CN101094719A - Catalytic materials and method for the preparation thereof - Google Patents

Abstract

The invention is related to catalytic materials and particularly to mesoporous molecular sieves embedded with a zeolite, which are thermally stable at a temperature of at least 900 DEG C, and to a method for the preparation of the catalytic materials. Said catalytic materials are suitable for applications in the field of hydrocarbon processing.

Description

Catalysis material and preparation method thereof

Invention field

Invention relates to mesoporous catalyst, the mesopore molecular sieve of particularly new embedding zeolite, and it has high thermal stability, also relates to the method for preparing catalysis material.Described catalysis material is suitable for the hydrocarbon manufacture field.

Background technology

Mesopore molecular sieve has caused scientist's attention as catalysis material, because its particular performances, as having the very big uniform hole of high surface, its size is at 2-50nm.Yet mesopore molecular sieve well known in the prior art is normally warm and hydro-thermal is unsettled, and hole wall is unbodied and they have faintly acid.And in the regenerative process of spent catalyst, the mesopore molecular sieve structure may be caved in after hydrocarbon processing.

(d＜2nm) the crystalline material industrialization in hole is used as the carrier of catalyst and catalyst to have pore size.Zeolite is the well-known example of this material.Because its special performances, as the possibility of high surface area, high-adsorption-capacity and adjustment adsorption capacity, zeolite is able to extensive use.In zeolite structured, may produce the activated centre, set up the activated centre and adjust the intensity and the quantity of acid sites.The aperture of zeolite is usually at the heat endurance and the chemical stability height of 0.4-1.2nm and zeolite.Yet the zeolite treatment molecule is limited greater than the ability of the molecule of zeolite pore, and zeolite inactivation in several reactions is quite fast.

US 5,198,203 disclose and developed in the early 1990s be called M41S one group of neat mesopore molecular sieve.M41S has C _iH _2i(CH ₃) N ⁺One group of meso-porous molecular sieve material that the silica of-cation (i＞7) and the aqueous solution of alumina precursor form under hydrothermal condition.This group in the most famous member be hexagon MCM-41, cube MCM-48 and the MCM-50 of disc structure.The aperture of mesopore molecular sieve can be adjusted between 2-10nm and form and can comprise pure silica or metal silicon/silicon dioxide (as the silica of Al-, V-and Ti-replacement).The meso-porous molecular sieve material of M41S group is unbodied natively and their hole system is neat.

US 5,246,689 and US 5,334,368 in the synthetic composition of the crystal phase that comprises super big hole is disclosed.Material is that the diameter in inorganic, porous, unstratified, hole is at 1.3-20mm.Pore-size distribution in single-phase scope is regular in a way.At least one peak of d-spacing is greater than 1.8nm in the X-ray diffracting spectrum.

EP 0 748 652 discloses one group of mesoporous material (MSA) with narrow pore-size distribution.Material is unbodied and complete unordered.The BET surface area of material is 672-837m ²/ g.

The mesoporous material of synthetic preparation is nonacid or its acidity is limited.By in the silicon dioxide structure of mesoporous material, mixing aluminium the quantity of the acid sites of mesoporous material is increased.Yet the acid intensity of aforesaid mesoporous material is less than the acid intensity of zeolite.

The whole bag of tricks of preparation mesoporous material is known in the prior art.Heat endurance, hydrothermal stability and the acidity of mesopore molecular sieve have been attempted increasing, as in meso-hole structure, introducing catalytic active species.Substantially, synthetic method comprises with one or more organic reagents and prepares silicon source solution that the PH of regulator solution then reclaims and the calcining precipitation to precipitation occurring.The aluminium source adds in the solution under the temperature that arbitrary steps before the synthetic beginning has improved.Several surfactants and template (organic reagent), component, solvent and reaction condition have been proposed.

US 5,942, a kind of method for preparing mesoporous material of 208 records, and this mesoporous material has improved hydrothermal stability with respect to MCM-41.Various salt in the method, have been used and with the PH of weak acid regulator solution.

EP0 795 517 has proposed a kind of method of synthesize meso-porous material, wherein uses silicon source and the mixture that comprises the organic formwork of fluorine.

US5,942,208 have described the preparation of mesopore molecular sieve, and this mesopore molecular sieve has heat endurance and the hydrothermal stability that is higher than traditional mesopore molecular sieve.Material boiled in water 12 hours and structure not variation basically.

The stable method with mesoporous material activity of selectable preparation is that zeolite is incorporated in the mesoporous wall.US 09/764,686 discloses the synthetic of the mesoporous material that uses Y-zeolite seed crystal, MFI zeolite seed crystal and beta-zeolite crystal seed.

CN1349929 proposes to use L-zeolite precursor formulations prepared from solutions MSA-3 and MAS-8.

Kloetstra et al, Micropor.Mesopor.Mater.6 (1996) 287 have reported that original position forms faujasite and MCM-41.Their method is based on the sequence of zeolite and MCM-41 and synthesizes.

Karlsson et al .Micropor.Mesopor.Mater.27 (1999) 181 disclose method while synthetic zeolite/MCM-41 phase of using hybrid template.

Be at growth on the zeolite and deposition MCM-41 or in gel, add under the situation of zeolite seed crystal that in synthetic method material can be two-phase or heterogeneous mixture, the perhaps zeolite of loose bonding and mesoporous material.

Two kinds of dissimilar templates in synthesize meso-porous material, have been used.This preparation method's reproducibility is difficult to.And, there is not chemical reaction between zeolite and the mesopore molecular sieve, the heat endurance of the material that obtains and hydrothermal stability may be low.

According to the situation of prior art, mesopore molecular sieve is widely used in the catalyst as mutually active or carrier.Several hydrocarbon conversion reactions are acid catalyzed.Based on their acid catalysis effect, known zeolites has activity in processes such as the open loop of the oligomerisation of the dimerization of two keys of alkene and skeletal isomerizationization, paraffin isomerization, cracking, alkene, alkene, cycloalkanes, alkylation, the exchange of aromatic alkyl, aromatic radicalization.Bifunctional catalyst with metal or metal oxide or sulfide phase is applied in the reaction, as isomerization, hydrocrack, catalytic dewaxing, dehydrogenation sulfuration, dehydrogenation oxidation, dehydrogenation nitrogenize and several hydrogenation of reformation, paraffin.The major defect that uses zeolite is that their deactivation are higher and processing is macromolecular limited in one's ability.

Can find based on foregoing need be based on the method for a kind of so thermally-stabilised and hydrothermally stable catalysis material of the catalysis material of the thermally-stabilised and hydrothermally stable of mesopore molecular sieve and preparation.And obviously needing a kind of catalyst, it has the zeolite type active site and reactant is short to the evolving path of accessibility height, reactant and the product of active site, with restriction side reaction and coking.

Goal of the invention

The purpose of invention provides a kind of new active catalyst material, and it has the zeolite structured mesopore molecular sieve of embedding, especially for hydrocarbon conversion reaction.

Another purpose of invention is the mechanically stable of embedding zeolite, the mesopore molecular sieve of thermally-stabilised and hydrothermally stable, has zeolite acidity.

Another purpose of invention is described preparation method with catalysis material of the zeolite structured mesopore molecular sieve of embedding.

Another purpose of invention is the described purposes of catalysis material in hydrocarbon conversion reaction with the zeolite structured mesopore molecular sieve of embedding.

The mesopore molecular sieve of embedding zeolite, the characteristic feature of its preparation method and purposes is set out in claims.

Summary of the invention

Do not wish to be subjected to following synthetic explanation and the theoretical restriction of considering, the principal character of invention is discussed below for the new catalytic material that is specially adapted to hydrocarbon conversion reaction with the zeolite structured mesopore molecular sieve of embedding.

The present invention relates to have the new active catalytic material of the zeolite structured mesopore molecular sieve of embedding.Invention also relates to the preparation method of mesopore molecular sieve of embedding zeolite, wherein synthetic be easily and repeatably and product show high catalytic activity.

Catalysis material with the zeolite structured mesopore molecular sieve of embedding is applicable to hydrocarbon conversion reaction and the processing that is specially adapted to high-molecular-weight hydrocarbons.This new catalytic material can be used as the particularly modified component of catalyst in the catalytic component of isomerization, aromatic alkylation, etherificate, hydrodesulfurization and the reformation etc. of dimerization, oligomerisation, alkene and the paraffin of hydrogenation, the alkene of Ppolynuclear aromatic or the prior art of cracking, hydrocracking, open loop, aromatic series.

Detailed Description Of The Invention

Have been found that raw catelyst of the present invention can avoid or at least obviously reduce problem relevant with zeolite catalyst and mesoporous catalyst in the prior art, raw catelyst is the mesopore molecular sieve of embedding zeolite, and it has high heat endurance and hydrothermal stability.The new mesopore molecular sieve of embedding zeolite is heat-staple at least 900 ℃ in the presence of air.

The invention provides the new mesopore molecular sieve of one group of embedding zeolite, it is mechanically stable, thermally-stabilised and hydrothermally stable.Material is very easy to repeat to obtain as shown in the Examples, and they show higher performance in several hydrocarbon conversion reactions.The new mesopore molecular sieve of this group embedding zeolite is named as mesoporous material (MM).Here mesoporous being meant has the 2-15nm hole and the hole is neat material.

The mesopore molecular sieve that the mesopore molecular sieve of embedding zeolite comprises the M41S group that is selected from the 2nd page of explanation has the mesoporous material that regular hole is with comprising.Preferred mesopore molecular sieve is selected from the mesoporous aluminoshilicate that is called as the MCM-41 group.

The mesopore molecular sieve embedding is selected from the zeolite in medium hole, and this zeolite is 10-person's ring-type zeolite such as MFI, MTT, TON, AEF, MWW and FER structure and large pore zeolite, and it is 12-person's ring-type zeolite such as BEA, FAU and MOR structure.The example of described zeolite group is ZSM-5, ZSM-23, ZSM-22, SAPO-11, MCM-22, ferrierite, β, Y-and X-zeolite and modenite.Preferred zeolite is MFI, MTT, AEF, MWW, MOR or BEA zeolite.

Catalysis material comprises the aluminium (Al) of 0.01-10wt-%.

Comprise the mesopore molecular sieve of the embedding zeolite among the present invention and comprise the catalyst of the combination that is selected from the known aluminium oxide of prior art, silica, clay and other carrier and carrier thereof, be specially adapted to industrial use and commercial use.Preferred vector comprises aluminium oxide or silica.The quantity of carrier is 10-90wt-%, based on the total weight of catalyst.

The raw catelyst material group with the zeolite structured mesopore molecular sieve of embedding among the present invention demonstrates 1400-500m ²The high-specific surface area of/g (BET), preferred 1200-600m ²/ g.

The X-ray powder diffraction pattern of the catalysis material among the present invention has shown mesopore molecular sieve and zeolite structured.The unit cell dimension of zeolite is with the number change of Al in the catalysis material.When the type of zeolite was MFI (code of material is MM5), unit cell dimension reduced with the quantity of aluminium, the 1.972nm of the 1.982nm when catalysis material contains 0.2wt%Al when catalysis material contains 3.9wt%Al.The variation of unit cell dimension with usually in zeolite observed variation opposite.

When zeolite type is BEA (code of material is MMBE), the size of structure cell is 1.428nm and 1.430nm, when zeolite type is MMW (code of material is MMMW22), the size of structure cell is 1.406nm and 1.436nm, when zeolite type was MOR (code of material is MMMO), the size of structure cell was 1.800nm and 1.806nm.

The d of mesopore molecular sieve MCM-41 ₁₀₀Spacing reduces along with the growth of zeolite content.D among the MM5 ₁₀₀Spacing is 4.4-3.8nm, d among MMBE and the MMMO ₁₀₀Spacing is 4.1-4.0nm, is 4.0-4.2 among the MMMW.

Pure zeolite and MCM-41 unit cell dimension and d mutually ₁₀₀Spacing is identical with their mechanical impurity.

d ₁₀₀The variation of spacing and unit cell dimension is the clear evidence of chemical bonding really between the zeolite of mesopore molecular sieve and embedding in the catalysis material among the present invention.

