12MR on its surface Hole, is the half of supercage, and the degree of depth is about 0.91nm (Science, 1994,264:1910).MWW structure Molecular sieve is because the pore passage structure of its uniqueness and physico-chemical property are in alkylation (US, 5600048,1997), aromatisation (catalysis journal, 2002,23:24), catalytic cracking (J.Catal., 1997,167:438) and isomerization The reaction such as (J.Catal., 1996,158:561) has broad application prospects.

Although MWW structure molecular screen has higher micropore specific area, but due to ten-ring aperture Restriction, the acidic site in supercage hardly results in utilization.In order to make the acidic site in supercage be fully used, A lot of researchs are devoted to introduce mesoporous in MWW molecular sieve or make ten-ring sine duct and interlayer in layer Supercage communicates, thus improves diffusion inside.

Compared with three-dimensional molecular sieve, the lamellar zeolite such as MWW is not because Coating combination closely shows The multiformity of structure and plasticity, and the most still can carry out structural modification further.The most right It is swelling that MCM-22P carries out interlayer, peels off (be partially stripped or be completely exfoliated), and intercalation, reaming and post The post processings such as support, can both be kept MWW Primary layer construction unit, be had again large aperture and Gao Bi The catalysis material of surface area, such as MCM-56 homologue, MCM-36, ITQ-2 and IEZ Series Molecules sieve.

Utilizing NaOH to process molecular sieve generate the most mesoporous document and summarize many, they lead to Cross the alkalescence utilizing NaOH to realize controlled molten silicon, thus generate between or crystal internal at molecular sieve crystal Substantial amounts of mesoporous, thus reach to improve the purpose of diffusion.Wu Peng etc. divide with the MCM-22 after roasting Son sieve is raw material, uses organic amine to protect the molten silicon of skeleton selectivity of high silicon MWW structure molecular screen, becomes Merit be prepared for mesoporous MCM-22 molecular sieve.Silicon molten with independent NaOH can cause structure collapse phase Ratio, the method introduces aperture at about 20nm while three dimensional structure converts with two-dimensional layered structure Intracrystalline is mesoporous, and molecular sieve crystallinity also remains intact, the silica alumina ratio of molecular sieve by 60 desiliconizations of raw material to 20～ 30.MCM-22 molecular sieve before and after roasting is processed, the most also by Xu Long childs etc. merely with NaOH The mesoporous of MCM-22 molecular sieve can be dramatically increased.

The post processing of MWW structure molecular screen focuses mostly in inorganic base NaOH process, due to NaOH's Strong basicity, thus desiliconization controllable degree is poor.Although molecule can optionally be protected by introducing organic amine Sieve skeleton frame, but the destruction of framework of molecular sieve is still unavoidably by NaOH.

Summary of the invention

An object of the present invention is to provide and a kind of is different from prior art, has special physico-chemical property MWW structure molecular screen.

The two of the purpose of the present invention are to provide and a kind of prepare the above-mentioned MWW structure being different from prior art and divide The method of son sieve.

Inventor has been surprisingly found that on the basis of lot of experiments, and MWW structure molecular screen is different from experience The sieve sample obtained after the alkaline matter for processing process of prior art, its pattern is by former " flower shape " Tightly packed being changed into lamellar loosely-packed, confusion degree dramatically increases, zeolite crystal more dispersion, compares table Area and pore volume increased, and have lower Na simultaneously⁺Content, shows as having and is different from routine Nitrogen at the BJH curve 3.8 ± 0.5nm of the specific nitrogen adsorption-desorption of MWW structure molecular screen takes off Attached amount and the adsorbance of specific 2,4,6-trimethylpyridine.Based on this, form the present invention.

In order to realize one of purpose, the MWW structure molecular screen that the present invention provides, it is characterised in that this molecule The BJH curve of nitrogen adsorption-desorption of sieve show the nitrogen desorption rate at 3.8 ± 0.5nm be 0.01～ 0.10cm³The adsorbance of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions is >=35 μmol/g。

In order to realize the two of purpose, present invention also offers a kind of preparation method, it is characterised in that by raw material MWW structure molecular screen, nitrogenous organic base R1, organic amine R2, deionized water mix homogeneously obtain mole Ratio is H₂O/SiO₂=5～100, R1/SiO₂=0.01～5, R2/SiO₂The mixture of=0～1, and should Mixture crystallization 5～72h reclaiming at 100～180 DEG C, wherein, described nitrogenous organic base R1, Selected from Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, dimethyl diethyl hydrogen-oxygen Change ammonium, monomethyl triethylammonium hydroxide, monomethyl tripropyl ammonium hydroxide, dimethyl dipropyl hydroxide At least one in ammonium, diethyl dipropyl ammonium hydroxide and an ethyl tripropyl ammonium hydroxide, described has Machine amine R2, selected from pentamethylene imines, hexamethylene imine, heptamethylene imines, homopiperazine, At least one in cycloheptyl alkanamine, hexamethylene alkanamine, Aminocyclopentane, aniline, piperidines and piperazine.

The MWW structure molecular screen that the present invention provides, pattern is lamellar loosely-packed, and confusion degree is notable Increasing, zeolite crystal is more dispersed.The preparation method provided, is to maintain MWW structure molecular screen On the premise of high-crystallinity, it is achieved its pattern changes, pattern is changed into lamellar pine by former " flower shape " gathering Dissipate and pile up；Specific surface area and the pore volume of the sieve sample after simultaneously processing all improve, and this technique effect is complete Entirely it is different from prior art and realizes the processing mode of the reaming of molecular sieve to sacrifice degree of crystallinity.

Accompanying drawing explanation

Fig. 1 is the SEM figure of D-1, A-1-1 and A-1-2 sample of comparative example 1 and embodiment 1 gained.

Fig. 2 is the SEM figure of D-2, A-2-1 and A-2-2 sample of comparative example 2 and embodiment 2 gained.

Fig. 3 is the SEM figure of D-3, A-3-1 and A-3-2 sample of comparative example 3 and embodiment 3 gained.

Fig. 4 is the SEM figure of D-3, A-4-1 and A-4-2 sample of comparative example 3 and embodiment 4 gained.

Fig. 5 is the SEM figure of D-3, A-5-1 and A-5-2 sample of comparative example 3 and embodiment 5 gained.

Fig. 6 is the SEM figure of D-3, A-6-1 and A-6-2 sample of comparative example 3 and embodiment 6 gained.

Fig. 7 is the SEM figure of D-3, A-7-1 and A-7-2 sample of comparative example 3 and embodiment 7 gained.

Fig. 8 is the SEM figure of D-3, A-8-1 and A-8-2 sample of comparative example 3 and embodiment 8 gained.

Fig. 9 is the SEM figure of D-3, A-9-1 and A-9-2 sample of comparative example 3 and embodiment 9 gained.

Figure 10 is the SEM of D-3, A-10-1 and A-10-2 sample of comparative example 3 and embodiment 10 gained Figure.

Figure 11 is the SEM of D-4, A-11-1 and A-11-2 sample of comparative example 4 and embodiment 11 gained Figure.

Figure 12 is the SEM of D-4, A-12-1 and A-12-2 sample of comparative example 4 and embodiment 12 gained Figure.

Figure 13 is comparative example 3, comparative example 5 and D-3, D-5 and D-6 sample of comparative example 6 gained SEM schemes.

Detailed description of the invention

A kind of MWW structure molecular screen, it is characterised in that the BJH of the nitrogen adsorption-desorption of this molecular sieve is bent Line shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.01～0.10cm³/ g, and its 20 DEG C absorption, The adsorbance of the 2,4,6-trimethylpyridine after 200 DEG C of desorptions is >=35 μm ol/g.

The MWW structure molecular screen of the present invention, has specific nitrogen adsorption-desorption parameter attribute, its nitrogen The BJH curve of gas adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.01～0.10 cm³/ g, and the BJH curve of the nitrogen adsorption-desorption of the MWW molecular sieve of prior art conventional hydrothermal synthesis Display nitrogen desorption rate >=0.20cm at 3.8nm³/g.Nitrogen desorption rate amount is the fewest, then molecule is described The more dispersion of sieve crystal grain.BJH curve shows that the method for testing of the nitrogen desorption rate at 3.8nm is in static state Carrying out on n2 absorption apparatus, measurement is purified sample and is pressing p/p the most on year-on-year basis₀Under the conditions of adsorbance to nitrogen.

The MWW structure molecular screen of the present invention, shows except having the BJH curve of nitrogen adsorption-desorption Nitrogen desorption rate at 3.8 ± 0.5nm is 0.01～0.10cm³Outside this specific technical characteristic of/g, also have There is specific 2，4，6-trimethylpyridine adsorbance, its adsorbance >=35 μm ol/g.2,4,6-trimethylpyridine is inhaled Attached amount is the most, then show that the accessibility in molecular sieve active center is the best.The MWW knot of conventional hydrothermal synthesis Structure molecular sieve, its adsorbance is respectively less than 35 μm ol/g.The adsorbance characterisitic parameter of 2,4,6-trimethylpyridine is Sieve sample is pressed into 10 to 20mg from blade, be placed in situ in pond, adsorb 2,4,6-in 20 DEG C Trimethylpyridine, and in the 2，4，6-trimethylpyridine of 200 DEG C of removing physical absorptions, by Fourier transform infrared Spectrum records.

The MWW structure molecular screen of the present invention, the BJH curve of nitrogen adsorption-desorption shows 3.8 ± 0.5 Nitrogen desorption rate at nm is preferably 0.01～0.08cm³After/g, and its 20 DEG C absorption, 200 DEG C of desorptions The adsorbance of 2,4,6-trimethylpyridine is 40～60 μm ol/g.It is furthermore preferred that the BJH of nitrogen adsorption-desorption Curve shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.01～0.05cm³/ g, and its 20 DEG C absorption, The adsorbance of the 2,4,6-trimethylpyridine after 200 DEG C of desorptions is 40～50 μm ol/g.

By SEM electromicroscopic photograph it can be seen that the molecular sieve of the present invention synthesizes with prior art conventional hydrothermal The accumulation pattern of molecular sieve be very different.Molecular Sieve Morphology in the present invention presents the loose heap of lamellar Long-pending, and the accumulation pattern of the MWW molecular sieve of prior art conventional hydrothermal synthesis, for " the flower of more rule Piece " shape and " lotus throne " shape be main, accumulation degree is the most regular.

The present invention still further provides the preparation method of the MWW structure molecular screen of the invention described above, its It is characterised by mixing raw material MWW structure molecular screen, nitrogenous organic base R1, organic amine R2, deionized water It is H that conjunction uniformly obtains mol ratio₂O/SiO₂=5～100, R1/SiO₂=0.01～5, R2/SiO₂=0～1 Mixture, and by this mixture crystallization 5～72h reclaiming at 100～180 DEG C, wherein, described Nitrogenous organic base R1, selected from Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, Dimethyl diethyl ammonium hydroxide, monomethyl triethylammonium hydroxide, monomethyl tripropyl ammonium hydroxide, two Methyl dipropyl ammonium hydroxide, an ethyl-trimethyl ammonium hydroxide, diethyl dipropyl ammonium hydroxide, a second In base tripropyl ammonium hydroxide, an oxypropyl trimethyl ammonium hydroxide and a propyl group triethylammonium hydroxide at least One, described organic amine R2, selected from pentamethylene imines, hexamethylene imine, heptamethylene imines, In 1,4-phenodiazine cycloheptane, cycloheptyl alkanamine, hexamethylene alkanamine, Aminocyclopentane, aniline, piperidines and piperazine at least A kind of.

Described mixture, preferred mol ratio is H₂O/SiO₂=5～50, R1/SiO₂=0.05～0.5, R2/SiO₂=0～0.5, preferred mol ratio is H₂O/SiO₂=10～25, R1/SiO₂=0.05～0.2, R2/SiO₂=0.1～0.3；Described crystallization is preferably to carry out 8～36h at for 140～160 DEG C, more excellent Choosing is at 150 DEG C of crystallization times 8～24h.

Described nitrogenous organic base R1, selected from Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl Ammonium hydroxide, dimethyl diethyl ammonium hydroxide, monomethyl triethylammonium hydroxide, monomethyl tripropyl hydrogen Amine-oxides, dimethyl dipropyl ammonium hydroxide, an ethyl-trimethyl ammonium hydroxide, diethyl dipropyl hydrogen-oxygen Change ammonium, an ethyl tripropyl ammonium hydroxide, an oxypropyl trimethyl ammonium hydroxide and a propyl group triethyl group hydroxide At least one in the quaternary ammonium bases such as ammonium, preferred nitrogenous organic base R1 is tetraethyl ammonium hydroxide, dimethyl At least one of diethyl ammonium hydroxide.Described organic amine R2, selected from pentamethylene imines, six methylenes Base imines, heptamethylene imines, 1,4-phenodiazine cycloheptane, cycloheptyl alkanamine, hexamethylene alkanamine, Aminocyclopentane, benzene At least one in amine, piperidines, piperazine, preferred organic amine R2 is hexamethylene imine, aniline, piperazine At least one in pyridine, piperazine.In a more preferred case, described nitrogenous organic base R1 is tetraethyl Ammonium hydroxide and/or dimethyl diethyl ammonium hydroxide, organic amine R2 is hexamethylene imine and/or piperazine simultaneously Pyridine.