The characteristic feature of the catalysis material among the present invention (mesopore molecular sieve of embedding zeolite) characterizes by the specific area (BET) of X-ray powder diffraction, ESEM, transmission electron microscope, use nitrogen absorption measurement and the acidity of use ammonia-TPD and pyridine-FTIR measurement.

The sum of acid activity point can characterize by the ability of catalysis material bonding highly basic molecule such as ammonia or pyridine.Total acidity characterizes by ammonia-temperature programmed desorption (TPD), and Bronsted and lewis acidity characterize by pyridine infrared spectrum (FTIR).

The acidity of catalysis material can be by introducing structure Al quantity and change zeolite, MCM-41 and MM mutually the content of middle aluminium (Al) adjust.Relation in Fig. 1 a and the 1b demonstration catalysis material of the present invention between acidity and the aluminium content.Fig. 1 a explanation total acidity illustrates that with linear relationship and Fig. 1 b that Al-content in the different MM catalysis materials becomes zeolite and MCM-41 catalysis material are in the degree that departs from the MM catalysis material aspect the total acidity.Shown that with Al content zeolite MCM-41 acidity is less under close aluminium content than the acid sites of MM5, MMBE and MMMW sample greater number.

Owing to do not have the standard of international uniform to be used for acidity measurement, the method for using below be described herein.

Acidity measurement passes through NH ₃-TPD implements.The total acidity of catalyst is used the temperature-program desorption (NH of AltamiraAMI-100 instrument by ammonia ₃-TPD) characterize.Sample size is 40mg.Total acidity is passed through NH ₃Temperature-dependent desorption characterizes.The acidity of sample is by the NH of 200 ℃ of absorption ₃And the NH of desorption between 100 ℃ to 500 ℃ ₃Calculate.NH ₃-TPD instrument is equipped with the thermal conductivity detector (TCD) (TCD) that GowMac company produces.Adopt the slope of 20 ℃/min and temperature linearity to increase to 500 ℃ and keep 30min.Use known NH ₃Volume content is 10% NH ₃The pulse of-He gaseous mixture comes quantitatively.

Acidity measurement also can be measured by pyridine-FTIR.The acidity of sample by infrared spectrum (ATIMattson FTIR) use pyridine (〉=99.5%, a.r.) characterize as probe molecule qualitative and quantitative measurment Bronsted and lewis acid point.Sample is pressed into thin self-supporting disk (10-12mg/cm ²).At first descend the vacuum desorption pyridine to obtain the distribution of acid sites intensity in different temperature (250,300 and 450 ℃) then at 100 ℃ of following absorption pyridine 30min.All collection of illustrative plates equal 2cm in spectral resolution under 100 ℃ ^-1Condition under record.1545cm ^-1And 1450cm ^-1Bands of a spectrum be respectively applied for identification Bronsted (BAS) and Lewis acid site (LAS).BAS and LAS quantity use molar extinction coefficient to calculate by the intensity of corresponding bands of a spectrum.

Acid sites is positioned on the surface of catalysis material.Total surface area and pore volume use N ₂-absorption and desorption evaluation.Average mesoporous surface area and mesoporous diameter use BJH (Barrer-Joyner-Halenda) equation by N ₂-desorption is estimated.There is the size restrictions effect in the aperture to reactant and product.The size of micropore depends on the structure of zeolite.Be defined as micropore according to the IUPAC diameter less than the hole of 2nm, the hole of diameter between 2 to 50nm is defined as mesoporous.

The N of MMBE ₂-adsorption as shown in Figure 2.At the bore dia 2.4-2.7nm of material intermediary of embedding, close with the 2.6nm maintenance in the mesopore molecular sieve.

The BJH desorption that MMBE intermediary pore diameter distribution is described as shown in Figure 3.

Table 1 has been showed surface area, pore volume and the aperture value of MM5, MMBE and MMMW and the data of the MCM-41 that is used to contrast, MFI and BEA, therefrom surface area and total pore volume decline when zeolite is embedded in the mesopore molecular sieve as can be seen.

Table 1 surface area and porosity

Sample	BET area (m 2/g)	Mesoporous area (the m of BJH 2/g)	Total pore volume (cm 3/g)	BJH bore dia (nm)
					Na-MCM-41-20	949	947	0.82	2.6
Na-MM5-2ZS	896	1145	0.814	2.5
					Na-MM5-4ZS	820	1009	0.713	2.6
Na-MM5-4ZS-2Al	867	1069	0.794	2.5
					Na-MM5-4ZS-2Al25	733	599	0.656	2.4
MFI ZSM-5	360	100	0.351	20*
					Na-MMBE-4B	879	884	0.692	2.7
Na-MMBE-4B-2AI	844	859	0.742	2.7
					Na-MMBE-4B-2AI35	793	684	0.835	2.6
BEA	585	85	0.254	None
					H-MM-MW22	854	838	0.755	2.5
H-MM-MW22-2Al	808	772	0.703	2.5
					H-MM-MW22-2Al-35	728	639	0.834	2.5

* interparticle pore size

Zeolite is differentiated by X-ray diffraction (XRD).When the suitable interior timestamp of use can characterize and MCM-41 unit cell dimension mutually from XRD figure.Use α-Al ₂O ₃Or TiO ₂(rutile) is as interior mark.

The size of MFI structure cell characterizes by ASTM D3942-97 method, uses α-Al ₂O ₃As interior mark.

The structure cell of BEA characterizes by improved ASTM D 3942-97 method, uses TiO ₂As interior mark and be positioned at 22 ° of 2 θ [302] reflection.

The structure cell of MWW is determined by improved ASTM D 3942-97 method, uses α-Al ₂O ₃As interior mark and be positioned at 7.2 ° of 2 θ [100] reflection.

The unit cell dimension of MMMO is not by there being the location estimation at peak under the interior mark condition.The estimation formula is $a_0=2*d_{\left[100\right]}/\sqrt{3}.$

The unit cell dimension of mesopore molecular sieve (MCM-41) is by J.S.Becker et al., and the method for record is estimated among the J.Am.Chem.Soc.114 (1992) 10834.

The size of zeolite structure cell is corresponding to the quantity of the Al that mixes in zeolite structured.The Al atom is greater than the Si atom, and therefore unit cell dimension increases along with the increase of Al quantity usually in most of zeolites.On the contrary, by table 2 (MFI, BEA, MWW and MOR a ₀Can find that value) unit cell dimension reduces along with the increase of Al quantity in the MM5 catalysis material in the zeolite of embedding.The variation of MCM-41 unit cell dimension (UCD) is uncorrelated with the quantity of Al, and it weakens along with the increase of MFI phase intensity.The variation of unit cell dimension is the clear evidence that chemical bonding takes place between the zeolite of mesopore molecular sieve and embedding really.

MCM-41 and be embedded in the aluminium content of MFI, BEA, MWW and MOR zeolite in the mesopore molecular sieve (MCM-41) and unit cell dimension is listed in the table below in 2.

Table 2 aluminium content and unit cell dimension

Sample	Al(％)	MCM-41a 0(nm)	MFI, BEA MWW and MORa 0(nm )
				MCM-41	2.5	3.5	-
Na-MM5-2ZS	0.2	4.4	1.982
				Na-MM5-4ZS	0.4	4.2	1.981
Na-MM5-4ZS-2Al	1.5	4.3	1.979
				Na-MM5-4ZS-2Al35	3.9	3.8	1.972
MFI ZSM-5	1.4	-	1.978
				Na-MM-BE-4B	1.0	4.0	1.428
Na-MM-BE-4B-2Al	2.4	4.1	1.428
				Na-MM-BE-4ZS-2Al35	6.0	4.1	1.430
Na-MM-MW22-2Al	2.2	4.2	1.426
				H-MM-MW22	0.8	4.1	1.406
H-MM-MW22-2Al	2.2	4.1	1.436
				H-MM-MW22-2Al-35	3.7	4.0	1.427
MCM-22	2.4	-	1.405
				Na-MM-MO	1.0	4.1	1.800
Na-MM-MO-2Al	4.6	4.1	1.800
				H-MM-MO	1.0	4.0	1.806
Pt/H-MM-MO	1.1	4.1	1.806

The heat endurance of catalysis material of the present invention is tested by in air the material of embedding being exposed under 1000 ℃.The XRD diffraction pattern of the MM5 of calcining as shown in Figure 4.Obtain identical collection of illustrative plates later on 1000 ℃ of heat treatments, as shown in Figure 5.This result proves that significantly catalysis material of the present invention is heat-staple under at least 1000 ℃.

Use (HRTEM) (PhilipsCM-200FEG transmission electron microscope, point resolution 0.24nm) to study in the nanostructured of catalysis material of the present invention by the high-resolution transmission electron microscope.Composition is measured with EDS (NORAN Voyager energy disperses the X-ray spectrometer).The HRTEM figure that in Fig. 6 a, shows the mesoporous material of embedding beta-zeolite of the present invention.Be used for contrast, the HRTEM figure of orderly MCM-41 material is shown in Fig. 6 b.

Below describe the preparation method of the mesopore molecular sieve of embedding zeolite in detail.

The method of the mesopore molecular sieve of preparation embedding zeolite comprises step:

A) by silicon source and aluminium source and structure directing agent (template R) preparation zeolite nuclear, perhaps preparation is used for the silicate or the alumino-silicate precursor of described zeolite nuclear and randomly removes template by substep calcination program;

B) by silicon source, aluminium source and surfactant (S) preparation mesopore molecular sieve gel mixture randomly;

C) the zeolite nuclear or silicate or the alumino-silicate precursor that add the step a) preparation in step b) in the mesopore molecular sieve gel mixture that obtains are dispersed in described zeolite nuclear or silicate or alumino-silicate precursor in the molecular sieve gel;

D) mixture to step c) carries out the gel maturation under stirring condition;

E) remain under the sufficient condition by the mixture with step c), comprise that about 100 ℃-Yue 200 ℃ of following static state or dynamical fashion stir, the hydro-thermal of carrying out described mixture is synthetic, until forming crystal;

F) reclaim crystal;

G) clean solid product;

H) the drying solid product and

I) by substep calcination program part or all remove surfactant (S) and if in step a), do not remove, optionally remove described structure directing agent, obtain the mesopore molecular sieve of embedding zeolite catalyst thus.

In step a) by silicon source and aluminium source and structure directing agent (template R) preparation zeolite nuclear.The silicon source is selected from silica, preferred cataloid, solid silica and gas-phase silica.

The aluminium source is selected from aluminum sulfate (Al ₂(SO ₄) ₃.18H ₂O), algeldrate, aluminate, aluminum isopropoxide and aluminium oxide.

Select suitable template zeolite structured with what obtain expecting.The example of normally used template is alkyl ammonium hydroxide, alkyl ammonium halide, alkylamine hydroxide and alkylamine halide such as bromination tetrapropyl ammonium, tetramethyl ammonium hydroxide, tetramethylammonium bromide, tetraethylammonium bromide, tetraethyl ammonium hydroxide, piperidines, pyrrolidines, octylame, ethylenediamine, 1,6-diamino hexane and hexamethylene imine.

The temperature of step a) can be carried out under static state or dynamic mode with preparation at 40-200 ℃.At last, template is randomly removed by the heat treatment step that is called substep calcination program in step a).The temperature of handling is 350-900 ℃.If do not remove template in the step a), can be selectively in step I) remove template, but preferably remove in step a).

In step b) by silicon source, optional aluminium source, and surfactant (S) preparation mesopore molecular sieve gel.The silicon source is selected from silicon compound and the inorganic silicon source with organic group.These silicon sources with organic group are tetraethoxysilane (TEOS), silicic acid tetramethyl-ammonium, silicic acid tetraethyl ammonium etc.The inorganic silicon source is sodium metasilicate, waterglass, cataloid, solid silica and gas-phase silica.The aluminium source is selected from aluminum sulfate (Al ₂(SO ₄) ₃.18H ₂O), algeldrate, aluminate, aluminum isopropoxide and aluminium oxide.The meso-hole structure of option table surface-active agent to obtain expecting.The suitable surfactant that uses is that general formula is C _nH _2n+1(CH ₃) ₃* the halogenation trimethyl ammonium compound of NX, n=12-18 wherein, X=Cl, Br.Preferred surfactant be selected from bromination just-cetyl trimethylammonium, chlorination just-cetyl trimethylammonium, cetrimonium bromide and cetyltriethylphosphobromide bromide ammonium.The temperature of step b) be 20-100 ℃ and the preparation under stirring condition, carry out.

Zeolite nuclear that under stirring condition step a) is prepared in the step c) or silica or alumino-silicate precursor add in the molecular sieve gel.The mixture that forms is a homogeneous phase, and zeolite nuclear or silica or alumino-silicate precursor scatter.In order to regulate the acidity of product, can add extra aluminium source.Described extra aluminium source is to be selected from aluminum alkoxide, the aluminium source with organic ligand of preferred aluminum isopropoxide.The stir speed (S.S.) of step c) is 50-1000rpm.Processing time is 10-500min.

In the step d) under stirring condition the maturation gel.Stir speed (S.S.) is 200-1000rpm, and the maturation time of gel is 30-1800 minute.

Hydro-thermal is synthesized at temperature 100-200 ℃ and is carried out in the step e).Time of material water thermal synthesis of depending on expectation is between 10h-300h.Hydro-thermal is synthesized and is carried out the continuous stirring mixture until forming crystal under dynamical fashion.

Recycling step e in the step f)) crystal is for example by filtering or the known method of other prior art.If desired, reclaiming, before the pH of mixture is being transferred to 6-8 as filtration.

In the step g) with water for example as the thorough cleaning step f of washing lotion) solid product that obtains.The temperature of water is from room temperature to 60 ℃.When removing from solid product, finishes material that do not expect when all, soluble to clean.

Step h) removes by the known method drying solid product of prior art in and desolvate.

Step I) partly or entirely removes surfactant (S) by the heat treatment step that is called substep calcination program in.Can be randomly in step I) remove template (R) when removing surfactant.The temperature of handling is 350-900 ℃.Firing rate is 0.2 to 10 ℃/min.Heat treated atmosphere is oxidisability, and in the end the step material is handled in air usually.Obtain the mesopore molecular sieve of embedding zeolite catalyst.

The gel solution of preparation mesopore molecular sieve in the preparation method adds the zeolite nucleator then and replaces the aluminium source with the zeolite nucleator under the appropriate condition.Suitably, the aluminium source is aluminum alkoxide and aluminum isopropoxide preferably.

Preferred surfactant be bromination just-cetyl trimethylammonium, chlorination just-hexadecane base trimethylammonium, softex kw or cetyltriethylammonium bromide.

The solvent that preferred distilled water or deionized water clean as material.

Zeolite nuclear is that not have the alumino-silicate precursor of structure directing agent and they can partly or entirely be crystal.Since crystal size different their may by or do not surveyed by XRD.Yet, can pass through their form of scanning electron microscopic observation.Zeolite nuclear has meta-stable phase, and it in the building-up process of catalysis material of the present invention, realizes the chemical bonding with the mesopore molecular sieve wall in the presence of surfactant.

After the aluminosilicate salt core is scattered in the mesopore molecular sieve gel solution strongly, under the condition that surfactant exists, in gel maturation process, form the middle phase complex of nuclear-surfactant, the chemical bonding and the degree of crystallinity of its enhancing and reinforcement mesoporous material wall.

Be used for zeolite structured alumino-silicate precursor and can pass through prior art (EP 23089, United States Patent (USP) 3308069, EP 102716, EP23089) preparation as zeolite nuclear as MFI, BEA, TON, MOR, MWW, AEF and FAU.

Provide two embodiment of the alumino-silicate precursor of preparation MFI and BEA structural zeolite nuclear at this.Yet other zeolite of mentioning is same being suitable for obviously.

Zeolite nuclear by the alumino-silicate precursor preparation is suitable for using in preparing gel.Chemical interaction and bonding are undertaken by nucleation in gel maturation process.The gel maturation is accelerated into nuclear process and secondary nucleation can occurs and form complex " zeolite nuclear-surfactant in the middle of mutually " thus with endorsing at zeolite, and it has strengthened the chemical property of microfacies and middle bonding between mutually.Microfacies is responsible for forming zeolite structured, and the centre is responsible for forming meso-hole structure mutually.

If add zeolite nuclear after the surfactant in adding alkaline medium or before adding zeolite nuclear, in the surface-active aqueous solution, soak zeolite nuclear and carry out the gel maturation then, help forming " zeolite nuclear-surfactant intermediate ".

Add order, particularly surfactant and the zeolite nuclear of reagent, the preliminary treatment of zeolite nuclear and gel maturation process are important for the formation of the chemical property of the bonding between micropore and the mesopore molecular sieve.In order to obtain the novel mesopore molecular sieve of peracidity embedding zeolitic material, after adding zeolite nuclear but before the gel maturation, add the aluminium source.

In order to increase uniformity and the dispersiveness of zeolite nuclear in gel solution, it is important carrying out strong stirring after the adding zeolite nuclear in the gel preparation course.

The catalysis material that obtains randomly converts corresponding proton form to by ammonium ion exchange and calcining.The suitable raw material that is used for ammonium ion exchange is ammonium salt such as ammonium nitrate or ammonium chloride.Catalysis material is handled under as 1 to 6 hour 25-80 ℃ and suitable time interval in the aqueous solution of ammonium salt.The alkaline earth of ammonium cation alternate material or base cations in processing procedure.Can adjust the ion-exchange degree by the time that changes processing, the concentration and the temperature of ammonium salt solution.After ion-exchange treatment, material dry and that calcining obtains is proton and ammonia to decompose ammonium ion.

According to catalysis material of the present invention, the mesopore molecular sieve of novel embedding zeolite can comprise the method that precipitation, deposition, sealing and selectivity remove out and carries out modification by being selected from.Dipping and ion-exchange are deposition process.In dipping, deposit from liquid phase and absorption, ion-exchange and selective reaction take place on carrier or carry out with carrier surface.In removing the liquid process, the crystal of non-individual layer forms on the surface.Use the solution of dilution in ion-exchange, the metal ion of expectation exchanges to the cation or the proton of material substitution solid material from solution.Goal response is depended in the method and the selection of modification.Preferred ion switching method during usually, when the low load that needs metal with than high dispersive.

It is necessary removing surfactant after synthetic finishing, with the mesopore molecular sieve of the embedding zeolite that obtains having high surface and high acidity.Calcining heat, the rate of heat addition and duration influence surface area, pore-size distribution and the aluminium position in structure.The bigger serface (by nitrogen adsorption assay) of the mesopore molecular sieve of synthetic novel embedding zeolite has confirmed that with different strong acidity (TPD by ammonia measures) substep calcination program is the very proper method of removing surfactant.

Removing template from the mesopore molecular sieve of embedding zeolite also is to carry out in substep calcination program.

The synthetic of mesoporous material can carry out under the condition that is with or without extra aluminium source.In catalysis material is synthetic, only need a kind of template.

Catalysis material can be sneaked into carrier or loads on the carrier by the known method of prior art.

Synthetic method is introduced the zeolite properties of expectation thus by bonding zeolitic material in mesoporous material and is kept the complete crystal degree of hole wall that causes of meso-hole structure to increase simultaneously.In the method, be used for the synthetic gel solution of product and only need one type template.

At the small crystals of the synthetic mesolite of mesoporous material as " nuclear " and can change the concentration of " nuclear " and the size of zeolite catalyst.This causes the zeolite nuclear concentration to increase and causes a large amount of microcellular structures of embedding and the mesoporous wall degree of crystallinity of increase in the mesopore molecular sieve.It also influences heat endurance and the hydrothermal stability and the acidity of material.The variation of zeolite nuclear size may influence the shape alternative of material.

The high thermal stability and the hydrothermal stability of the mesopore molecular sieve of embedding zeolite such as MFI, BEA, MWW and MOR structure among x-ray diffraction pattern, ESEM and nitrogen adsorption characterization result confirmation the present invention.

And, at different hydrocarbon conversion reactions, as just-butane and 1-isomerization of butene and the oligomerisation of 1-decene in used catalyst can be fully or almost completely regeneration, and the maintenance of catalytic activity has also illustrated the stability of catalysis material.

The preparation method makes the characteristic acidity in the design mesopore molecular sieve become possibility.The characteristic acidity of meso-porous molecular sieve material can be used the aluminium source and change the Si/Al ratio of gel solution and change different zeolites nuclear and design.The characterization result of the ammonia TPD of H-MM5, H-MMBE and H-MMMW catalyst and different test reactions as just-the butane isomerization confirms to show aspect these materials of different acidity it is being successful in design.

The hole wall of mesoporous material is unbodied in MCM-41, but their show the degree of crystallinity that increases along with the adding of zeolite.Product mesolite structure cell of the present invention is different from the structure cell in zeolite and the mesopore molecular sieve mechanical impurity, and the structure cell of mesopore molecular sieve is greater than its structure cell in mechanical impurity.

Other principal character of product is that most of zeolite facies are chemically bound in mesopore molecular sieve.Product is heat-staple under at least 900 ℃ of temperature in air.

The method of the mesopore molecular sieve of the embedding zeolite of invention and this material of preparation obviously is different from the disclosed product of prior art and method and has shown several advantages.

Shown in XRD and SEM figure and surface area measurement, the new MM5 mesopore molecular sieve of embedding MFT structure is heat-staple until at least 1000 ℃, and MMBE is at least 900 ℃.

By with the ion-exchange of aqueous ammonium nitrate solution, then change at the cation of 100 ℃ of dryings and the MM5 that carries out 500 ℃ of calcinings, MMBE, MMMW and MMMO, as the Na-type among the embodiment, convert the proton type of corresponding M M5, MMBE, MMMW and MMMO to, shown in XRD figure, do not change structure, the hydrothermal stability of new material has been described.Known MCM-41 structure at high temperature with after water contacts is caved in.

Carry out metal-modified to MM5, MMBE, MMMW and MMMO, (use the aqueous solution of chloroplatinic acid to carry out 24 hours as particularly platinum modification of noble metal among the embodiment at 80 ℃, then 100 ℃ of dryings with 450 ℃ of calcinings), XRD figure shows the structure that can't influence MM5 and MMBE.This illustrative material is stable in acid medium.

The proton type of the mesopore molecular sieve of embedding MFI structure just-show very high activity in the reaction of butane and 1-isomerization of butene.The H-MM5 catalyst just showing-butanes conversion increases with acidity.

The proton type of the mesopore molecular sieve of embedding MFI and BEA structure shows very high activity in the 1-dimerizing olefins.H-MM5 and H-MMBE catalyst show that 1-decene conversion ratio increases and increases along with acidity.The proton type of the mesopore molecular sieve of embedding MFI structure shows very high activity and catalyst non-inactivation in the isobutene dimerization.

H-MM5 and the holomorphosis in air of H-MMBE catalysis material.The material of regeneration shows in 1-isomerization of butene and the oligomerisation of 1-decene and raw catelyst catalytic activity much at one.One of subject matter of known MCM-41 catalyst is regeneration, and promptly meso-hole structure caves in after the regeneration.The catalytic activity of the new mesopore molecular sieve of embedding zeolitic material in two reactions, keep clearly stating regeneration after structure be stable.

Pt-MM5 just-show that very high conversion and catalysis material keep its catalytic activity after regeneration in the butane isomerization.

Pt-MMBE demonstrates the high selectivity of divided ring product.

Therefore needn't be for MM5 and MMBE mesoporous material with the modification after synthetic to strengthen heat endurance and hydrothermal stability.The high thermal stability of new material and hydrothermal stability are embedded in the mesopore molecular sieve wall owing to using said method with zeolite as MFI and BEA structure.

The new mesoporous material of this group need not to be used for cracking, the aromatic alkylation of isomerization, the hydrocarbon of oligomerisation, the alkene of dimerization, the alkene of alkene, aromatization, etherificate, dehydration and the ring-opening reaction of light hydrocarbon through the further modification of active material just being can be used as catalyst.Metal-modified material shows high activity in the isomerization of lightweight paraffin.Similarly, when using the manner known in the art modification, metal-modified material also is activated in isomerization, hydrogenation, hydrogen cracking, hydrodesulfurization, hydrogenation deoxidation, hydrodenitrogeneration, dehydrogenation, reformation, Fischer-Tropsch reaction and the oxidation reaction of long-chain paraffin.Metal in the catalyst can be form metallic state, oxide or sulfide or with any other form of prior art known way modification.