In preparation method of the present invention, described raw material MWW structure molecular screen is selected from the most fired removing mould Plate agent and/or through the MWW structure molecular screen of roasting removed template method, wherein it is preferred that the most fired Removed template method.Described raw material MWW structure molecular screen can be MCM-22 (US4954325, Mobil/CN103771435A,RIPP)、MCM-49(US5236575,Mobil)、MCM-56(US 5362697, Mobil), SSZ-25 (US5202014, Chevron) and UZM-8 (US 6756030B1, UOP) MWW structure Si-Al molecular sieve etc. various direct hydrothermal synthesis, it is also possible to be ITQ-2 and MCM-36 The MWW structure molecular screen obtained Deng MCM-22P is processed.Although to ITQ-2 and MCM-36 molecular sieve can also carry out the processing procedure of offer of the present invention, but examines from the simple angle of technique Considering, described raw material MWW structure molecular screen is directly to process the MWW structure molecular screen of Hydrothermal Synthesis More preferable effect can be obtained and technique is simple.

The preparation method that the present invention provides, R1/SiO in described mixture₂=0.05～0.5, R2/SiO₂= 0～0.5, i.e. R2/SiO₂Ends of range point value be zero in the case of, expression can individually use nitrogenous organic Alkali R1.Individually the mode of nitrogenous organic base R1 is used to be particularly suited for raw material MWW crystallization of molecular sieves complete Whole situation, the most typically requires that the relative crystallinity of raw material MWW structure molecular screen is >=100%.Should Mode can realize the ratio table of MWW structure molecular screen Product samples on the premise of degree of crystallinity is declined slightly Area, pore volume and 2,4,6-trimethylpyridine adsorbance all dramatically increase.

In the preparation method that the present invention provides, use nitrogenous organic base R1 and organic amine R2 to process simultaneously Mode is particularly suited for crystallizing imperfect or degree of crystallinity lossy MWW structure molecular screen, the most relatively The degree of crystallinity MWW structure molecular screen less than 90%.Which can promote secondary crystallization, significantly improves Degree of crystallinity is more than at least 5%.The described relative crystallinity MWW structure molecular screen less than 90%, can To include because crystallization time is inadequate or the template consumption too low crystallization caused incomplete MWW molecular sieve, Can also be to crystallize MWW structure molecular screen MWW structure after have lost degree of crystallinity completely to divide Son sieve.Use under the mode that nitrogenous organic base R1 and organic amine R2 processes simultaneously, MWW structural molecule Sieve Product samples realizes specific surface area, pore volume and 2,4,6-trimethyl on the premise of degree of crystallinity significantly improves Pyridine adsorption amount all dramatically increases.It addition, ion exchange degree can become apparent from, Na⁺It is down to 0.05 weight % Hereinafter, Product samples can roasting direct can be that H-type molecular sieve uses as acidity without ammonium exchange process Catalyst activity component is for reactions such as alkylation, aromatisation, cracking, isomerization.

Described recovery product, its process is known to those skilled in the art, including solid-liquid separation, washing, It is dried and roasting, the most numerous at this states.The present invention can implement but be not limited to this concrete recovery product Process be after hydrothermal crystallizing completes, temperature of reaction system is down to room temperature, crystallization product through solid with female Liquid separate, wherein solid through deionized water wash to pH value close to 7, then at 100 DEG C dry after, with 2 DEG C The heating rate of/min is warming up to 550 DEG C of roasting 10h removed template methods, obtains the knot of the MWW after roasting Structure molecular sieve.

Below by embodiment, the present invention is further described, but not thereby limiting the invention Content.

In embodiment and comparative example, X-ray diffraction (XRD) the crystalline phase figure of sample is at Siemens D5005 It is measured on type x-ray diffractometer.It is to spread out between 22.5 °～25.0 ° with sample and authentic specimen at 2 θ Penetrate the ratio of diffracted intensity (peak height) sum of characteristic peak to represent the sample degree of crystallinity relative to authentic specimen, I.e. relative crystallinity (on the basis of comparative example 1 sample sample, its degree of crystallinity is calculated as 100%).

In embodiment and comparative example, BJH curve shows that the test of the nitrogen desorption rate at 3.8nm uses The AS-3 static nitrogen adsorption instrument that Quantachrome instrument company produces is in test condition: sample is placed in sample Product processing system, is evacuated to 1.33 × 10 at 300 DEG C^-2Pa, heat-insulation pressure keeping 4h, purify sample；Survey Examination process: at liquid nitrogen temperature-196 DEG C, measures purification sample and is pressing p/p the most on year-on-year basis₀Under the conditions of to nitrogen Adsorbance.

In embodiment and comparative example, the adsorbance characterisitic parameter of 2，4，6-trimethylpyridine is by sieve sample Be pressed into 10 to 20mg from blade, be placed in situ in pond, adsorb 2，4，6-trimethylpyridine in 20 DEG C, And in the 2，4，6-trimethylpyridine of 200 DEG C of removing physical absorptions, Fourier transform infrared spectroscopy record.

Comparative example 1

This comparative example illustrates the MCM-22 molecular sieve prepared according to the method for US 4954325.

By sodium metaaluminate (traditional Chinese medicines group, analytical pure) and sodium hydroxide (Beijing Reagent Company, analytical pure) Being dissolved in deionized water, stirring is to being completely dissolved, by solid silicone (Haiyang Chemical Plant, Qingdao, butt 97%) Add above-mentioned solution, add hexamethylene imine (HMI), after stirring, gained mixture colloid Mol ratio is: 0.18NaOH:SiO₂: 0.033Al₂O₃: 0.30HMI:15H₂O.Then by gained Mixture is transferred in airtight crystallizing kettle, and crystallization temperature is 145 DEG C, dynamic crystallization 72h, takes out after cooling Product, through filtering, washing, is dried and after roasting, obtains sample.

The XRD diffraction pattern of test sample, 25 to 35 ° of θ angles, product is MCM-22 molecular sieve, labelling For D-1, it is set to 100% with the degree of crystallinity of this D-1 sample, the relative crystallinity of embodiment sample hereafter Data are as benchmark.

By sem test, pattern is that " flower shape " is assembled, and zeolite crystal size is about 3.0～4.0 μm。

The BET of test sample analyzes its specific surface area and pore volume, specific surface area and pore volume and is respectively 451 m²/ g and 0.55cm³/g。

Its Na of XRF analysis₂O content is 0.65wt.%.