The material of invention also can be removed middle use as absorption, absorption or selectivity in different separation techniques.

Below exemplary embodiment invention and actual embodiment thereof are described better, yet obviously to those skilled in the art scope of invention never be limited to these embodiment.

Embodiment

Embodiment 1 (contrast)

According to US 3,926,784 preparation ZSM-5 zeolites

Raw material is alumina silicate, aluminum sulfate, bromination triisopropylamine (TPABr), sodium chloride, sulfuric acid and water.

Mix 3.5g alumina silicate and 4.41 water and prepare solution A.

Mix 107g aluminum sulfate, 438g TPABr, 1310g NaCl, 292g H2SO4 and 61 water and prepare solution B.Solution joins in the reactor under the stirring of 250r/min mixing speed.Temperature rises to 100 ℃ and pressure gradually and rises to 8bar.Reaction is 6 days under stirring condition.Cooling reactor.Filter the solid product (ZSM-5) that forms, with the warm water cleaning with 110 ℃ of dried overnight.Calcination product is removed template, carries out ion-exchange and calcines the proton type (H-ZSM-5) for preparing zeolite with ammonium nitrate.

Embodiment 2-4 (contrast)

According to EP 0 784 652 preparation MSA section bar material

The raw material that synthetic MSA section bar material uses is aluminum isopropoxide (Al-i-C ₃H ₇O) ₃, tetraethyl orthosilicate (Si (C ₂H ₅O) ₄) and tetrapropylammonium hydroxide (TPA-OH).

TPA-OH, (Al-i-C ₃H ₇O) ₃Mixed 40 minutes down at 60 ℃ with water.The solution that obtains is heated to 85 ℃ and forms clear solutions.Add liquid Si (C through dropping funel then ₂H ₅O) ₄The mixture that obtains stirred 3 hours.Reactant mixture cooled off 20 hours under continuous stirring condition.The second alcohol and water that evaporation generates after the cooling, solid gel is 100 ℃ of dryings.The mill-drying solid and 550 ℃ the calcining 8 hours.

In following table 3, list prepared MSA type Preparation of catalysts and performance.

Table 3

Synthetic parameters	Embodiment	2 MSA-1	Embodiment 3 MSA-2	Embodiment 4 MSA-3
					Si/Al(mol/mol)	50	12	5
TPA-OH/ water (mol/mol)	0.18	0.18	0.18
				Properties of product
Si/Al(mol/mol)	54	11.5	4.8
				BET surface area (m 2/g)	650	440	310
Micropore surface amasss (m 2/g)	380	340	210
				Average pore size (nm)	1.4	1.4	1.4
Mesoporous surface area (m 2/g)	270	100	80

Embodiment 5 (contrast)

Preparation mesopore molecular sieve H-MCM-41

By the synthetic Na-MCM-41 of preparation solution A, B and C.By mixing gas-phase silica and distilled water continuous stirring preparation in 15 minutes solution A.In sodium metasilicate, add silicic acid tetramethyl-ammonium and mixture stirring preparation in 20 minutes solution B by continuous stirring.Dissolving bromination four decyl trimethyl ammoniums stir 20 minutes preparation solution C in distilled water.Mixture stirred 20 minutes again after under agitation slowly (15 minutes) added solution A and add B with solution B.Under agitation with solution C slowly (20 minutes) join in the mixture of A and B and after adding solution C mixture stirred again 20 minutes.Under agitation add aluminum isopropoxide, the mixture that obtains gel maturation 2 hours under stirring condition to gel mixture (A+B+C).Control pH and gel introduced the polytetrafluoroethylene (PTFE) cup place autoclave.Synthesize at 100 ℃ and carried out 48 hours.

After synthetic the finishing, the reactor chilling is cleaned it with the filtration mesoporous material with distilled water.The Na-MCM-41 that obtains is 110 ℃ of dryings with 550 ℃ of calcinings 10 hours.The Na-MCM-41 of sodium type uses the 1M aqueous ammonium nitrate solution 80 ℃ of ion-exchanges 2 hours, then with the NH that obtains ₄-MCM-41 with distilled water clean, dry and calcining.

Embodiment 6-8

The mesopore molecular sieve that embedding MFI is zeolite structured

Preparation MFI zeolite nuclear

Preparation is used to prepare three kinds of different solutions A, B and the C of MFI zeolite nuclear.Add the 10.5g gas-phase silica to 81.2ml distilled water and prepare solution A.Dissolving 2.2gNaOH and 0.3g Al (OH) in 9.4ml distilled water ₃The preparation solution B.Solution B is added in the solution A, and the gel mixture that obtains stirred 20 minutes.In 3.8ml water, dissolve 3.7g bromination tetrapropyl ammonium and stir 20 minutes preparation solution C.In gel mixture (A+B), add solution C and stirred 15 minutes and add 55ml water.The gel mixture that obtains stirred 20 minutes again.Synthesize at 150 ℃ and carried out 18 hours.Synthetic finish the back filtering product, with distilled water clean, dry and calcining, obtain the MFI zeolite and examine.

Embodiment 6a

Do not use the aluminium source, the synthetic zeolite structured mesopore molecular sieve of embedding MFI, Na-MM5-96h-4ZS

By the synthetic Na-MM5-96h-4ZS of preparation solution A, B and C.Mix 8.3g gas-phase silica and 51.7g distilled water and continuous stirring (r.m.p.196) preparation in 20 minutes solution A.Under continuous stirring (r.m.p.180), in the 11.7g sodium metasilicate, add 18.1g silicic acid tetramethyl-ammonium and mixture and stir 20 minutes preparation solution B.Dissolving 26.3g bromination four decyl trimethyl ammoniums and vigorous stirring (r.m.p.336) preparation in 20 minutes solution C in 174.3g distilled water.Mixture stirred 20 minutes again after slowly (15 minutes) were added solution B and added solution B in solution A under the vigorous stirring (r.m.p.320).Mixture stirred 20 minutes again after slowly (20 minutes) were added solution C and added solution C in mixture (A+B) under the vigorous stirring (r.m.p.336).

Then the above-mentioned preparation of 4.2g MF I nuclear be scattered under the condition in the gel mixture (A+B+C) in 20 minutes in vigorous stirring (r.m.p.340).Further vigorous stirring (r.m.p.340) gel made the MFI homogeneous phaseization of dispersion in 35 minutes.Gel solution maturation 3 hours under room temperature and stirring (r.m.p.180) condition then.The pH of control gel and gel introduced in the polytetrafluoroethylene (PTFE) cup.Put into autoclave then.Synthesize at 100 ℃ and carried out 96 hours.After synthetic the finishing, reactor cooling 30 minutes and with the meso-porous molecular sieve material of the embedding MFI structure that obtains mixes with distilled water, dry and with the thorough cleaning of distilled water 3 hours.Dry Na-MM5-96h-4ZS and in Muffle furnace, use substep calcination program 450 ℃ of calcinings 10 hours.

Embodiment 6b

The proton type of preparation above-mentioned material, H-MM5-96h-4ZS

10g Na-MM5-96h-4ZS (Na type, above-mentioned preparation) exchanges 24 hours with 1M ammonium nitrate or aqueous ammonium chloride solution at room-temperature ion.The NH that obtains after the ion-exchange ₄-MM5-96h-4ZS with distilled water thoroughly clean, dry and in Muffle furnace, use substep calcination program 450 ℃ of calcinings.

The XRD figure spectrum of the H-MM5-96h-4ZS that obtains is close with the collection of illustrative plates of Na-MM-5-96h-4ZS, illustrates that the water treatment of new mesoporous material and subsequent heat treatment do not influence stability of structure.

Embodiment 7

Use the mesopore molecular sieve of the synthetic embedding MFI structure in aluminium source, Na-MM5-96h-4ZS-2AI

Embodiment 7a

Synthetic Na-MM5-96h-4ZS-2AI

By the synthetic Na-MM5-96h-4ZS-2AI of preparation solution A, B and C.Mix 8.3g gas-phase silica and 51.7g distilled water and continuous stirring (r.m.p.196) preparation in 20 minutes solution A.In the 11.7g sodium metasilicate, add 18.1g silicic acid tetramethyl-ammonium and mixture under continuous stirring (r.m.p.180) condition and stir 20 minutes preparation solution B.In 174.3g distilled water, dissolve 26.3 brominations, four decyl trimethyl ammoniums and prepared solution C in 20 minutes in vigorous stirring (r.m.p.336).Mixture stirred 20 minutes again after slowly (15 minutes) were added solution B and added solution B in solution A under vigorous stirring (r.m.p.320).Mixture stirred 20 minutes again after slowly (20 minutes) are added solution C and added solution C in mixture (A+B) under the vigorous stirring (r.m.p.336).

4.2g MFI nuclear was scattered under the condition in the gel mixture (A+B+C) in vigorous stirring (r.m.p.340) in 20 minutes then.Further vigorous stirring (r.m.p.340) gel made the MFI homogeneous phaseization of dispersion in 35 minutes.Add the 2.3g aluminum isopropoxide then and stirred 20 minutes.The gel solution that obtains maturation 3 hours under stirring at room (r.m.p.180) condition.The pH of control gel and gel introduced place autoclave in the polytetrafluoroethylene (PTFE) cup then.Synthesize at 100 ℃ and carried out 96 hours.After synthetic the finishing, with the reactor chilling with filter the mesoporous material that obtains and thoroughly clean with distilled water.Na-MM5-96h-4ZS-2AI that drying obtains and usefulness substep calcination program calcining in Muffle furnace.

Embodiment 7b

Preparation H-MM5-96h-4ZS-2AI

10g Na-MM5-96h-4ZS-2AI (above-mentioned preparation) and 1M aqueous ammonium nitrate solution ion-exchange at room temperature 24 hours.After the ion-exchange mesoporous material with distilled water thoroughly clean, dry and in Muffle furnace with substep calcination program 450 ℃ of calcinings 4 hours.The XRD figure spectrum of the H-MM5-96h-4ZS-2AI that obtains is close with the collection of illustrative plates of Na-MM-5-96h-4ZS-2AI, illustrates that the water treatment of new mesoporous material and subsequent heat treatment do not influence stability of structure.

Embodiment 8

Use the mesopore molecular sieve of the synthetic embedding MFI structure in aluminium source, Na-MM5-96h-4ZS-2AI-35

Embodiment 8a

Synthetic Na-MM5-96h-4ZS-2AI-35

By the synthetic Na-MM5-96h-4ZS-2AI-35 of preparation solution A, B and C.Mix 4.5g gas-phase silica and 51.7g distilled water and continuous stirring (r.m.p.196) preparation in 20 minutes solution A.In the 11.7g sodium metasilicate, add 18.1g silicic acid tetramethyl-ammonium and mixture under continuous stirring (r.m.p.180) condition and stir 20 minutes preparation solution B.Dissolving 26.3 brominations, four decyl trimethyl ammoniums and vigorous stirring (r.m.p.336) preparation in 20 minutes solution C in 174.3g distilled water.Mixture stirred 20 minutes again after slowly (15 minutes) were added solution B and added solution B in solution A under vigorous stirring (r.m.p.320) condition.Mixture stirred 20 minutes again after slowly (20 minutes) were added solution C and added solution C in mixture (A+B) under vigorous stirring (r.m.p.336) condition.4.2gMFI nuclear with embodiment 6 preparations was scattered under the condition in the gel mixture (A+B+C) in vigorous stirring (r.m.p.340) in 20 minutes then.Further vigorous stirring (r.m.p.340) gel made the MFI homogeneous phaseization of dispersion in 35 minutes.Add the 2.3g aluminum isopropoxide and stirred 20 minutes to mixture then.The gel solution that obtains at room temperature stirred under (r.m.p.180) condition maturation 3 hours.The pH of control gel and gel introduced place autoclave in the polytetrafluoroethylene (PTFE) cup then.Synthesize at 100 ℃ and carried out 96 hours.After synthetic the finishing, with the reactor chilling with filter the mesoporous material that obtains and thoroughly clean with distilled water.Na-MM5-96h-4ZS-2AI-35 that drying obtains and usefulness substep calcination program calcining in 450 ℃ Muffle furnace.

Embodiment 8b

Preparation H-MM5-96h-4ZS-2AI-35

10g Na-MM5-96h-4ZS-2AI-35 (above-mentioned preparation) exchanges 24 hours with the 1M aqueous ammonium nitrate solution at room-temperature ion.After the ion-exchange mesoporous material through thoroughly clean, dry and with calcination program step by step in Muffle furnace 450 ℃ of calcinings.

The XRD figure spectrum of the H-MM5-96h-4ZS-2AI-35 that obtains is close with the collection of illustrative plates of Na-MM-5-96h-4ZS-2AI-35, illustrates that the water treatment of new mesoporous material and subsequent heat treatment do not influence stability of structure.

Embodiment 9

The MM5 material of preparation platinum modification, Pt-H-MM5-96h-4ZS-2AI

Method by dipping makes 5g H-MM5-96h-4ZS-2AI load 2wt%Pt.By using the chloroplatinic acid aqueous solution in rotary evaporator, to carry out the 2wt%Pt dipping in 24 hours at 80 ℃.The MM-5-96h-2AI of dipping 2wt%Pt is 100 ℃ of dryings with 450 ℃ of calcinings.The XRD figure spectrum of Pt-H-MM5-96h-4ZS-2AI shown in Figure 5 is close with the collection of illustrative plates of Na-MM-5-96h-2AI, illustrates that the mesopore molecular sieve of new embedding zeolite has hydrothermal stability.

Embodiment 10

The MM5 material of preparation platinum modification, Pt-H-MM5-96h-4ZS-2AI-35

Method by dipping makes 5g H-MM5-96h-4ZS-2AI-35 load 2wt%Pt.By using the chloroplatinic acid aqueous solution in rotary evaporator, to carry out the 2wt%Pt dipping in 24 hours at 80 ℃.The MM-5-96h-2AI-35 of dipping 2wt%Pt is 100 ℃ of dryings with 450 ℃ of calcinings.

The XRD figure spectrum of Pt-H-MM-5-96h-4ZS-2AI-35 is close with the collection of illustrative plates of Na-MM-5-96h-2AI-35, illustrates that the mesopore molecular sieve of new embedding zeolite has hydrothermal stability.

Embodiment 11-13

The mesoporous material of embedding BEA-structure

Preparation BEA zeolite nuclear

Mix 7.8g NaAlO ₂With 60ml distilled water and stirred 10 minutes and add 74g tetraethyl ammonium hydroxide (TEA-OH, 40%) and stirred 20 minutes to this solution.Add the 145.4g cataloid and stirred 25 minutes to above-mentioned solution.

The gel that obtains places the autoclave neutralization to be put in the polytetrafluoroethylene (PTFE) cup.Synthesize and carried out 65 hours at 150 ℃ with static schema.Filtration product after synthetic the finishing is cleaned with distilled water, 110 ℃ of dryings with 550 ℃ of calcinings 7 hours, obtains the BEA zeolite.

Embodiment 11a

Do not use the aluminium source, the mesopore molecular sieve of synthetic embedding BEA structure, Na-MMBE-96h-4B

By the synthetic Na-MMBE-96h-4B of preparation solution A, B and C.Mix 8.3g gas-phase silica and 51.7g distilled water and continuous stirring (r.m.p.196) preparation in 20 minutes solution A.In the 11.7g sodium metasilicate, add 18.1g silicic acid tetramethyl-ammonium under the continuous stirring (r.m.p.180) and mixture is stirred 20 minutes preparation solution B.In 174.3g distilled water, dissolve 26.3 brominations, four decyl trimethyl ammoniums in 20 minutes under the condition in vigorous stirring (r.m.p.336) and prepare solution C.Mixture stirred 20 minutes again after slowly (15 minutes) were added solution B and added solution B in solution A under vigorous stirring (r.m.p.320) condition.Mixture stirred 20 minutes again after slowly (20 minutes) were added solution C and added solution C in mixture (A+B) under vigorous stirring (r.m.p.336) condition.

The BEA zeolite nuclear precursor for preparing previously of 3.7g adds in the gel mixture (A+B+C) under vigorous stirring (r.m.p.350) condition then, gel maturation 3 hours under (r.m.p.180) condition of stirring.The pH of control gel also introduces gel and places autoclave in the polytetrafluoroethylene (PTFE) cup then.

Synthesize at 100 ℃ and carried out 96 hours.After synthetic the finishing, the mesoporous material that obtains of reactor chilling and filtering and thoroughly clean just with distilled water.The Na-MM-BE-96h-4B that drying obtains and with the calcining of substep calcination program.

Embodiment 11b

Preparation H-MMBE-96h-4B

10g Na-MMBE-96h-4B (above-mentioned preparation) exchanges 24 hours with 1M ammonium nitrate or aqueous ammonium chloride solution at room-temperature ion.After the ion-exchange mesoporous material with distilled water thoroughly clean, dry and with calcination program calcination step by step.

The XRD figure spectrum of the H-MMBE-96h-4B that obtains is close with the collection of illustrative plates of Na-MMBE-96h-4B, illustrates that the water treatment of new mesoporous material and subsequent heat treatment do not influence stability of structure.

Embodiment 12

Use the mesopore molecular sieve of the synthetic embedding BEA structure in aluminium source, Na-MMBE-96h-4B-2AI

Embodiment 12a

Synthetic Na-MMBE-96h-4B-2AI

By the synthetic Na-MMBE-96h-4B-2AI of preparation solution A, B and C.Mix 8.3g gas-phase silica and 51.7g distilled water and continuous stirring (r.m.p.196) preparation in 20 minutes solution A.In the 11.7g sodium metasilicate, add 18.1g silicic acid tetramethyl-ammonium and mixture under the continuous stirring (r.m.p.180) and stir 20 minutes preparation solution B.Under 20 minutes conditions of vigorous stirring (r.m.p.336) under the condition in 174.3g distilled water dissolving 26.3 brominations four decyl trimethyl ammoniums prepare solution C.Mixture stirred 20 minutes again after slowly (15 minutes) were added solution B and added solution B in solution A under vigorous stirring (r.m.p.320) condition.Mixture stirred 20 minutes again after slowly (20 minutes) were added solution C and added solution C in mixture (A+B) under vigorous stirring (r.m.p.336) condition.

3.7g BEA zeolite nuclear precursor (above-mentioned preparation) added in gel mixture (A+B+C) stirring to 25 minutes under vigorous stirring (r.m.p.350) condition then, added the 1.9g aluminum isopropoxide then and stirred 20 minutes.The gel that obtains was stirring under (r.m.p.180) condition maturation 3 hours.The pH of control gel and gel introduced place autoclave in the polytetrafluoroethylene (PTFE) cup then.Synthesize at 100 ℃ and carried out 96 hours.After synthetic the finishing, the reactor chilling is thoroughly cleaned with the filtration mesoporous material and with distilled water.The Na-MMBE-96h-4B-2AI that drying obtains also uses substep calcination program calcining 10 hours.

Embodiment 12b

Preparation H-MMBE-96h-4B-2AI

10g Na-MMBE-96h-4B-2AI (Na type, above-mentioned preparation) and 1M aqueous ammonium nitrate solution ion-exchange at room temperature 24 hours.After the ion-exchange meso-porous molecular sieve material with distilled water thoroughly clean, dry and with substep calcination program in Muffle furnace with calcination program calcination step by step.

The XRD figure spectrum of the H-MMBE-96h-4B-2AI that obtains is close with the collection of illustrative plates of Na-MMBE-96h-4B-2AI, illustrates that the water treatment of new mesoporous material and subsequent heat treatment do not influence stability of structure.

Embodiment 13

Use the mesopore molecular sieve of the synthetic embedding BEA structure in aluminium source, Na-MMBE-96h-4B-2AI 35

Embodiment 13a

Synthetic Na-MMBE-96h-4B-2AI-35

By the synthetic Na-MMBE-96h-4B-2AI-35 of preparation solution A, B and C.Mix 4.4g gas-phase silica and 51.7g distilled water and continuous stirring (r.m.p.196) preparation in 20 minutes solution A.In the 11.7g sodium metasilicate, add 18.1g silicic acid tetramethyl-ammonium and mixture under continuous stirring (r.m.p.180) condition and stir 20 minutes preparation solution B.Vigorous stirring (r.m.p.336) was dissolved 26.3 brominations, four decyl trimethyl ammoniums in 20 minutes and is prepared solution C in 174.3g distilled water under the condition.Mixture stirred 20 minutes again after slowly (15 minutes) were added solution B and added solution B in solution A under vigorous stirring (r.m.p.320) condition.Mixture stirred 20 minutes again after slowly (20 minutes) were added solution C and added solution C in mixture (A+B) under vigorous stirring (r.m.p.336) condition.3.7g BEA zeolite nuclear precursor (above-mentioned preparation) added in gel mixture (A+B+C) stirring to 25 minutes under vigorous stirring (r.m.p.350) condition then, added the 1.9g aluminum isopropoxide then and stirred 20 minutes.The gel that obtains was stirring under (r.m.p.180) condition maturation 3 hours.The pH of control gel and gel introduced place autoclave in the polytetrafluoroethylene (PTFE) cup then.Synthesize at 100 ℃ and carried out 96 hours.After synthetic the finishing, the reactor chilling is thoroughly cleaned with the filtration mesoporous material and with distilled water.The Na-MMBE-96h-4B-2AI-35 that drying obtains and with the calcining of substep calcination program.

Embodiment 13b

Preparation H-MMBE-96h-4B-2AI-35

10g Na-MMBE-96h-4B-2AI-35 (above-mentioned preparation) and 1M aqueous ammonium nitrate solution ion-exchange at room temperature 24 hours.After the ion-exchange meso-porous molecular sieve material with distilled water thoroughly clean, dry and in Muffle furnace, calcine with calcination program step by step.The XRD figure spectrum of the H-MMBE-96h-4B-2AI-35 that obtains is close with the collection of illustrative plates of Na-MMBE-96h-4B-2AI-35, illustrates that the water treatment of new mesoporous material and subsequent heat treatment do not influence stability of structure.

Embodiment 14

The MMBE material of preparation platinum modification, Pt-H-MMBE-96h-4B-2AI

Method by dipping makes 5g H-MMBE-96h-4B-2AI-35 (above-mentioned preparation) load 2wt%Pt.By using the chloroplatinic acid aqueous solution in rotary evaporator, to carry out the 2wt%Pt dipping in 24 hours under the condition at 80 ℃.The H-MMBE-96h-2AI of 2wt%Pt is flooded in dry and calcining.The XRD figure spectrum of Pt-H-MMBE-96h-4B-2AI is close with the collection of illustrative plates of parent Na-MM-BE-96h-4B-2AI, illustrates that new mesopore molecular sieve has hydrothermal stability.And more Pt modification H-MMBE-96h-4B-2AI does not influence the structure of parent.

Embodiment 15

The MMBE material of preparation platinum modification, Pt-H-MMBE-96h-4B-2AI-35

Method by dipping makes 5g H-MMBE-96h-4B-2AI-35 load 2wt%Pt.By using the chloroplatinic acid aqueous solution in rotary evaporator, to carry out the 2wt%Pt dipping in 24 hours under the condition at 80 ℃.The H-MMBE-96h-2AI-35 of 2wt%Pt is flooded in dry and calcining.The XRD figure spectrum of Pt-H-MMBE-96h-4B-2AI-35 is close with the collection of illustrative plates of Na-MMBE-96h-4B-2AI-35, illustrates that new mesopore molecular sieve has hydrothermal stability.And more Pt modification H-MMBE-96h-4B-2AI-35 does not influence the structure of parent.