The BJH curve of nitrogen adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.22 cm³The adsorbance of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions is 22 μm ol/g.

Embodiment 1

This example demonstrates that molecular sieve and preparation method that the present invention provides.

In above-mentioned comparative example 1, MCM-22 sample the most fired, containing hexamethylene imine is MCM-22P molecular sieve, through roasting, the MCM-22 sample that removed hexamethylene imine be MCM-22C molecular sieve.

Tetraethyl ammonium hydroxide solution (TEAOH, 25wt.%) is added in deionized water, then will MCM-22P or MCM-22C molecular sieve adds in above-mentioned solution, continues to stir, gained mixture Colloid mol ratio is SiO₂: 0.1TEAOH:15H₂O.Gained mixture colloid is transferred to airtight crystalline substance Change in still, dynamic crystallization 16h at crystallization temperature is 150 DEG C, takes out product, through filtering, washing after cooling Wash, be dried and after roasting, molecular screen primary powder after being processed, sample after the process that MCM-22P is corresponding Numbered A-1-1；The numbered A-1-2 of sample after the process that MCM-22C is corresponding.

Test sample obtains XRD diffraction pattern, and A-1-1 is MCM-22 molecular sieve, and A-1-2 is MCM-49 Molecular sieve, relative crystallinity is respectively 105% and 96%.

SEM shows that A-1-1 sample and A-1-2 pattern are changed into by " flower shape " gathering of sample D-1 Lamellar loosely-packed.

BET molecular sieve shows: specific surface area and the pore volume of A-1-1 molecular sieve are respectively 481m²/ g and 0.65cm³/g；And the specific surface area of A-1-2 molecular sieve and pore volume are respectively 476m²/ g and 0.63cm³/g。

The Na of XRF analysis A-1-1 and A-1-2₂O content is respectively 0.25wt.% and 0.23wt.%.

The BJH curve of nitrogen adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.10 cm³/ g and 0.10cm³The absorption of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions Amount is 38.2 μm ol/g and 36.7 μm ol/g.

Comparative example 2

The process of MCM-49 molecular sieve is prepared in the explanation of this comparative example according to the method for US 5326575.

By sodium metaaluminate (traditional Chinese medicines group, analytical pure) and sodium hydroxide (Beijing Reagent Company, analytical pure) Being dissolved in deionized water, stirring is to being completely dissolved, by solid silicone (Haiyang Chemical Plant, Qingdao, butt 97%) Add above-mentioned solution, add hexamethylene imine, after stirring, gained mixture colloid mol ratio For: 0.18NaOH:SiO₂: 0.040Al₂O₃: 0.30HMI:15H₂O.Then gained mixture is turned Moving in airtight crystallizing kettle, crystallization temperature is 145 DEG C, dynamic crystallization 72h, takes out product, warp after cooling Filter, wash, be dried and after roasting, obtain sample.

The XRD diffraction pattern that test sample obtains, 25 to 35 ° of θ angles, product is MCM-49 molecular sieve, It is labeled as D-2.

Relative crystallinity is 100%；Grain size is about 3.0～4.0 μm；BET analyzes specific surface area and hole Volume is respectively 462m²/ g and 0.56cm³/g。

Its Na of XRF analysis₂O content is 0.58wt.%.

The BJH curve of nitrogen adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.20 cm³The adsorbance of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions is 26 μm ol/g.

Embodiment 2

Tetraethyl ammonium hydroxide solution (25wt.%) is added in deionized water, then by comparative example 2 MCM-49 the most fired, containing hexamethylene imine adds in above-mentioned solution, continues to stir. Gained mixture colloid mol ratio is SiO₂: 0.1TEAOH:15H₂O.Then, by gained mixture Being transferred in airtight crystallizing kettle, crystallization temperature is 150 DEG C, dynamic crystallization 16h, takes out product after cooling, Through filtering, washing, being dried and after roasting, obtain modified molecular screen primary powder, sample number into spectrum is A-2-1.

Ibid, difference is to replace MCM-49 the most fired for comparative example 2, containing hexamethylene imine It is changed to comparative example 2 through roasting, the MCM-49 that removed hexamethylene imine.Obtain modified molecule Sieving former powder, sample number into spectrum is A-2-2.

Test obtains XRD diffraction pattern, A-2-1 and A-2-2 is MCM-49 molecular sieve, relatively crystallizes Degree is respectively 103% and 96%.

The pattern of SEM test display sample A-2-1 and A-2-2 is assembled transformation by " the flower shape " of D-2 For lamellar loosely-packed.

BET molecular sieve shows: specific surface area and the pore volume of A-2-1 molecular sieve are respectively 475m²/ g and 0.67cm³/g；And the specific surface area of A-2-2 molecular sieve and pore volume are respectively 471m²/ g and 0.62cm³/g。

Its Na of XRF analysis₂O content is respectively 0.21wt.% and 0.18wt.%.

The BJH curve of nitrogen adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.09 cm³/ g and 0.10cm³The absorption of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions Amount is 40.3 μm ol/g and 38.7 μm ol/g.

Comparative example 3

This comparative example illustrates that the method according to embodiment in CN103771435A 1 is with hexamethylene imine and benzene Amine is the process of template synthesis MCM-22 molecular sieve.

By sodium metaaluminate (traditional Chinese medicines group, analytical pure) and sodium hydroxide (Beijing Reagent Company, analytical pure) Being dissolved in deionized water, stirring is to being completely dissolved, by mound, sea silica gel (Haiyang Chemical Plant, Qingdao, SiO₂Content It is 97%) add above-mentioned solution, add hexamethylene imine (TCI company of Japan, analytical pure), benzene Amine (Beijing Chemical Plant, analytical pure).Mixture colloid mol ratio is 0.18NaOH:SiO₂: 0.033Al₂O₃: 0.10HMI:0.20AN:15H₂O, crystallization temperature 145 DEG C, under self-generated pressure, with 300 turns per minute Mixing speed crystallization 72 hours, takes out product, through filtering, washing and be dried and after roasting, obtains after cooling Sample.

Test obtains the XRD diffraction pattern of sample, and 2 θ angles are 5 to 35 °, and sample is MCM-22 molecular sieve, compiles Number for D-3, relative crystallinity is 101%；

SEM tests, and the grain size of D-3 sample is about 3.0～4.0 μm；

BET analyzes its specific surface area and pore volume is respectively 450m²/ g and 0.55cm³/g；

XRF analysis Na₂O content is 0.55wt.%.

The BJH curve of nitrogen adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.20 cm³The adsorbance of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions is 28.7 μmol/g。

Embodiment 3

Tetramethyl ammonium hydroxide solution (25wt.%) is added in deionized water, then by comparative example 3 MCM-22 the most fired, containing hexamethylene imine and aniline adds in above-mentioned solution, continues stirring Uniformly.Gained mixture colloid mol ratio is SiO₂: 0.1TMAOH:15H₂O.Then, by gained Mixture is transferred in airtight crystallizing kettle, and crystallization temperature is 150 DEG C, dynamic crystallization 16h, takes out after cooling Product, through filtering, washing, is dried and after roasting, obtains modified molecular screen primary powder, and sample number into spectrum is A-3-1。

Ibid, what difference was comparative example 3 is the most fired, containing hexamethylene imine and aniline MCM-49 replaces with comparative example 3 MCM-22 the most fired, without hexamethylene imine and aniline and (roasts MCM-22C molecular sieve after burning, it is identical with MCM-49 molecular sieve XRD diffraction maximum).Changed Molecular screen primary powder after property, sample number into spectrum is A-3-2.

Test obtains XRD diffraction pattern, and A-3-1 is MCM-22 molecular sieve, and A-3-2 is that MCM-49 divides Son sieve, relative crystallinity is respectively 94% and 92%.

Pattern is changed into lamellar loosely-packed by " flower shape " gathering.

BET analyzes display, A-3-1 sample specific surface area and pore volume be respectively 502m²/ g and 0.60 cm³/g；And the specific surface area of A-3-2 sample and pore volume are respectively 491m²/ g and 0.62cm³/g。

Its Na of XRF analysis₂O content is respectively 0.10wt.% and 0.11wt.%.

The BJH curve of nitrogen adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.08 cm³/ g and 0.07cm³The absorption of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions Amount is 42.1 μm ol/g and 40.3 μm ol/g.

Embodiment 4

Tetramethyl ammonium hydroxide solution (25wt.%) and piperidines (PI) are added in deionized water, then will In comparative example 3, MCM-22 the most fired, containing hexamethylene imine and aniline adds in above-mentioned solution, Continue to stir.Gained mixture colloid mol ratio is: SiO₂: 0.1TMAOH:0.3PI:15H₂O。 Then, being transferred in airtight crystallizing kettle by gained mixture, crystallization temperature is 150 DEG C, dynamic crystallization 16h, Take out product after cooling, through filtering, washing, be dried and after roasting, obtain modified molecular screen primary powder, sample The numbered A-4-1 of product.

Ibid, difference is MCM-22 the most fired for comparative example 3, containing hexamethylene imine and aniline Replace with that comparative example 3 is the most fired, MCM-22 without hexamethylene imine and aniline.Obtain modified Molecular screen primary powder, sample number into spectrum is A-4-2.

Test obtains XRD diffraction pattern, A-4-1 and A-4-2 is MCM-22 molecular sieve, relative crystallinity It is respectively 113% and 108%；

SEM tests, and sample topography is changed into lamellar loosely-packed by " flower shape " gathering of D-3；

BET analyzes display: specific surface area and the pore volume of A-8-1 molecular sieve are respectively 483m²/ g and 0.64 cm³/g；And the specific surface area of A-8-2 molecular sieve and pore volume are respectively 492m²/ g and 0.63cm³/g；

Its Na of XRF analysis₂O content is respectively 0.01wt.% and 0.02wt.%.

The BJH curve of nitrogen adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.08 cm³/ g and 0.07cm³The absorption of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions Amount is 42.1 μm ol/g and 40.2 μm ol/g.

Embodiment 5

Tetraethyl ammonium hydroxide solution (25wt.%) is added in deionized water, then by comparative example 3 MCM-22 the most fired, containing hexamethylene imine and aniline adds in above-mentioned solution, continues stirring Uniformly.Gained mixture colloid mol ratio is SiO₂: 0.1TEAOH:15H₂O.Then, by gained Mixture is transferred in airtight crystallizing kettle, and crystallization temperature is 150 DEG C, dynamic crystallization 16h, takes out after cooling Product, through filtering, washing, is dried and after roasting, obtains modified molecular screen primary powder, and sample number into spectrum is A-5-1。

Ibid, what difference was comparative example 3 is the most fired, containing hexamethylene imine and aniline MCM-22 replaces with that comparative example 3 is the most fired, MCM-22 without hexamethylene imine and aniline.? To modified molecular screen primary powder, sample number into spectrum is A-5-2.

Test obtains XRD diffraction pattern, and A-5-1 is MCM-22 molecular sieve, and A-5-2 is that MCM-49 divides Son sieve, relative crystallinity is respectively 100% and 96%.

Pattern is changed into lamellar loosely-packed by " flower shape " gathering.

BET analyzes display, A-5-1 sample specific surface area and pore volume be respectively 500m²/ g and 0.67 cm³/g；And the specific surface area of A-5-2 sample and pore volume are respectively 495m²/ g and 0.65cm³/g。

Its Na of XRF analysis₂O content is respectively 0.20wt.% and 0.15wt.%.

The BJH curve of nitrogen adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.05 cm³/ g and 0.05cm³The absorption of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions Amount is 46.1 μm ol/g and 43.4 μm ol/g.

Embodiment 6

Tetraethyl ammonium hydroxide solution (25wt.%) and piperidines (PI) are added in deionized water, then will In comparative example 3, MCM-22 the most fired, containing hexamethylene imine and aniline adds in above-mentioned solution, Continue to stir.Gained mixture colloid mol ratio is: SiO₂: 0.1TEAOH:0.3PI:15H₂O。 Then, being transferred in airtight crystallizing kettle by gained mixture, crystallization temperature is 150 DEG C, dynamic crystallization 16h, Take out product after cooling, through filtering, washing, be dried and after roasting, obtain modified molecular screen primary powder, sample The numbered A-6-1 of product.

Ibid, difference is MCM-22 the most fired for comparative example 3, containing hexamethylene imine and aniline Replace with that comparative example 3 is the most fired, MCM-22 without hexamethylene imine and aniline.Obtain modified Molecular screen primary powder, sample number into spectrum is A-6-2.

Test obtains XRD diffraction pattern, A-6-1 and A-6-2 is MCM-22 molecular sieve, relative crystallinity It is respectively 112% and 110%；

BET analyzes display: specific surface area and the pore volume of A-6-1 molecular sieve are respectively 485m²/ g and 0.72 cm³/g；And the specific surface area of A-6-2 molecular sieve and pore volume are respectively 494m²/ g and 0.63cm³/g；

Its Na of XRF analysis₂O content is respectively 0.03wt.% and 0.02wt.%.