Embodiment 16-18

Ion-exchange prepares Pt-H-MMBE:

The various H-MMBE materials of weighing 2g: H-MMBE-96h-4B (embodiment 16) in 2 liters of flasks, H-MMBE-96h-4B-2AI (embodiment 17) and H-MMBE-96h-4B-2AI-35 (embodiment 18).Add 1 and lift away from the water that son exchanges.Reflux condenser is placed on the flask top.Flask is placed in the water-bath, 70 ℃ of temperature and vibration 110.Flask was placed 1 hour with this understanding.Reflux condenser is replaced by the dropping funel that has exhaust outlet then.The 0.01MPt-solution of measuring 52ml adds dropping funel.Pt-solution slowly (15 of about per minutes) drips in the flask, 70 ℃ of temperature and vibration 110.The Pt interpolation time is 53 minutes.Dropping funel replaces with reflux condenser and flask was placed 24 hours with this understanding.

Use fritted glass crucible to filter the interior reactant mixture of flask with suction.The material that obtains cleans and filters once more with 1 water that lifts away from the son exchange in flask, and this operation is carried out twice.The fritted glass crucible that has material after cleaning for the second time was positioned in 80 ℃ of baking ovens 16 hours.

After 16 hours drying material is transferred in the crucible and in stove and calcines.Temperature rises to 300 ℃ with the speed of 0.2 ℃/min by 21 ℃.

Embodiment 19-28

The mesopore molecular sieve that embedding MWW is zeolite structured

Preparation MWW zeolite nuclear

Preparation is used to prepare the two kinds of solution A and the B of MWW zeolite nuclear.Add the 87.58g sodium metasilicate to 42ml distilled water and prepare solution A and stirred 15 minutes, in 25 minutes, dropwise add the 16.7g cyclohexane, agitating solution 20 minutes to this solution.Add the 7.35g concentrated sulfuric acid to 224ml distilled water, stir 10 minutes afterwards to wherein adding 8.9g aluminum sulfate and stirring 20 minutes preparation solution B.In solution A, slowly add solution B under the intense agitation.Gel is introduced the polytetrafluoroethylene (PTFE) cup place the 300ml autoclave.Synthesize revolving the shape pattern and under 150 ℃, carried out 96 hours.Filtration product after synthetic the finishing is cleaned with distilled water, 110 ℃ of dryings with 550 ℃ of calcinings 8 hours, obtains MWW zeolite nuclear precursor.

Embodiment 19a

Do not use the aluminium source, the mesopore molecular sieve of synthetic embedding MWW structure, Na-MM-4MW22

By the synthetic Na-MM-4MW22 of preparation solution A, B and C.Mix 8.3g gas-phase silica and 51.7g distilled water continuous stirring (r.m.p.196) preparation in 20 minutes solution A.In the 11.7g sodium metasilicate, add 18.10g silicic acid tetramethyl-ammonium and mixture under continuous stirring (r.m.p.180) condition and stir 20 minutes preparation solution B.Vigorous stirring (r.m.p.336) was dissolved 26.3 brominations, four decyl trimethyl ammoniums in 20 minutes and is prepared solution C in 174.3g distilled water under the condition.Mixture stirred 20 minutes again after slowly (15 minutes) were added solution B and added solution B in solution A under vigorous stirring (r.m.p.320) condition.Mixture stirred 20 minutes again after slowly (20 minutes) were added solution C and added solution C in mixture (A+B) under vigorous stirring (r.m.p.336) condition.

Then above-mentioned preparation 4.22g MWW zeolite nuclear precursor added under the condition in 20 minutes in the gel mixture (A+B+C) in vigorous stirring (r.m.p.340), gel disperseed to make the MWW homogeneous phaseization in 35 minutes further stirring (r.m.p.340).After this gel (r.p.m180) maturation at room temperature 3 hours under stirring condition.The pH of control gel and gel introduced place autoclave in the polytetrafluoroethylene (PTFE) cup then.Synthesize at 100 ℃ and carried out 96 hours.

After synthetic the finishing, mixes, filter with distilled water with reactor cooling 30 minutes and with the meso-porous molecular sieve material of embedding MWW structure and with the thorough cleaning of distilled water 3 hours.Synthetic Na-MM-4MW22 calcined 10 hours down at 550 ℃ with substep calcination program 110 ℃ of dryings with in Muffle furnace.

Embodiment 19b

Preparation H-MM-4MW22

10g Na-MM-4MW22 (Na type, above-mentioned preparation) exchanges 24 hours with 1M ammonium nitrate or aqueous ammonium chloride solution at room-temperature ion.The NH that obtains after the ion-exchange ₄-MM-4MW22 meso-porous molecular sieve material thoroughly cleans, calcined 4 hours at 450 ℃ with substep calcination program 110 ℃ of dryings 12 hours with in Muffle furnace with distilled water.

Embodiment 20

Use the mesopore molecular sieve of the synthetic embedding MWW structure in aluminium source, Na-MM-4MW22-2AI

Embodiment 20a

Synthetic Na-MM-4MW22-2AI

By the synthetic Na-MM-4MW22-2AI of preparation solution A, B and C.Mix 8.3g gas-phase silica and 51.7g distilled water and continuous stirring (r.m.p.196) preparation in 20 minutes solution A.In the 11.7g sodium metasilicate, add 18.1g silicic acid tetramethyl-ammonium and mixture under continuous stirring (r.m.p.180) condition and stir 20 minutes preparation solution B.Vigorous stirring (r.m.p.336) was dissolved 26.3 brominations, four decyl trimethyl ammoniums in 20 minutes and is prepared solution C in 174.3g distilled water under the condition.Mixture stirred 20 minutes again after slowly (15 minutes) were added solution B and added solution B in solution A under vigorous stirring (r.m.p.320) condition.Mixture stirred 20 minutes again after slowly (20 minutes) were added solution C and added solution C in mixture (A+B) under vigorous stirring (r.m.p.336) condition.

4.2g above-mentioned preparation MWW zeolite nuclear precursor added gel mixture (A+B+C) in 20 minutes under the condition in vigorous stirring (r.m.p.340).Gel further stirs the MWW homogeneous phaseization that (r.m.p.340) made dispersion in 35 minutes again.Add 2.3g aluminum isopropoxide and stirring 20 minutes then.Gel was stirring under (r.m.p.180) condition maturation 3 hours.The pH of control gel and gel introduced place the 300ml autoclave in the polytetrafluoroethylene (PTFE) cup then.Synthesize and under 100 ℃, carried out 96 hours.

After synthetic the finishing, thoroughly cleaned 3 hours with the meso-porous molecular sieve material of reactor chilling and filtration embedding MWW structure with distilled water.Synthetic Na-MM-4MW22-2AI is 110 ℃ of dryings and use substep calcination program 550 ℃ of calcinings 10 hours.

Embodiment 20b

Preparation H-MM-4MW22-2AI

10g Na-MM-4MW22-2AI (Na type, above-mentioned preparation) and 1M ammonium nitrate or aqueous ammonium chloride solution ion-exchange at room temperature 24 hours.The NH that obtains after the ion-exchange ₄-MM-4MW22-2AI meso-porous molecular sieve material thoroughly cleans, uses 110 ℃ of dryings 12 hours with in Muffle furnace substep calcination program 450 ℃ of calcinings 4 hours with distilled water.

The XRD figure spectrum of the H-MM-4MW22-2AI that obtains is close with the collection of illustrative plates of Na-MM-4MW22-2AI, illustrates that the water treatment of new mesoporous material and subsequent heat treatment do not influence stability of structure.

Embodiment 21

Use the mesopore molecular sieve of the synthetic embedding MWW structure in aluminium source, Na-MM-4MW22-2AI-35

Embodiment 21a

Synthetic Na-MM-4MW22-2AI-35

By the synthetic Na-MM-4MW22-2AI-35 of preparation solution A, B and C.Mix 4.5g gas-phase silica and 51.7g distilled water and continuous stirring (r.m.p.196) preparation in 20 minutes solution A.In the 11.7g sodium metasilicate, add 18.10g silicic acid tetramethyl-ammonium and mixture under continuous stirring (r.m.p.180) condition and stir 20 minutes preparation solution B.Vigorous stirring (r.m.p.336) was dissolved 26.3 brominations, four decyl trimethyl ammoniums in 20 minutes and is prepared solution C in 174.3g distilled water under the condition.Mixture stirred 20 minutes again after slowly (15 minutes) were added solution B and added solution B in solution A under vigorous stirring (r.m.p.320) condition.Mixture stirred 20 minutes again after slowly (20 minutes) were added solution C and added solution C in mixture (A+B) under vigorous stirring (r.m.p.336) condition.

4.2g the MWW zeolite nuclear precursor of embodiment 19 preparations was distributed under the condition in the gel mixture (A+B+C) in vigorous stirring (r.m.p.340) in 20 minutes.Gel further stirs the MWW homogeneous phaseization that (r.m.p.340) made dispersion in 35 minutes again.Add 2.3g aluminum isopropoxide and stirring 20 minutes then.Gel was stirring under (r.m.p.180) condition maturation 3 hours.The pH of control gel and gel introduced place the 300ml autoclave in the polytetrafluoroethylene (PTFE) cup then.Synthesize at 100 ℃ and carried out 96 hours.

After synthetic the finishing, the meso-porous molecular sieve material of reactor chilling and the embedding MWW structure that obtains mixed, filters with distilled water and with the thorough cleaning of distilled water 3 hours.Synthetic Na-MM-4MW22-2AI-35 was 110 ℃ of dryings 12 hours and use substep calcination program to calcine 10 hours at 550 ℃ in Muffle furnace.

Embodiment 21b

Preparation H-MM-4MW22-2AI-35

10g Na-MM-4MW22-2AI-35 (Na type, above-mentioned preparation) and 1M aqueous ammonium nitrate solution ion-exchange at room temperature 24 hours.The NH that obtains after the ion-exchange ₄-MM-4MW22-2AI-35 meso-porous molecular sieve material thoroughly cleans, calcined 4 hours at 450 ℃ in Muffle furnace in 110 ℃ of dryings 12 hours and use substep calcination program with distilled water.

The XRD figure spectrum of the H-MM-4MW22-2AI-35 that obtains is close with the collection of illustrative plates of Na-MM-4MW22-2AI-35, illustrates that the water treatment of new mesoporous material and subsequent heat treatment do not influence stability of structure.

Embodiment 22

The H-MM-4MW22-2AI of preparation platinum modification

Method by dipping makes 5g H-MM-4MW22-2AI load 2wt%Pt.By using the chloroplatinic acid aqueous solution in rotary evaporator, to carry out the 2wt%Pt dipping in 24 hours at 80 ℃.100 ℃ of dryings with at 450 ℃ of H-MM-4MW22-2AI that calcine dipping 2wt%Pt.The XRD figure spectrum of Pt-H-MM-4MW22-2AI is close with the collection of illustrative plates of parent Na-MM-4MW22-2AI, illustrates that the mesopore molecular sieve of new embedding MWW structure has hydrothermal stability.

Embodiment 23

The H-MM-4MW22-2AI-35 of preparation platinum modification

Method by dipping makes 5g H-MM-4MW22-2AI-35 load 2wt%Pt.By using the chloroplatinic acid aqueous solution in rotary evaporator, to carry out the 2wt%Pt dipping in 24 hours at 80 ℃.100 ℃ of dryings with at 450 ℃ of H-MM-4MW22-2AI-35 that calcine dipping 2wt%Pt.The XRD figure spectrum of Pt-H-MM-4MW22-2AI-35 is close with the collection of illustrative plates of Na-MM-4MW22-2AI-35, illustrates that the mesopore molecular sieve of new embedding MWW structure has hydrothermal stability.

Embodiment 24-28

The mesopore molecular sieve that embedding MOR is zeolite structured

Preparation MOR zeolite nuclear

Preparation is used to prepare the two kinds of solution A and the B of MOR zeolite nuclear.By adding 37.8g Ludox AS 30 to the 6.7g piperidines and stirring 15 minutes preparation solution A.By adding 44ml distilled water to 4.6g NaOH and stirring and added 5.9g aluminum sulfate in 10 minutes then and stir 15 minutes preparation solution B again.Vigorous stirring slowly added solution B under the condition in 15 minutes in solution A.Gel is introduced the polytetrafluoroethylene (PTFE) cup place the 300ml autoclave then.Synthesize and carried out 48 hours at 200 ℃ to revolve the shape pattern.Filtration product after synthetic the finishing is cleaned with distilled water, 110 ℃ of dryings with 550 ℃ of calcinings 10 hours, obtains MOR zeolite nuclear precursor.