The BJH curve of nitrogen adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.08 cm³/ g and 0.07cm³The absorption of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions Amount is 43.1 μm ol/g and 41.5 μm ol/g.

Embodiment 7

TPAOH solution (25wt.%) is added in deionized water, then by comparative example 3 MCM-22 the most fired, containing hexamethylene imine and aniline adds in above-mentioned solution, continues stirring Uniformly.Gained mixture colloid mol ratio is SiO₂: 0.1TPAOH:15H₂O.Then, by gained Mixture is transferred in airtight crystallizing kettle, and crystallization temperature is 150 DEG C, dynamic crystallization 16h, takes out after cooling Product, through filtering, washing, is dried and after roasting, obtains modified molecular screen primary powder, and sample number into spectrum is A-7-1。

Ibid, what difference was comparative example 3 is the most fired, containing hexamethylene imine and aniline MCM-22 replaces with that comparative example 3 is the most fired, MCM-22 without hexamethylene imine and aniline.? To modified molecular screen primary powder, sample number into spectrum is A-7-2.

Test obtains XRD diffraction pattern, and A-7-1 is MCM-22 molecular sieve, and A-7-2 is that MCM-49 divides Son sieve, relative crystallinity is respectively 95% and 93%.

Pattern is changed into lamellar loosely-packed by " flower shape " gathering.

BET analyzes display, A-7-1 sample specific surface area and pore volume be respectively 488m²/ g and 0.68 cm³/g；And the specific surface area of A-7-2 sample and pore volume are respectively 502m²/ g and 0.62cm³/g。

Its Na of XRF analysis₂O content is respectively 0.38wt.% and 0.39wt.%.

The BJH curve of nitrogen adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.10 cm³/ g and 0.09cm³The absorption of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions Amount is 40.3 μm ol/g and 39.5 μm ol/g.

Embodiment 8

TPAOH solution (25wt.%) and piperidines (PI) are added in deionized water, then will In comparative example 3, MCM-22 the most fired, containing hexamethylene imine and aniline adds in above-mentioned solution, Continue to stir.Gained mixture colloid mol ratio is: SiO₂: 0.1TPAOH:0.3PI:15H₂O。 Then, being transferred in airtight crystallizing kettle by gained mixture, crystallization temperature is 150 DEG C, dynamic crystallization 16h, Take out product after cooling, through filtering, washing, be dried and after roasting, obtain modified molecular screen primary powder, sample The numbered A-8-1 of product.

Ibid, difference is MCM-22 the most fired for comparative example 3, containing hexamethylene imine and aniline Replace with that comparative example 3 is the most fired, MCM-22 without hexamethylene imine and aniline.Obtain modified Molecular screen primary powder, sample number into spectrum is A-8-2.

Test obtains XRD diffraction pattern, A-8-1 and A-8-2 is MCM-22 molecular sieve, relative crystallinity It is respectively 110% and 103%；

BET analyzes display: specific surface area and the pore volume of A-8-1 molecular sieve are respectively 488m²/ g and 0.65 cm³/g；And the specific surface area of A-8-2 molecular sieve and pore volume are respectively 497m²/ g and 0.65cm³/g；

Its Na of XRF analysis₂O content is respectively 0.07wt.% and 0.06wt.%.

The BJH curve of nitrogen adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.08 cm³/ g and 0.07cm³The absorption of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions Amount is 40.4 μm ol/g and 38.6 μm ol/g.

Embodiment 9

Dimethyl diethyl Ammonia (DEDMAOH, 25wt.%) is added in deionized water, Then MCM-22 molecular sieve the most fired in comparative example 3, containing hexamethylene imine and aniline is added Enter in above-mentioned solution, continue to stir.Gained mixture colloid mol ratio is SiO₂: 0.1 DEDMAOH:15H₂O.Being transferred in airtight crystallizing kettle by gained mixture, crystallization temperature is 150 DEG C, Dynamic crystallization 16h, takes out product after cooling, through filtering, washing, be dried and after roasting, obtain modified Molecular screen primary powder, production code member A-9-1.

Ibid, difference is MCM-22 the most fired for comparative example 3, containing hexamethylene imine and aniline Molecular sieve replaces with that comparative example 3 is the most fired, MCM-22 molecule without hexamethylene imine and aniline Sieve.Obtain modified molecular screen primary powder, production code member A-9-2.

Test obtains XRD diffraction pattern, and A-9-1 is MCM-22 molecular sieve, and A-9-2 is that MCM-49 divides Son sieve, relative crystallinity is respectively 98% and 98%；

The pattern of SEM test display A-9-1 and A-9-2 is changed into sheet by " flower shape " gathering of D-3 Shape loosely-packed；

BET analyzes display: specific surface area and the pore volume of A-9-1 molecular sieve are respectively 499m²/ g and 0.59 cm³/g；And the specific surface area of A-9-2 molecular sieve and pore volume are respectively 499m²/ g and 0.60cm³/g；

Its Na of XRF analysis₂O content is respectively 0.40wt.% and 0.44wt.%.

The BJH curve of nitrogen adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.06 cm³/ g and 0.06cm³The absorption of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions Amount is 44.3 μm ol/g and 42.1 μm ol/g.

Embodiment 10

This example demonstrates that molecular sieve and preparation method that the present invention provides..

Dimethyl diethyl Ammonia (25wt.%) and piperidines (PI) are added in deionized water, Then MCM-22 molecular sieve the most fired in comparative example 3, containing hexamethylene imine and aniline is added Enter in above-mentioned solution, continue to stir.Gained mixture colloid mol ratio is SiO₂: 0.1 DEDMAOH:0.3PI:15H₂O.Then, gained mixture is transferred in airtight crystallizing kettle, crystallization Temperature is 150 DEG C, dynamic crystallization 16h, takes out product after cooling, through filtering, washing, is dried and roasting After, obtain modified molecular screen primary powder, production code member A-10-1.

Ibid, difference is MCM-22 the most fired for comparative example 3, containing hexamethylene imine and aniline Molecular sieve replaces with MCM-22 the most fired in comparative example 3, without hexamethylene imine and aniline and divides Son sieve.Obtain modified molecular screen primary powder, production code member A-10-2.

Test obtains XRD diffraction pattern, A-10-1 and A-10-2 is MCM-22 molecular sieve, relative crystallinity It is respectively 110% and 110%；

SEM tests display, and " flower shape " gathering of the equal D-3 of A-10-1 and A-10-2 pattern is changed into sheet Shape loosely-packed；

BET analyzes display: specific surface area and the pore volume of A-10-1 molecular sieve are respectively 499m²/ g and 0.65 cm³/g；And the specific surface area of A-10-2 molecular sieve and pore volume are respectively 506m²/ g and 0.60cm³/g。

Its Na of XRF analysis₂O content is respectively 0.05wt.% and 0.11wt.%.

The BJH curve of nitrogen adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.06 cm³/ g and 0.06cm³The absorption of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions Amount is 40.4 μm ol/g and 38.6 μm ol/g.

Comparative example 4

This comparative example is with hexamethylene imine and aniline as template according to the method in CN103771435A Agent synthesis MCM-22 molecular sieve.

A certain amount of sodium metaaluminate (traditional Chinese medicines group, analytical pure) and sodium hydroxide (Beijing Reagent Company, Analytical pure) be dissolved in deionized water, stirring to being completely dissolved, by mound, sea silica gel (Haiyang Chemical Plant, Qingdao, SiO₂Content is 97%) add above-mentioned solution, (TCI company of Japan analyzes to add hexamethylene imine Pure), aniline (Beijing Chemical Plant, analytical pure).Mixture colloid mol ratio is: 0.18NaOH: SiO₂: 0.033Al₂O₃: 0.05HMI:0.25AN:15H₂O, crystallization temperature 145 DEG C, under self-generated pressure, With 300 turns per minute mixing speed crystallization 72 hours, take out product after cooling, through filtering, washing and be dried After roasting, obtain sample.

Test obtains XRD diffraction pattern, 25 to 35 ° of θ angles.Product is MCM-22 molecular sieve, is labeled as D-4, Relative crystallinity is 83%；

SEM test display grain size is about 2.0～4.0 μm；

BET analyzes its specific surface area and pore volume is respectively 375m²/ g and 0.44cm³/g；

XRF analysis Na₂O content is 1.36wt.%.

The BJH curve of nitrogen adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.18 cm³The adsorbance of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions is 18 μm ol/g.

Embodiment 11

Tetraethyl ammonium hydroxide solution (25wt.%) and piperidines (PI) are added in deionized water, then will In comparative example 4, MCM-22 molecular sieve the most fired, containing hexamethylene imine and aniline adds above-mentioned In solution, continue to stir.Gained mixture colloid mol ratio is SiO₂: 0.1TEAOH:0.3PI: 15H₂O.Then, being transferred in airtight crystallizing kettle by gained mixture, crystallization temperature is 150 DEG C, dynamically Crystallization 16h, takes out product after cooling, through filtering, washing, be dried and after roasting, obtain modified molecule Sieving former powder, production code member is A-7-1.

Ibid, difference is the most fired in comparative example 4, containing hexamethylene imine and aniline MCM-22 molecular sieve replaces with the most fired in comparative example 4, without hexamethylene imine and aniline MCM-22 molecular sieve.Obtaining modified molecular screen primary powder, production code member is A-7-2.

Test obtains XRD diffraction pattern, A-11-1 and A-11-2 is MCM-22 molecular sieve, relative crystallinity It is respectively 110% and 101%；

SEM tests display, A-11-1 and A-11-2 pattern is changed into by " flower shape " gathering of D-4 Lamellar loosely-packed.

BET analyzes display: specific surface area and the pore volume of A-11-1 molecular sieve are respectively 471m²/ g and 0.62 cm³/g；And the specific surface area of A-11-2 molecular sieve and pore volume are respectively 485m²/ g and 0.60cm³/g。

Its Na of XRF analysis₂O content is respectively 0.11wt.% and 0.25wt.%.

The BJH curve of nitrogen adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.05 cm³/ g and 0.05cm³The absorption of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions Amount is 46.2 μm ol/g and 46.1 μm ol/g.

Embodiment 12

Dimethyl diethyl Ammonia (25wt.%) and piperidines (PI) are added in deionized water, Then by the most fired in comparative example 4, the MCM-22 molecular sieve containing hexamethylene imine and aniline adds Enter in above-mentioned solution, continue to stir.Gained mixture colloid mol ratio is: SiO₂: 0.1 DEDMAOH:0.3PI:15H₂O.Then, gained mixture is transferred in airtight crystallizing kettle, crystallization Temperature is 150 DEG C, dynamic crystallization 16h, takes out product after cooling, through filtering, washing, is dried and roasting After, molecular screen primary powder after being processed, production code member A-12-1.

Ibid, difference is the most fired in comparative example 4, containing hexamethylene imine and aniline MCM-22 molecular sieve replace with comparative example 4 the most fired, do not contain hexamethylene imine and aniline MCM-22 molecular sieve.Molecular screen primary powder after process, production code member A-12-2.

Test obtains XRD diffraction pattern, A-12-1 and A-12-2 is MCM-22 molecular sieve, relative crystallinity It is respectively 104% and 100%；

SEM tests display, A-12-1 and A-12-2 pattern is changed into sheet by D-4 " flower shape " gathering Shape loosely-packed；

BET molecular sieve shows: specific surface area and the pore volume of A-12-1 molecular sieve are respectively 450m²/ g and 0.57cm³/g；And the specific surface area of A-12-2 molecular sieve and pore volume are respectively 493m²/ g and 0.54 cm³/g。

Its Na of XRF analysis₂O content is respectively 0.29wt.% and 0.20wt.%.

The BJH curve of nitrogen adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.07 cm³/ g and 0.06cm³The absorption of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions Amount is 42.0 μm ol/g and 40.6 μm ol/g.

Comparative example 5

The explanation of this comparative example is individually with process and the product of inorganic alkali-treated raw materials MWW structure molecular screen.

In this comparative example, raw material MWW structure molecular screen is in above-mentioned comparative example 3, the most fired, contain There is the MCM-22 molecular sieve of hexamethylene imine.

Sodium hydroxide (NaOH, 96wt.%) is added in deionized water, then by MCM-22 molecular sieve Adding in above-mentioned solution, continue to stir, gained mixture colloid mol ratio is SiO₂: 0.1NaOH: 15H₂O.Gained mixture colloid is transferred in airtight crystallizing kettle, at crystallization temperature is 150 DEG C dynamically Crystallization 16h, takes out product after cooling, through filtering, washing, be dried and after roasting, molecule after being processed Sieve former powder, the numbered D-5-1 of sample after corresponding process.

Ibid, what difference was comparative example 3 is the most fired, containing hexamethylene imine and aniline MCM-22 replaces with that comparative example 3 is the most fired, MCM-22 without hexamethylene imine and aniline.? To modified molecular screen primary powder, the numbered D-5-2 of sample after corresponding process.