Embodiment 24a

Do not use the aluminium source, the mesopore molecular sieve of synthetic embedding MOR structure, Na-MM-MO-4MO-96h

By the synthetic Na-MM-MO-4MO-96h of preparation solution A, B and C.Mix 8.3g gas-phase silica and 51.7g distilled water and continuous stirring (r.m.p.196) preparation in 20 minutes solution A.In the 11.7g sodium metasilicate, add 18.10g silicic acid tetramethyl-ammonium and mixture under continuous stirring (r.m.p.180) condition and stir 20 minutes preparation solution B.Vigorous stirring (r.m.p.336) was dissolved 26.3 brominations, four decyl trimethyl ammoniums (Fluka) preparation solution C in 20 minutes in 174.3g distilled water under the condition.Mixture stirred 20 minutes again after slowly (15 minutes) were added solution B and added solution B in solution A under vigorous stirring (r.m.p.320) condition.Mixture stirred 20 minutes again after slowly (20 minutes) were added solution C and added solution C in mixture (A+B) under vigorous stirring (r.m.p.336) condition.

Then the above-mentioned preparation of 3.7g MOR zeolite nuclear precursor added under the condition in 20 minutes in the gel mixture (A+B+C) in vigorous stirring (r.m.p.350), gel is further stirring the MOR homogeneous phaseization that (r.m.p.350) made dispersion in 30 minutes.After this gel under stirring condition (r.p.m180) room temperature maturation 3 hours.The pH of control gel and gel introduced place 300 autoclaves in the polytetrafluoroethylene (PTFE) cup then.Synthesize at 100 ℃ and carried out 96 hours.

After synthetic the finishing, the meso-porous molecular sieve material of reactor chilling and embedding MOR structure mixed, filters with distilled water and with the thorough cleaning of distilled water 3 hours.Synthetic Na-MM-MO-4MO-96h calcined 10 hours at 550 ℃ 110 ℃ of dryings with substep calcination program.

Embodiment 24b

Preparation H-MM-MO-4MO-96h

10g Na-MM-MO-4MO-96h (Na type, above-mentioned preparation) and 1M ammonium nitrate or aqueous ammonium chloride solution ion-exchange at room temperature 24 hours.The NH that obtains of ion-exchange ₄-MM-MO-4MO-96h meso-porous molecular sieve material thoroughly cleans, calcined 4 hours with substep calcination program at 450 ℃ 110 ℃ of dryings 12 hours with in Muffle furnace with distilled water.

The XRD figure spectrum of the H-MM-MO-4MO-96h that obtains is close with the collection of illustrative plates of Na-MM-MO-4MO-96h, illustrates that the water treatment of new mesoporous material and subsequent heat treatment do not influence stability of structure.

Embodiment 25

Use the mesopore molecular sieve of the synthetic embedding MOR structure in aluminium source, Na-MM-MO-4MO-96h-2AI

Embodiment 25a

Synthetic Na-MM-MO-4MO-2AI

By the synthetic Na-MM-MO-4MO-96h-2AI of preparation solution A, B and C.Mix 8.3g gas-phase silica and 51.7g distilled water and continuous stirring (r.m.p.196) preparation in 20 minutes solution A.In the 11.7g sodium metasilicate, add 18.10g silicic acid tetramethyl-ammonium and mixture under continuous stirring (r.m.p.180) condition and stir 20 minutes preparation solution B.Vigorous stirring (r.m.p.336) was dissolved 26.34 brominations, four decyl trimethyl ammoniums in 20 minutes and is prepared solution C in 174.3g distilled water under the condition.Mixture stirred 20 minutes again after slowly (15 minutes) were added solution B and added solution B in solution A under vigorous stirring (r.m.p.320) condition.Mixture stirred 20 minutes again after slowly (20 minutes) were added solution C and added solution C in mixture (A+B) under vigorous stirring (r.m.p.336) condition.

The MOR zeolite nuclear precursor of 3.7g embodiment 23 preparations was added under the condition in the gel mixture (A+B+C) in vigorous stirring (r.m.p.350) in 25 minutes.Under vigorous stirring (r.p.m350) condition, add the 1.9g aluminum isopropoxide then and stirred gel 30 minutes.Gel was stirring under (r.m.p.180) condition maturation 3 hours.The pH of control gel and gel introduced place the 300ml autoclave in the polytetrafluoroethylene (PTFE) cup then.Synthesize at 100 ℃ and carried out 96 hours.

After synthetic the finishing, the meso-porous molecular sieve material of reactor chilling 30 minutes and embedding MOR structure mixed, filters with distilled water and with the thorough cleaning of distilled water 3 hours.Synthetic Na-MM-MO-4MO-96h-2AI is 110 ℃ of dryings and use substep calcination program 550 ℃ of calcinings 10 hours.

Embodiment 25b

Preparation H-MM-MO-4MO-96h-2AI

10g Na-MM-MO-4MO-96h-2AI (Na type, above-mentioned preparation) exchanges 24 hours with 1M ammonium nitrate or aqueous ammonium chloride solution at room-temperature ion.The NH that obtains after the ion-exchange ₄-MM-MO-4MO-96h-2AI meso-porous molecular sieve material with distilled water thoroughly clean, 110 ℃ of dryings 12 hours with use the 450 ℃ of calcinings 4 hours in Muffle furnace of substep calcination program.

The XRD figure spectrum of the H-MM-MO-4MO-96h-2AI that obtains is close with the collection of illustrative plates of Na-MM-4MO-96h-2AI, illustrates that the water treatment of new mesoporous material and subsequent heat treatment do not influence stability of structure.

Embodiment 26

Use the mesopore molecular sieve of the synthetic embedding MOR structure in aluminium source, Na-MM-MO-4MO-2AI-35

Embodiment 26a

Synthetic Na-MM-MO-4MO-2AI-35

By the synthetic Na-MM-MO-4MO-2AI-35 of preparation solution A, B and C.Mix 4.4g gas-phase silica and 51.7g distilled water and continuous stirring (r.m.p.196) preparation in 20 minutes solution A.In the 11.7g sodium metasilicate, add 18.10g silicic acid tetramethyl-ammonium and mixture under continuous stirring (r.m.p.180) condition and stir 20 minutes preparation solution B.Vigorous stirring (r.m.p.336) was dissolved 26.3 brominations, four decyl trimethyl ammoniums in 20 minutes and is prepared solution C in 174.3g distilled water under the condition.Mixture stirred 20 minutes again after slowly (15 minutes) were added solution B and added solution B in solution A under vigorous stirring (r.m.p.320) condition.Mixture stirred 20 minutes again after slowly (20 minutes) were added solution C and added solution C in mixture (A+B) under vigorous stirring (r.m.p.336) condition.

3.7g the MOR zeolite nuclear precursor of embodiment 45 preparations added under the condition in the gel mixture (A+B+C) in vigorous stirring (r.m.p.320) in 25 minutes.Add 1.9g aluminum isopropoxide and stirring 20 minutes then.Gel is stirring under (r.m.p.180) condition room temperature maturation 3 hours.The pH of control gel and gel introduced place the 300ml autoclave in the polytetrafluoroethylene (PTFE) cup then.Synthesize at 100 ℃ and carried out 96 hours.

After synthetic the finishing, the meso-porous molecular sieve material of reactor chilling 30 minutes and the embedding MOR structure that obtains mixed, filters with distilled water and with the thorough cleaning of distilled water 3 hours.Synthetic Na-MM-MO-4MO-96h-2AI-35 was 110 ℃ of dryings 12 hours and use substep calcination program 550 ℃ of calcinings 10 hours.

Embodiment 26b

Preparation H-MM-MO-4MO-96h-2AI-35

10g Na-MM-MO-4MO-2AI-35 (Na type, above-mentioned preparation) exchanges 24 hours with 1M ammonium nitrate or aqueous ammonium chloride solution at room-temperature ion.The NH that obtains after the ion-exchange ₄-MM-MO-4MO-2AI-35 meso-porous molecular sieve material thoroughly cleans, calcined 4 hours at 450 ℃ in Muffle furnace in 110 ℃ of dryings 12 hours and use substep calcination program with distilled water.

Embodiment 27

The H-MM-MO-4MO-96h-2AI-35 of preparation platinum modification

Method by dipping makes 5g H-MM-MO-4MO-96h-2AI-35 load 2wt%Pt.By using the chloroplatinic acid aqueous solution in rotary evaporator, to carry out the 2wt%Pt dipping in 24 hours at 80 ℃.100 ℃ of dryings with at 450 ℃ of MM-MO-4MO-96h-2AI-35 that calcine dipping 2wt%Pt.The XRD figure spectrum of Pt-H-MM-MO-4MO-96h-2AI is close with the collection of illustrative plates of parent Na-MM-MO-4MO-96h-2AI-35, illustrates that the mesopore molecular sieve of new embedding MOR structure has hydrothermal stability.

Embodiment 28

Preparation platinum modification H-MM-MO-4MO-96h-2AI-35

Method by dipping makes 5g H-MM-MO-4MO-2AI-35 load 2wt%Pt.By using the chloroplatinic acid aqueous solution in rotary evaporator, to carry out the 2wt%Pt dipping in 24 hours at 80 ℃.100 ℃ of dryings with at 450 ℃ of HMM-MO-4MO-2AI-35 that calcine dipping 2wt%Pt.The XRD figure spectrum of Pt-H-MM-MO-4MO-96h-2AI-35 is close with the collection of illustrative plates of Na-MM-MO-4MO-96h-2AI-35, and the hydrothermal stability of the mesopore molecular sieve of new embedding MOR structure is described.

Embodiment 29

Heat stability testing

In air, heat materials of the present invention and carried out thermally-stabilised test in 24 hours at 700 ℃, 800 ℃, 900 ℃ and 1000 ℃.Above-mentioned processing is afterwards by BET and XRD analysis material.The XRD figure of the sample of 1000 ℃ of processing as shown in Figure 5.BET or XRD detect the display material structure and do not have difference.

Embodiment 30

The mechanically stable property testing

The mechanical stability of testing material of the present invention with the powder of 20000 newton's pressure extrusion material.The small pieces that form are pulverized and are sieved different particle diameters.The XRD and the BET that analyze varigrained screening powder by XRD and BET characterize.Do not observe the different of XRD figure spectrum or BET surface area and pore-size distribution.The results are shown in following table 4, list the N of mechanically stable property testing ₂The example of-absorption measurement result.

Table 4

Surface area and porosity (are used N 2Absorption method is surveyed)	BET area (m 2/g)	BJH area (m 2/g)	BET hole body (cm 3/g)	BJH pore volume (cm 3/g)	BET bore dia (_)	BJH bore dia (_)
							H-MM5-96h-4ZS 0.6-0.85	775	731	0.594	0.513	32	28
H-MM5-96h-4ZS ＜0.007	748	682	0.563	0.489	31	29

Embodiment 31

The reproducibility of method

Repeat the preparation process (embodiment 8) of identical material of the present invention with different scales.This batch as shown in table 5 shows quite similar performance, and the result of reproducibility test has been described.

Table 5

	Si(wt％)	Al (wt％)	Si/Al	MCM-41a 0 (_)	MFIa 0 (_)
						Embodiment 8	42.3	3.9	10.4	38	19.72
Embodiment 8 (10x enlarges scale)	42.7	3.8	10.9	36	19.73

Embodiment 32-41

Material of the present invention is used for the oligomerisation of 1-decene as catalyst

The high activity of catalyst of the present invention, low inactivation and recyclability have been shown with the oligomerisation of the 1-decene that material of the present invention is catalyst.In the oligomerisation of 1-decene, tested the comparative catalyst of catalyst of the present invention and prior art.Test is carried out under stirring condition in batch reactor.Reaction temperature is 200 ℃.Reaction time is 24 hours.Reactor pressure is about 20 crust (bar).

By GC and GC-distillation analysis product, based on the carbon number identification peak of molecule.In GC analyzed, carbon number was considered as lubricant composition greater than 20 molecule.The molecule of boiling is considered as lubricant molecule more than 343 ℃ in the GC-distillation analysis.