Test sample obtains XRD diffraction pattern, and D-5-1 is MCM-22 molecular sieve, and D-5-2 is MCM-49 Molecular sieve, relative crystallinity is respectively 88% and 80%.

SEM display D-5-1 and D-5-2 sample topography is changed into by " flower shape " gathering of sample D-1 Lamellar loosely-packed.

BET molecular sieve shows: specific surface area and the pore volume of D-5-1 molecular sieve are respectively 461m²/ g and 0.71cm³/g；And the specific surface area of D-5-2 molecular sieve and pore volume are respectively 446m²/ g and 0.67cm³/g。

The Na of XRF analysis D-5-1 and D-5-2₂O content is respectively 3.29wt.% and 3.48wt.%.

The BJH curve of nitrogen adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.13 cm³The adsorbance of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions is 28 μm ol/g.

Comparative example 6

The explanation of this comparative example processes process and the product of raw material MWW structure molecular screen with inorganic base and organic amine Thing.

Sodium hydroxide (96wt.%) and piperidines (PI) are added in deionized water, then by comparative example 3 In the most fired, MCM-22 containing hexamethylene imine and aniline add in above-mentioned solution, continue to stir Mix uniformly.Gained mixture colloid mol ratio is: SiO₂: 0.1NaOH:0.3PI:15H₂O.So After, gained mixture is transferred in airtight crystallizing kettle, crystallization temperature is 150 DEG C, dynamic crystallization 16h, Take out product after cooling, through filtering, washing, be dried and after roasting, obtain modified molecular screen primary powder, sample The numbered D-6-1 of product.

Ibid, difference is MCM-22 the most fired for comparative example 3, containing hexamethylene imine and aniline Replace with that comparative example 3 is the most fired, MCM-22 without hexamethylene imine and aniline.Obtain modified Molecular screen primary powder, sample number into spectrum is D-6-2.

Test obtains XRD diffraction pattern, D-6-1 and D-6-2 is MCM-22 molecular sieve, relative crystallinity It is respectively 93% and 90%；

BET analyzes display: specific surface area and the pore volume of D-6-1 molecular sieve are respectively 481m²/ g and 0.74 cm³/g；And the specific surface area of D-6-2 molecular sieve and pore volume are respectively 470m²/ g and 0.65cm³/g；

Its Na of XRF analysis₂O content is respectively 3.63wt.% and 3.26wt.%.

The BJH curve of nitrogen adsorption-desorption shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.12 cm³/ g and 0.10cm³The absorption of the 2，4，6-trimethylpyridine after/g, and its 20 DEG C absorption, 200 DEG C of desorptions Amount is 33.1 μm ol/g and 30.1 μm ol/g.

Claims

1. a MWW structure molecular screen, it is characterised in that the nitrogen adsorption-desorption of this molecular sieve BJH curve shows that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.01～0.10cm³/ g, and its 20 DEG C suctions The adsorbance of 2,4,6-trimethylpyridine after attached, 200 DEG C of desorptions is >=35 μm ol/g.

2. nitrogen adsorption-the desorption of this according to the molecular sieve of claim 1, wherein, described molecular sieve BJH curve show the nitrogen desorption rate 0.01～0.08cm at 3.8 ± 0.5nm³/ g, and its 20 DEG C suctions The adsorbance of 2,4,6-trimethylpyridine after attached, 200 DEG C of desorptions is 40～60 μm ol/g.

3. nitrogen adsorption-the desorption of this according to the molecular sieve of claim 1, wherein, described molecular sieve BJH curve show that the nitrogen desorption rate at 3.8 ± 0.5nm is 0.01～0.05cm³/ g, and its 20 DEG C The adsorbance of the 2,4,6-trimethylpyridine after absorption, 200 DEG C of desorptions is 40～50 μm ol/g.

4. according to the molecular sieve of claim 1, it is characterised in that Molecular Sieve Morphology presents the loose heap of lamellar Long-pending.

5. the preparation method of the MWW structure molecular screen of claim 1-4, it is characterised in that by raw material MWW structure molecular screen, nitrogenous organic base R1, organic amine R2, deionized water mix homogeneously obtain mole Ratio is H₂O/SiO₂=5～100, R1/SiO₂=0.01～5, R2/SiO₂The mixture of=0～1, and should Mixture Crystallizing treatment 5～72h reclaiming at 100～180 DEG C, wherein, described nitrogenous organic base R1, selected from Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, dimethyl diethyl Ammonium hydroxide, monomethyl triethylammonium hydroxide, monomethyl tripropyl ammonium hydroxide, dimethyl dipropyl hydrogen Amine-oxides, an ethyl-trimethyl ammonium hydroxide, diethyl dipropyl ammonium hydroxide, an ethyl tripropyl hydrogen-oxygen Change at least one in ammonium, an oxypropyl trimethyl ammonium hydroxide and a propyl group triethylammonium hydroxide, described Organic amine R2, selected from pentamethylene imines, hexamethylene imine, heptamethylene imines, Isosorbide-5-Nitrae-phenodiazine cycloheptyl At least one in alkane, cycloheptyl alkanamine, hexamethylene alkanamine, Aminocyclopentane, aniline, piperidines and piperazine.

6. according to the method for claim 5, wherein, described raw material MWW structure molecular screen is not The MWW structure molecular screen of fired removed template method.

7. according to the method for claim 5 or 6, wherein, described raw material MWW structure molecular screen One or more molecules in MCM-22, MCM-49, MCM-56, SSZ-25 and UZM-8 Sieve.

8. the phase of according to the method for claim 5, wherein, described raw material MWW structure molecular screen To degree of crystallinity less than 90%.

9. the mol ratio of according to the method for claim 5, wherein, described mixture is H₂O/SiO₂= 5～50, R1/SiO₂=0.05～0.5, R2/SiO₂=0～0.5.

10. the mol ratio of according to the method for claim 5, wherein, described mixture is H₂O/SiO₂= 10～25, R1/SiO₂=0.05～0.2, R2/SiO₂=0.1～0.3.

11. according to the method for claim 5, and wherein, described nitrogenous organic base R1 is tetraethyl hydrogen-oxygen Change ammonium and/or dimethyl diethyl ammonium hydroxide.

12. according to the method for claim 5, wherein, described organic amine R2 be hexamethylene imine, At least one in aniline, piperidines and piperazine.

13. according to the method for claim 5, and wherein, described nitrogenous organic base R1 is tetraethyl hydrogen-oxygen Changing ammonium and/or dimethyl diethyl ammonium hydroxide, organic amine R2 is hexamethylene imine and/or piperidines simultaneously.

14. according to the method for claim 5, and wherein, described mixture is when 140～160 DEG C of crystallization Between 8～36h.