The catalyst that uses in the test is regenerated down at 540 ℃ in air in Muffle furnace.The architectural overview of 1-decene oligomerisation reaction test is in following table 6.

Table 6

Embodiment	Catalyst	Conversion ratio %	The lubricant selectivity, %	The lubricant productive rate, %
					32	ZSM-5(ex.1)	20	3	0.5
33	MSA-1(ex.2)	0.5	87	0.4
					34	MSA-3(ex.4)	1	87	0.9
35	MCM-41(ex.5)	45	97	29
					36	H-MM5-96h4ZS2Al35(ex.9)	71	97	69
37	H-MMBE-96h-4B-2Al(ex.12)	78	94	73
					38	H-MMBE-96-4B-2Al35(ex.13)	80	93	74
39	H-MM5-96h4ZS2Al35 Regen.	70	98	69
					40	H-MMBE-96h-4B-2Al Regen.	76	96	73
41	H-MMBE-96-4B-2Al35 Regen.	79	93	72

Regen.=regeneration

Embodiment 42 and 43

Material of the present invention is as the isobutene reaction of catalyst

As the isobutene reaction test that catalyst carries out, demonstrate the high activity and the low inactivation of catalyst of the present invention with material of the present invention.In fixed bed reactors under the condition of 100 ℃ of reaction temperatures, 20 crust (bar) and WHSV20 detecting catalyst.Observe the high activity and the non-inactivation of this catalyst.Catalyst and the isobutene reaction example of comparative catalyst (embodiment 1) in the isobutene dimerization of embodiment 8 in Fig. 7, have been contrasted.

Embodiment 44-47

Material of the present invention is the paraffin isomerization test of catalyst

Just-purpose of butane isomerization test is for interactional chemical property, the formation of strong Bronsted acidity point and the hydrothermal stability of new material in the mesopore molecular sieve that confirms embedding MFI structure among the present invention.Just-the butane isomerization as the assessment acidity of catalyst test reaction.New mesoporous molecular sieve catalyst with proton type is just carrying out-butane isomerization assessment acidity.H-type (H-MM5-96h-4ZS-2AI-35) catalyst of finding minimum Si/Al ratio shows the highest just-butanes conversion, clearlys show that the formation of strong Bronsted acid point and the new mesopore molecular sieve of embedding MFI structure form chemical bond really.

The regeneration of H-type and Pt-H-MM5 catalyst was carried out 2 hours at 450 ℃ in air.The purpose of regeneration is to assess whether can regain catalytic activity, owing to generate the hydrothermal stability that water also can further be assessed catalyst in the catalyst regeneration process in the regenerative process.Confirm that H-type and Pt modified catalyst almost completely regain catalytic activity, confirm the hydrothermal stability of structure.

In the fixed-bed micro-reactor that quartz is made research proton catalyst and 2wt%Pt-H-MM5-96h-4ZS-2AI catalyst just-butane is to the isomerization reaction of iso-butane.Experiment is 0.3-1.0g in the amount near the catalyst that carries out under the normal pressure and use.With hydrogen as carrier gas with reactant just-butane sends into reactor.With the online product analysis that carries out of the gas chromatograph that FI detector and capillary column are housed.Just-and the results are shown in the table 7 of butane isomerization test reaction, be illustrated in 450 ℃, WHSV 1.23h ^-1, just-butane/hydrogen ratio be under 1: 1 the condition just-the butane isomerization reaction.

Table 7 just-conversion ratio of butane

Embodiment	Catalyst	Conversion ratio (wt%)
			44	H-MM5-96h-4ZS-2AI	40
45	H-MM5-96h-4ZS-2AI-35	70
			46	Pt-H-MM5-96h-4ZS-2AI-35-C-Fesh	87
47	Pt-H-MM5-96h-4ZS-2AI-35-C-Reg	85

Embodiment 48 and 49

Material of the present invention is the 1-isomerization of butene test of catalyst

The purpose of 1-isomerization of butene reaction test is for the chemical interaction of the mesopore molecular sieve that confirms embedding MFI structure of the present invention, the formation of strong Bronsted acid point and the hydrothermal stability of new material.

The 1-isomerization of butene is the test reaction of different-butylene as research 1-isomerization of butene also.Further purpose is whether to regain catalytic activity after studying the possibility of used catalyst regeneration and assessing catalyst regeneration.Find used catalyst, after the 1-isomerization of butene, can regenerate.And regeneration catalyst shown almost identical 1-butene conversion (97.2mol%) with corresponding raw catelyst (97mol%), the hydrothermal stability of catalyst also is described.

The 1-isomerization of butene of having studied proton type H-MM5-96h-4ZS-2AI catalyst in the fixed-bed micro-reactor that quartz is made is the reaction of isobutene.Near normal pressure at 350 ℃, WHSV 10h ^-1Experimentize under the condition.With 1: 1 ratio reactant 1-butylene is sent into reactor as carrier gas with nitrogen.With the online product analysis that carries out of the gas chromatograph that FI detector and capillary column are housed.After GC, place the condenser product liquid sample of heavy compounds for convenience.Took out first sample in back 10 minutes at drive (TOS), preceding 10 sample rooms took out every 1 hour, and sample subsequently took out in per 3 hours.

Embodiment 50

Material of the present invention is as the open-loop test of catalyst

In the 50ml autoclave, under 20 crust Hydrogen Vapor Pressure conditions, test activity and the selectivity of catalyst of the present invention in the naphthalane ring-opening reaction at 250 ℃.(10ml～9.0g) adds to and contains 1g in the reactor of the catalyst of 250 ℃ of regeneration with naphthalane under the room temperature.Filling hydrogen boosts to 10 Ba Ran post-reactors and is placed in 250 ℃ of oil baths.When the temperature of reactor reaches 250 ℃.Hydrogen Vapor Pressure is adjusted into 20 crust.Reaction time is 5 hours.Reactor is quickly cooled to-10 ℃ then.The cooling post-reactor is weighed.Discharge autoclave pressure.Product to the shuttle and GC-sample that taking-up contains catalyst takes out by pin with filter.Catalyst of the present invention with embodiment 16 preparation carries out catalysis, the conversion ratio of naphthalane be 81% and the open-loop products selectivity be 32%.

Embodiment 51 and 52

Material of the present invention is the hydrocrack test of catalyst

In autoclave, under 30 crust Hydrogen Vapor Pressure conditions, test activity and the selectivity of catalyst of the present invention (embodiment 17) in hydrocarbon hydrocracking reaction in 300 ℃ (embodiment 51) and 350 ℃ (embodiment 52).Under the room temperature mineral wax mixture (about 80g) is added in the reactor that contains 400 ℃ of catalyst of regenerating down of 2g.Reactor boosts to 30 crust by hydrogen then.When the temperature of reactor reached 300 ℃ (embodiment 51) and 350 ℃ (embodiment 52), Hydrogen Vapor Pressure transferred to 30 crust.Reaction time is 65 hours.The cooling post-reactor is weighed.Discharge autoclave pressure.By the GC assay products.The conversion ratio of paraffin is that the pyrolysis product selectivity is 100% in 60% (embodiment 51) and 65% (embodiment 52) and the two kinds of situations.

Claims (16)

1. catalysis material is characterised in that described catalysis material be the mesopore molecular sieve of embedding zeolite and described catalysis material at least 900 ℃ temperature is heat-staple.

2. the described catalysis material of claim 1 is characterised in that described catalysis material specific area is 1400-500m ²/ g, preferred 1200-600m ²/ g.

3. claim 1 or 2 described catalysis materials are characterised in that described catalysis material comprises the mesopore molecular sieve that is selected from the M41S group, is preferably selected from the mesopore molecular sieve of MCM-41 or MCM-48.

4. each described catalysis material among the claim 1-3, be characterised in that described catalysis material comprises the medium hole zeolite that is selected from MFI, MTT, TON, AEF, MWW and FER zeolite or is selected from the large pore zeolite of BEA, FAU, MOR zeolite, preferred zeolite is MFI, MTT, AEF, BEA, MWW or MOR zeolite.

5. each described catalysis material among the claim 1-4 is characterised in that described mesopore molecular sieve is that MCM-41 or MCM-48 and described zeolite are MFI or BEA or MWW or MOR zeolite.

6. each described catalysis material among the claim 1-5 is characterised in that described catalyst is a proton type, cationic or metal-modified.

7. catalyst is characterised in that described catalyst comprises each the described catalysis material of claim 1-6 of 90-10wt-% and the carrier of 10-90wt-%.

8. the method for the mesopore molecular sieve of preparation embedding zeolite is characterised in that this method comprises the following steps:

A) prepare zeolite nuclear by silicon source and aluminium source and structure directing agent, perhaps prepare the silicate or the alumino-silicate precursor of described zeolite nuclear and randomly remove structure directing agent by substep calcination program;

B) prepare the mesopore molecular sieve gel mixture by silicon source, optional aluminium source and surfactant;

C) the described zeolite nuclear or silicate or the alumino-silicate precursor that add the step a) preparation in step b) in the described mesopore molecular sieve gel mixture that obtains are with described zeolite nuclear or silicate or alumino-silicate precursor homogeneous phaseization and be dispersed in the described molecular sieve gel;

D) under stirring condition, carry out the gel maturation of the mixture of step c);

E) remain under the sufficient condition by the mixture with step d), comprise that about 100 ℃-Yue 200 ℃ of following static state or dynamical fashion stir, the hydro-thermal of carrying out described mixture is synthetic, until forming crystal;

F) reclaim crystal;

G) clean solid product;

H) the drying solid product and

I) by substep calcination program part or all remove surfactant (S) and if in step a), do not remove, optionally remove described structure directing agent, obtain the mesopore molecular sieve of embedding zeolite catalyst thus.

9. the method for the mesopore molecular sieve of the described preparation embedding of claim 8 zeolite is characterised in that the silicon source in the step a) is selected from silica, is preferably selected from cataloid, solid silica and gas-phase silica.

10. the method for the mesopore molecular sieve of claim 8 or 9 described preparation embedding zeolites, one or more silicon sources in the step b) that are characterised in that are selected from the silicon compound with organic group and are selected from the inorganic silicon source, the silicon source that preferably has organic group is tetraethoxysilane, silicic acid tetramethyl-ammonium or silicic acid tetraethyl ammonium, and the inorganic silicon source is sodium metasilicate, waterglass, cataloid, solid silica or gas-phase silica.

11. the method for the mesopore molecular sieve of each described preparation embedding zeolite among the claim 8-10 is characterised in that described aluminium source is selected from aluminum sulfate (Al ₂(SO ₄) ₃18H ₂O), algeldrate, aluminate, aluminum isopropoxide and aluminium oxide.

12. the method for the mesopore molecular sieve of each described preparation embedding zeolite among the claim 8-11 is characterised in that it is C that described surfactant is selected from general formula _nH _2n+1(CH ₃) ₃* the Arquad compound of NX, n=12-18 wherein, X=Cl, Br, and preferred described surfactant be bromination just-cetyltrimethyl ammonium, chlorination just-hexadecane base trimethyl ammonium, softex kw and cetyltriethylammonium bromide.

13. the method for the mesopore molecular sieve of each described preparation embedding zeolite among the claim 8-12 is characterised in that extra aluminium source is selected from aluminum alkoxide, preferred aluminum isopropoxide.

14. among the claim 1-6 the described catalyst of each described catalysis material or claim 7 or according to Claim 8-13 in the mesopore molecular sieve of embedding zeolite of each preparation process the preferred purposes in cracking, aromatic alkylation, light hydrocarbon aromatization, etherificate, dehydration and the ring-opening reaction of dimerizing olefins, olefin(e) oligomerization, isomerisation of olefin, hydrocarbon at hydrocarbon.

15. the purposes of the described catalysis material of claim 6 in the isomerization of lightweight paraffin, the isomerization of long-chain paraffin, hydrogenation, hydrocracking, hydrodesulfurization, hydrogenation deoxidation, hydrodenitrogeneration, dehydrogenation, reformation, Fischer-Tropsch reaction and oxidation reaction.

16. claim 13 or 14 described in the oligomerisation of 1-decene, isobutene dimerization, just-purposes in butane isomerization, 1-isomerization of butene and the naphthalane open loop.

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